CONTENTS

INVITED KEYNOTE ........................................................................................................................................................ 1

STATUS OF METHANOL AS ALTERNATIVE FUEL FOR ENGINES IN CHINA ............................................................................. 2
TECHNICAL CHALLENGES TO AIR EMISSION CONTROL FOR COAL FIRED FACILITIES IN CHINA........................................... 3
RESEARCH DEVELOPMENT AND CHALLENGE OF FLOW BATTERY TECHNOLOGY ................................................................ 4
FUEL CELL VEHICLE POWER-TRAIN TECHNOLOGY PLATFORM RESEARCH AND DEVELOPMENT ........................................ 5
PERFORMANCE ASSESSMENT OF GREEN ENERGY SYSTEMS .............................................................................................. 6

AIR EMISSION CONTROL, REDUCTION AND MITIGATION .............................................................................. 7

RECENT ADVANCES IN CO2 CAPTURE TECHNOLOGIES INTEGRATION WITH SOLAR ENERGY ............................................. 8
EXAMINING THE EFFECTS OF ELECTRIFICATION ON IMPROVING THE CO2 EMISSION INTENSITY OF GDP IN BEIJING FROM 1996
TO 2012.............................................................................................................................................................................. 18
THE EFFECT OF ELECTROSTATIC FORCES ON GRANULAR FILTRATION EFFICIENCY FOR NANOAEROSOL PARTICLES ........ 29

ENERGY SAVING AND STORAGE ............................................................................................................................ 36

ADAPTIVE BATTERY STATE-OF-CHARGE AND CAPACITY DUAL ESTIMATOR WITH MULTI-SCALE EXTENDED KALMAN
FILTERS .............................................................................................................................................................................. 37
ELECTROCHEMICAL BEHAVIOR OF THE CHARGING LI-ION BATTERIES WITH DIFFERENT ELECTROLYTE SALT
CONCENTRATIONS ............................................................................................................................................................ 44
EFFECTS OF SALT CONCENTRATION ON THE ELECTROCHEMICAL AND THERMAL BEHAVIORS OF LITHIUM ION CELLS ... 52
PARAMETRIC STUDY OF BUILDING-INTEGRATED DUAL-FUNCTION SOLAR COLLECTOR UNDER WATER HEATING MODE
WITH NATURAL CIRCULATION .......................................................................................................................................... 62
PERFORMANCE OF A SHELL-ENCAPSULATED EVACUATED-TUBE SOLAR COLLECTOR INCORPORATED WITH A
COMPOUND CURVED SURFACE CONCENTRATOR ............................................................................................................. 70

WIND ENERGY ............................................................................................................................................................. 82

THE AEROELASTIC DAMPING ANALYSIS OF FLEXIBLE BLADES OF HORIZONTAL AXIS WIND TURBINE BASED ON
NONLINEAR AEROELASTIC COUPLING RESPONSE ............................................................................................................ 83
AN AXIAL SYMMETRY AUGMENTED WIND WHEEL AND ITS OPTIMIZED DESIGN ............................................................ 98
BATTERY SIZING FOR RESIDENTIAL WIND TURBINE SYSTEMS CONNECTED TO THE GRID .............................................. 105
EFFECTS OF THE AERODYNAMIC DAMPING ON THE TOWER LOAD OF OFFSHORE HORIZONTAL AXIS WIND TURBINES
........................................................................................................................................................................................ 116
VECTOR AUTO REGRESSIVE MODELS WITH EXOGENOUS VARIABLES FOR PREDICTING WIND SPEED ........................... 128
RESEARCH ON THE AERODYNAMIC CHARACTERISTICS OF A HYBRID LIFT/DRAG-BASED VERTICAL AXIS WIND TURBINE
........................................................................................................................................................................................ 140
i

TM

ECO-GREENERGY : THE FUTURE OF SMALL HYBRID WIND-SOLAR ENERGY GENERATION SYSTEM ............................. 154
NUMERICAL SIMULATION OF TRANSIENT FLOW ON VERTICAL AXIS WIND TURBINE WITH THE POWER-AUGMENTED
STATOR VANES ................................................................................................................................................................ 161
TECHNOLOGY ROADMAPPING FOR WIND TURBINE INDUSTRY: CASE OF THE IRAN ...................................................... 172
AUTOMATIC GENERATION CONTROL OF WIND ENERGY SYSTEM .................................................................................. 185

ENERGY MANAGEMENT IN ENGINES AND VEHICLES ................................................................................... 199

OPTIMAL ENERGY SCHEDULING OF GRID CONNECTED PV-DIESEL HYBRID SYSTEM TO POWER HEAT PUMP WATER
HEATER ............................................................................................................................................................................ 200
PERFORMANCE AND ENVIRONMENTAL EVALUATION OF AN ON-SITE WASTE-TO-ENERGY CONVERSION SYSTEM BY
USING EXHAUST AIR ENERGY RECOVERY TURBINE GENERATOR .................................................................................... 208
THEORETICAL ANALYSIS OF ENGINE WASTE HEAT RECOVERY SYSTEM BASED ON CO2 BRAYTON AND ORGANIC RANKINE
CYCLE ............................................................................................................................................................................ 216
THERMAL AND ECONOMIC ANALYSIS ON A COMBINED DIESEL ENGINE-ORGANIC RANKINE CYCLE (DE-ORC) SYSTEM
USED IN COOLANT HEAT RECOVERY OF DE .................................................................................................................... 225

ENGINE COMBUSTION WITH HIGH EFFICIENCY AND LOW EMISSIONS ................................................. 238
RESEARCH ON THE GENERIC TRENDS OF ENGINE PERFORMANCES IN A HEAVY DUTY SI LNG ENGINE AND APPLICATION
IN SIMULATION BASED PERFORMANCE DEVELOPMENT ................................................................................................ 239
NUMERICAL SIMULATION RESEARCH ON CORNSTALK REBURNING IN A PULVERIZED COAL COMBUSTOR ................... 253
A HIGH EFFICIENCY LOW EMISSION THERMODYNAMICS CYCLE FOR PRIME MOVERS BASED ON TIMED CONSTANT
VOLUME COMBUSTION .................................................................................................................................................. 263
A LOW PRESSURE DIRECT GAS INJECTION SYSTEM FOR A FOUR STROKE LPG DIESEL DUAL FUEL ENGINE ................. 274

GREEN BUILDING ...................................................................................................................................................... 283

THE COOLING LOAD CALCULATION OF A LARGE SYSTEM IN AN ENVIRONMENTAL CONTROL SYSTEM AT A SUBWAY
STATION INSTALLED WITH PLATFORM SCREEN DOORS .................................................................................................. 284
STUDY ON THE INFLUENCE OF ENVELOPE INSULATION MATERIALS ON THE BUILDING ENERGY CONSUMPTION ........ 292
NUMERICAL SIMULATION AND FLAMMABILITY ANALYSIS ON R32 LEAKAGE OF INDOOR AIR-CONDITIONER .............. 297
THERMAL PERFORMANCE OF USING A PCM SHUTTER IN BUILDINGS ........................................................................... 304
MODELLING OF RESIDENTIAL LIGHTING LOAD PROFILE USING ADAPTIVE NEURO FUZZY INFERENCE SYSTEM (ANFIS) ........... 317
OPTIMAL APPLIANCE SCHEDULING FOR HOUSEHOLD ENERGY MANAGEMENT ............................................................ 329
INDOOR HUMAN THERMAL COMFORT OPTIMAL CONTROL WITH SOLAR AIR HEATER DRIVEN DESICCANT COOLING
SYSTEM ........................................................................................................................................................................... 338

RENEWABLE AND CLEAN ENERGY TECHNOLOGIES ....................................................................................... 350

ii

PERFORMANCE ANALYSIS OF DIRECT METHANOL FUEL CELLS BY COATING DIFFERENT PROPORTIONS OF CATALYSTS ONTO FUEL
CHANNELS ........................................................................................................................................................................ 351
A TEST STUDY ON THE EFFICACY OF FOUR TIMES SERIES MODELS INVOLVING SHORT MEMORY, LONG MEMORY AND
HARMONIC PHENOMENA IN MODELLING AND FORECASTING SOLAR RADIATION DATA .............................................. 360
THE SOLAR ENERGY POTENTIAL OF SOUTH EASTERN ANATOLIA REGION IN TURKEY AND THE POTENTIAL USE OF
DEGREE ........................................................................................................................................................................... 370
HYGROSCOPIC EFFICIENCY ANALYSIS OF DESICCANT COATING HEAT EXCHANGERS WITH DIFFERENT SOLID DESICCANTS
........................................................................................................................................................................................ 382
THE MECHANICAL ANALYSIS AND EXPERIMENTAL VERIFICATION OF SCREEN-PRINTED FRONT ELECTRODE FOR
CRYSTALLINE SILICON SOLAR CELLS ................................................................................................................................ 390
DESIGN AND FABRICATION A DIRECT METHANOL FUEL CELL WITH THE THERMO ACTUATION BUBBLE REMOVAL
MECHANISM ................................................................................................................................................................... 401
REPOWERING OF AN EXISTING POWER PLANT BY MEANS OF GAS TURBINES AND SOLID OXIDE FUEL CELL ................ 410
GEOTHERMAL ENERGY SOURCES IN SIRNAK REGION-TURKEY ....................................................................................... 424
PROPOSAL AND ANALYSIS OF MID-TEMPERATURE SOLAR THERMOCHEMICAL HYBRIDIZATION POWER SYSTEM FOR
IMPROVING OFF-DESIGN PERFORMANCE ...................................................................................................................... 432
SYNTHESIS OF A NOVEL HUMIC ACID-BASED POLYCARBOXYLIC DISPERSANT FOR COAL WATER SLURRY...................... 447
MODELING FOR PASSIVE ALKALINE MEMBRANE DIRECT METHANOL FUEL CELL .......................................................... 456
START-UP OF HT-PEMFC .................................................................................................................................................. 466
STRUCTURE OPTIMIZATION OF SEGMENTED THERMOELECTRIC GENERATOR ............................................................... 475
A MODEL PREDICTIVE CONTROL APPROACH FOR OPERATION EFFICIENCY IN A VERTICAL SHAFT IMPACT CRUSHING
PROCESS .......................................................................................................................................................................... 485
INVESTIGATION ON INTERMITTENT HEAT PUMP DRYING PROCESS OF GREEN SOYBEAN ............................................. 494
NUMERICAL AND EXPERIMENTAL RESEARCH ON MULTI-STAGE PUMP AS TURBINE SYSTEM ........................................ 504
INFLUENCE OF THE PROPORTION OF DIFFUSE RADIATION ON CPC RECEPTION PERFORMANCE .................................. 514
SIMULATION AND ANALYSIS OF LIQUID-VAPOR SEPARATION CONDENSER IN AN ORGANIC RANKINE CYCLE ............... 525
A NEW APPROACH TO MODEL CONCENTRATING SOLAR CELLS UNDER NON-UNIFORM ILLUMINATION ...................... 538
SOLAR THERMAL DISSOCIATION OF CO2: TOWARDS HIGHER EFFICIENCIES ................................................................... 552
CHIMNEY EFFECT OF SOLAR HYBRID-DOUBLE WALL WITH PCM OF NA2CO310H2O ..................................................... 561
EFFECTIVE THERMAL CONDUCTIVITY OF MOF-5 POWDER UNDER A HYDROGEN ATMOSPHERE .................................. 573
SUSTAINABLE DESIGN OF A SMART GRID PHOTOVOLTAICS SYSTEM FOR SUBARTIC REGIONS ...................................... 587
HEAT DISSIPATION PERFORMANCE ANALYSIS OF HIGH HEAT FLUX RADIATOR ............................................................... 601

iii

EXPERIMENTAL INVESTIGATION OF SUPERCOOLING REDUCTION AND FREEZING POINT DEPRESSION OF ETHYLENE

GLYCOL SOLUTION BASED NANOFLUID........................................................................................................................... 612
NUMERICAL INVESTIGATION ON MOLTEN SALT MIXED CONVECTION IN BOTTOM-HEATED HORIZONTAL SQUARE TUBE
........................................................................................................................................................................................ 618
THERMODYNAMIC PERFORMANCE OF PARALLEL FLOW MICROCHANNEL CONDENSER WITH LIQUID-VAPOR
SEPARATION .................................................................................................................................................................... 627
INVESTIGATION ON THE CAPACITIVE PERFORMANCE OF THE POLYANILINE/MODIFIED GRAPHITE COMPOSITE
ELECTRODES.................................................................................................................................................................... 641
PREPARATION AND PROPERTIES OF NOVEL SIDE-CHAIN TYPE SULFONATED POLY (ETHER SULFONE ) MEMBRANES FOR
FUEL CELL APPLICATIONS ................................................................................................................................................ 647
THE EFFECTS OF HUMIDIFICATION TEMPERATURE ON THE PERFORMANCE OF A SINGLE PEM FUEL CELL WITHOUT AN
EXTERNAL COOLING CONTROLLER ................................................................................................................................. 656
LEAN METHANE PREMIXED COMBUSTION OVER CATALYTICALLY STABILIZED ZIRCONIA FOAM BURNER ...................... 663

BIOFUELS, BIOMASS AND BIOENERGY .............................................................................................................. 676

THE APPLICATION OF SULFONATED POLY(ARYLENE ETHER SULFONES) MEMBRANES IN
THE
DUAL-CHAMBER
MICROBIAL FUEL CELLS ................................................................................................................................................... 677
DISTRIBUTION AND CHARACTERIZATION OF LIQUID PRODUCTS FROM SOYBEAN OIL HYDROCRACKING WITH
COMMERICAL PETROLUEM CATALYST ............................................................................................................................ 686
USING BANANA PSEUDOSTEM SAP AS AN ELECTROLYTE IN BATTERIES ......................................................................... 694
PROSPECTIVE USE OF ANTIOXIDANTS IN 2

ND

GENERATION BIODIESEL FOR DIESEL ENGINES IN AUSTRALIA ................. 701

EFFECT OF COPPER OXIDE, ZINC OXIDE AND CALCIUM OXIDE ON THE CONVERSION OF BIO-ETHANOL TO
HYDROCARBONS OVER HZSM-5 CATALYST ..................................................................................................................... 714
DRY REFORMING OF METHANE OVER OIL PALM SHELL ACTIVATED CARBON AND ZSM-5 SUPPORTED COBALT CATALYST
........................................................................................................................................................................................ 723
COMPARISON OF CEIBA PENTANDRA, NIGELLA SATIVA AND THEIR BLENDS AS PROSPECTIVE BIODIESEL FUELS FOR IC
ENGINES .......................................................................................................................................................................... 731
ENERGY AND EXERGY ANALYSIS OF A LARGE SCALE BIOMASS GASIFICATION PROCESS ................................................ 742
SEPARATION OF SOLID PHASE PRODUCTS FROM HYDROTHERMAL LIQUEFACTION OF RICE STRAW ............................ 754
EFFECT OF TORREFACTION PRETREATMENT ON GASIFICATION OF BIOMASS ................................................................ 764
THE NOVEL TECHNOLOGY FOR BIO-DIESEL PRODUCTION FROM COOKING AND WASTE COOKING OIL BY
HETEROGENEOUS CATALYSTS AND MICROWAVE IRRADIATIONT.................................................................................... 775
PRODUCTION OF BIOELECTRICITY IN MFC BY PSEUDOMONAS FRAGI DRR-2 (PSYCHROPHILIC) ISOLATED FROM GOAT
RUMEN FLUID ................................................................................................................................................................. 786
STUDY ON THE EFFECT OF PH ON BIOGAS PRODUCTION FROM FOOD WASTE BY ANAEROBIC DIGESTION .................. 799
ENERGY CONSUMPTION ANALYSIS OF FRUIT AND VEGETABLE HOT WATER TREATMENT EQUIPMENT ........................ 806
iv

HYDROTHERMAL CARBONIZATION (HTC): AN INNOVATIVE PROCESS FOR LOW QUALITY LIGNOCELLULOSIC BIOMASS
CONVERSION TO HYDROCHAR FOR REPLACING COAL ................................................................................................... 816
DEVELOPMENT OF A REDUCED N-BUTANOL/BIODIESEL OXIDATION MECHANISM FOR A DUAL FUEL ENGINE ............. 830
EXPERIMENTAL AND NUMERICAL STUDIES ON RESIDENTIAL HEATING EQUIPMENT BURNING BIOMASS BRIQUETTES.............843
TECHNOECONOMIC ANALYSIS OF BIODIESEL PRODUCTION: A CASE STUDY OF JATROPHA CURCAS AND CALOPHYLLUM
INOPHYLLUM .................................................................................................................................................................. 856
REVIEW OF NON-EDIBLE BIOFUEL RESOURCES IN AUSTRALIA FOR SECOND GENERATION (2G) BIOFUEL CONVERSION
........................................................................................................................................................................................ 867
REVIEW OF BIODIESEL PRODUCTION FROM MICROALGAE: A NOVEL SOURCE OF GREEN ENERGY ............................... 879
ONE-STEP PREPARATION FOR IRON-DOPED TIO2 NANOTUBES: CHARACTERIZATIONS, SONOCATALYTIC ACTIVITIES AND
REACTION KINETIC STUDIES ............................................................................................................................................ 889
SYNTHESIS
AND
PROPERTIES
OF
NOVEL
MULTIBLOCK
COPOLYIMIDES
CONSISTING
OF
BENZIMIDAZOLE-GROUPS-CONTAINING SULFONATED POLYIMIDE HYDROPHILIC BLOCKS AND NON-SULFONATED
POLYIMIDE HYDROPHOBIC BLOCKS AS PROTON EXCHANGE MEMBRANES ................................................................... 903
EFFECTS OF DYNAMIC DRIVING CYCLE ON THE PERFORMANCE DEGRADATION OF PEM FUEL CELL BY SEGMENTED FUEL
CELL ................................................................................................................................................................................. 917
RESEARCH STATUS ON ENERGY RECOVERY FROM FOOD WASTE .................................................................................. 930
EFFECT OF INTERACTION BETWEEN VORTICES AND BLADES ON PERFORMANCE OF H-DARRIEUS VERTICAL-AXIS HYDRO
TURBINE .......................................................................................................................................................................... 939

POSTER ...................................................................................................................................................................... 949

WIND SPEEDS INTERVAL FORECASTS USING BACK PROPAGATION NEURAL NETWORK OPTIMIZED BY CUCKOO SEARCH
OPTIMIZATION ALGORITHM ........................................................................................................................................... 950
ECONOMIC AND ENVIRONMENTAL ANALYSIS OF HYBRID POWER SYSTEM FOR A SEMI-ARID REGION ........................ 962
RENEWABLE ENERGY REGULATORY POLICIES IN CHINA BASED ON SYSTEM DYNAMICS ............................................... 970
OPTIMIZATION OF NEURAL NETWORK FOR A BIOMASS-FIRED BOILER STEAM SYSTEM USING IMPROVED IMMUNE
ALGORITHM .................................................................................................................................................................... 981
RESEARCH ON THE RELATIONSHIP BETWEEN SOLAR CELL POWER OUTPUT AND THE THERMAL ENVIRONMENT WITH
DIMENSIONLESS METHOD .............................................................................................................................................. 992
DEGRADATION CHARACTERISTICS OF MEMBRANE ELECTRODE ASSEMBLY UNDER DRIVE CYCLE TEST PROTOCOL .... 1005
A PARTIALLY IMPREGNATED AGGLOMERATE MODEL FOR THE PEM FUEL CELL CATHODE CATALYST LAYER ................ 1014
EFFECT OF RECIRCULATION VAPOR QUALITY ON PERFORMANCE OF A DIRECT STEAM GENERATION SOLAR FIELD ... 1029
KINETICS AND THERMODYNAMICS INVESTIGATION OF SUPERCRITICAL REACTIVE EXTRACTION FOR JATROPHA CURCAS
L. SEEDS IN BIODIESEL PRODUCTION ............................................................................................................................ 1041
NATURAL ZEOLITE MINERALS AS STORAGE OF SOLAR ENERGY .................................................................................... 1054
v

THE GEOTHERMAL ENERGY CONVERSION BETWEEN FLASH-BINARY AND DOUBLE FLASH POWER SYSTEM .............. 1060
A NEW GAS CONCENTRATION DISTRIBUTION METHOD OF PROTON EXCHANGE MEMBRANE FUEL CELL .................. 1073
STUDY OF PATHWAYS TO MAXIMIZE ENGINE EFFICIENCY FOR FUTURE ENGINES ........................................................ 1087
OPERATING PRESSURE OPTIMIZATION OF A PEMFC POWER SYSTEM .......................................................................... 1105
CFD SIMULATION AND EXPERIMENTAL INVESTIGATION ON LIQUID FLOW OUTSIDE EVAPORATION TUBES AND ITS
INFLUENCE ON HEAT TRANSFER ................................................................................................................................... 1117
MEASUREMENT AND PREDICTION OF COMPRESSIVE BEHAVIOUR OF MEMBRANE ELECTRODE ASSEMBLY IN PROTON
EXCHANGE MEMBRANE FUEL CELL .............................................................................................................................. 1131
ANALYSIS ON MEA CAPTURE CO2 SYSTEM ENERGY CONSUMPTION CHARACTERISTICS UNDER THE IMPACT OF
OPERATING PARAMETERS CHANGED AND ENERGY-SAVING POTENTIAL PATHWAYS EXPLORE .................................... 1137

vi

Invited Keynote

Status Of Methanol As Alternative Fuel For Engines In China

Chunde Yao
State Key Laboratory of Engines, Tianjin University, Tianjin, Weijin Road 92#, 300072, China
Phone: (86) 22-27406649, Fax: (86) 22-27383362, Email: arcdyao@tju.edu.cn

Abstract

To meet the demand of fuel for internal combustion engines is a great challenge to China at present time. That more and
more petroleum oil need to import from overseas year by year has made a big burden to the government. To take
methanol as alternative fuel has become an important means at present time. The report will present the status of
methanol as alternative fuel for vehicle engines in China related to techniques. Meanwhile, it will introduce a new way
to make methanol to be used on compression ignition engine called Diesel/Methanol Compound Combustion (DMCC),
and to reform methanol into the gas with hydrogen rich applied to spark ignition engines.
The performance of the engine with DMCC could be remained the same as the baseline engine with pure diesel fuel.
Meantime, the exhaust emissions of the engine could meet the requirements of China IV (equal to Euro IV) legislation
without any urea as reduction. The field testing results for a HD truck modified with DMCC system illustrated that, for
the same power output, methanol could make about 30% power contribution for the engine, and less 2.0L of methanol
to substitute for 1.0L diesel fuel, fuel economy improved 6.66%.
The hydrogen-rich gases from methanol reformer are made by methanol dissociated with the heat recycled from the
exhaust emission of an engine. The testing results indicate that the engine can operate using a very lean fuel mixture due
to the wide ignition limit of the hydrogen-rich gases. When the excessive air/fuel ratio is higher than 1.4, NOx is
reduced by 90%, and CO emission is ultra-low, while the HC level is nearly the same as that of gasoline. In addition,
while maintaining the power output of the engine, lean burning of the hydrogen-rich gases and recycling partial exhaust
heat significantly improve the brake thermal efficiency of methanol.

Biography

Prof. Yao Chunde, was born in June, 1955. He graduated from Hefei Poly-technical University in February 1982. And
then he got his Masters degree and PhD in 1984 and 1988 respectively. At present time, he is Professor of Tianjin
University, the deputy director of State Key Laboratory of Engines, the member of Board of directors of Society for
Engineering Thermo-physics of China.
He once studied in the Aachen University of Technology of Germany, majoring in diesel engines for high efficiency and
low emissions (1993-1994) and worked in the advanced engine technique development company of Wisconsin, USA
(1995).
He has long been engaged in the research and teaching of I.C. Engine combustion fundamentals dealing with methanol
utility. He has fulfilled five projects granted by National Natural Science Foundation of China and many other projects
from different fields. He has authored or co-authored to publish more than 210 papers in various journals. He has
achieved 12 invent patents.
In recent years, he founds the theory for dual fuel combustion in CI engines and introduces a new combustion mode
called as diesel/methanol compound combustion (DMCC), which has been successful for heavy duty vehicle. In
addition, he is also working on improving gasolines burning efficiency with the bio-additive extracted from palm oil.

Technical Challenges To Air Emission Control For Coal Fired Facilities In China
Zhongchao (Chao) Tan
Department of Mechanical & Mechatronics Engineering
Department of Civil & Environmental Engineering
Director, Air Pollution Research & Innovation Laboratory
University of Waterloo
E3 3154, 200 University Ave. W., Waterloo, ON , N2L 3G1
Phone: (519) 888-4567 ext. 38718 Fax: (519) 885-5862 Email: tanz@uwaterloo.ca
Abstract
Air pollution in China has become a national challenge. According to the latest study of WHO, 1.2 million people die of
air pollution every year in China. It was estimated that $55.6 billion investment is needed for the effective control of
major air emissions in China. While the Chinese government continues to put forward more and more stringent air
emission standards and policies, the battle with air pollution will last for a few decades. And it should be longer than
European or North American countries. One of the reasons behind this challenge is the heavy reliance on dirty coals as
the dominating energy resources. Coal combustion accounts for more than 2/3 the energy production in China and this
situation will not change in short term.
Combustion of coals results in multiple air pollutants, among which fine particulate matter, sulfur dioxide (SO2) and
nitric oxides (NOx) are converted into smog. Source emissions of particulates are mainly controlled by electrostatic
precipitator and baghouse filters; SO2 is mainly controlled by wet scrubbing. Both are well developed technologies. The
latest target is NOx, and SCR is dominating, driven by the latest air pollution prevention standard (2013). It is generally
considered as expensive and unreliable. It works well for PM and SO2 free flue gases, such as those from natural gas
fired facilities. Inconsistent coal quality may fail the filtration or ESP systems. Failure of filtration or ESP systems
directly affects downstream air cleaning units, such as clogging the SCR reactors. Change in facility load also results in
unstable temperature and failure of SCR; High sulfur contents in coal related flue gases destroy the SCR catalysts
quickly. A typical system has a life time of only 2-3 years, or even shorter. An alternative approach is absorption, which
is also referred to as the 'wet' approach. It can be further classified into two subcategories, indirect absorption and direct
absorption. In an indirect absorption process, NO is oxidized into soluble NO2 and then absorbed by wet scrubber.
The oxidants include, but are not limited to, ozone, photocatalysts, KMnO4, etc. The high cost is associated with the
large amount of oxidants needed. Recent research is focused on simultaneous direct absorption of both SO2 and NOx
using one single absorbent. These absorbents include EDTA, H2O2, and cobalt based solvents; the latter is the most
recently emerging approach. It also requires effective cleaning of dust to reduce the costs for separation of suspended
solids in waste water. All in all, effective air emission control requires a systematic approach to the control of multiple
air pollutants.
Biography
Dr. Zhongchao Tan is an Associate Professor of Thermal Engineering at the Department of Mechanical and
Mechatronics Engineering at the University of Waterloo, Waterloo, Ontario, Canada. He is also affiliated with the
Department of Civil & Environmental Engineering. Prior to this position, he was an Assistant Professor and later on
promoted to Associate Professor at the University of Calgary from July 2004 to August 2010. He received his B.Sc.
and M.Sc. degrees, both in Thermal Engineering, in 1996 and 1999, respectively, from Tsinghua University, Beijing,
China. He received his Ph.D. degree in Bioenvironmental Engineering in 2004 from the University of Illinois at
Urbana-Champaign (UIUC), Illinois, USA. As the Director of the Air Pollution Research and Innovation Laboratory
(APRIL) at the University of Waterloo, Dr. Tans research focuses on air monitoring, air emission control and indoor air
cleaning equipment and systems. He has published about 50 peer reviewed journal articles and more than 45 prestigious
conference papers; he is writing the book entitled Air Pollution and Greenhouse Gas Emission Control to be published
by Springer in summer, 2014. He is an Editorial Advisory Board Member of The International Journal of Chemical
Reactor Engineering (IJCRE) and Sustainable Environment Research. And he was invited to serve on the Canadian
Environmental Technology Verification (ETV) Program Technical Advisory Committee (2013), and Indoor
Environment Research Program Technical Advisory Committee of the National Research Council Canada, Institute for
Research in Construction (NRC-IRC) (2012-2016).

Research Development And Challenge Of Flow Battery Technology

Huamin Zhang
Division of energy storage, Dalian Institute of Chemical Physics, Chinese Academy of Science, Zhongshan Road 457,
Dalian, 116023, Email: zhanghm@dicp.ac.cn
Large scale energy storage is one of the most critical technologies to ensure the smooth and consistent power output of
renewable energies. Flow batteries (FBs) are among the most suitable candidates for large-scale energy storage due to
their advantages like high safety, flexible design, high efficiency, long cycle life, etc. And numerous demonstrations
illustrated that flow battery can meet the demands of large-scale energy storage and is suitable for the applications like
renewable energy generation and the distributed energy supply etc. Flow batteries could be divided into different types
via changing the electrochemical couples with multivalent ions, e.g. NaSx/Br flow battery, Zn/Br flow battery, Zn/Cl
flow battery, Zn/Ni flow battery, Zn/Ce flow battery, Fe/Cr flow battery, and V/polyhalide flow battery and vanadium
flow battery (VFB ) etc. The Zn/Br, Fe/Cr and VFB flow batteries are currently in the process of demonstration.
Among different flow battery technologies VFBhas a unique advantage over other flow batteries due to the fact that
their positive and negative electrolytes are identical in their discharged states. This makes shipment and storage of
electrolyte more simple and inexpensive further greatly simplifies its management during operation.However, the
relatively low power density of VFB leads to its too high cost and their reliability still need to be further improved.
Therefore significant efforts were focused on improving the power density or operating current density of stacks. Dalian
Institute of Chemical and Physics (DICP) has devoted to VFB research for more than 10 years from materials to system
integration, where a spin-off company (Rongke power Co.Ltd) was established in 2008, and the demonstrations of VFB
in different application field were carried outincluding the world largest 5MW/10MWh VFB system installed in 2013.
To reduce the VFB cost, high power density stacks were designed and fabricated in recent years by optimizing the
materials and structure. The operating current density of 2kW stacks was increased from 80 mA/cm 2 to 160 mA/cm2,
with the energy efficiency more than 80%. (Fig 1), which can induce the cost to around 40%.

2kW VFB stacks

Performance of 2kW VFB stack
Figure 1.High power density VFB stacks developed by DICP.
To further improve the power density and lower the cost of flow batteries, other kind of flow batteries like single flow
battery, organic/inorganic metal free flow battery and non aqueous flow batteries were proposed and investigated. And
quite impressive progress was received on zinc-nickel single flow battery (ZNB) due to its advantages of low cost and
high energy density and the simple design (without membranes) and earth abundant raw materials. The current
challenges for ZNB is coming from the low operating current density and short cycle life induced by zinc accumulation.
Quite recently, very impressive progress was obtained in our groups by optimizing the materials (electrodes) and the
battery structure. The operating current density of ZNB was successfully improved from 20 mA/cm2 to 80 mA/cm2 and
the problem zinc accumulation was solved. The cycle life test indicated that: no obvious zinc accumulation was found
even after running more than 3000 cycles. Other groups had very important contribution on none aqueous flow battery
and organic/inorganic flow battery as well.
In this presentation, the development of different kinds of flow batteries will be summarized and the challenge and
possible solutions will presented as well.
References
[1] Cong Ding, Huamin Zhang, Xianfeng Li, Tao Liu, and Feng Xing,J. Phys. Chem. Lett,4 (2013) 12811294
[2] Yuanhui Cheng, Huamin Zhang, Qinzhi Lai, Xianfeng Li, Dingqin Shi, Liqun Zhang, J. Power Sources,
241( 2013)196-202
[3] Brian Huskinson1, Michael P. Marshak, Changwon Suh, Suleyman Er2, Michael R. Gerhardt1, Cooper J.
Galvin,Xudong Chen, AlanAspuru-Guzik, Roy G. Gordon, Michael J. Aziz1, Nature, 505 (2014) 195-198
4

Biography
Prof. Huamin Zhang is the Head of Energy Storage Division at Dalian Institute of
Chemical Physics, Chinese Academy of Sciences (DICP-CAS), he currently
serves as the Director of the State key laboratory of flow battery, the chief scientist
of national 973 project on flow battery, the Director of National Flow Battery
Standardization Technical Committee, and vice Chairman of China Energy Society.
He is the Vice President and CTO of Dalian Rongkepower Co., LTD. His research
interests include the topic of energy and energy storage, e.g. fuel cells, flow
batteries and batteries with high specific energy density. Professor Zhang has
co-authored more than 260 research papers published in refereed journals and
more than 230 patents. Prof. Zhang received various awards such as Japan
Chemical Society Academic Award, Four ministries Outstanding Scientific and
Technological Achievements Awards Scientific and Technological Progress Award
in Dallian and Provincial S&T Progress Award for his achievement in research.

Fuel Cell Vehicle Power-Train Technology Platform Research And Development

Tong Zhang
Director of Clean Energy Automotive Engineering Center of Tongji University, Email: tzhang@fcv-sh.com
Abstract
Based on the advanced fuel cell systems, batteries and motors, we will break through the core technology in advanced
fuel cell vehicle powertrain system, including grasp the fuel cell vehicle powertrain system and vehicle integration
technology. We will focus on these points as follow:
1. Research on the durability of fuel cell system
2. Research on the environmental suitability of fuel cell powertrain system
3. Set up Fault Diagnosis system
4. Propose the solution for step-down the input voltage, and provide a high efficiency in the whole range of output
voltage.
5. Optimize the key components in fuel cell vehicle powertrain.
6. Optimize the control strategy in fuel cell vehicle powertrain.
7. Balanced mix of vehicle technologies in Battery Electric Vehicles, Plug-in Hybrids and Fuel Cell Electric Vehicles.
Biography
Prof. Tong Zhang is a professor of School of Automotive Engineering of Tongji
University and Director of Clean Energy Automotive Engineering Center. He was
previously General Manager of Shanghai Fuel Cell Vehicle Powertrain Co.Ltd., a
High-Tech enterprise focusing on electric vehicle development in China and R&D
projects manager in Ford of Europe, Germany.
Devoted to the developing and commercializing of new energy vehicles in China, he
leads the national project the research of Fuel Cell Vehicle powertrain system platform,
and has been in charge of some other new energy vehicle projects, whose achievement
includes FCVs for the Beijing Olympic Games and the EXPO 2010 in Shanghai.
He graduated from Tsinghua University (P.R. China) with Bachelor Degree, and received
Doctor-Ing. Degree from TU Berlin, Germany.

Performance Assessment Of Green Energy Systems

Ibrahim Dincer
Professor of Mechanical Engineering
University of Ontario Institute Technology
Abstract
Green energy systems concept has become a new trend in many initiatives. By definition it essentially covers the energy
systems with no or minimum environmental impact and offer better sustainability for future. These systems are mainly
associated with renewable energies. One of the most critical issues about such systems appears to be performance
assessment which requires right efficiencies (such as energy and exergy efficiencies) and right performance coefficients
(such as energetic and exergetic coefficients of performance). Since there are also several situations where system
integration and multigeneration arrangements are carried out, it becomes even more critical to accomplish the
performance assessment. This presentation will introduce green energy systems and their applications, including most
recent ones from my group; discuss performance evaluation criteria, parameters, issues, utilizations and implications;
and highlight the necessity for system integration and multigeneration.
Biography
Ibrahim Dincer is a full professor of Mechanical Engineering in the Faculty of Engineering and Applied Science at UOIT.
He is Vice President for Strategy in International Association for Hydrogen Energy (IAHE) and Vice-President for
World Society of Sustainable Energy Technologies (WSSET). Renowned for his pioneering works in the area of
sustainable energy technologies he has authored and co-authored numerous books and book chapters, more than 1000
refereed journal and conference papers, and many technical reports. He has chaired many national and international
conferences, symposia, workshops and technical meetings. He has delivered more than 250 keynote and invited lectures.
He is an active member of various international scientific organizations and societies, and serves as editor-in-chief,
associate editor, regional editor, and editorial board member on various prestigious international journals. He is a recipient
of several research, teaching and service awards, including the Premiers research excellence award in Ontario, Canada in
2004. He has made innovative contributions to the understanding and development of sustainable energy technologies and
their implementation. He has actively been working in the areas of hydrogen and fuel cell technologies, and his group has
developed various novel technologies/methods/etc.

Air Emission Control, Reduction And Mitigation

RECENT ADVANCES IN CO2 CAPTURE TECHNOLOGIES INTEGRATION WITH

SOLAR ENERGY
S. Deng1*, R.K. Zhao1, S. Haussener2, Y.N. Liu3, L. Zhao1
1. Key Laboratory of Efficient Utilization of Low and Medium Grade Energy (Tianjin University), Ministry
of Education of China, Tianjin, 300072, China
2. Laboratory of Renewable Energy Science and Engineering, EPFL, Station 9, 1015 Lausanne,
Switzerland
3. School of Mechanical Engineering, Tianjin University, Tianjin, 300072, China
*TJU_S.Deng@foxmail.com

ABSTRACT
Carbon dioxide (CO2) capturing technologies can reduce the specific CO2 emissions from fossil fuelfired power plants. These technologies of capturing CO2 produce a concentrated stream of CO2 at
high pressure that can be transported to a storage site. Typical near and midterm CO2 capture
technologies are commonly based on chemical absorption, e.g. via a monoethanolamine-based
(MEA) absorbent. These technologies include an energy intensive regeneration process and,
consequently, consumes a great amount of energy to sustain a steady operation.
Renewable energy sources have been proposed to support CO2 capturing technologies in order to
further reduce the specific CO2 emissions. An especially well suited candidate is solar thermal energy.
It has already been used as an effective and clean energy source in industrial applications for drying,
heating, and cooling since the last century. Solar energy can meet the energy requirement of MEA
CO2 capturing processes, i.e. 120 C, with a reduction of the energy penalty from an extract steam.
In this paper, recent advances in CO2 capturing technologies integrated with renewable energy
sources are presented. Special emphasis is put on the integration of solar energy in CO2 capturing
technologies. We discuss major concerns for possible integration options including dynamic
performance matching, performance evaluation, and economics. Cutting-edge technologies in this
field such as direct, solar-driven CO2 capture from ambient air are briefly introduced. Future works for
possible integration options are suggested.
Keywords: solar thermal utilization, renewable energy, carbon capture, CCS
INTRODUCTION
Summary for policymakers in the Fifth Assessment Report (AR5) was released by the
Intergovernmental Panel on Climate Change (IPCC) on Sep. 2013. The conclusion shows that the
warming of the climate system is unequivocal, human influence on the climate system is clear, and
limiting climate change will require substantial and sustained reductions of greenhouse gas emissions
(IPCC, 2013). Among greenhouse gas control technologies, CO2 Capture and storage (CCS), which
realize a CO2 capture from various power systems, a separation from other gases, a transportation to
a storage site and a storage away from the atmosphere for a very long time, is an emerging
technology for a large-scale low-carbon fossil energy utilization (IPCC, 2005).
In order to facilitate the development of CCS technology, worldwide research groups, organizations,
institutions and governments have launched a major research campaign and initiated a series of
integrated demonstrations. USA, established an Interagency Task Force to CCS co-chaired by the
Department of Energy (DOE) and the Environmental Protection Agency (EPA) on Feb. 2010, with
proposing a plan to overcome the barriers to the widespread, cost-effective deployment of CCS within
ten years (EPA, 2010). As of Apr. 2011, USA has 89 CCS demonstration projects/pilots in active or
completed status (NETL, 2011). Founded in 2005, the European Technology Platform for Zero
Emission Fossil Fuel Power Plants aim to make CCS technology commercially viable by 2020 via an
EU-backed demonstration program (10-12 projects) (ZEP, 2005). In December 2008, the EU
established both a legal framework for CO2 storage and funding to support up to 12 CCS
demonstration projects. In July 2009, the European Council and the European Parliament adopted a
Commission proposal for a European Energy Programme for Recovery (EEPR). Moreover, 12 CCS
projects applied for assistance under the EEPR and six representative projects make substantial
progress in 2010 (European Commission, 2010).
CCS has been identified as a priority research and development direction in China since the launch of
the 11th Five-Year Plan (2006-2010) (MOST, 2012). In addition, it was proposed as well in the critical
research areas of advanced energy technologies in National Medium- and Long-Term Program for
Scientific and Technological Development (2006-2020). Until 2014 (the 4th year in the 12th Five-Year
Plan), more than 30 CCS projects, which involve the CO2 capture, transportation, storage, and
enhanced oil recovery, have been demonstrated in China (Administrative Centre for Chinas Agenda

21, 2012). Many of CCS projects or researches include a strong level of international cooperation
programmes with Australia, the European Commission, Norway, and the USA (IEA, 2010).
However, high energy consumption becomes one of the main barriers for CCS promotion. Taking the
mature post-combustion capture with MEA method as an example, a large amount of heat (3.5-4 GJ
per tonne CO2) is required for the regeneration of MEA solvent and the energy lost due to CO2
capture and compression is equal to an efficiency decrease of 25% in the power plant (Pellegrini et
al.,2009). The research on a MEA capture system in Huaneng Beijing coal-fired power plant shows
that the consumptive cost is app. 25.3 US$ per tonne CO2 for a 80-85% capture rate and 99.7%
purity, and the cost of electricity (COE) increase by 0.02 US$/kWh (Huang et al., 2010). Renewable
energy, such as solar energy, can be integrated in the CCS system as a sustainable energy source.
This paper will provide a review of the recent advances in the integration of solar energy with CCS
systems based on a literature research.
DATA SOURCE

Fig.1. Paper amount on CCS research from 1998 to 2013 with TOP 10 countries and academic organizations.

The reported data of existing researches on CCS are collected from publishing papers indexed by
SCOPUS from Jan. 1998 to Dec. 2013. As shown in Fig.1, the paper amount has increased from the
order of magnitude 10 to 1000 during the last 15 years and shows an approximate increasing trend
without regard to a slight fall in 2012. In addition to quantity, the quality of research on this topic can
be reflected by the academic level of international journal which accepts related research results. The
TOP 10 of the international academic journal, which are leading in the publish amount of CCS
research papers, include Energy, International Journal of Greenhouse Gas Control, Applied Energy,
etc. These journals are widely accepted as high-impact representatives by researchers. The TOP 10
countries and research organizations in the published paper amount are also shown in Fig.1.

Fig.2. Distribution of paper amount on CCS research topics.

Fig.2 shows a distribution of these published papers on various research topics of CCS. The energy
topic takes a majority. The largest proportion, or 25.1%, of papers focus on energy research. The
higher percent on the energy research field would even achieved if some results of energy-efficiency

performance in engineering projects/pilots are obtained. As mentioned in section 1, most of the nearand mid- term CO2 capture technologies are energy intensive. That may be also one of the reasons
why the biggest category of research topic is energy.
The review work presented in this paper is based on collecting data in the above-mentioned time
range and related topics. The paper is organized following a conventional method for technology
category in which the location of CO2 separation point was used as the technology boundary for
classification.
POST-COMBUSTION CO2 CAPTURE (Post-C CC)
As for the solar-assisted CCS (S-ACCS) system in the post-combustion category, the earliest
public description can be found in a world patent invented by Wibberley (2006). The system
diagram was shown in Fig.3. The concept design is based on the conventional post-combustion
technology by which CO2 in flue gas from plants can be absorbed by a suitable solvent. The
solvent is thereby converted into a CO2-enriched medium in a absorber. The desorption of CO2
from rich medium in a stripper can produce separate CO2 by heating. A solar energy field will
provide the thermal energy to the stripper (100-120oC) as the sole thermal source to meet the
demand of the regeneration heat. Because no backup heat source, such as extraction steam from
the low pressure turbine stages, was considered in the system, solvent storage vessels are used
for solar thermal energy storage. No claims to features of the solar collecting system are contained
in the patent due to a black box description of the solar field.

Fig.3. Diagram of baseline system (Wibberley, 2006)

Fig.4. Diagram of S-ACCS system with three-stage flash (Plaza et al.,

2010)

National Energy Technology Laboratory (NETL) presents a raw performance comparison among
12 CCS cases in which a solar-thermal case is included. Although the system diagram is not
provided, solar thermal energy, as described, is used to regenerate CO2 capture solvents, so that
a large portion of the parasitic penalty associated with the technology can be absolved. The
modelling of the solar system, which is conducted via THERMOFLEX, can provide calculated
results of solar-heating capacity, fluid-side pressure drop for given conditions of solar irradiance
and field operating. The comparison results show that solar-assisted MEA system is 6% higher in
efficiency over the base case without solar thermal utilization. However, cost, land requirement and
intermittent operation will limit the technology development.
Plaza, et al proposed a three-stage flash configuration to replace the stripper in MEA system. In
this way, higher temperature (>120oC) operating temperature can be achieved through a preheater
for a better separation efficiency. In addition, solar thermal energy, which is supplied to preheater
(Fig.4), can be yielded by solar collector with a high concentration ratio. The simulation results
show that the separation performance can be improved by 6% through three-stage flash. The
research focused on the alternate stripper configuration, so no details of the solar system are
reported.

10

Fig.3. Diagram of S-ACCS system with two thermal sources (Ordorica-Garica,

2011)

Fig.4. Diagram of S-ACCS system with output of compression work

(Cohen et al., 2011)

Ordorica-Garica, et al discussed three hybrid systems for combining the benefits of concentrating
solar thermal (CST) technology and fossil-fueled energy systems. The system structure in the
second case, so called solar-assisted post-combustion CO2 capture (SAPCAP) is similar to the
proposed one in Louiss patent. The difference is that two thermal sourcessolar thermal energy
and extraction steam are used to meet the thermal energy demand in the reboiler of stripper. So,
steam generated by solar energy field can partly offset the steam extracted from the plant. Relative
to the conventional post process with chemical absorption that normally requires the steam from
the turbine, the efficiency loss associated with CO2 capture can reduced in the SAPCAP. The
author also considered thermal energy storage (TES) in the solar energy system. The application
potential of the integration concept in SAPCAP was discussed briefly without detail parameters of
the system.
Cohen, et al presented an initial review of solar technologies for supplying energy to the CO 2
capture system, especially focus on high temperature systems. In addition to existing S-ACCSs,
the author also proposed a new system structure in which steam generated using solar energy is
used for CO2 compression as well as solvent stripping. Superheated steam above 900kPa/350oC
might be required if using solar steam to drive CO2 compressors and lower temperature saturated
steam (120-150oC) can be used for solvent stripping. The system diagram is shown in Fig. 4. In
addition, the feasibility of applying various solar collectors in post-combustion CO2 capture are
discussed in terms of operating temperature, efficiency and cost. The author concluded that
parabolic troughs and central receivers are technically able to provide energy to CCS system,
especially when coupled with thermal storage; low temperature solar thermal systems might
integrate better with solvent stripping equipment, and author believed that a more rigorous analysis
is required to definitively assess the feasibility of S-ACCS.
Table 1. Comparison between feasibility researches (Mokhtar, et al, 2012; Li, et al, 2012).
(Mokhtar, et al, 2012)
(Li, et al, 2012)
Parameters
NSW, AUS
Alice Springs, AUS; Beijing, CHN; Denver, USA
Location
300MW, coal-fired
520MW, coal-fired
Power plant
Linear Fresnel concentrators
Vacuum tube collector; Parabolic trough collector
Solar collector
Solid sensible storage
Phase change material
Thermal storage
Net annual benefits
Total capital requirement; Cost of CO2 avoidance; Cost of
Evaluated index
electricity
Solar load fraction, solar collector Location, solar collector and PCM cost, CO2 recovery
Variable
cost, carbon and electricity price
ratio

Mokhtar, et al and Li, et al performed a feasibility study and techno-economic assessment of SACCS, respectively. The main differences between two researches are shown in Table 1. Through
system assessment, Mokhtar, et al concluded that a border acceptance of S-ACCS is sensitive to
the boundary conditions: electricity prices, carbon taxes, cost of equipment, etc. With a raise of
electricity and carbon prices, the cost advantage of this technology will increase. Li, et al also
believed that this technology can effectively increase power generation and reduce the electrical
efficiency penalty from a technical viewpoint. The COE and COA are sensitive to the price of solar
thermal collectors, CO2 recovery ratio, although they are mainly determined by the local climatic
conditions. Two researches are both based on comparative study which has a baseline case with
option varies.

11

CO2 transport
Boiler

Turbines

Flue gas clean

Coal
Condersor

Stripper

Absorber

Reboiler
Pump

Regenerater

Turbines

Solar energy collector

ORC
Pump

Fig.5. Diagram of hybrid power system (Zhao et al., 2012)

Fig.6. Diagram of S-A CCS integrated with solar-ORC (Tan et al.,

2013)

Zhao et al proposed a structure for S-ACCS system, so called hybrid power system (Zhao et al.,
2012). In this system (Fig.5), the CO2 capture penalty is still completed by steam extracted from
the low-pressure turbine. Solar heat at approximately 300oC from parabolic troughs is integrated
into the regenerative Rankine cycle to heat the high-pressure feed water so that the high-quality
steam extractions of cycle (S9/S10/S11) can be replaced and the steam can expand efficiently in
the high-pressure turbine. The thermodynamic performance of the system was evaluated in terms
of operating parameters, energy conversion and economic efficiency. Compared to the abovementioned system using the solar energy to replace the low-quality steam for capture, the
proposed system can benefit from a lower annual cost of solar field and higher solar-to-electric
efficiency.
Feasibility of integrating a solar-driven Organic Rankine Cycle (ORC) system into a power plant
with amine-based CCS system was discussed by Tan et al. The system diagram is shown in Fig.6.
The electricity generation of ORC system is used for auxiliary devices, such as: solvent pumps,
and condensate heat is used to regenerate solvent. Based on supply-side conditions from
parabolic trough collector and demand-side conditions of the MEA CCS system, four candidate
working fluids, e.g. toluene, octane, are analyzed for possible system performance based on
simulation. Economic analysis and comparison among several typical CCS systems are conducted
based on levelized cost of electricity (LCOE), cost of carbon (COC) and net present value (NPV).
Researchers also presented an economic condition of subsidy electricity price for a potential
application of the developed system.

Fig.7. Technology solution summary for solar-assisted post-combustion CCS system

A summary of integrating solution was illustrated in Fig.7. Most of the research focus on the post-C
CC system with MEA solvent, although two researches proposed using solar thermal energy in

12

Pump

relatively lower temperature to CCS systems with NH3 method. In this case, lower requirement for
the solar collecting part can be easily met by the low cost scheme. For the MEA method, parabolic
trough collector (PTC) is considered to be a proper mid-temperature thermal source for cogeneration, no matter output work is directly used for CO2 compression or transferred to power. In
such a solar-driven co-generation system, after passing the power production unit, working fluid
can release the condensate heat to the demand side of post-C CC system. Thus, the total
utilization efficiency of solar thermal energy may be higher than direct-heat supply, although the
cost is higher. However, a trade-off between the power plant efficiency and solar energy utilization
efficiency may result in a more general design of S-ACCS in which solar heat is only used for
enhancing power efficiency of plant with/without post-C CC system. Based on the classification
method of CCS systems (Schrag, 2007), even solar thermal energy is not directly used for CCS,
but for a less coal or fossil consumption, such kind of solar-assisted system is also a CCS system.
Thus, a comprehensive comparison among different integration solution is necessary so that a
clear S-ACCS technology framework can be obtained with the feasible economical boundary.
PRE-COMBUSTION CO2 CAPTURE (Pre-C CC)
By integrating solar thermal energy, thermochemical conversion can be possible as an emissionfree process, not only because the quality of the primary feedstock was improved, but also
because the by-product CO2 steam can be easily connected to mature CCS technologies. Some
thermochemical process for solar fuels, such as solar steam gasification and solar steam reforming
with CO2 separation, can also be considered as a preprocessing part of pre-combustion CCS
system.

Fig.8. Diagram of LEHSOLCC (Li et al., 2013)

Fig.9. Basic diagram of solar-powered pre-combustion CO2 capture with

single-pass reactor (Giaconia., 2013)

A gas-steam combined cycle integrated with a solar thermo-chemical process and CO2 capture,
named LEHSOLCC (Low CO2 Emission Hybrid Solar Combined Cycle) (Fig.8), was developed by Li
et al. In addition to fossil fuel, solar thermal energy was used in this hybrid power system through PTC
and tower. The PTC can be used to provide heat at ~200oC for a generation of steam. Furthermore,
solar tower technology is used as thermal source for membrane reformer by which CH4 and steam
can be conversed to pure H2 (13 line) and CO2-rich syngas (line 12). With a pre-combustion
decarbonization, the syngas is finally processed in a MEA absorber in which more than 90% CO2 can
be removed. By providing thermal energy to the methane steam reforming, solar energy is converted
into the reformed syngas chemical energy so that not only power generation efficiency is higher, but
also CO2 capture is accomplished with a low energy penalty. The simulated results of specific
emission per electricity generation and exergy efficiency show a possible advantage to a conventional
natural-gas fired gas-steam combined cycle power plant. The similar system scheme was introduced
in (Giaconia, 2013) and the difference is a concentrating solar power (CSP) plant was integrated into
the system as a sole thermal source for steam-generation, pre-heating, and membrane reaction.
Molten salts are used as working medium of heat transfer and storage up to 550-660oC
Giaconia also introduced a solar-powered steam reforming system with a single-pass reactor (Fig. 9).
The main product is hydrogen/methane blends and the by-product is 10-18%vol CO2 steam. Two
storage tanks system of CSP was applied to supply 550oC molten salts to the single-pass reactor for
syngas. The CO2 can be captured via MEA or NH3 method.
OXYGEN-COMBUSTION CO2 CAPTURE (O-C CC)

13

Fig.10. System structure of CO2-capturing power generation system using

gasified coal and solar heat (Pak and Kousugi., 2002)

Fig.11. Flowsheet diagram of solar thermal hybrid H2O turbine power

generation system (Gou et al., 2007)

Pak and Kousugi proposed a solar-assisted power system with an oxygen-combustion CO2 capturing.
The thermal energy from PTC was used for generating steam to a drum boiler (Fig.10). In place of air,
pure oxygen was input into the combustor with saturated steam and fuel so that a flue gas of mostly
CO2 and water vapor can be finally provided to cooling units, resulting in higher concentrations of CO2
at low pressure. The calculated results show that the net generation efficiency of the proposed system
is 40.1%, which correspond to a fuel savings of 18.5%, compared to a conventional coal gas
combined cycle power generation system.
An update system to the one proposed by Pak and Kousugi was presented in (Gou et al., 2007). As
shown in Fig.11, the solar thermal utilization loop was simplified to a direct-evaporation process in the
middle-temperature solar collector. Moreover, a low pressure turbine (LPT) in figure 11 was used to
replace a recuperator in the reference system of figure 10. A comparison result shows that a net
solar-to-electric efciency of 95.90% and an exergy efciency of 55.88% at the average collector
temperature 272.8oC,which is 21.61 percentage points higher than those of the reference system.
CHEMICAL LOOPING COMBUSTION CO2 CAPTURE (CLC CC)
Direct combustion of carbonaceous fuel, no matter where the CO2 separation point is located,
produces CO2 diluted by N2, which lead to a decrease in the efficiency of power plant with CO2
capture. Applying the chemical looping combustion (CLC), the stoichiometric oxygen needed for CO2
and water formation is supplied by the solid oxygen carrier in a fuel reactor, so that a nitrogen-free
mixture can be obtained with a complete combustion. Then, the high-concentration CO2 formed can
be recovered by directly condensing water vapor without an additional energy intensive process for
CO2 separation. Although it is commonly classified as one kind of OC CC system, CLC CC can
achieve both an increase in power generation efficiency simultaneously with a lower energy penalty.
As shown in Fig.13, concentrated solar radiation from heliostat field is reflected into the solar fuel
reactor. The sensible solar thermal heat can be stored and released at a temperature of 1102 and
1386K, respectively, through a thermochemical conversion. NiO, which is used as an oxygen carrier
particle, is reduced within the fuel reactor and re-produced in the air reactor. By an indirect transfer of
oxygen from the air to the fuel, the proposed solar-chemical loop combustion (CLC) hybrid system
stores the solar thermal heat within the fuel reactor at a relatively low temperature, and released it into
the air reactor at a higher temperature. The simulation results show that 70% of the absorber solar
energy in the solar fuel reactor can be stored for an efficient application in energy storage.
A solar-hybrid combined cycle with CLC integrating solar thermal energy at 200oC was proposed in
(Hong et al, 2010). The schematic flow diagram of the system is shown in Fig.12. Concentrated solar
thermal energy (200oC) is used in a pre-heater for an evaporation of methanol fuel and in a fuel
reactor for an endothermic reaction at 150oC, 1 bar. The simulation results show that the new cycle
can achieve a 55% CO2 separation with no energy penalty. During the reaction,solar thermal energy
can be converted into the chemical energy and stored in the solid fuel of FeO.In the oxidation reactor,
FeO is oxidized and the stored solar thermal energy can be released as thermal energy at 1000C.
Thus, the energy grade of the solar thermal energy at 200C can be upgraded compared with that of
direct combustion and this lead to to 13% higher work out, compared to that of the conventional solarassisted power plant which use solar thermal energy (450oC) for a saturated steam generation.

14

Fig.12. Flow diagram of the solar-hybrid thermal cycle with CLC (Hong et al.,
2010)

Fig.13. Configuration of solar-CLC hybrid system (Jafarian et al., 2013)

As shown in Fig.13, concentrated solar radiation from heliostat field is reflected into the solar fuel
reactor. The sensible solar thermal heat can be stored and released at a temperature of 1102 and
1386K, respectively, through a thermochemical conversion. NiO, which is used as an oxygen carrier
particle, is reduced within the fuel reactor and re-produced in the air reactor. By an indirect transfer of
oxygen from the air to the fuel, the proposed solar-chemical loop combustion (CLC) hybrid system
stores the solar thermal heat within the fuel reactor at a relatively low temperature, and released it into
the air reactor at a higher temperature. The simulation results show that 70% of the absorber solar
energy in the solar fuel reactor can be stored for an efficient application in energy storage.
DIRECT CO2 CAPTURE

Fig.14. Scheme of the CO2 capture process from air using concentrated
solar power (Zedtwitz-Nikulshyna, 2009)

Fig.15. Packed tower prototype for a direct capture from air

(Mahmoudkhani et al, 2009)

CO2 capture from the air, referred to as direct capture, is a potential option to directly control
CO2 concentration in the atmosphere without a limitation on distributed emission sources.
Moreover, the capture plant can be located far away from cities and near the storage site for
a lower cost in transportation. However, compared to CO2 capture from flue gas, direct
capture from ambient air is believed unfavorable because of the higher Gibbs free energy
change needed to separate a much more diluted gas (Nikulshina et al., 2009). Solar energy
can provide an efficient heat supply to such direct capture plant for a sustainable
development.
A carbonation-calcination thermochemical cycle based on CaO is present in (ZedtwitzNikulshyna, 2009). Using concentrated solar energy on reactors, CO2 can be continuously
removed from ambient air. The entire thermochemical cycle process can be realized through
two-step reactors, as shown in Fig. 14. A uidized-bed solar reactor is applied to accomplish
the carbonation at 300700K and the calcination at 1227oC, with reacting particles directly

15

exposed to high-ux solar irradiation. With an internal heat recovery, the total thermal energy
requirement is 2473 KJ/Mol CO2.
A prototype of packed tower for a direct CO2 capture was developed by Mahmoudkhani et al.
The height of the tower is 6.5m and absorbent is NaOH or KOH. The tower is operated at a
pressure drop of less than 27 Pa in the packing with a 7m/s air speed. The contractor of the
tower is designed for a 50% capture rate at each run. The energy consumed for CO2 capture
is about 30kJ/mol CO2. At least 85% of the contractor's energy requirements are due to the
pump, so 90% work of fluid pump can be reduced through an intermittent operation with a 5%
duty cycle. A full scale design is also introduced briefly which is featured by a cross flow slab
design of contractor. The possible integration solution for solar energy could be solar thermal
utilization for the heating process or solar PV for the air fan and fluid pumps in the tower.
DISCUSSION AND SUMMARY
Table2. Energy penalty or energy requirement for CCS system.
Seperation point location
CLC-C CC 3
O-C CC 2
Pre-C CC 2
Energy penalty / energy requirement
2%
33%
32%
1. Chemical absorption method used in Post-C C system (Rubin et al, 2012)
2. Definition for energy penalty can also be found in (Rasmussen, 2012)
3. Efficiency decrease due to capture (Baker et al., 2009)

Post-C CC 1
30-43%

The energy penalty is the central determining factor when it comes to CO2 capture technology
used for flue gas. As reviewed above, various CCS systems have different separation points
of CO2, e.g., the separation point of the post-C system was located in the existing outlet of the
flue gas, while the separation point of the CLC C system was placed in the fuel chamber
without combustion. With the advance of the separation point in operation process, the
energy requirement for CO2 capture was decreased (Table 2), however, the distance to the
industrial application would become longer.
Although CCS integrated with solar energy (CISE) allows a significant saving of plenty
energy, several problems need to be addressed for a possible promotion in the future. The
capital cost of the solar system (solar field and thermal utilization system) would be roughly
half that of the base coal-fired plant with CO2 capture (Cohen et al., 2011). Compared to the
base coal-fired plant with CO2, the price of solar thermal collector has to be decreased to 2/3
or even less of the current price for a reasonable cost of CO2 avoidance. As an intermittent
contributor of energy, solar energy commonly applied the thermal storage device for more
operation time. Otherwise, solar field area and capital cost would increase sharply with an
oversized capacity of solar collector. Molten nitrates and thermal oil are commonly chosen as
heat transfer fluid and storage medium for high- and middle- temperature solar concentration
system, respectively.
With more integrated solutions are considered for CISE, a tradeoff between the technological
maturity and the cost will become a primary consideration. For example, although it
consumes more energy due to its near-ending location of the separation point, the solarassisted Post-C C system might be a feasible and efficient method for the existing coal-fired
plants in coal-domain resource countries at the current stage. Thus, such kind of CISE based
on Post-C can be used as near- or middle-term technologies for an energy-saving design in
CCS system. On the contrary, CISE, which is based on advance energy system, may need
more demonstration projects to show its real operation performance. The CISE can be
considered as one of innovation and rational ways to exploit solar energy, as it directly
reduces the carbon footprint of the current energy system.
ACKNOWLEDGEMENT

This work is finally supported by Seed Money 2014 from Cooperation & Development Center
(CODEV) of COLE POLYTECHNIQUE FDRALE DE LAUSANNE. This work was also
supported by open funding of Key Laboratory of Efficient Utilization of Low and Medium
Grade Energy, Ministry of Education of China under Contract No.2014-4201.
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17

EXAMINING THE EFFECTS OF ELECTRIFICATION ON IMPROVING THE CO2

EMISSION INTENSITY OF GDP IN BEIJING FROM 1996 TO 2012
a*

Li Li , Jianjun Wang , Xiaozhe Yun , Xinquan Ge , Yingmei Yanga

School of Economics and Management, Beijing Information Techonology and Information Science
University, Beijing, 100192,China
b
School of Economics and Management, North China Electric Power University, Beijing 100026, China
lilinw2001@126.com
a

ABSTRACT
Beijing, positioned as an international metropolis, had made great efforts to accelerate the step to
improve the efficiency of carbon emission related activities. Statistics shows that the CO2 emissions
intensity of GDP in Beijing had reduced substantially during the last few years, coupling with
moderate increase in total CO2 emissions quantities. This paper uses the logarithmic mean divisia
index (LMDI) technique to explore role of electrification in contributing to the reduction of CO2
emissions intensity of GDP in Beijing. By first grouping the CO2 emissions into two categories, those
arising from the activities of industries, and the activities of households, the change of CO2 emissions
intensity was further decomposed to the effects of industrial carbon emission coefficient (ICEC),
industrial electrification (IE), industrial electricity consumption of added-value (IECAV), industrial
structure (IS), household CO2 emission coefficient (HCEC), household electrification (HE), household
per capita electricity consumption (HPEC) and household per capita GDP (HPGDP). The
decomposing results show that the improvement of CO2 emissions intensity of GDP of Beijing in
1996-2012 was mainly contributed by the industrial activities (Fig.1), which completed almost 82.83%
of the total reduction. Among all the influencing factors, the contributions of IECAV, IS and IE ranked
the top three, accounting for 41.24%, 19.21% and 19.08% of the total improvement respectively. The
household contributions were mainly made by the increase of HPGDP and HPEC. Although the
electrification of industrial and household sides totally completed 21.64% of the reduction in CO2
emissions intensity of GDP, the period with largest reduction in CO2 emissions intensity of GDP also
experienced obvious increase in electrification rate, which implies the possibility and potential to
further improve the CO2 emissions intensity of GDP by increasing the level of electrification in the
future for Beijing.
Keywords: CO2 emissions intensity of GDP, electrification, LMDI, industry, household.
INTRODUCTION
Rapid urbanization and anthropogenic disturbance have contributed to such challenges, especially
the rise of greenhouse gas (GHG) emissions. Global warming caused by GHG emissions is
associated not only with eco-crises such as meteorological disasters and ecological damage, but also
represents a threat to global economic activity (Malla, 2009). Reducing carbon emissions and
improving the energy efficiency attracted worldwide attention including both the developing and
developed countries and regions. Many countries developed kinds of mechanisms and measures to
reduce the carbon emissions for providing better living environment, the same things happened in
China, especially in the capital, Beijing, which is also the countries political, economic and cultural
center.
Beijing, positioned as an international metropolis, had made great efforts to create an enjoyable,
harmony and sustainable environment to welcome people all around the world. As the capital of
China, Beijing started its urbanization process just when the People republic of China founded in
1949, which was accelerated since the country opened the reform window to the world in 1978. The
rapid urbanization process intensively accumulated the wealth for the city, and improved peoples
living standards, while also caused serious air pollution problems. As a result, the Beijing government
began to enact several plans to secure the air pollution since 1990s, including moving the energyintensive industrial plants from the cities center to remote areas or neighboring provinces like Hebei
province and Tianjin city, restructuring the industrial structure toward less-energy consumed and lesspollution emitted pattern, substituting fossil fuels by more clean energy like electricity and natural gas
and so on.
Because of these efforts made by the government and cooperated by other social entities, the CO2
emission intensity of GDP in Beijing had been reduced from 0.647 tons/1,000 Yuan in 1996 to 0.0814
tons/1,000 Yuan in 2012 (Fig. 1). The achievement was contributed by many efforts. Just as many
other researches pointed out, any one of the following factors, like structure change (Wu, 2013) and
energy intensity (Jeong, 2013), eco-industrial park (Jung, 2012), population growth (Gonzlez, 2012)
and fossil fuel substitution (Mahony, 2013) can be the driving forces in reducing the carbon/ CO2
emissions. Figure 1 also shows that the electrification rate in Beijing also increased substantially

18

during the research period, especially in 1996-2000, in which the decrease of CO2 emission intensity
of GDP was most obvious compared to other period. It seems that the electrification rate is also an
driving forces in improving CO2 emission intensity of GDP in Beijing, and researches examining the
role of electrification in reducing carbon emissions are rare, which is the mainly topic of this work. The
LMDI method was used to analyze the problem because of its robust theoretical foundations, strong
adaptability, and desirable properties, including the potential for perfect decomposition, in which no
unexplained residual term appears in the results [Ang, 1998; 2000; 2001; 2004; 2005].

Fig. 1 Trend of CO2 emission intensity of GDP and electrification rate in Beijing in 1996-2012

The remainder of the paper is organized as follows: In Section 2, we introduce the LMDI method for
decomposing the CO2 emissions intensity of GDP based on electrification factor, and explain the data
set used. Section 3 presents a time series and a period-wise analysis and comparisons of the results.
Finally, the conclusions are summarized in Section 4.
DECOMPOSITION METHODOLOGY
Electrification rate
According to Susumu yoda[Susumu, 1986; 1999], there are two basic ways to define the

electrification rate:
1) the percentage of electric power generation out of total primary energy, which can be
expressed as

PEG
PE
(1)

where, E is electrification rate, PEG is the primary energy used for power generation in tons of
coal equivalent (tce), and PE is the total primary energy in tce.
and 2) percentage of electricity demand in the total energy demand, which can be expressed
as

ELt EL *

Et
Et
(2)

where, EL and ELt is the electricity demand in kwh and tce respectively, Et is the total energy
demand in tce, and is the coefficient used to covert the electricity demand in kwh to
electricity demand in tce. We used equation (2) to express the electrification rate in this work
since most of the electricity consumed in Beijing are generated by other provinces and
transmitted to this huge city.
LMDI method
The LMDI method is used to decompose the CO2 emission intensity of GDP, and By first
grouping the CO2 emissions into two categories, those arising from the activities of industries,
and the activities of households, the change of CO2 emissions intensity was further
decomposed to the effects of industrial CO2 emission coefficient (ICEC), industrial
electrification (IE), industrial electricity intensity of added-value (IEIAV), industrial structure
(IS), household CO2 emission coefficient (HCEC), household electrification (HE), household

19

per capita electricity consumption (HPCEC) and household per capita GDP (HPGDP), defined
as

CG C / GDP
CI / GDP CH / GDP

CIj / EIj EIj / ELIj

EL

Ij

/ AVIj

AV

Ij

/ GDP CH / EH EH / E pH E pH / R R / GDP

ICEC j * IEIAV j * IS j * 1/ IE j HCEC * HPCEC * 1/ HE * 1/ HPGDP

j
(3)
where CG: CO2 intensity of GDP; C: CO2 emissions; CI: industrial CO2 emissions; CH:
household CO2 emissions; CIj, EIj, ELIj, AVIj: sector js CO2 emissions, energy consumption,
electricity consumption, added-value; CH, EH, EpH, R: household CO2 emissions, energy
consumption, electricity consumption, population.
Under the LMDI approach, the total change in CO2 emission intensity of GDP (CG) through
time (0 to T) is the sum of changes in industrial CO2 emission intensity of GDP (CIG) and
household CO2 emission intensity of GDP (CHG), and this can be expressed as (Tan, 2011;
Subhes, 2010)

CG CIG CHG
(4)
where,
CIG ICEC j IEIAV j IS j 1/ IE j

(5)

CHG HCEC HPEC 1/ HE 1/ HPGDP

(6)
where ICECj is the change of industrial carbon emission coefficient, (1/IEj ) is the change of
industrial electrification, IEIAVj is the change of industrial electricity intensity of added-value,
ISj is the change of industrial structure, HCEC is the change of household CO2 emission
coefficient, (1/HE) is the change of household electrification, HPEC is the change of
household per capita electricity consumption and (1/HPGDP) is the change of household
per capita GDP, and these variables are calculated by

ICEC jT
*
ICEC W jI ln
ICEC
j
j0

(7)

1/ IE jT
*
(1/ IE ) W jI ln
1/ IE
j
j0

IE jT
I*
W j ln
j

IE j 0

(8)

IEIAV jT
*
IEIAV W jI ln
IEIAV
j
j0

(9)

IS jT
*
IS W jI ln
IS
j
j0

(10)

20

Where W jI in the above equations is the logarithmic weighting scheme specified in the
following:

W jI L(W jI,0 ,W jI,T ) / L(W jI,0 ,W jI,T )

*

(11)

L(WjI,0 ,WjI,T ) (WjI,T WjI,0 ) ln(WjI,T WjI,0 )

(12)
W jI

ICEC j * IEIAV j * IS j * 1/ IE j

ICEC

* IEIAV j * IS j * 1/ IE j

(13)
Similarly,

HCECT
HCEC L(CH ,T , CH ,0 ) ln

HCEC0
(14)

HPECT
HPCEC L(CH ,T , CH ,0 ) ln

HPEC0
(15)

1/ HET
(1/ HE ) L(CH ,T , CH ,0 ) ln
1/ HE0

HE0
L(CH ,T , CH ,0 ) ln

HET

(16)

1/ HPGDPT
(1/ HPGDP) L(CH ,T , CH ,0 ) ln
1/ HPGDP0

HPGDP0
L(CH ,T , CH ,0 ) ln

HPGDPT

(17)

where

L(CH ,T , CH ,0 )

CH ,T CH ,0
ln(CH ,T ) CH ,0
(18)

CH HCEC * HPEC * 1/ HE * 1/ HPGDP

(19)
Research data

The data on the energy consumption, gross domestic products, electricity consumption and
population used in this work was collected from Statistical yearbook of Beijing City (19972013) published in the official website of Beijing Municipal Bureau of Statistics (BSIN, 2013).
The data on CO2 emissions was calculated by the CO2 emissions coefficient (Wang, 2014)
multiplying the total consumption of each kind of energy.
Currently there are two ways used to define the value of in equation (2), one of which is
called energy calorific value and the other one is called energy equivalent value. The energy
calorific value method compares the electricities mechanical equivalent of heat with the
equivalent coals, which means that 1kw/h electricity equals to 0.1229 kg equivalent coal
because 1kw/h electricities mechanical equivalent of heat is 3.6MJ and 1kg equivalent coals
is 29.3MJ. The energy calorific value method can not reflect the conversion efficiency of

21

primary energy to electricity, while the energy equivalent value use the real primary energy
consumption used for conversing electricity to define the value of , and this can effectively to
trace the primary energy consumption of end electricity use. So in this work we use the energy
equivalent value method to define the value of . and in this regard the factor called coal
equivalent of electricity supplying is used to express the value. The data on coal equivalent
of electricity supplying is collected from China Electric Power Yearbook (1996-2012).
RESULTS ANALYSIS
Changes in electrification Level
The electrification level in Beijing increased from 26.83% in 1996 to 39.71% in 2012, by
48.01%. The increase was most obvious during the period of 1996-2000 and keep a relative
flat trend since 2001 (Fig.2). The elcetrification level of the primary industry is highest and also
fluctuated most dramatic compared to other industries. The elcetrification level of tertiary
industry is more fluent during the research period, which was always in the interval of 35% to
40%. The household electrification level is rather low in 1996, which is below 20%, while
increased to more than 40% in 2002, and kept a relative higher level since that time. The
elcetrification level of the secondary industry is lowest compared to the primary industry,
tertiary industry and average level, while increased substantially in 2000 and ranked top 2 by
the end of 2012.

Figure1 The electrification level in Beijing

Change in the aggregate CO2 emission intensity of GDP

The CO2 emission intensity of GDP in Beijing were reduced by 87.41% in 2012
compared to the level in 1996, the contribution of each explanatory factor during different
period was showed in Fig.3. It can be clearly seen that the role of each factor varied
significantly in different periods.

Figure 3 explanatory factors contributions to the reduction of CO 2 emission intensity of GDP

22

Generally speaking, the industrial totally completed 82.83% of the improvement in CO2
emission intensity of GDP, and the household completed 17.17%. The industrial side played a
very important role in improving the CO2 emission intensity of GDP, especially in 2006-2010
and 2011-2012, in which the industry completed 87.33% and 88.67% of the entire reduction
respectively. Among the explanatory factors in the industry side, the role of IEIAV was most
obvious compared to other factors during the entire research period, which contributed to
41.14% of the reduction in CO2 emission intensity of GDP. The contributions of SE and SS are
rather close which made 19.08% and 19.21% reductions. The roles of other factors were not
as obvious as the roles of IEIAV, IE and IS. Among the explanatory factors in the household
side, the increse in the HPGDP played the most important role in reducing the CO 2 emission
intensity of GDP, while the HCEC played the least important role.

Figure 4 industrial and household contributions in improving the CO2 emission intensity of GDP

Driving forces for the changes of mainly explanatory factors

Industrial CO2 emission coefficient

The reduction of industrial CO2 emission coefficient totally contributed 3.29% of the reduction
in CO2 emission intensity, and the positive contribution was most dramatic in 2001-2005
(Fig.3), which was mainly contributed by the improvement of secondary industrial CO 2
emission coefficient. That may because of the reduction in the consumption of cleaned coal,
coke and blast furnace gas, of which the CO2 emission coefficient is relatively higher than
other kinds of coal-fuels. It can been clearly seen that the contribution of ICEC was obviously
negative in 2006-2010 (Fig.4), which made the positive contribution of the ICEC in improving
the CO2 emission intensity looked less important during the entire research period. That was
also mainly contributed by the increase in secondary industrial CO 2 emission coefficient. Two
reasons can explain this phenomenon, one of which is the substantial increase in oil-fuels
consumption with higher CO2 emission coefficient than other kinds of fuels. Such as the crude
oil, the total consumption of the secondary industry was 7961.200 tons in 2006, while
increased to 11162.900 tons in 2010, by 40.22%. The another reason is that the naphtha,
lubricants, petroleum, white spirit, bitumen and petroleum are not counted in the Statistical
Yearbook 2006, while they appeared in the Statistical Yearbook 2010 which contributed to the
increase in CO2 emission during the period 2006-2010.

23

Figure 4 the contribution of ICEC in improving the CO2 emission intensity during the research period

Industrial electrification
The IE totally made 19.08% of the contribution in improving the contribution of CO2 emission
intensity in 1996-2012, and its role was most obvious in 1996-2000 (Fig.5), which contributed
to 46.51% of the reduction of CO2 emission intensity during that period. The contribution was
mainly made by the secondary industry, which made 44.35% of the contribution. That mainly
because the electricity consumption of the secondary industry increased sharply from
14969.68 GW in 1996 to 21726.04 GW in 2000, while the total energy consumption slightly
reduced from 24.77 million tons/tce to 24.248 million tons/tce, which means there existed
large scale of substitution between electricity and fossil energy for the secondary industry, and
this played an important role in reducing the CO2 emission intensity. Meantime, the electricity
consumption of the tertiary industry also increased dramatically in 1996-2000, which increased
from 6172.86 GW in 1996 to 10643.22 GW in 2000, by 72.42%. However, because the total
energy consumption of the tertiary industry also increased substantially during that period,
which increased from 6.98 million tons/tce to 10.81 million tons/tce, by 54.83%, the entire
contribution of tertiary industrial electrification to the reduction of CO 2 emission intensity was
not so obvious in 1996-2000.

Figure 5 the contribution of IE in improving the CO2 emission intensity during the research period

The contribution of IE in improving the CO2 emission intensity in other periods was not so
obviously as the period of 1996-2000, especially in 2006-2010 and 2010-2012. The relatively
lower contribution was also mainly made by the secondary industry because of the faster
growth in electricity consumption and lower increase in total energy consumption, which
means that there still existed substitution between electricity and fossil energy in secondary
industrial energy consumption, although the substitution was not as obvious as the period of
1996-2000. The primary industry always played a relative little role in contributing to the
reduction of CO2 emission intensity because of its little share of energy consumption. The
contribution of IE for the tertiary industry was negative in 2001-2005 and 2011-2012, that
mainly because of the relatively lower growth of the electricity consumption compared to the
total energy consumption.
Industrial electricity intensity of added-value
The improvement in IEIAD totally contributed to 41.24% of the reduction in CO 2 emission
intensity of GDP in 1996-2012, whose role surpassed any other explanatory factors, and its
role was most obvious in the period of 2006-2010, which completed nearly 70% of the
improvement. The contribution of IEIAD also kept very high levels in the periods of 2001-2005
and 2011-2012, which contributed to 51.98% and 63.38% of the improvement respectively.
While the contribution of IEIAD in 1996-2000 was very low, that mainly because during that
time the IEIAD of primary industry and secondary industry increased in some little what, and
this was caused by the relatively faster growth in the electricity consumption compared to the
growth in the added-value. The contribution of IEIAD in improving the CO2 emission intensity
of GDP in 2001-2012 was mainly made by the secondary industry, of which the IEIAD reduced
from 0.18 KWh/RMB to 0.079 KWh/RMB, by 57.11%. The sharp decrease of IEIAD of the
secondary industry implies that there was great improvement of electricity consumption
efficiency for the secondary industry in Beijing, of which the IEIAD was far lower than the

24

countries average level (Chinas average secondary industrial IEIAD was 0.156 KWh/RMB in
2012).

Figure 6 the contribution of IEIAD in improving the CO2 emission intensity during the research period

Industrial structure
The change in industrial structure totally contributed to 19.21% of the improvement in CO 2
emission intensity in 1996-2012, ranking top two of all the explanatory factors. The
contribution of IS was slightly higher than the contribution of industrial electrification in the
entire research period. The IS contribution was mainly made by the economic share reduction
of the secondary industry, of which the role was most obvious in 2006-2010, when the 2008
summer Olympic Games successfully hold in Beijing. The another peak of the reduction in the
economic share of secondary industry happened in 1996-2000, which experienced the times
of preparing the approval for 2008 summer Olympic Games in Beijing and lots of heavy
industrial factories were removed to other provinces. The share of the tertiary industry in the
economy increased steadily during the research period, from 55.96% in 1996 to 76.46% in
2012, which made -2.77% of the reduction inCO2 emission intensity in the 1996-2012.
Because this negative contribution is rather lower than the positive contribution of secondary
industry, the total change in industrial structure still played a very important role in improving
the CO2 emission intensity of GDP.
Household side explanatory factors
Among all the household side explanatory factors, the household per capital GDP (HPGDP)
made the highest contribution (Fig 3), which completed 41.71% of the household side
contribution. The role of HPGDP was most obvious in 2006-2010, which experienced a period
of sharp increase in the commodity price, especially the house property price and came up
with the increase in household income, which encouraged the household people to spend in
commerce industry, and thus relatively reduced the household CO2 emissions.
The household CO2 emission coefficient made the lowest contributions because of the
substantial increase in the consumption of gasoline in 1996-2012 (Fig 3), which increased
from 164.800 tons to 2602.270 tons, expanding by 14.79 times. This mainly caused by the fast
growth of motor vehicle population (Fig 8), which increased from 921,000 in 1996 to 5200,000
in 2012, and the private owned motor vehicle population also increased from 140,000 to
4075,000, by 28.11 times.

25

Figure 7 contribution of IS in improving the CO2 emission intensity during the research period

Figure 8 motor vehicle population in Beijing in 1996-2012

Sources: BJTMB, 2013; IN, 2009; PN, 2005; BIN, 2013

The household electrification (HE) also played a very unimportant role in contributing to the
reduction of CO2 emission intensity of GDP over the entire research period. However, the role
was very obvious in 1996-2000, which was caused by the suddenly growth of household
electrification rate, raised from 19.88% to 35.01%, while in the following 12 years this factor
only increased 2.62%.
The role of household per capital electricity consumption (HPEC) was more important than
HCEC and HE, which made 34.89% of the household side contribution in improving the CO 2
emission intensity of GDP, next to the contribution of HPGDP. The contribution of HPEC was
also most obvious in 1996-2000, during which the HPEC increased from 172.74 KWh/year per
capital to 344.00 KWh/year per capital, by 99.14%. The following years also experienced a
fast growth in the HPEC, and by the end of 2012, this factor had increased to 782.07
KWh/year per capital, which was nearly 5 times of the level in 1996. The fast growth in HPEC
and increase in HE showed that there existed an obvious period of substitution between
electricity and fossil energy in the household side, especially in 1996-2000, which jointly
contributed to the household side reduction in CO2 emission intensity of GDP.
CONCLUSION
The CO2 emission intensity of GDP in Beijing reduced substantially during last few years,
coupling with the moderate increase in energy consumption and CO2 emissions. This was
cooperated contributed by many factors, and among which, the industrial side factors
completed most of the improvement in CO2 emission intensity of GDP, especially during the
periods of 2006-2010 and 2011-2012. After decomposing the industrial side effects into the
effects of industrial CO2 emission coefficient (ICEC), industrial electrification rate (IE),
industrial electricity intensity of added-value (IEIAV) and industrial structure (IS), it is found that
the IEIAV made the largest contribution, followed by IS and IE, and the contribution of ICEC
was least because the increase in oil-fuels consumption. The IE played the most important
role in 1996-2000, in which the decrease in CO2 emission intensity of GDP was also most
dramatic, and the secondary industry made the largest contribution. The secondary industrial

26

IEIAV played the most important role in the following years, and its contribution was most
obvious in 2006-2010, in which the contribution of IS also reached its peak point because of
2008 Beijing Summer Olympic Games effects on industrial structure change and energy
efficiency improvement.
Although the household role in contributing to the reduction in CO2 emission intensity of
GDP is not as obvious as the industrial role, the contribution is still very meaningful. After
decomposing the household effects into the effects of household CO 2 emission coefficient
(HCEC), household electrification rate (HE), household per capital electricity consumption
(HPEC) and household per capital GDP (HPGDP), it is found that the contribution of HPEC
and HPGDP were most important in completing the household contribution in the entire
research period, and the contribution of HCEC is very small because of the ever-increasing
consumption in gasoline caused by soar in private motor vehicle population. The role of IE
was most obvious in the period of 1996-2000, in which the overall household contribution in
reducing the CO2 emission intensity of GDP also reached its peak point.
Our findings show that the period with substantial decrease in CO 2 emission intensity of GDP
also experienced incredible increase in electrification rate both of the industry and household
side, and in which the role of the electrification rate in improving the CO 2 emission intensity of
GDP was most obvious. This certifies the fact that the increase in electrification level can
improve the CO2 emission intensity of GDP in Beijing. However, the reduction of CO2 emission
intensity of GDP across the overall period of 1996-2012 was mainly contributed by the
improvement in electricity consumption efficiency, which implies that there is still the potential
to increase the electrification level in Beijing in the near future, especially for the tertiary
industry.
ACKNOWLEDGEMENT
This study is financially supported by Beijing Philosophy and Social Science Foundation Project
(13JGC074), Collaborative Innovation Center of the Beijing World Urban cycle economy
(industry), Fundamental Research Funds for the Central Universities and National Natural
Science Foundation of China (71373030).
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Ang BW, Zhang FQ, 2000. A survey of index decomposition analysis in energy and environmental
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Ang BW, Liu FL, 2001. A new energy decomposition method: perfect in decomposition and
consistent in aggregation. Energy 26:537-48
Ang BW, 2004. Decomposition analysis for policymaking in energy: which is the preferred
method?. Energy Policy 32:1131-1139
Ang BW, 2005. The LMDI approach to decomposition analysis: a practical guide. Energy Policy
33: 867-71
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Statistical
Information
Net
(BSIN),
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data.
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China business intelligence network (CBIN), 2013.The private moter vehicle population in Beijing
was
4075,000
by
the
end
of
2012.
Available
on:
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Domingo Gonzlez, Manuel Martnez, 2012. Changes in CO2 emission intensities in the Mexican
industry. Energy Policy 51: 149-163
Intelligent network (IN), 2009. Change of motor vehicle population in Beijing from 1982 to August
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Kyonghwa Jeong, Suyi Kim, 2013. LMDI decomposition analysis of greenhouse gas emissions in
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Leya Wu, Weihua Zeng, 2013. Research on the Contribution of Structure Adjustment on Carbon
Dioxide Emissions Reduction based on LMDI Method. Procedia Computer Science 17: 744-751
People net (PN), 2005. The surge in private moter vehicle population in Beijing. Available on:
http://auto.people.com.cn/GB/1049/3524449.html, accessed on March 27, 2014
Seok Jung, Kyoung-Jin An, Gjergj Dodbiba, Toyohisa Fujita, 2012. Regional energy-related carbon
emission characteristics and potential mitigation in eco-industrial parks in South Korea:
Logarithmic mean Divisia index analysis based on the Kaya identity, Energy, 46: 231-241

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Seok Jung, Kyoung-Jin An, Gjergj Dodbiba, Toyohisa Fujita. Regional energy-related carbon
emission characteristics and potential mitigation in eco-industrial parks in South Korea:
Logarithmic mean Divisia index analysis based on the Kaya identity. Energy; 2012; 46: 231-241
Sunil Malla, 2009. CO2 emissions from electricity generation in seven Asia-Pacific and North
American countries: A decomposition analysis, Energy Policy 37: 1-9
Tadhg O' Mahony, 2013. Decomposition of Ireland's carbon emissions from 1990 to 2010: An
extended Kaya identity. Energy Policy 59: 573-581
Susumu yoda, 1986. Electrification and future energy supply. Proceedings of the 8th IAEE
International Conference, 1986. Tokyo, Japan
Susumu Yoda, Kaoru Ishihara, 1999. The advent of battery-based societies and the global
environment in the 21st century. Journal of Power Sources 8182: 162-169
Subhes C. Bhattacharyya, Wataru Matsumura, 2010. Changes in the GHG emission intensity in
EU-15: Lessons from a decomposition analysis. Energy 35: 3315-3322
Wang Jianjun, Li Li, 2014. Empirical Analysis on Relation Between Electricity Consumption and
Carbon Emission Based on Stochastic Impacts by Regression on Population, Affluence and
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Zhongfu Tan, Li Li, Jianjun Wang, Jianhui Wang, 2011. Examining the driving forces for improving
Chinas CO2 emission intensity using the decomposing method. Applied Energy, 88: 4496-4504

28

THE EFFECT OF ELECTROSTATIC FORCES ON GRANULAR FILTRATION

EFFICIENCY FOR NANOAEROSOL PARTICLES
Raheleh Givehchi1

Zhongchao Tan1*

Chao Yan1

Qinghai Li2

Department of Mechanical and Mechatronics Engineering,

University of Waterloo
200 University Ave. W., Waterloo, Ontario, Canada N2L 3G1
*Email: tanz@uwaterloo.ca
2

Department of Thermal Engineering

Tsinghua University, Beijing, China, 100084
Email: liqh@tsinghua.edu.cn

ABSTRACT
The removal efficiency of granular filtration for nanosized NaCl particles was investigated
experimentally. The ranges of particle tested were about 6-250 nm in diameter under the room
conditions. Three sizes of homogenous glass beads (2, 4 and 6 mm in diameter) were used in the
test each at three media thicknesses (2.5, 7.6 and 12.7 cm), and at three flow rates (23, 45 and 65
liters per minute). The results show that the effect of electrostatic force had opposite effect on
filtration efficiency of particles smaller and great than 20 nm. Electrostatic force improved the
filtration efficiencies of large particles and reduced that of smaller ones.
keywords: Nanoaerosol, Granular filtration; Electrostatic force

INTRODUCTION
Nanoaerosol particles prevail in many energy industries such as engine exhaust, syngas from a
biomass gasification process, nanosized catalysts for clean combustion, solar panel production,
and nanotechnology based air cleaning devices. Nanoparticles may pose a health risk because
they can readily enter the human body through inhalation and able to translocate from the lung to
other organs and they can accumulate in tissues and cause significant effects. Effective separation
and capture of nanoaerosol particles help reduce their negative impact on health and the
environment.
Among all of the methods for removing the nanoaerosol particles for their carrier gases, filtration is
the simplest and most widely used method. A great amount of works have been conducted with the
fibrous filters, membrane filters and fabric filters; however, the study on granular filtration for air
cleaning received much less attention. Granular filtrations have high removal efficiency for a wide
range of particle size and temperature (Golshahi et al., 2009, Gebhart et al., 1985). One of the
advantageous of granular beds is their reusability. Also, the capital and operating cost of granular
filtrations are reasonable than the other equipment.
Our earlier publication (Golshahi et al., 2009) showed that granular filtration could effective remove
nanoaerosol particles from the air at a high efficiency. However, the experimental results did not
agree with classic filtration models, which electrostatic forces were commonly ignored because
electrostatic forces in filtration cannot be readily calculated. On the other hand, it is not clear
whether this simplification is justified or not in filtration theories. This study focuses on the effect of
electrostatic forces on removal granular filtration efficiency. We experimentally study the filtration
efficiency of airborne nanoparticles by granular filtration with and without neutralizing the aerosol
particles. By comparing their efficiencies, we hope to gain some understanding of the effects of
electrostatic forces on nanoaerosol filtration.

EXPERIMENTAL SETUP
The experimental setup is shown in Fig.1. It includes four main sections: an aerosol generation
device, a neutralizer, a granular filter bed and nanoaerosol particle measurement devices. A
collision-type atomizer (TSI model 3076) was used to generate the polydisperse sodium chloride
(NaCl) smaller than 350 nm or so. The particle diameter range was adjustable by the compressed
gas pressure and the concentration of sodium chloride in the feed solution; we used the

29

concentration of 0.1 g/l as recommended by the manufacturer. After aerosol generation, a diffusion
dryer (TSI model 3062) was used after the atomized to dry the particles. These particles could be
neutralized after they pass through the diffusion dryer before entering the granular filter.
Excess air

Filter
Compressed air

Packed bed
Flow meter

Diffusion dryer
Neutralizer
Exhuast

Atomizer

DMA
CPC
Fig.1. Schematic diagram of experimental set up

Fig. 2. shows the schematic diagram of the granular filter, which was the same as the one used by
Golshahi et al. (2009). And it is briefly introduced as follows. A cylindrical cross-section unit was
used instead of a rectangular one in order to decrease the formation of stagnant zones in the
corners. Gas enters the filter from the bottom of the bed in a counter-current flow mode. There was
a fixed height of 9 cm between the base of the filter unit and the level where the gas first interacted
with the granules (h=0). This fixed thickness below h=0 was used to slow down the gas flow and
acted as a flow straightener. Homogenous glass beads in three sizes (2, 4 and 6 mm in diameter) in
combination with three bed thicknesses of 2.5, 7.6 and 12.7 cm were. All the experiments were
tested at room temperature to avoid the effect of temperature.

Fig.2. Schematic diagram of the granular filtration

The aerosol particle removal efficiencies were determined with and without the neutralizer.
Monodisperse particles were selected from the polydisperse ones by a differential mobility analyzer
(DMA) (TSI model 3080) followed by the condensation particle counter (CPC) (TSI model 3772) to
determine the concentration of particles in different diameters according to the particle mobility
sizes. The system was used in both upstream and downstream of the granular filtration to
determine the concentrations of particles before and after the filtration.
To study the effects of different flow rates, the air flow rates were 23, 45 and 65 liter per minute. The
slow flow rate was in order to enhance the effect of diffusion which is the dominated mechanism for
nanoparticle filtration. A thermal mass flow meter (TSI model 3063) used to adjust the main stream
flow rate to meet the criteria of the isokinetic sampling. A dust collector was used to make the

30

system under vacuum and an opening was provided after the aerosol generator to balance the air
in the system. The fractional filtration efficiency () was calculated as follows:
(1)

100%

where Cin is the upstream concentration and Cout is the downstream concentration. Both
concentrations are measured so close to the inlet and outlet of the packed bed and could include
the particles that entered the system not generated by the atomizer. However, there may be some
particles captured by the granules before the system worked. So that would underestimate the
efficiency of the bed. To minimized this error, the packed bed was purged for an hour before the
next test operation to make the system reach a steady state and the number of the suspended
particles was very small compared to the generated particles, it was expected that this case may
not result in a significant effect on determining the absolute value of the filtration efficiency.

RESULT AND DISCUSSION

Fig.3 shows the effect of electrostatic forces on the removal efficiency vs. particle diameter. The

x-axis is particle diameter in nm, y-axis removal efficiency. Dashed line are for the results
without neutralizer, and solid lines with neutralizer. The top labels are, in the order, glass bead
diameter, bed height, and air flow rate. All of the experimental data in the figures were calculated
by averaging three or more replications with the average standard deviation of less than 4%. The
removal efficiency for the whole ranges of ultrafine particle at the room conditions with three sizes
of homogenous glass beads (2, 4 and 6 mm) and three media thicknesses (2.5, 7.6 and 12.5 cm) at
three flow rates (23, 45 and 65 L/min) with the effect of electrostatic forces and without the effect of
the electrostatic forces were presented.
2mm 2.5cm 45lpm

2mm 2.5cm 23lpm

100

100

80

80

60

60

40

40

20

20
0

0
1

10

100

1000

10

100

2mm 2.5cm 65lpm

100
80
60
40
20
0
1

10

100

1000

31

1000

2mm 7.6cm 45lpm

2mm 7.6cm 23lpm

100

100

80

80

60

60

40

40

20

20
0

0
1

10

100

1000

10

100

1000

2mm 7.6cm 65lpm

100
80
60
40
20
0
1

10

100

1000

2mm 12.7cm 23lpm

2mm 12.7cm 45lpm

100

100

80

80

60

60

40

40

20

20

0
1

10

100

1000

0
1

10

100

1000

2mm 12.7cm 65lpm

100
80
60
40
20
0
1

10

100

1000

Fig.3. Particle removal efficiency (x-axis: particle diameter in nm, y-axis: removal efficiency, dashed line: without neutralizer,
solid line: with neutralizer; top label: glass bead diameter, bed height, and air flow rate)

Note that all aerosol particles carry charges after exiting the atomizer. Without using the neutralizer,
these charges cause electrostatic forces between the particles and collectors. By passing through
the neutralizer, the particles were believed not to carry the charge and they become neutralized.
With this presumption, we can say that the neutralizer had positive effects for particles bellow about
20 nm (or so) because it may remove the repulsive forces between the particles and collectors. On
the other hand, it has adverse effect on larger particles because it has removed the effect of
attractive force between the particles and collectors. Besides, without electrostatic forces, for small

32

particles, the dominant mechanism is Brownian diffusion which is high enough to keep removal
efficiency at a level. As particle size increasing, the effect of diffusion reduces and the effects of
other mechanisms dont increase very much; therefore, the total efficiency declines.
With the presence of electrostatic effects (charges), bigger particles can get more charges as they
have larger superficial areas and the enhanced electrostatic effects can compensate the loss of
diffusion effects. The results are the same as the theoretical analysis that are discussed now.
Some studies have been done in charging the small and large particles. Among them, Marlow et al.
(1974) demonstrated that there was a significant difference in polarity between the larger and
smaller ones, which pass through the same bipolar charger. In charging process of polydisperse
particles, due to unequal charging rates, large and small particle may show different polarities.
Since the polarity of the collector in the packed bed was certain, there must be a repulsive force for
either large or small particles.
For nanoaerosol particles the analytical solution of the transient charging equation have been
obtained following the Fuchs theory (1963). In this theory he divided the space surrounding a
particle into two regions. In the outer region ions move according to the continuum diffusion
equation, whereas in the inner region they move as in a vacuum, it means that they have no
collision with air molecules. By assuming the above the ion attachment coefficient (the probability
that ions attach to given particles) is
(2)

Hoppel et al. (1986) showed that for aerosols with particle sizes less than 20 nm or so the
probability that a particle acquires two or more net charges of either sign is practically zero. So
there are only three different charges for aerosols below 20 nm: neutral particles, singly positive
particles and singly negative particles.
Alonso et al. (2002) recalculated the ion attachment rate coefficient of Fuchs theory (1963) for the
particle diameter range between 2 and 20 nm with using the values of ionic mass of m+=150 and
m-=80 amu, and ion mobilities of Z+=1.15 and Z-=1.65 cm2/v.s. So the probabilities of the ion
attachments into the natural particle, positive and negative one are as follow:
2.19 10

(3)

3.02 10

(4)

5.68

3.38

0.522

0.042

0.0017

0.000027

10

(5)

2.15

4.20

0.526

0.038

0.0014

0.000020

10

(6)

For example
shows the probability of attaching the positive ion to the neutral particle. Fig.4
shows the probabilities of collision the ions into the particles via the diameter of particles by the
Alonso theory. As we can see from this chart, the probability of attachment of negative ions into
positive particles is greater than the probability of attachment of positive ions into negative particles.
Besides, the probability of attachment of negative ions into neutral particles is greater than the
probability of attachment of positive ions into neutral particles. So at the end of the neutralizing
process negatively charged particles are predominant over positive ones for particle bellow about
20 nm. Since the glass beads were exposed to atmosphere, where negative ions present. It is very
likely the glass beads were already charged with negative ions. As a result, the removal efficiency
for particles smaller than 20 nm was reduced because the glass beads tend to repel the incoming
aerosol particles.

33

Attachment Rate Coefficient (cm3/s)

0.0000025

0.000002

0.0000015
P+ 0
P- 0

0.000001

P+ P-+

0.0000005

0
0

10

15

20

25

Particle diameter, nm

Fig.4. Diagram of charging probability via particle diameter by Alonso Theory

On the other hand, Christopher et al. (2009) examined the positive unipolar diffusion charging in the
range of 50-200 nm. He showed that particles can get more net charges by increasing the size of
them. For instance the 200 nm particle can get eleven positive ions. So the electrostatic forces
cause larger particles to be removed at a high efficiency with the present of electrostatic forces.
So by the above analysis we concluded that during the process of neutralizing, small particles
bellow 20 nm get different charges from the larger ones and because of this they have shown
different behavior through the filtration. Small particles have the same charges as granules so the
electrostatic forces can have adverse effect on filtration efficiency. On the other hand, larger
particles and granules have different charges so the electrostatic forces increase the filtration
efficiency.

CONCLUSION
The existence of electrostatic forces has distinct effects on filtration efficiency for large and small
nanoaerosol particles. The experimental results showed that, with the effect of the electrostatic
forces, the filtration efficiency was kept at a high level for particles above 20 nm. For particles below
about 20nm, the efficiency decreased with decreasing particle size.
Nomenclature
c

mean thermal velocity

upstream concentration

downstream concentration

diffusion Coefficient of an ion

dielectric constant

Boltzmann constant

temperature

ion electric mobility

collision probability

radius of the limiting sphere

electrostatic potential energy of the ion

34

ion attachment coefficient

attachment rate coefficient of the positive ion to the neutral particle
attachment rate coefficient of the negative ion to the neutral particle
attachment rate coefficient of the positive ion to the negative particle
attachment rate coefficient of the negative ion to the positive particle

ACKNOWLEDGEMENTS
This research was supported by Natural Sciences and Engineering Research Council of Canada
(NSERC) and Canadian Foundation for Innovation (CFI).

REFERENCES
Alonso, M., A. Hernandez-Sierra and F. J. Alguacil, 2002. Diffusion charging of aerosol
nanoparticles with and excess of bipolar ions. J. Ohusics a: Mathematical and General 35:
6271-6280.
Christopher J.H. Jr., L. Lin, D-R. Chen, and B. Pratim, 2009. Estimating aerosol particle charging
parameters using a Bayesian inversion technique, Aerosol Science 40: 295-306.
Fuchs, N. A. 1963. On the stationary charge distribution on aerosol particles in a bipolar ionic
atmosphere. Pure Applied Geophysics 56(1): 185193.
Gebhart, J., and J. Heyder. 1985. Removal of aerosol particles from stationary air within porous
media. Journal of Aerosol Science 16(2):175187.
Golshahi, L., J. Abedi and Z. Tan. 2009. Granular Filtration for Airborne Particles: Correlation
between Experiments and Models. The Canadian Journal of Chemical Engineering 87: 726-731.
Hoppel, W.A., and G.M. Frick. 1986. Ion Attachment Coefficients and the Steady State Charge
Distribution on Aerosols in a Bipolar Ion Environment. Aerosol Science and Technology 5: 1-21.
Marlow, W.H., and J. R. Brock, 1974. Calculation of Bipolar charging of aerosols. Journal of colloid
and interface science 51: 23-31.

35

Energy Saving and Storage

36

ADAPTIVE BATTERY STATE-OF-CHARGE AND CAPACITY DUAL ESTIMATOR

WITH MULTI-SCALE EXTENDED KALMAN FILTERS
Rui Xiong, Hongwen He
School of Mechanical Engineering, Beijing Institute of Technology
No. 5 South Zhongguancun St, Haidian Dist, Beijing 100081, China
rxiong6@gmail.com(R. Xiong), hwhebit@bit.edu.cn(HW. He, Corresponding author)

ABSTRACT
Accurate estimations of battery parameter and state play an important role in promoting the
commercialization of electric vehicles. We derive and implement a multi-scale extended Kalman
filters (EKF) algorithm based battery control algorithm for dual estimating the State of Charge (SoC)
and capacity. With two RC networks based lumped parameters battery model, various time scales
based dual EKF algorithm has been employed to build a dual estimation approach, which can not
only estimate the SoC accurately with micro time scale, but can also estimate the capacity with macro
time scale reliability. Results are presented for a high-power lithium ion battery, and results show the
proposed approach can achieve the control idea well and both the maximum error for SoC estimation
and capacity are less than 4%.
Keywords: Electric vehicles; state-of-charge; capacity; Extended Kalman filter; multi-scale;
battery.

1 INTRODUCTION
Hybridization and electrification of vehicle propulsion systems have become key trends in the
automotive industry in recent years. These trends are considered as primary instruments for
increasing the total efficiency and decreasing or even eliminating carbon dioxide (CO2) emissions,
PM2.5 and other pollutants from vehicles. Batteries form key components not only for pure battery
electric vehicles (BEVs) but also for intermediate storage of electrical energy in hybrid EVs (HEVs).
Currently only lithium-ion batteries (LIBs) are considered as a highly prospective technology for
automotive applications because of its good performance characteristics and promising potential for
cost reduction [1]. However, to satisfy the operation voltage and traction power requirements of
electric vehicles, battery packs have to be made up of hundreds of cells connected in series or
parallel to overcome the limitations of low energy density, low cell capacity and low cell voltage. But
how to avoid the adverse effect of cell inconsistency on battery pack performance and prolong the
service life of both the pack and the cells are posing tremendous technological challenges to battery
State-of-Charge (SoC) and capacity estimation techniques. Its accurate estimation is not only
beneficial for the efficient vehicular energy management, but also for the diagnosis and prognosis of
the battery behavior. The lithium -ion battery is widely used in many fields because of its advantages
of high voltage, long cycle-life, high specific energy and high specific power, which also makes it a
promising candidate for the electric vehicles (EVs). As a battery cell ages, the cell capacity and
resistance directly limit the pack performance through capacity and power fade, respectively. These
two degradation parameters are often used to quantify the cell state of health (SoH). Thus, to manage
the battery efficiently, an accurate SoC and capacity estimation method are very important [2-3].
Recent literature reports various approaches to estimate the SoH with a focus on the capacity
estimation. Joint/dual extended Kalman filter (EKF) with an enhanced self-correcting model were
proposed to simultaneously estimate the SoC, capacity and resistance [4-6]. However, the variation of
the cell capacity is very slow, therefore with a simple joint/dual EKF can hardly estimate the SoH
accurately; therefore, on the basis of our work in the SoC estimation with EKF technology[7], the
paper will propose a multiple dimensioned EKF based SoC and capacity dual estimation approach.
A key contribution of this paper is that a multiple dimensioned EKF is employed for a data drivenbased SoC and capacity joint estimator for Lithium-ion battery was proposed and evaluated under
highly transient loading profiles.
In this paper, with the second-order RC networks based dynamic universal battery model and AEKF
algorithm, a data driven based general SoC and capacity estimation approach for lithium-ion battery
is proposed. A description of the dynamic universal battery model is given in Section 2. A data driven
based multiple dimensioned EKF joint estimation approach for battery SoC and capacity is depicted
in Section 3. The experiment and evaluation for the proposed estimation approach is illustrated in
Section 4. Finally, conclusions are drawn in Section 5.

37

2 LUMPED PARAMETERS BATTERY MODEL

For model-based control system technology, the precision and complexity of battery model are very
important. The authors in [8] collected seven commonly used equivalent circuit models, including the
Shepherd model, Unnewehr Universal Model, Nernst model, combined model, the Rint model, the
first-order RC Thevenin model, the second-order RC model. The research results show that the
second-order RC model, which has higher precision, is more suitable for the voltage estimation of the
Lithium-ion battery. Therefore, we select the second-order RC model and replace its open circuit
voltage part with OCV functions which takes the SoC as the variable to strengthen the links of the
model's performance with battery's SoC and improve the models accuracy further, then the structure
for the second-order RC networks based dynamic universal battery model (abbreviated as SRUB
model) is shown in Fig.1. The electrical behavior of the proposed model can be expressed by Eq. (1).
From [4], we use the simply electrochemical function model to build the OCV and shown in Eq. (2).

C1

C2

R1

R2

I p1

I p2

Ro

U oc

IL

Ut

Fig.1. Schematic diagram for the second-order RC based universal battery model

1
1

U1 C R U1 C I L
1 1
1

1
1
U2
IL
U 2
C
R
C
2 2
2

U U U U I R
oc
1
2
L o
t

(1)

Where Uoc and IL are the open circuit voltage and load current (assumed positive for discharge,
negative for charge) respectively. Ut and Ro are the terminal voltage and ohmic resistance
respectively. The second-order RC networks are used to describe the relaxation effect
(concentration polarization and electrochemical polarization performance) including polarization
resistance R1 and R2, and polarization capacitance C1 and C2, U1 and U2 are the polarization voltage
across C1 and C2 respectively, Ip1 and Ip2 are the current flow over the polarization resistance R1
and R2 respectively.

Uoc K0 K1 z K2 z K3 ln z K4 ln(1 z )

(2)

Where z is the abbreviation of the SoC, Ki (i=0, 1, 2, 3, 4) are the constants chosen to make the
Uoc model fit the SoC-OCV data well.

3 SOC AND CAPACITY JOINT ESTIMATION METHOD

3.1 STATE OF CHARGE DEFINITION
SoC is a relative quantity that describes the ratio of the remaining capacity to the present
maximum available capacity of a battery, given by[9,10]:

1 k
i I L,t dt
Cn 0
Where zk is the SoC at the kth sample time, z0 is the initial SoC, IL,t is the instantaneous load
current; I is the Coulomb efficiency, which is the function of the current and the temperature.

z k z0

38

(3)

It is noted that the Cn is the maximum available capacity, and the available SoC ranges are
01.
A discretization of Eq.(3) is:
zk zk-1 i I L,k t Cn

(4)

Where t represents the sampling interval. Eq.(4) is the basis of the iterative calculation of
SoC.
3.2 MULTI- SCALES EKF JOINT ESTIMATION APPROACH
The extended Kalman filter has been widely used for parameter identification and state
estimation in battery control system [6].In order to use EKF for the joint estimation; we must first
have a system model in a state-space form. Specifically, we assume a very general framework for
discrete-time lumped dynamic systems.

k ,l A k ,l k ,l Bk ,l uk ,l k ,l , k ,L k ,0 rk ,l
y C D u
k ,l
k ,l k ,l
k ,l
k ,l
k ,l

(5)

Where k ,l is the vector of system states at the time tk,l = tk,0 + lt, for 1 l L, with t, being a
fixed sampling interval between two adjacent measurement points, and k and l being the two timescales indices for capacity and SoC estimation respectively; uk,l is the vector of observed
exogenous inputs; k,0 is the parameters vector, yk,l is the vector of system observations (or
measurements); wk,l and rk,l are the vectors of process noise for states and model parameters
respectively, rk,l is the vectors of measurement noise. Note that L represents the level of time-scale
separation and that k ,0 k 1,L . With the system defined, we aim at estimating both the system
states and model parameters from the noisy observations y. The matrices A, B, C and D
describe the dynamics of the system, and are time varying and determined by looking up for the
parameters table.
An implementation process of multiple dimensioned EKF joint estimation approach is follows:

Step1: Initialization

T
0 E 0 , E 0 0 0 0 ,

k ,l

(6)

T
0,0 E 0,0 , E 0,0 0,0 0,0 0,0
k ,l

Step2: Single-sampling interval (t) scale EKF, for l 1

, L , computer:

Time-update equations

k1,l A k 1,l 1 k1,l 1 Bk 1,l 1uk 1,l 1 k 1,l 1

A
AT

k 1,l k 1,l 1 k 1,l 1 k 1,l 1 k 1,l 1

(7)

Measurement-update and state estimation equations

T
T

K C
C

C
+
k 1,l k 1,l k 1,l k 1,l k 1,l k 1,l k 1,l

k 1,l k 1,l K k 1,l y k 1,l Ck 1,l k 1,l Dk 1,l u k 1,l k 1,l

I K k 1,l Ck 1,l
k 1,l
k 1,l

Step3: Multi-sampling intervals (Lt) scale EKF, for k 1

(8)

, , computer

Time-update equations

k 1,L k 1,0

k 1,L k 1,0 qk 1,0

(9)

39

Measurement-update and state estimation equations

T
T

K
C

C
C
+
k 1,L k 1,L k 1,L k 1,L k 1,L k 1,L rk 1,L

k 1,L k 1,L K k 1,L y k 1,L Ck 1,L k 1,L Dk 1,Lu k 1,L

I K k 1,LCk 1,L
k 1,L
k 1,L

(10)

Where the covariance matrices and are estimation errors for parameters and state
respectively. K k 1,L and K k -1,l are the Kalman gain matrixes for system parameters and state at
the time of tk,L = tk,0 + Lt and tk,l = tk,0+ lt respectively.
3.3 DUAL ESTIMATION FOR BATTERY SOC AND CAPACITY
With the estimation process, we can get the SoC and capacity estimation approach with the joint
estimation algorithm, and the implementation flowchart of the data driven-based SoC and capacity
joint estimation approach shown in Fig.2.
Current (C)

FUDS Profiles

2
1
0
-1
0

10
15
20
Time (min)

25

Current IL,k
Li-ion battery

30

C1

C2

R1

R2

I p1

I p2

Ro

Uoc

Parameters table

IL

SDUB Model

Uoc, C1, R1,C2, R2, Ro

Model updating

Ut

U t,k 1,l

U t,k 1,l

ek 1,l U t,k 1,l U t,k 1,l

Error

ek 1,l

Output SoC and

k-1k

Time update EKFC

k 1, L k 1, 0

Time update EKFx

k 1,l Ak 1,l 1 k1,l 1 Bk 1,l 1uk 1,l 1 k 1,l 1

Kalman gain update EKFC

T
T
Ck1,L Ck1,Lk1,L Ck1,L +rk1,L
k1,L

Kk1,L

Kalman gain update EKFx

Kk1,l

k1,l

Correction - EKFC

k 1,l

k1,l k1,l Ck1,l +k1,l

Correction - EKFx

k 1,L k1,L K k 1,L ek 1,L

k 1,l k1,l K k 1,l ek 1,l

Multi-sampling intervals

l=L?

Multi-scale dual EKF algorithm Single sampling interval

Fig.2 An implementation flowchart of the data driven-based SoC and capacity joint estimation approach

The FUDS cycle based charge-discharge currents are loaded on the lithium-ion cells and the
battery model simultaneously. Terminal voltage error between the observer and the experimental
data is adaptively reduced by updating the Kalman gain matrix. And the noise matrixes and
Kalman gain will be updated with the innovation- error. Then the updated gain is used to
compensate for the state estimation and parameter error. When the SoC estimate length is longer
than L sampling intervals, the SoC estimate transmit to parameter capacity and then the capacity
estimate will send to state estimate, lastly, the SoC and capacity estimate are then fed back to
update the parameters of the battery model for the SoC estimation at the next sampling time.

40

4 VERIFICATION AND DISCUSSION

This section will verify and evaluate the proposed joint estimation approach with dual EKF.
4.1 EXPERIMENT
The 32Ah and 3.2V lithium-ion battery is used for out test, and the actual maximum available
capacity is 26.5Ah. Firstly, we carry out the specific test to identify the parameters of the SRUB
model. The identify process is shown in Ref. [7].
The second test was a sequence of 14 urban dynamometer driving schedule (UDDS) cycles,
which was separated by 96A discharge pulses and 5 min rests, and spread over the 9312.6%
SoC range. The current, terminal voltage and SoC as a function of time are plotted in Fig. 3.
Where the Fig.3 (a) is the current profiles, Fig.3(b) is the zoom profile for one UDDS profiles, the
Fig.3(c) is the terminal voltage profiles, and the Fig.3(d) is the SoC profiles.

50

50

current (A)

(b) 100

current (A)

(a) 100

0
-50
45

90

135 180 225 270 315 360 405

t (min)

5min rest

60

(d)

65

70

75

80
85
t (min)

90

95

100

1
0.8

3.8
3.6

SoC

terminal voltage (V)

0
-50

0
(c)

3C discharge

3.4

0.6
0.4
0.2

3.2
3
0

45

90

0
0

135 180 225 270 315 360 405

t (min)

45

90

135 180 225 270 315 360 405

t (min)

Fig.3 The UDDS profiles: (a) current; (b) zoom current profile; (c)Terminal voltage; (d) SoC

4.2 VERIFICATION

0.02

0.8

0.6

-0.02
-0.04
-0.06
0

45

90

20

135

SoC error

180 225
t (min)

270

bound(-4%)

315

360

0.4

0
0

405

bound(3%)

0
-20
-40
-60
0

observer
true value

0.2

45

90

135

180 225
t (min)

270

315

360

405

45

90

(d) 35
Capacity (Ah)

SoC error (%)

(c)

SoC (%)

(b) 1

Voltage error (%)

(a) 0.04

135

180 225
t (min)

C0=32

270

C0=20

360

405

reference value

30
25
20
0

45

90

135

180 225
t (min)

270

Fig.4 The estimated result with multi-scales dual EKF approach: (a) terminal voltage estimation profiles; (b)SoC estimation profiles;
(c) SoC estimation error profiles; (d) Capacity estimation profiles

41

315

315

360

405

Provided that the initial matrix for the noise information, state, we can estimate the terminal voltage,
SoC abd capacity. Herein, the initial SoC offset was set at 0.43, in other words, the SoC0 is equal
to 0.5 and the initial capacity is 32Ah. The results are shown in Fig.4.
The terminal voltage estimation results are shown in Fig.4(a), and we can find its maximum error
less than 4% and main less than 2%. The SoC estimation results is shown in Fig.4(b), and the
error behavior is shown in Fig.4(c), where we can find the SoC estimation error is less than 4%.
The Fig.4 (d) is the capacity estimation results, when we set the initial capacity is 20Ah, we can get
the capacity and plot the results together with the result of 32Ah. We can find the error initial
capacity will be corrected quickly with the proposed method, of course, the L is 60s here.
To evaluate the capacity estimation accuracy, we plot the result shown in Fig.5.

capacity error (%)

0.25

C0=32

0.2

C0=20

0.15
0.1
0.05
0
0

45

90

135 180 225 270 315 360 405

t (min)

Fig.5 The capacity estimation accuracy

From Figure.5, we can find the maximum capacity estimation error is less than 4% after some a
certain intervals, which is because the capacity is a slow variation process.
Therefore, the proposed multi-scale framework with dual EKF is for efficient and which uses
different time-scale separation. The proposed framework was applied to the Lithium-ion battery
system for SoC and capacity estimation, the accuracy is good enough for practical application.

5. CONCLUSIONS
Based on the above analysis, the main concluding remarks can be made below:
(1) To model the dynamic performance of Lithium-ion batteries accurately, based on our research
experience the second-order RC networks based dynamic universal battery model is employed for
terminal voltage and state estimations. Where, the electrochemical model is used to build a
relationship between the SoC and the open circuit voltage characteristic of the battery, therefore
the model not only has the advantages of simulation accuracy for the terminal voltage, but also
having a contribution to improve SoC estimation accuracy through an efficient closed-loop
feedback.
(2) To predict the SoC and capacity precisely, based on the proposed model we have employed
the dual EKF to carry out the joint estimation for SoC and capacity.
(3) To solve the traditional dual method applied for battery system that the convergence
performance of the capacity estimation is not good enough for practical application, we have
proposed multi-scale dual EKF estimation approach, and we have built an implementation
flowchart of the data driven-based SoC and capacity joint estimation approach.
(4) The results show that the dual estimation accuracy for the battery SoC and capacity are
accurate for practical application, and both of the maximum error is less than 4%.

ACKNOWLEDGEMENT
This work was supported by the National High Technology Research and Development Program of
China (2011AA11A290,2012AA111603,2013BAG05B00) in part, the National Natural Science
Foundation of China (51276022) and the Higher school discipline innovation intelligence plan
(111plan) in part, and the Program for New Century Excellent Talents in University (NCET-110785) in part.

42

REFERENCES
[1] Waag Wladislaw, Fleischer Christian and Sauer Dirk Uwe, 2014, Critical review of the methods
for monitoring of lithium-ion batteries in electric and hybrid vehicles. Journal of Power Sources 258:
321-339.
[2] Xiong Rui, Sun Fengchun, Gong Xianzhi and Gao Chenchen, 2014, A data-driven based
adaptive state of charge estimator of lithium-ion polymer battery used in electric vehicles. Applied
Energy 113: 1421-1433.
[3] Lee S, Kim J, Lee J, and Cho BH, 2008, State-of-charge and capacity estimation of lithiumion
battery using a new open-circuit voltage versus state-of-charge. Journal of Power Sources 185:
13671373.
[4] Gregory L Plett, 2004, Extended Kalman filtering for battery management systems of LiPBbased HEV battery packs. Part 1: Background. Journal of Power Sources 134: 252261.
[5] Gregory L Plett, 2004, Extended Kalman filtering for battery management systems of LiPBbased HEV battery packs. Part 2: Modeling and Identification. Journal of Power Sources 134:
262276.
[6] Gregory L Plett, 2004, Extended Kalman filtering for battery management systems of LiPBbased HEV battery packs. Part 3: State and Parameter Estimation. Journal of Power Sources 134:
277292.
[7] Xiong Rui, Gong Xianzhi, Mi Chunting Chris, Sun Fengchun, 2013, A robust state-of-charge
estimator for multiple types of lithium-ion batteries using adaptive extended Kalman filter. Journal
of Power Sources 243: 805-816.
[8] He Hongwen, Xiong Rui, Guo Hongqiang and Li Shuchun, 2012, Comparison study on the
battery models used for the energy management of batteries in electric vehicles. ENERGY
CONVERS. MANAGE 64:113-121.
[9] Xiong Rui, He Hongwen, Sun Fengchun, Zhao Kai, 2013, Evaluation on State of Charge
Estimation of Batteries With Adaptive Extended Kalman Filter by Experiment Approach. IEEE
Transactions on Vehicular Technology 62: 108-117.
[10]Sun Fengchun, Hu Xiaosong, Zou Yuan, Li Siguang, 2011, Adaptive unscented Kalman
filtering for state of charge estimation of a lithium-ion battery for electric vehicles. Energy 36: 35313540.

43

ELECTROCHEMICAL BEHAVIOR OF THE CHARGING LI-ION BATTERIES WITH

DIFFERENT ELECTROLYTE SALT CONCENTRATIONS
Sijie Zhang, Rui Zhao, Junjie Gu, Jie Liu
Carleton University, Department of Mechanical and Aerospace Engineering
1125 Colonel By Drive, Ottawa, Ontario, Canada K1S 5B6
sijiezhang@cmail.carleton.ca; ruizhao2@cmail.carleton.ca;
jgu@mae.carleton.ca; jliu@mae.carleton.ca

ABSTRACT
Based on a 1D electrochemical model, a series of galvanostatic charge processes for lithium ion
batteries using different initial electrolyte salt concentrations are simulated and investigated. From
the simulation results, several electrochemical characters, such as the charge curve, the
end-of-charge salt concentration, the anode potential, and the reaction depth distribution reflected
by the Li-ion concentration, are found to be able to be affected by the initial electrolyte salt
concentration. Specifically, the Li-plating phenomenon commonly appeared in the charge course is
studied with respect to different salt concentrations and the corresponding solution is provided by
changing the thickness ratio of the anode and cathode, which can also be used to extend the
charging time. Overall, in this study, a better understanding of the relevance between the
electrochemical behaviors of a battery during charge and the initial electrolyte salt concentration is
achieved and the important role of the electrolyte salt concentration in the performance and health
of lithium ion battery is emphasized.
Keywords: electrolyte salt concentration, lithium ion battery, charge, electrochemistry

INTRODUCTION
Lithium ion batteries have been commercialized since the early 1990s. Thanks to the high
power density, low self-discharge rate and minimal memory effect, the Li-ion battery has been
widely considered to be one of the most promising energy sources for consumer electronics and
automotive applications (Asxen et al., 2008). To date, numerous different types of Li-ion batteries
have been developed based on different electrode materials, electrolytes and separators as well as
on the different properties and performances needed for different uses.
A very important step in recognizing the affecting factors of the electrochemical behaviors of a
battery is to inspect the influence of each specification individually. To realize this by simulation,
diverse electrochemical models for Li-ion battery have been developed over the past two decades.
A 1D electrochemical battery model was firstly built by Doyle et al. (1993) based on the LiMn2O4
cathode, which laid the foundation for this area. Later, Gu and Wang (2000) coupled an
electrochemical model with a thermal model and tracked the coupling temperature variations during
charge and discharge, which were used to calibrate the electrochemical model for the temperature
dependent parameters. In both of the models, the electrolyte salt used was LiPF6 in a non-aqueous
liquid mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC), and the concentration of
the binary solution was 2M. While in some other works (Smith and Wang, 2006; Wu et al., 2013),
the electrolyte concentration used in the model was 1.2M. To date, no much research interest has
been focused on the investigation of how the electrolyte salt concentration impacts the
electrochemical behaviors of lithium ion batteries during charging. Actually, this parameter is fairly
critical since it can be directly related to the transportation of lithium ions across the electrochemical
chain, the diffusion environment for cations and anions, and many other important electrochemical
processes, and finally influences the overall performance and cycle life of the lithium ion battery.
In this study, several galvanostatic charge processes are simulated on three Li-ion battery cells
with different initial electrolyte salt concentrations. The charge curves are firstly described and
studied, followed by analyses on several internal electrochemical parameters, including the
end-of-charge electrolyte salt concentration and the Li-ion distribution across the active material
particles. Then, the capability of the simulated batteries to prevent the lithium plating is evaluated,
and finally, a proper solution to Li-plating is proposed
EXPERIMENTAL
The electrochemical model used for battery performance simulation, as shown in Fig.1, is
reproduced from the model proposed by Doyle et al. (1993), in which three regions are involved:
negative electrode (LiyC6), positive electrode (LixMn2O4) and separator. Both the LiyC6 and LixMn2O4
are porous composite insertion particles, and the electrolyte is composed of LiPF6 in 1:2 v/v
ethylene and dimethyl carbonate non-aqueous liquid mixture. The initial electrolyte salt

44

concentrations used in the simulation are set at 1000 mol m-3, 1500 mol m-3 and 2000 mol m-3 for
Cell #1, Cell #2, and Cell #3, respectively, and the relationship between salt concentration and
conductivity is given by:
= 1.0793 104 + 6.7461 103 5.2245 103 2 + 1.3605 103 3 1.1724
104 4
(1)

Figure 1. Schematic presentation of the electrochemical model.

During the charge course, Li-ions migrate from the cathode to the anode and the electrons
move through the external circuit to the anode to complete the electrochemical reaction. Because of
the salt diffusion limitation, the concentration of the salt at the anode is lower than that at the
cathode. In simulation, all the three cells are involved in 2C (3.5 A m-2) and 4C (7 A m-2)
galvanostatic charge processes and the differences in selected electrochemical properties caused
by the different electrolyte salt concentrations are discussed in the following section.
RESULTS AND DISCUSSIONS
First, the charge curves of Cell #1-3 under 4 C charge rate are compared in Fig. 2. It can be
seen that the cells with different initial electrolyte salt concentrations have very different charging
responses in the entire charge course, although their voltage increases in the first few seconds are
similar, which is due to the comparable ohmic over potential. Among these three cells, Cell #1, as
indicated by the blue line in Fig. 2, generally takes the shortest charging time (150 s) and yields the
steepest charging curve, suggesting an unstable electrochemical reaction taking place and an
incomplete utilization of the active material, i.e., a low capacity obtained from charging. In contrast,
the charge process for Cell #3 lasts as long as 750 s until the voltage reaches 4.5 V and the overall
voltage curve is more stable compared to the other cells. Cell #2 with the moderate salt
concentration performs medially, with a stop voltage of 4.4 V and a charge time of 500 s.

45

Figure 2. Voltage curves of Cells #1-3 with different initial salt concentrations during a 4 C
galvanostatic charge course.
Then the internal electrochemical variations are investigated. The electrolyte salt
concentrations along the cells at the end of the 4 C charge course are depicted in Fig. 3. As can be
seen, in Cell #1 (with the lowest initial concentration, 1000 mol m-3), a great portion of the anode
has a zero salt concentration at 150 s, which indicates not only a low conductivity of the electrolyte
but also an early stop of the charge, and this can be explained through the reaction mechanism of
the charging battery. During the charge process, the right region of the anode is filled with the
Li-ions coming from the cathode prior than the left part. Once the right region is fully intercalated,
the Li-ions need to move further to the left to complete the electrochemical reaction. However, as
the charge proceeds, the electrolyte salt concentration at the left region of the anode tapers to 0
due to the concentration polarization, the diffusion of Li-ion from right to left is then constrained,
which finally leads to the early stop of the charge process. With a 500 mol m-3 greater initial salt
concentration, Cell #2 can be charged for 500 s before the salt concentration on the left part of the
anode drops to zero, thereby increasing the charge capacity. As for Cell #3, the electrolyte salt
concentration at the left of the anode still remains 200 mol m-3 at the end of charge, which promises
a longer charge time and higher capacity.

Figure 3. Electrolyte salt concentrations along the cells with different initial salt concentrations at the
end of charge.
The ratio between the average and maximum Li-ion concentration in the active material solid
particles is another important electrochemical parameter that implies the depth and stability of the

46

electrochemical reaction across an electrode. A higher value of this ratio indicates a smoother
insertion of Li-ions into the active material particles. Since the anode is the receiver of lithium ions
during the charge process, the Li-ion concentration ratio for the anode particles should be of
particular concern. Fig. 4 gives the ratios along the anodes of the three cells with different initial
electrolyte salt concentrations. As is shown, Cell #3 has the highest ratio curve among all the cells
and the value varies slightly from 0.42 to 0.55, which demonstrates an evenly distributed reaction
depth and therefore a uniform lithiation reaction across the anode. For the other two cells, however,
the ratio profiles are much lower and the ratio values along the anodes of Cell #1 and Cell #2
increase from 0.096 to 0.15 and from 0.18 to 0.45, respectively. The low ratio for Cell #1 indicates a
poor utilization of the active materials in the anode particles, while the great variation of the ratio
along Cell #2 reflects an insufficient supply of Li-ions at the end of charge.

Figure 4. The ratio of the average to maximum Li-ion concentration in electrode particles at the end
of charge.
Finally, the capability of the cells to prevent the anode from lithium plating (Li-plating) is studied.
Li-plating has been widely reported for generating numerous adverse effects on the health of Li-ion
battery (Harris et al., 2010; Ratnakumar and Smart, 2010). The so-called dendrite growth on the
interface between the anode and the separator can lead to internal short-circuit and pre-mature
failure of the battery. Meanwhile, Smart and Ratnakumar (2011) claimed that the presence of
metallic Li on the anode generally induces further degradation in the anode/electrolyte interface,
and the Li metal is known to be very reactive towards electrolytes. In view of numerous existing
literatures based on both experimental trials and theoretical studies, it is reasonable to conclude
that Li-plating can pose a serious threat to the safety and reliability of the Li-ion battery. Generally,
the potential difference between the solid particles and the electrolyte can reflect the likelihood of
the occurrence of the lithium plating, and a sub-zero value indicates the ability to react. In Fig. 5, the
potential differences are plotted along the anodes of the cells at 150 s when Cell #1 stops charge
due to the zero concentration. Although the potential differences (also called anode potential) in all
the cells are higher than zero, the curve for Cell #1 greatly drops by 0.95 V across the anode, while
Cell #2 and Cell #3 only experience slight decreases of 0.17 V and 0.1 V, respectively. Since the
front of the anode (right end in the figure) is filled with lithium ions earlier than the back (left end in
the figure), if plating of lithium were to occur, it would be expected to occur at the anode/separator
interface first. The potential difference at the right end of the anode of Cell #1 does not reduce to 0
due to the early stop of the simulation; in real case, the charge process could be continued through
the control system of a charger or tester, therefore the lithium plating would probably occur. To
verify this possibility, a simulated 2 C galvanostatic charge, instead of 4 C, is carried out with all the
cells. As shown in Fig. 6, at 1650 s, negative potential differences can be observed at the right part
of the anode for Cell #1 and Cell #2, while for Cell #3 with the highest initial salt concentration, the
potential difference still remain positive at the anode/separator interface.

47

Figure 5. Potential differences between active solid particles and electrolyte across the anodes of
Cell #1-3 under 4 C galvanostatic charge at 150 s.

Figure 6. Potential differences between active solid particles and electrolyte across the anodes of
Cell #1-3 under 2 C galvanostatic charge at 1650 s.
In order to prevent the Li-plating phenomenon and the early stop of the charging process, an
increase of the ratio between the anode thickness and the cathode thickness can be performed.
Therefore, in simulation, the thickness of the cathode is adjusted from 0.174 mm to 0.1 mm, which
is the same with the anode, thus the thickness ratio increases from 0.575 to 1. To clearly depict the
effect of this change on the charge process, the voltage curves of three adjusted cells under 7 A m-2
charge course are drawn in Fig. 7. As can be seen, by increasing the ratio, the charge time for Cell
#3, which has the highest initial salt concentration, reduces from 750 s to 520 s, and this can be
mainly attributed to the loss of active materials in the cathode, i.e., less Li-ions are available in the
cell to react. For the modified Cell #2, interestingly, the charge curve almost overlaps the curve of
Cell #3, which indicates a sufficient utilization of the active materials and a weaker impact of the
initial electrolyte salt concentration on the performance of the cell. Although the Cell #1 after being
modified is still the cell that undergoes the fastest charge process, its improvement compared to the
original cell is obvious, provided that the charge time increases dramatically (40%) from 150 s to
210 s and the maximum voltage also rises from 4 V to around 4.2 V.

48

Figure 7. Voltage curves of adjusted Cells #1-3 with different initial salt concentrations during a 7 A
m-2 galvanostatic charge course.
To clearly illustrate the improvement of the capabilities of the adjusted cells to prevent the
Li-plating at the end of the charging process, the anode potentials vs. (Li+/Li) of the three cells under
3.5 A m-2 charge course are presented in Fig. 8. As shown, all of the three cells are kept out from
reaching a negative potential vs. Li+/Li at the end of charge, which suggests that the Li metal is
unable to form on their anodes. Improved performance can also be indicated by the potential
variations across the anodes. Cell #1, the most possible cell to suffer the Li-plating, has a potential
difference variation of 0.23 V along the entire anode with the original electrode geometry, whereas
the value decreases to around 0.13 V after changing the thickness ratio of the electrodes.
As are evident from the charge curves, Fig. 7, and the anode potential curves at the end of
charge, Fig. 8, the cells with adjusted thickness ratio show better performances both on the charge
process and on the Li-plating prevention when compared with the original cells. This is mainly due
to the decrease of the amount of Li-ions which will insert into the anode particles. When thinner
cathode is used, the anode capacity utilization will be correspondingly lower, resulting in a decrease
in the range of the stoichiometric coefficient, x, for the anode material, LixC6. From the model of
Doyle et al. (1993), the anode open-circuit potential can be expressed as:
ref, = 0.16 + 1.32 exp(3.0x)
+ 10.0 exp(2000.0x)

(2)

And the corresponding curve for the anode potential at different states of charge is depicted in Fig.
9. It can be seen that at the fully charged state, where x is close to 0.7 in this figure, the anode open
circuit potential approaches 0. From the simulation, the x in the original highest salt concentration
cell is 0.75 at the anode/separator interface, which is larger than the cell with thinner cathode,
whose final x is 0.56. It is then clear that the cell with adjusted thickness ratio can better hinder the
Li-plating during the whole course of charge.

49

Figure 8. Potential differences between active solid particles and electrolyte across the anodes of
adjusted Cell #1-3 under 3.5 A m-2 galvanostatic charge at 1120 s.

Figure 9. The open-circuit potential of petroleum coke (Li xC6) as a function of state of charge
relatively to the potential of solid lithium.
CONCLUSION
The influence of electrolyte salt concentration on the changes of several key electrochemical
properties of lithium ion battery during charging have been studied. An electrochemical cell model
consisting of electrodes and separator has been developed to simulate a series of galvanostatic
charge processes for the cells with different initial electrolyte salt concentrations. The cell with the
lowest initial salt concentration ends the charge prematurely as a result of the zero concentration at
the anode, while the cells with higher initial salt concentrations can last the charge for several times
longer. As far as the electrochemical reactions are concerned, the Li-ion intercalation in the cell with
the lower electrolyte salt concentration takes place more non-uniformly and incompletely than the
other cells. Additionally, the low initial salt concentration cell has a higher risk for lithium plating,
especially on the interface between the anode and the separator, which can destroy the health and
threaten the safety of the battery. Finally, by varying the ratio of the thickness of the anode and
cathode thickness, the Li-plating behavior can be theoretically well controlled, and meanwhile the
performance of the charge for Li-ion battery can be significantly improved.
ACKNOWLEDGMENT
This work is financially supported by the Natural Sciences and Engineering Research Council
(NSERC) of Canada.

50

REFERENCES
Axsen J., Andrew F.B., Kenneth S.K. (2008). Batteries for Plug-in Hybrid Electric Vehicles (PHEVs):
Goals and the State of Technology circa 2008. Institute of Transportation Studies, University of
California, Davis, Research Report UCD-ITS-RR-08-14.
Doyle M., Fuller T.F., Newman J. (1993). Modeling of Galvanostatic Charge and Discharge of the
Lithium/Polymer/Insertion Cell. Journal of The Electrochemical Society, 140, 1526-1533.
Gu W.B., Wang C.Y. (2000). Thermal-Electrochemical Modeling of Battery Systems. Journal of The
Electrochemical Society, 147, 2910-2922.
Harris S.J., Timmons A., Baker D.R., Monroe C. (2010). Direct in situ Measurements of Li Transport
in Li-ion Battery Negative Electrodes. Chemical Physics Letters, 485, 265-274.
Ratnakumar B.V., Smart M.C. (2010). Lithium Plating Behavior in Lithium-ion Cells. ECS
Transactions, 25, 241-252.
Smith K., Wang C.Y. (2006). Power and Thermal Characterization of a Lithium-ion Battery Pack for
Hybrid-Electric Vehicles. Journal of Power Sources, 160, 662-673.
Smart M.C., Ratnakumar B.V. (2011). Effects of Electrolyte Composition on Lithium Plating in
Lithium-Ion Cells. Journal of the Electrochemical Society, 158, A379-A389.
Wu B., Yufit V., Marinescu M., Offer G.J., Martinez-Botas R.F., Brandon N.P. (2013). Coupling
Thermal-Electrochemical Modelling of Uneven Heat Generation in Lithium-ion Battery Packs.
Journal of Power Sources, 243, 544-554.

51

EFFECTS OF SALT CONCENTRATION ON THE ELECTROCHEMICAL AND

THERMAL BEHAVIORS OF LITHIUM ION CELLS
Rui Zhao, Sijie Zhang, Jie Liu, Junjie Gu
Carleton University, Department of Mechanical and Aerospace Engineering
1125 Colonel By Drive, Ottawa, Ontario, Canada K1S 5B6
ruizhao2@cmail.carleton.ca; sijiezhang@cmail.carleton.ca;
jliu@mae.carleton.ca; jgu@mae.carleton.ca

ABSTRACT
Recently, the identification of various electrolyte variables affecting the behaviors of Li-ion battery
has been performed. Among these variables, the electrolyte salt concentration has been found to
be a primary parameter that can influence the battery not only on its electrochemical properties but
also on the associated thermal performance. In this paper, a 1D electrochemical model coupled
with a 3D thermal model is employed to simulate the discharge process of Li-ion battery and to
present the electrochemical and thermal behaviors of the battery cells using different initial
electrolyte salt concentrations. It has been shown that the Li-ion batteries with either too high or too
low salt concentration have the risk of stopping discharge prematurely due to the solubility and zero
concentration problems. Furthermore, the heat generated from the cell components, such as
electrodes and separator, can be affected by the relevant electrochemical parameters and be
reflected in the temperature evolution of the battery cell.
Keywords: lithium ion battery, electrolyte salt concentration, electrolyte conductivity, heat
generation.
INTRODUCTION
Lithium ion (Li-ion) batteries have replaced the nickel-based systems in small-electronics,
automobile, satellite, and several other applications over the past few years. Determination of the
electrochemical and thermal behaviors of Li-ion battery discharging under different conditions has
been an important subject for the industry. For example, a review of the high temperature operation
tests on Li-ion batteries was conducted by Bandhauer et al. (2011), through which they concluded
that the battery performs differently in various aspects, such as the capacity supply and degradation
rate, when operating at different temperatures. Other investigators employed different discharging
modes, e.g., constant current discharge (Ramadass et al., 2002), pulsed discharge (Savoye et al.,
2012) and high rate discharge (Smith and Wang, 2006), in order to evaluate the performance of
Li-ion batteries used for different applications that operate in respective modes. Also, the impact
from the configuration of the battery system was studied by Fan et al. (2013), and it was
demonstrated that an improper cell layout can lead to an uneven heat distribution across the battery
pack, which is widely believed to damage the system silently and irretrievably and promote safety
issues.
Despite that significant efforts in the past have been focusing on the evaluation of the battery
performance under various external conditions like temperature and discharging profile, the
understanding of many internal processes undergoing in the battery during discharge has not been
clear. Therefore, in recent years, many studies have attempted to identify the contributions made by
individual intrinsic specifications to the change of the properties and behaviors of Li-ion battery. Lu
and Lin (2001) claimed that large particle size and wide size distribution of the electrode active
material particles can raise the difficulty of lithium ions diffusing in the particles during reaction.
Nanotechnology was used with carbon coating to improve the conductivity of electrode as well as
the diffusion rate, through which an enhanced cycle life and an increased rate capacity were
achieved (Li and Zhou, 2012). Reports of the batterys heat and current distribution changing with
the electrode thickness also exist. In this work, the electrolyte salt concentration is acknowledged
as a significant factor in determining the properties and performance of Li-ion battery from both
electrochemical and thermal perspectives. A 1D electrochemical model is coupled with a 3D
thermal model in this study to simulate the electrochemical reaction process inside the battery cells
with different initial electrolyte salt concentrations during the discharge process, and the variations
with respect to the electrochemical and thermal behaviors are also carefully inspected.
MATHEMATICAL MODEL

52

In this work, a coupling model consisted of a 1D electrochemical part and a 3D thermal part is
built for simulation, in which the heat generation from the electrochemical model and the
temperatures obtained from the thermal model are mutually used as inputs for each other.
The electrochemical model is based on previous work (Doyle et al.,1993), and a schematic
illustration of it is shown in Fig. 1. Totally five main regions are involved: two current collectors
(aluminum and copper foil), positive composite electrode, negative composite electrode and
separator. A typical electrode is composed of active insertion material particles, electrolyte, binder
and conductive filler, while a separator consists of porous polymer part and electrolyte part.
LixMn2O4 and LiyC6 are used as the positive and negative active materials in this study, respectively.
The binary electrolyte of LiPF6 in ethylene and dimethyl carbonate (1:2 v/v) permeates both
separator and electrodes. During discharge, the Li-ions de-intercalate from the anode and
intercalate into the cathode through a highly conductive electrolyte solution, while the electrons flow
through the external circuit in the reverse direction of the current.

Figure 1. Schematic of the 1D electrochemical cell model.

In the 3D thermal model, the heat generation and convective heat dissipation are balanced
with the accumulated internal energy:

= h ( )

+ ( +
+ )

(1)

where h denotes the heat transfer coefficient for convection, is the convective area, is
the ambient temperature and this equation illustrates the evolution of the cell temperature, , with
time.
The total heat generation is the sum of irreversible heat (reaction heat), reversible heat
(entropy heat) and ohmic (joule) heat. Volume specific irreversible heat generated in a finite control
volume is equal to the reaction current density, , multiply the over-potential, , which is
expressed as the difference between the calculated potential and the open circuit voltage, U.

= (
)

(2)

The reversible heat is generated on both electrodes due to the entropy changes in intercalation
and de-intercalation reactions during discharge, and it is directly related to the reaction current
density, the temperature of electrode and the / term, which are different for two electrodes,
as given by (Sirinivasan and Wang, 2003):

53

(3)

The ohmic heat term rising in the discharge process is a result of the motion of lithium ions
through the solid and electrolyte phase, and it can be expressed as:
2
2
= eff (
) + eff (
)

eff
2
(1
+

(ln )
+0 )

(4)

where the first term on the right hand side indicates the heat source from the solid active material
particles, while the second and the third terms denote the heat generated in the electrolyte, and the
currents arise from the ions motion are driven by the potential and concentration difference,
respectively.
Based on the above illustrated coupling model, the influence of the initial electrolyte salt
concentration on the electrochemical property and thermal response of lithium ion battery will be
discussed and analyzed by introducing battery cells with different concentrations, i.e., 1000, 1500
and 2000 mol m-3, and the relation between the electrolyte conductivity and the salt concentration is
given by:
= 1.0793 104 + 6.7461 103 5.2245 103 2 + 1.3605 103 3 1.1724
104 4
(5)
The correlation of these two variables is plotted in Fig. 2. It can be observed that in the range from 0
to 4000 mol m-3, the value of electrolyte conductivity peaks at around 1000 mol m-3 while tends to 0
at both ends which is believed to be due to the zero concentration effect and the solubility problem
at high concentrations. This correlation will be used in the following analysis on the electrochemical
and thermal behavior of Li-ion cells with different electrolyte salt concentrations.

Figure 2. Correlation between electrolyte salt concentration and electrolyte conductivity.

RESULTS AND DISCUSSIONS
As an overview, Fig. 3 shows the end-of-discharge electrolyte salt concentration curves across
the cells with various initial concentrations, namely 1000 mol m-3, 1500 mol m-3 and 2000 mol m-3.
The horizontal axis does not include the current collectors, and so do the following diagrams. As
can be seen, the lower the initial salt concentration is, the higher tendency the concentration has to
taper down to 0 at the interface between the cathode and the current collector at the end of
discharge. While at the anode/current collector interface, the highest concentration (4000 mol m-3)

54

is obtained in the cell with the highest initial salt concentration. Both of these phenomena are mainly
attributed to the Li-ion diffusion limitation in the electrolyte. Note that the variation of the electrolyte
concentration on the separator is smaller than that in both anode and cathode. This is due to the
Li-ions in both electrodes are involved in the electrochemical reaction, where the ions are produced
or consumed, which increase the variation of concentration across the electrodes. While in the
separator no reaction occurs, therefore a relatively smaller gradient can be seen.

Figure 3. Electrolyte salt concentration curves at the end of discharge for cells with 1000, 1500 and
2000 mol m-3 initial electrolyte salt concentrations.
As a significant representation of the performance of a Li-ion battery system, the voltage
curves of different cells are given in Fig. 4. It should be noted that all the cells stop discharging at
around 220 s, far less than the ideal discharge time for the 8C process (450 s). This is due to the
fact that the ideal discharge time is determined only based on the C rates, with the discharge time
under 1C rate of 3600 s, however, in real cases, the increase in the discharge rate will exacerbate
the ohmic drop (IR) and the polarizations, which can lead to the early stop of the discharge. In Fig.
4, the initial potential drop is as high as 0.6 V (from 4.2V to 3.6 V), and the cell with the highest initial
salt concentration has a relatively higher potential drop than the other two cells due to the higher
ohmic drop. Among the three cells, the cell with 1500 mol m-3 initial salt concentration has the most
stable voltage curve during the discharge period compared to the others, indicating a higher power
output and a better stability of the internal electrochemical reactions. Cell with the lowest initial salt
concentration has a relatively higher output voltage before 150 s, which is due to the smaller ohmic
drop during that period, but suffers a dramatic drop in the voltage at the end of discharge as a result
of the premature stop of the electrochemical reaction. While for the cell with the highest initial salt
concentration, the voltage curve is relatively lower than the others during the major course of
discharge due to the lower salt conductivity, but in the end the cell outperforms the cell with lowest
electrolyte concentration thanks to the non-zero conductivity.

55

Figure 4. Voltage curves of the cells with different initial electrolyte salt concentrations during 8C
galvanostatic discharge.
In the thermal perspective, Fig. 5 presents the average heat generation rates of the cells. From
the figure, the cell with 1000 mol m-3 initial electrolyte concentration exhibits the lowest heat
generation rate at first due to its high electrolyte salt conductivity. However, a rapid increase of the
curve can be observed from around 170s owing to the zero salt concentration at the positive
electrode, which corresponds to a low solution conductivity. Compared with this cell, the heat
generation rates of the other two cells increases more steadily during the whole discharge period on
account of the non-zero salt concentration across them. However, the cell with 1500 mol m-3 initial
salt concentration generates less heat than the 2000 mol m-3 one due to the higher overall salt
conductivity.

Figure 5. Average heat generation rates of the cells with different initial salt concentrations.
To further elaborate the thermal issue accompanied with the cells during the galvanostatic
discharge course, the total heat generation rates of the cells are depicted in Fig. 6 at different
depths of discharge. As can be seen, the cell with the lowest initial electrolyte salt concentration
shows a weaker exothermic behavior on the anode and a stronger and more unstable behavior on
the cathode as compared to the other ones, especially at the end of discharge. It is also noticeable
that the total heat generation rate varies dramatically at the left region of the cathode at 200 s. The
instability and non-uniformity can be accounted for by the zero concentration of the electrolyte at
the right part of the cathode, which results in all the currents as well as the electrochemical
reactions being undertaken by the rest part of the cathode where the supply of lithium ions is

56

sufficient, thus leading to a large amount of heat being generated at the left region. As the initial
electrolyte slat concentration goes higher (Fig. 6b &c), more heat is generated by the anode than by
the cathode due to the higher salt concentration at the anode, which determines a lower
conductivity.

Figure 6. Heat generation rates at different depths of discharge across the components in cells
using different initial electrolyte salt concentrations: a) 1000 mol m-3, b) 1500 mol m-3 and c) 2000
mol m-3.
In order to determine the contribution of three heat sources on the total heat generation, Fig.
7a, b and c separately depict the heat generation rate of irreversible heat source, reversible heat
source and ohmic heat source in Li-ion batteries using different initial electrolyte salt concentrations

57

at 100 s and 200 s.

In the irreversible heat diagram, the heat generated from the anode is almost unchanged when
different concentrations are used or as the discharge proceeds. Knowing that during discharge the
Li-ions diffuse from the center of the electrode solid particles to the surface to react and then
transfer from the solid phase to the electrolyte phase, the conductivity of electrolyte, and hence the
electrolyte concentration, has no significant influence on the electrochemical reaction on the
negative electrode, therefore the irreversible heat generation remains fairly constant at the anodes
of the three cells. As for the cathode, however, great variations are observed at the end of
discharge (200 s) for all the cells, especially the one with 1000 mol/m3 initial electrolyte salt
concentration. According to Fig. 3, the salt concentration of this cell finally drops to zero at the right
part of its cathode, which undoubtedly restricts the transport of Li-ions and hence shuts down the
reactions at that region, as revealed by the zero reaction heat generation rate at the right of the
cathode. Whereas at the left, more and more Li-ions are gathered. With continuous electrons
produced by the anode reaction and transported from the external circuit to the reaction region (left
part of the cathode), all the electrochemical reactions in cathode take place at this portion, thus the
reaction heat and reaction current density here markedly increase. Comparably, cells with higher
initial salt concentrations have flatter irreversible heat generation curves across the cathodes.
Similar pattern can be observed in the reversible heat source profile. As is the case of the
irreversible heat, the reversible heat is also linked with the reaction current density, and the battery
with the lowest initial salt concentration can produce a large current density during the
electrochemical reaction at the left region of its cathode, leading to a relatively high reversible heat
generation rate in this part. Moreover, the fluctuating heat generation across the cathode and the
difference of the reversible heat generated on the anodes at two assigned time points are mainly
attributed to the changes in the value of / at different depths of discharge.
Rather than showing a good stability in the anode heat generation as the irreversible heat and
reversible heat do, the ohmic heat source exhibits a very different generation profile on the anode
when different electrolyte concentrations are employed or when measured at different time points,
i.e., 100 s and 200 s. As shown in Fig. 7c, more heat is generated in the cell using higher initial salt
concentration or being discharged for a longer time (at 200 s). The explanation could be based on
the fact that the low electrolyte conductivity in cell with high initial salt concentration limits the
motion of Li-ions on the anode, and thus leading to an increase in ohmic heat generation during the
course of discharge, especially at the last period. While on the cathode, the difference in heat
generation of different batteries is small, and this can be attributed to the specific process of the
electrochemical reactions. During intercalation, the left part of the cathode receives the Li-ions first
and hence is the prioritized region for them to react and insert, thus less Li-ions move forward,
resulting in that the ohmic effect on the cathode decrease gradually as towards the right side.
Meanwhile, considering the thickness of cathode is greater than anode in the simulation, although
the salt concentration at the right side of cathode drops down to zero, the concentration at its left
side is high enough for ions transportation (see Fig. 3). Even for the battery using the lowest initial
electrolyte concentration, the final concentration reaches 1000 mol/m3 at the left end of cathode,
which is corresponding to the highest conductivity shown in Fig. 2. As a result, the heat generation
arise from the transportation of ions on the cathode varies slightly.
The combination of the three heat sources can give a clear explanation on the previously
discussed average heat generation rates and total heat sources. Because both the irreversible and
reversible heat change much slighter than the ohmic heat on the anodes, the difference in the total
heat generation on the anode among the cells can be mainly attributed to the ohmic heat source,
which also explains the higher average heat generation rate in cell with higher initial salt
concentration except at the end of discharge. By contrast, the ohmic heat on the cathodes remains
basically stable due to the different mechanism of heat generation. The great increase in heat
generation rate of the cell with lowest initial salt concentration at the end of discharge is mainly
owing to the irreversible and reversible heat which are associated with the reaction current density.

58

Figure 7. Comparison of a) irreversible heat, b) reversible heat and c) ohmic heat in three cells with
different initial salt concentration at two selected time points (100 s and 200 s):.
As a consequence of the difference in the heat generation rates, the temperature elevation in
each cell also yields different patterns. From the temperature response curves shown in Fig. 8, it
can be seen that the cells with the lowest and medium initial salt concentrations have nearly
identical temperature response attributed to the similar heat generation rate, except the fact that the
temperature curve of the cell with the lower initial salt concentration stops at around 210 s due to
the early stop of the discharge, and the high heat generation rate at the end of discharge cannot be
immediately reflected by the temperature curve because of the long response time. As for the cell
with the highest initial salt concentration, a similar trend with its heat generation curve is followed,

59

and its temperature is higher than the other two cells during the entire course of discharge.

Figure 8. Temperature curves of the cells with different initial salt concentrations during discharge.
CONCLUSION
This paper presents a study on the influence of the initial electrolyte salt concentration on the
electrochemical and thermal behavior of Li-ion battery. Based on a well-designed coupling model
and a primarily identified correlation between electrolyte concentration and electrolyte conductivity,
several interesting results are obtained and used for the battery analysis:
1. At the end of discharge, the electrolyte salt concentration of the cell with lowest initial
concentration drops down to 0 at cathode and thus leading to a premature stop of the discharge.
2. The difference in electrochemical variables results in different thermal responses inside the cells.
The cell with the lowest electrolyte concentration has the lowest heat generation rate except at the
end of discharge, while the highest concentration cell generates more heat than the others
throughout the discharge period.
3. The irreversible and reversible heat contribute most to the high heat generation rate at the end of
discharge for the cell with the lowest initial salt concentration, while the ohmic heat mainly
determines the high heat generation rate of the cells with 1500 and 2000 mol/m3 initial salt
concentrations in major period of the discharge.
4. In terms of the individual electrodes, as the electrolyte concentration increases, more heat is
generated at the anode, while less heat is generated at the cathode.
ACKNOWLEDGMENT
This project is financially supported by Natural Sciences and Engineering Research Council
(NSERC) of Canada.
NOMENCLATURE
A
Ac
ce
cp
F
h
jLi
li
qi
R
T
t 0+
T
U
x
Greek Letters

Area, m2
Convection surface area, m2
Electrolyte salt concentration, mol/m3
Specific heat capacity, J/kgK
Faradays constant, 96487 C/mol
Convective heat transfer coefficient for the cell and the surrounding, W/m2K
Reaction current resulting in production or consumption of a species, A/m3
Thickness of species i, m
Heat generation rates of different heat sources, W
Universal gas constant, 8.314 J/molK
Time, s
Transference number of lithium ion with respect to the velocity of the solvent
Temperature, K
Open circuit voltage of an electrode reaction, V
Coordinate along the cell width, m
Over-potential, V

60

i
k

Subscripts
amb
e
irrev
n
o
p
rev
s
Superscripts
eff
Li

Potential of phase i
Conductivity of electrolyte, S/m
Density, kg/m3
Conductivity of active materials in the electrodes, S/m
Ambient
Electrolyte
Irreversible heat
Negative electrode
Ohmic heat
Positive electrode
Reversible heat
Solid particle phase/separator
Effective
Lithium species

REFERENCES
Bandhauer T.M., Garimella S., Fuller T.F. (2011). A Critical Review of Thermal Issues in Lithium-ion
Batteries. Journal of The Electrochemical Society, 158, R1-R25.
Doyle M., Fuller T.F., Newman J. (1993). Modeling of Galvanostatic Charge and Discharge of the
Lithium/Polymer/Insertion Cell. Journal of The Electrochemical Society, 140, 1526-1533.
Fan L., Khodadadi J.M., Pesaran A.A (2013). A Parametric Study on Thermal Management of an
Air-cooled Lithium-ion Battery Module for Plug-in Hybrid Electric Vehicles. Journal of Power
Sources, 238, 301-312.
Lu C.H., Lin S.W., (2001). Influence of the particle size on the electrochemical properties of lithium
manganese oxide. Journal of Power Sources, 97-98, 458-460.
Li H., Zhou H. (2012). Enhancing the performances of Li-ion batteries by carbon-coating: present
and future. Chemical Communications, 48, 1201-1217.
Ramadass P., Haran B., White R., Popov B.N. (2002). Capacity Fade of Sony 18650 Cells Cycled
at Elevated Temperatures: Part I. Cycling Performance. Journal of Power Sources, 112,
606-613.
Savoye F., Venet P., Millet M., Groot. J. (2012). Impact of Periodic Current Pulses on Li-ion Battery
Performance. IEEE Transactions on Industrial Electronics, 59, 3481-3488.
Smith K., Wang C.Y. (2006). Power and Thermal Characterization of a Lithium-ion Battery Pack for
Hybrid-Electric Vehicles. Journal of Power Sources, 160, 662-673.
Srinivasan V., Wang C.Y. (2003). Analysis of Electrochemical and Thermal Behavior of Li-ion Cells.
Journal of The Electrochemical Society, 150, A98-A106.

61

PARAMETRIC STUDY OF BUILDING-INTEGRATED DUAL-FUNCTION SOLAR

COLLECTOR UNDER WATER HEATING MODE WITH NATURAL CIRCULATION
a,

Chenglong Luo *, Jie Ji , Jihai Xiong , Min Fan , Chongwei Han

Institute of Energy, Jiangxi Academy of Sciences, Nanchang 330029, China
b
Department of Thermal Science and Energy Engineering, University of Science and Technology of
China, Hefei 230027, China
c
China Academy of Space Technology, Beijing 100094, China
* Fax: 86-791-88175782, Email: xxlong@ustc.edu
a

Abstract
The novel building-integrated solar thermal system named as building-integrated dual-function solar
collector is able to provide passive space heating in cold winter and water heating in warm seasons.
In this study, a validated dynamic numerical model was used to make a parametric study on the
novel system for the warm period operation under the water heating mode with natural circulation.
For thermal insulation of backboard and operating water weight were two great important factors of
the novel system, their influence on the water heating performance and the thermal effect on the
building environment were calculated and analyzed. The case results show that for the novel system
at the water heating mode with natural circulation under the climate condition, the operating water
weight within 40-50kg/m2 is appropriate in summer while in autumn the appropriate operating water
weight is higher and around 60kg/m2, and the appropriate thickness of the thermal insulation of
backboard is around 0.05m.
Keywords: building-integrated dual-function solar collector, passive space heating, water heating,
natural circulation, thermal load, summer overheating.
1. Introduction
Globally, buildings are responsible for approximately 40% of the total world annual energy
consumption [1]. Some major consumptions are in lighting, ventilating, space heating/cooling, and
water heating. Parallel to the worsening of energy related stress and environmental degradation
issues in the world, much effort in the building sector has been on promoting solar energy utilization.
To this, the applications of solar thermal technology with passive space heating and water heating
as the two major approaches have been highly successful.
Focusing on reducing energy consumption for space heating in building, much work has been done
to study and use passive space-heating systems, such as the Trombe wall system [2, 3], composite
Trombe-Michel wall [4], PV-Trombe wall to enhance the function of traditional Trombe wall system [5],
and the Barra-Costantini system whose absorber is a thin metal plate [6]. Although these systems
have been well developed, hurdles remain such as the low annual utilization rate in places with hot
and lengthy summer, the difficulty in getting access to the two vents at the outside, and the often
suffering problem of summer overheating [7, 8]. Therefore, a novel building-integrated solar thermal
system which was named as the building-integrated dual-function solar collector (BI-DFSC) and
able to provide passive space heating in cold winter and water heating in warm seasons, was
proposed [9]. In the reference [9], a testing BI-DFSC system mounted on the exterior wall of a testing
hot-box was introduced and two original dynamic numerical models for its both operating modes
were respectively established and validated. Then, the theoretical model for the BI-DFSC system at
the water heating mode with natural circulation of flow was expanded to be adapt to that system
mounted on a practical air-conditioned room and used to study the thermal behavior of the novel
collector system under the water heating mode with natural circulation [10].
The concept of single facade water heating collector has been proposed for decades, but very few
studies were reported in literature. Rockendorf and Janssen [11] made experimental study on a
glazed solar water heater without thermal insulation layer between absorber and wall; the result
showed that more than 75% of the absorbed solar heat could be removed by the circulating water
stream. Further theoretical work was done by Tomas Matuska and Borivoj Sourek [12]; the study
showed that facade collector increased indoor temperature by less than 1oC, and therefore affected
little the indoor comfort condition. Based on the typical meteorological data of Hong Kong, Chow et
al. in a case study found that the annual efficiency of arrays of facade-integrated solar water heating
collectors at tall building could reach 38.4% on average, giving a solar fraction of 53.4% [13].
The present work also focused on the BI-DFSC system under the water heating mode with natural
circulation of flow. Based on the existent expanded theoretical model, numerical simulation was
carried out. Two great important factors, the designed thermal insulation of the novel collectors
backboard and the operating water weight in the water storage tank, were focused, and their
influence on the water heating performance and the thermal effect on the building environment
respectively in summer and warm spring/autumn days was calculated and analyzed.

62

2. Description of the BI-DFSC system

Fig. 1 shows the schematic diagrams of the BI-DFSC system, of which Fig. 1(a) highlights the
passive space heating components and Fig. 1(b) shows the water heating components. Summarily,
this system not only performs passive space heating in cold winter, but also as a faade water
heating collector when space heating is no longer required. The key component of the system is a
modified solar collector named as dual-function solar collector (DFSC) whose detail was presented in
Ref. [9]. In this case study, the only difference of the design parameters of the collector is that the
thickness of thermal insulation of the collectors backboard was variable.

Fig. 1 Schematic diagram of the dual-function solar collector integrated with building: (a) passive space heating (sectional view); (b)
water heating (south view).

3. Mathematic model
The detailed model of a BI-DFSC system at the water heating mode with natural circulation has been
given in our former paper [10], so only the primary equations are given below.
3.1 Water-heating collector model
The heat flow through the front glazing is considered as one-dimensional. In the X-direction (Fig. 1
referred), the heat balance at a finite glass element gives:
gcg

Tg
t

(g g ) Ssolar
x
x

(1)

where g, cg and g are the density, specific heat capacity and thermal conductivity of glass,
respectively; Tg is the glass temperature and Ssolar is the source function resulting from the absorption
of short wave radiation. If qsolar is the solar radiation intensity on the glass surface, dg and g are the
thickness and transmissivity of glass, respectively, then
Ssolar (1 g )qsolar / d g

(2)

At the outside surface of the front glazing, the energy flow is described by
g

Tg

ha,g (Ta Tg )

(3a)

(hp,g hr,p,g )(T m p Tg )

(3b)

x 0

Similarly, at the inside surface,

g

Tg
x

x dg

In the above equations, Ta is the ambient temperature; Tmp is the mean temperature of the absorber
plate; ha,g and hp,g are the convective heat transfer coefficients at the outside and inside surfaces of
glazing respectively; hr,p,g is the average radiative heat transfer coefficient between the glazing and
the absorber plate.
The heat conduction at the absorber plates can be considered as one-dimensional along the Zdirection (vertical). The energy balance at a small element of the aluminum plate can be presented
as:

63

wpd p Acp

Tp
t

wpd p

T
(T Tp )

(p p ) p g qsolar wp hp,g (Tg Tp )wp hp,in (Tin Tp )wp hr,p,g (Tg Tp )wp t
z
z
Rp,t

(4)

where wp is the width of individual aluminum plate; p, cp, dp and p are the density, specific heat
capacity, thickness and thermal conductivity of the aluminum fin, respectively; p is the solar
absorptivity of the absorber plate; Tp and Tt are the instantaneous temperatures of the aluminum
plate and the copper tubing, respectively; Tin is the surface temperature of the insulation backboard;
hp,in is the convective heat transfer coefficient at the back surface of the aluminum plate; and Rp,t,
given by (wp/8pdp), represents the total thermal resistance between the absorber plate and the
copper tubing.
The one-dimensional heat balance equation of a copper tube along the Z-direction is:
Dt d t t ct

(T T )
Tt

T
Dt d t (t t ) Dt ht,in (Tin Tt ) Dt hw,t (Tw Tt ) p t
t
z
z
Rp,t

(5)

where t, ct, dt and t are the density, specific heat capacity, thickness and thermal conductivity of the
copper tube, respectively; Dt is the diameter of the copper tubing; Tw is the temperature of water
flowing in the copper tube; ht,in and hw,t are the convective heat transfer coefficients at the outside and
inside surfaces of the copper tube, respectively.
3.2 Building faade model
3.2.1 Heat transmission through building envelope
The heat transfer across the building wall can be described by the following energy flow equation:
c

T
T
(
)S
t x x

(6)

where S is the source term, which is virtually zero except for windows.
The boundary condition at the exterior wall surface is

T
x

f ( x)

x 0

(7)

x 0

And for the south faade,

T
x

qsolar hc,o (Ta T0 )

x 0

The boundary condition at the interior surface is

T
x

xL

hc,i (Tindoor TL ) q j ,i qsolar,sh,i

j i

(8)

In the above equations, qsolar is the net short wave radiation exchange with the surroundings; Tindoor
is the indoor air temperatures, specially, it is set as constant in the case of air-conditioned room; hc,o
and hc,i are the convective heat transfer coefficients at exterior and interior wall surfaces, respectively;
N is the number of enclosing walls; qj,i is the linearized net long wave radiative gain at room surface i
from surface j; qsolar,sh,i is the distribution of transmitted shortwave radiant energy through the shading
device and onto the room surface i. The terms, qsolar, qj,i and qsolar,sh,i, are all zero for window. For
other wall components, qj,i is given by:
q j ,i hrj ,i Ai (T j Ti )

(9)

where hrj,i is the linearised radiative heat transfer coefficient for surface i from j, Ai is the area of
surface i, Ti and Tj are the temperatures of surfaces i and j, respectively.
The radiative heat transfer coefficient hrj,i can be determined by [14]:
hrj ,i

N
i j fi j (T j2 Ti 2 )(T j Ti )
(1 k ) fi k f j k
i j Aj (T j2 Ti 2 )(T j Ti )
2
[1 (1 i )(1 j ) f i j Ai / Aj ]
k 1 Ak [1 (1 i )(1 j )(1 k ) f i k f k j f j i ]

(10)

where N is the number of walls (not including the window), subscripts i, j, k refers to the relevant
surfaces, A is the surface area, is the surface emissivity, and f with subscript is the view factor
between the relevant surfaces (i.e. fi->k is the view factor from surface i to surface k).
As a simplification, the distributions of solar radiation through shading device to the room surfaces
(except window) were calculated by the diffuse transmission technique. Similar to the method of
determining the long wave radiative exchanges between the room surfaces, the distribution of
shortwave energy among the room surfaces can be estimated by
qsolar,sh,i

N
i fi sh Ai g qsolar (1 sh )
(1 k ) f i k f sh k
i g qsolar (1 sh ) Ash
2
[1 (1 i )(1 sh ) fi sh Ai / Ash ]
k 1 Ak [1 (1 i )(1 sh )(1 k ) f i k f k sh f sh i ]

(11)

where the subscript sh stands for shading device; gqsolar is the incident solar radiation on the shading
device; with subscript stands for the solar absorptivity of the corresponding room surfaces; sh and
sh are the reflectivity and the transmissivity of the shading device.
3.2.2 Coupling between the collector model and the built environment

64

The insulation backboard and its attached building wall are considered as one whole unit in the
coupled simulation model. Thus the outside boundary condition of the composite wall is governed by
the working condition of the solar collector, whereas the indoor boundary is the same as the other
walls expressed by Eq. (8). This is given by:

T
x

hp,in (Tp Tin ) ht,in (Tt Tin )

(12)

x 0

3.3 Convective heat transfer coefficients

3.3.1 Convective heat transfer coefficients at wall
The thermal convection at the outside surfaces of the building is considered as forced convection,
and natural convection is assumed at the inside surfaces. The forced convective heat transfer
coefficient is given by the McAdams empirical equation [15] as follows:

(13)

hc 5.6 3.8V

The natural convective heat transfer coefficient is given by the Khalifa and Marshell expression [16],
i.e.

(14)

hc 2.03T 0.14

where T is the surface-to-air temperature difference.

3.3.2 Convective heat transfer coefficients at the collector
At the water heating mode, the natural convective heat transfer coefficient of the air-gap side
surfaces is given by
Nua

hc

(15)

where Nu and a are the Nusselt number and thermal conductivity of air respectively; and is the
depth of the air gap. The Nusselt number is determined by [17]

(16)
where H is the panel height, Pr is the Prandtl number, and is the kinematic viscosity of air. The
Grashof number is given by
Nu 0.197(Gr Pr )1/ 4 ( / H )1/ 9

Gr

g T 3

(17)

where g and are respectively the gravitational constant and the coefficient of heat expansion of air,
and T is the temperature difference between the two adjacent surfaces.
3.4 Space thermal load computation
Generally, there are many influencing factors on the rooms thermal load, i.e. the room walls, the
ventilation, the occupants etc. To simplify and emphasize the effect of the modified solar collector, the
effect of the occupants is omitted and the only two effects of the room walls and the ventilation in the
typical form of infiltration air flow are considered in this case.
The heat exchange between each room surface and the room air was computed by the finite
difference method. For an air-conditioned space, the thermal load contributed by the room wall i can
be determined with the use of Eq. (8) in that
Li hc,i (TL Tindoor )

(18)

L ( Lw LACR )

(19)
(20)

and the total thermal load is then

Lw hc,i (TL Tindoor )

LACR

ACR aVroom
(Ta Tindoor )
3600

(21)

where Li is the thermal load contributed by the room surface i, and L is the space thermal load of
the entire room in which the first term Lw represents the thermal load contributed by all the walls
and the second term LACR represents the thermal load contributed from infiltration air flow. The
symbol + carries a positive value for cooling load and a negative value for heating load. ACR is
the building air change rate and means the volume change per hour. a is the density of air. Vroom
is the room volume. Notes that to simplify the model in follow study case it is assumed the ACR is
zero, thus, the tern of the thermal load, LACR, is omitted.
4. Results and discussion
From the concept, it is known that the periods when the BI-DFSC system works in the water heating
mode are summer and warm spring/autumn days. Because the thermal behavior of the novel system
will be different for the much different situation between summer and warm spring/autumn days, the
analysis is hence necessary to be made for summer and warm spring/autumn days respectively.
Therefore, two kinds of measured weather data of city of Hefei in China were used in the simulation
runs. The one was about the typical summer day, and the other one was on the typical warm autumn

65

day. Moreover, numerical evaluations of the system thermal performance with and without the
modified design were performed with practical room design conditions. The more details of the room
conditions, the weather data and the process of numerical simulation were described in Ref. [10].
4.1 Performance for water heating
The water heating performance was shown by the maximum temperature of the water in the water
storage tank during the day, and the results for the summer day operation cases and the autumn day
operation cases are respectively shown in Figs. 2 and 3, in which a range of the operating water
weight from 40kg/m2 to 70kg/m2 and the thickness of the thermal insulation of the backboard from
0cm to 11cm were chosen for displaying, as well as in the following figures.

Fig. 2 Maximum water temperature as a function of operating water weight per the area of the collector at different thickness of
thermal insulation of backboard during a typical summer day.

Fig. 3 Maximum water temperature as a function of operating water weight per the area of the collector at different thickness of
thermal insulation of backboard during a typical autumn day.

It can be seen that the two influence factors performed similar feature either in the summer or in the
autumn. Thus, it can take the situation in the summer for analysis. As observed from Fig. 2, the
maximum water temperature dropped with the increase of the operating water weight but increased
with the increasing of the thickness of the thermal insulation of the backboard. The effect of the
operating water weight was found to be much visible in all cases, but that of the thermal insulation of
the backboard was visible only when the thickness of the thermal insulation of the backboard was
less than 5cm. Take the operating water weight in 50kg/m2 for an example, the maximum water
temperature increased from 42.9 to 49.9 with the thickness of the thermal insulation of the

66

backboard increased from 0m to 0.05m, but it only increased to 50.8 when the backboard had a
11cm thick thermal insulation. The result indicates that the maximum water temperature was mainly
influenced by the operating water weight when the thickness of the thermal insulation of the
backboard reached to 5cm. Therefore, it suggests that for maximizing the water heating performance
of the BI-DFSC system at the water heating mode with natural circulation of flow, the optimal
thickness of the thermal insulation of the backboard was around 5cm with taking into account that the
thicker of the thermal insulation of the backboard means the bigger of the frame of the collector and
the higher first cost.
During the warm spring/autumn periods, the BI-DFSC system will heat up the make-up water to a
higher temperature level since the solar heat gain at the south faade is increased [10]. Referring to
Figs. 2-3, when the thickness of the thermal insulation of the backboard was 5cm, the maximum
water temperatures were 47.3, 43.7, 41.1 and 39.2 on the summer day, and during the
autumn day they were 56.7 , 49.9 , 45.2 and 41.7 , respectively corresponding to the
operating water weight in 40 kg/m2, 50 kg/m2, 60 kg/m2 and 70 kg/m2. It is recommended that the
water temperature for domestic solar water heaters should be heated to reach to 45 in compliance
with the PRC (People Republic of China) test methods on domestic solar water heating systems,
thus, in order to meet the temperature requirements, the operating water weight within 40-50kg/m2
was appropriate on the summer day while on the autumn day the appropriate operating water weight
was higher and around 60kg/m2.
4.2 Thermal effect on building
The thermal effect on building is shown by comparing with the daily cooling/heating loads of the airconditioned rooms with and without the novel collector. Fig. 4 shows the result for the summer
operation cases. Figs. 5 and 6 give the results for the autumn operation cases respectively from the
effect on the daily cooling load and the daily heating load. In the figures, the horizontal lines are the
baselines and indicate the cooling/heating load of the room without the collector.
It can be observed from Fig. 4 that on the summer day, the daily cooling load of the room with the
collector dropped with the increase of the operating water weight and the thickness of the thermal
insulation of the backboard, but the influences of the two factors show different feature. As given in
the figure, the daily cooling load was affected by the thickness of the thermal insulation of the
backboard significantly, but influenced by the operating water weight little. When there was no
thermal insulation structure, the building cooling load had 35-41% increase by 8185.9kJ which was
the value of the daily cooling load of the case without collector, and when the thermal insulation
thickness increased, the building cooling load reduced rapidly at first and then gradually tended
towards stability. While the thickness reached to 5cm, the cooling load of the room with collector
decreased to be less than that of the room without the collector, and the value of the reduction was in
range of 1%-3% of 8185.9kJ. Then the cooling load reduced by 7%-8% of 8185.9kJ corresponding to
the thermal insulation in thickness of 11cm. Significantly, in all the summer cases the most change of
the daily cooling loads was only about 6% of the daily cooling load of the room without the collector
when the operating water weight changed from 40kg/m2 to 70kg/m2.

Fig. 4 Effect of thermal insulation of backboard on daily cooling load of the room with the collector at different operating water
weight comparing with cooling load of the room without the collector, during a typical summer day.

67

As shown in Figs. 5 and 6, the variation lines of the daily cooling/heating load of the room with the
collector in the autumn operation cases have similar trend with that in the summer operation cases,
but because on the autumn day, the building room had both heating and cooling demands [10], there
were also some different features in the autumn operation cases. For the autumn cases, the increase
of the operating water weight and the thickness of the insulation of the backboard both reduced the
daily cooling load of the room with the novel collector, but increased the daily heating load. Moreover,
from the comparison of the space thermal loads with and without the collector, the result shows that
on the autumn day, both the daily cooling loads and the daily heating loads of the case with the
collector had absolute difference between that of the case without the collector. Corresponding to the
thermal insulation in thickness of 11cm, the cooling load increased by 37%-40% (from 3584.8kJ to
4900.0kJ-5009.4kJ) and the heating load reduced by 55%-59% (from 706.3kJ to 319.2kJ-287.5kJ).
With the results of the summer cases taken into consideration, it is found that in summer the thermal
effect of the collector on the room can be avoid by the design of the thermal insulation of the
backboard, but in autumn, the influence can not be removed by it, only be reduced.

Fig. 5 Effect of thermal insulation of backboard on daily cooling load of the room with the collector at different operating water
weight comparing with cooling load of the room without the collector, during a typical day in autumn.

Fig. 6 Effect of thermal insulation of backboard on daily heating load of the room with the collector at different operating water
weight comparing with cooling load of the room without the collector, during a typical autumn day.

5. Conclusion
The BI-DFSC system can works for passive space heating in cold winter season but for water
heating and as a faade water heating collector in warm seasons. Based on an existent theoretical
model, numerical simulation was carried out to show the influence of the thermal insulation of the

68

backboard and the operating water weight on the thermal performance of the BI-DFSC system under
water heating mode with natural circulation. The results are given as follow:
(1) The maximum water temperature drops with the increase of the operating water weight but
increased with the increasing of the thermal insulation of the backboard. The effect of the operating
water weight on the water heating performance is much visible, but that of the thermal insulation of
the backboard was visible only when the thickness of the thermal insulation of the backboard is less
than 5cm.
(2) In order to meet the temperature requirements, the appropriate operating water weight within 4050kg/m2 is appropriate on typical summer days while on warm autumn days the appropriate
operating water volume is higher and around 60kg/m2.
(3) For the two influence factors on the thermal effect on building, the thermal insulation of the
backboard is the dominant factor, while the influence of the operating water weight is slight and
neglectable; the cooling load reduces with the increase of the thickness of the thermal insulation of
the backboard either in summer or autumn, but space heating load increases in autumn.
(4) By comparing with the thermal loads of rooms with and without the collector, it can be seen that
the thermal effect is evitable in summer, but in autumn it is not inevitable because the cooling load of
the room with the collector has an evidently positive difference, and the heating load must reduce.
(5) Overall, the appropriate thickness of the thermal insulation of backboard is around 5cm for
minimizing the size of the collector framework, the first cost and the thermal effect on the building and
maximizing the water heating performance.
Acknowledgements
The study was sponsored by the National Science Foundation of China (NSFC), Project Number:
51366004, and the Jiangxi Provincial Key Technology R&D Program, China, Project Number:
2011BBE50031.
References
[1] Abdeen, M. O. (2008). Energy, environment and sustainable development. Renewable and
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Development of a Solar Chimney with Built-in Latent Heat Storage Material for Natural
Ventilation. International Journal of Green Energy 4(3):313-324.
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laminar natural convective motion in a trombe-wall channel. Energy 19(2):259-268.
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simulation model. Building and Environment 37(1):109-121.
[5] Jiang, B., Ji J., Yi H. (2008). The influence of PV coverage ratio on thermal and electrical
performance of photovoltaic-Trombe wall. Renewable Energy 33(11):2491-2498.
[6] Luca, B., Roberto, D., Marco, S. (1998). Energy analysis of a passive solar system. Revue
Gnrale de Thermique 37:411-6.
[7] Gan, G. (1998). A parametric study of Trombe walls for passive cooling of buildings. Energy
and Buildings 27:37-43.
[8] Yakubu, G. S. (1996). The Reality of Living in Passive Solar Homes: A User-Experience
Study. Renewable Energy 8(1-4):177-181.
[9] Ji, J., Luo, C.-L., Chow, T.-T., Sun, W., He, W. (2011). Modeling and validation of a buildingintegrated dual-function solar collector. Proceedings of the Institution of Mechanical
Engineers, Part A: Journal of Power and Energy 225:259-269.
[10] Ji, J., Luo, C.-L., Chow, T.-T., Sun, W., He, W. (2011). Thermal characteristics of a buildingintegrated dual-function solar collector in water heating mode with natural circulation. Energy
36(1):566-574.
[11] Rockendorf, G., Janssen, S., Felten, H. (1996). Transparently insulated hybrid wall. Solar
Energy 58:33-38.
[12] Tomas, M., Borivoj, S. (2006). Facade solar collectors, Solar Energy 80:1443-1452.
[13] Chow, T.-T., Fong, K.-F., Chan, A.-L.-S., et al. (2006). Potential application of centralized
solar water heating system for high-rise residential building in Hong Kong. Applied Energy
83:42-54.
[14] Clarke, JA. (2001). Energy simulation in building design (2nd edition). ButterworthHeinemann, p. 254.
[15] McAdams, W. H. (1954). Heat Transmission (3rd edition). New York: McGraw-Hill, p. 249.
[16] Khalifa, A. J. N., Marshall, R. H. (1990). Validation of Heat transfer coefficients on interior
building surfaces using a real-sized indoor test cell. Heat mass transfer 33:2219-2236.
[17] Yang, S.-M., Tao, W.-Q. (1998). Heat transfer (In Chinese, 3rd edition). Beijing: Higher
Education Press, China, p. 186-187.

69

PERFORMANCE OF A SHELL-ENCAPSULATED EVACUATED-TUBE SOLAR

COLLECTOR INCORPORATED WITH A COMPOUND CURVED SURFACE
CONCENTRATOR
a,b

a
b

a,c

Hongfei Zheng , Jing Dai , Zehui Chang , Yuehong Su , Huifang Kang , Yanyan Ma

School of Mechanical Engineering, Beijing Institute of Technology, Beijing 100081, China

Institute of Sustainable Energy Technology, Department of Architecture and Built Environment,

University of Nottingham, Nottingham NG7 2RD, UK

c

College of Energy and Power Engineering, Inner Mongolia University of Technology, Hohhot, 010051,

China

Corresponding author: E-mail address: hongfeizh@bit.edu.cn; Tel.: +86 10 6891 2510; Fax: +86 10

6841 2865.

ABSTRACT
This paper presents design and testing of a shell-encapsulated solar collector for wall-amounting
installation. The designed solar collector is based on the combination of a novel compound curved
surface concentrator and an aluminum concentric solar receiver, which is contained in a glass
evacuated-tube. As there is no joint between the double-skin glass evacuated-tube and the
aluminum concentric solar receiver, the difficulty of vacuum keeping for a glass-metal joint is
avoided. The cavity shell provides an additional thermal insulation to reduce heat loss of the
designed solar collector. The working principle of the compound curved surface concentrator is
described. The ray-tracing results are given to show the effect of deviation angle of the concentrator
on its optical efficiency, hence determine its maximum acceptance angle. A prototype of the
designed solar collector has been constructed and tested under the sunny winter weather condition.
The experimental results indicate that the hot water temperature higher than 80 C with a daily
average efficiency of about 45~50% has been achieved at the average ambient temperature below
0 C, so the designed solar collector can produce hot water at a useful temperature in winter.
Keywords: compound curved surface, concentrator, solar collector, shell-encapsulated
1 INTRODUCTION
Generically, there are two types of solar collectors being used widely, i.e., conventional flat
plate collectors and recently-developed glass evacuated-tube collectors. They have their individual
advantage and disadvantage. The flat plate solar collectors have the advantage of bearing
mechanical stress, no immediate leaking once partly damaged and easier architectural integration,
while their disadvantage is low operating temperature in winter and subject to the problem of
freezing damage. Reversely, the glass evacuated-tube collectors can maintain a sufficiently high
operating temperature at the ambient temperature below the freezing point in winter, for example, at
the outdoor temperature higher than 10 C, the collection temperature can exceed 45 C. However,
they have the disadvantage of easily being damaged under mechanical stress especially for the
large scale system. The evacuated-tube solar collectors have significantly higher efficiency than the
flat plate collectors at higher collection temperature or lower ambient temperature owing to vacuum
thermal insulation. Zambolin and Del Col [1] have experimentally compared these two types of solar
collectors and found that the evacuated-tube collector could maintain an efficiency of above 50% at
the average hot water temperature of about 60 C, ambient temperature of 20 and solar
irradiance of 700W/m2. Solar concentrators could be used to enhance the thermal performance of
the evacuated-tube collectors for higher operating temperature application or the situation of low
solar irradiation. The concentration-type solar collector designed by Keith et al [2] has an optical
efficiency of 65% and a thermal efficiency of better than 50% at fluid temperatures of 200 C without
tracking the sun. In comparison, Rabl et al [3] had studied combination of non-evacuated solar
collectors with compound parabolic concentrators (CPC). Li and Wang [4] have investigated a
combined trough parabolic concentrator and evacuated-tube solar collector system and measured
an efficiency of about 70 % at the outlet water temperature of 105 C. Adsten et al [5] have proposed
a so-called MaReCo design of solar concentrators for stationary installation. Mills [6] and Norton [7]
gave many researches to Symmetric and asymmetric linear compound parabolic concentrators
which it is very useful for us to design some novel concentrators.
On the other hand, in some situation the collector need be mounted on the wall. For example,
in very high building the users hope to fix their solar collector on the south wall if it is available. Ji [8]
described a wall-mounted hybrid photovoltaic/water-heating collector. The evacuated-tube solar
1

70

collectors are particularly suitable for wall-mounting installation in the area of high latitude
[9]
.However, the vacuum tube collector is cram with water which adds its heat mass so that it gives
very low temperature hot water in winter. In order to get higher temperature thermal energy, Adsten
[5]
introduced several CPC-collector designs for stand- alone, roof- or wall installation and gave
some evaluation to them. Blanco [10] and Mills [11] also researched the characteristics of asymmetric
CPC solar collectors with tubular receiver and indicated that they can be used in some special
occasion.
In addition, the receiver used in the compound parabolic concentrator is very important. Mills [11]
discussed the problems about evacuated tube solar receivers mounted in special concentrator.
Tripanagnostopoulos [12] also discussed the problem about CPC solar collectors coupling with flat
bifacial absorbers. All of the previous work is to pursuit the higher working temperature of the
collector or let the collectors be able to operate in winter.
This study will present design and testing of a new-type solar collector based on incorporation
of a novel compound curved surface concentrator with an aluminum concentric solar receiver
enclosed in a glass evacuated-tube. The designed solar collector would be suitable for
wall-mounting installation in the area of high latitude.
2 DESIGN OF THE SYSTEM
The use of a novel compound curved surface solar concentrator is a key element in the design
of a new-type solar collector hot water system for wall-mounting installation. Combined with the
glass evacuated-tube solar receiver, the solar collector system would be able to provide hot water
at the temperature of above 70 C in the winter. The detailed innovative design is described as
follows:
2.1 DESIGN OF THE COMPOUND CURVED SURFACE CONCENTRATOR
The key component of the proposed new-type solar collector system is a novel trough-type
compound curved surface concentrator, the cross-section of which is shown in Figure 1.
2dA

y
B'

2dA

2dB

2dB
B

4
d
2

D
E

C
F1
F2

Fig.1 A cross-sectional view of the

surface concentrator
Fig.1 A cross-sectional compound
view of curved
the Compound
curved surface concentrator

The compound concentrator consists of two upper parabolic mirrors formed from a paraboloid
1, two plane mirrors 2 and a parabolic mirror 3 at the base. The heights of the two upper
parabolic mirrors are not equal to give a tilted aperture, the angle of which is associated with
geographic latitude. The central line of a tubular receiver 4 overlaps with the focus line of the
paraboloid 1 while it may slightly above the focus line of the paraboloid 3. The incoming rays
within a certain angle to the symmetrical axis of the concentrator are mainly reflected by the upper
parabolic mirrors to the receiver 4 and the rest are reflected by the plane mirrors and the base
parabolic mirror, which may re-reflect the reflected rays from the mirrors 1 to the receiver 4.
2.1.1 Design considerations
On the cross-section of the concentrator as shown in Figure 1, AD and BC are the left and
right sections of the parabolic curve 1 with its focus on the point F1, which may be described by:
2 p1 ( y l ) x 2 , (for upward opening, P1>0)
(1)
where, P1 is the focal parameter, and l is the vertical distance from the vertex of the parabolic curve
1 to the x axis.
The parabolic curve is truncated with a straight line AB, which therefore forms the aperture of
the parabolic curve. The tilt angle of the line AB may be the same as local geographic latitude.
The straight line DE and CG are vertical to with the x axis and symmetrical about the y axis. The
distance between DE and CG and their reasonable lengths are chosen in accordance with the
diameter of the tubular receiver and also in order to maximize the acceptance angle. EOG is a
section of the parabolic curve 3 with its focus at the point F2 and its vertex on the x axis. The EOG
may be described by:

2 p2 y x 2 , (for upward opening, P2>0)

(2)
2

71

where, p2is the focal parameter. Therefore, the cross-section of the compound curved surface
comprises of the parabolic curved segments AD and BC, straight line segments DE and CG, and
parabolic curved segment EOG.
2.1.2 Geometric concentration ratio and maximum acceptance angle
As shown in Figure 1, the two angles 2 d A and 2 d B are formed between the tangent lines
from the points A (xA, yA) and B (xB, yB) to the cross-section circle of the receiver 4. They may be
given by:

sin d A

d /2
2

( xF1 xA ) ( yF1 y A )

d /2

( xA / 2 p1 ) 2 p1

(3)

sin d B

d /2
2

( xB xF1 ) ( yB yF1 )

d /2
( xB / 2 p1 ) 2 p12

(4)
As xA2 xB2 , there is d A d B . It is obvious that the angle d A or d B represents the maximum
allowable deviation angle of the concentrators symmetrical axis from the incoming rays in order to
reflect the rays from point A or B to the tubular receiver 4. Because the incoming rays from the left
may hardly strike on the mirror AD, so d A may be considered as the lower acceptance angle of
the concentrator. All the incoming rays from the right at the deviation angle no larger than d A can
be directly reflected to the receiver by the parabolic mirror AD. Similarly, d B may be considered as
the upper acceptance angle of the concentrator. In fact, each point on the parabolic mirrors AD and
BC has its individual maximum allowable deviation angle. According to Equations (4) and (5), the
individual maximum allowable deviation angle obviously increases when the point is moving down.
Therefore, when the deviation angle is larger than d A or d B , part of the incoming rays can still be
reflected directly to the receiver by the lower part of the parabolic mirrors AD and BC and the rest
may reach the receiver through the second reflection by the plane mirror 2 and base parabolic
mirror 3. For this reason, the maximum acceptance angle d max could be much larger than d A
and d B . A little more detail about d max will be discussed in the following section. If the tilt angle of
the compound curved surface concentrator is adjusted to follow the sun, the angle d A ( d B ) could
be used to determine the time interval for adjusting the tilt angle. In other words, this angle can also
represent the maximum allowable tracking deviation.
The geometrical concentration ratio of the compound curved surface concentrator may be
defined as:

AB
d

(5)
where, AB is the width of the aperture AB and d is the diameter of the tubular receiver. If using the
width of the aperture AB and the diameter of the tubular receiver to define the geometrical
concentration ratio, then C is, C

AB
d

Eq. (1) ~ (5) may be used to determine the acceptance angle and geometrical concentration
ratio of the concentrator for a given geometry. For example, assuming that the concentrator had the
following geometrical parameters: d=50mm, l=12mm, p1=44, p2=50, xB=108mm and 26.5 ,
there is that d A =6. The maximum receiving angle max is 18, and the geometric concentrating
ratio C=1.84 (for the perimeter of the tubular receiver) or C=5.8 (for the diameter of the tubular
receiver).
2.1.3 Tracking accuracy requirement
Ideally, if the trough concentrator could track the sun accurately, all incoming sunlight would be
reflected by the trough surface to the focus, reaching the receiver. However, if there is a tracking
error, that is, the symmetrical axis of the trough being deviated from the sunlight as shown in Figure
2. For any receiver being used, there is a maximum allowable deviation angle which may depend
on the position on the trough surface. This angle actually represents tracking accuracy requirement
for a certain point. As seen from Figure 2, the maximum deviation angle d changes with the
3

72

position of point on the trough surface.

Fig.2 illustrated diagram of tracking error

For the design parameters described in the previous section, the variation of d with the
position of point was computed and shown in Figure 3. It is clear that the tracking accuracy
requirement for different point is different. For example, d 9.3 for x 108mm and d 5.3
for x 143.7mm . It can be found that the tracking accuracy requirement will be higher when a
reflection point is more distant from the focus point. The minimum value of these calculated
maximum allowable deviation angle may be considered as the tracking accuracy requirement of the
whole trough if all incoming sunlight is expected to reach the receiver.

Tracking accuracy requirement/

32
28
24
20
16
12
8
4
40

60

80

100

120

140

160

Distance from original point/ mm

Fig.3 Variation of tracking accuracy requirement with the distance

2.1.4 Ray-tracing analysis

The compound curved surface concentrator with the above assumed geometrical parameters
was modeled in the 3D design software Pro/ENGINEER, and the physical model was saved as
IGES format, and then was imported into the optical simulation software LightTools for ray-tracing
analysis. The incident rays were assumed to be parallel and the number of rays was set at 100.
Ray-tracing simulation was performed for various deviation angles. Figure 4 shows the ray-tracing
results for the clockwise deviation angles of 10, 12and 17and the anticlockwise deviation angles
of 6, 7and 15.
It is apparent that the deviation angle affected how many of the incoming rays can reach the
receiver. In order to compare this effect between different deviation angles, it would be convenient
to define an ideal optical efficiency which is the ratio of the number of rays reaching the receiver to
the total number of incoming rays. According to the results of ray-tracing analysis, the relationship
between the ideal optical efficiency and deviation angle can be obtained and is shown in Figure 5. It
can be seen that when the deviation angle of the concentrators symmetrical axis is between 10
clockwise and 6 anticlockwise, all incoming rays can reach the receiver, so the ideal optical
efficiency is 1.0. When it is 17 clockwise, the ideal optical efficiency is 0.81, and when it is 17
anticlockwise, the

73

Clockwise deviation by 10

Clockwise deviation by 17

Clockwise deviation by 12

Anticlockwise deviation by 6 Anticlockwise deviation by 7 Anticlockwise deviation by 15

Fig.4 Ray-tracking for various deviation angles of the concentrator

ideal optical efficiency is only 0.58. The reason for this difference could be explained as follows: as
discussed in the previous section, the individual maximum allowable deviation angle of each point
on the parabolic mirrors 1 decreases when the point is moving up. As the height of the leftward
parabolic mirror is larger than the rightward parabolic mirror, the average maximum allowable
deviation angle of the leftward parabolic mirror is smaller than the rightward one, hence less
percentage of the incoming rays are reflected to the receiver when the deviation angle is larger than
d A and d B . It can be also expected that the complete curve of the ideal optical efficiency would
look almost symmetrical about the vertical line crossing the clockwise deviation angle of 12, but
actually the rightward section of curve is slightly steeper than the leftward section. The two end
points of the flat section of the curve are corresponding to the upper and lower acceptance angle.
The maximum acceptance angle may be determined by extending the efficiency curve to intercept
with the 0% efficiency line. It is worthwhile to mention that Fig.5 would look somewhat different if a
fixed density of rays instead of a given number is chosen for ray-tracing analysis.

1.00
0.95

Optical Efficiency

0.90
0.85
0.80
0.75
0.70
0.65
0.60
0.55
-20

Clockwise
-15

-10

-5

Anticlockwise
0

10

15

20

Deviation Angle

Fig.5 The relationship between the ideal optical efficiency and deviation angle of the concentrator

2.2 DESIGN OF THE SUN TRACKING SYSTEM

5

74

As discussed above, the designed compound curved surface concentrator has a lower
acceptance angle of 6 and upper acceptance angle of 12, which together gives an overall
acceptance angle of 18. So, sun tracking is necessary in order that the concentrator could collect
the direct solar radiation as much as possible. For the wall-mounting installation, the change in the
solar incidence angle is up to 90, so the daily number of tilt angle adjustment is 5. Either manual
operation or automatic tracking could be used to achieve this adjustment. For the designed solar
collector, it was intended to use a single-axis automatic solar tracking system with the tracking
accuracy of about 2 and the tracking time interval of ten minutes in accordance with the lower
acceptance angle of 6. This tracing system adopts the light-operated excitation mode. A set of
electronic photometric sensors were mounted on the concentrator to detect the deviation angle of
the concentrator from the sun rays. In response to the signal input of this deviation angle, a micro
control panel calculates and output a control signal to drive the servo motor to adjust the
concentrator to be at the minimum deviation angle.
2.3 DESIGN OF THE RECEIVER
The solar receiver is another key component. A double-skin glass evacuated-tube
incorporated with a concentric aluminum pipe was used as the solar receiver. The outer dimension
of the glass evacuated-tube was 58mm 2100mm . The concentric aluminum pipe includes three
layers as shown in Figure 6. The outer aluminum has a diameter of 42mm and a length of 1900mm,
and its surface was coated by an oxidation film to form an effective tubular solar absorption surface.
Compared with the conventional finned U-tube solar absorbers, the concentric absorber has an
annular water channel on the inside of the tubular solar absorption surface, so the thermal
resistance could be minimized. In addition, the double-skin glass evacuated-tube does not have
any junction with the aluminum concentric pipe, hence the possibility of vacuum leakage could also
be minimized.

Glass vaccum tube

medium inlet

14

medium

58mm

outlet

4m

Fig.6 An aluminum concentric pipe receiver comprising of a glass evacuated-tube

2.4 DESIGN OF THE SHELL-ENCAPSULATED SOLAR COLLECTOR

The schematic structure and experimental prototype of the designed solar collector are shown
in Figure 7. The solar collector is comprised of an encapsulation shell 1, a combined manual and
automatic tracking mechanism 2 and 3, several small-size trough-type compound curved surface
concentrators 4, a glass cover 5 and several glass evacuated-tube solar receivers 6. The
working principle of the solar collector is: (1) the solar rays are incident on the compound curved
surface collector 4 through the glass cover 6; (2) the rays are reflected to the surface of the
receiver 5 ; (3) the solar radiation is transformed into heat through absorption by the selective
6

75

coating on the outer aluminum pipe; (4) the heat transfer fluid enters the inner tube of the concentric
aluminum pipe, and then it flows into the annular channel between the middle pipe and outer pipe,
where it absorbs heat and its temperature increases along the channel; (5) the heat transfer fluid
transports heat to the hot water storage tank through the circulation line, and it release heat to
water through the immerged coil heat exchanger to increase the water temperature. Compared with
the common evacuated-tube solar collectors, the designed concentration-type solar collector uses
less number of evacuated tubes for the same solar collection area, so the overall amount of heat
transfer fluid in the tubes could be reduced. This may help reduce the overall thermal inertia and
hence lead to a fast thermal response. Due to the use of solar concentration, the solar collector
may be able to provide a usable water temperature in the cold winter and not subject to the frosting
problem, so it is especially suitable for the high-latitude regions and winter with a smaller solar
elevation angle.
2

1- 2- 3-

5- tracker; 3- draw bar; 4- compound curved surface concentrators;

1-packaging shell;4-
2- manual regulation
6-
3

5-glass cover; 6- glass evacuated-tube collector

Fig.7 The schematic structure and photo of the prototype shell-encapsulated solar collector

The dimension of the prototype wall-mounting solar collector was 2.3m2.0m0.3m. The
inside of the encapsulation shell was attached with a cystosepiment board of about 20mm thick and
a little glass wool as the thermal insulation layer to reduce heat loss. The solar collector included
five trough-type compound curved surface concentrators. The tracking system was behind the
trough concentrators, so it was seen from outside. Each trough concentrator had a width of 260mm
and a length of 1900mm to give an aperture area of 0.494m2. The reflective surface of the
concentrators had a grade 9 hardness and a total reflectance of larger than 92% with the diffuse
reflectance less than 10% and specular reflectance equaling to 88%. The glass cover and
encapsulation shell was jointed to form an enclosed cavity. The glass cover was a 4mm thick
low-iron float flat glass with the light transmittance of 0.88 that exceeds the requirement of GB
11614-2009. Although the glass cover reduces the amount of solar radiation entering the solar
collector, it provides dust-proof for the concentrators and the enclosed cavity could help reduce
heat loss from the evacuated-tube solar receiver.
3 PERFORMANCES TESTING OF THE PROTYPE SOLAR COLLECTOR
3.1 EXPERIMENTAL SYSTEM
As shown in Figure8, the experimental system included a prototype wall-mounting
shell-encapsulated solar collector, a water tank, a circulation pump, a feed container, a heat
exchange coil and a circulation pipe. A 20mm thick thermal insulation layer was applied to the
circulation line and water tank to reduce heat loss. The working principle of the experimental
system is as follows: the incoming solar radiation is concentrated and collected by the solar
collector to heat up the heat transfer fluid inside, then the heated working fluid flows to the water
tank where its heat is released to the water. The cooled working fluid after heat release is circulated
by the pump to the solar collector to be heated again. With the process continuing, the water
temperature in the water tank gradually rises. When it reaches to a certain degree, it is ready to be
used.

76

3
2

4
5

1- 2- 3-

1 - a novel compound curved surface concentrator; 2 - circulating pipe; 3 - water outlet; 4 - water tank;
5-
6-
5- 4-
heat exchange
coil; 6 - water
inlet; 7 -7-
oil tank;8-
8 - pump
Fig.8 Schematic experimental system for testing the prototype shell-encapsulated solar collector

30
25
20
15
10
5
0
-5
-10

80
70
60
o
Temperature / C

950
900
850
800
750
700
23/01/2010
650
25/01/2010
600
550
500
450
400
350
09:00 10:00 11:00 12:00 13:00 14:00 15:00 16:00

Ambient Temperature /

Solar irradiation / W/m2

2.
The performance testing was conducted in Beijing (N39o57, E116o19) with the ambient
temperature in the range of -1 ~ -9 oC. The volume of the water tank was 80L with an initial water
temperature at 11.6 oC. In the experiment, the solar irradiance was automatically recorded by a
TRM-2 solar test system (including the TBQ-DI solar radiation table) with the accuracy 5%. The
calibrated k-type thermocouples were used to measure temperatures at various points on the
system. The data were recorded by a TT-12 temperature data logger, which reading interval could
be adjusted.
3.2 EXPERIMENTAL RESULTS AND ANALYSIS
3.2.1 Efficiency testing
In order to validate the designed solar collector for application in winter, two days 23/01/2010
and 25/01/2010 with lower ambient temperature were chosen for the experiment. The prototype
solar collector was placed vertically to simulate the wall-mounting installation. The system was in
automatic tracing model. The ambient and water temperatures and solar irradiance on vertical
plane were recorded every 20min. The recorded data are shown in Figures 9~10.

50

23/01/2010
25/01/2010
average
temperature
of water

40
30
20

internal temperature of shell

10
0
09:00 10:00 11:00 12:00 13:00 14:00 15:00 16:00
Local Time/hh:mm

Local Time/hh:mm

Fig.9 Change of the solar irradiance and

ambient temperature with local time

Fig.10 Change of water temperature

and shell temperature with local time

It can be seen from the solar irradiance values in Figure 9 that two chosen days for testing
were sunny and cloudless, but the ambient temperature was below -1 oC. As shown in Figure 10,
the prototype solar collector had heated the storage water up to nearly 80 oC by 3:00 pm, so it could
fully meet the requirement of domestic hot water in winter in colder areas. The water temperature
almost increased linearly with time at the beginning and exceeded 65 oC at around 2:00pm, and
then the rate of temperature rise began to decrease because the solar radiation started to decrease
in the afternoon while the heat loss of the system continued to increase with the increasing water
temperature. It can also be seen that the enclosed cavity generally had a temperature of above 20
o
C. This would clearly help to reduce heat loss to the ambient compared with the situation of
exposing the evacuated-tube solar receivers to the ambient temperature of below 0 oC in the winter.
The daily average efficiency is a key parameter to characterize a solar collector, and it may be
defined as follows:
MC p (te t s )
d
Ac H
8

77

(6)
where d - the daily average efficiency, M and Cp are the amount and specific heat of water, ts- the
initial average temperature of the water tank (oC), te- the final temperature of the water tank (oC), Hthe daily cumulative solar radiation exposure (MJ/m2) and Ac is the aperture area of the solar
collector , which was 2.47m2.
Substituting the experimental data into Equation (6) gives that the daily average efficiency of
51.3% for the 23rd January and 50.1% for the 25th January, respectively. The small difference in the
efficiencies for these two days may be due to the difference in the average operating temperatures.
The unsteady-state efficiency is a reflection of thermal conversion efficiency changing with
time, and it may be defined as [13]:

MC p (ti 1 ti )

Ac ( H i 1 H i )

(7)
where - the unsteady-state efficiency, M - the water mass in the water tank (Kg),Ac - the aperture
area of the solar collector (m2),Cp - the specific heat of water (KJ/kgC); t - the average water
temperature in the water tank (oC), H - the cumulative solar irradiation (MJ/m2) and the subscripts
i+1 and i stand for the start state and end state of each time interval.
By inserting the experimental data into Equation (7), the unsteady-state efficiency at
different time can be obtained and plotted against the normalized temperature difference
(tm ta ) / I as shown in Figure 11. The unsteady-state efficiency displays an approximate quadratic
relationship with the normalized temperature difference. The least square regression of the data in
Figure 11 gave the following formula:
0.65

Unsteady state efficience/

0.60
0.55
0.50
0.45
0.40
0.35

this work
glass vaccum tube collector
with heat pipe
flat plate collector

0.30
0.25
0.20

0.03

0.06

0.09

0.12

0.15

Normalization temperature difference / (m K)/W

Fig.11 Unsteady-state efficiency curves for three types of solar collectors

2

0.632 0.983Ti* 5.084Ti*

(8)

Figure 11 also shows the unsteady-state efficiency curves for an efficient flat solar collector
and an evacuated-tube heat-pipe solar collector for comparison[15]. It can be seen that when the
water temperature equals to the ambient temperature, i.e, (tm ta ) / I 0 , the y - intercept of the
unsteady-state efficiency curve of the designed solar collector is 0.632, which is higher than other
two solar collectors. This indicates that the heat loss of the designed solar collector might be
considerably reduced due to the use of the solar concentrator and cavity shell. The unsteady-state
efficiency curves of three solar thermal collectors are in a common trend, i.e., with the rise of the
operating temperature their efficiencies decrease at different slopes, among which the efficiency
curve of flat solar collector has the steepest slope. The slope of the efficiency curve of the designed
solar collector is similar to that of the common evacuated-tube heat-pipe solar collector, but slightly
lower at higher temperature. This is mainly because the thermal insulation of the designed solar
collector is not as good as that of the common evacuated-tube solar collector, thus a considerable
amount of heat is lost at the water tank and circulation pipe.
The system was also tested in the non-tracking mode for comparison, in which the trough was
fixed during a day test. But the tilt angle (between the symmetrical axis of the trough and the ground)
was adjusted between different days. For example, the angle was 50on 06/11/2009 and 40on
23/11/2009, respectively. Other conditions were same as that of automatic tracing mode.
The experimental results on two typical shiny days are given in Figure 12. Based the data, the

[14]

78

daily efficiency is calculated to be 44.5% and 38%, respectively. This indicates that the tilt angle has
important influence on the efficiency. Compared with the efficiency of about 50% for the tracking
mode, it can be seen that use of sun-tracking is important for obtaining a high efficiency.
90
1000

Solar irradiation(W/m2)

70

800

Water temperature( C)

80

900

60

700
600

50

500

40
30

06/11/2009
23/11/2009

400

20

300

09:00 10:00 11:00 12:00 13:00 14:00 15:00 16:00 17:00

Local time(hh:mm)

Fig.12 The change trend of solar irradiance and water temperature with local time

50

800

45

Water temperature( C)

1000

Solar irradiation(W/m )

3.2.2 Testing of hot water displacement at a controlled temperature

The experiment was also conducted to investigate the thermal performance of the prototype
solar collector with a periodical displacement of hot water at a controlled temperature. The system
was in non-tracking mode. The concentrating trough was fixed with the tilt angle of 50 in the
experiment. Such the testing was made on several shiny days with the setting temperature of 45 oC
at which the cold water was fed into the tank to displace hot water. When the temperature of the
outflow water reached a certain degree (40 oC or 35 oC), the water feed was halted. Figures 13~14
show the recorded values of solar irradiance and water temperature.

600
400
200
0

07/11/2009
21/01/2010
22/01/2010

40
35
30
25

10:00 11:00 12:00 13:00 14:00 15:00 16:00

07/11/2009
21/01/2010
22/01/2010

10:00 11:00 12:00 13:00 14:00 15:00 16:00

2

Solar irradiation(W/m )

Local time(hh:mm)

Fig.13 Change of solar irradiation with local time

Fig.14 Change of water temperature with

local time

According to Equation (6), the daily average thermal efficiency of the prototype solar collector
hot water system on the 22nd January may be calculated as follows:
C p ti mi
i
d
0.52
Ac H
(9)

ti is the change of average water temperature between for the i th displacement and
th
the (i 1) th displacement, mi is the amount of water for the i displacement. It is clear that

Where,

the thermal efficiency of the system with a periodical displacement of hot water is slightly larger
than that with a closed water tank. The reason is that the prototype system in the former situation
operated at a lower temperature, hence less heat loss to the ambient. It also can get the efficiency
on 7th November 2009 and 21st January 2010 to be 45% and 48%. It can be found easily that the
efficiency in the controlled temperature mode is bigger due to its operation temperature to be lower
and heat loss to be reduced.
4 CONCLUSIONS
In order to overcome the drawback of conventional solar collectors in winter, that is its
10

79

unavailability due to low water temperature or even freezing, this paper has presented a new
design of solar collectors based on combination of a novel compound curved surface concentrator
and an aluminum concentric solar receiver contained in a double-skin glass evacuated-tube. A
prototype solar collector has been constructed and encapsulated in a glass-covered shell, the
cavity in which provides an additional thermal insulation. The performance of the prototype has
been tested for a sunny winter weather condition and wall-mounting installation. The experimental
results indicate that when the average ambient temperature was below 0C, the water temperature
can be heated up to 80 C with a daily average efficiency of about 50%. Therefore, the designed
solar collector could produce useful hot water in winter. The designed solar collector has the
following advantages:
(1) The designed solar collector employs a novel compound curved surface concentrator, the
number of evacuated tubes used per unit of solar collection area is reduced and so does the
amount of heat transfer fluid inside the solar collector. Therefore, the thermal response of the
system would be fast. This would be beneficial for application in winter when the period of sunshine
is short and the ambient temperature is low.
(2) A heat transfer fluid, which can operate between 30C and 200C, is used to transport the
collected solar heat to the water tank through a circulation pump and a heat exchange coil. The
heat transfer fluid has a low freezing point and would help to prevent the solar collector from
cracking and explosion due to the potential freezing in winter.
(3) The solar collector uses an aluminum concentric pipe as the solar receiver. The fluid channel is
directly on the inside of the solar absorption surface, so heat transfer would be fast and efficient. In
addition, there is no joint between the evacuated-tube and the aluminum concentric solar receiver,
so this has avoided the difficulty of vacuum keeping for a glass-metal joint.
ACKNOWLEDGEMENT
This work is supported by the National Natural Science Foundation of China (No.51076016,
51006009). The authors would also like to thank the European Commission for a Marie Curie
Fellowship grant (PIIF-GA-2010-275038).
REFERENCE:
[1] E. Zambolin and D. Del Col, 2010, Experimental analysis of thermal performance of flat plate
and evacuated tube solar collectors in stationary standard and daily conditions. Solar Energy 8:
1382-1396.
[2] K.A. Snail, J.J. O'Gallagher, R. Winston, 1984, A stationary evacuated collector with integrated
concentrator. Solar Energy 33: 441-449.
[3] A. Rabl, J. O'Gallagher, R. Winston, 1980, Design and test of non-evacuated solar collectors
with compound parabolic concentrators. Solar Energy, 25: 335-351.
[4] M. Li, L.L. Wang, 2006, Investigation of evacuated tube heated by solar trough concentrating
system, Energy Conversion and Management 47: 3591-3601.
[5] M. Adsten, A. Helgesson, B. Karlsson, 2005, Evaluation of CPC-collector designs for
stand-alone, roof or wall installation. Solar Energy 79: 638-647.
[6] D.R. Mills, J.E. Giutronich, 1978, Asymmetrical non-imaging cylindrical solar concentrators.
Solar Energy 20: 45-55.
[7] B. Norton, P.C. Eames, Y.P. Yadav, 1991, Symmetric and asymmetric linear compound parabolic
concentrators: the state-of-the-art in optical and thermophysical analysis. Int. J. Ambient Energy 12:
171-190.
[8] J. Ji, J. Han, T.T. Chow et al, 2006, Effect of fluid flow and packing factor on energy performance
of a wall-mounted hybrid photovoltaic/water-heating collector system. Energy and Buildings 38:
13801387.
[9] W.M. Shen, 2006, Balcony wall type solar water heaters: promote the combination of solar water
heaters and building energy efficiency, Transactions of the CSAE 22: 194-198.
[10] M. E. Blanco, E. Gomez-Leal, J. M. Gordon, 1986, Asymmetric CPC solar collectors with
tubular receiver: geometric characteristics and optimal configurations. Solar Energy 37: 49-54.
[11] D.R. Mills, A. Monger, G.L. Morrison, 1994, Comparison of fixed asymmetrical and symmetrical
reflectors for evacuated tube solar receivers. Solar Energy 53: 91-104.
[12] Y. Tripanagnostopoulos, P. Yianoulis, S. Papaefthimiou, S. Zafeiratos, 2000, CPC solar
collectors with flat bifacial absorbers.Solar Energy 69: 191-203.
[13] Z.N. He, 1992, Study on unsteady-state efficiency equations for solar water heaters. Journal of
acta energiae solaris sinica 13: 1-7.
[14] J.H. Li, Q. Jang, 2001, Experimental research on a high efficient Flat plate solar collector.
Journal of acta energiae solaris sinica 22: 131-135.
[15] S.Y. Yan, R. Tian, S. Hou et al, 2008, Analysis on unsteady state efficiency of glass evacuated
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solar collector with an inserted heat pipe. Journal of engineering thermophysics 29: 323-326.

12

81

Wind Energy

16
82

THE AEROELASTIC DAMPING ANALYSIS OF FLEXIBLE BLADES OF

HORIZONTAL AXIS WIND TURBINE BASED ON NONLINEAR AEROELASTIC
COUPLING RESPONSE
1

Wenwei Mo *, Deyuan Li *, Lei Xu , Yushen Fang , Guolin He

School of Electromechanical Engineering, Guangdong University of Technology, Guangzhou, China

510006;
2
School of Mechatronics Engineering, University of Electronic Science and Technology of China,
3
Chengdu, China 611731; School of Mechanical & Automative Engineering, South China University of
Technology, Guangzhou, China 510640
Address: Room 613, the NO.2 Engineering Facility Building, Guangdong University of Technology,
Guangzhou Higher Educational Mega Center, China
E-mails: * mowenwei02@gmail.com / * lidey@gdut.edu.cn

ABSTRACT
Aeroelastic damping of large wind turbine blades have a decisive role in the safe and stable operation
of blades. An effective method to analyze aeroelastic damping of flexible blades of large wind turbine
based on nonlinear aeroelastic coupling response was presented, and structural damping and
aerodynamic damping of the blades during operation were analyzed in this paper. First, a nonlinear
aeroelastic mechanics model of the flexible blades containing aerodynamic model and dynamic
response model was established. Then the time-domain nonlinear aeroelastic coupling response of
blades combined with Blade Element Momentum (BEM) theory was numerically simulated. The 5MW
offshore wind turbine blade of the United States Renewable Energy Laboratory (NREL) was chosen
for research subject, and the transfer function of the blade was obtained by analyzing the blade
dynamic response under the action of pulse excitation, and both the structural damping in blade
flapwise vibration and that in edgewise vibration were calculated by the half-power bandwidth
method; Next, the blade aeroelastic damping taking aerodynamic force into account was obtained by
analyzing blade aeroelastic response signals under stable and random wind speeds via FFT, and the
structural damping and aerodynamic damping were distinguished, which thus lay a foundation for
confirming the boundary of blade aeroelastic stability. This work is significant and feasible for guiding
blade structural and aerodynamic shape design, and helpful for the confirmation of blade aeroelastic
stability boundary.
Keywords: wind turbine, aeroelastic coupling, aeroelastic stability, aeroelastic damping,
aerodynamic damping.
1.

INTRODUCTION

Blades of Wind turbine are elastic bodies with long spanwise distance, short chord length and small
stiffness, which vibrate easily. Due to the obvious increase of wind turbine power, the blades are
increasingly becoming larger and tend to vibrate under time-varying wind speed during operation.
This vibration, which is the so-called aeroelastic stability problem, is actually caused by the coupling
effects among aerodynamic forces acted on wind wheel, inertia force and elastic deformation of
blade. Once the aeroelastic instability occurs, the blade will oscillate dramatically or even be
damaged in a short time, which resulting in serious consequences. So the aeroelastic stability
analysis as well as the relevant analysis on aeroelastic damping and aerodynamic damping have
aroused increasing attention during the modern wind turbine blade design process and the whole
wind turbine running safely and stably(Holierhoek et al., 1994; Meng, 2011 ).
The relatively serious nonlinear aeroelastic vibration caused by the flexible blade of wind turbine
embodies in the fact that the feedback from the large elastic deformation of blade to the aerodynamic
load cannot longer be ignored. Since the strong coupling of the two, aeroelastic damping analysis of
blade should be carried out based on the blade aeroelastic coupling response. Currently, scholars
abroad tend to analyze the measured response signals of wind turbine during operation, Thomsen
(Thomsen et al., 2000) sampled the attenuating response signal under certain wind speed for the
purpose of analysis by using the eccentric mass to generate periodical actuating force, and got the
blade aeroelastic damping, but didnot distinguish structural damping from aerodynamic damping.
Hansen (Hansen et al., 2006) adopted modal analysis approach and stochastic subspace
identification method to analyze the response of wind turbine under the random air current turbulence
and calculated the damping. Analysis on the measured signals is, of course, a relatively accurate

83

method to confirm the system damping, however, it is just suitable for analyzing the wind turbine
during operation , rather than for providing guide in blade design phase. Moreover, there are still
difficulties in obtaining characteristics of damping under stable wind speed because of the random
change of natural wind speed and its direction. Wang (Wang et al., 2013) obtained damping ratio of
each order mode by using mode superposition method and calculating eigenvalue and eigenvector
via solving system coefficient matrix, and then judged whether blade fluttered based on the damping
ratio. During the analysis process, the blade response and aerodynamic loads were calculated
respectively without aeroelastic coupling simulation, thus the signals obtained is probably unreliable
for large flexible blade.
In this study, a nonlinear aeroelastic mechanics model of the flexible blade was established, and an
effective method for numerically solving differential equations were studied, and the time-domain
simulation of blade aeroelastic coupling response was realized. In multibody system (MBS) method
(Hong, 1999), real mechanical systems components are discreted into a number of rigid bodies,
then the system can be described with a finite number of differential equations. This method has
already been adopted on the aeroelastic analysis of wind turbine blade (Zhao et al., 2007;
Gebhardt et al., 2012). The aeroelastic coupling mathematical model was built automatically via a
computer simulation programme and this model, dynamic equations, was numerically solved. At
each integral time step, a subprogram was called to calculate the time-varying aerodynamic load
which acted on the momentarily deformed blade, therefore the aeroelastic coupling simulation was
realized. The 5MW offshore horizontal axis wind turbine blade of the United States Renewable
Energy Laboratory (NREL) (Jonkman, et al., 2009) was chosen as research subject, and the transfer
function (or called frequency response function, FRF) (Jin, et al., 2008) of the blade was obtained by
analyzing the blade dynamic response under the action of pulse excitation, and both the frequencies
of blade flapwise vibration and those of edgewise vibration were calculated and their corresponding
structural dampings were obtained by the half-power bandwidth method (Li, et al., 2009); Then the
blade time-domain response of flapwise and edgewise vibrations under stable and random wind
speeds were analyzed. Finally the aeroelastic and aerodynamic dampings of flapwise and edgewise
modes were obtained by analyzing these responses in frequency domain. The work in this study can
be carried out in the blade design phase and can analyze the blade aeroelastic and aerodynamic
dampings under various wind speeds, helpful for confirming blade aeroelastic stability boundary and
for analyzing blade aeroelastic stability of operating wind turbine.
2.

VIBRATION DAMPING OF WIND TURBINE BLADE

During the operation of wind turbine, blades are collectively affected by mechanical load, inertial force
and aerodynamic force, and the nonlinear vibration with large amplitude occurs due to the blade
relatively large deformation. This nonlinear vibration damping, called aeroelastic damping, includes
structural damping and aerodynamic damping because the aerodynamic force couples the blade
elastic deformation mutually.
The structural damping of wind turbine blade is a kind of resistance generated by material internal
structural friction caused by the deformation when the blade is vibrating, and plays an important role
in preventing blade aeroelastic instability such as stall flutter, flagwise and edgewise vibration, etc,
though it is not a high value; The aerodynamic damping is another kind of resistance acting on the
rotating blade, and normally defined as the work done by the aerodynamic force during a vibration
cycle of blade. Aerodynamic damping may be positive or negative, and if aerodynamic damping is
negative and its absolute value is larger than structural damping, the blade aeroelastic instability will
occur. Thus, accurately identifying the aeroelastic damping and distinguishing the structural damping
from aerodynamic damping are significant for the blade design and the wind turbine running safely
and stably.
2.1. Confirmation of blade system vibration damping via half-power bandwidth method
The vibration damping ratio can be identified by half-power bandwidth method (Li, et al., 2009) for a
vibration system. In the case of small damping, when the frequency ratio is w wn 1 2 2 , here
wn is defined as a certain order natural frequency of system, is the damping ratio corresponding to
this order mode, and the value of amplification factor reaches its maximum H ( w) max which is
defined as system quality factor Q , as:

84

Q H ( w) max 1 (2 1 2 )
(1)
When 1 ,which is low damping, the formula above approximates as :

Q 1 (2 )
(2)
Half-power point is: value of w satisfying the equation |H( w )|2= Q 2 2 is defined as system halfpower point, a frequency when the response amplitude is 0.707 times of amplitude. In the case of
small damping, there are two half-power points, noted as w 1 and w 2. In addition, the difference
w = w 1 w 2 is called the system bandwidth which defines the range of resonance region.
Assume that 1 and ignore the item 2 , as

(w wn )2 1 2
(3)
namely

w1 wn 1 2 (1 )wn
(4)

w2 wn 1 2 (1 )wn
(5)
The bandwidth w w2 w1 2 wn , namely,

wn w 1 (2 ) Q
(6)
System quality factor Q equals the ratio between system natural frequency and bandwidth, so, the
value of Q and damping ratio can be confirmed according to the equation above once the
system bandwidth is calculated.
2.2. Nonlinear dynamic equation of flexible blade aeroelastic coupling
Multibody dynamic model is set up by using the R-W method of computational multibody system
dynamics (Hong, 1999). In order to accurately approximate the flexible behavior of blade in
aeroelastic coupling analysis and obtain a reasonable result which is coincide with actual one with as
less degrees of freedom (DOFs) as possible, Super-Elements (SEs) (Zhao et al., 2007) are
introduced into the multi-body system model to set up the dynamic modeling of flexible blade. As
shown in figure 1, a SE consists of 4 rigid bodies. To reflect the bending and torsional deflections of
a SE, body B1 and B2, body B3 and B4 are connected by cardanic joints respectively, while body B2
and B3 are connected by revolution joint. Springs and dampers are used to elastically constrain the
motion of two connected rigid bodies. Therefore, each SE has five DOFs, including four rotational
DOFs and one torsional DOF. The pure planar bending of the SE is represented by the generalized
coordinates of the two cardanic joints, which are 1 , 2 , 4 and 5 while the pure torsional motion
of the SE is represented by the generalized coordinate 3 of the revolution joint.

85

Fig.1. Super-Element model

The 61.5 m flexible blade of 5MW offshore horizontal axis wind turbine blade of NREL is chosen as
research subject, and it is discretized into four SEs to set up its topological configuration. Since the
last rigid body in a SE is rigidly connected to the first rigid body of the next adjacent SE, these two
rigid bodies can be merged into one rigid body (the merged bodies are shown in Fig. 2 as B4, B7
and B10). Consequently, a blade is divided into 13 rigid bodies with total 21 DOFs. The blade root
(body B1). An inertial coordinate system XYZ is set at the ground and blade coordinate system
XYZ , which is used for the reference frame for the blade flapwise and edgewise vibrations, is set
at the blade root. The distance of OO' equals the length between the center of mass (CM) of hub
and blade root to simulate the blade rotation around shaft of wind wheel. The discrete blade is
shown in Fig. 2.

Fig. 2. Regular mark number of each rigid body, inertial coordinate

system XYZ and blade coordinate system XYZ.
Fig.3. Generalized coordinates and force element springs.

According to the regular labeling method of R-W method, each rigid body and joint are assigned
unique numbers respectively, for instance, each body is marked as Bi (i =1~13), while its inscribed
joint is labeled as Hi (i=1~13). Joint point of H1 is set at the inertial coordinate systems origin, and
those of the rest inscribed joints Hi are set at the location of 1/4 length of blade chord (showed in
Fig. 3). B1 represents the rigid body fixed at the hub and its motion is constrained, whereas for
anyone of the rest of bodies, Bi, the relative motion of its inscribed joint Hi can be represented by
the related relationship between a coordinate system fixed at body Bi and that fixed at its inscribed
body.
Using the rotational DOFs of each joint as generalized coordinates, the vector of generalized
coordinates describing the topological configuration of the flexible blade MBS is obtained as:

q(t ) ( q1 ,

, q21 )T

(7)

86

The first and second derivatives of q(t) with respect to time are vectors of generalized velocities
and generalized accelerations respectively. As for a system with tree structure consisting of N
bodies (N =13 in this study), assume that the mass of each rigid body is mi and central tensor of
inertia is Ji, while Fi and Mi are the pivot vector of external force and moment with respect to the
mass center respectively, which act on the body. The second order ordinary differential equations
of the blade MBS can be derived from general dynamical equations based on the principle of
virtual displacement, as:
Zq z 0
(8)

Where Z is the generalized mass matrix, z the generalized force vector, whose exact formulations
can be found in a reference (Hong, 1999). Combining with initial conditions, Eq. (8) can be solved
through numerical integration, then the kinematic variables q(t ) q(t ) and q(t ) can be
calculated.
During the rotation, blade is restricted by various geometric constraints or driving constraints, such as
the control on the wind wheel rotational speed or shaft torque, imposed by the control system, which
leads to that the generalized coordinates describing the position and the topological configuration
of blade MBS are non-independent with each other, and if the number of independent constraint
equations of the system is s , as follow

1 ,

, s )T 0

(9)
so the number of independent variables of system generalized coordinates is just n s .
Combining Eq. (8) with Eq. (9), the dynamic equations of blade MBS with Lagrange multiplier
(Hong, 1999; Schiehlen, 1997) can be given as
Zq qT z

(10)
where q is the Jacobi matrix of system constraint equations, a s x n matrix. =(1, s) T the
Lagrange multiplier vector whose elements correspond to the constraint equations. Eq. (9) and
(10) constitute a closed set of differential-algebraical equations (DAEs).
A constraint equation is set up to restrict the blade rotational speed to rated one, as

q1 et 0
(11)
where q1 represents the rotational degree of freedom of blade with respect to hub, while e is the
rated speed 12.1r/min, the minus represents that the blade rotates clockwise. Here Baumgarte
stabilization method (BSM) (Baumgarte, 1972) is used to calculate the dynamic response of blade.
The time-domain response of blade under various mechanical or aerodynamic loads can be
obtained through solving the dynamic equations of blade MBS. Since the set of equations is
nonlinear, time-varying loads are acted on time-varying CM position of each rigid body at each time
step during numerical integration, therefore nonlinear aeroelastic coupling is realized.

3.

THE CONFIRMATION OF STRUCTURAL DAMPING RATIO OF BLADE FLAPWISE AND

EDGEWISE MODES

Although the blade dynamic mechanics model can calculate the response of the blade MBS under
the influence of external loads, the explicit formulations of the mass, stiffness and damping matrix
of system cannot be obtained. Consequently, the natural frequencies and modes cannot be
obtained directly through the eigenvalues by solving these matrices. In this study, the frequencies
of blade flapwise and edgewise vibrations are obtained by calculating the transfer function based

87

on the dynamic response of blade under pulse excitation, and the structural damping
corresponding to each order mode are calculated through half-power bandwidth method.
x 10

2.5

FFT of load (N)

Load (N)

4
3
2
1
0
0

0.01

0.02

x 10

2
1.5
1
0.5
0
0

0.03

100

Time (s)

200

300

400

500

Frequency (Hz)

(a)Triangle pulse load

(b) Frequency spectrum

Fig.4. Triangle pulse load and its frequency spectrum

Appling a triangle impulse load (shown in Fig. 4) on the rigid body B4, inside and outside the rotor
plane respectively (see Fig. 4 (a) for the time-domain curve while 4 (b) for the frequency-domain
curve), to stimulate the coupling vibrations among rigid bodies of blade. For a vibrating system, the
transfer function (or FRF) is defined as the ratio of the Fourier transform of output x(t ) to that of
input f (t ) , which is
H ( ) X ( ) F ( )
(12)

Where

X ( ) x(t ) e j t d t
0

(13)

F ( )

f (t ) e j t d t

(14)
The input function of body Bi in frequency-domain, Fi(), is obtained by using the Fourier
transform of input function (triangle impulse load in time-domain); while the output function
in frequency-domain Xi is obtained by using the Fourier transform of output function (time-domain
displacement response of rigid body Bi in a flapwise or edgewise direction ), thus each rigid bodys
transfer function Hi () is calculated by Eq. (12). This method has been verified in a reference (Mo
et al., 2013).

0.05

FRF (m/N)

Displacement (m)

0.1

0
-0.05
-0.1
0

10

20

30

40

50

Time (s)

Fig.5. Flagwise displacement of blade tip

Frequency (Hz)

Spanwise
position (m)

Fig.6. The frequency-amplitude characteristic of FRF of each rigid body of

blade in flagwise direction

88

-0.8

FRF (m/N)

Displacement (m)

-0.7

-0.9
-1
0

10

20
30
Time (s)

40

50

Fig.7. Edgewise displacement of blade tip

Spanwise
position (m)

Frequency (Hz)

Fig.8. The frequency-amplitude characteristic of FRF of each rigid body of blade in

edgewise direction

Fig. 5 and 7 show displacement responses of blade tip in flapwise and edgewise directions
respectively, and Fig. 6 and 8 show the frequency-amplitude characteristic of FRF of each rigid
body of blade in flagwise and edgewise directions respectively.
The structure damping ratio of each order mode calculated via half-power bandwidth method and
the blade flapwise and edgewise vibration frequencies are shown in Table 1.
Table 1. The structural damping ratio corresponding to the first and second order modes of blade flapwise and edgewise
vibration
First order
Second order
First order
Second order
Number of
flapwise mode
flapwise mode
edgewise mode
edgewise mode
rigid body
(f=0.72Hz)
(f=1.88Hz)
(f=1.10Hz)
(f=3.90Hz)
B1
0
0
0
0
B2
0.012674
0.009389
0.009043
0.002482
B3
0.012481
0.009146
0.009031
0.002475
B4

0.012436

0.009187

0.009007

0.002479

B5

0.012441

0.009200

0.008995

0.002481

B6

0.012393

0.009095

0.008992

0.002477

B7

0.012452

0.009174

0.008983

0.002476

B8

0.012492

0.009241

0.008975

0.002474

B9

0.012525

0.009296

0.008970

0.002477

B10

0.012554

0.009472

0.008964

0.002419

B11

0.012584

0.008535

0.008958

0.002514

B12

0.012604

0.009027

0.008954

0.002506

B13

0.012609

0.009072

0.008952

0.002503

4.

AEROELASTIC COUPLING RESPONSE OF BLADE

The aeroelastic coupling simulation is carried out by adding the aerodynamic load calculation
model to the multibody system dynamics model. Blade-Element Momentum (BEM) theory, which is
the most generally adopted theory in aerodynamic analysis of wind turbine, is used to calculate
the aerodynamic loads acted on each rigid body of blade in this paper, Prandtls tip correction
(Holierhoek et al., 1994) is used as well. Assume that the aerodynamic loads on each crosssection of rigid body Bi (i =1~13) are same, and that they always act on the aerodynamic center
( the location of 1/4 blade chord length, which near the leading edge) of CM cross-section of Bi .
According to the blade element theory, the thrust FT and the torque Q of a circular area inside the
rotor plane can be expressed as

FT 0.5B cW 2 (CL ( )cos CD ( )sin )L

(15)

89

Q 0.5B cW 2 (CL ( )sin CD ( )cos )Lr

(16)

The thrust and torque can also be obtained using momentum theory, which are
FT 4 r U 2 (1 a)aFL
(17)

Q 4 r 3 U(1 a)aFL
(18)
Where B is the number of blades; the air density; c the chord length of CM cross-section of body
Bi; W the resultant speed from tangential velocity r and inflow wind speed U ; CL and CD are the
lift and drag coefficient respectively, they are functions of angle of attack ; L the length of body Bi
along spanwise direction; the air inflow angle ; r the radial distance from the rotor center to the
CM of body Bi ; the rotational angular speed of wind wheel; the axial flow induction factor;
the tangential flow induction factor; F the tip loss factor.
When the deformation of blade is large, taking into account the effects of flapwise and edgewise
velocities on the aerodynamic forces, the air inflow angle and the angle of attack can be
calculated by

tan

U (1 a) Veop

r (1 a ) Veip

(19)

(20)
where is the twist angle of the blade element; Ve-op and Ve-ip are the flapwise velocity and
edgewise velocity at aerodynamic center of body Bi respectively. Combining Eq. (15) ~ (20) with
the two dimensional airfoil lift-drag characteristics data, the needed physical parameters can be
calculated by iteration method. The exact iteration procedure can be found in a reference (Li et al.,
2012).
The aeroelastic responses of 5MW wind turbine blade under stable wind speed (11.4m/s) and
random wind speed (Yuan et al., 2007) (shown in Fig. 9) are numerically simulated. The blade
length of this wind turbine is 61.5m and the height of the hub is 90m above the ground and the
diameter of wind wheel is 126m. The blade operates atrated rotational speed (12.1r/min).
Wind speed (m/s)

14

Random wind speed

Stable wind speed

13
12
11.4
11
10
0

10

20

30

40

50

Time (s)

Fig. 9. The time history curves of stable and random wind speeds

During the simulation, the aerodynamic model is called by the MBS dynamics model to calculate
aerodynamic forces at each time step if the current time t is less than the termination time tend,
these forces will be treated as external forces and applied to the BMS model to compute the CM
velocity, angular velocity and attitude coordinates of each body of the blade at the next time step.
Then these obtained velocities and coordinates are applied to get the aerodynamic forces at the

90

next time step, and these aerodynamic forces will be coupled to the structural dynamics
calculation. In this way, the loop will be carried out until the termination time of simulation.
Because the stable wind speed or the random wind speed cannot offer enough external excitation
for the blade, sine swept frequency excitation is applied to generate forced vibration for the blade
during aeroelastic coupling, which is helpful for identifying the aeroelastic damping in the low order
modes of blade transfer function. In this study, sweeping around the first and second order natural
frequencies in flapwise direction and edgewise direction under two kinds of wind speed is carried
out. Take the frequency sweep of first order flapwise mode for example to interpret some important
variables. E.g., Fig.10 shows the changing curve of frequency of frequency sweep signal, sweep
bandwidth expands to 2 w , and period of sweeping the bandwidth back and forth is 10s. The
amplitude of driving force is 50000N.

Frequency (Hz)

0.75
0.74
0.73
0.72
0.71
0.7
0

10

20

30

40

50

Time (s)

Fig.10. The frequency changing curve of frequency sweep signal

The results of numerical simulation of aeroelastic coupling are as follow:

The time-domain displacement responses of blade tip in flapwise and edgewise directions under
stable and random wind speed, which couple the first order flapwise sine frequency sweep
excitation, are shown in Fig.11. Though there are still some slight differences, the trends of
displacements of blade tip under these two kinds of wind speed are basically approximate
because the random wind speed includes average wind speed and fluctuating wind speed,
whereas the value of average wind speed is the same as that of stable wind speed (11.4m/s). In
addition, from the picture we can know that the blade bends backward (in flapwise direction) under
aerodynamic normal force, and the deformation of blade tip is maximum, about 5.5m, then the
blade tip vibrates around its equilibrium position. The amplitude of edgewise vibration is larger than
that of flapwise vibration because of the periodical effect of gravity inside the rotor plane.
Compared with the curves shown in Fig.11, the blade tip vibrates much more frequently (shown in
Fig. 13), because the sweeping frequencies are around the second order natural frequencies of
blade in flapwise and edgewise directions, which are higher than the first order sweeping
frequencies.
The time-varying aerodynamic forces of blade tip in edgewise direction under first order flapwise
sine frequency sweep excitation are shown in Fig.12. The changing trends of these forces under
the two kinds of wind speed are also basically approximate, but the existence of fluctuating wind
speed in the random wind speed will affect the angle of attack, and consequently affects the
aerodynamic forces. It is also worth pointing out that aerodynamic tangential force (the component
of aerodynamic force in edgewise direction) is zero when the values of components of
aerodynamic lift force and drag force inside rotor plane are same but their directions are opposite.
While Fig.14 displays the aerodynamic forces of blade tip in edgewise direction under second order
flapwise sine swept frequency excitation. During the stable operation of blade, the maximum of
these time-varying forces reduce dramatically from about 8000N in unstable phase to about
4000N.

91

Displacement (m)
Aerodynamic force (N)

Time (s)

Time (s)

Fig.11. Flagwise and edgewise displacements of blade tip under

stable and random wind speed under first order flapwise sine
frequency sweep excitation
Fig. 12. The time-varying edgewise aerodynamic forces
of blade tip under first order flapwise sine frequency
sweep excitation

92

-0.7
-0.8
-0.9
-1

Displacement (m)

-1.1
21

21.5

22

22.5

23

23.5

Aerodynamic force (N)

Time (s)

Time (s)

Fig.13. Flagwise and edgewise displacements of blade tip under

stable and random wind speed under second order flapwise sine
frequency sweep excitation
Fig.14 The time-varying edgewise aerodynamic forces of
blade tip under second order flapwise sine frequency
sweep excitation

5.

THE ANALYSIS OF BLADE AEROELASTIC DAMPING AND AERODYNAMIC DAMPING

The results of aeroelastic coupling response are obtained under stable wind speed and random
speed in previous section, while the analysis of the damping is carried out in this section. The
flapwise displacement and the edgewise one are processed by the FFT, and the frequencyamplitude characteristics of flapwise displacements of blade tip under two kinds of wind speed,
coupling first order sine frequency sweep excitation, are shown in Fig. 15(a). Because the blade
rotational speed is 12.1r/min, its rotation frequency is 0.2Hz, and the first order natural frequency
in flapwise direction is 0.72Hz, so there are two crests at these two frequencies in the curve of
frequency-amplitude characteristics. The shapes of crest corresponding to the two frequencies are
well matched with each other, while the two curves are not consistent in the range between 0
0.2Hz, because the fluctuating wind speed of random wind speed also contains other low
frequency excitation elements. The frequency-amplitude characteristics of edgewise
displacements of blade tip, shown in Fig.16(a), are similar to that of the edgewise ones shown in
Fig.15(a), and the only difference between the two figures is that the second crest appear at the
position of second natural frequency of blade in edgewise direction, 1.88Hz. This is because the
analyzed signals contain second order sine frequency sweep excitation.

93

Frequency amplitude (m)

0.3

0.2Hz
Stable wind speed

0.25

Random wind speed

0.2
0.15
0.72Hz

0.1
0.05
0
0

0.5

1.5

Frequency (Hz)

Frequency amplitude (m)

1.2

1.10Hz

Stable wind speed

Random wind speed

0.8
0.6
0.2Hz

0.4
0.2
0
0

0.5

1.5

Frequency (Hz)

(a) Frequency-amplitude characteristics of FFT of

flagwise displacement of blade tip
(b) Frequency-amplitude characteristics of FFT of
edgewise displacement of blade tip

Fig.15. Frequency-amplitude characteristics of FFT of flagwise and edgewise displacements of blade tip under stable wind
speed and random wind speed, coupling first order sine frequency sweep excitation

Frequency-amplitude characteristics of blade tip edgewise displacement which couple the first and
second order sine frequency sweep excitations are plotted in Fig. 15(b) and Fig. 16(b) respectively.
There are crests at the first and second natural frequencies, 1.10Hz and 3.90Hz, in the curves.
Similarly, there is also a crest at 0.2Hz in these two figures, which proves that periodical excitation
simultaneously exerts effects both in flapwise direction and in edgewise direction during blade
rotation. This excitation mainly results from the blade weight, therefore blade weight cannot be
ignored.

94

Frequency amplitude (m)

0.3

0.2Hz
Stable wind speed
Random wind speed

0.25
0.2
0.15
0.1

1.88Hz

0.05
0
0

Frequency (Hz)

Frequency amplitude (m)

0.45
0.4

0.2Hz

Stable wind speed

Random wind speed

0.35
0.3
0.25
0.2
0.15
0.1
0.05
0
0

3.90Hz

Frequency (Hz)

(a) Frequency-amplitude characteristics of FFT of

flagwise displacement of blade tip
(b) Frequency-amplitude characteristics of FFT of
edgewise displacement of blade tip

Fig.16 Frequency-amplitude characteristics of flagwise and edgewise displacements of blade tip under stable wind speed and
random wind speed, coupling second order sine frequency sweep excitation

The aeroelastic damping ratios of each rigid body are calculated via half-power bandwidth method
and combining with the structural damping ratios, the aerodynamic damping ratios under stable and
random wind speeds are listed in Table 2 and 3 respectively. From the tables, we can know that
under the two kinds of wind speed, all the aeroelastic damping ratios of first and second order
modes in flapwise and edgewise directions are positive; all the aerodynamic ratios of first order
edgewise mode and those of second order flapwise mode are positive; even though the
aerodynamic damping ratios of first order flapwise mode are negative, but their absolute values
are less than their corresponding structural damping ratios (shown in Table 1). So aeroelastic
instability of the blade will not occur. In addition, all the aerodynamic damping ratios of second
order edgewise mode under stable wind speed are negative, while a part of those of second order
edgewise mode under random wind speed are positive, which proves that the aerodynamic
damping ratio is related to wind speed.
As mentioned previously, the random wind speed includes average wind speed which equals the
stable wind speed(11.4m/s), thus the damping ratios under the two kinds of wind speed have the
same magnitude.
Table 2. The aeroelastic and aerodynamic damping ratio corresponded to the first and second modes of blade flapwise and edgewise vibrations
(stable wind speed 11.4m/s)
First order mode damping
Second order mode damping
Number aeroelastic aerodynamic aeroelastic aerodynamic aeroelastic aerodynamic aeroelastic aerodynamic
of rigid damping of damping of damping of damping of damping of damping of damping of damping of
body 1st falpwise 1st falpwise 1st edgewise 1st edgewise 2nd falpwise 2nd falpwise 2nd edgewise 2nd edgewmode
mode
mode
mode
mode
mode
mode
ise mode
B1
0
0
0
0
0
0
0
0
B2
0.011808
-0.000866
0.020863
0.011820
0.010499
0.001110
0.002038
-0.000444

95

B3

0.011777

-0.000704

0.020839

0.011808

0.010565

0.001419

0.002038

-0.000437

B4

0.011786

-0.000650

0.020849

0.011842

0.010498

0.001311

0.002040

-0.000439

B5

0.011788

-0.000653

0.020859

0.011864

0.010477

0.001277

0.002047

-0.000434

B6

0.011808

-0.000585

0.020837

0.011845

0.010561

0.001466

0.002055

-0.000422

B7

0.011828

-0.000624

0.020833

0.011850

0.010592

0.001418

0.002086

-0.000390

B8

0.011852

-0.000640

0.020818

0.011843

0.010641

0.001400

0.002037

-0.000437

B9

0.011820

-0.000705

0.020772

0.011802

0.010551

0.001255

0.002037

-0.000440

B10

0.011839

-0.000715

0.020737

0.011773

0.010632

0.001160

0.002034

-0.000385

B11

0.011853

-0.000731

0.020661

0.011703

0.010825

0.002290

0.002052

-0.000462

B12

0.011883

-0.000721

0.020583

0.011629

0.010604

0.001577

0.002044

-0.000462

B13

0.011887

-0.000722

0.020555

0.011603

0.010610

0.001538

0.002041

-0.000462

Table 3. The aeroelastic and aerodynamic damping ratio corresponded to the first and second modes of blade flapwise and edgewise vibrations
(random wind speed)
First order mode damping
Second order mode damping
Number aeroelastic aerodynamic aeroelastic aerodynamic aeroelastic aerodynamic aeroelastic aerodynamic
of rigid damping of damping of damping of damping of damping of damping of damping of damping of
body 1st falpwise 1st falpwise 1st edgewise 1st edgewise 2nd falpwise 2nd falpwise 2nd edgewise 2nd edgewmode
mode
mode
mode
mode
mode
mode
ise mode
B1
0
0
0
0
0
0
0
0
B2
0.011803
-0.000871
0.020542
0.011499
0.010252
0.000863
0.002206
-0.000276

6.

B3

0.011795

-0.000686

0.020542

0.011511

0.010241

0.001095

0.002194

-0.000281

B4

0.011798

-0.000638

0.020539

0.011532

0.010294

0.001107

0.002315

-0.000164

B5

0.011797

-0.000644

0.020542

0.011547

0.010359

0.001159

0.002740

0.000259

B6

0.011796

-0.000597

0.020540

0.011548

0.010395

0.001300

0.004174

0.001697

B7

0.011797

-0.000655

0.020539

0.011556

0.010433

0.001259

0.003284

0.000808

B8

0.011806

-0.000686

0.020537

0.011562

0.010438

0.001197

0.002197

-0.000277

B9

0.011821

-0.000704

0.020534

0.011564

0.010397

0.001101

0.002284

-0.000193

B10

0.011864

-0.000690

0.020522

0.011558

0.010213

0.000741

0.002050

-0.000369

B11

0.011966

-0.000618

0.020508

0.011550

0.009191

0.000656

0.002375

-0.000139

B12

0.012067

-0.000537

0.020509

0.011555

0.010621

0.001594

0.002275

-0.000231

B13

0.012111

-0.000498

0.020506

0.011554

0.010787

0.001715

0.002227

-0.000276

CONCLUSIONS

The superelement is used to scatter the flexible blade in this studies, and the mechanics model of
flexible blade is set up by applying modeling approach of multibody dynamics, and the dynamic
response of blade under under pulse excitation is calculated. Once the transfer function is obtained
based on the response, the structural damping can be calculated through half-power bandwidth
method.
It is convenient to realize the blade real-time aeroelastic couping simulation under stable wind speed
and random wind speed by combining the MBS and aerodynamic loads model. The sine swept
frequency excitation is added to the blade during the coupling simulation and the aeroelastic damping
taking into account the aerodynamic force is obtained by analyzing the response signal of blade, and
the structural damping and aerodynamic damping are distinguished.
Under the two kinds of wind speed, only the aerodynamic damping ratios of first order flapwise mode
and those of second order edgewise mode are negative, but all their absolute values are less than
their corresponding structural damping ratios. So the blade areoelastic instability will not occur.
Aeroelastic damping is related to wind speed, because the aeroelastic damping consists of the
aerodynamic damping which is related to wind speed and structural damping which is the natural
property of blade itself.

96

This work is significant and feasible for the guide of blade structural and aerodynamic shape design,
and helpful for the confirmation of blade aeroelastic stability boundary .
ACKNOWLEDGEMENT
The present work has been funded by the National Natural Science Foundation of China (51276043 ).
REFERENCES
Baumgarte E, 1972, Stabilization of constraints and integrals of motion in dynamic systems.
Computer Methods in Applied Mechanics and Engineering 1:1-16.
Gebhardt CG, Preidikman S, Jrgensen MH, et al, 2012, Non-linear aeroelastic behavior of large
horizontal-axis wind turbines: A multibody system approach. International Journal of Hydrogen
Energy 37: 14719-14724.
Hansen MH, Thomsen K, Fuglsang P, et al, 2006, Two Methods for Estimating Aeroelastic
Damping of Operational Wind Turbine Modes from Experiments. Wind Energy 9:179-191.
Holierhoek JG, 2008, Aeroelasticity of Large Wind Turbines. Delft : Delft University of Technology.
Hong JZ, 1999, Computational dynamics of multibody system. Beijing: Higher Education Press.
Jin X, Yang EB, Zhao L, 2008, Signal processing principle & application (Second Edition). Beijing:
Tsinghua University press.
Jonkman J, Butterfield S, Musial W, et al, 2009, Definition of a 5-MW reference wind turbine for
offshore system development. Springfield: U.S.National Rene- wable Energy Laboratory.
Li C, Ye Z, Gao W, Jiang Z, 2012, Modern land-sea wind turbine calculation and simulation.
Shanghai: Science and Technology Press of Shanghai.
Li XL, Yu DF, Sun FC, 2009, Foundation of Mechanical Vibration (Second Edition), Beijing: Beijing
Institute of Technology Press.
Meng FZ, 2011, Aero-elastic Stability analysis for large-scale wind turbines. Delft : Delft University
of Technology.
Mo WW, Li DY, Xia HJ, et al, 2013, Multibody dynamic modeling and dynamic characteristics
analysis of flexible blades for a horizontal axis wind turbine. Journal of Vibration and Shock 32: 99105.
Schiehlen W, 1997, Multibody system dynamics: roots and perspectives, Multibody System
Dynamics 1:149188.
Thomsen K, Petersen JT, E. Nim , et al, 2000, A Method for Determination of Damping for
Edgewise Blade Vibrations. Wind Energy 3:233246.
Wang W, Liao MF, Khn M, 2013, Study on flutter of Three-dimensional Model of Wind Turbine
Blades, Noise and Vibration Control (5):90-96.
Yuan B, YING HQ, Xu JW, 2007, Simulation of Turbulent Wind Velocity Based on Linear Filter
Method and MATLAB Program Realization. Structural Engineers 23:55-61.
Zhao XY, Maier P, Wu JY, 2007, A new multibody modelling methodology for wind turbine
structures using a cardanic joint beam element. Renewable Energy 32:532546.

97

An axial symmetry Augmented Wind

Wheel and Its Optimized Design
Sun Xiaojing1,2 ,Ziyin Cao3, Yueqing Zhuang3 ,Diangui Huang1,2* ,Cao Yang4 ,Wu Guoqing4
(1.University of Shanghai for Science and Technology, Shanghai, 200093)
(2. Shanghai Key Laboratory of power energy in multiphase flow and heat transfer, Shanghai 200093)
(3. Shanghai University, shanghai 200072)
(4. Nantong University, Nantong, 226600)
Tel/Fax: 86-21-55897317, email:dghuang@usst.edu.cn
Abstract--An axial symmetry augmented vertical axis wind wheel, which is suitable for arbitrary wind
directions, is proposed in this paper. In order to improve the capacity of the wind turbine, a set of
collection-shield boards are installed symmetrically around the rotating S-type wheel. The flow fields
around this type of wind wheel are numerically simulated using the commercial CFD software
FLUENT. The optimized design of geometrical parameters of the wheel and collection-shield boards is
done using the orthogonal design method. The numerical results show that the output power of the
optimized augmented wind wheel is nearly 3 times larger than the conventional wind wheel.
Index Terms--collection-shield, vertical axis, wind energy

INTRODUCTION

t is well known that the output power of wind turbines is proportional to the cube of entrance wind
velocity. This indicates that even small increase of the wind velocity could result in large
improvement of the output power [1]. Therefore, many research efforts have been dedicated to finding
an effective method to increase the wind velocity approaching the wind turbine. Among others, one
method is to install a diffuser behind the wind turbine, which can reduce the pressure behind the
turbine, thereby leading to an increase of the air flow rate through the rotor, hence an increase of the
entrance wind velocity. Gilbert and Foreman [2], Igra [3], Nagai and Irabu [4] and Phillips et al [5]
have reported their attractive studies regarding diffuser-augmented wind turbines. Their research shows
that the maximum power rating can be extended substantially with a diffuser installed around the wind
rotor.
The main advantage of vertical axis wind turbines (VAWTs), such as Savonius wind turbine or
Darrieus wind turbines, is its single moving part (the rotor) where no yaw mechanisms are required,
thus simplifying the design configurations significantly[6]. However, the power coefficients of

VAWTs are much lower than that of HAWTs. In order to raise the competitive power of VAWTs,
An axial symmetry augmented vertical axis wind wheel is introduced in this paper. As Fig. 1 shows,
a set of collection-shield boards (2) is installed symmetrically around the rotating vertical S-type wheel
(1). By using the commercial CFD software FLUENT, the simulation of flow fields for this new kind
of wind wheel is conducted. The geometrical parameters of the wheel and collection-shield boards are
then optimized by the orthogonal design method. The final results show that the output power of the
optimized this type wind wheel is much greater than that of the conventional wind wheel.

1
98

Fig. 1. Sketch of the augmented vertical axis wind wheel

NEW TYPE AUGMENTED WIND WHEEL

Fig. 2 shows the cross-sectional view of this type of augmented wind wheel. All the collectionshield boards have the same geometrical shape. For the instantaneous configuration shown in Fig. 2,
the internal region between board A and B, B and C, and C and D constitute three convergent flow
paths, which are used to collect wind energy and also to induct the wind to blow towards the impeller.
On the other hand, the internal region between board A and F, F and E, and E and D are served as three
diffusers to reduce the pressure at the exit of the impeller. Because the collection-shield boards are
installed symmetrically, this type of wind wheel is suitable for arbitrary incoming wind direction[7].

Fig. 2. Cross-sectional view of the augmented vertical axis wind wheel

Fig. 3 shows the shape of the blade. For the sake of convenience, the shape is composed of two
sections: a straight line OP and an arc PQ. Line OP is tangent to the arc. If the radius of the rotor is
fixed, the blade shape can be determined by two geometrical parameters, and , as shown in Fig. 3.

2
99

Fig. 3. Blade shape

Fig. 4 shows the shape of the collection-shield board. The board is orthogonal to the large circle
outside and forms an angle with respect to the inner circle. denotes the clearance between the rotor
and the collection-shield board.

Fig. 4. Shape of collection-shield board

The output power of this new wind wheel is dependent on several parameters, such as the number of
blades, the shape of blades, the number of collection-shield boards, the angle , the diameter of rotors,
the clearance between rotors and collection-shield boards and so on.

COMPUTATIONAL RESULTS AND COMPARISON

The flow fields of conventional wind wheel and this type augmented wind wheel are
respectively simulated using FLUENT. It is an unsteady problem. When the wheel rotates, the
flow field oscillates periodically. For unsteady calculations, the dual-time-step algorithm is
adopted. In every physical time step, a 30 pseudo time-step sub-iteration is used to reduce the
continuity and velocity residual errors. Fig. 5 shows the iteration history of this type augmented
wind wheel.
The other details of numerical method, turbulent model, computational domain and grid,
boundary conditions and so on for these simulations are described in reference[8].
In order to validate the effects of this type of augmented vertical axis wind wheel, some
experiments have been conducted before this computation[9].

3
100

Fig. 5. Iteration history

When the wind blows from left to right, the rotor will rotate clockwise. Fig. 6 is the pressure
contour of conventional wind wheel and this type augmented wind wheel at a certain time.
Comparing the two figures in Fig. 6, we can see that, at the OA section, the pressure on the
concave surface of the new wind wheel is higher than that of the conventional one, whereas the
pressure on the convex surface of the new wind wheel is lower than that of the conventional one.
A remarkable low-pressure region appears on the convex surface of the OA section of the new
wind wheel. At the OB section, the pressure on the convex surface near tip area of the new wind
wheel is much lower in comparison with the conventional one. These characteristics of the flow
field show that the output power of the new wind wheel is much higher than that of the
conventional one.

Fig. 6. Pressure contour of the conventional wind wheel and the new wind wheel

Fig. 7 gives the pressure distribution along the OA section of the two kinds of wheels. It shows
clearly that the pressure difference between two surfaces of the blade of this type wind wheel is much
higher than that of the conventional one. Fig. 8 gives the pressure distribution along the OB section.
The pressure near the tip on the convex surface of the new wind wheel is much lower. These results are
consistent with that in Fig. 6.

4
101

Fig. 7. Pressure distribution on OA section

Fig.8. Pressure distribution on OB section

Fig. 9. Torque coefficient

Fig. 9 shows a comparison of the torque coefficient Cm between the new wind wheel and the
conventional one. The torque coefficient is defined as Cm N / (v3 AL / 2) , where N is torque is
density, and v is reference velocity, A is reference area, and L is reference length. Here, Cm 0
means that the output of wind wheel is positive. This figure shows that the torque of wind wheel is
periodic. Obviously, output torque of the new wind wheel is much greater than the conventional one.

5
102

DESIGN OPTIMIZATION
The outer circle radius of collection-shield board, R, is taken to be 2 meters. Wind speed is 12m/s.
Speed of rotation is 100rpm.
The orthogonal experimental method, invented by L.G. Hua [10], can be used to optimize a system
with several parameters. The rotor radius r, the number of blades n1, the number of collection-shield
boards n2, the blade control parameters and , the angle and the gap are optimized using the
orthogonal experimental method. There are seven design parameters in total, and every design
parameter is optimized based on six equidistant levels. The L66 (67 ) orthogonal table is shown in Table
I, and 36 numerical experiments are conducted subsequently.
TABLE I.
L6667ORTHOGONAL TABLE

Averaged
torque
Nm
3
20.21

11.96

8.47

5.57

3.36

1.85

0.2 46 0.125 45
16 16 5
0.2 48 0.15 47.5 18 6
0.2 50 0.175 50 20 7
0.3 40 0.075 42.5 16 6

5.82

0.3 42 0.1
45 18
9 0.3 44 0.125 47.5 20
10 0.3 46 0.15 50 10
11 0.3 48 0.175 37.5 12

6.63

27.4

20.46

12.62

12 0.3 50 0.05 40 14
13 0.4 40 0.1 47.5 10
14 0.4 42 0.125 50 12
15 0.4 44 0.15 37.5 14

10.21

14.54

11.47

4.99

16 0.4 46 0.175 40 16
17 0.4 48 0.05 42.5 18
18 0.4 50 0.075 45 20
19 0.5 40 0.125 37.5 16

2.43
56.93

29.61

58.95

20 0.5 42 0.15 40 18
21 0.5 44 0.175 42.5 20
22 0.5 46 0.05 45 10
23 0.5 48 0.075 47.5 12

27.71

19.53

8.63

1.52

24 0.5 50 0.1
50 14
25 0.6 40 0.15 42.5 10
26 0.6 42 0.175 45 12
27 0.6 44 0.05 47.5 14

4.16

27.53

32.92
37.32

28 0.6 46 0.075 50 16
29 0.6 48 0.1 37.5 18
30 0.6 50 0.125 40 20
31 0.7 40 0.175 47.5 16

15.79

2.48

16.81

36.14

32 0.7 42 0.05 50 18
33 0.7 44 0.075 37.5 20

51.79

58.65

No r/R
1
2
3
4
5
6

/(2r)

0.2 40 0.05 37.5 10

0.2 42 0.075 40 12
0.2 44 0.1 42.5 14

n1 n2

6
103

34 0.7 46 0.1
35 0.7 48 0.125
36 0.7

50 0.15

40 10
42.5 12 2
45 14 3

7
8

64.27
35.34

8.22

The 36 numerical results were analyzed using the orthogonal method as described in [6], then a set
of optimum design parameters were obtained. It is r/R=0.5, n1=2, n2=5, =40, =200mm, =47.5,
=20. Finally, an additional numerical experiment was performed with these optimum design
parameters. The result showed that the averaged torque with the optimum parameters is 71.00Nm.
In order to compare the averaged torque of the optimum collection-shield wind wheel with that of
the conventional one, the average torque of conventional wind wheel with the same rotor size and same
blade shape was also calculated. The result is 26.12Nm. It is apparent that the output of the new
collect-shield wind wheel is 272% that of the conventional same size wind wheel. Even though the
sweeping area of the new collection-shield wind wheel is two times of the conventional one, the
utilization ratio of wind energy of the new collect-shield wind wheel is still much higher than the
conventional one.

CONCLUSIONS
Comparing with the conventional S type wind wheel, the capacity of this type collection-shield wind
wheel has been improved substantially. Both the output power and the utilization ratio of wind energy
of the new collect-shield wind wheel are enhanced remarkably. The result of design optimization
shows that the rotor with 2 blades is the best, that is somewhat beyond our anticipation and is worth of
mentioning. This order of nature was also proved by experiment in reference[9].

ACKNOWLEDGEMENTS
This work was supported by National Natural Science Foundation of China Grant
Nos. 11202123 and No. 51376096.

REFERENCES
[1] K. Abe and Y. J. Ohya, "An investigation of flow fields around flanged diffusers using CFD,"
Journal of Wind Engineering and Industrial Aerodynamics, vol. 92, pp. 315-330, Mar. 2004.
[2] B. L. Gilbert and K. M. Foreman, "Experiments with a diffuser-augmented model wind
turbine, " Trans. ASME, Journal of Energy Resources Technology, vol. 105, pp. 46-53, Mar.
1983.
[3] O. Igra, "Research and development for shrouded wind turbines," Energy Conversion and
Management, vol. 21, pp. 13-48, Jan. 1981.
[4] M. Nagai and K. Irabu, "Momentum theory for diffuser augmented wind turbine," Trans.
JSME, vol. 53, pp. 1543-1547, 1987 (in Japanese).
[5] D. G. Phillips, P. J. Richards and R. G. J. Flay, "CFD modelling and the development of the
diffuser augmented wind turbine," Proc. of the Computational Wind Engineering, pp. 189-192,
2000.
[6] Mazharul Islam, David S.-K. Ting and Amir Fartaj, Aerodynamic models for Darrieus-type
straight-bladed vertical axis wind turbines, Renewable and Sustainable Energy Reviews,
Vol.12, no.4, pp1087-1109,2008.
[7] Zi-Yin Cao, Dian-Gui Huang, Wind turbine with wind collection-shield boards, Journal of
Engineering Thermophysics, Vol.29,No.6,pp960-962, 2008.
[8] Zi-Yin Cao, Research on the characteristics of wind turbine with wind collection-Shield
Pattern,[master Thesis]. Shanghai, Shanghai University,2008.
[9] Wan-Li Zhou, Zi-Yin Cao,, Yu-Xiang Li, Dian-Gui Huang, Experimental research on the
characteristiic of wind wheel with wind collection-shield pattern, Journal of Engineering
Thermophysics, Vol.30, No.4,pp598-600, 2009.
[10] K. T. Fang and C. X. Ma, Orthogonal experimental method, Beijing: Science Press, 2001, pp.
35-82

7
104

BATTERY SIZING FOR RESIDENTIAL WIND TURBINE SYSTEMS CONNECTED

TO THE GRID
1

Ying She , Jing Shi , Ergin Erdem

1
2
Nanchang Hangkong University , North Dakota State University
1
Nanchang, Jiangxi Province 330063, China
1410 14th Avenue N., Fargo, ND 58108, U.S.A.2

sheying1980@hotmail.com, jing.shi@ndsu.edu, ergin.erdem@my.ndsu.edu

ABSTRACT
Residential wind turbine (RWT) systems with battery storage as a form of wind power application
provide reliable electricity supply to families and carry potential for increasing the adoption of wind
energy. However, the battery banks are often expensive and the capacity needs to be determined to
match up with the system requirement. In this paper, we develop a modeling approach to determine
the suitable configuration of an on-the-grid RWT system with battery storage, by considering the
stochastic nature of wind speed, load demand, and outage events. The objective is to minimize the
total electricity cost of the customer. The uniqueness of this study is that we consider the RWT
system with battery storage is grid-connected, and it can both buy electricity when the wind power is
not available and sell excess generated power to the grid. In other words, in the economic analysis,
not only the costs of energy generation and electricity purchasing are taken into account, but also the
profit from selling energy from the RWT system is included. Based on a case study on a
representative household in California, battery storage is sized with a variety of RWT power ratings,
and the adoption of battery storage can be clearly justified.
Keywords: Residential wind turbine, battery storage, sizing, optimization.
INTRODUCTION
In recent years, wind power has become a main alternative supply for both off-grid and gridconnected power resources with the government support plus the steady progress of wind power
generated technology. The U.S. wind industry reached 51,630 MW of cumulative wind capacity by
the end of September 2012 (AWEA, 2012).
Wind power generation exhibits seasonality in long and short terms. In long term, wind generation
is usually higher in winter as compared with summer. In short term, wind generation is relatively
higher during the evening as compared with day time. The short term seasonality actually poses a
major challenge for residential wind turbine customers because the evening time has much lower
load demand. In order to use wind power more efficiently and reduce intermittence of wind
generation, battery banks are often incorporated into the wind generation systems. However,
compared with the traditional inexpensive grid-connected electricity consumption, the high cost of
installation and maintenance of the wind turbine systems with battery storage is apparently a major
challenge. Therefore, there is a strong need for obtaining an optimal configuration for a wind
system with battery storage to lower the total cost.
This study investigates how a suitable battery capacity matches with a certain power rated on-thegrid residential wind turbine (RWT) to minimize the cost, under two government incentive policies:
(1) buy-back policy which allows users sell excess electricity back to the utility; (2) Production
Tax Credit (PTC), which can cover most of the purchasing and installation cost for RWT with
battery system. The suitable configuration is obtained by reacting to the variation of wind speed,
household electricity consumption, and electricity price. In the research, two aspects are
considered, namely, demand shifting capability and backup for outage.
LITERATURE REVIEW
Hybrid renewable systems, referring to two or more renewable power source (Yang et al., 2009),
can work as alternatives to provide more clean electricity and reduce dependence on conventional
energy, such as oil, coal. However, the intermittence of renewable energy sources, such as wind
and solar, makes these systems unreliable as independent power sources. To improve the
feasibility of hybrid energy systems and use renewable energy resources more efficiently, hybrid
system sizing needs to be investigated. It refers to searching for the optimal configuration, among
a set of system components, under which the hybrid can meet a series of desired targets, such as
the fixed load satisfaction, lowest energy cost and the least pollutant emission.

105

In several studies (Elhadidy and Shaahid, 1999; Shrestha and Goel, 1998; Hessami et al. 2011),
the feasibility of hybrid renewable energy systems is identified as the major concern. Using hourly
mean wind-speed data for the period 1986-1997 and 1991 recorded at Dhahran, Saudi Arabia,
Elhadidy and Shaahid (1999) investigate optimal sizing of battery storage for hybrid wind/diesel
power system. In the hybrid system simulation, two 10 kw wind turbines and a diesel back-up are
selected, the capacity of battery storage is determined to satisfy the annual energy consumption of
a typical family house(41,500 KWh). The results show a trade-off between size of the storage
capacity and diesel operation hours. Shrestha and Goel (1998) use the Loss of Load Hours (LOLH)
as a criterion to assess the reliability of a stand-alone PV system with battery storage. An energy
generation simulation for various configurations of system devices (PVs and batteries) is
presented. In (Hessami et al., 2011), the performance is studied for eight different hybrid wind
power systems located in isolated communities. The results demonstrate the economic and
technical superiority of the hybrid wind-diesel-battery system compared with other systems. Based
on average daily solar of Dhahran, Kingdom of Saudi Arabia, Shaahid and Elhadidy (2008) assess
the feasibility and economic viability of utilizing a designed hybrid PV-diesel-battery power system
to meet the load of a typical residential building. In a similar method (Bekele and Palm, 2010), a
design method of hybrid PV-wind-based system is investigated for a typical hypothetical
community of 200 families. The total net present cost (NPC) and cost of energy (COE) are
calculated for various combinations of system devices. Then optimization results can be ranked
according to these economic criteria. The results show that the most cost effective system set-up
does not include any renewable components. In both methods, National Renewable Energy
Laboratorys (NREL) Hybrid Optimization Model for Electric Renewable (HOMER) software has
been employed as the optimization tool.
In most of literatures (Gavanidou and Bakirtzis, 1992; Gavanidou and Bakirtzis, 1992; Yang et al.,
2008; Diaf et al., 2007), the sizing problem has been addressed with technical and economic
considerations. The optimal configurations of a hybrid power system can be determined when they
meet the desired system reliability with the lowest energy cost. For the technical part, the indices
adopted include the Loss of Load Hours (Shrestha and Goel, 1998), the difference of generated
and demanded power (Kellogg et al., 1998), the Loss of Power Supply Probability (LPSP) (Yang et
al., 2008; Diaf et al., 2008; Shen, 2009; Celik et al., 2008), the desired System Performance Level
(SPL) (Maghraby et al., 2002). The hybrid renewable energy systems are designed to satisfy the
above technical indices to realize a fixed system autonomous level. The most popular criteria is
LPSP which is defined as the probability that an insufficient power supply results when a hybrid
system (e.g., PV array, wind turbine and battery storage) is unable to satisfy the load demand (Lu
et al., 2002).
The economic analysis focuses on the system cost. Several economic criteria have been
developed. Net present cost (NPC), cost of energy (COE) and levelized cost of energy (LCE)
(Ould Bilal et al., 2012) have been taken as most popular indicators for economic analysis.
Especially, the LCE index is a comprehensive and more effective benchmark in that it combines
the characteristics of the first two parameters. The cost of generating energy (COE, US$/kWh) is
also used as an economic criteria, which is calculated as the total annual cost of the hybrid system
per KWh. The total annual cost is sum of the annualized capital cost (ACC) of the system and the
annual maintenance cost (AOM).
Numerous mathematical models have been applied to achieve sizing optimization both technically
and economically. The models use the approaches of trade off/risk method, linear programming
(Kerllogg et al. 1996, Rahman and Chedid, 1997), dynamic programming, genetic programming
(Koutroulis et al., 2006, Ould Bilal et al., 2010). The trade off/risk method is applied to build a
hybrid renewable energy generation system either stand-alone or grid-connected (Gavanidou and
Bakirtzis, 1992). In (Kerllogg et al. 1996), the least squares algorithm is used to obtain the best
design of a hybrid wind/PV system for a small ranch home in Montana, U.S.A. By considering wind
speed, solar radiation and load demand, Kellogg et al. (1998) develop an iterative procedure in
simulating the operation of hybrid PV/WG systems. The optimal mixture is obtained by making the
average difference between power generation and demand equal to zero within the desired period
of time. The desired System Performance Level (SPL) is used in a PV power system sizing
problem (Maghraby et al., 2002). SPL means that the number of days that the load cannot be
satisfied. Probabilistic methods like Markov chain are adopted in this paper.
A sizing method of stand-alone PV/wind/diesel/battery systems is proposed by Bilal and Sambou
(2011), which is based on energy generation simulation using genetic algorithm for various
numbers of system devices (e.g., PVs, wind turbines, solar regulators, inverters, diesel generators

106

and batteries, etc.). The optimal configuration ensures the lowest Levelized Cost of Energy (LCE)
and pollutant emission are satisfied simultaneously. LCE is defined by

LCE

J ( x)
Eannual

(1)
where J(x) is composed of the capital cost of energy, maintenance and operation cost of energy,
and the replacement cost of energy; Eannual is the annual consumed energy (KWh/year).
In (Koutroulis et. al, 2006), genetic algorithm is used to minimize the cost of stand-alone PV/WG
systems while maintaining that the load energy requirements are completely covered. The
proposed method is applied to a residential household power generation system. The simulation
results show that the hybrid PV/WG systems feature lower system cost compared to the cases
where either exclusively WG or exclusively PV sources are used. Using a similar method, a hybrid
solar-wind-battery system is optimized by Ould Bilal et al. (2010), the annualized cost system and
the LPSP are two minimization targets.
Based on the total net energy production and the energy delivered to the load, Celik (2008)
calculates the cost payback time (CPBT) for a residential PV system with battery storage with the
fixed LLP level. LLP is similar to LPSP, which means the percentage of energy deficit over the total
energy demand within a certain period of time.
When determining the optimal configuration for a hybrid system, instantaneous wind speed
variations are considered in some works. Zamani and Riahy (2008) develop a modified power
curve to calculate the wind power energy. The major difference between a traditional power curve
and a modified one is that the latter considers not only wind speed but also wind dynamics. The
case study shows that the method can provide more accurate calculation. Roy et al. (2010) use
the wind speed probability distribution function to replace recorded wind speed data for its
accuracy uncertainty and unavailability at the site of interest.
Furthermore, in some literature, reducing pollutant emission has also been considered, besides
the desired reliability requirement and energy cost. In (Ould Bilal et al., 2010), the CO2 emission is
evaluated. Multi-objective algorithms (Dufo-Lopez and Agustin, 2008) and design space are two
major methods used in sizing hybrid systems. In (Roy et al., 2009), the design space, a graphical
depiction of all feasible design options is identified on a rotor diameter vs. rated power diagram.
Lopez and Agustin design a hybrid energy system minimizing the three objectives of minimizing
the cost of energy, pollutant emissions (CO2), and unmet load) simultaneously, by using a multiobjective evolutionary algorithm (MOEA) and genetic algorithm (GA). According to the methods
proposed by Dufo-Lopez and Agustin (2011), the optimal size of a stand-alone PV-wind-diesel (or
gasoline) system with batteries storage are determined by minimizing both the Levelized Cost of
Energy (LCOE) and CO2 Life Cycle Emissions (LCE). The Hybrid Optimization by Genetic
Algorithms (HOGA) software using Multi-Objective Evolutionary Algorithms (MOEAs) has been
applied. The demerit is that it cannot provide different probable design alternatives.
In the existing studies, various methods have been developed and different technological and
economic metrics have been employed, but many of the studies have four points in common.
Most of works are performed using deterministic models to search optimal configuration of
hybrid energy system (wind turbine/PV) and battery capacity.
The criteria for choosing the optimal configuration is based minimum system cost as well
as the required autonomy level is.
Most of those hybrid energy systems studied are off grid and located in the remote area.
Last, the small generator owners are not able to sell excess energy to utilities.
In this paper, we use a stochastic method to determine the suitable battery capacity for any power
rated RWT system, by considering stochastic nature of wind speed, load demand, and outage
events. Our RWT system with battery storage is grid-connected and it can both buy electricity from
the grid when wind power is not available and sell excess wind power to the grid.
MODELING OF THE RWT SYSTEM COMPONENTS
Before the phase of optimal sizing, a Residential Wind Turbine (RWT) system with battery storage
needs to be modelled. For such a system, as depicted in Fig 1, two principal subsystems are
included, the wind turbine and battery storage. Other accessories are also necessary, which
include converters, inverters, and a change controller. A methodology for modelling RWT
components is described below.

107

Although this model is also can used for a stand-alone system, it is designed for a residential
customer connected with the existing grid. In this case, the load demand can be satisfied from both
the wind turbine and the grid, the excess wind power also can be sold to the grid.

Wind energy

Convert

Inverter

AC/DC

Residential
Customer
Load
AC/DC

Grid

Inverter

Convert

AC/DC
Change
controller
Transformer
Battery
Fig.1 Diagram of RWT System with Battery Storage

Modelling of a wind turbine

Different wind turbines have different power curves. In this study, we adopt the following equation
to simulate the power output of a wind turbine:

v k vCk
(vC v vR )
PR k
k
vR vC

Pw (v)
PR
(v R v v F )

0 (v v and v v )
C
F

(2)
Where PR is the rated power output; VC is the cut-in wind speed; VR is the rated wind speed; VF is
the cut-off wind speed; k is the Weibull shape parameter. The power generated by the RWT can
be separated into three parts, namely, (1) wind power sold to grid, W g(t), (2) wind power stored in
the battery, W b(t), and (3) wind power consumed by the household, W l(t).
Modelling of battery storage
Lithium battery is chosen as the energy storage for the RWT system. The battery can be charged
from two sources: (1) the power generated from the RWT, W b(t), when the total output of the RWT,
W r(t), is greater than the household load, H(t); and (2) the power purchased from the grid, Gb(t),
when the market electricity price(MEP) at time t is lower than the average MEP. Also, the
residential customer can sell the amount of electricity, Bg(t), to the grid from the battery storage by
discharging. The battery also can discharge for satisfying the residential load for the amount of
Bl(t).
Electricity consumption
The electricity consumption, H determines the requirements of power supply from the following
three sources: (1) power generated by RWT and consumed by customer, W l(t), (2) electricity
purchased from the grid and consumed directly, Gl(t), (3) power discharged from battery storage,

108

Bl(t). The loads can be either DC or AC. The load models are simulated according to the dynamic
demand loads.
Electricity price
There are various kinds of market electricity price. In general, the electricity price can be
categorized as retail and wholesale prices. The price for a customer purchasing electricity from the
utility is denoted as Pb(t), while the price for a customer selling electricity to the utility is
represented by Ps(t). Both Pb(t) and Ps(t) are dependent upon time and location. However, since
only one residential customer is considered in this study, the price will only change with time,
namely, the peak, partial-peak and off-peak price. In addition, for simplicity, Ps(t) is assumed to be
the same as Pb(t).
Incentive policies
A large number of measures have been introduced and carried out worldwide to promote the
adoption of RWT systems. For example, the US government has placed several renewable
incentives to help lowering the RWT system cost. Those policy incentives can be grouped into two
categories: (1) Public Utility Regulatory Policy, launched in 1978. Under this obligation, small
power generators can sell extra electricity to the grid. (2) Federal and State Production Tax Credit
(PTC) is the main mechanism in the U.S. to support renewable energy. According to this policy,
owners of renewable power generator can obtain tax credit to cover part of capital initial cost. For
instance, under the obligation of California State PTC, owner of small wind turbine can get tax
credit up to 50% of total capital cost of wind power system (DSIRE, 2012).
MODEL FORMULATION
The objective of this research is to determine a suitable configuration for an on-the-grid RWT
system with battery storage among a list of configurations, and ensure the customers electricity
cost is minimized, which include the system cost and expenditures on electricity purchase from the
utility. There are two major constraints: (1) the load energy requirements are satisfied more during
outage, and (2) the wind power should be wasted less. The configuration should be determined
according to the following three indexes: the customers total electricity cost; the outage rate; the
waste wind power.
Customers total electricity cost
The total customers electricity cost, Ct, can be expressed as follows:

Ct Cr Cb Cg R
(3)
Where Cr is the cost for producing the wind power at hour t.

Cr Wr

COw / Yw
Ean

(4)
Where COw is the sum of RWT installation cost and replacement/maintenance cost in the lifespan
of the RWT system; Yw is the lifetime year of the system; and Ean is the annual energy generated
from the system. The battery life time is represented by the number of charge cycles. Therefore,
the cost of battery used per kWh can be calculated by the following equation:

Cb [ Bl (t ) Bg (t )]

Bc
Bmax

(5)
where Bc is the cost of using battery bank per charge cycle, and Bmax is the capacity of the battery
bank.
The cost for purchasing electricity from the grid, Cg, can be calculated by the following equation:

Cg Pb [Gl (t ) Gg (t )]

(6)
Where R is the profit which comes from the electricity sold to the grid.

R Ps [Wg (t ) Bg (t )]

(7)

109

For the purpose of economic evaluation, the tax credit subsidy is set at 30% of total RWT system
investment (includes the wind turbine and battery bank). Note that inflation rate and discount rate
are not considered in this research.
Outage frequency
When a grid outage occurs, the on-the-grid residential customer can obtain electricity supply from
the wind turbine or battery discharge. If the two resources can satisfy the household load demand,
the residential will not suffer from the grid outage. In this research, if the chosen combination of
battery capacity and RWT can successfully satisfy the load demand during an outage event
created by Monte Carlo simulation, the event is defined as a successful interruption avoidance
event. Outage rate is expressed as

OU 1

sum( N (t ))
8760

(8)
Where N(t) is a successful interruption avoidance event, sum(N) is the total successful
interruption avoidance event, 8760 is the total number of hours in a year.

Wasted wind power

With the grid outage occurs at time t, the energy generated by wind turbine, W l(t), or stored in
battery bank W b(t) can be used instead. If the total wind power W r(t) is more than Wl(t) and W b(t)
combined, the excess electricity will be wasted, because it cannot be sold to the grid during
outage. The wasted energy is defined as W w(t), which can be calculated during the Monte Carlo
simulation.
MONTE CARLO SIMULATION
This paper proposed a simulation to investigate the optimal configuration of RWT with battery
storage for a residential customer. It is intended to reflect stochastic events based on the
residential demand profiles, the outage statistics and the incorporation of wind power.
The process of the proposed Monte Carlo simulation for RWT with battery storage system
optimization is illustrated in the flow chart as presented in Fig.2.

Battery specs

Wind turbine
specs

Wind
Speed

Residential
load profile

Monte Carlo Simulation

RWT
Market electricity price
Optimal sizing
Cost of RWT
Store the optimal
parameters

Economic analysis
Fig. 2 Overview of battery sizing for on-the-grid RWT by considering grid outage

110

Outage
statistics

Simulation process
The process starts by acquiring the annual input data, which includes the hourly wind speed,
market electricity price, hourly load profile. The data of specified RWT and battery bank is also
input at this stage. In the Monte Carlo simulation, random outage events are created from random
numbers in which the frequency of outage is based on the probability of the local outage statistics.
The outage occurrence time is assumed to 1hour in this research.
If outage occurs at time t, W w(t) and N(t) can be determined as a function of W r(t), Bl(t), H(t), D(t),
Dd(t), Dmin(t), Dmax(t). There are several conditions about W w(t) and N(t):
(1) W r(t)H(t), H(t) can be satisfied during outage occurrence time, a successful interruption
avoidance event happens and N(t) equals to 1. If H(t) and battery charge are both satisfied
by electricity generated by RWT, there will exist wind power waste, which can be calculated as
follow expression:
Ww (t ) Wr (t ) ( H (t ) Dc )
If
,
Dmax D(t ) Dc
(9)
or
Ww (t ) Wr (t ) H (t ) ( Dmax D(t ))
if
Dmax D(t ) Dc
(10)
(2) When Wr (t ) H (t ) , if Dc Wr (t ) H (t ) or D(t ) Dmim Wr (t ) H (t )

N (t ) will be equal to 1; otherwise N (t ) equals to 0

If outage does not occur at time t, N(t) equals to 1 and W w(t) equals to 0. The simulation will
decide whether to buy or sell electricity from or to the grid according to the price and the relations
among H(t), W r(t), D(t), Dd(t), Dmin(t), Dmax(t). The principles are:
(1) When W r(t)H(t) and the price is higher than the average price, all the extra electricity
generated by the RWT will be sold to the grid.
(2) When W r(t)H(t) and the price is lower than the average price, the extra electricity will be
stored in the battery bank first. Then the left electricity will be sold to the grid.
(3) When W r(t)H(t) and the price is higher than the average price, the battery bank will discharge
to meet the customers load demand first. Then, the system will resort to the grid.
(4) When W r(t)H(t) and the price is lower than the average price, the customer will buy electricity
from the grid directly.
CASE STUDY
Case study setup
The developed methodology is applied for a hypothetical residential customer located in California,
U.S.A. The hourly averaged wind speed data for this study is taken from San Clemente Island
Data, Instrumentation Data center (MIDC) at National Renewable Energy Laboratory. The wind
speed data at different heights are adopted to comply with the different types of wind turbine. The
hourly load profile of a typical residential customer in California is taken from Southern California
Edison (SCE) for year 2013. The statistics of the outage information are obtained from California
Public Utilities Commission, which covers the outage events from 1998-2013 for 5 major utility
companies served in California (CPUC, 2013). The outage statistics of Edison company is chosen
because the load profile data is obtained from the same company. The electricity pricing
information is obtained from Pacific Gas and Electric (PG&E, 2014), which supplies electricity in
California. The information consists of peak, partial-peak and off-peak spot market prices of
different tiers. In this research, supplemented by RWT system, the residential customer has no
need to purchase too much electricity from the utility. Hence, the baseline price is used in the
analysis.
Table 1. PG&E residential time-of-use electric rate schedule
Time -of-Use
Total Energy Rates ($/KWh)
Period
Peak
Partial-Peak
Baseline
$0.2958
$0.1805

Off-Peak
$0.1038

Based on a typical residential customers load profile located in California, several different rated
power RWTs and battery capacity are chosen to apply to the proposed approach. The component
costs of the RWT system with battery storage of different types are summarized in Table 2. The
annual operational and management cost is assumed to be 1% of the initial system capital cost.
Meanwhile, according to California State PTC, the customer of small wind turbine can receive a

111

maximum of 50% capital cost credit back. Therefore, in this study, 30% of the total system costs
including capital, maintenance, and battery bank are assumed to be covered by PTC.
Table 2. Costs of RWT system components
Components
Initial
Maintenance
cost
cost
Wind turbine (1.0KW)
$2,500
25$/year
Wind turbine (1.5KW)
$3,750
37.50$/year
Wind turbine (2.0KW)
$6,250
63$/year
Wind turbine (2.5KW)
$8,500
85$/year
Wind turbine (3.0KW)
$10,000
100$/year
Wind turbine (3.5KW)
$11,000
110$/year
Wind turbine (4.0KW)
$12,000
120$/year
Battery bank (100Ah)
$400
Null
Battery bank (200Ah)
$600
Null
Battery bank (300Ah)
$1,600
Null
Battery bank (400Ah)
$2,500
Null
Battery bank (500Ah)
$4,000
Null

Life time

Annual
power
output
2000 KWh
3,000 KWh
5,000 KWh
7000 KWh
8,500 KWh
9,500 KWh
12,000 KWh
Null
Null
Null
Null
Null

25 yrs
25 yrs
25 yrs
25 yrs
25 yrs
25 yrs
25 yrs
3000cycle
3000cycle
3000cycle
3000cycle
3000cycle

Unit cost
0.063$/KWh
0.063$/KWh
0.063$/KWh
0.061$/KWh
0.059$/KWh
0.058$/KWh
0.050$/KWh
0.13$/cycle
0.2$/cycle
0.53 $/cycle
0.83$/cycle
1.33$/cycle

Adjusted unit
(70% unit cost)
0.044$/KWh
0.044$/KWh
0.044$/KWh
0.043$/KWh
0.041$/KWh
0.041$/KWh
0.035$/KWh
0.09 $/cycle
0.14$/cycle
0.37$/cycle
0.58$/cycle
0.93$/cycle

Results and analysis

The results of Monte-Carlo simulation and the economic evaluation of a on-the-grid RWT system
with battery storage are showed in Tables 3-5.
Table 3. Customers total electricity cost under different configurations of wind turbine and battery bank
Battery
Cost
100Ah
200Ah
300Ah
400Ah
RWT
1.0 KW
$358.16
$338.42
$243.01
$245.04
1.5 KW
$375.34
$195.70
$438.13
-$106.99
2.0 KW
$358.16
-$877.00
$242.72
-$392.32
2.5 KW
$213.12
-$879.00
-$831.00
-$451.87
3.0 KW
-$753.21
-$921.34
-$875.74
-$835.22
3.5 KW
-$1630.00
-$1650.00
-$1604.00
-$877.27
4.0 KW
-$1816.00
-$1837.00
-$1787.00
-$1606.00

500Ah
$297.74
-$50.00
-$49.20
-$771.45
-$813.88
-$1548.00
-$1730.00

customers total electricity cost

1000

Cost($)

500
100Ah

0
-500

1.5

2.5

3.5

200Ah
300Ah
400Ah

-1000

500Ah
-1500
-2000
RWT(KW)

Fig. 3. Customers total electricity cost with respect to the rating combinations of RWT and battery bank

From Table 3 and Figure 3, it can be observed that when battery capacity is fixed, with the
increase of rated power of RWT, the residential customers total cost of electricity decreases.
When the rated power of RWT is fixed, with the increase of battery capacity, the same observation
can be obtained. The optimal configuration is 4KWh wind turbine combined with a 200 Ah battery
bank, under which the customer can earn $1,837. Meanwhile, the electricity supply can be
guaranteed. Considering the life span of 25 years for the RWT, the waste of 36 KWh wind power is
almost negligible.

112

cost

Table 4. Outage frequency under various configurations of wind turbine and battery bank
Outage Battery
100Ah
200Ah
300Ah
400Ah
RWT
1.0 KW
0.0007
0.001
0
0.0001
1.5 KW
0.0003
0
0.0003
0
2.0 KW
0.0005
0
0
0
2.5 KW
0.0004
0
0
0
3.0 KW
0
0
0
0
3.5 KW
0
0
0
0
4.0 KW
0
0
0
0

500Ah
0.0005
0.0002
0
0
0
0
0

Table 4 shows that when the battery capacity and the rated power of RWT are both small, the
outage frequency is relatively high. This is certainly intuitive because larger battery banks and
RWT capacities can reduce the occurrence of power supply disruption. Table 5 shows that smaller
battery banks and rated powers of RWT can lead to less wasted wind power. However, if the long
life span of the system is taken into consideration, all those configurations are thought to be
effective.

Table 5. Wasted generated power under various configurations of wind turbine and battery bank
Waste
RWT
1.0 KW
1.5 KW
2.0 KW
2.5 KW
3.0 KW
3.5 KW
4.0 KW

Battery
100Ah
2.18
1.30
1.83
10.87
12.53
69.24
16.73

200Ah

300Ah

400Ah

500Ah

1.64
2.02
18.40
15.45
20.56
37.79
36.08

1.80
1.00
1.79
16.96
20.89
32.60
37.45

1.96
7.65
5.73
1.01
24.56
12.79
33.22

0.74
4.09
3.59
10.09
3.83
47.09
24.55

Based on the actual load profile, outage statistics and wind speed, the electricity cost of a typical
residential customer without the RWT system is obtained as $40,213. This indicates that even with
no tax credit policy, this system can still bring monetary benefits to the customer. Table 6
summarizes the customers total electricity cost under various combinations of RWT rating and
battery capacity, when no tax credit policy is available.
Table 6.Customers total electricity cost under various configurations of wind turbine and battery bank
Battery
Cost
100Ah
200Ah
300Ah
400Ah
RWT
1.0 KW
$358.16
$338.42
$243.01
$245.04
1.5 KW
$375.34
$195.70
$438.13
-$106.99
2.0 KW
$358.16
-$877.00
$242.72
-$392.32
2.5 KW
$213.12
-$879.00
-$831.00
-$451.87
3.0 KW
-$753.21
-$921.34
-$875.74
-$835.22
3.5 KW
-$1630.00
-$1650.00
-$1604.00
-$877.27
4.0 KW
-$1816.00
-$1837.00
-$1787.00
-$1606.00

500Ah
$297.74
-$50.00
-$49.20
-$771.45
-$813.88
-$1548.00
-$1730.00

CONCLUSIONS
This paper proposes a methodology to find the optimal configuration for on-the-grid RWT system
with battery storage for a residential customer from a list of configurations on RWT power ratings
and battery capacity. By adopting such systems, we consider the beneficial aspects of cost
savings and mitigating power outages. The approach is coded in Matlab, and uses Monte Carlo
simulation to generate key random variables. It is found that for a residential family in California
U.S.A, the addition of battery storage can indeed reduce the total cost and the disruption of power

113

supply to the household. In the future, a new stochastic optimization model that is more general
and robust needs to be developed to solve this problem.
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115

EFFECTS OF THE AERODYNAMIC DAMPING ON THE TOWER LOAD OF

OFFSHORE HORIZONTAL AXIS WIND TURBINES
a

Xiong Liu

a,b

, Cheng Lu , Gangqiang Li , Yan Chen , Hongche Guo

School of Mechanical, Materials and Mechatronic Engineering, University of Wollongong, NSW 2522,
Australia
b
School of Engineering, Shantou University, Shantou 515063, China
c
Jinan Railway Vehicles Equipment Co. LTD, Jinan 250022, China
Authors' e-mails: xiongliu1975@gmail.com

ABSTRACT
In the present work, the effects of aerodynamic damping on the tower load of offshore horizontal axis
wind turbines (HAWTs) are investigated. The aerodynamic load analysis is based on the blade
element-momentum (BEM) theory, with the consideration of transient aerodynamics, including
dynamic wake and dynamic stall. The wave load is calculated using Morisons equation. The
structural dynamics of the tubular tower is modelled using finite element method (FEM), while the
tower is treated as a cantilever and discretised using two-node beam elements. An aerodynamic
damping model is presented and the methods of calculating the damping ratio of variable speed
HAWTs are introduced, based on which the time-varying aerodynamic damping can be
instantaneously calculated and applied to the time-domain solution of the equation of motion of the
tower. Power production load cases of a 5 MW offshore HAWT operating in turbulent wind fields are
simulated. It is found that when considering aerodynamic damping, the deflection of the tower top
can be significantly reduced. Moreover, the fatigue loads of the tower are calculated according to the
Germanischer Lloyd (GL) regulation. The results indicate that aerodynamic damping can greatly
affect the fatigue loads of the offshore HAWT tower.
Keywords: offshore wind turbine; aerodynamic damping; wave load; dynamic response; fatigue
load
INTRODUCTION
In recent years, wind power has gained rapid development due to the significant reduction of its
energy cost. Currently wind power has reached a global capacity of 318 GW and for the past 5 years
increased in installed capacity by 12-30% each year (GWEC, 2014). The emerging problem is that in
some countries the best onshore spots have already been occupied and the public will no longer
accept a significant increase of onshore wind power capacity. The exploitation of the huge offshore
wind resource, with considerably less environmental impact than large onshore wind farms, will then
become crucial in providing for future green energy needs (Khn, 2001).
Although offshore wind resources are of better quality and more abundant, the more severe
environment demands extra design considerations for offshore wind turbines to ensure safe
operation. One important problem to take into account is the combined effects of wind and wave
loading. To accurately estimate the lifetime loading, attentions should be paid to the damping
estimation as well as the load calculation methods, because damping is crucial for lifetime predictions
as it can significantly reduce the amplitude of vibrations (Shirzadeh et al., 2013). The damping of an
offshore wind turbine consists of a combination of structural damping, soil damping, hydrodynamic
damping and aerodynamic damping, within which the aerodynamic damping may play key role in
restraining vibrations (Petersen et al., 1998; Khn, 2001; Salzmann and Tempel, 2005; Hansen et
al., 2006; Shirzadeh et al., 2013). Previous researches indicate that the aerodynamic damping can
reach one hundred times the structural damping for wind turbine blades (Liu et al., 2010) and ten
times the structural damping for towers (Khn, 2001). As damping has an important impact on the
fatigue damage, research is still required to gain more knowledge of the aerodynamic damping
effects of offshore wind turbines and to allow for accurate lifetime prediction.
In the following sections, an aerodynamic damping model is presented to incorporate the timedomain load analysis of offshore horizontal axis wind turbines (HAWTs). Through simulations of
power production load cases of a 5 MW offshore HAWT, the influences of aerodynamic damping on
the deflection and the fatigue load of the tubular tower are discussed.
FINITE ELEMENT MODEL AND THE EQUATION OF MOTION OF THE TOWER
To simplify the problem, an offshore HAWT with a tubular tower installed on a monopile foundation is
studied. The HAWT tower usually has a large aspect ratio and can be treated as a cantilever.
Therefore it is discretised using two-node beam elements (Clough and Penzien, 1993). According to

116

the principle of minimum potential energy, the finite element dynamic equation of motion of the tower
is obtained as (Clough and Penzien, 1993)

Mx(t ) Cx (t ) Kx(t ) P(t )

(1)

where M is the mass matrix, C the damping matrix, and K the stiffness matrix; (t), (t), x(t) are the
acceleration, velocity and displacement vectors of the finite element node respectively; P(t) is the
time-varying load matrix.
ANALYSIS OF OFFSHORE HAWT TOWER LOADING
For an offshore HAWT, the major components of the loading exerted on the tower (see Fig. 1) are
the wave loads, the windage loads, the tower self-weight, and the loads fed in at tower top from
the rotor and nacelle including aerodynamic and gravitational loads. As the aerodynamic damping
provided by the rotor mainly affects the tower response in the fore-aft direction (i.e. the along-wind
direction) and is negligible in the side-to-side direction (Khn, 2001), in the following sections, only
loads affecting tower deflection in the fore-aft direction are analysed.
M YT
FXT

Windage loads

Tower top

Tower

Platform
Sea level
d

Wave loads
Seabed

Fig.1. Loads acting on an offshore HAWT tower.

To account for the loads and deflections, a blade coordinate system and a tower coordinate system
(GL, 2005) are defined in Fig. 2. In the blade coordinate system: ZB is radially along blade axis; XB is
in direction of the rotor axis; YB is perpendicular to the blade axis and rotor axis. In the tower
coordinate system: ZT is vertically upwards; XT is horizontally pointing downwind; YT is
perpendicular to ZT and XT.
M ZB

M ZT

M XB

FZT

M XT

FZB

M YB

FYB

M YT

ZB
YB

XB

FXB

ZT

FYT

YT

a. Blade coordinate system

FXT

XT

b. Tower coordinate system

Fig.2. Coordinate systems for loads and deflections.

117

Aerodynamic Loads
In this study, aerodynamic loads of the wind turbine blade are calculated using the blade elementmomentum (BEM) theory (Burton et al., 2001; Spera, 2009). As BEM theory is developed for a wind
turbine operating in steady wind, it is amended by introducing dynamic inflow and dynamic stall
models to account for the transient aerodynamics caused by wind turbulence, yawing, rotational
speed regulation and pitch regulation (Liu et al., 2010), which are common to a wind turbine
operating in the field.
BEM theory is based on the momentum theory and blade element theory. In the momentum theory,
the wind turbine rotor is considered as an energy extracting actuator disc rotating in a stream tube
(Burton et al., 2001; Spera, 2009). The axial force T and torque Q per unit length on the annulus of
the actuator disc can then be obtained based on the conservation of momentum in both axial and
rotational directions as

dT
4 U 2 ra(1 a )
dr
dQ
4 Ur3a' (1 a )
dr

(2)
(3)

where is the air density, U the upstream wind velocity, r the radius, a the axial flow induction factor,
a the tangential flow induction factor, the rotational velocity.

The blade element theory is based on airfoil aerodynamics (Burton et al., 2001; Spera, 2009).
Considering a blade section at radius r, the normal force and tangential force per unit length are
given as

dFXB 1
W 2cCL cos CD sin
dr
2
dFYB
1
W 2cCL sin CD cos
dr
2

(4)
(5)

where CL and CD are the lift coefficient and drag coefficient of the airfoil respectively, W the relative
velocity of airflow at the blade section, the inflow angle, and c the airfoil chord length. Eqs. (2) to (5)
can be solved using a Newton-Raphson iteration.
The momentum theory assumes that the induced velocity flow field reacts instantaneously to the
changes in blade loading, while in reality the full effect of these changes takes a finite time to change
the induced flow field (Burton et al., 2001). The dynamics associated with this process is commonly
referred to as dynamic inflow, which is taken into account using the model based on the work of Pitt
and Peters (1981). The model is applied at actuator annuli level and consequently Eq. (2) is
amended as (Liu et al., 2010)

dT
4 U 2 ra(1 a ) 8Ur 2 a
dr

(6)

Eq. (6) can then be used to replace Eq. (2) in the momentum theory. It is evident that it introduces a
time lag into the calculation of inflow which is dependent on the radial station.
When a wind turbine is operating in steady condition, static values of lift and drag coefficients of
airfoils can be applied to Eqs. (4) and (5) to estimate the blade loads. However, in reality wind
turbines work in highly unsteady conditions. The wind turbulence, yawing, pitch and rotational speed
regulation can all lead to dynamic variations of the angle of attack of the airfoil and the resulted
transient airfoil aerodynamics can considerably affect the loading on the blade. To account for these
effects, the Beddoes-Leishman (B-L) dynamic stall model (Leishman and Beddoes, 1989) is
employed to calculate the transient airfoil aerodynamics. As wind turbine airfoils are relatively thick
and work at low Mach numbers (Hansen et al., 2004), the flow can be assumed incompressible and
the leading edge separation is assumed not to be a dominating phenomenon. Therefore two
elements of the original B-L model are utilised (Bossanyi, 2008): 1) the indicial response functions for

118

the modeling of attached flow; 2) the time lagged Kirchoff formulation for the modeling of trailing edge
separation and vortex lift. Using B-L model, the unsteady lift coefficient CL and drag coefficient CD can
then be obtained during time-domain simulation and consequently applied to Eqs. (4) and (5).
Through integrations of Eqs. (4) and (5), the normal and tangential forces over the whole blade can
be obtained and transmitted to the tower top. Considering the number of blades B, the rotor azimuth
angle , the shaft tilt angle , and the rotor cone angle , the force exerted on the tower top in the
fore-aft direction (see Fig. 1) may be given as

FXT BFXB sin sin BFYB cos cos sin sin cos

(7)

Wave Loads
Hydrodynamic loading on offshore structures is made of several components, including viscous drag
loading, inertia loading, dynamic pressure loading, diffraction loading and etc (Khn, 2001). If a
member is small compared with the wavelength, the water particle motions are only locally affected
by the member and the forces can be calculated from the drag and inertia components using
Morisons equation (Ris, 2002). In this study, the diameter of the cross-section of the tower and pile
is considered to be less than 1/5 of the wavelength, while in this condition, using Morisons equation
to estimate wave loading is enough and other components can be neglected. Thus the horizontal
force on the structure per unit length at level z is expressed as (Morison et al., 1950)

dFw 1
1
w D 2U wCM w D U w U wCD
dz
4
2

(8)

where z is the depth below the still water measured negatively downward, w the density of water,
CM the hydrodynamic inertia coefficient, CD the hydrodynamic drag coefficient, and Uw the
horizontal wave-induced velocity.
The horizontal wave-induced velocity and acceleration can be estimated using the first-order linear
wave theory (Ris, 2002):

coshk ( z d )
sin(t )
sinh(kd )
coshk ( z d )
U w Aw 2
cos(t )
sinh(kd )

U w Aw

(9)

(10)

where Aw is the wave amplitude, the angular velocity ( = 2/Tp), Tp the wave period, k the wave
number, d the water depth, and t the time.
Windage and gravitational Loads
For a tubular tower, the windage load (Ris, 2002) per unit length at height z in the fore-aft
direction may be simply given as

dFW 1
U 2 DCD
dh
2

(11)

where h is the height above the sea level, D the outer diameter of the tower station, CD the
aerodynamic drag coefficient of the tower station.
To account for the gravitational loads which will affect the tower deflection in the fore-aft direction, the
rotor together with the nacelle is treated as a point mass. If the sum of their masses is ms and the
mass centre is at (xs, ys, zs) in the tower coordinate system, the tower top moment MYT (see Fig. 1)
can be obtained as

M YT ms gxs

(12)

119

where g is the gravitational acceleration.

AERODYNAMIC DAMPING
As mentioned above, for an offshore HAWT the tower motion may be resisted by structural damping,
soil damping, hydrodynamic damping and aerodynamic damping. The structural damping is related
to the material used. For a steel tubular tower, the structural modal damping ratio is usually less than
1% and in general a value of 0.5% is applied. While the foundation in the seabed and the pile in the
water in this study are assumed relatively rigid, the soil damping and hydrodynamic damping can be
neglected. The aerodynamic damping experienced by a structure in the air is generally less than the
structural damping, but this does not apply to a HAWT, where the aerodynamic damping is induced
by the rotor aerodynamics and could be much higher than the structural damping (Khn, 2001; Liu et
al., 2010).
The Mechanism of Aerodynamic Damping
Fig. 3 shows the generation of aerodynamic damping. If the tow top experience a perturbation in the
wind direction with velocity xtop, the apparent out of plane velocity component of a blade section, U(1a), will be reduced by xtop according to the BEM theory (see Fig. 3(a)). This will lower the angle of
attack, , resulting in a reduction of the lift force, dL, and drag force, dD, for attached flow conditions.
Consequently, the thrust force, dFXB, is reduced by dFXB, acting as a resistance to the downwind
motion. Likewise a perturbation of the tower top against the wind direction increases both the angle
of attack and the thrust force (see Fig. 3(c)), while the thrust force increment also resists the initial
perturbation. In either situation the alteration of the thrust force is against the disturbing tower top
motion and this is experienced as aerodynamic damping (Khn, 2001).

d F XB d F XB

r (1 a ' )

U (1 a ) x to p

dD

r (1 a ' )

dL

CL

a. tower top motion in

wind direction

d F XB d F XB

r (1 a ' )

U (1 a ) x to p

U (1 a )

CL

d F XB

CL

b. no tower top motion

c. tower top motion against

wind direction

Fig.3. Velocity and force diagram for vibrating blade according to tower top motion, adapted from K hn (2001).

When the airfoil is operating in stall, the aerodynamic damping can be lower or even negative,
meaning that the flow supplies energy to the tower. This may result in a potentially self-exciting
system if the aerodynamic damping supplied by the rotor becomes negative. The stall induced
vibration will occur when the energy cannot be removed through structural damping, leading to
damages of the structure (Petersen et al., 1998; Khn, 2001; Liu et al., 2010).
Aerodynamic damping also occurs in the tower top lateral motion but the interaction is much less
pronounced. In normal sea state, the waves usually propagate in the direction of the wind. It was also
demonstrated that this assumption is conservative and thus acceptable to assume that the wind and
waves are aligned (GL, 2005). Therefore, we would expect that the aerodynamic damping will reduce
the tower vibrations caused by waves and consequently alleviate the tower fatigue loads.
Aerodynamic Damping Model

120

As mentioned above, the aerodynamic damping is induced by the interaction between the structural
motion and the rotor aerodynamics. Accordingly it can be derived based on the analysis of the rotor
aerodynamics incorporating the tower top motion.
The derivation can be started from considering a constant speed wind turbine (Freris, 1990;
Salzmann and Tempel, 2005). Considering the velocity components of an airfoil shown in Fig. 3, let
Ur = r(1 + a) and Ud = U(1 - a) xtop. If assuming small inflow angle (cos 1), high tip speed ratio
(Ur >> Ud) and attached flow (CL >> CD), Eq. (4) may be reduced to

dFXB 1
U r2C L c
dr
2

(13)

As Ur >> Ud, one can assume

Ud
Ur

(14)

A constant speed HAWT gives

dU d
Ur

(15)

The slope of the lift coefficient can be written as CL = dCL / d. While the inflow angle = +
and the twist angle is a constant, one can get

dCL CL' d CL'

dU d
Ur

(16)

Differentiation of Eq. (13) gives

1
dF 1
d XB U r2cdC L U r cC L' dU d
2
dr 2

(17)

As shown in Fig. 3, the change in apparent axial wind speed Ud is due to changes in the wind speed
and the structural motion. Therefore

dU d u x

(18)

where u is the change in the axial wind speed and x the structural velocity whose sign is positive
when in the direction of the wind.
Eq. (17) can be rewritten as

dF 1
T ' d XB U r cC L' (u x )
dr 2

(19)

For a 1 DOF mass-spring system, the equation of motion mx + Kx = T applies and can be rewritten
as

1
1
mx U r cCL' x Kx U r cCL' u
2
2

(20)

Eq. (20) suggests that the aerodynamic damping per unit length is

121

dca 1
U r cC L'
dr 2

(21)

The aerodynamic damping of the entire rotor can then be obtained by integration of Eq. (21) along
the blade:

ca

B R '
CLcrdr
2 R0

(22)

where R0 is the blade root radius, and R the rotor radius.

Consequently the aerodynamic damping ratio for the nth mode can be defined as

ca
B

2M nn 4M nn

R0

CL' crdr

(23)

where Mn is the nth modal mass, and n the nth natural frequency.
For a variable speed HAWT, the change of wind speed results in the change of rotor speed, thus Eq.
(15) no longer applies and should be replaced by

U
d d d
Ur

(24)

Although the change in rotor speed is slow, it cannot be neglected. To simplify the derivation, a
correction factor b is introduced and Eq. (24) is changed to

d b

dU d
Ur

(25)

For a variable speed HAWT, Eq. (23) can then be replaced by

ca
B

2M nn 4M nn

R0

CL' bcrdr

(26)

It should be noted that the above derivation is based on the neglect of the drag term. At high wind
speeds near cut-out, the drag term may considerably contribute to the thrust thus can no longer be
neglected. The larger drag term will lead to more aerodynamic damping. Therefore using Eq. (26)
is an approximation and may under-predict the aerodynamic damping at high wind speeds.
RESULTS AND DISCUSSION
Applying the proposed model, a 5 MW offshore HAWT (see Table 1 for the turbine parameters) is
studied. The offshore HAWT is assumed to operating in turbulent wind fields. Fig. 4 shows the
longitudinal component of a turbulent wind field with an average wind speed of 12 m s-1 at hub centre
and a turbulence intensity of 19.6%.
Table 1. Parameters of the studied HAWT.
Wind turbine class
IEC IIA
Rotor diameter (m)
118
Blade length (m)
57
Number of blades
3
Hub height (m)
81
Rated wind speed (m s-1)
12.3
Rotational speed (r min-1)
7.5 13.9
Tower height (m)
79
Tower base diameter (m)
5.5
Tower top diameter (m)
3.8

122

Tower material
Water depth (m)
Structural damping ratio

Q-345
20
0.5%

Wind speed [m s-1]

20
15
10
5
0

100

200

300
Time [s]

400

500

600

Fig.4. Longitudinal wind speed at hub height.

0.06

0.8

d = 0.93(dUd / Ur ) - 9e-6

Correction factor b

0.04

0.02
0
-0.02

0.4

20.82m
30.5m
40.72m
52.01m

0.2

-0.04
-0.06
-0.06

0.6

-0.04

-0.02

0
dUd /Ur

0.02

0.04

0.06 00

a) Linear regression for determining b

10
15
Wind speed at hub centre [m s-1]

20

b) b as a function of wind speed and radius

Fig.5. Determination of correction factor b.

Operating in the 12 m s-1 turbulent wind field, the relationship between d and dUd / Ur at a blade
section 30.5 m from hub centre is shown in Fig. 5(a). It is found that linear regression of the data
points gives a straight line almost exactly passing the origin. Therefore the slop of the obtained line
can be considered as the correction factor b in Eq. (25) at this blade section for 12 m s-1 wind.
Through simulations using a number of turbulent wind fields with different mean wind speeds, the
relationship between correction factor b and mean wind speed at different blade sections can be
revealed. Fig. 5(b) shows correction factor b as a function of wind speed at four blade stations. It is
found that higher wind speed corresponds to more correction. Also, the blade section closer to the
hub centre needs more correction. Clearly, within the normal operational wind conditions, the
correction factor considerably deviates from 1 in most cases, which suggests that the correction
factor should be taken into consideration when determining the aerodynamic damping of a variable
speed wind turbine.
Also using the 12 m s-1 wind field (see Fig. 4), the time history of the first modal aerodynamic
damping ratio of the tower in the fore-aft direction during power production is calculated and shown in
Fig. 6. During this period, we can find that the aerodynamic damping ratio is varying between 0.6%
and 3.4%, averaged to a value of 2.8%. In this case, the overall aerodynamic damping ratio of the
tower maintains positive, which can restrain the vibration. As the structural damping ratio of a tubular
steel HAWT tower is around 0.5%, much lower than the aerodynamic damping ratio, surely the
aerodynamic damping will dominate the structural response of the tower.

123

25

Aerodynamic damping ratio

0.04
0.03
0.02
0.01
0
0

100

200

300
Time [s]

400

500

600

Fig.6. Time history of the first modal aerodynamic damping ratio of the tower in for-aft direction (12 m s-1 turbulent wind field used)

To implement the time-domain load analysis, Eq. (1) is solved using Newmark method (Clough and
Penzien, 1993), with the overall damping ratio introduced by superposition of aerodynamic and
structural damping ratios, while the aerodynamic damping ratio is calculated instantaneously during
simulation. A power production load case is simulated using the 12 m s-1 wind field (see Fig. 4) and
the influence of aerodynamic damping on the tower deflection is shown in Fig. 7. In order to give a
clearer comparison, only the tower top deflection results between 100 s and 400 s are displayed. It is
clear that the aerodynamic damping considerably affects the tower deflection by reducing the
vibration amplitude. If considering the aerodynamic damping, the mean decrease of the tower top
vibration amplitude in the simulation duration is about 14.8%. Therefore in the wind turbine design
procedure, in order to predict accurate tower deflection and fatigue load, it is very important to take
into account the aerodynamic damping. It should also be noted that the tower of large-scale HAWT
undergoes considerable deflection in the fore-aft direction, even if it is operating in an ordinary
turbulent wind field. In this case (see Fig. 7), the maximum tower top deflection can reach 0.7 m,
which may be big enough to influence the structural stability and turbine security, thus we should
sufficiently take into account the dynamic response of the tower in the design stage.
0.8

Deflection [m]

0.6
0.4
0.2
0
-0.2
100

With aerodynamic damping

Without aerodynamic damping
150

200

250
Time [s]
Fig.7. Tower top deflection during power production (12 m s-1 turbulent wind field used)

300

350

According to the Germanischer Lloyd (GL) regulation, the damage equivalent fatigue loads of the
tower over its lifetime are calculated. As the wind turbine class of the 5 MW HAWT is IEC IIA, a
Rayleigh wind speed distribution with an annual mean wind speed of 8.5 m s-1 is assumed for loading
calculation. The combined wind wave distribution is determined using scatter diagrams of a specific
offshore site obtained from long term statistics, including wave height, wave period and wind speed.
Table 2 shows the wave parameters for two wind speeds and the combined wind wave probability
density, which are used in the time-domain simulations of fatigue load cases.
Table 2. Wave Parameters and the probability density of wind in conjunction with waves (only showing two wind speeds)
Tp [s]
Tp [s]
Wind speed
Wind speed
Aw
Aw
[m s-1]
[m s-1]
[m]
[m]
5.71
6.08
6.42
9.65
10.10
10.71
1.43
0.0693
5.01
0.0022
12
1.78
0.0461
24
5.78
0.0015
2.29
0.0232
6.53
0.0007

124

400

As the fatigue loading mostly comes from power production, only power production load cases (DLC
1.2) are simulated subsequently to evaluate the fatigue loads. In order to investigate the influence of
aerodynamic damping on the tower fatigue loading, each load case is simulated using three
conditions: 1) considering only the wind; 2) considering only the waves; 3) with both wind and waves
in action. The equivalent fatigue loads are then figured out for each load component assuming 1.0
107 cycles in the turbine lifetime of 20 years. Fig. 8 gives the obtained equivalent fatigue load of tower
base moment My, showing the load values for three conditions. It is found that the actual fatigue load
is significantly less than the superposition of the fatigue load of considering only the wind and that of
considering only the waves. Moreover, it is less than the fatigue load of considering only the waves,
which means that the introduction of wind does not increase but reduces the fatigue load
considerably. This is mainly due to the aerodynamic damping analysed above, which restrains the
tower vibrations induced by hydrodynamic forces as the wind and waves are co-directional.

Tower base moment M y [kNm]

10

10

8
6
4
2

Only wind

Only waves Wind&waves Superposition

Fig.8. Lifetime weighted equivalent fatigue loads: My at tower base

CONCLUSIONS
In the present study, a comprehensive load analysis model including the calculation of transient
aerodynamic loading, wave loading and structural dynamics of the tower is proposed. An
aerodynamic damping model is introduced to account for the damping caused by the rotor
aerodynamics, based on which the influence of aerodynamic damping on the offshore HAWT tower
load can be investigated.
It is found that the aerodynamic damping can significantly affect the structural response and the
fatigue load of the tower. When considering aerodynamic damping, the tower top deflection of the 5
MW offshore HAWT can be reduced by 14.8% in a normal turbulent wind field. Also, the life-time
fatigue load of the tower under the combined effects of wind and waves can be alleviated to be lower
than that with only waves in action. Therefore in the wind turbine design stage, the aerodynamic
damping should be taken into account to obtain a safe and optimised design.
The developed simulation code provides a valuable platform for future studies. Also, the positive
aspects of the aerodynamic damping give a perspective of reducing the wind turbine fatigue load
through actively introducing aerodynamic damping during operation via controlling the rotor
aerodynamics.
ACKNOWLEDGEMENT
This research is co-supported by the National Natural Science Foundation of China (Grant No.
51276106), the Specialized Research Fund for the Doctoral Program of Higher Education (Grant No.
20124402110005), and the Key Project of Chinese Ministry of Education (Grant No. 212130). The
authors are grateful for their financial supports.
NOMENCLATURE
a
axial flow induction factor, dimensionless
a
tangential flow induction factor, dimensionless
Aw
wave amplitude, m
b
correction factor, dimensionless

125

B
c
ca
CD
CL
CM
CT
C
d
D
F
g
h
k
K
L
m
M
M
P
Q
r
R
t
T
Tp
U
Uw
W

number of blades, dimensionless

chord length, m
aerodynamic dampin, N s m-1
drag coefficient, dimensionless
lift coefficient, dimensionless
hydrodynamic drag coefficient, dimensionless
thrust coefficient, dimensionless
damping matrix
water depth, m
diameter, m; drag force, N
force, N
gravitational acceleration, 9.8 m s-2
height, m
wave number, dimensionless
stiffness matrix
lift force, N
mass, kg
moment, N m; modal mass
mass matrix
load matrix
torque, N m
radius, m
rotor radius, m
time, s
thrust, N
wave period, s
wind velocity, m
wave induced velocity, m s-1
relative velocity, m s-1

Greek Letters

air density, kg m-3

water density, kg m-3
w

inflow angle, rad

azimuth angle, rad

shaft tilt angle, rad

rotor cone angle, rad; twist angle, rad

wave angular velocity, rad s-1; natural frequency, Hz

rotor rotational speedrad s-1

modal aerodynamic damping ratio, dimensionless

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127

VECTOR AUTO REGRESSIVE MODELS WITH EXOGENOUS VARIABLES FOR

PREDICTING WIND SPEED
1

Ergin Erdem , Ying She , Jing Shi , Steve Hsueh Ming Wang
1
2
3
North Dakota State University , Nanchang Hangkong University , University of Alaska Anchorage
1
1410 14th Avenue N., Fargo, ND 58108, USA
2
Nanchang, Jiangxi Province 330063, China
3
3211 Providence Dr., Anchorage, AK 99508, USA
ergin.erdem@my.ndsu.edu, sheying1980@hotmail.com, jing.shi@ndsu.edu, hswang@alaska.edu

ABSTRACT
In this study, we develop a vector auto regressive process with exogenous variables for forecasting
the wind speed for very short term (i.e., 10 minutes ahead) and short term (i.e., 1 hour ahead)
horizons. Meteorological variables such as air pressure, air temperature, wind shear, and relative
humidity are incorporated into the vector auto regressive model. The classification of the wind
direction and wind speed pairs into the corresponding groups are conducted by the k-means
clustering approach and incorporated into the model as exogenous variables represented by
categorical variables. Vector auto regressive models with exogenous variables are compared against
the traditional auto regressive moving average based approach that is commonly used for forecasting
the wind speed using the selected performance measures. The analysis reveals that the vector based
auto regressive approach outperforms the traditional auto regressive moving average for both
forecasting horizons of 1-hour and 10-minutes. It also indicates that on the average, the vector
autoregressive approach performs 4.415% and 9.98% better in terms of the mean absolute and
mean square error for 1-hour ahead forecasting. For very short term forecasting (10-min), the vector
autoregressive models with exogenous variables still perform constantly better as compared to the
traditional auto regressive moving average models albeit with smaller difference in terms of
performance measures. The analysis reveals that for 10-min ahead forecasting, the relative
differences in terms of mean absolute and mean square errors between the two methods are 4.415%
and 1.385% respectively. In conclusion, it can be seen that incorporating the meteorological variables
into model and developing classification scheme for the contribution of the wind speed to the wind
direction helps improving the forecasts for wind speed especially for very short and short term
periods. Further research is called for developing new approaches for incorporating meteorological
variables for improving the accuracy of wind speed forecasting.
Keywords: Wind speed, wind direction, vector autoregressive model with exogenous variables,
meteorological variables.
INTRODUCTION
Wind is one of the most promising energy sources for generating electricity. It is a renewable,
clean, and plentiful energy source. The share of electricity generated from wind based resources is
increasing over the years. Wind turbines that are used for generating electricity can be constructed
both on land (on-shore) and on the platforms located at lake, seas and oceans (off-shore). Wind
turbines might be used for providing electricity for the isolated locations, or might be used for
feeding national power grid. Usually, offshore wind is stronger and more persistent, but
construction and maintenance costs of the wind turbines for those locations are higher as
compared to onshore counterparts (Spera, 1994).
The role of wind energy in overall energy markets is increasing. In the world, 83 countries are
providing electricity from wind based sources, and 25% of the electricity of Denmark is produced
from wind based resources (Dvice, 2014). As of 2010, in overall 2.5% of electricity worldwide is
generated from wind based resources. It grows rapidly more than 10% per annum (GWEC, 2012).
Wind farms are the locations that are used for converting the wind energy into electric electricity.
Individual wind turbines might produce outputs in up to 8 MW (Wind Power Monthly, 2014),
whereas the output for wind farms consisting of several hundred wind turbines might reach to 1
GW or more (Terra Gen Press Release, 2012).
The amount of power that might be generated from wind based resources is pretty much
consistent over the years, but might fluctuate significantly over shorter time periods. It might differ
with respect to the time of the day and the season of the year along with other factors. Since wind
is an intermittent energy source, and the proportion of electricity generated from wind based
resources is increasing, the accurate forecasting of wind power is an important aspect.

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The wind power is strongly associated with the wind speed. Usually, for certain wind speed below
the threshold, no power is obtained. For wind speeds above a threshold level, in order to prevent
damage to the turbines, the wind turbines are shut down. These threshold wind speeds (i.e.,
minimum and maximum wind speeds that a turbine operates) are also known as cut-in and cut-out
speeds respectively. The power generated from the wind turbine increases cubically with the
increasing wind speed up until rated output power and stays constant until the cut-out speed. In
that regard, in order to predict the wind power, accurate forecasting of the wind speed carries an
important concern.
In this paper, we develop a mixed regression model based on the Vector Autoregressive model
with exogenous variables (VARX) for forecasting the wind speed. The model incorporates
meteorological factors factors (such as pressure, temperature, humidity) as well as wind related
characteristics (i.e., wind speed and direction). In order to incorporate the wind direction, a
classification scheme is utilized, and with respect to the classification, dummy variables
representing category of the wind direction in terms of the wind speed is included in the regression
model.
LITERATURE REVIEW
There are numerous studies in the literature regarding forecasting wind power output and direction.
Since the market proliferation rate of the electricity obtained from wind based resources are
increasing, forecasting the wind power output accurately contributes to planning and operations of
the power grid in a more effective and efficient manner. Forecasting the wind power can effectively
contribute to the solution of many problems regarding the grid operations such as standards of
interconnection, competitive market design, real time grid operations, ancillary service
requirements and costs, quality of power, capacity of transmission system, stability and reliability
of power system, optimal reductions in green house, and optimal reductions in green house gas
emissions (Wu and Hong, 2007; Lund, 2005). Additionally, improved forecasts help with
functioning day ahead and hour ahead markets (Soman et al., 2010; Negevitsky et al., 2010). It
has been indicated that the forecasting errors might contribute up to the 10% of the costs for
selling wind energy (Pinson et al, 2010).
The forecasting of wind power output can be classified according to the specified time horizon. It
has been indicated that the length of time horizon might span from few seconds (very short term)
to 1 week or more (long term). Generally very short-term forecasts are used for the electricity
market clearing and regulation purposes whereas long term forecasts are used for unit
commitment decisions, reserve requirement decisions, and maintenance scheduling. In between
those categories, short term and medium term forecasting is also used (Soman et al., 2010).
There is a variety of methods that have been used for predicting wind speed. The most basic one
is the persistence method (i.e., nave predictor) which basically is providing forecast as the value
of the wind speed experienced in previous period. Albeit the simplicity of the approach, it has been
still used by the industry, and for very short term forecasting, the approach provides fairly good
results (Potter and Negnevitsky, 2006). On the other hand, numerical weather prediction methods
rely on the physical approach which involves solving complex mathematical model that involve
meteorological variables such as temperature, humidity, etc. The approach provides fairly good
results for the long term forecasting under steady weather conditions (Candy and English, 2009,
Potter and Negnevitsky, 2006)
Additionally, along with the physical based models, the statistical approaches based on neural
network and auto regressive moving average (i.e., ARMA) based approaches are also popular.
There are various variations of neural network such as feed forward, multi-layer perceptrons,
recurrent neural network, radial basis functions, and Adaline networks, etc. (Soman et al., 2010).
Among ARMA models, fractional ARMA models (Kavasseri and Seetharaman, 2009), ARMA
models with exogenous variables (i.e., ARMAX) (Yang and Huang, 1996), grey predictors (El Fouly
et al., 2006), exponential smoothing (Cadenas et al, 2010), and linear prediction (Riahy and Abedy,
2008) based approaches are popular. Usually, statistical based methods are useful and accurate
for short to short-medium term prediction of wind power and wind speed (Soman et al., 2010).
Along with the statistical and physical based methods, non-conventional approaches based on
information science, control theory, artificial intelligence, and data mining approaches are also
beginning to emerge. Some of these approaches also combine the spatial information by
incorporating the correlation between different wind sites for forecasting purposes (Damousis et al.,

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2004) based on the assumption that the patterns in wind speed in some location is to some degree
repeated at another wind site by some time lag. Among the unconventional models, wavelet
transforms (Fichaut and Ranchin, 2002), ensemble forecasting (Sloughter et al., 2010), entropy
based training (Bessa et al., 2009), fuzzy logic (Damousis and Dakapoulos, 2004) are proposed in
the literature. These methods can be combined with other methods thus leading to hybrid
approaches. Hybrid approaches such as combining the artificial neural network and the fuzzy logic
is good at very short term forecasts whereas combining numerical weather prediction with the
neural network provides good estimates for the medium and long term forecasts (Soman et al.,
2010).
The studies featuring incorporating wind direction and other related variables in the prediction of
wind speed starts in 1980s. Geets (1984) indicates wind direction and air related variables can be
integrated into Kalman filter approach for improving the results In that line, Damousis et al. (2004)
incorporates wind direction for prediction of wind speed by developing a membership function for
the wind speed, and using the genetic algorithm based training, they develop the fuzzy logic based
approach for predicting the wind speed. Sideratos and Hatziargyriou (2007), combining the fuzzy
logic and neural networks, develop an advanced statistical methods based on the self-organized
mapping. The model uses the forecasts for wind direction and wind speed as meteorological
variables as well as the past wind power outputs for predicting the wind power. Watson (1992)
discusses the numerical weather prediction model for forecasting wind speed and wind direction
for reducing the fossil fuel related costs for start/stop operations of the wind turbine along with the
spinning reserve. Lin et al. (1996) develop neural network models that combine wind speed and
wind direction for prediction purposes. Marti et al. (2004) develop the power curve and power
output model by incorporating two different approaches involving the power direction. The first
approach features density corrected wind speed that is based on predictions of sea level pressure
and 2 meters level and the second approach involves downscaling based on principal components
for selecting regressor for multiple regressions. These approaches use the adaptive local
polynomial regression with the dependence on the wind direction. Nielsen et al. (2004) develop a
model to estimate the quantiles of the prediction error based on the regression model. The
regression model incorporate forecasted power from wind power prediction tool, wind power
prediction tools and forecasts from High Resolution Limited Area model on air density, friction
velocity, wind speed, and wind direction. Bao et al. (2009) use the Bayesian model averaging for
producing the density function from ensemble forecasts incorporating wind direction as well as
wind speed.
Erdem and Shi (2010) employ different types of ARMA based model for developing joint models
for forecasting wind speed and direction simultaneously. Palomares and de Castro (2003) apply
statistical downscaling method which is adjusted based on seasons and wind direction to predict
the wind speed. Gallardo et al. (2008) launch a CASANDRA project. The project features a power
curve model based on the multivariate regression over wind farm data (wind speed, direction,
pressure and temperature), and model output statistics corrected winds, and other variables
obtained from the mesoscale model.
Other than the wind speed, various approaches incorporate the other meteorological variables
(pressure, temperature, etc.). In that regard, Akylas (1997) develop the multi-variable regression
over the time series obtained from the meteorological masts. Those meteorological masts capture
meteorological variables such as wind speed, temperature, pressure, and pressure tendency. As
previously mentioned, CASANDRA project developed by Gallardo et al. (2008) features
multivariate regression incorporating different weather related attributes. Ramirez-Rosado et al.
(2009) use the meteorological variables obtained from numerical weather prediction model to
develop neural networks. Fan et al. (2009) develop two-stage hybrid network with Bayesian
clustering by using the support vector regression, and use the model to predict the wind speed up
to 48 hours. The proposed model take the wind pressure, temperature, elevation of wind turbines
located in the wind farms into consideration. Yesilbudak et al. (2013) use the k-nearest neighbor
classification model for forecasting wind speed for very short term forecasting horizon. The
meteorological variables used in this study are wind direction, air temperature, atmospheric
pressure and relative humidity parameters. Hocaoglu and Karanfil (2013) identify the bi-relational
causal relationship between different meteorological variables (wind speed, pressure and
temperature) by employing the Granger causality and impulse response analysis. The authors
suggest that incorporating this relationship might help enhancing the models that are used for
predicting the wind speed.

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Based on the literature review, it can be seen that various approaches have been developed for
forecasting the wind speed. Some approaches also incorporate the other meteorological variables.
Our approach combines classification algorithm and statistical based VAR (vector auto regressive)
methodology for forecasting the wind speed for very short term (i.e., 10 minutes) and short to
medium term (1 hour). In the next section, we present the methodology and provide the data
sources that are used as the input for predicting the wind speed.
METHODOLOGY
In the model, we develop two approaches for forecasting the wind speed for very short term (i.e.,
10 minutes) and short term (1 hour). The first approach involves the traditional auto regressive
moving average for forecasting the wind speed. The second approach incorporates the
meteorological variables and the wind direction as well in a mixed model that incorporate not only
past observations of the wind speed, but also past observations of the meteorological variables as
well as the classification of the forecasts for the wind direction. The second methodology is
comprised of four sub-stages which can be expressed as follows;
Classification of wind speed with respect to wind direction: Using the k-means
algorithms, the classification of the wind directions with respect to the associated wind
speed is conducted. For this purpose, three different clusters are formed. Number of
clusters is decided based on the trade-off between capturing the variation among wind
directions with respect to wind speed, and the model coherence. Based on the trial and
error, number of clusters to be formed is decided as 3. Using the k-means clustering
algorithm, corresponding past wind speed-direction observations are classified into three
different clusters.
Forecasting the wind direction: For this purpose, the linked ARMA based models is
used for forecasting the wind direction. Using the link function, the circular variable (i.e.,
the wind direction) is converted to the linear variables for the prediction purposes. Using
the ARMA methodology, after the wind directions in linearized forms are obtained, using
the inverse link functions, these variables are converted back to the actual wind directions.
Forecasting the wind speed: In this step, a mixed linear regression model that
incorporates the past meteorological variables as well as the wind direction clusters are
used. The mixed regression model is composed of two parts. The first part is the Vector
Auto Regressive part (VAR) that incorporates the meteorological variables. These
variables are;
Wind speed (m/s)
Pressure (mBar)
Temperature (C)
Wind shear (s-1)
Relative Humidity (%)
Apart from the VAR part, the second part incorporates the categorical variables that are used for
representing the clusters associated with the wind direction. This mixed model leads to Vector
Autoregressive with exogenous variables (i.e., VARX) model. In the next subsections, more
information regarding the established methodology is provided.
ARMA Model
An ARMA model which can be denoted by ARMA (p,q) can be expressed as follows (Montgomery
et al., 2008):
p

i 1

j 1

yt i yt i j et j et ,

(1)

where is the mean of the underlying process, i is the ith autoregressive coefficient, and j is
the jth moving average coefficient, and et is the residual term at time period t. Note that the based
on the assumptions, error term is normally distributed with mean 0, and yt is the wind speed
observed or forecasted at time period t.
Linked ARMA model
A linked ARMA model incorporates the link function to convert the circular variables to the linear
variables. After the circular variables are transformed into the linear variables, using the ARMA
based approach, the forecasts are provided. Various link functions exist in the literature; we adopt
the cumulative distribution function based on standardized normal distribution following Erdem and

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Shi (2011). To do so, we make use of the linked function which is expressed in Eq. (2) as (Fisher
and Lee, 1994),

1
g (u ) 2 ((u ) )
2

(2)

1
g 1 (b) 1 ((b ) / 2 )
2

(3)

where (u) is the standardized normal cumulative distribution function, and is the mean wind
direction parameter. Accordingly, the inverse of the probit link function is presented in Eq. (3),

where -1 is the probit function (i.e., inverse of the standardized normal distribution function. Note
that Eq. (3) is the inverse link function that is used for converting the circular variables back to the
linear variables. Based on the ARMA approach, forecasting of the linearized forms of the circular
variables are conducted. Using Eq. (4), the forecasted variables are converted back to the circular
variables to obtain the forecasts of the wind speed.

tan 1 ( S / C ) S 0, C 0

tan ( S / C ) C 0

tan ( S / C ) 2 S 0, C 0

where S is the sum of the sine values of all the angles with respect to the north axis (i.e.,
n

i 1

i 1

S sin i ), C is the sum of the cosine values with respect to north axis (i.e., C cos i ).
K-means Algorithm
K-means algorithm is one of the basic classification algorithms. The algorithm is used for
categorizing the wind directions with respect to the corresponding wind speed. Associated wind
directions are assigned to the corresponding clusters based on the proximity of the wind speedwind direction to the particular cluster center (i.e., centroid). Based on the inclusion of those pairs,
the center for those clusters is updated. The procedure is iterative in nature and consists of mainly
two steps. In the first step, each observation pair is assigned to the particular cluster based on the
partitioning according to the Voronoi Diagrams. In that instance, each observation (xp) is assigned
to only one cluster Si(w) (i.e., cluster), where p represents the index of the observation, b
represents the index of the cluster, and w represents the index of step, and Sb(w) represents the
center location of the cluster. After the clusters are formed, the subsequent step is updating the
location of the centroids for the new steps. These two steps follow each other in iterative manner
until the total distance of the pairs to the center of the clusters is minimized. Mathematically, it can
be expressed as follows (Lloyd, 1982);

Assignment step

(5)
where mc(w) is the mean of cluster c at step w.

Update step

(6)
The problem is NP-hard in nature and there are heuristic approaches for solving the classification
algorithm. A heuristic version of the k-means algorithm is developed and implemented. Three
different clusters (that are low, medium, and high) are formed and wind direction-wind speed pairs
are assigned with respect to those clusters.

VARX Model
After forming the clusters and forecasting the wind direction next step is developing the VAR
model with exogenous variables (i.e., VARX). VARX model incorporates six types of
meteorological variables namely wind direction, wind speed, temperature, pressure, relative
humidity, and the wind shear. Using the classification algorithm described in the previous section,
the wind direction speed pairs are grouped in the corresponding bins, and represented by the
dummy variables indicating the categories that particular wind speed and direction is assigned to.

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(4)

Three different clusters are represented by two dummy variables. If the wind direction and speed
belongs to the first category, both of the variables (i.e., z1 and z2) take the value of 0, if the pair
belongs to the second category, the z1 variable takes the value of 1, and z2 takes the value of 0, if
the wind speed-pair direction belongs to the third category then the z2 variable takes the value 1,
and z1 variable takes the value of 0. Using the classification algorithm that is described in the
previous section, clusters tare formed and represented by the dummy variables. Those dummy
variables represent corresponding clusters for forecasting wind direction. The VARX model, which
is comprised of autoregressive terms belonging to five different meteorological variables and the
categorical variable representing the wind direction, can be represented as;
p

i 1

i 1

yt i y (t i ) ki wk (t i ) z1q1 z 2 q 2
(7)
where q1 and q2 are the coefficients associated with the categorical variables, is the constant
term, i are the autoregressive components belonging to the past observations of the wind
speed, y(t i ) is the value of the wind speed observed at ith period prior to the current period, and
m1 and m2 are the values of the corresponding dummy variables, ki is the coefficient of the
meteorological variable of type k for time period i, and wk (t i ) is the actual value of the
meteorological variable that is observed i periods prior to the current period. Note that the first
meteorological variable is temperature, the second one is the relative humidity, the third variable is
the pressure, and the fourth variable is wind shear and categorical variables represent the wind
directions. For scaling purposes relative humidity and pressure is divided into 100, and
incorporated into mathematical model.
In this study, we consider the mean absolute error (MAE) and mean square error (MSE) for
assessing the quality of the forecast, which can be expressed with the following formulas by Eqs.
(8) and (9) respectively;
N

MAE

yt yt'
t 1

(8)

N
N

MSE

( yt yt' ) 2
i 1

(9)

where yt is the realized value at time period t, and yt' is the forecast pertaining to that period, and
N is the number of data points.
WIND DATA
The data is obtained from meteorological mast from the wind site located in Colorado, USA. As
previously mentioned, relative humidity, temperature, wind shear, wind direction information are
captured by using the instruments placed in the meteorological mast. The data are recorded
continuously and averaged over every 10 minutes and one hour to obtain the wind attributes as
well as the meteorological variables. The data belongs to the period of January 1, 2012 and
December 31, 2012.
For short term forecasting (with a forecasting horizon of 1 hour), the yearly data averaged on
hourly basis is used. In total, there are 8,784 data points in which 7,000 data points are used for
the model building, and the remaining 1784 data points are used for testing the model based on
MAE and MSE measures.
For very short term forecasting (with a forecasting horizon of 10 minutes), the data pertaining two
months (i.e., January and February, 2012) is used. For this purpose, the data is averaged over 10
minutes. Out of 8,640 data points, in order to establish a common platform between the efficacy of
the model for very short term and short term forecasting, similar number of data points are used for
model building and model testing correspondingly. In short, 7,000 data points are used for model
building purpose, while the remaining 1,640 points are used for testing purpose. Based on the
performance measures, the developed VARX models are tested against their ARMA counterparts.
In the next section, more information is provided in the underlying model structure. Along with the

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model coefficients, the comparison between the models based on the MAE and MSE measures
are provided.
RESULTS
Basically two different model structures with respect to the forecasting horizon (very short term and
short term) are constructed. As previously suggested, the very short term planning horizon
incorporates 10-min ahead forecasts, while the short term forecasts provides the 60- min ahead
forecasts. Both are conducted in rolling one-step ahead forecast manner. For the short term
forecasting, based on the Bayesian Information Criterion (i.e., BIC), corresponding values for
different model structures are compared. Note that BIC can be approximated for large sample
sizes based on the following formula (Wit et al., 2012);
BIC 2 ln L d ln(n)
where L is the maximized value of the likelihood function of the underlying ARMA process, n is the
sample size, and d is the number of estimated parameters. Based on the BIC values, ARMA(2,2) is
chosen. Additionally, an analysis is performed to measure the correlation of wind speed with
respect to other meteorological variables. As a result, the following correlation coefficients are
obtained for 10-min and 1-hour data.
Table 1. Correlation coefficients between wind speed and other meteorological variables
Averaged over 10-min
Wind speed
Air temperature
0.369332
Relative humidity
-0.48431
Air pressure
-0.28198
Wind shear
0.096679
Wind direction
0.468147

Averaged over 1-hour

-0.02918
-0.31152
-0.35734
0.88309
0.365679

Based on Table 1, it is concluded that the correlation between air temperature and wind speed is
significant based on 10-min averaged data. However, for the data averaged over 1 hour, the
correlation is not significant. Similarly, wind shear is strongly correlated with wind speed based on
the data averaged over 1 hour, but the correlation between the wind shear and wind speed is not
significant when data is averaged over 10 minutes.
The model coefficients are estimated using the maximum likelihood method by using SAS 9.2 TM.
The results are provided in Table 2. In a similar fashion, the corresponding BIC values are
calculated for different VARX model based on the order of auto-regression terms. The model that
provides lowest BIC value is chosen as the underlying model. It turns out that VARX model that
incorporates the autoregressive term up to third order provides the lowest BIC value. The model
parameters are estimated in two stages. In the first stage, the unrestricted VARX model is run in
SAS 9.2TM. In the second stage, the model coefficients that have associated p values greater than
0.1 are restricted to be equal to 0. Based on this approach, the following results that are presented
in Table 3 are obtained.
It has been indicated that the wind speed up to autoregressive order of 3 plays a significant role in
forecasting the wind speed. In a similar fashion, temperature and relative humidity up to
autoregressive order of 2 are significant, for pressure and wind shear; only first term
autoregressive coefficients (i.e., the coefficients associated with one period prior) are significant.
The categorical variables are significant indicating that wind directions pertaining to the second
and third group contributes positively to the wind speed, whereas the contribution of the second
group is higher than the contribution of the third group. In terms of MAE and MSE values, the
comparison is provided in Table 4.
Table 2. ARMA model coefficient for 1 hour ahead prediction
Short Term Forecasting Horizon (1-hour ahead)
Model parameters
ARMA (2,2)
1.475515***
1

2
1
2

-0.50477***
0.55436***
0.16613***
0.143161***

***: Significant at 1%

134

(10)

Table 3. VARX model coefficient for 1 hour ahead prediction

Wind speed
Wind speed
1
2
3
Temperature (C )
1
2
Relative humidity/100 (%)
1

Coefficient value
0.91402***
-0.16322***
0.09311***
0.08039***
-0.08159***
-1.5967***

1.07457*

Pressure/100 mBar (mm)

-3.6674***

Wind shear

-3.54262***

Wind direction coefficients

0.61215***

0.06621**

Constant term

30.90954***

***:Significant at 1%
**:Significant at 5%
*: Significant at 10%

Table 4. Corresponding MAE and MSE values for the models

MSE
VARX
3.154861
ARMA(2,2)
3.469839
Relative difference
9.983957%

MAE
1.293287
1.341397
3.719959%

The MAE value pertaining to the traditional ARMA model on the average is 3.72% worse as
compared to the VARX model. When the MSE values are compared, the difference is even more,
that reaches to approximately 10%. This significant difference in terms of MSE values are
important in terms of predicting the wind power output, since the generated power is directly
proportional to the cube of the wind speed in the given range. In terms of the very short term
forecasting (i.e., 10-min ahead), a similar approach is followed. Table 5 provides the results for the
ARMA model for one step 10-min ahead forecasting. The analysis on the VARX model reveals the
coefficients presented in Table 6. Note that similar to the previous approach, the variables that has
significance level above 10% is restricted to have the value of 0. The MAE and MSE values
associated with the ARMA and VARX based models are provided in Table 7.
Table 5. ARMA model coefficients for 10-min ahead prediction
Short Term Forecasting Horizon (10 min ahead)
Model parameters

1
2
3
4

ARMA (5,1)
1.00989***
-0.04041***
-0.06432**
0.06626***
0.159133**

***:Significant at 1%
**:Significant at 5%

Examining Table 6, it can be seen that compared to the 1-hour ahead forecasting, fewer variables
that are associated with the meteorological variables are significant for the prediction of wind
speed at 10-min ahead. Comparing Tables 4 and 7, it can be observed that the forecasting power
of VARX model over the ARMA counterpart diminishes, but there is still some significant difference
between the two approaches both in MAE and MSE values. The ARMA based approach performs
approximately 4.4% worse as compared to VARX counterpart, and for the MSE values, the
difference is reduced to 1.38%. Note that for one hour forecast, ARMA (2,2) model provides the
best results; while for the 10-min forecast, ARMA(4,0) performs the best in terms of the BIC value.
Table 6. VARX model coefficient for 1 hour ahead prediction
Wind Speed
Wind Speed
1
Relative humidity/100 (%)
1

135

Coefficient Value
0.20243**
-76.0149**

Wind direction coefficients

1
1
2

75.1798**
0.54673***
0.94013**
6.95848***

Constant term
***: Significant at 1%
**: Significant at 5%

Table 7. Corresponding MAE and MSE values for the models

VARX
ARMA(4,0)
Relative difference

MSE
2.946603
2.987438
1.385813%

MAE
1.169026
1.220642
4.415336%

The forecasted values provided by the VARX and ARMA models and the actual values are
compared for 120 data points both for 1-hour and 10-min forecasts. The results are provided in
Figures 1 and 2 for 10-min ahead and 1 hour ahead forecasting, respectively.

Figure 1. Comparison of actual values versus predicted values for 10-min ahead forecasting

Figure 2. Comparison of actual values versus predicted values for 1 hour ahead forecasting

CONCLUSIONS
In this paper, we develop the vector autoregressive with exogenous variables approach for
forecasting wind speed 10-min and 1 hour ahead, Rather than incorporating the wind direction
related variables into the vector autoregressive approach directly, using the classification scheme,
the clusters that these wind direction speed pairs are classified into, are represented as separate
groups in the vector autoregressive models as exogenous variables. For this purpose, along with
the wind direction, four different types of meteorological variables (i.e., pressure, relative humidity,

136

temperature, and wind shear) are incorporated into vector autoregressive equation. Different
orders of autoregressive terms are compared using the BIC values to decide on the best model.
Our approach, as compared to the benchmark ARMA based approach, provides significantly better
results especially for the 1 hour ahead forecasting. It can be seen that for the short term (10-min
forecasting), the performance of both models are similar, Especially, the difference between the
performance measures in terms of the MSE values reaches 10%, which is quite significant
especially for the wind power prediction based on the fact that for certain intervals, the wind power
is directly proportional to the cube of the wind speed. As a future research direction, the
development of the Kalman filter based approaches involving meteorological variables would be
considered. In line with this approach, different constructs for building the state space models
would be examined to improve forecasting of the wind speed.

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139

Research on the Aerodynamic Characteristics of

A Hybrid Lift/drag-based Vertical Axis Wind Turbine
Xiaojing Sun1,2, Yajun Chen3, Guoqing Wu3* ,Diangui Huang 1,2*
(1.University of Shanghai for Science and Technology, Shanghai, 200093)
(2. Shanghai Key Laboratory of power energy in multiphase flow and heat transfer, Shanghai
200093)
(3. Nantong University, Nantong, 226600)
(Tel: 021-55897317, Email: dghuang@usst.edu.cn; wgq@ntu.edu.cn)

Abstract Compared with a drag-type vertical axis wind turbines (VAWT), one of the
greatest advantages for a lift-type VAWT is its higher power coefficient (Cp).
However, the lift-type VAWT is not a self-starting turbine and its starting torque is
very low. In order to take advantage of a high starting torque of the drag-type VAWT,
a hybrid lift/drag type of VAWT is designed in this paper and the aerodynamic and
starting performances of the proposed turbine are studied by the numerical simulation
method. Numerical results indicate that the power coefficient of the hybrid lift/drag
type VAWT declines when the distance increases between its drag blades and the
center of rotation of the turbine rotor, but the starting torque of this type of turbine can
be significantly improved. Studies also show that unlike the lift-type VAWT, the
hybrid lift/drag type VAWT could be able to solve the problem of low startup torque.
However, the installation position of the drag blade is very important. If the drag
blade is mounted very close to the spindle, the starting torque of the hybrid lift/drag
type VAWT may not be improved at all. In addition, it has found that the power
coefficient of the studied VAWT is not as good as expected and possible reasons have
been provided in the paper after analyzing the pressure distribution along the surfaces
of the aerofoil-shaped blades of the turbine.
Key words: vertical axis wind turbine; lift-type VAWT; hybrid lift/drag type VAWT; starting
torque; power coefficient

1. Introduction
At present, horizontal axis wind turbine (HAWT) has been widely used.
However, the vertical axis wind turbine (VAWT) has many advantages, and people
are paying more and more attention to it. The main advantage of VAWT is that it has
a single moving part (the rotor) and also no yaw mechanisms are required. Therefore,
the configurations of VAWT are usually very simple [1]. Besides, the manufacturing
costs are lower, the fabrication is easier, and the installation and maintenance are
more convenient than the HAWT. There are two types of VAWTs: those that operate
using lift, and those that operate using drag [2]. The typical structure of the drag-type
VAWT is the S-type (Savonius) wind turbine, which is composed of two or more
semi-cylindrical blades rotating around an axis parallel to the blades. The advantages
of this kind of wind turbine are the high starting torque, and good self starting
capability. But both the rotating speed and power coefficient of this type of turbine
are low [3]. The other main type of VAWT is the Darrieus type which have various
forms, including H-type and -type. Although the lift-type VAWT can not self start,

140

it has higher power coefficient (Cp) and are typically more efficient than other types
of VAWTs [4].
In order to improve the starting torque of the lift-type VAWT, this paper studies
a hybrid lift/drag type VAWT, which has combined the benefits of the Savonius-type
blade and the Darrieus-type blade, applying both the drag and lift forces of wind
power. The two-dimensional cross section of a hybrid lift/drag type VAWT is shown
in Fig.1. When there are lift-type blades alone, it is a typical lift-type VAWT.
Different hybrid lift/drag type VAWTs are analyzed and named respectively as
coupled_1, coupled_2, coupled_3 and coupled_4 according to the different
installation position of drag-type blades as shown in Table1. The drag-type blades of
coupled_1 are installed in the rotational center, while the drag-type blades of
coupled_2, coupled_3 and coupled_4 are respectively installed at 50mm, 100mm and
150mm outside the rotational center. The three inner blades, each shaped like a
half-cylinder with radius of 250mm as well as three outer blades, shaped like aircraft
wings, rotate together about a central axis. The lift type of blades is NACA0018
airfoil with the chord length of 500mm. In this study, computational fluid dynamics
(CFD) software is used to conduct numerical simulations of steady and unsteady flow
around this hybrid type VAWT rotor in order to study its aerodynamic and starting
performance.

Fig.1 Top view of the physical model

Table 1 Simulated VAWTs named based on the distance (d) between
the drag-type blades and the center of rotation axis
d (mm)
Simulated VAWTs
0
coupled_1
50
coupled_2
100
coupled_3
150
coupled_4
It is generally assumed that that the hybrid lift/drag type VAWT will not only have
the higher starting torque than that of the lift-type VAWT , but also have the high Cp
as the lift-type blades and drag-type blades work together to produce power [5, 6,7].
However, in this research, it is found that the hybrid lift/drag type wind turbine does
have a higher starting torque than that of the lift-type turbine, but its Cp decreases.
2. Establishment of Numerical Model

141

2.1 Governing equations

Numerical solution is based on the finite volume method. The governing equations
for incompressible fluid flow include continuity (conservation of mass) and the
Navier-Stokes equations (conservation of momentum) [8], which are expressed,
respectively, as follows.
u i
0
x i
(1)
u j
u j
u j
p

(u i
)

( t )

t
xi
xi xi
xi
(2)
wherej=1,2 i=1,2.
2.2 Selection of Turbulence Model
The model of Eq. (2) reflects the fact that the flow around the rotating blade is
turbulent, and closure of the RANS equations are achieved using the shear stress
transport model.
Simulations were performed using different turbulence models, such as the
k-epsilon and k- turbulence models and Spalart-Allmaras (S-A) model, to see how
the predictions were affected by the different turbulence models. It has been found
that the power and torque coefficients obtained using different turbulence models
were all in good agreement with the published experimental results. Finally, the S-A
model was selected due to its computational stability, fast convergence, and ease of
use.
2.3 Computational domain
The physical domain used in this study is shown in Fig.2. The wind turbine is
placed in the middle of the computational domain at a distance of twenty rotor
diameters (20D) from the upstream boundary. Besides, the downstream exit boundary
is located at 40D from the center of the rotor, in order to minimize the influence of
boundary conditions. The computational domain is divided into a moving zone
rotating with the turbine blades and a stationary zone.
2.4 Computational mesh generation
The computational domain was meshed using unstructured grid consists of
triangular element in order to maximize the number of cells in the area of interest
while minimizing cells in the far field. The grid is locally refined in an attempt to
resolve the boundary layer near the surface of the rotor blade and reduce the
numerical errors. As the quality of the computational gird is essential to the accurate
and stable numerical analysis, a grid independence test is performed in this work to
find the optimal number of cells of the computational domain mesh. The VAWT
model of coupled_1 is used in all the grid independence tests.

142

Fig.2 Schematic of the simulation domain

Table 2 Grid independence test for the unsteady simulation
cells
Grid
N(Nm)
40,800
Grid1
-15.780
45,780
Grid2
-31.412
52,460
Grid3
-53.420
61,600
Grid4
-72.078
68,500
Grid5
-72.078
Table 2 shows the results of grid independence test study performed with CFD
calculations. Here, N represents the dynamic torque of the wind turbine coupled_1.
This table shows that the number of cells obtained with the Grid4 and Grid5 are
satisfactory in predicting coherent simulation results.
2.5 The computational set-up
Assuming the wind blows from left to right, the boundary conditions imposed on
the boundaries of the computational domain are as follows:
(1) Inlet boundary: pressure inlet and the given pressure is 49.6125Pa, which is
equivalent to the wind speed of 9m/s.
(2) Outlet boundary: pressure outlet and the given static pressure is 0Pa (relative
pressure).
(3) Wall boundary: the upper and lower boundary conditions are wall, as the
simulated wind turbine is assumed to rotate in a wind tunnel. No slip rotating wall
boundary conditions are used along the blade surfaces.
(4) Slip plane: there is the sliding mesh interface between the rotating and the
stationary girds, thus ensuring the continuity in the flow field.
3. Numerical Simulation of Unsteady Flow and Aerodynamic Performance of the
Hybrid Lift/Drag VAWT
In this paper, CFD software is used for numerical simulation of the aerodynamic
performance for wind turbines blade wheel at rated wind speed, which is set at 9m/s.
The second-order upwind discretization and the pressure-based implicit algorithm are
adopted for solving the flowfield. For this study, computations are done with 250

143

physical time steps during a rotation period of the rotor and the time step size is set as
T/250. In all the simulations 20 iterations per time step are used. It has been found that
after the result has converged, the torque coefficient of the rotor shows a clearly time
period trend and the final torque coefficient is then calculated by averaging the results
during one revolution of the rotor.
N represents torque and is calculated using the following equation:
1
N Cm v2 AL
2
(3)
where, is the air density. v is the standard unit velocity. A is the standard unit
area. L is the standard unit length. Cm is torque coefficient.
P represents the power output of the turbine and is calculated as follows:
P = N
(4)
where, N is the torque and is the rotors angular velocity.
Cpis the power coefficient defining the aerodynamic efficiency of the wind
turbine rotor and its
equation is given below:
P
Cp
1
SV13
2
(5)
where, P is the actual power extracted from the wind. S is the swept area of the
turbine rotor. V1 is the wind speed.
The tip speed ratio for wind turbines is the ratio between the rotational speed
of the tip of the turbine blade and the actual velocity of the wind, and is calculated as
follows:
2 Rn R

V1
V1
(6)
where, n is the rotational speeds of the rotor. R is the radius of the rotor.
Starting torque is the driving torque of the machine which overcomes mechanical
friction and
drag at zero rotational speed [8].
3.1 Numerical model validation
A validation study has been conducted, in which a Darrieus turbine studied in Ref.[8] is also
simulated using our numerical model, and results of this validation will assist in determining the
appropriate turbulence models, boundary conditions, mesh characteristics and other CFD modeling
techniques used in this work. The main geometric features of the tested mode is given in

Table 3 and a comparison between the published results achieved from Ref.[8] and
the results achieved by our model is illustrated in Fig. 3.
Table 3 Main features of the tested model [8]
Blade profile
NACA0021
c(mm) chord lengthen
85.8
D (mm) the diameter of
1030
the rotor

144

60
50

Cp(%)

40
30
20
10
0
1.20

1.70

2.20
2.70
Tip Speed Ratio

3.20

Fig.3 Comparison among wind tunnel measured Cp curve () [8],

numerically Cp curve () [8] and numerically Cp curve () obtained in this
work for a wind speed at test section entrance of 9 m/s.
From Fig.3, it can be seen that the numerical results obtained in Ref.[8] is much
higher than those measured, which indicates that the numerical solutions obtained in
Ref.[8] may suffer numerical instability and thus contain large errors. In contrast, the
numerical results obtained in this work are much close to the results from the model
tests, proving the accuracy of our numerical simulations. However, the predicted
optimum value of tip speed ratio that makes power coefficient maximum Cp is
larger than that measured in Ref.[8].
Subsequently, the established numerical model is used to simulate the flow field
around the hybrid lift/drag wind turbines with different geometric configurations.
3.2 Results analysis
3.2.1Comparison of starting torque
Under a certain wind speed, the torque generated by wind when the rotor is
stationary directly determines turbines starting performance. In order to study the
starting characteristics of the hybrid lift/drag type wind turbine, a series of simulations
on the static torque performance of this type of turbine at different static azimuth
angles have been performed.
Four hybrid lift/drag wind turbines with different geometric configurations, which
are numbered coupled_1, coupled_2, coupled_3 and coupled_4, are simulated. For the
purpose of comparison, a Darrieus-type (lift-based) turbine is also numerically
analyzed, which has the same rotor diameter, number of lift-type blades and the blade
airfoil section as the hybrid turbine. Due to symmetry, the azimuth angles studied
are only in the range from 0 to 108 degrees, in a clockwise fashion. The values of
static torque of all the simulated wind turbines at different azimuth angles are given in
Table 4, and Fig.4 is a plot of static torque coefficient versus azimuth angle curves of
all the simulated turbines.
Table4 Static torque of all the wind turbines at different positions

(degree

Darrieus-typ
e

Coupled_1
( Nm)

Coupled_2
( Nm)

145

Coupled_3
( Nm)

Coupled_4
( Nm)

( Nm)
3.917
6.908
9.153
13.205
10.966
7.572
17.652
12.231
9.108
1.640

)
0
12
24
36
48
60
72
84
96
108

5.827
11.614
15.443
15.600
9.991
21.969
15.449
23.623
1.766
2.968

10.883
18.203
19.668
16.158
10.620
24.813
16.029
22.945
4.338
6.220

16.547
24.332
24.780
16.882
10.915
22.300
12.322
20.638
3.473
11.343

23.518
29.089
28.976
20.115
11.631
22.709
13.400
22.217
5.833
17.911

35.0

Lift
coupled_1
coupled_2
coupled_3
coupled_4

Starting Torque

30.0
25.0
20.0
15.0
10.0
5.0
0.0
0

30

60

90

120

150 180 210

Angle()

240

270 300

330

360

Fig.4 Starting torque of wind turbines

From Fig.4, it can be found that the minimum torque of the lift-type vertical axis

turbine is 1.640 N m when is 108 , 228 and 248 respectively. However, the
minimum starting torque of coupled_1, coupled_2, coupled_3 and coupled_4 are
1.766Nm, 4.338 Nm, 3.473, 5.833 Nm respectively and the corresponding angular
position of minimum torque coefficient appeared are at 96 , 216 and 336 for all the
three cases.
For the turbine of coupled_4, its drag-type blade is placed farthest from the center
of rotation of the turbine rotor, but its starting torque has been significantly improved
and the turbine can be self-starting at any azimuth angle. This result suggests that the
hybrid lift/drag turbine has the advantage of high starting torque, but the position of
its drag-type blade seems to be very important. If the drag-type blade is placed very
close to the spindle of the turbine, there will be no improvement in the starting
performance of this hybrid type turbine. With the distance between the drag-type
blade and the center of the turbine rotor increasing, the starting torque of the hybrid
turbine is also gradually increased.
3.2.2 Comparison of power coefficient (Cp)
In order to compare the power coefficient Cp between the Darrieus-type VAWT
and the hybrid VAWT, CFD simulations of the wind turbine rotating motion have
been conducted at a certain wind speed.

146

Aerodynamic characteristics of the studied wind turbines rotating at a certain speed

have been achieved and the rotation speeds examined are 70rpm, 83rpm, 97rpm,
111rpm, 125rpm, 138 rpm, respectively, as shown in Table 5.
Table 5 Different rotation speeds used in the numerical model
Simulated
Darrieus-type coupled_1
coupled_2
coupled_3
turbines
83
70
70
70
rotating
97
83
83
83
speed
111
97
97
97
(rpm)
125
111
111
111
138
125
125
125

70
83
97
111
125
Lift
coupled1
coupled2
coupled3
coupled4

40.0
35.0

Cp

coupled_4

30.0
25.0
20.0
15.0
1.15

1.35

1.55

1.75

1.95

2.15

2.35

2.55

Tip Speed Ratio

Fig.5 Comparison of the variation of the predicted power coefficient with tip speed
ratio for four studied turbines
Fig.5 is a comparison of power coefficient among four simulated turbines. The
abscissa is the tip speed ratio, between the turbine tip speed and the wind speed and
the vertical axis is the predicted power coefficient Cp. From Fig.5, it can be seen that
the optimum tip speed ratios of three hybrid turbines that maximizes the power
coefficient Cp are all around 1.75. However, compared to the Darrieus-type turbine,
the power coefficients of the hybrid turbines are all reduced. Among the hybrid
turbines, the power coefficient Cp of turbine coupled_1 is the highest, while turbine
coupled_4 shows the lowest Cp. Therefore, the distance from the drag-type blade to
the center of the wind turbines rotor d apparently influences the power output of the
hybrid turbines. When the drag-type blade is placed far away from the axis of rotation,
the Cp of the hybrid turbine can be considerably reduced.
The calculated averaged dynamic torque of the Darrieus-type VAWT and the
dynamic torques produced respectively by the lift-type blades and the drag-type
blades of hybrid turbine coupled_4 are compared in Fig.6.

147

lift
lift(coupled_4)
drag(coupled_4)

Averaged Torque

50.0
40.0
30.0
20.0
10.0
0.0
-10.0
1.0

1.5

2.0
Tip speed ratio

2.5

3.0

Fig.6 Comparison of dynamic torque of the Darrieus-type turbine with those

generated by the lift-type and drag-type blades of turbine
coupled_4
As can be seen in Fig.6, the dynamic torque of the Darrieus-type VAWT is slightly
higher than that generated by the lift-type blade of the hybrid turbine coupled_4.
Moreover, the torque of the drag-type blade of turbine coupled_4 is fairly small which
indicates that the drag-type blades almost do not make any positive contributions to
the power output of the hybrid lift/drag type VAWT. Thus, this result suggests that it
would be wrong to assume that both the lift-type and drag-type blades of the hybrid
lift/drag type VAWT can do positive work during their operation.
In addition, possible reasons that the Cp of hybrid lift/drag type VAWT is smaller
than that of a conventional Darrieus type wind turbine have also been investigated in
this paper. When the turbine rotor is rotated to different azimuth () positions, static
pressure distributions on the blade airfoil surface are analysis and provided in Fig.7 (a)
~ (l), in which two curves represent the airfoil shaped blades of the Darrieus turbine
and the hybrid turbine coupled_4, respectively.

148

149

10

150

11

The relative position parameters of the blade d

of the blade d

The relative position parameters

Fig.7 Static pressure distribution on the surface of the airfoil shaped blade of the
rotor at different azimuth positions
Fig.7 (a) shows the static pressure distribution on the airfoil surface when is 0
and the blade is parallel to the wind. In this position, the pressure difference between
pressure and suction surface of the blade is relatively small and as a result, neither the
blade of the Darrieus type VAWT nor the airfoil-shaped blade of the hybrid lift/drag
VAWT capture the energy of the wind.
Fig. 7 (b) shows the blade surface static pressure distribution when is 30. It has
been found that a large pressure difference between pressure and suction surface
appears in the 40% front part of the blade, which means that only a region of 40% of
the chord length of the blade body can generate power and the rest 60% of the blade
almost does not work. From Fig. 7(6), it has also been noted that the pressure
distribution on the blade of the Darrieus type VAWT is nearly identical to that of the
hybrid type VAWT.
Fig. 7(c) illustrates the pressure distribution on the airfoil-shaped blade surface
when is 60. This result confirms that the leading edge of the blade does negative
work. On 5% to 35% chord of the lift blade, pressures on pressure surface are higher
than that on suction surface. But on the left 65% blade, the difference pressure
between pressure and suction surface is very small. It can also be found that there is
little difference between the pressure on the blade of Darrieus type VAWT and that on
the airfoil shaped blade of the hybrid type VAWT.
Fig.7(d) shows the pressure distribution on the airfoil-shaped blade surface when
is 90. The pressures on the pressure side of the blade are found to be higher than
those on suction surface on the surface of the front 60% blade, otherwise, on the left
40% blade, the pressures on pressure surfaces are lower. It can also be found that the
difference of pressure between pressure surface and suction surface of the lift-type
VAWT is significantly larger than that of the hybrid type turbine.

151

12

Fig.7(e) shows the pressure distribution on the airfoil surface when is 120. It
suggests that the pressures on the pressure surface are higher than that on suction
surface on the surface of the front 35% chord of the lift blade. Difference of pressure
on the lift blade between pressure surface and suction surface of the lift-type VAWT
is a little larger than that of the hybrid lift/drag type turbine. It has also be found that
the pressures on the pressure surface are a little lower than those on suction surface on
the rest 65% blade surface.
Fig.7(f) shows that the pressure distribution on the airfoil surface when is 150,
which is similar to the results obtained in Fig.7(c) , but the pressure difference
between pressure and suction surface becomes a little larger.
Fig.7(g) shows that the pressure distribution on the airfoil surface when is 180. It
can be seen that on front half of the blade, the pressures on the pressure surface are
higher than that on suction surface, while the pressures on the pressure surfaces are
lower than those on suction surface on the rest half of the blade. There is almost no
difference between the pressure on the blade of Darrieus type VAWT and the pressure
on the lift type blade of hybrid VAWT.
Fig.7(h) shows that the pressure distribution on the airfoil surface when is 210. It
shows that the pressures on the pressure surface are always higher than those on the
suction surface. The pressure difference between the pressure and suction surface at
the leading edge is the largest. From the front 20% chord to trailing edge of the blade,
pressure difference between pressure and suction surface is relatively small. It can be
seen that the pressure distribution on the blade of the lift-type VAWT is similar to that
on the lift type blade of the hybrid VAWT.
Fig.7(i) shows that the pressure distribution on the airfoil surface when is 240. It
shows that the pressures on pressure surface are always higher than that on suction
surface. The pressure difference on the surface near the leading edge of blade is larger
than that on the surface of other positions. It can also be found that the difference of
pressure between pressure surface and suction surface of the Darrieus-type VAWT is
larger than that of the hybrid type turbine.
Fig.7(j) and (k) respectively show the pressure distribution on the airfoil surface
when are 270 and 300, which are similar to the results displayed in Fig.7(i). The
pressure difference between pressure and suction surface of (j) is the largest among all
the results demonstrated in Fig.7.
Fig.7(l) shows that the pressure distribution on the airfoil surface when is 330. It
can be seen that pressures on the pressure surface are higher than that on the suction
surface of the front 70% chord of the lift blade, although the pressure difference
between pressure and suction surface is small. To the Darrieus type VAWT, the
largest pressure difference between pressure and suction surface appears at the front
30% of the blade, however, for the hybrid type VAWT, it appears at the front 40% of
the blade.
In general, the pressure difference on the lift type blade of turbine coupled_4 is
lower than that on the lift blade of the Darrieus turbine at most of blade operating
positions, which is a possible reason resulting in poor power coefficient Cp of the
hybrid type VAWT. That is, the Darrieus type VAWT has much stronger capability in
extracting energy from the wind compared with this hybrid lift/drag type VAWT.
4. Conclusion
This study indicates that the hybrid lift/drag type VAWT whose lift type and drag
type blades are appropriately combined can achieve a higher starting torque than that

152

13

of a conventional Darrieus type VAWT. In addition, the starting torque of this hybrid
VAWT is increased when its drag-type blade is moved away from the center of
rotation of the turbine rotor. However, the power coefficient of the hybrid type turbine
is lower than that of the Darrieus type VAWT and can be further reduced with the
increase of the distance from its drag-type blade to the center of the turbine rotor.
5. Further work
In an attempt to improve the starting torque of the Darrieus type VAWT and also
remain its high power coefficient Cp, a new hybrid type VAWT can be designed and
the position of its drag-type blades can be automatically adjusted. When the turbine
rotor at rest begins to rotate, its drag-type blades are originally located 150mm from
the axis of the rotors rotation, creating very high starting torque and thus this turbine
can be self starting at low wind speeds. Once the turbine rotates, its drag-type blades
can be moved from its original position to a position as close as possible to the axis of
the rotors rotation in order to achieve high power coefficients. A small scale model
of this envisaged hybrid wind turbine will be constructed in the future and its
aerodynamic characteristics will be studied through wind tunnel testing.
Acknowledgments
The authors would like to acknowledge the support provided by the National
Natural Science Foundation of China (60974049 and 61004053) and the School
Natural Science Research Project of Nantong University(10Z077 and 10Z020). The
corresponding author is Guoqing Wu.
References

[1] M.Islam, D.S.k.Ting and A.Fartaj, Performance Analysis of a Smaller Capacity

Straight-bladed VAWT with Prospective Airfoils, Renewable and Sustainable Energy Reviews,
Vol.12 (2008)No.4, p.1087-1109.
[2] H.J.Tian, T.L.Wang and Y.Wang, SUMMARIZE OF THE DEVELOPMENT OF THE
VERTICAL - AXIS WIND TURBINE, Applied Energy Technology, (2006) No.11, p. 22-27.

[3] French] D. LeGourieres. Theory and Design of Wind Turbine. Machinery Industry
Press,
(1987), p.122-151.
[3] Y.Li. Technology seminars of vertical axis wind turbine (Two).
Renewable Energy,
(2009)No.2, p.119~121.
[4] Y.Li: Technology seminars of vertical axis wind turbine (Three).
Renewable Energy, (2009) No.3, p. 120-122.
[5] J.J.Qu, M.W.Xu and Z.J.Li: A kind of coupled lift-drag type wind axis wind
turbine. Renewable Energy Resources, (2010) No.1, p.101-104.
[6]G.C.Zhang, Z.H.Xu and Y.zhang: The computational study of a kind coupled
lift-drag type wind axis wind turbine. Journal of Shenyang Institute of
Aeronautical Engineering, (2010) No.5, p.29-32.
[7] Chen Jian,Jan Kumbernuss,Zhang Linhua,et al.Influence of Phase-Shift and
Overlap Ratio on Savonius Wind Turbines Performance[J].Journal of Solar
Energy Engineering, 2012(134):19.
[8] M. Raciti Castelli, A. Englaro and E. Benini: The Darrieus wind turbine:
Proposal for a new performance prediction model based on CFD. Energy, (2011)
Vol.36(8), p.4919- 4934.

153

14

ECO-GREENERGYTM: THE FUTURE OF SMALL HYBRID WIND-SOLAR

ENERGY GENERATION SYSTEM
a,

a,b

W.T. Chong *, W.K. Muzammil , A. Fazlizan , H. Taheri , M. Gwani , L.H. Chew , S.C. Poh
a

Department of Mechanical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala

Lumpur, Malaysia
b
School of Engineering and Information Technology, University Malaysia Sabah, Jln UMS,
88400 Kota Kinabalu, Sabah, Malaysia
c
Faculty of Law, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Corresponding author: chong_wentong@um.edu.my (W.T. Chong)

ABSTRACT
Developments on small hybrid wind-solar energy generation systems for applications in
urban and remote areas have gained much attention due to the flexibility of the system to be
deployed anywhere without being connected to the electrical grid. In this paper, a novel
shroud-augmented vertical-axis-wind-turbine (VAWT) and solar photovoltaic (PV) panel
hybrid energy generation system is introduced. The standalone hybrid system has a
compact design that harmoniously integrates a VAWT with the novel omni-direction-guidevane (ODGV) and solar PV panel to power an LED lighting system which may be used to
light building compounds, resorts, beaches, sky gardens, parks, mountain ranges or forests.
The ODGV is designed to surround the VAWT for wind power augmentation by guiding the
oncoming airflow and creates a venturi effect to increase the wind-stream speed before it
interacts with the wind turbine blades. The ODGV can be used in low wind speed regions by
improving the starting behavior of the VAWT. Wind tunnel tests were carried out in which
the VAWT was positioned in a free-running condition and it was found that the ODGV
reduced the self-starting wind speed of the wind turbine to 4 m/s (bare VAWT self-starting
wind speed was 7.35 m/s). Furthermore, the ODGV increased the power output of the
VAWT by 3.48 times compared with the bare VAWT at its peak torque. Apart from using the
green energy generated from the hybrid system to power the LED lights, additional energy
can be stored in a battery or used to supply energy demand for other appliances (e.g. CCTV
camera). With these benefits, the system may be used to alleviate the usage of fossil fuels
in energy generation and therefore building a more sustainable future.
Keywords: Hybrid renewable energy; omni-direction-guide-vane; wind energy; solar energy;
vertical axis wind turbine; on-site power generation
INTRODUCTION
Renewable energy sources i.e. wind and solar energy are recognized as potential sources for free,
clean and inexhaustible energies. In European cities, organizations involved in planning are urged to
place wind turbines closer to populated areas due to the decreasing number of economic sites
(Wagner, Bareiss, and Guidati, 1996). However, for a wind turbine to be used in an urban area,
issues such as the structural strength of the wind turbines, failures of blades, acoustic pollution (due
to large wind turbine blades) and electromagnetic interference should be addressed (Knight, 2004,
Oppenheim, Owen, and White, 2004). As such, on-site energy generation using micro or small wind
turbines have been explored by researchers for the past few decades in order to integrate wind
energy machines into urban settings. This is to ensure that the issues troubling the use of wind
turbines in urban areas can be overcome. Conversely, autonomous and self-powered systems at
remote locations (environmental parameters data logger, water level monitoring for flood prevention,
telecommunication installations for surveillance and emergency response) may be equipped with
solar or wind energy systems or a combination of both to supply small electrical loads. The concept of
on-site renewable energy generation is to extract energy from renewable sources close to the area
where the energy is required. The advantages of using a hybrid wind-solar energy generation system
have been discussed in literatures (Andrews, 1976, Beyer, Gabler, and Luther, 1988, Gabler and
Luther, 1988, Ter Horst et al., 1986). These advantages, however, depend on the climatic pattern and
distribution of wind and solar energy resources. The benefits include:

Overall costs for self-powered systems may be reduced drastically

154

High reliability without backup power sources

Supplying load demand under varying weather conditions

Due to these advantages and to further improve the performance of the wind turbine, this paper
presents the Eco-GreenergyTM small hybrid wind-solar energy generation system. It incorporates the
novel omni-direction-guide-vane (ODGV) for integration with a vertical axis wind turbine (VAWT) and
solar photovoltaic panel for on-site standalone energy generation that can be deployed in urban or
remote areas.
WORKING PRINCIPLES AND GENERAL ARRANGEMENT
This renewable energy system combines the hybrid wind-solar energy generation, energy-saving
lighting and rain water collection system into one compact design. The concept harmoniously
integrates a wind turbine, solar photovoltaic panel and a power-augmentation device called the omnidirection-guide-vane. Conventional method of extracting power from the wind in areas where there is
an uncertainty of wind speed and turbulence generated from the surrounding obstacles is not
efficient. The ODGV overcomes the inferior aspect of the low wind speed by creating a venturi effect
through the use of guide vanes to increase the natural wind-stream speed before entering the wind
turbine. The general arrangement of this system is shown in Fig. 1.

Fig. 1. General arrangement of hybrid wind-solar outdoor lighting system.

The system comprises of a pole and a light source where a reflecting cover shrouds the light source
and bottom part of the VAWT. Multiple lamps can be adapted to be fitted under the reflecting cover.
The pole can have heights in the range of between 2 to 30 meters above ground level. The reflecting
cover provides a reflecting surface for light source to illuminate a street, park or its surroundings. The
ODGV has multiple guide vanes surrounding the VAWT to face the oncoming wind stream from all
directions. The center drive shaft of the VAWT is directly connected to the generator. The solar panel
is strategically placed on top of the upper wall duct. The energy generated from the VAWT and solar
panel is used to power the light source. Moreover, any excess energy generated from the system can
be stored in a battery or fed into the grid line. The upper wall duct forms a collector for rain water flow
towards the center of the duct or through the ODGV. The inclined panels guide the rainwater through

155

a rainwater passage that shares a center axis as the VAWT. On top of the water passage, a water
mesh is fitted to filter foreign objects from entering the passage. The stored water can be used to
water plants or flushing of the micro-turbine. It can also be treated, stored and used for general
purpose. Additionally, the shrouds of the ODGV surrounding the VAWT prevents the blade to fly off
and cause any injuries to the surrounding people, thus enhancing the security feature of the system.
Design of omni-direction-guide-vane (ODGV)
As discussed, the proposed VAWT integrated with ODGV is a compact renewable energy system that
overcomes inferior wind speed by guiding and increasing the speed of the natural wind-stream
through the ODGV, as shown in Fig. 2. The wind turbine can be in any form of new or existing VAWT
(lift-type or drag-type) or combination of VAWTs (e.g. Darrieus wind turbine coupled with egg-beater
type/S-rotor type). The guide vanes are used to guide the wind stream to a better angle of attack for
wind turbine blades. The guide vanes are designed to create a venturi effect in order to increase the
speed of wind before it interacts with the wind turbine. The channels in which the wind streams flow
through are formed by the surfaces of upper wall duct, lower wall duct and guide vanes. The ODGV
consists of several (more than 2) guide vanes that surrounds the VAWT. The guide vanes can be
adapted in the form of straight plate, curve plate or multiple straight segments plate with constant or
variable thickness, as shown in Fig. 2.

Fig. 2. Omni-direction-guide-vane (ODGV).

The cross sectional area of the intake of ODGV is preferably two time or more than the cross
sectional area of the exit of guide vanes. The inclination angle of upper and lower duct wall is
preferably 10 degrees to 80 degrees from the horizontal plane. By inducting higher wind speed into
the VAWT; smaller and lighter rotating parts of wind turbine can be used to create the same power
output, with lesser load on the bearing of turbines and reduced moment of inertia for better starting
behavior. By using smaller wind turbine inside the ODGV, it can eliminate or further minimize the
electromagnetic interference issue and noise level caused by large wind turbine with long blades.
Moreover, using smaller parts in the overall system will result in a lower cost design. In order to
minimize power consumption, LED lamp is adapted as the light source due to its durability. A battery
can be adapted to store energy generated from the wind turbine and solar panel. Excess of energy
generated from the system can be used to power other electrical appliances or fed into the grid. A
compartment housing to place the hybrid controller and battery can be placed at the bottom of the
pole. An artists impression of the system is shown in Fig. 3.

156

TM

Fig. 3. An artists impression of the Eco-Greenergy

hybrid wind-solar energy generation system.

EXPERIMENTAL STUDY OF THE OMNI-DIRECTION-GUIDE-VANE

The experiment was conducted to show that the ODGV fitted on the Eco-GreenergyTM hybrid windsolar energy generation system can improve the performance of the wind turbine. In the following
sub-sections, the ODGV design to be used in the experiment is presented, wind tunnel testing was
carried out and the results from the experiment are tabulated and discussed.
Omni-direction-guide-vane (ODGV)
The design shown in Fig. 4 is used for the experimental study of the ODGV and its effects on the
performance of the VAWT. The ODGV has four pairs of guide vanes, with each pair tilted at angles of
20 and 55 as shown in Fig. 5(a). The guide vane pairs are designed equally spaced from each
other, and around a cylinder with tapered feature at the outer radial band. The radial placement of the
guide vanes permits the wind to be captured from all directions without the use of a yawing
mechanism.

Fig. 4. Dimensions of the ODGV (Chong et al., 2013).

Preliminary testing on the ODGV

An initial testing was conducted to simulate oncoming airflow in a real world environment where the
wind stream is swirling and turbulent. Oncoming wind stream from three different directions, i.e. 0,
30and 60were simulated through the use of three industrial fans arranged in parallel. An ODGV

157

model with dimensions shown in Fig. 4 was used to enclose a Wortmann FX630137 5-bladed VAWT,
as shown in Fig. 5(b). The experiment concluded that the ODGV increased the rotor rotational speed
to about two times more than a bare VAWT. This significant result proves that the ODGV can improve
the performance of a wind turbine.

(a)

(b)

Fig. 5. (a) The arrangements of the guide vanes (Chong et al., 2013) (b) The 5-bladed H-rotor VAWT.

Wind tunnel test

Fig. 6. A schematic side view of the experimental test rig in a wind tunnel (Chong et al., 2013).

A wind tunnel test was conducted at the Aeronautics Laboratory, University Teknologi Malaysia.
Similarly, the ODGV and VAWT parameters from the preliminary test were used in the wind tunnel
test, as shown in Figs. 4 and 5. Fig. 6 illustrates the experimental set-up of the VAWT which is
shrouded by the ODGV. Two different configurations were carried out during the experiment:

A bare VAWT without ODGV

An ODGV integrated VAWT

158

Initially, the wind speed in the wind tunnel was increased steadily until the VAWT started to rotate.
This is to assess the self-starting characteristics of the wind turbine for both of the configurations. The
wind turbine for this initial assessment was subjected to the inertia and bearing friction only (no
external load). Subsequently, in order to evaluate and compare the rotational speed and power
generated by the wind turbine for both the configurations, a 6 ms-1 wind speed was used for the
following experiments. Hysteresis brake was used to apply loads on the shaft rotor. By adjusting the
brake, the load exerted on the shaft is increased steadily until it reaches the maximum when the
rotational speed of the rotor is stabilized. The maximum torque and power generated by the wind
turbine is recorded and calculated accordingly.
RESULTS AND DISCUSSIONS
Self-starting behavior
The results from the assessment of self-starting behavior of the VAWT are tabulated in Table 1. Under
the same test conditions, the bare wind turbine started to rotate at a recorded wind speed of 7.35
m/s1. Meanwhile, the ODGV integrated VAWT self-started at a reduced wind speed of 4 m/s1. With
lower self-starting wind speed, the ODGV improves the performance of the wind turbine and
increases the operating hours of the wind energy system. At 6 m/s1 wind speed, the ODGV integrated
VAWT recorded a maximum rotational speed of 256 rpm, as opposed to the maximum rotational
speed of 91 rpm recorded by the bare VAWT. Hence, by using the ODGV, the rotor rotational speed
of the wind turbine was increased by about 182%.
Table 1. Assessment of self-starting characteristics of ODGV integrated VAWT and a bare VAWT (Chong
et al., 2013).
Parameter
1

Self-starting wind speed (m/s )

1

Maximum rotational speed at 6 m/s (rpm)

ODGV integrated VAWT

Bare VAWT

4.00

7.35

256

91

VAWT performance
Table 2 shows the summary of the VAWT performance for both the configuration types. As discussed
previously, the wind speed of the wind tunnel was set to 6 m/s1. The bare VAWT produced a
maximum torque of 11.25 mN.m at a steady rotational speed of 77.4 rpm. As a result, 0.1252 W was
generated after calculating the losses due to bearing frictions.
-1

Table 2. VAWT performance results at wind speed of 6 m/s (Chong et al., 2013).
Parameter

ODGV integrated VAWT

Bare VAWT

Augmentation ratio

Maximum torque (mN.m)

23.64

11.25

2.10

Rotational speed (rpm)

144.4

77.4

1.87

Power generated (W)

0.4352

0.1252

3.48

The ODGV integrated VAWT recorded a maximum torque of 23.64 mN.m at a steady rotational speed
of 144.4 rpm. Thus, 0.4352 W of power was produced. The augmentation ratios in power generated
and maximum torque by comparing both of the configuration types are 3.48 and 2.10 respectively.
CONCLUSIONS
This paper introduces a novel invention designed to utilize wind and solar energy to provide power for
outdoor lighting. The outdoor light system comprises of a pole, an omni-direction-guide-vane and a
light source (LED lamp) fitted at the lower part of the ODGV, where a reflecting cover shrouds the
light source to enhance its luminosity and provide better light distribution. A vertical axis wind turbine
is enclosed within the ODGV, in which the ODGV has multiple flow channels formed by the guide
vanes, upper and lower wall ducts inclined at an angle of 10 to 80 degrees from the horizontal plane.
The guide vanes are designed to create a venturi effect and thus the speed of the natural windstream entering the wind turbine intensifies. This improves on the weak and turbulent characteristics
of wind in urban areas. From the wind tunnel testing, the ODGV successfully improved the selfstarting characteristics of the VAWT. At a wind speed of 6 m/s1 in the wind tunnel, the rotor rotational
speed recorded an increase of 182% at free-running condition. Furthermore, the power output at
maximum torque for the ODGV integrated VAWT is 3.48 times higher than the bare VAWT.

159

Assessment of both of these wind turbine configuration types (bare and integrated ODGV) with both
having the same specifications (blade length, swept area and aerofoil profile) reveals that the ODGV
integrated VAWT improves on the many disadvantages of a bare VAWT. Furthermore, the on-site
energy generation capability of the system eliminates the issues concerning conventional street
lighting system such as trench wiring and landscape replacement after trenching. This novel design
promotes the use of renewable energy in urban areas and thus can be implemented to reduce
greenhouse gas emissions by minimizing the dependencies on fossil fuel reserves for energy
generation.
ACKNOWLEDGEMENT
The authors would like to thank the University of Malaya for the assistance provided in the patent
application of this design (Patent no: PI 2013700243), and the research grant allocated to further
develop this design under the University of Malaya Research Grant (RP015C-13AET) and
Postgraduate Research Grant (PG047-2012B). Special appreciation is also credited to the Ministry of
Education Malaysia (MOE) for the research grant (Fundamental Research Grant Scheme, FRGS
FP053-2013B).
REFERENCES
Andrews, J.W. 1976. "Energy-storage requirements reduced in coupled wind-solar generating
systems." Solar Energy no. 18 (1):73-74.
Beyer, H.G., H. Gabler, and J. Luther. 1988. "Elektrische Solar/Wind Hybridsysteme." In Tagungsbericht
6. Int. Sonnenforum, 106-113. Berlin, Germany.
Chong, W.T., A. Fazlizan, S.C. Poh, K.C. Pan, W.P. Hew, and F.B. Hsiao. 2013. "The design, simulation
and testing of an urban vertical axis wind turbine with the omni-direction-guide-vane." Applied
Energy.
Gabler, H., and J. Luther. 1988. "Wind-solar hybrid electrical supply systems-results from a simulation
model and optimization with respect to energy pay back time." Solar Wind Technol. no. 5:239247.
Knight, J. 2004. "Breezing into town." Nature no. 430:12-13.
Oppenheim, D., C. Owen, and G. White. 2004. "Outisde the square: Integrating wind into urban
environments." Refocus no. 5:32-35.
Ter Horst, E.W., K. Blok, E. A. Alsema, and W.C. Turkenburg. 1986. "Optimization of hybrid
autonomous energy systems." In Proc. 7th European Community Photovoltaic Solar Energy
Conf., 257-262. Sevilla, Spain.
Wagner, S., R. Bareiss, and G. Guidati. 1996. Wind turbine noise. Berlin: Springer.

160

NUMERICAL SIMULATION OF TRANSIENT FLOW ON VERTICAL AXIS WIND

TURBINE WITH THE POWER-AUGMENTED STATOR VANES
a,

W.T. Chong *, A. Fazlizan , K.H. Wong , S. Julai , C.J. Tan and L.F. Sim
a

Department of Mechanical Engineering, Faculty of Engineering, University of Malaya,

50603 Kuala Lumpur, Malaysia
b

Department of Mechanical and Industrial Engineering, College of Engineering,

Qatar University, Doha, Qatar
*

Corresponding author: chong_wentong@um.edu.my

ABSTRACT
The energy crisis encourages the application of vertical axis wind turbine (VAWT) in many
cities around the world. However, the shadow effect of the high rise building in urban area
always causes inconsistent incoming wind flow to the VAWT, hence causes low efficiency. In
order to improve the performance of the VAWT, this paper presents the numerical study on a
novel power augmented stator vanes integrated with the VAWT. These stator vanes
constructed from six plates which evenly distributed around the VAWT. By channelling the
wind flow to a better angle of attack of the VAWT blades, it can reduce the starting torque and
increase the coefficient of power of the VAWT. A 2D simulation was conducted by using
commercial computational fluid dynamics software, FLUENT 14.0, on the single bladed NACA
0015 VAWT. The simulation applied the shear stress transport (SST) k- turbulence model
for the transient flow of the VAWT. Sliding mesh method was used to simulate the relative
motion of the stationary vanes and the rotating VAWT with tip speed ratio 5.1. The simulation
result is validated by the experiment data published by the Sandia National Laboratories.
From the simulation, it shows that the coefficient of torque is increased by 134.2% compare to
the bare VAWT. This improvement is due to minimise of the negative torque especially on
azimuth angle 90 degree and the second half cycle. As a result, this power augmented stator
vanes can solve the low efficiency problem of VAWT which installed in urban area.
Keywords: Vertical Axis Wind Turbine, Computational Fluid Dynamics, Stator Vanes, SST k Turbulence model, Coefficient of Power.

INTRODUCTION
The increase of the energy demand around the world and the depletion of fossil fuel, have led
to the application of renewable energy as alternative energy source. Besides that, the
environmental issue that human being faced, for instance, ozone depletion and global
warming, make this green energy getting higher share in total energy generation.
Among these green energy sources, wind energy has been developed rapidly especially in
urban area. The main advantages for this building integrated wind turbine are it utilising the
natural wind energy resources, provide better power distribution, and the economic
exploitation of roof top of the building (Toja-Silva, Colmenar-Santos, & Castro-Gil, 2013) Wind
turbine is a mechanical device which converts the kinematic wind flow energy to the electric
energy. Generally, there are two types of wind turbine which are the vertical axis wind turbine
(VAWT) and the horizontal axis wind turbine (HAWT).
There are several advantages of VAWT compare to HAWT. Among these advantages, first,
the construction of VAWT is much simpler than HAWT. VAWT is omni-direction to the
incoming wind; therefore it does not need yaw mechanism to detect the wind direction where
HAWT is highly depending on this yaw mechanism. Due to the omni-direction incoming wind,
the VAWT have small sway space and footprint for the installation, where the blades
operation space is small. Besides, less noise produce and visual impact, less obstruction to
birds and the low installation height from ground, make this wind turbine become popular in

161

urban area. However, the main drawback for the VAWT compare to HAWT is low efficiency in
self-starting mechanism (Aslam Bhutta et al., 2012; Eriksson, Bernhoff, & Leijon, 2008;
Mohamed, 2012; Toja-Silva et al., 2013)
Wind turbines need to have certain wind speed as the cut-in wind speed to create a starting
torque for it to rotate and generate electricity. Research shows that in order to create the
maximum ratio of the lift force to the drag force (L/D ratio) of the blade, the streamline of the
wind need to be in the direction of the optimum angle of attack for the wind turbine blade
(Chong et al., 2013a). For VAWT, although wind can come from any angle, but not all the
blades can always create the maximum L/D ratio. The L/D ratio varies with the azimuth angle.
In many cities around the world, the wind speed is low throughout the year. This is due to the
shadow effect created by the high rise building. Therefore the efficiency of the VAWT is
always the main concern to all researchers. Over the years there are many innovative design
of the VAWT including the use of shroud to increase the total power generated. According to
Yao et al. using 8 baffles blades evenly distributed to the drag type Savonius VAWT in the
cowling tower, the research shows that the design increase the power coefficient by increase
the wind speed reaching the wind turbine and reduce the negative torque by adjusting the
wind direction (Yao, Tang, & Wang, 2013).
Similar to M ller et al., their research adapt an old form of wind energy converter in modern
building integration. The design can increase the theoretical efficiency about 48% and the
optimistic state up to 61% (Mller, Jentsch, & Stoddart, 2009). Ducted wind turbine which
introduce by Grant et al. install the wind turbine at the edge of the buildings roof which
improve the power coefficient higher than the Betz limit. However, the main drawback for the
design is the wind turbine can only operate with the wind direction perpendicularly (Toja-Silva
et al., 2013). The Zephyr turbine used stator vanes distributed evenly with reversed winglets.
The in-coming wind will enter the ring of stator blades which direct the wind to leave at
particular angle of attack and strike with the Savonius rotor hence increase the power
generated. This stator blade reduce the turbulence flow hence decrease the aerodynamic
loading on the blade. The optimum TSR for this design is 0.4, when the wind further increase
the TSR, the power coefficient obtained will be reduced (Pope et al., 2010).
For Chong et al. research on the omni-directional power augment guide vane (PAGV) which
is a hybrid renewable energy system consists solar power generation and rain water collector
for urban high rise building. The system utilise the PAGV which surrounds the VAWT that
orients the air inlet and wind speed to the blades. It shows that the improvement on the selfstarting behaviour where it lower down the cut in speed with the omni-direction PAGV, hence
the working hour will be increased. The rotor speed is increased as much as 182% and the
power output is increased by 3.48 times at the peak torque. The design of the vane can
minimize the negative torque created on the lift type wind turbine (Chong et al., 2013; Chong,
Fazlizan, Poh, Pan, & Ping, 2012; Chong, Naghavi, Poh, Mahlia, & Pan, 2011; Chong et al.,
2013).
This paper presents a novel design of power augmented stator vanes system which can
improve the performance of the VAWT. Numerical method was used to study and analysed
the fluid flow on the system. From this study, result shows that with the power augmented
stator vanes system able to increase the coefficient of torque of the VAWT greatly. Moreover,
the system is compact and easy to retrofit on existing VAWT; therefore it is suitable to be
installed at urban area where the wind speed is uncertain.

NOVEL DESIGN OF POWER-AUGMENTED STATOR VANES

An innovative design of power augmented stator vanes is designed and integrated with the
VAWT to increase the efficiency which built on the building in urban area. This system is in
cylindrical shape with stators vanes constructed by 6 plates evenly distributed around the
wind turbine. Each of the stator vanes was tilted 25 degree from the rotational axis of the
VAWT. Fig. 1 shows the top view of the stator vanes system. The outer diameter of the
system is double of the diameter of the VAWT.

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The main function of these stator vanes is able to deflect the incoming wind flow to hit with the
optimum angle for the blades of the lift type VAWT. By channelling the wind flow, higher lift
force will be create on the blades of the VAWT at the first half cycle, hence the cut in speed
for the VAWT can be reduced. Besides, with these vanes, it will direct the wind flow out from
the VAWT and able to minimise the negative torque created on the second half of the
rotational cycle.
a

Fig. 1. Top view for the stator vanes system a) at 0 degree, b) rotated 30 degree azimuth angle

NUMERICAL METHOD
The commercial computational fluid dynamics (CFD) software, ANSYS FLUENT 14.0 was
used to simulate the current work. This study involved simulate and compare the bare single
bladed NACA 0015 lift type VAWT and the integrated power-augmented stator vanes system.
This VAWT is selected in the study is due to the availability of reference experiment data
which accomplished by Oler et al. published by Sandia National Laboratories. (Oler, 1983).
The simulation is verified Olers experiment data.
According to Olers experiment, a straight-one-bladed rotor with NACA 0015 was built and
operated in a water tow tank with 10 meters length, 5meters width and 1.25 meters depth.
The chord to radius (C/R ratio) value is 0.25, and the experiment conducted by using water as
working fluid that facilitate relatively low frequency measurements while working at
appropriate blade Reynolds numbers. Besides, the blade forces and pressures are more
easily to be measured. The summary of the experiment data as shown in table 1 (Oler, 1983):

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Table 1: Olers experiment parameter

Parameter

Value

Airfoil

NACA 0015

Chord length, c (m)

Rotor tip speed, R

0.1524
(m/s)

0.457

Reynolds number, Re

67,000

Towing speed (m/s)

0.091

Rotor radius, R (m)

0.61

Tip speed ratio, TSR

5.1

In this 2D simulation, sliding mesh method is used to compute the relative motion between
the rotating VAWT to the power augmented stator vanes. This method able to simulate time
periodic motion which is the solution repeats with period related to speeds of the moving
domain. The concept of this method allows two or more adjacent meshes to move relatively in
each other, and the flow flux will cross the mesh interface.

Geometry modelling

When using the sliding mesh method, two or more cell zone is needed, and each cell zone
must be bounded by at least one interface, where it meets with other opposing cell zone.
Therefore, in this study, two mesh files which identified as the airfoil and the tunnel were
created. Fig. 2 show the mesh for the airfoil whereas Fig. 3 shows the meshes of the tunnel.
For the VAWT mesh, it divided to two regions which are the main grid and the subgrid. The
NACA0015 single bladed profile located in the subgrid where more fine mesh was created.
Whereas, the tunnel space mesh, it modelled according to the Olers experiment tunnel size.
The power-augmented stator vanes located at the center of the tunnel mesh.

Fig. 2. Airfoil mesh

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Fig. 3 Tunnel mesh

For the NACA 0015 airfoil which located in the subgrid, in order to create fine cell near to the
wall, the mesh created using edge sizing along the airfoil edge with bias factor. Fine mesh is
important for compute the coefficient of torque correctly. Fig. 4 shows the NACA0015 mesh
file.The total of elements and the method for the meshing is shown in table 2.

Fig. 4. NACA 0015 mesh

Table 2: Mesh sizing and method

Mesh

Airfoil

Tunnel

Region

Sizing
(m)

Main grid

0.01

Sub grid

0.001

ODGV space

0.01

Face sizing
Face sizing, Mapped
face meshing
Face sizing

Tunnel space

0.05

Face sizing

ODGV wall

0.003

Edge sizing

Method

Total Nodes

Total
elements

322833

32355

72814

71155

Boundary condition
The boundary conditions are show in Fig. 5 below. The inlet is defined as velocity inlet, which
the flow velocity magnitude is constant whereas the outlet was set to be pressure outlet. For
the side boundary and the NACA 0015 airfoil, it was defined as stationary no slip wall.

165

Fig. 5. Boundary condition

Table 3 below shows the computational condition for the simulation. For the turbulence model, k-
SST model was selected for the simulation, where it blends the accurate formulation of the k-

model at the near-wall region with the free stream independence of k- model at the far
field. The time step size was calculated from the tip speed ratio (TSR) where
TSR,

Where
= rotational speed
R = VAWT radius
= incoming wind speed

In this simulation each time step denote 10 degree azimuth angle rotate. Total 10 cycles was
computed for the comparison of the coefficient of torque. The simulation was repeated for the
power augmented stator vanes rotated 15 degree and 30 degree to simulate the condition
where the wind flow from different direction.
Table 3: Computational conditions

Computational conditions
Type

Pressure-Based

Time

Transient

Velocity formulation

Absolute

2D space

Planar

Viscous Model

k-

Material

Water

Density

998.2 kg/m3

Viscosity

1.003 x 10-3 kg/m.s

Pressure

101,325 Pa

Blade Motion Type

Moving Mesh(Rotational)

Reference Frame

Absolute

Inlet Boundary Type

Velocity Inlet

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Velocity inlet

0.091 m/s

Outlet Boundary Type

Pressure Outlet

Residual error

1 x 10-4

Pressure-velocity Coupling

SIMPLE scheme

Gradient

Green-Gauss Cell Based

Interpolating Scheme (Momentum)

Interpolating Scheme (Turbulence Kinetic
Energy)
Interpolating Scheme (Specific Dissipation
Rate)

2nd Order Upwind

Transient Formulation

2nd Order Implicit

2nd Order Upwind

2nd Order Upwind

RESULT AND DISCUSSION

Validation of Simulation Result

The torque coefficient that capture from the simulation versus azimuth angle was plotted and
compared to the experiment data at TSR 5.1. From the simulation results, it demonstrates a
good agreement curve pattern with the Olers experiment date. Fig. 6 show the torque
coefficient versus azimuth angle. According to Roy et al. shows that although the shear stress
transport (SST) k- turbulence model has a general agreement with the actual experiment
result, the 2D simulation result show over predicted compare to experiment data, whereas for
3D simulation will obtain a better result (Roy & Saha, 2013).

Coefficient of torque, Ct

Coefficient of Torque Versus Azimuth Angle

3.0
2.0
1.0
0.0
-1.0

45

90

-2.0

135

180

225

270

315

360

Azimuth angle, o
Oler's strain gage data

SST k-w simulation

Fig. 6. Coefficient of Torque versus Azimuth Angle

Validation of Simulation Result

Fig. 7 shows the coefficient of torque versus azimuth angle for the bare VAWT and the VAWT
integrated with power augmented stator vanes system. From the simulation result, the power
augmented stator vanes show a high the coefficient of torque at azimuth angle 30 degree until 90
degree compare to bare VAWT irrespective of the angle of the wind direction. Besides, for second
half cycle, the stator vanes system also able to create some positive torque to improve VAWT
performance. The average coefficient of torque for is tabulated in table 4 below.

167

Coefficient of Torque versus Azimuth Angle

Coefficient of torque

6.0
5.0
4.0
3.0
2.0
1.0
0.0
-1.0 0

45

90

135

180

225

270

315

-2.0
Azimuth angle, o
bare VAWT
stator vanes rotated 15 deg.

stator vanes
stator vanes rotated 30 deg.

Fig. 7. Coefficient of Torque versus Azimuth Angle

Table 4: Average coefficient of torque

Average coefficient of torque

Bare
VAWT
0.2158

Stator
vanes
0.5055

Stator vanes
rotated 15 deg.
0.3669

Stator vanes
rotated 30 deg.
0.4008

Compare to the bare VAWT, the stator vanes increase the average coefficient of torque about
134.2%.The increase of coefficient of torque at the first quarter of the cycle is mainly due to the
high velocity and volume of wind flow hit with the optimum angle of attack of the airfoil. Fig. 8
shows the velocity vector for the power augmented stator vanes with the airfoil at 0 degree
azimuth angle. From this figure, it shows that the second vanes which highlighted in yellow circle
deflect the wind flow and channel it to the side. This observation is aligned with the research
conducted by D.Kim & M.Gharib. In the research, Kim showed that the efficiency of the counterrotating wind turbine can be increased by a deflector as shown in Fig. 9. The deflector used to
increase the wind flow velocity by tailoring free-stream flow and hence the power output is cube of
the wind velocity (Kim, D.,& Gharib, M., 2013)

168

360

Fig. 8. Velocity vector for airfoil at 0 degree azimuth angle

Fig. 9. Schematics of counter-rotating VAWTs with an upstream deflector (Kim, D.,& Gharib, M., 2013)

CONCLUSION
The performance of VAWT integrated with the power-augmented stator vanes was investigated. A
2D CFD simulation was computed on NACA0015 single bladed lift type VAWT at TSR 5.1 and
0.091m/s incoming wind velocity. From the simulation, it showed that the performance of the
VAWT improve significantly by utilise the stator vanes. The stator vanes channelled the incoming
wind to a better angle of attack of the lift type VAWT cause the coefficient of torque increase
greatly especially at the first quarter of the cycle. Besides, the negative torque created at the
second half cycle was been minimized. The average coefficient of torque was increase about
134.2 % compare to the bare VAWT. This cost effective stator vanes system can be retrofit to the
current VAWT to increase the output power especially for the high rise building at urban area.

ACKNOWLEDGMENT

169

The authors would like to thank the University of Malaya for the facilities and assistance provided
in the patent application (Patent pending: PCT/MY2012/000274), and the research grant allocated
under the project PG047-2012B (Postgraduate Research Grant. Sincere gratitude is also
dedicated to the Malaysian Ministry of Higher Education (MOHE) for the Exploratory Research
Grant Scheme (ER014-2013A).

NOMENCLATURE

c
L/D
PAGV
R
Re
R
SST
TSR
VAWT

Chord length, m
lift force to the drag force
power augment guide vane
Rotor tip speed , m/s
Reynolds number
Rotor radius, m
shear stress transport
Tip speed ratio
vertical axis wind turbine

REFERENCE

Aslam Bhutta, M. M., Hayat, N., Farooq, A. U., Ali, Z., Jamil, S. R., & Hussain, Z. (2012).
Vertical axis wind turbine A review of various configurations and design techniques.
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Chong, W. T., Fazlizan, A., Poh, S. C., Pan, K. C., Hew, W. P., & Hsiao, F. B. (2013). The
design, simulation and testing of an urban vertical axis wind turbine with the omni-directionguide-vane. Applied Energy(0).
Chong, W. T., Fazlizan, A., Poh, S. C., Pan, K. C., & Ping, H. W. (2012). Early development of
an innovative building integrated wind, solar and rain water harvester for urban high rise
application. Energy and Buildings, 47(0), 201-207.
Chong, W. T., Naghavi, M. S., Poh, S. C., Mahlia, T. M. I., & Pan, K. C. (2011). Technoeconomic analysis of a windsolar hybrid renewable energy system with rainwater collection
feature for urban high-rise application. Applied Energy, 88(11), 4067-4077.
Chong, W. T., Pan, K. C., Poh, S. C., Fazlizan, A., Oon, C. S., Badarudin, A., & Nik-Ghazali,
N. (2013b). Performance investigation of a power augmented vertical axis wind turbine for
urban high-rise application. Renewable Energy, 51(0), 388-397.
Eriksson, S., Bernhoff, H., & Leijon, M. (2008). Evaluation of different turbine concepts for
wind power. Renewable and Sustainable Energy Reviews, 12(5), 1419-1434.
Kim, D., & Gharib, M. (2013). Efficiency improvement of straight-bladed vertical-axis wind
turbines with an upstream deflector. Journal of Wind Engineering and Industrial
Aerodynamics, 115(0), 48-52.
Mohamed, M. H. (2012). Performance investigation of H-rotor Darrieus turbine with new airfoil
shapes. Energy, 47(1), 522-530.
Mller, G., Jentsch, M. F., & Stoddart, E. (2009). Vertical axis resistance type wind turbines
for use in buildings. Renewable Energy, 34(5), 1407-1412.
Oler, J. W. S., J.H.; Graham,B.J.Im,G.H. (1983). Dynamic Stall Regulation of the Darriues
Turbine. Sandia National Laboratories (SAND 83-7029 UC-261), Albuquweque, New Mexico.
Pope, K., Rodrigues, V., Doyle, R., Tsopelas, A., Gravelsins, R., Naterer, G. F., & Tsang, E.
(2010). Effects of stator vanes on power coefficients of a zephyr vertical axis wind turbine.
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Roy, S., & Saha, U. K. (2013). Review on the numerical investigations into the design and
development of Savonius wind rotors. Renewable and Sustainable Energy Reviews, 24(0),
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Toja-Silva, F., Colmenar-Santos, A., & Castro-Gil, M. (2013). Urban wind energy exploitation
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Yao, Y. X., Tang, Z. P., & Wang, X. W. (2013). Design based on a parametric analysis of a
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171

TECHNOLOGY ROADMAPPING FOR WIND TURBINE INDUSTRY: CASE OF THE

IRAN
a

Maryam Daneshmand-Mehr , Sepehr Ghazinoory

b,

c,

Mohammad R. Arasti Hami Yousefdehi

a: Department of Industrial Engineering, Payam-e-Noor University, Tehran, Iran,

maryamdm@yahoo.com
b: Department of Information Technology Management, Tarbiat Modares University, Tehran, Iran,
ghazinoory@modares.ac.ir
c: Department of Management & Economics, Sharif University of Technology, Tehran, Iran,
arasti@sharif.ac.ir
d: Faculty of Entrepreneurship,Tehran University,Tehran, Iran, h.yousefdehi@gmail.com

ABSTRACT:
The aim of the study is presenting an integrated technology roadmapping process for wind
turbine industry. As the human societies grow, the amount of energy especially electricity
usage grows as well. Whereas the resources of fossil energies are going to decrease, the
price of them are growing daily and the human need to have clean environment, other
energy resources must be considered. Renewable energies are considered to develop in
many of countries. Iran is one of the countries, which has paid attention to develop
renewable energies. Wind is one of the renewable energies which Iran has a good capacity
because of its climate circumstances. Since, roadmapping is one of the visual tools for
strategic planning that visualizes an entire strategy on one page it has been focused for
providing a common visual framework for mapping strategy in wind industry in Iran. In this
paper we present a roadmapping framework for wind turbine industry in Iran. In this
framework, we have applied PROMETHEE decision making to achieve integrated decisions
in wind turbine industry in roadmapping process. A generic roadmap with three layers,
market, product and technology is presented for aforementioned industry in Iran.
Keywords: Technology Roadmapping; Wind turbine industry; PROMETHEE ; Decision making;
Iran
1- INTRODUCTION
There is a pressing need to accelerate the development of advanced energy technologies in
order to address the global challenges of clean energy, climate change and sustainable
development. According to newest investigation which has been presented by Mousavi et al.
(2012), the wind power will be more competitive to fuel-based power plants. The results of their
investigations shows that wind farms will have a generation cost less than fossil fuel plants. Wind
energy is a clean and environmentally friendly energy source. There are no emissions to air or
water, nor greenhouse gases, it requires no mining or drilling for fuel, and produces no toxic waste.
Therefore, the wind energy is the most advanced of the new renewable energy technologies, but
there is still much work to be done. Since, the implementation of Iran Economic Development Plan
has increased gas and oil prices in Iran, more investment and development in wind power sector
are expected.
A roadmap are needed to identify the key tasks that must be undertaken in order to achieve a
vision of over 1000 MW of wind energy capacity by 2015 in Iran. Governments, industry, research
institutions and the wider energy sector will need to work together to achieve this goal. The
roadmap aims to identify the primary technological tasks that must be addressed in order to
achieve its vision for wind energy deployment. Wind turbine industry in Iran has been investigated
for this mean. An integrated roadmap with 10-year time frame and three layers are presented. In
this paper, we have presented a framework for integrating decisions in roadmapping process with
the concept of PROMETHEE as a decision making method. The objective of the study is

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presenting an integrated roadmapping process in industry level where you are encountered with
market, product and technology as the layers of a generic roadmap. Decisions for each layer are
made integrally with decisions of other layers. Therefore in wind turbine industry among 10 years,
the decisions about market, products and technologies are planned.
2- LITERATURE REVIEW
Renewable energy sources which are included solar electric, wind, geothermal, biomass and
small and low- impact hydro can be used to produce electricity with fewer environmental impacts.
The modern age of wind power blew in the late 1970s, and the first wind plants began to appear in
California in the 1980s. Today, wind power is the fastest-growing new source of electricity
worldwide. According to Charles McGowin, wind-power technical leader at the Electric Power
Research Institute (EPRI), the industry is growing at 20 to 30 percent annually and has become:
the most economical renewable energy resource as a result of the large growth in the market.
Technology Innovation Office (2006) reports that although wind power is becoming a mature
technology, large-scale wind integration presents some unique challenges due to its intermittent
nature.
Amer and Daim (2010) have mentioned that roadmapping as a tool for strategic planning are
used to national, industry/sector and organization level. Technology Roadmapping (TRM) is a very
flexible and powerful approach widely used in industry for strategy planning and integrating
business and technology. Goals and objectives of renewable energy roadmaps are different at
these three levels. At national level, roadmaps focus on future energy security, energy
dependence, energy policy formulation and environment protection. At industry/sector level,
roadmaps are used to identify vision, common needs and evaluate barriers, constraints and risks
faced by the industry from technical, political and commercial aspects. In addition, they have
mentioned that one of the roadmaps objectives in industry/sector level is providing direction to
future of the industry. American Wind Energy Association (2002) (AWEA) has published a 20-year
industry plan for small wind turbine technology. The roadmap of the U.S. small wind points to
technology, market, and policy goals and the specific actions necessary to meet these goals. For
roadmapping, technology, market and policy barriers were recognized for near-term (0-3 years),
mid-term (4-10 years) and long-term (11+ years). In addition, market potential, technology
opportunities were determined in roadmapping process.
Daim et al. (2012) have considered the environmental concerns, rising cost and dependency
on fossil fuel, business opportunities, government involvement and availability of natural wind
resources as market drivers which are the basis of the roadmap. Based on aforementioned
aspects, they have presented a four-layer roadmap for wind energy in the Pacific Northwest. They
have presented a roadmap for each layer analysis. The presented roadmap is included
components of technologies, technology, products and market drivers as four layers. They have
pointed that the linkages and connections between the aforementioned layers are derived from
functionality, research and future assumptions based on detailed research in these areas. But,
there is not mentioned to detail of how it has been done. In other words, it seems that the
decisions and preferences are made in each layer separately. Then linkages are done. The Korea
Institute of Energy Research (KIER), has presented an execution flowchart to formulate a longterm (2006 to 2015) strategic Energy Technology Roadmap (ETRM) with three stages which,
serves to identify the primary energy technologies that should be developed. Lee et al. (2009)
have identified technology and clustered them in 3 sectors, technology analysis, capacity analysis
accordance with analyzed technologies and core technology selection are the aforementioned
stages. At last individual ETRMs are formulated. A master TRM are shaped at first for showing the
improvement of technology or new technologies. Then an individual roadmap is shaped for a
system technology in various recognized criteria which is the layer of the roadmap. It seems that
products are introduced after locating technologies in the roadmap. Therefore, the resource based
view concept is applied in TRM.
There are some researches in field of wind energy in Iran. Fadai (2007) has investigated Irans
feasibility of manufacturing wind turbines. The capability of manufacturing small wind turbine
(<10MW) was %100 in Iran. Najafi and Ghobadian (2011) have investigated Irans wind energy
resources and development. According to their research, Iran with generating 47 MW (Megawats)

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of electricity from wind energy ranked 30th in the world in 2006. Iran had 130 MWh wind power
capacity ranked 38th in 2009. The main wind power plants locations have been introduced as well.
Bagheri Moghaddam et al. (2012) have presented creative imitation and proactive localization as
Irans directional strategies of wind turbine industry. Technological capability in manufacturing
main parts of wind turbines in different sizes have been presented by Bagheri Moghaddam et al.
(2011). They have shown the potential and effective states of technological capability for the main
parts of each size of wind turbines. Aslani and Antila (2012) have identified a set of important
investment indicators which are considerable from private sector viewpoint in Iran. Technical,
business and policies, environmental criteria are three main investment criteria groups. Each of
them has some sub criteria.
3- MATERIAL AND METHODS
3-1- Energy and Wind energy in Iran
Iran, located in the Middle East region, had a population of 74.5 million in 2011 and is a
developing country. The status of energy and wind energy in Iran are briefly introduced in the
following two sections.
3-1-1- Irans energy status
Iran is a member of the Organization of the Petroleum Exporting Countries (OPEC), ranks among
the worlds top three holders of both proven and natural gas reserves. Iran is OPECs 2nd largest
producer and exporter after Saudi Arabia (Figs. 1 and 2). Najafi and Ghobadian (2011) have
presented that half of Irans total domestic energy consumption is natural gas, while the remaining
half is oil. In addition, according to what Bagheri Moghaddam et al. (2011) have mentioned that oil
and gas have allocated 80% of Irans export share and 90% of electricity. Najafi and Ghobadian
have presented that Iran produced about 5% of global production and was 4th largest exporter in
the world in 2008 as well. Fig. 3 shows the status of total energy consumption by type in 2008 in
Iran.

Fig.1. Top proven world oil reserves (billion barrels) in 2010 (Najafi and Ghobadian 2011).

Fig.2. World natural gas reserves (Trillion cubic feet) in 2010 (Najafi and Ghobadian 2011).

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174

Fig.3. Total energy consumptions in Iran by type 2008 (Najafi and Ghobadian 2011).
Research center of Parliament of Islamic Republic of Iran has studied the latest status of
"new energies in Iran. According to this report which is investigated by Darvish Tavangar et al.
(2012) the renewable energies due to their simple technology against nuclear energy technology
on the one hand and also due to not create problems such as nuclear waste on the other hand,
play an important role in new energy systems in the world.
Studies of the estimates of wind energy potential in Iran show that only in 26 regions of the country
(including more than 45 suitable sites), nominal capacity of sites is about 6500 MW by considering
an overall yield of 23%, while nominal capacity of the total power plants of the country is 60000
MW. Concerning solar energy, 11 projects are in operation or under implementation by the Ministry
of Energy in the whole country which are related to solar energy. The total of solar power
generation of the country in 2004 is equal to 14020 kW that has increased to 67000kW at the end
of 2010. Also, the total nominal capacity of biogas plants is 1860 kW, the total of scientific capacity
is 1665 KW and non-specific production is 5967 GW.
3-1-2- Irans wind energy
Aslani and Antila (2012) have mentioned that from geographical situation, Iran is located in
the path of main air currents between Asia, Europe, Africa, Indian Ocean and Atlantic Ocean.
Iranians were the first people to create added value of wind energy using windmills. A number of
these windmills which date back to 200 years B.C., are still at work in some rural regions of
Khorasan province. Due to its geographical location and heterogeneous climate, Iran has good
renewable energy resources. With regard to Iran wind energy, for instance, after current analyses,
a 15 GW potential is confirmed by German company and is estimated up to 40 GW. But
considering the installed wind capacity (approximately 100 MW), by the end of 2009, Iran had the
world's 38th ranking. This ranking is not sufficient for Iran with regard to available wind capacities
and abundant wind power development stimuli. The demand for energy is growing rapidly in Iran
because of its social and economic development. Iran has not a successful experience in wind
energy development like some other countries. However, there are also some countries which are
developing wind sector rapidly and increasing significant wind energy capacity each year. Actually,
there are main factors which prevent Iran from developing wind sector by reviewing its
development briefly. The role of development level and economic dependency to fossil resources
in wind innovation system is studied. In addition, there are many problems that Irans industry is
faced, like disordering, financial and sanction.
3-2- Wind Industry in Iran

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Based on GWEC report, which have been mentioned by Najafi and Ghobadian (2012) and
Bagheri Moghaddam et al. (2011), Iran is the only country that have installed wind power on a
large scale in the Middle East. Iran had wind power capacity of 130MW in 2009 ranked 38th in the
world.
Because of the major cost of investment in wind powerhouse is the cost of wind turbine (75%),
wind turbine industry are investigated.
3-2-1- Wind turbine classifications
The most popular wind turbine is 3-blade turbine. This turbine has four main sections: nacelle,
rotor, tower and foundation. A popular wind turbine classification is in terms of produced energy or
power (Kilo Watt). According to what Bagheri Moghaddam et al. (2011) have presented, three
main groups of wind turbine are: small, intermediate and large. Small wind turbine (
KW); its
applications are in farm, home for ice making, water pumping. Intermediate wind turbine (10-250
KW), in which is used for village power, hybrid systems and distributed power. Large wind turbine
(250-+2MW) is used central station wing farms and distributed power. Large wind turbine is
classified in two groups: onshore and offshore. With regard to the high capacity available for
onshore wind resources in Iran, and also the high costs of offshore turbines compared to onshore
turbines, feasibility studies currently carried out in Iran focus on using big onshore turbines.
3-3- Roadmapping for wind turbine in Iran
As we mentioned in literature review, a generic roadmap is included three layers which are:
market, product/service and technology layer. Integrated decisions are put in roadmap so that
consider all layers. A framework for integrated decisions in roadmapping is presented in Fig. 4.
Wind industry strategy, market, products and technologies are analyzed. Alternatives and criteria
for this industry in Iran are recognized. Alternatives are ranked under the recognized criteria.

Fig.4. A framework to develop wind turbine industry roadmap in Iran

3-3-1- Directional Strategy

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Industry is defined as a group of organizations having similar products or processes.

Directional industry strategy is defined as macro-decisions, at the level of an industry, on how to
develop the industry. All abilities involved in activities related to production can be considered as
technological capability.
Bagheri Moghaddam et al. (2012) have been defined an appropriate directional strategy in the
form of a tridimensional matrix to develop wind industry by identifying Irans technological
capability (leadership or followership) and product/market maturity (existing or emerging) in wind
turbine industry at a domestic (Iran) and global level. Therefore, Iran is a follower in terms of
technological capability. They have shown that creative imitation and proactive localization are
appropriate directional strategies in developing wind turbine industry in Iran.
3-3-2- Market analysis
Using wind energy in a country often entails the development of the related industries. Most
of the countries involved in wind electricity are also competent in turbine industry and
manufacturing wind turbine components (e.g. Denmark, Germany, Netherlands, and recently
China and India). According to Bagheri Moghaddam et al. (2011) and (2012) have presented, the
installed capacity dispersion of the worlds wind turbines until 2009 indicates that 48% of the total
installed capacity of wind power is in Europe, 25% is in Asia, 24% is in North America, and the
remainder exists in other parts of the world. By investigating wind turbine market share, evaluating
the competitive environments and investigating the trend of wind turbine prices around the world, it
can be resulted that wind turbine market around the world is in its late growth period and early
maturation. Whilst, Irans wind turbine market is being formed and it will experience a considerable
growth over the next few years. In addition, Iran is a follower country in wind power industry and
has an emerging domestic market. Global Wind Energy Council have reported in 2012 that, Iran
has started exporting its technology into neighboring countries, including Armenia and Pakistan.
Another potential market for Iranian wind technology is Georgia, where prospective projects are
currently being examined. Therefore, it can be considered that there are two segments for market
in wind industry: domestic and global markets.
3-3-3- Product analysis
The size dimension of wind turbine around the world is between 300 KW and 6.15 MW. The
most prevalent products are 1.5 and 2 MW. Therefore, these products are in third group, large
wind turbine. Large wind turbine is classified to 1-1.5MW, 1.6-2MW and more than 2MW.
Fadai (2007) investigated the ability of producing the small turbine (
KW) and their component
is 100%. There are 14 main parts of each wind turbine that must be assembled. Some of them are
produced in the country and used in other industries. These are as follows: foundation, transformer
and electrical parts, yaw gear, main shaft and chassis. Bearing and ball bearing must be imported
because of inability to mass produce and some limitation in Irans market. Bagheri Moghaddam et
al. (2011) have investigated technological capabilities in producing of 6-remained components
such as tower, gearbox, generator, hub, control and screw system and yaw, blade. According to
their research, three groups of turbines are considered as products, <1.5 MW, between 1.5 and 3
MW and more than 3 MW.
3-3-4- Technology analysis
As we mentioned before, a 3-blade turbine contains four main parts: nacelle, rotor, tower and
foundation. Nacelle is the main section of a turbine which contains energy production and power
transformation system. Rotor contains blade and hub. Types of tower are: concrete, steel and
hybrid (combination of concrete and steel). In following paragraph the anatomy of a wind turbine is
described briefly.
Rotor: The rotor for a typical utility-scale wind turbine includes three high-tech blades, a hub, and a
spinner. The blades are one of the most critical aspects for a wind turbine and are considered a
strategic component by wind turbine OEMs. Most manufacturers create multiple blade types for a

6
177

single wind turbine in order to enhance performance in different wind conditions. The blades range
in size from about 34 to 55 meters and are made of laminated materials such as composites,
balsa wood, carbon fiber, and fiberglass that have high strength-to-weight ratios. Nacelle: The
nacelle of a wind turbine is the box-like component that sits atop the tower and is connected to the
rotor. The nacelle contains the majority of the approximately 8,000 components of the wind turbine
such as the gearbox, generator, main frame, etc. The nacelle housing is made of fiberglass and
protects the internal components from the environment. The nacelle cover is fastened to the main
frame, which also supports all the other components inside the nacelle. The main frames are large
metal structures that must be able to withstand large fatigue loads. Construction: Once the nacelle,
blades, and tower sections are delivered to the wind farm site, construction of the wind farm can
begin. The tower is normally fitted with a base flange, which can be attached to the foundation by
screwed rods cast into concrete or bolted to an embedded tower stub. For the foundation, a variety
of slab, multi-pile and mono-pile solutions have been used for tubular towers, determined by the
condition of the ground where the turbine is being installed. Tower: The nacelle and generator are
mounted on top of a high tower to allow the blades to take advantage of the best winds. The power
available to a wind turbine is proportional to the cube of the wind speed. Therefore, a 10%
increase in wind speed would result in a 33% increase in available power. Towers are typically
made of three or four tubular steel sections coated with paints and sealants and joined by flanges
and bolts. Todays wind turbine tower is usually about 80-100 meters tall.
Technology trend of turbine has shown that the main part of turbine with the most radical
change is nacelle. The other parts have incremental changes. So to examine future technology of
turbine we address nacelle as a main parts of technology in roadmapping process. Wind turbines
are classified in nine groups based on the type of nacelle. These nine groups are as follows:
Baseline Drive Train, Integrated Baseline Drive Train, Single PM Drive Train, Direct Drive Train,
Multi-PM Drive Train, Multi-Induction Drive Train, Klatt Drive Train, Heller-De Julio Drive Train,
Henderson Drive Train. By considering Baseline Drive Train as a base model, the COE1 of each
type of nacelle are shown in Table 1. The items number 4, 7, 8 and 9 of the Table 1, have high
cost of parts. In contrast, their produced energy is low. In addition, item number 6 has low COE
and lowest equipment cost but its produced energy is low. By applying the capability-attractiveness
matrix model and the related criteria which have been introduced by Ghazinoory et al. (2009), the
Nacelle technologies of wind turbine are ranked. Table 2 is the expert opinion based on capability
and attractiveness criteria. Table 3 is the arithmetic means of capability and attractiveness criteria
for each Nacelle technology. The results are shown in Fig.5 as a capability-attractiveness matrix.
Table 1. Types of nacelle and their COEs
Row

1
2
3
4
5
6
7
8
9

Type of nacelle

Baseline Drive Train

Integrated Baseline Drive
Train
Single PM Drive Train
Direct Drive Train
Multi-PM Drive Train
Multi-Induction Drive Train
Klatt Drive Train
Heller-De Julio Drive Train
Henderson Drive Train

Gearbox / Non Gearbox

Rate of COE

Type of Product
(Turbine)

Gearbox
Gearbox

Base model
5%

<1.5 MW
>3 MW

Gearbox/Non Gearbox
Non Gearbox
Gearbox/Non Gearbox
Gearbox
Gearbox
Gearbox
Gearbox

13%
6%
11%
9%
1%
3%
1%

>2 MW
>2 MW
>5-6 MW
>5-6 MW
These Technologies
are in viable stage.

Table 3. Capability-attractiveness of nacelle technology

R
o

Type of nacelle

Gearbox / Non Gearbox

Capability

Attractiveness

Technology areas

Baseline Drive Train

Integrated Baseline Drive Train

Gearbox
Gearbox

7.3
5.2

5.5
7

Position Protection
Position Protection

w
1
2
3

- Cost Of Energy

7
178

3
4
5
6
7
8
9

Single PM Drive Train

Direct Drive Train
Multi-PM Drive Train
Multi-Induction Drive Train
Klatt Drive Train
Heller-De Julio Drive Train
Henderson Drive Train

Gearbox/Non Gearbox
Non Gearbox
Gearbox/Non Gearbox
Gearbox
Gearbox
Gearbox
Gearbox

Development area

5.5
5.7
3.8
3.2
2.3
3
3.7

7.2
7.4
7
5.9
5.5
4.6
5.1

Position Protection
Position Protection
Inception & development
Inception & development
Inception & development
scanning
(These Technologies are
in viable stage)

Position Protection area

8.0

attractiveness

7.0

3.8, 7.0

6.0

3.2, 5.9
2.3, 5.5
7.3; 5.5
3.7, 5.1
3.0, 4.6
Replacement area

5.0
4.0

5.7, 7.4
5.2,5.5,
7.07.3

Scanning area

3.0
2.0
1.0
0.0
0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

capability
Fig.5. Capability-attractiveness matrix of Nacelle Technology
3-3-5- Alternatives determination
Results of analyzing market, product and technology in wind turbine Industry can be put in
Lindsay framework to get alternatives for selection. Md and Mg are named domestic and global
market respectively. Pji , shows a product (wind turbine) in which j is the group number of product
(j=1 for <1.5MW, j=2 for 1.5-3MW and j=3 for more than 3MW) and i is the index of applied
technology.
We are encountered with alternatives such as Scenario (ijk) (Ti , Pji , M k ) . Ti can be
expressed with (FTi1 , BTi2 , TTi3 , NTi4 ) so that, FT is foundation technology, BT is blade and hub
technology, TT is tower technology and NT is nacelle technology. The index is the number of the
specified technologies. For example 1 i 4 9 because there are 9 identified technologies for
nacelles. These technologies are independent. Therefore, there is not any limitation for
developing each technology.
There are various technologies for nacelle of the wind turbine (9 models). Based on
aforementioned, there are not any problems in production capability for tower, foundation and hub
in Iran. The technology of blade is high-tech and relates to the row materials. So, technologies are
that of nacelle technology and have been introduced in Table 1. As a result, the columns of the
other technologies in Lindsay framework are eliminated (see Fig. 6). By this way, 17 alternatives
are recognized that must be ranked for locating in roadmap. Lindsay (1999) has presented a
framework for market-product-technology. Lindsay framework for wind turbine is presented in Fig.
6.
T1

T2

T3

T4

T5

T6

T7

T8

T9

Md

Nacelle Technologies

Products

P11
P23
P24

*
*

8
179

Mg

Markets
*
*
*

*
*

Product
(turbine)
efficiency

COE of
products

4
6
7

3
7
7

P32
P33
P34
P35
P36
P37
P38
P39

*
*
*
*
*
*
*

*
*
*
*
*
*
*
*

*
*
*
*
*
*
*
*

7
8
9
7
6
5
6
6

Fig.6. Market-Product-Technology framework for wind turbine

3-3-6- Criteria determination
Criteria determination is done by analyzing the strategies of each segments of markets or
industry analysis. In this paper, the criteria are determined for each layer. Capabilityattractiveness matrix is considered as a criterion for technology layer, turbine efficiency and cost of
energy are considered as product layer criteria. Massive strategy of the country in wind turbine
industry is considered as a criterion for market layer.
3-3-7- Integrated decisions and Roadmapping
The steps of proposed method are followed:
1- The time frame for wind turbine industry roadmap is considered 10 years.
Experts believe that time frame longer than 10 years are not suitable. In spite of maturity and
stability of wind technology, planning in shorter time frame and updating the roadmap is more
accordance with creative imitation which is our directional strategy.
2- 17 Triple ordered as alternatives are determined according to what have been mentioned
in section 3-3-5.
3- Criteria determination
3-1- The capability- attractiveness matrix method which has been presented by Ghazinoory et al.
(2009) is applied for 9 nacelle technologies, which have been presented in (Table 2). For this
purpose, six capability criteria and eight attractiveness criteria are investigated for aforementioned
nacelle technologies.
3-2- Nacelle technologies are ranked based on nearest distance with the northeast angle of
protection position of this matrix. In this case, the ranking of these technologies are T1,T4,T3 and
T2 in position protection area. T5,T6 and T7 in development and T9 and T8 in scanning area.
3-3- Turbine (product) efficiency and COE (cost of energy) as two product criteria have been
evaluated by experts. This information is put as two columns in Figure 7 in order to accumulate the
information.
3-4- Country strategy is a criterion for market criteria. Country strategy can be import replacement
strategy or export development strategy. Therefore, this problem must be solved in each kind of
strategy.
4- The weights of criteria are equal.
5- Applying PROMETHEE method
6- Put the alternatives in roadmap by considering acquiring time of technologies.
By considering the import replacement strategy, the evaluation of 17 alternatives under 3groups
criteria, are shown in Table 4. The last column of this table, is the net flows of each alternative by
using PROMETHEE, with U-shape preference function and q=3 for each criteria.
4- RESULLTS AND DISCUSSION
According to import replacement strategy and using PROMETHEE method in integrating decisions
in 3 layers of the wind turbine roadmap, the ranking of the alternatives are (T1,P11,Md),
(T4,P34,Md) , (T4,P24,Md), (T3,P33,Md), (T2,P32,Md) and (T3,P23,Md), (T7,P37,Md),
(T6,P36,Md) respectively. By considering export development strategy and solve the problem
again, the results would be (T4,P34,Mg), (T3,P33,Mg), (T2,P32,Mg), (T3,P23,Mg), (T7,P37,Mg)
and both (T6,P36,Mg) and (T5,P35,Mg) , respectively. These results are accordance with the
experts ideas. The experts insist on T3 and T4 for technology in first grade and T2 in second
grade. Turbines with more than 3 MW have preference to turbine between 1.5 to 3 MW. These
ideas can be seen in the results of problem solution by PROMETHEE model. In spite of T1 is in

9
180

7
9
9
8
5
3
4
3

position protection area of capability-attractiveness matrix and has nearest distance to the best
point of this matrix, it is near to the replacement area. Currently, attractiveness of T1 is going to
reduce although its capability is increasing. So, it is going to move to replacement area soon.
Therefore, (T1,P11,Md) which has the first ranking can be legitimized. According to results of
method, the roadmap is shaped Fig. 7. There are some information about Irans capabilities in six
parts of turbine in Table 5 . Some of them are the components of nacelle. So, the ranked
alternatives are accordance with the information of this table. For example, product more than 3
MW with nacelle technology T4 has the high ranked. The nearest time to have this product is 4
years. Gearbox and generator as two main parts of nacelle have the required potential. As can be
seen, the alternatives with domestic market are located the first ranking in this roadmap. This
happens because we havent informed about the massive strategy of country. So we have
proposed two status as we mentioned before. Each of these two status are happen with a
percentge in real world. For example, the importance of import replacement strategy and export
development strategy may be 40% and 60% for massive country strategy.
The ranking have been shown with the sequence on vertical direction. Inaddition, accessing time
of technology which have been shown in Figure 8 is optimistic.1-year tolorance can be considered
for T1,T3 and T4. A 2-year-tolorance is considered for T2 and T7.

5-

CONCLUSION

Roadmapping is the most popular visual tool for strategic planning. It is used to different levels
such as nation, industry and corporate levels. In this research wind turbine industry in Iran are
investigated. A framework for roadmapping in industry level for wind turbine has been presented.
PROMETHEE, one of the out ranking decision making method, have been considered to make
integrated decisions in roadmapping process. For this mean, we have considered alternatives in
an ordered triple (Technology, Product, Market) by using Lindsay framework. Nacelle technologies
are considered as determinant technology situation. Products are turbines with under 1.5MW,
between 1.5 to 3 MW and more than 3 MW. Markets are segmented to domestic and global
markets. In addition, some criteria have been introduced. This method can make decisions across
the layers of the roadmap. In other word, the alternatives are ranked according to role of each
them in some criteria simultaneously. Wind turbine industry in Iran is the industry which we have
applied the aforementioned method for achieving a roadmap. 10-year time frame is proposed for
planning. The ranking of the alternatives under capability-attractiveness, efficiency and COE of
product and country massive strategy criteria are shown in Fig. 8. There are some suggestions for
future investigations to have better results. First, the country massive strategy must be determined.
Therefore we dont encounter a gap data and we dont have to consider a limited assumption. In
addition, the market can be segmented in detailed country which can be our aim market.
Table 4. Alternatives and their scores under criteria (import replacement strategy)
Row

Alternative

Technology area

Technology
priority

Product
efficiency

Cost of
energy

Country
strategy

((Ti,Pji,Mk)

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16

(T1,P11,Md)
(T3,P23,Md)
(T3,P23,Mg)
(T4,P24,Md)
(T4,P24,Mg)
(T2,P32,Md)
(T2,P32,Mg)
(T3,P33,Md)
(T3,P33,Mg)
(T4,P34,Md)
(T4,P34,Mg)
(T5,P35,Md)
(T5,P35,Mg)
(T6,P36,Md)
(T6,P36,Mg)
(T7,P37,Md)

Position Protection
Position Protection
Position Protection
Position Protection
Position Protection
Position Protection
Position Protection
Position Protection
Position Protection
Position Protection
Position Protection
Inception/development
Inception/development
Inception/development
Inception/development
Inception/development

9
7
7
8
8
6
6
7
7
8
8
5
5
3
3
1

4
6
6
7
7
7
7
8
8
9
9
7
7
6
6
5

3
7
7
7
7
7
7
9
9
9
9
8
8
5
5
3

9
9
1
9
1
9
1
9
1
9
1
9
1
9
1
9

0.28
0.11
-0.16
0.19
-0.08
0.14
-0.125
0.16
-0.11
0.25
-0.016
0.016
-0.25
0.016
-0.25
0.05

17

(T7,P37,Mg)

Inception/development

-0.22

Parts

Status

10
181

Products (Wind Turbine)

Effective
Tower
Potential
Effective
Gearbox

Potential
Effective

Generator

Potential
Effective

Hub
Potential
Control and
screw system
and yaw
Blade

>3MW

1.5-3MW

<1.5MW

Construction with 100%

duplicated design

Construction with 100%

naturalized design

Construction with 100%

naturalized design

Construction with 100%

naturalized design

Construction with 100%

naturalized design

Construction with a
percentage of naturalized
design
Assembly
Construction with a
percentage of naturalized
design
Assembly
Construction with 100%
duplicated design
Construction with 100%
naturalized design
Construction with 100%
naturalized design

Effective

Awareness of Use

Potential

Ability to Use

Effective

Awareness of Use

Potential

Ability to Use

Assembly

Assembly

Construction with a percentage

of naturalized design

Construction with a percentage

of naturalized design

Assembly
Construction with 100%
duplicated design
Construction with 100%
naturalized design
Construction with 100%
naturalized design

Assembly
Construction with a percentage
of naturalized design
Construction with 100%
naturalized design
Construction with 100%
naturalized design
Construction with 100%
naturalized design
Construction with 100%
naturalized design
Assembly
Construction with a percentage
of naturalized design

Maintenance and repair

Construction with 100%
naturalized design
Maintenance and repair
Construction with 100%
naturalized design

Table 5. Technological capabilities in producing 6 parts of wind turbine in Iran

Fig. 7: Technology Roadmap of Irans wind Industry for 10 years. ( import replacement
strategy are considered as country massive strategy )

11
182

Table 2 : Expert assessment of capability-attractiveness matrix of nacelle technologies

12

183

The significance of national security

issues in acquiring the technology
The comparative position of the new
technology vis--vis the competitive
technologies
time required to acquire technology
and gain proficiency in using it
Coordination with government
financial budget allocations for
technology development
Public perceptions of technological
outcomes and their use by the
general public
Quality improvement and customer
satisfaction
Having competitive advantage in
production and exports
Ease of access to required natural
and mineral resources
Coordination with national
technological priorities
Access to natural and mineral
sources required in technology

Baseline
T
Drive
1
Train
Integrat
ed
T
Baseline
2
Drive
Train
Single
T PM
3 Drive
Train
Direct
T
Drive
4
Train
MultiT PM
5 Drive
Train
MultiT Inductio
6 n Drive
Train
Klatt
T
Drive
7
Train
HellerT De Julio
8 Drive
Train
Henders
T
on Drive
9
Train

development
Access
to the required equipment
and hardware in technology
development
Access to technical knowledge and
the required information in technology
development
Adequacy of the infrastructure in
exploiting technology
Access to expert labor required in
technology development
Wind
turbine
Nacell
Technologi
es

Technology Attractiveness Criteria

(Ghazinoory et al. 2009)
Technology Capability Criteria
(Ghazinoory et al. 2009)

REFERENCES:
Amer, M., Daim, T.U. (2010). Application of technology roadmaps for renewable energy sector.
Technological Forecasting & Social Change , 77, 1355-1370.
American Wind Energy Association (AWEA). (2002). The U.S. Small Wind Turbine Industry
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Aslani, A., Antila, E. (2012). Reviewing the Situation of Renewable Energy Alternatives in the
Investment Indexes Identified By Private Sector (Case Study:Iran). INTERNATIONAL JOURNAL
OF ADVANCED RENEWABLE ENERGY RESEARCH , 1 (2), 5-11.
Bagheri Moghaddam,N., Mousavi,S.M., Moallemi,E.A., Nasiri, M. (2012). Formulating directional
industry strategies for renewable energies in developing countries: The case study of Iran's wind
turbine industry. Renewable Energy , 39, 299-306.
Bagheri Moghaddam,N., Mousavi,S.M., Nasiri,M., Moallemi,E.A., Yousefdehi,H. (2011). Wind
energy status of Iran: Evaluating Irans technological capability in Manufacturing wind turbines.
Renewable and Sustainable Energy Reviews , 15, 4200-4211.
Daim, T.U., Amer, M., Brenden, R. (2012). Technology Roadmapping for wind energy: case of the
Pacific Northwest. Journal of Cleaner Production , 20, 27-37.
Darvish Tavangar, M., khoei, H.,Fani yazdi, S.S. (2012). Studing the latest status of new energies
in Iran. Research center of Parliament of Islamic Republic of Iran.
Fadai, D. (2007). The feasibility of manufacturing wind turbines in Iran. Renewable and
Sustainable Energy Reviews , 11, 536-542.
Ghazinoory, S., Divsalar, A. ,Soofi, A.S.,. (2009). A new definition and framework for the
development of a national technology strategy: The case of nanotechnology for Iran. Technological
Forecasting and Social Change , 76 (6), 835-848.
Lee a,S.K., Mogi, G.,Kim, J.W. (2009). Energy
technologyroadmapforthenext10years:ThecaseofKorea. Energy Policy , 37, 588596.
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Power Administration.

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184

AUTOMATIC GENERATION CONTROL OF WIND ENERGY SYSTEM

ASMA AZIZ, AMANULLAH MTO, GM SHAFIULLAH, ALEX STOJSEVSKI

Deakin University, Australia
aazi@deakin.edu.au

AbstractWith increasing integration of renewable energy along with environmental

constraints, design and operation of interconnected modern power system is getting
more complex. Automatic generation control (AGC) has become one of the important
control problems for upcoming challenges of future interconnected power system
operation and control. The analysis and design of AGC system in a deregulated
complex environment plays a vital role in automation and eventually reliable operation
of power system at a satisfactory and reliable level. In the past decade, wind power has
become a generation technology of significance and currently it is the most widely
utilized low to zero emission renewable energy technology in a number of countries.
Modern electric power systems are facing a tough challenge in real-time balancing of
demand and supply due to unpredictability and variability of wind power. Although
voluminous literature exists for AGC applications in conventional power system; very
few studies deal with wind energy system. An attempt has been made in this paper to
review the existing literature for preliminary AGC application in wind power system
along with an insight to new AGC research challenges for wind integrated power
system.
KeywordsAutomatic Generation Control, Load Frequency Control, Area Control Error, Wind
Power System, Intelligent Control, Inertia supported Wind Power System, FCAS.

I.

PREMISES FOR AUTOMATIC GENERATION CONTROL AND WIND ENERGY

With increasing environmental change concerns, limited fossil fuel reserves and increasing
electrical energy consumption, renewable energy sources (RES) development has become a
necessity. Present power system is undergoing several changes in its basic structure which
are associated with the adoption of new power production technologies and rapid integration
of RES. There has been a tremendous increase in generated megawatts by these RES all
over the world. These sources having new production and nonlinear control technology imply
new energy management system (EMS) in modern power systems. Talking about applying
energy management in modern power system, supervisory control and data acquisition
(SCADA), Automatic Generation Control (AGC), system stability, security control and electrical
load management make up the major units (Stanton et al., 2007). Recent studies have found
that the renewable integration impacts on system frequency and power fluctuation are nonzero
and become more significant at higher sizes of penetrations. AGC represents a remarkable
economical function of EMS system for regulating the balance and for distributing the
imbalance between designated units.
Growing concern about climate change has heightened the urge for cost effective operation of
power with high levels of wind energy penetration. According to a 2013 published key report by
Renewable Energy Division (RED) of the International Energy Agency (IEA) (IEA, 2013), wind
power deployment has more than doubled, approaching 300 GW cumulative installed
capacities led by China (75 GW), the United States (60 GW) and Germany (31 GW). Wind
power now provides 2.5% of global electricity demand and up to 30% in Denmark, 20% in
Portugal, 18% in Spain. According to latest figures from NTNDP-AEMO (AEMO 2013), wind is
estimated to comprise 84% of all new renewable generation by 2020 in Australia. Fig. 1
depicts the cumulative wind energy market forecast for different regions 2012-2017. There is
20% per annum growth forecast for global installed wind energy capacity (GWEC, 2012).
The power output of a wind turbine, which converts an uncertain energy flux to electricity, has
an additional source of uncertainty. Wind power density is a stochastic process that is a
function of both space and time. Wind power generation introduces uncertainty in power

185

system operation and it is continuously variable and difficult to predict. Modern electric power
systems are facing a critical challenge in real-time balancing of demand and supply due to
unpredictability and variability of wind power. Fluctuations in the summated output of all wind
farms connected to a power system will cause frequency to fluctuate and may change the
anticipated power output of dispatchable generation (affecting dispatch in the next few hours
and unit commitment in the next few days). Unexpected sudden changes in the summated
output of wind farms, due to either a widespread change in wind conditions or in response to a
power system disturbance are contingencies that must be assessed for their implications for
reserve requirements.

Fig 1: Cumulative forecast by Region 2012-2017 (GWEC, 2012)

A. BASICS OF FREQUENCY REGULATION

Each country has listed the limit for under and over frequency in their relevant grid codes. For
maintenance of a desired frequency in an interconnected power system, balance must be
preserved for power generation with power consumption. With any imbalance, frequency
deviation occurs which activates frequency regulation. As shown in fig.2, frequency regulation
refers to number of aspects, namely the inertial regulation of power system, which acts in few
seconds, the governor regulation which is primary response reacting in 1s to 10s of seconds,
and the AGC regulation, which is the secondary response acting in a time frame of tens of
seconds to minutes. For smaller power systems with low inertia or system with low primary
frequency response, frequency stability may be a problem when large amount of wind is
integrated to the system. The sensitivity of any power plant depends upon the response time
taken by the automatic generation controller to control the frequency change due to load
variation of governor control. With increased penetration of wind energy, system operators
have begun to study AGC problems, especially in terms of the frequency response
performance at wind turbine level and wind far level.

Fig 2: Frequency Trace Following a Contingency Event (McCalley 2010)

The analysis and design of AGC system in a more deregulated complex environment plays a
vital role in automation & eventually reliable operation of power system at a satisfactory level.
The purpose of AGC ancillary service is to control the real power output of electric generators
within a control area with respect to variations in system frequency and tie-line loading so as
to maintain schedule system frequency and establish interchange within other areas within
prescribed limits. System frequency and real power output data are periodically sent by
SCADA system to AGC system which intermittently calculates the area control error to adjust
the set points of respective system. If the load is increased, AGC system increases the
mechanical torque by increasing the system flow rate to turbine to compensate the load by
increasing the generators output in an area. Real time balance between generation and load
is basically indicated by network frequency dictated by combined system inertia. In case of a

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significant frequency drop, the generators droop characteristic must be corrected in order to
find a new operation mode giving nominal frequency.
A block diagram representing primary and secondary frequency regulation in a general power
system is given in Fig. 3. It shows that by changing the generation at primary regulation level
and restoration of the frequency to the nominal value at secondary level, AGC system
maintains the frequency constant in power system. The adjustments are transmitted by the
SCADA system to power plants where they are realized via remote terminal units (RTUs)
(Strauss, 2003).

Fig 3: Automatic Generation Control of a Modern Power System

B. AREA CONTROL ERROR

Present power systems is divided into various control areas each constituting coherent group
of generators. It is required to control and set the generation output power according to energy
market load-demand economics and area control error (ACE). ACE is the real time
representation of utilitys obligation to regulatory authority for maintaining net power
inflow/outflow along with a small bias obligation to maintain frequency. Generation change
output is measured by ACE which is calculated as the difference between actual and desired
tie-line interchange and difference between actual frequency and scheduled frequency along
with frequency bias setting. The ACE is calculated according to Eq. (1) (NERC, 2005)
ACE
(1)

(NIA

NIS)

10B

(FA

FS)

IME,

Where,
ACE is the Area Control Error in MW. Negative values denote a condition of under generation
and positive values denote over generation.
NIA is the algebraic sum of the actual flows on all tie lines or interconnectors (MW). It is
defined as the algebraic sum of the MW flow on the area tie lines.
NIS is the algebraic sum of the scheduled flows on all tie lines or interconnectors (MW). It is
defined as the mutually prearranged intended net MW flow on the area tie lines, including
dynamic schedules.
NIA NIS is basically tie-line interchange error or flat tie-line control which compares the net
tie-line actual inflow / outflow with power scheduled to be sold or bought. Flow into a system is
defined as negative while flow out as positive value.
B is the frequency bias setting (MW/0.1Hz). Frequency bias is the utilitys obligation to
generate or absorb power to regulate the total system frequency.
FA is the actual frequency (Hz).
FS is the scheduled frequency (Hz).
IME is Interchange (tie line) Metering Error which is accounted from meters installed at end of
tie-lines.
Fig. 4 gives a general AGC model with renewable energy included. Transmission system
operators (TSOs) control the amount of wind power to be captured by sending balance control
or delta control signals to AGC capable wind plants.

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Figure 4: Generalized AGC model considering renewable power regulation (Bevrani 2010)

For example, if the renewable energy included is large wind penetration, corresponding ACE
signal representing generated wind power changes can be given as Eq. (2) (Bevrani et al.,
2010)
ACE = B f + ( (Ptie-Con, act Ptie-Con, sched) + (Ptie-WTG, act Ptie-WTG, estim)) - IME,
(2)
Where,
Ptie-Con, act is actual conventional power and Ptie-Con, sched is scheduled conventional power.
Ptie-WTG, act is actual Wind power and Ptie-WTG, estim is estimated Wind power.
B f is frequency bias setting multiplied with frequency changes between scheduled and
actual. B sign is negative. This is also known as flat frequency control.
More advance formula for ACE can be found from WECC (WECC, 2006). Stability of a system
or requirement for more generation with demand variation is indicated through ACE.
Minimization of ACE is the main goal of AGC which is a dynamic study where disturbance is
small. For worthy AGC design, there should not be an enormous increase in ACE signal and
ideally it should be zero. ACE should not be allowed to drift or vary much over a certain time
period. ACE is allocated to various units of a control area whose participation in AGC depends
upon energy market economic dispatch. AGC makes up as part of real time energy market
dependent upon load forecast. AGC set points and system dispatch requirements are used to
calculate the cost of load following imposed on system due to variable wind power. Thus, AGC
systems cost in modern power system consist of load frequency control time frame, economic
dispatch; interchange scheduling of individual generators in many generating units.

II.

AGC & WIND ENERGY: PAST & PRESENT ACHIEVEMENTS

The AGC problem has been extensively studied during the last four decades and it has been
one of the most highlighted issues in the design and operation of independent and
interconnected power systems. Fig. 5 represents the general study line of conventional power
system which has been followed for AGC research. Load-Frequency Control (LFC) is used as
part of AGC to maintain a constant frequency and to regulate tie line flows. LFC represents
the first implementation of a higher-level control system. It has made the operation of
interconnected systems possible and today it is still the basis of any advanced concept for
guidance of large systems. A peculiarity of LFC lies in the fact that each partner in the
interconnected system has equal rights which are limited only by the installed power in the
area and the capability of the tie-lines: thus it is not a centralized control system when total
interconnection is considered.

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Fig 5: Conventional Power System study line for AGC

Cohn has extensively studied the static aspect of net interchange tie line bias control strategy
(Cohn, 1957). On the static analysis basis Cohn has inferred that, for the minimum interaction
between control areas, the frequency bias setting of a control area should be matched to the
combined generation and load frequency response of the areas. However, no analysis has
been made regarding deciding the magnitude of gain settings for the supplementary
controllers. Concordia & Kirchmeyer have studied AGC problem of two equal thermal hydro
systems by simulating system differential equations (Concordia et al., 1953). Although they
have extensively studied the effect of variation of several parameters on the dynamic
responses, no explicit methods have been proposed by them for optimization of controllers. It
is the IEEE working group which provided the standard definition for power system AGC
(IEEE, 1970). AGC as defined by IEEE is the regulation of the power output of electric
generators within a prescribed area in response to changes in system frequency, tie-line
loading, or the regulation of these to each other, so as to maintain the scheduled system
frequency and / or the established interchange with other areas within predetermined limits
(IEEE, 1970) (IEEE, 1979) (Hassan et al., 2011). AGC has now advanced fast from the period
when the task was accomplished manually, through the days of analog systems to the present
application of sophisticated and refined digital & intelligent control systems.
The first optimal control concept for megawatt-frequency control design of interconnected
power systems was addressed by Elgerd and Fosha (Elgerd et al.,, 1970) (Fosha et al.,, 1970)
which was concerned with classical approach to determine the optimum integrator gain for
area control errors. With changing power system scenario and constraints; variations to AGC
definitions along with dynamic modeling of system had been presented over past time periods
(Jaleeli et al., 1992) (IEEE, 1979). System nonlinearities and dynamic behaviors such as
governor dead-band and generation rate constraint, load characteristics, and the interaction
between the frequency-real power and voltage-reactive power control loops for the AGC
design procedure have been considered (Concordia et al., 1957) (Wu et al., 1978). Complete
digital Load frequency control was also designed and investigated to match the generation to
the varying system demand and economic dispatch program so that the total system cost is
minimized (Mello et al., 1973). Power system load frequency control had also been tested by
applying the variable structure control to make the controller insensitive to the plant parameter
variation (Benjamin et al., 1982). One of the study dealt with AGC incorporated with SCADA.
An AGC algorithm for the supervisory control and data acquisition (SCADA) of the ellenic
interconnected system was developed (Vournas et. al., 1982).
In a mixed power system, it is usual to find an area regulated by hydro generation
interconnected to another area regulated by thermal generation or gas generation, solar
generation, wind generation or in combination. With increasing RESs integration into grid, its
a necessity to explore their impacts on AGC at the planning stage and in real time operation. It
has been indicated by recent investigations that large penetration of wind energy will have an
impact on modern power system frequency regulation along with AGC systems and other
control operation issues. AGC is expected to be a major player in management of short term
uncertainty of renewable power system output as well as in mitigation of short term impacts
due to variable generation forecast error. Thus lot of research is underway to review and
analyze wind energy association with AGC performance criteria, capabilities and technologies
for ensuring proper system performance. Fig. 6 illustrates the line of thoughts being followed
for studying AGC impact of wind energy penetration. Incorporating energy storage systems
(Kunnish et al., 1986) (Banerjee et al., 1990) and development of intelligent controllers (Jaleeli
et al., 1992) (Kothari et al., 1989) (Sheirah et al., 1984) (Kannish, 1984) for dynamic
performance are two important approaches being followed by researchers for investigating

189

AGC system for wind based system. Michael et al. developed a methodology to enable wind
farm participation in automatic generation control using energy storage devices (Michael
2012). Energy storage devices are used to neutralize the uncertainty of wind power plant
output and maximize the dispatch ability.

Fig 6: Present Wind Energy study line for AGC

With reduced uncertainty, Wind farms are shown to have better AGC performance. G.
Alejandro developed an AGC modeling framework for studying the impact of variability and
uncertainty in wind-based electricity generation on power system frequency (Garcia, 2012).
Third order model of conventional system and first order model of wind system was used in
this study with the assumption of small forecast error. AGC in wind system interconnected with
thermal system was investigated in a study and it was concluded that operational impacts of
the wind power fast fluctuations are largely absorbed by the thermal units large mechanical
and thermal time constants as well as control dead-bands and the system dynamics varies
with the size of the AGC time delay. (Luo et al., 2006) (Luo et al., 2007) (Hadi et al., 2008).
They used conventional PI regulator in their AGC response study which can be further
improved with intelligent controllers and combination of multigenerational hydro thermal power
system. Lalor, A. Mullane, and M. J. O'Malley investigated dynamic interactions between wind
power and system frequency concluding that the displacement of conventional generation with
wind results in increased rates of change of system frequency (Lalor et al., 2005). Bart et al.
developed a procedure for power system imbalance control by program responsible parties
PRPs via minimization of their energy program deviations and the assessment of AGC
performance with high integration of wind power (Bart et al., 2007). They conclude that the
capabilities of the generation mix are increasingly challenged at higher wind power
penetrations and additional reserves are required for keeping area control error at the same
level. A recent study by Aho, Buckspan, Pao and Fleming on NRELs 550kW 3-bladed
Controls Advanced Research Turbine (CART3) indicates that AGC performance is fast and
accurate for wind power giving best results at high wind speed (Aho et al., 2013). It was also
inferred that with an accurate forecasting available, AGC error gets reduced over multiple
turbines. Variani & Tomsovic propose a two-tier structure of flatness-based control resulting in
distributed automatic generation control (AGC) of a multi-machine system with high
penetration of wind energy (Variani et al., 2013). Jose et al. designed and tested AGC as a
hierarchical system for wind farms with real wind farms data (Jos et al., 2002). Good AGC
performance was observed with better grid integration during simulations with introduction of
variable wind, large electrical disturbance. An automatic generation control system for a wind
farm with variable speed turbines is addressed by Amenedo; Arnalte & Burgos. The proposed
integrated control system includes two control levels referred as supervisory system and
machine control system. (Amenedo et al., 2002). Blade pitch and generator torque control was
used for reference power signal tracking at plant level was used for AGC study at wind plant
level (Hansen et al., 2006).
Conventional AGC model assume a direct physical connection generators set point change
and secondary control signal provided by the transmission system operators.
The
conventional LFC designs based on classical control have less adaptability, are not very
efficient and therefore not suitable for modern power systems with large interconnections,
varied structure and more penetration of renewable energy sources, specifically wind energy
with varied uncertain source and exigent demand for power quality. It is expected the
application of modern robust, automatic and intelligent control techniques to the LFC schemes
will be more adaptive and appealing approach for wind based power system to overcome
impositions set up by technical standards of energy market regulators. Issue of load frequency

190

control has been in focus over long period. Application of several intelligent control techniques
have been researched for the frequency regulation in conventional power system; however,
the large integration of wind energy system have created a gap in theory and application with
just few reports available on the intelligent frequency control design in the presence of wind
power units. Goutham & Ali developed mathematical model for an isolated wind and diesel
turbine generators with SMES unit and concluded that fuzzy gain scheduled PI controller has
good transient and steady state performance over fixed gain PI controllers for frequency
control (Goutham et al., 2012). More investigation needs to be done for advance controllers
incorporating fuzzy logic. Dhanalakshmi & Palaniswami analyzed Neuro-Fuzzy controller
based on Adaptive Neuro-Fuzzy Inference System (ANFIS) architecture for Load frequency
control of an isolated wind-micro hydro-diesel hybrid power system to regulate the frequency
deviation. Neuro-Fuzzy Controller gives best performance by damping out the frequency
deviation and attaining the steady state value with less settling time (Dhanalakshmi et al.,
2012). Bevrani & Daneshmand studied a new decentralized fuzzy logic-based LFC schemes
for interconnected large scale power system for simultaneous minimization of system
frequency deviation and tie-line power changes incorporating the particle swarm optimization
technique to satisfy LFC objectives concerning the integration of wind power units (Hassan et
al., 2012). Verma & Kumar investigated the role of DFIG-based wind turbine towards LFC in a
two-area hydro-thermal power system in an open access environment. The modified inertial
control scheme is used for the DFIG which provides inertial support to the system during
transients and arrests the fall in frequency (Verma et al., 2012). Bhongade, Tyagi & Gupta
studies a multi area AGC scheme with WTG. They propose to keep grid frequency to nominal
value by applying genetic algorithm GA for PID controller tuning. Further it was observed that
WTG integration increases overall system inertia resulting in poor damping and reduction of
the maximum deviations i.e. in the system frequency (Bhongade et al., 2012).
III.

AGC & WIND ENERGY: NEW PERSPECTIVES & CHALLENGES

A. SPATIALLY DISTRIBUTED AGC

A comprehensive literature exist which deals with lots of variability and uncertainty in wind
power output (Undrill, 2010) (Martinez et al., 2010) (Illian, 2010) (Mackin, 2010). Wind
variability ramp down event is not as abrupt as sudden loss of conventional generator and not
as smooth as load ramp-down daily cycles (Garcia, 2012). Inspite of technological
development and implementation, there is a limitation on ability of modern wind energy based
power system in contributing to regulating frequency under few seconds after a contingency.
Most of the solution proposed in literature mimics the traditional AGC response of
synchronous generators. In a highly wind penetrated power system, with varying wind power
and load uncertainties, there is a spatial variation of frequency standards and required
regulation over control area. So for wind energy system (WES), traditional lumped ACE input
changes to distributed ACE and conventional AGC changes to spatially differentiated
frequency regulation. One of the studies indicates that wind farms spread over large
geographical area have relatively low regulation limits (Holttinen, 2006). As shown in fig. 7,
power fluctuation smoothens out for greater wind diversity over a spatial region. At normal operation,
the power output of a wind farm can vary up to the 15% of installed capacity within 15 minutes
(Ackermann, 2005). The spatial distribution and intermittency of wind resources affect power system
on time scale being followed by AGC and raise the cost of wind based electricity. Advance
investigation is needed for such spatially distributed & large aggregation of wind turbines on
AGC. AGC system along with economic dispatch of respective electric network needs
improved modelling to account for unique features of wind generation and mitigating its
variability effect.

191

Figure 7: Real and reactive power output of wind power plant a) for single turbine b) For sixteen turbines (Martinez et al., 2012)

B. INERTIA SUPPORTED AGC

It is well known that AGC action is preceded by primary regulation activity in a power system.
Load Frequency control (LFC) action assumes same area control error (ACE) throughout the
concerned power system but this assumption does not completely satisfy with wind power
based system. High wind penetration in power system induces large imbalances and brings
instability and power quality issues. With secondary regulation getting exhausted due to wind
load variability, it is very likely that primary control actions of power electronics based
generation technologies also reducing frequency regulation capabilities in case of a fault
(Miller et al., 2011). Primary regulation is provided by power system inertia which controls the
system frequency rate of change in case of an imbalance of load and demand in the system.
Power system rotational inertia is normally time-variant and gets reduced non-uniformly with
respective grid topology.

Figure 8: Impact on RoCoF (Muljadi et al., 2012)

Variation of frequency with time with and without inertia support is shown in Fig.8. Rate of
change of frequency (RoCoF) improves with inetia and droop control enabled in wind power
system. Frequency regulation and hence Sensitivity and stability of total system is largely
dependent upon total system inertia. A high stable power system has high inertia and low
RoCoF. Primary inertial control can improve frequency nadir but do little for improving settling
time as inertia of a system is directly related to generating machines masses and respective
prime movers. Due to energy economics, quantity of synchronous generators operating will be
less in case of low load demand and high penetration of wind energy, leading to reduced total
grid system inertia. Total system inertia changes with displacement of synchronous generators
in case of wind integrated system and managing total system frequency thus stability without
inherent inertial response will be difficult. Studies indicate that power system having equal
value of spinning reserves but having different inertia levels express varied frequency
responses in case of any contingency. Research indicates that low inertia will have worst
effect for power system having slow frequency response (Andreas et al., 2014). So modern
wind based systems are supplementing their inertial response by adopting additional
controllers and using energy storage systems and synchronous condensers. Varied
decentralized and/or distributed control methodologies to implement inertial and AGC
response at turbine level and real scale power plant level needs more attention as research in
this field appears to be sparse. AGC study of these advanced inertial control supported wind
system with high RoCoF ride-through capability is still very nascent & needs more attention
and investigation.

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C. INTELLIGENT AGC
In a book titled intelligent automatic generation control, Bevrani and Hiyama advocates the
usage of an intelligent configuration as best solution for improving the contribution of a
renewable power plant (such as a wind farm) in AGC function (Hassan et al., 2011). It has
been established that overall deviations in grid frequency and regulation time can be reduced
by incorporating intelligent controllers and distributed AGC in a general power systems
operating under restrictions and certain operating ranges. With the availability of highly
capable variable generators, automatic response to frequency is getting improved for wind
plants. Pitch angle control and rotor seed control have been deduced as popular frequency
control techniques at turbine level (Juankorena et al., 2009) (Ma et al., 2010). Absence of
intelligent controllers in a wind penetrated system can cause stability problems and penalties
causing consequent losses in revenues. Application of intelligent algorithms incorporating high
degree of optimization and control strategies can better respond to existing complex variables
of power system models and helps AGC in mitigating the demand and load imbalance in
interconnected system. More advanced simulation involving high fidelity system models and
control capability is needed to analyze the full potential and impact of AGC for wind penetrated
system. These needs to be real time verified and investigated for wind integrated system with
application of intelligent techniques like fuzzy logic, neural networks, genetic algorithms, multi
agent systems.
D. FRT CAPABLE AGC
With increasing renewable energy penetrations in modern power system, all national TSOs
have put stringent ride through capability limits on these power systems. Ride through
capability refers to the ability of generators to remain stable and connected during normally
cleared electrical faults on a transmission grid. As per various national grid codes, their wind
plants are required to limit their active power as a function of system frequency in case of over
frequency event. Australian grid code (Western Power, 2011) requires their wind plant to
provide ride through multiple faults even though it is not cleared during reclosing sequence of
transmission lines. Further, FRT capabilities vary with different types of turbine-generator and
corresponding controllers too. More involvement of type 3 & 4 wind turbine by displacing
synchronous generators will result in higher RoCoF and instability in total system. For longer
duration faults, turbine blade pitching strategies along with turbine converter control becomes
necessary. FRT compliance is generally assessed at point of connection (PCC) while
manufacturers specify operating range of wind turbine generators at its low voltage (LV)
terminals. Depending upon SCR at PCC and wind turbine type, there can be varying stress on
different parts of turbine when it is subjected to near - to- generator disturbances. Integration
of wind energy with network having low short circuit ration (SCR) has increased risk of system
instability even though with FRT capable wind turbines. Wind farms with such fault ride
through (FRT) capabilities are very likely to deteriorate frequency regulation as frequency
deviations generally results in voltage instability. As a result, energy withdrawn by FRT action
may increase the size of any contingency and thus the magnitude of frequency deviations
leading to total system instability. More Research needs to be conducted for assessing the
AGC performance of these FRT capable wind system.
E. AGC AS FCAS OUTPUT
Fig. 9 depicts a basic layout of wind farm and control signals. Wind farm controller installed at
PCC receives control set-points from TSO and further maintains control signals at individual
turbines. In a deregulated environment, energy market participant are required to make
supplementary control contributions to transmission system operator (TSO) for stable and
reliable power system. In order to meet control area performance criteria, AGC participants
must track and keep record of instantaneous fluctuations in demand load for continuous
duration so as to keep ACE within limits. For a transmission system operator, assignment of
control duties gets constricted with presence of wind system. System operator aims to
minimize the payments to participants for providing AGC ancillary service while renewable
participant strives to maximize their revenues. Frequency control, one of the ancillary service
requirements are calculated on the basis of contingency size, total inertia of power system and

193

load demand. Frequency control Ancillary service (FCAS) availability holds a very important
value for high wind penetrated power system with low inertia.

Figure 9: Basic layout of wind farms and control signals (Bluhm et al., 209 )

According to Australias NEM, it is compulsory for generators>= 30 MW to participate in FCAS

(Thorncraft et al., 2007). Primary control and secondary control makes up an important factor
in regulating market for balance responsibility. AGC manages continuous correction of
frequency deviations up to f1 as regulation raise or regulation low service as part of market
based ancillary service in Australian market. North American Electric Reliability Corporation
(NERC) has enacted control performance standard (CPS) for evaluating frequency control
performance in a control area. Control areas must not be less than 95 % compliant with CPS1
and no less than 85% compliant with CPS2 (NERC, 2014). A Study by Wang & McCalley
indicates that CPS1 & CPS2 deteriorates with increasing wind penetration and this effect is
observed more for large interconnected systems (Wang 2013). Improved load forecasting
along with better AGC is required to improve these control performance standards. According
to European Network for Transmission System Operators for Electricity (ENTSO-E), all TSOs
must ensure regulation service which should be at least 50% operational within 15 seconds
and fully operational within 30 seconds of any contingency exceeding 20mHz (ENTSO-E,
2004). A very fast response is needed to seize frequency decline and control frequency nadir
within first 5-10 seconds. Energy storage technologies have fast response making them
suitable for providing frequency regulation ancillary services. According to a report by
California Energy Commission (CEC), application of energy storage for regulation purpose
can be around two to three times as effective as adding a combustion turbine to the system
(KEMA, 2010). Besides technology, market policies as well as system infrastructure also
plays vital role satisfactory AGC performance in a renewable energy integrated power system.
More research in terms of technology, policies and infrastructure is needed for incorporating
AGC in wind system to enable their active participation in FCAS, better energy economics and
compliance to control performance standards. Proper management of FCAS can be a key
factor for better penetration of wind in a deregulated complex power system.

IV.

CONCLUSION

Figure 10: New Challenges for Wind-AGC

194

Imbalance between energy production and its consumption is best indicated by frequency in a
power system. Primary and secondary regulation comes into act to return the balance in the
system. Research has established that higher wind penetration induces large variations in
system frequency and reduces regulation capability to large contingencies. A number of
solutions have been proposed to mitigate wind penetration effect on frequency regulation but
research on impacts of wind energy on secondary regulation performance and its integration
with electricity market is still very sparse. AGC is expected to be a major player in
management of short term uncertainty of renewable power system output as well as mitigation
of short term impacts due to variable generation forecast error. It is expected that application
of modern robust, automatic and intelligent control techniques to the LFC schemes will be
more adaptive and appealing approach for wind based power system to overcome impositions
set up by technical standards of energy market regulators. Still a lot of research is required to
review and analyze wind energy association with AGC performance criteria, capabilities and
technologies for ensuring cost effective, industry prone frequency regulation system leading to
a stable wind integrated large power system. With improved turbine and intelligent controller
technologies, AGC researchers have to look deeply into several new aspects for achieving
long term economic sustainability of wind energy. As reflected in fig. 10, Modern wind AGC
system differentiates itself from conventional AGC system by being spatially distributed AGC
which also considers synthetic inertia and fault ride through capable wind system. The
intelligent AGC strives to emerge as an important FACS output for a highly wind penetrated
power system. Effective research and implementation of these terminologies in AGC will help
wind energy market participants to make better contributions to frequency control ancillary
services to transmission system operator (TSOs) and an overall more reliable power system.

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198

Energy Management In Engines And Vehicles

24
199

OPTIMAL ENERGY SCHEDULING OF GRID CONNECTED PV-DIESEL HYBRID

SYSTEM TO POWER HEAT PUMP WATER HEATER
S. Sichilalu, Xiaohua Xia
Centre of New Energy Systems, Department of Electrical, Electronic and Computer Engineering
University of Pretoria, Pretoria 0002, South Africa
E-mails: sichgroup@yahoo.com (Sam Sichilalu); xxia@postino.up.ac.za (Xiaohua Xia)

ABSTRACT
The aim of this paper is to develop an optimal energy scheduling strategy model for a grid-connected
photovoltaic (PV)-Diesel generator hybrid system to power heat pump water heaters (HPWH). The
system comprises of PV modules, Diesel generator (DG), domestic loads and the HPWH. The cost
function of this model is to minimize energy and fuel cost while maximizing use of greener and
cheaper energy whenever available. The time-of-use (TOU) electricity tariff is taken into account in
the optimal scheduling model. The control variables are the power flows from various sources of our
system model. This scheduling strategy can be implemented to shift the maximum demand and
provide security of supply while meeting technical and operational constraints of renewable energy
sources. A case study was carried out on 3x16kW HPWH in Pretoria South Africa. Simulations run
for a year on selected date using actual measured coefficient of performance (COP) of the HPWH.
The optimal results show how TOU affects the PV and DG power scheduling to the HPWH. The
energy savings are as well presented in this paper.
Keywords: Heat pump water heater; Optimal scheduling; Photovoltaic; Diesel generator; Time-ofuse tariff.

INTRODUCTION

The HPWHs have gained wide usage (Chua et al., 2010) in offering economical means of
heat recovery from the environment for industrial and domestic applications. Most
predominant usage of the HPWH is for water and space heating(Verhelst et al., 2012). Heat
pumps have low energy consumption, approximately two thirds (P.G Rousseau 2000) less
than resistive element water heaters due to its COP. The integration of the distributed
renewable energy sources into homes provides a huge potential to power the low demand
loads like heat pumps. The hybrid PV system powering heat pumps is an effective tool
(T.Ikegami and Y. Iwafune, 2012) for demand side management (DSM). Several hybrid
systems powering small communities and domestic loads are presented in (H.Tazvinga 2013,
Ashok, 2007, Ismail et al., 2013). However, there is little research in grid-tied PV system to
power the heat pumps, making them uneconomical (P.G Rousseau 2000) in most developing
countries. The optimized models of PV/PV-thermal collector hybrid systems were developed in
(El-Sebaii et al., 2010, Castaeda et al., 2013, Ishaque and Salam, 2011). In (T.Ikegami and Y.
Iwafune, 2012) attempts on an ideal model for optimal control of a hybrid PV system to power
HPWH for DSM are presented. However, our paper provides a first attempt for a greener,
practical and economically attractive optimal control model for a grid-connected PV-Diesel
hybrid system which considers the TOU tariff to power the HPWH. This paper is developed
based on our previous research as presented in(S. Sichilalu 2014) .The scheduling strategy of
our model can be adopted by home owners intending to turn their dwelling into energy positive
building and as well as using renewable energy.
This paper is structured as follows: Section 2 is the mathematical formulation of the model,
Section 3 is composed of simulation results/discussion and section 4 is the conclusion.

200

MATHEMATICAL FORMULATION OF THE MODEL

Model layout

Figure1. Schematic layout of the model to power heat pump water heater

Objective function
The objective function is expressed in a discrete-time domain to minimize energy and fuel cost
J while maximizing the usage of the greener and cheaper energy whenever available. The
diesel generator (DG) comes on only when the PV and grid energy proves to be
uneconomical. The weighting factor k is adjusted based on the desired effects (i.e. savings
on energy) of the customer.
N
N
N
N

min J t S 1 Cb, j P2 , j P5 , j 2 Cf (aP32, j bP3, j c) 3C s P4, j 4 P6, j

j 1

j 1
j 1
j 1

(1)
where; Cb, j is the time of use electricity tariff in [R/kWh] , C f is the fuel cost of the DG [R/litre],
C s is feed-in tariff of renewable energy from solar PV in [R/kWh], t S is the sampling time (h),
th

Pi , j is the power output at j sampling interval, i 1,2,... 6 with i being the power flow within

the i th branch of the hybrid system , N is the last sampling interval and k is a weighting
factor where k 1,2,... 4 .
Control variables and constraints
In this study the control variables are the power flows: P1, j , P2, j , P3, j , P4, j , P5, j , P6, j , 1 j N

201

P1, j P2, j P3, j Php, j 1 j N ,

(2)
P5, j P6, j PDLj 1 j N ,

(3)
0 P1, j P4, j P6, j PPV , j 1 j N ,

(4)
0 P3, j PDG 1 j N ,

(5)
Pimin Pi Pimax ,

(6)

The objective function is given by equation Eq. (1) having linear constraints and quadratic cost
function .The fmincon function in MATLAB Optimization Toolbox is used.
The function to be minimized is formulated as min f ( x) shown below;

min f ( x)

such

C ( x) 0

Ceq ( x) 0
A x b
Aeq x beq

lb x ub

that

(7)
Where C (x) and Ceq(x) are the nonlinear equality and inequality constraints respectively.
The A x and Aeq x represents the linear inequality and equality constraints, while lb and ub
are the lower and upper bounds.

RESULTS AND DISCUSSION

Heat pump power consumption

The optimal results in Fig.2 show that the grid is maintaining the power supply to the HPWH
from mid night till about early mornings, while the DG is zero as it is uneconomical to run
during the period when the TOU is off- peak. However, as the tariff is approaching to standard
period the DG comes on to supplement the grid due to the fact that grid energy starts to
become expensive. During sunrise solar PV begins generating power which goes to
supplement the DG and grid as the tariff gets into peak period. The cheaper greener energy
from the PV takes over supply to the HPWH and excess is used for domestic loads while the
other is sold to the grid as shown in Fig.7. The month of December is characterized by cloud
cover and high humidity that affects PV energy production. The hot water demand is as well
relatively high in our case study as most people are on vacation during the month of
December. The same trend is observed for the month of March in Fig.3, though the thermal
demand is low and the grid energy is mostly used in the evenings when the solar PV energy is
not available. The TOU tariff legend in Fig.2 applies to all graphs in this paper.
16
15

flows(kW)
Power flows(kW)

14

Optimal scheduling- December

off-peak
PV-HPWH(P1)

standard

peak

Grid-HPWH(P2)

DG-HPWH(P3)

10
12

105
8

202

HPWH(Pph)

Fig.2. HPWH optimal power scheduling - December

PV-HPWH(P1)

Power flows(kW)

15

Grid-HPWH(P2)

DG-HPWH(P3)

HPWH(Pph)

10

10 11 12 13 14 15 16 17 18 19 20 21 22 23 24
Time (Hours)

Fig.3. HPWH optimal power scheduling - March

The month of June in Fig.5 is fairly different from the month of December, the heat pump runs
throughout the day to maintain the required thermal demand. The DG runs almost the entire
day supplementing the grid during the period when PV energy is unavailable. This high
thermal demand is due to the winter period in South Africa while at the same time solar
irradiance is low because of the geographical location of the sun. In August, Fig.6 is relatively
still cold, but the sun irradiance is at its best in the southern hemisphere and the ambient
temperatures are high which improves the COP.
PV-HPWH(P1)

Grid-HPWH(P2)

DG-HPWH(P3)

HPWH(Pph)

Power flows(kW)

15
10

10 11 12 13 14 15 16 17 18 19 20 21 22 23 24
Time (Hours)

Fig.5. HPWH optimal power scheduling - June

PV-HPWH(P1)

Grid-HPWH(P2)

DG-HPWH(P3)

HPWH(Pph)

Power flows(kW)

15
10

10

11 12 13 14
Time (Hours)

Fig.6. HPWH optimal power scheduling - August

Domestic appliances power consumption

203

15 16

17 18

19 20

21 22

23

24

The domestic loads consume relatively low energy in our case study. The greener energy from
the PV is used to power the domestic load in Fig.7 during the day time, while most of it is
being sold to the grid. The model is designed to have only the PV and the grid supply the
domestic loads while the DG is a backup power for the HPWH. Unlike the situation observed
in the month of December for the heat pump power consumption pattern, here in Fig.7 the
domestic loads are fairly moderate and constant. The energy produced by the PV is mostly
used to supplement the HPWH, domestic load and the remainder is sold to the grid as shown
in Fig.7-10.

Grid-Loads(P5)

Power flows(kW)

PV-Loads(P6)

Loads(Pdl)

PV-Grid(P4)

10 11 12 13 14 15 16 17 18 19 20 21 22 23 24
Time (Hours)

Fig.7. Domestic loads optimal power scheduling - December

Power flows(kW)

15

Grid-Loads(P5)

PV-Loads(P6)

Loads(Pdl)

PV-Grid(P4)

10

10 11 12 13 14 15 16 17 18 19 20 21 22 23 24
Time (Hours)

Fig.8. Domestic loads optimal power scheduling - March

The domestic peak loads are in the winter period as shown in Fig.9 -10 and the PV energy
sells to the grid is drastically reduced .The optimal control strategy trend is similar to the above
figures.

Grid-Loads(P5)

Power flows(kW)

PV-Loads(P6)

Loads(Pdl)

PV-Grid(P4)

10 11 12 13 14 15 16 17 18 19 20 21 22 23 24
Time (Hours)

204

Fig.9. Domestic loads optimal power scheduling June

6

Grid-Loads(P5)

PV-Loads(P6)

Loads(Pdl)

PV-Grid(P4)

Power flows(kW)

5
4
3
2
1
0

10

11

12

13

14

15

16

17

18

19

20

21

22

23

24

Time (Hours)

Fig.10. Domestic loads optimal power scheduling - August

Energy bills
The optimal energy savings are shown in Table 1. The model yields the highest energy
savings in the month of March of 53.12%. The bills include the cost of fuel for running the
diesel generator, energy consumed by the HPWH and domestic loads. The model excludes
the initial capital investment and amortization. However, from the savings it can be concluded
that the payback period will be shorter.

Table 1. Daily energy costs and savings

Energy bills [Rand /Day]

Current bill

Optimal bill

Solar energy sells

Total optimal bill

December
March
June
August

3496.91
2192.45
8285.69
5881.58

1888.54
1027.75
6018.69
3598.68

103.35
227.08
36.62
63.30

1785.20
800.68
5982.07
3535.38

Savings
(%)
46
53.12
27.36
38.81

CONCLUSION

The presented optimal model has energy savings of up to 53.12 %. Our model is a novel
solution to increase the market penetration of HPWHs from the current 16% (P.G Rousseau
2000) in South Africa. The PV payback period is short with the current attractive feed-in tariff
in South Africa. Dwellings have the potential of being energy positive during daytime.

NOMENCLATURE

Pi

Control variables which are the power flow in i-th branch of the PV-Grid system

205

CB j

Electricity buying price [R/kWh] based on TOU tariff.

Php, j

Power consumption of the heat pump during hour t

PDL, j

Power consumption of the domestic appliances during hour t

PPV , j

Photovoltaic power generation during hour t

South African Rands

REFERENCES

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dynamic modeling and energy management strategies of a stand-alone PV/hydrogen/batterybased hybrid system. International Journal of Hydrogen Energy, 38, 3830-3845.
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radiation on horizontal and tilted surfaces in Jeddah, Saudi Arabia. Applied Energy, 87, 568576.
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206

P.G Rousseau , G. P. G. 2000. Enhancing the impact of heat pump water heaters in the South African
commercial sector Energy 25, 51-70.
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system for heat pump water heaters. Applied Energy Conference VI, June 1-3, 2014. Taipei,
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Heater under Different Objective Functions. IEEE International Conference on Power System
Technology ,POWERCON 2012, art. no. 6401437.
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and Buildings, 45, 43-53.

207

PERFORMANCE AND ENVIRONMENTAL EVALUATION OF AN ON-SITE

WASTE-TO-ENERGY CONVERSION SYSTEM BY USING EXHAUST AIR
ENERGY RECOVERY TURBINE GENERATOR
,a

W.T. Chong* , A. Fazlizan , S.Y. Yip , S.C. Poh , W.Z.W. Omar

a

and W.P. Hew

Department of Mechanical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala

Lumpur, Malaysia

UMPEDAC, Level 4, Wisma R&D, University of Malaya, Jalan Pantai Baharu, 59990 Kuala Lumpur,
Malaysia
c

c, d

Centre of Electrical Energy Systems, Universiti Teknologi Malaysia, 81310 UTM, Johor Bahru,
Malaysia

Aeronautical, Automotive and Offshore Engineering Department, Faculty of Mechanical Engineering,

Universiti Teknologi Malaysia, 81310 UTM, Johor Bahru, Malaysia
*

Corresponding author: chong_wentong@um.edu.my

ABSTRACT
An assembly of two vertical axis wind turbines (VAWTs) and an enclosure is installed above a
cooling tower to harness the discharged wind for electricity generation. The enclosure
consists of guide-vanes and diffuser-plates, is used to enhance the rotational speed of the
turbines for power augmentation. The angle of the guide-vanes is optimized to ensure the
oncoming wind stream impinges the rotor blades of the turbine at an optimum angle. The
diffuser-plates are tilted at an optimum angle to increase the discharged airflow rate. The
performance of the system is tested in the laboratory followed by a field test on an actual size
cooling tower. The VAWT performance is increased in the range of 7 - 8% with the integration
of enclosure. There is no significant difference in the current consumption of the fan motor
between the bare cooling tower and the one with installed VAWTs. With the presence of this
system, approximately 17.5 GWh/year is expected to be recovered from 3000 units of cooling
towers at commercial areas, assuming the cooling tower is driven by a 7.5 kW fan motor and
operates 16 hours/day. This amount of recovered energy can also be translated into 13%
2
reduction in CO emission.
Keywords: Cooling tower, Energy recovery, De-carbonization, Wind turbine, On-site energy
generation, Renewable energy.

INTRODUCTION
Energy security is a major challenge in relation to achieving environmental goals and in
striving for sustainable development. Global energy consumption has nearly doubled during
the past 30 years and is projected to keep increasing. In 2008, world primary energy
consumption from all sources was recorded at 514 EJ (EJ is exajoule =1018 J) and 80% of it
was generated from fossil fuels. It is projected to increase to 1000 EJ or more by the year
2050 (Moriarty & Honnery, 2012). This trend is significant in developing countries and
effective measures are necessary to reduce energy consumption while maintaining economic
growth. Committee on Energy and Global Warming, Science Council of Japan has pointed
two major areas need to be focused which are energy supply and energy utilization ("Energy
and Global Warming: Equitable Allocation of Efforts for Sustainable Society," 2007).
On the supply side of energy, an internationally coordinated framework is indispensable to
ensure worldwide supply of various energy sources while dealing with global warming issues.
More aggressive introduction of renewable energy sources, such as photovoltaic, wind, and
biomass, is encouraged in order to counter global warming, ensure energy security, and

208

improve energy accessibility. With respect to utilization of energy, energy-efficiency efforts

should be reinforced to contribute further to mitigation of global warming and improvement of
energy security. As one of the answer to these issues, this article presents an innovative way
of to recover energy from a system which promotes energy efficiency.
The exhaust air energy recovery turbine generator is designed to recover part of energy
discharged from an exhaust air system. Commonly, exhaust air systems are used in
industries, buildings and air conditioning applications to discharge heat or for ventilation. It will
discharge the air in high velocity. The kinetic energy in the discharged air is to be recovered
using the energy recovery turbine generator. In this article, the investigation of installing the
exhaust air energy recovery turbine generator on a cooling tower is presented.

BASIC PRINCIPLE OF COOLING TOWER

In Malaysia, year 2008, the residential and commercial sector was the largest sector
consuming electricity by 44,453 GWh/year, which contributed to 51.8% of energy
consumption (NEB, 2009). Air conditioners are shown the major energy users (57%) in office
buildings, followed by lighting (19%) and other appliances (6%) (Saidur, 2009). Turning on the
air conditioners are now become necessary in order for the working environment to be
conducive. Cooling tower is a part of the air conditioning system where it works to dissipate
heat to the environment. According to the Cooling Technologies Institute (CTI), a cooling
tower is a heat rejection device, which extracts waste heat to the atmosphere through the
cooling of a water stream to a lower temperature.
Fig. 1 illustrates the working principle of a cooling tower. Hot water from a process flows
downward through the inner space of cooling tower while the tower fan draws ambient air
upwards across the water. This working principle of cooling tower is called the cross-flow
direct-contact induced-draft cooling tower. From the contact of water-air in the control volume
of the cooling tower, the heat from the water is transferred to the air by latent and sensible
cooling. An efficient cooling tower should have an efficient fan in order to draw a desired
amount of air at a desired flow rate. The performance of a cooling tower fan is investigated by
a number of parameters, i.e. air flow rate, pressure, air velocity and fan motor power
consumption.

Fig. 1. Cross-flow direct-contact induced-draft cooling tower

209

GENERAL SET-UP AND WORKING PRICIPLE OF THE EXHAUST AIR ENERGY

RECOVERY TURBINE GENERATOR
The general set-up of the innovative exhaust air energy recovery system is depicted in Fig. 2.
It is comprised of 2 vertical axis wind turbines (VAWTs) mounted in cross-wind orientation on
the top of a cooling towers outlet to harness the discharged air for electricity generation. The
entire system is held by a supporting structure and it can be mounted either in a horizontal or
a vertical orientation without blocking the discharged air flow. The installation position of the
system depends on the oncoming discharged air direction to the VAWTs. The whole system
is installed horizontally with the supporting structure at both ends of the transmission shaft of
the VAWT (bearing at a side and generator at the other side) where the discharged air is
blown from beneath in a vertical direction. In contrary, under the condition of discharged air
blowing sideways, the system can be installed vertically with the generator situated on the
floor. With the aim of the designed system not causing negative impacts on the cooling tower
performance, a predefined optimum position above the cooling towers outlet is identified
based on discharged air speed profile for placement of the two VAWTs.

Fig. 2. General set-up of the exhaust air energy recovery system above a cooling tower.
The VAWTs are integrated with an enclosure which fitted with several guide-vanes together
with two diffuser-plates (power-augmentation features) to maximize the wind power
generation. Guide-vanes are arranged in between the VAWTs and cooling towers outlet at a
predefined angle to form multiple air flow channels. By referring to Fig. 3, the VAWTs torque
distribution in the shaded with dark green areas experiences positive torque while the red,
yellow and orange areas are negative. This torque distribution is obtained by analyzing the
force on the surface of the rotor blades for a given wind speed (Gerard & Jeremie, 2010). The
installed guide-vanes will lead the discharged wind stream to the positive torque areas which
are advantageous in terms of efficiency as they are matched to the optimum angle of the
VAWTs.

210

Fig. 3. Torque distribution area of a VAWT.

The output power, Poutput of the rotor is defined as,
Poutput = x
where is the torque in Nm and is the angular velocity in rad/s. Output power will increase
significantly when the wind stream is guided to the positive torque areas because turbine
blades are moved by a higher thrust force. In addition to that, the diffuser-plates are tilted
outwardly at an optimum angle relative to their vertical axis causing a flow augmentation
effect which greatly helps to increase the discharged airflow. Both of the VAWTs are capable
of spinning at a high rotational speed (RPM) above the cooling tower, and a suction effect is
created due to low pressure region around the rotor. Consequently, the volumetric flow rate of
air increases for interaction with the VAWTs, resulting in a higher energy output.

METHODOLOGY
Indoor laboratory test was conducted as an initial step to study the applicability of the
designed exhaust air energy recovery system. The positive effect of adding an enclosure
(equipped with diffuser-plates and guide-vanes) was examined in this experiment. Fig. 4
shows the laboratory test set-up on a scaled model of a cooling tower.
A scaled down laboratory model of a cooling tower was fabricated for indoor laboratory test. It
consists of a cooling fan with a diameter of 0.7 m and a cylindrical duct with a diameter of 0.8
m. The cooling fan is enclosed inside the cylindrical duct. Two sets of 5-blade H-rotor wind
turbines with 0.3 meter rotor diameter are positioned at a height of 0.26 m measured from the
fan outlet to the transmission shaft of the wind turbine. Diffuser-plates were mounted on the
outlet of the circular duct with a slant angle of 7relative to its vertical axis. At the bottom of
the cooling tower model, there was a gap of 0.195 m from the floor (with the air inlet area of
2
0.5329 m ).
This laboratory tests were performed in four configurations, i.e.:
1) Cooling tower model only
2) Cooling tower model with VAWTs
3) Cooling tower model with VAWTs integrated with diffuser-plates
4) Cooling tower model with VAWTs integrated with diffuser-plates and guide-vanes

211

Fig. 4. Indoor laboratory test set-up on the scaled model of cooling tower.
Four rows of guide-vanes were positioned in between the VAWTs and cooling tower outlet
within the diffuser-plates. Wind turbine rotational speed was measured with hand held laser
tachometer for every configuration of guide-vanes angle setting. The angle of guide-vane A
was adjusted first starting from 0 until 180 as shown in Fig. 5 to determine the optimum
angle which gives maximum rotational speed while guide-vane B, C and D remained at
angle 90 (assuming 90 is similar to the scenario without guide-vane). These procedures
were repeated for the remaining guide-vanes once the optimum angle for guide-vane A was
obtained. The turbine rotational values were only recorded once the rotation of the VATWs
stabilized and an average value was tabulated to ensure accurate value obtained.

Fig. 5. Guide-vanes adjustment method

The effect of adding guide-vanes was studied by comparing the turbine rotational speeds
when there are no guide-vanes and when the guide-vanes are adjusted to their optimum
angles. Meanwhile, other measurements had been recorded to identify the difference in
performance and operating parameters among all the test set-up configurations. The fan
motor current consumption was measured by using a mini clamp meter at the power cable. A
hot wire anemometer was used to measure the air intake speed of the scaled model of the
cooling tower at four intake points after the rotational speed of the wind turbine had stabilized.

RESULT AND DISCUSSION

212

Determination of optimum angle of guide-vane

Table 1 presents the rotational speed of the wind turbine at different angles of the guidevanes. It was observed that when the angle of guide-vane was adjusted in 10step from 0to
180, the recorded RPM of the VAWT will increase slowly up to a maximum value and then
gradually reduce.
Both guide-vane A and D give maximum RPM value at the angle of 40. However, the
increment value is not significant as compared to the situation when guide-vane set at 90
since both of the guide-vanes A and D were located at the fans outlet position with lowest
wind speed. For guide-vane B and C (which are located nearer to the center of the cooling
fan that has higher discharged wind speed), the maximum RPM of the VAWTs was obtained
at the angle of 70. The thrust force that acts on the turbine blade is the highest where the
maximum rotational speed for the VAWTs are recorded with the average value of 480 rpm.
Based on the measurement results, the guide-vanes A, B, C, and D should preferably
be located at the angles of 40, 70, 70and 40respectively, so that the maximum output of
the VAWTs can be achieved.

Table 1: Rotational speed of VAWTs at different angle of guide-vanes.

VAWT
Guide-vane
Angle
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180

VAWT A(rpm)
Guide-vane
Guide-vane
A
B
464.5
425.9
467.7
429.6
469.9
430.1
470.0
436.0
471.7
458.5
471.3
469.9
470.2
478.0
471.1
482.2
471.6
480.5
471.4
471.9
471.2
464.8
471.0
458.1
468.6
457.6
467.0
454.5
465.9
458.0
464.4
456.4
465.3
451.6
463.8
445.3
466.5
429.4

VAWT B (rpm)
Guide-vane
Guide-vane
C
D
413.4
474.0
404.7
474.3
414.1
477.0
422.9
477.8
431.6
480.1
449.3
480.0
469.2
478.2
478.9
477.5
478.7
477.8
471.9
478.0
448.9
478.7
441.2
478.0
438.5
476.8
433.6
476.5
431.4
475.2
433.6
473.4
456.5
474.1
450.5
475.9
445.2
476.2

Wind turbine rotational speed measured when the RPM has stabilized
Performance evaluation of the scaled down model of the designed system
Table 2 shows the results from all the test set-ups obtained from the laboratory test. The
results of the first set-up (cooling tower model only) were taken as baseline throughout the
entire experiment where the fan motor power consumption was recorded at 203.84 W and the
average intake air speed was at 1.90 m/s. After the installation of the VAWTs, the VAWTs

213

were able to self-start with the stabilized rotational speed for turbine A at 438.0 rpm and
turbine B at 444.7 rpm. Air intake flow rate increased from 1.01 m3/s to 1.31 m3/s with the
inclusion of the diffuser-plates as compared to the situation with VAWTs only. The air intake
flow rate was determined by multiplying the average intake air speed with the discharged air
area. The increase is due to the suction force resulting from the lower pressure region around
the VAWTs, i.e. the Bernoullis principle.
Table 2 Indoor laboratory test results on the scaled down working model of cooling tower

Parameter

Average intake air speed (m/s)

Air intake flow rate (m3/s)
VAWT A rotational speed (rpm)
VAWT B rotational speed (rpm)
Fan motor power consumption (W)

Cooling tower
model without
VAWTs

Cooling tower
model with
VAWTs

1.90
1.01
203.84

2.15
1.14
438.0
444.7
200.20

Cooling tower
model with
VAWTs
integrated with
diffuser-plates
2.47
1.31
465.6
468.6
199.51

Cooling tower
with VAWTS
integrated with
diffuser-plates
and guide-vanes
2.52
1.34
474.7
475.3
199.81

The rotational speed of the VAWTs was improved significantly with the presence of the guidevanes. By making a comparison between both cases whereby one with VAWTs only and the
other with the guide-vane arranged at their respective optimum angle, the average intake air
speed (measured from the bottom of the cooling tower) was increased by 32.63%.
Nonetheless, the RPM value for both turbine A and turbine B was improved as well at the
range from 7-8%. However, a minimum increment in power input to the fan motor was
detected with the value of 0.3 W, as compared with the test condition of diffuser-plates
installation. This scenario occurred due to guide-vanes causing a minimum blocking effect to
the fan motor. The slight increase in power may be also due to the increase in intake air flow
rate that is handled by the fan motor. Since the increment value of the fan power is lower as
compared with the condition for cooling tower only (1.97% lower compared to original
systems power consumption), the small negative effect as a result from the guide-vanes does
not affect the original performance of the cooling tower and no additional load was exerted on
the motor. Besides, the small increment in fan motor input power (0.15%) can be
compensated by the power recovered by the VAWTs.

ESTIMATION OF POWER RECOVERED BY THE ON-SITE EXHAUST AIR RECOVERY

SYSTEM
Table 3 shows the detailed calculation of the power estimation that is able to be recovered by
3000 units of cooling towers. 1 kW of power can be produced when an optimized exhaust air
energy recovery system with 2 units of VAWTs is mounted above a cooling tower. Suppose
that the cooling tower with 2 m diameter outlet is driven by a 7.5 kW fan motor and operates
for 16 hours per day, 131.4 GW of power consumption would be required for the operation of
3000 similar units of cooling towers in a year. As a result, an amount of 17.5 GW/year of
power is expected to be recovered by the installation of the system which is equal to 13% of
the energy consumed by the fan motor.
Table 3 Projection of power recovered from 3000 units of cooling tower
Mode

Operating hours

No. unit of cooling

tower

Fan motor power

consumption

Total power
recovered

Day
Year

16 hours
5840 hours

1 unit
3000 units

7.5 kW
131.4 GW

1 kW
17.5 GW

CONCLUSION

214

A green energy generation system which greatly helps in CO 2 emissions reduction by

conserving a portion of energy consumption had been presented. It is a system that is
expected to recover 13% of the cooling towers power consumption by converting wasted
wind resources to electricity. At the same time, 13.3% of CO 2 emission reduction could be
achieved when the on-site exhaust air energy recovery system is installed above the cooling
tower. Since the system is equipped with wind power-augmentation devices (guide-vanes and
diffuser-plates), better performance of the VAWTs was achieved.
According to indoor test measurements, the VAWTs mounted above the cooling tower outlet
were capable of self-starting with the rotational speed for VAWT A at 438.0 rpm and VAWT
B at 444.7 rpm. The VAWTs performance was further increased by 7 8 % with the
integration of the enclosure (diffuser-plates and guide-vanes arranged at their optimum
angles).
This system is retrofit-able and safe to be used at any existing exhaust air systems. Safety
issues such as blade fly off or bird strikes are taken into consideration by the design of the
enclosure (the VAWTs are contained within it). Moreover, this designed system is cost
effective as it has a fast payback period. Based on the preliminary economic analysis, this
system possesses 4 years payback period which assure the secure investment of wind
turbine system. The detailed economic analysis will be included in future studies.
ACKNOWLEDGEMENTS
The authors would like to thank the University of Malaya for the assistance provided in the
patent application (Patent pending: PCT/MY2012/000274), and the research grant allocated
to develop this design under the High Impact Research Grant (D000022-16001) and
Postgraduate Research Grant (PG106-2013A). A special appreciation is credited to Truwater
Cooling Towers Sdn. Bhd. as an industrial partner to assist in the field test by providing the
testing facilities, manpower, and fabrication materials.
REFERENCES
. Energy and Global Warming: Equitable Allocation of Efforts for Sustainable Society. (2007):
Committee on Energy and Global Warming, Science Council of Japan.
Gerard, M, & Jeremie, R. (2010). Wind turbines: Type, economics and development. New
York: Nova Science Publisher Inc.
Moriarty, Patrick, & Honnery, Damon, (2012), What is the global potential for renewable
energy?
Renewable and Sustainable Energy Reviews, 16(1): 244-252. doi:
http://dx.doi.org/10.1016/j.rser.2011.07.151
NEB. (2009). National Energy Balance 2008. Selangor: Malaysia Energy Centre.
Saidur, R., (2009), Energy consumption, energy savings, and emission analysis in Malaysian
office buildings. Energy Policy, 37(10): 4104-4113. doi: 10.1016/j.enpol.2009.04.052

215

Theoretical Analysis of Engine Waste Heat Recovery System Based on CO2

Brayton and Organic Rankine Cycle
Chengyu Zhang, Gequn Shu*, Hua Tian, Haiqiao Wei, Xiaoning Li, Xuan Wang

State Key Laboratory of Engines, Tianjin University, Tianjin 300072, China;

*Corresponding authors contact email: sgq@tju.edu.cn

ABSTRACT
This article explores a non-conventional combined cycle constituting a topping carbon dioxide
Brayton cycle and a bottoming organic Rankine cycle (ORC) to recover waste heat from engine
exhaust gas. Based on the first and second law of thermodynamics, the combined system is evaluated using system net output power W net, thermal efficiency th, exergy efficiency e as objective
functions. Taking system size into consideration, the volumetric flow rate at turbine inlet is discussed as well. As the Brayton cycle is coupled to the ORC via a heat exchanger, and the heat
transferred from CO2 to ORC working fluid R123 largely counts on the efficiency of regenerator RHT
in Brayton cycle, R. So it is also discussed in detail. The results show that a maximum output power
of 29.38kW is acquired with a maximum Brayton cycle pressure of 20MPa when R is 0.9, and
corresponding thermal efficiency is 24.6%. The combined system is suitable to recover waste heat
from engines, as Brayton can extend the temperature range of heat source and achieve a decent
performance, thus improving the security and fuel economy of engines. Considering system performance and size together as a whole, a lower compressor inlet temperature is preferable.
Keywords: CO2;Brayton;ORC;Waste heat recovery

Nomenclature
cp
constant-pressure specific heat (kJ/kgK)
E
exergy (kW)
h
specific enthalpy (kJ/kg)
Q
heat (kW)
I
exergy destruction or loss (kW)
m
mass flow rate (kg/s)
W
power (kW)
s
specific entropy (kJ/kg)
P
Pressure (MPa)
T
temperature (K)
V
volumetric flow rate(m3/s)
Greek letters

efficiency
R
efficiency of regenerator
Subscripts
crit
critical

Introduction

all
f
e
P
R
s
T
C
H
CP
net
cond
max
HT
LT

combined system
working fluid
exergy
pump
regenerator
system
turbine
condenser or cooler
heater
compressor
net output
condensation
maximum
high temperature loop,i.e
CO2 Brayton cycle
low temperature loop, i.e.
ORC

mer[1].Therefore, it is of great significance to

make full use of this part of energy in this respect.
Among all technologies for waste heat recovery, the organic Rankine cycle (ORC) has
been regarded as a very promising solution as it
can not only achieve high thermal efficiency, be
easy to downsize system volume but
cost-effective as well[2,3]. However when applying it to recover ICEs exhaust heat, how to
match the exhaust and organic working fluid is a
problem[4], due to the fact that most organic
working fluids decomposition temperature is

Currently, energy conservation and emission reduction have drawn great attention from
the public, as a result of the energy shortage
and environment pollution. Internal combustion
engines (ICEs) consume a large amount of fossil fuel and mostly have a detrimental influence
on the environment. Apart from that, only about
1/3 of fuel energy is able to convert to useful
work while the remainders are mainly released
to the ambience in the form exhaust gas, coolant
water
etc.,
especially
the
for-

216

much lower, which can pose a threat to the

systems safety. What is more, traditional
one-stage ORC cannot utilise exhaust heat
completely. For that reason, some solutions
have been presented. It is noticeable that Miller
proposed an innovative combined system by
integrating thermoelectric generator (TEG) with
ORC [5], and Gequn Shu developed its mathematic model further [6]. Some researchers
added a thermal-oil circuit between exhaust gas
and ORC to prevent the organic working fluids
decomposition [7,8]. However, in that way
high-grade heat energy is entirely lost.
As a typical thermodynamic cycle, Brayton
cycle is widely used in aerospace industry, ship
propulsion and solar power application etc.[9].
J.P. Liu explored the idea of using Brayton air
cycle as bottoming cycle to recover exhaust
heat. The cycle is simple as no condenser is
needed, but limited by the compression work
and heat transfer performance, its performance
is not so desirable [10].CO2 is non-flammable,
non-toxic, eco-friendly and economical. Apart
from that, it has beneficial thermophysical properties, proper critical temperature and pressure
[11]. It is popular in the area of refrigeration and
air-conditioning, and its property and applications are discussed in detail in Ref.[12]. The
concept of using CO2 as working fluid for Brayton is not new, and it achieves a good performance in terms of output power and thermal
efficiency[9,11,13], but studies of CO2 Brayton
cycle for engine waste heat recovery are rare.
Regarding it as a bridge between exhaust gas
and ORC cannot only ensure systems safety as
the maximum temperature limit of CO2 can
reach 2000K, but make full use of this part of
energy as well.
This paper comes up with the CO2 Brayton-ORC combined cycle, and the model is established by Engineering Equation Solver (EES).
The performance of the simulation model is
analysed in terms of system net output power
Wnet, thermal efficiency th and exergy efficiency
e, volumetric flow rate is also considered because weight and size are both important factors in vehicle applications.

that the fuel is in perfect combustion. Therefore,

the composition of the exhaust gas is identified
as follows: CO2=15.2%, H2O=6.0%, N2=73.0%,
O2=5.8%. Taking the acid dew point into consideration, the final exhaust temperature after
exchanging heat is set to be over 393K[8].
Table 1. Main parameters of the diesel engine
Parameter
value

Unit

Rated output power

235.8

kW

Egine Efficiency

41.81%

Exhaust temperature

792.2

Exhaust mass flow rate

0.2752

kg/s

Fuel consumption

47.79

kg/h

CO2 Brayton-ORC system

Fig.1 shows the configuration of the CO2
Brayton-ORC combined system. Specifically,
CO2 Brayton cycle consists of the heater HHT,
cooler C1,HT, C2,HT, turbine THT, compressor CPHT
and regenerator RHT, while the ORC system is
made up of the heater H1,LT, H2,LT ,condenser CLT,
turbine TLT and pump PLT. These two heaters in
the ORC system use rejected heat of the C1,HT,
residual exhaust heat as heat source respectively. The ORC system is connected with the
Brayton system via the H1,LT, which acts as C1,HT
as well. The reason why Brayton cycle needs an
additional cooler C2,HT is that in Brayton cycle,
compressor inlet temperature affects system
performance greatly, typically, the higher it is,
the worse system performance in terms of
thermal efficiency and output power, hence,
C2,HT is used to make sure CO2 works at a relatively low temperature. As a typical dry fluid,
R123 is applied in ORC system for its good
performance in ORC process[14]. The main
parameters of CO2 and R123 are listed in Table
2.

System Description

ICE system
Here an inline 6-cylinder 4-stroke supercharged commercial diesel engine is selected
as topping cycle, and its main parameters are
presented in Table 1. We assume the engine to
work at rated condition under the hypothesis

217

HHT

C
9

H2,LT

Exhaust

A
H1,LT

C1,HT

10
11

12
PLT

7 C2,HT 1

THT

TLT

Engine

CLT

water

CPHT

goes into the turbine THT and expands to produce mechanical work (non-isentropic expansion process). The low pressure CO2 (state 5)
flows into the regenerator to take part in the
regeneration process mentioned before. Eventually, it is cooled in cooler C1,HT and C2,HT. As for
the ORC, low-pressure saturated R123 participates in exchanging heat with CO2 and exhaust
(isobaric heating process), corresponding to
process 12-8-9. In the next stage, after expansion (9-10), it goes through the condenser CLT
before being boosted to a certain pressure by
the pump PLT.

RHT
3

CO2 Brayton cycle

ORC
Fig.1 Configuration of CO2 Brayton-ORC system
Table 2. Properties of working fluids
Working fluid Tdecomposition(K)
Pcrit(MPa)

Tcrit(K)

CO2

2000

7.377

304.1

R123

600

3.662

456.8

Fig.2 T-s diagram of the combined system

Fig.2 displays the corresponding thermodynamic processes. CO2 (state 1) is compressed by compressor CPHT (non-isentropic
compression process), it (state 2) then enters
the regenerator RHT and to be heated by the
low-pressure CO2 exits from the turbine THT
(regeneration process). After that, it (state 3) is
further heated by exhaust at the heater HHT
(isobaric heating process). Subsequently, it
(state 4) goes into the turbine THT and expands
to produce mechanical work (non-isentropic
expansion process). The low pressure CO2
(state 5) flows into the regenerator to take part in
the regeneration process mentioned before.
Eventually, it is cooled in cooler C1,HT and C2,HT.
As for the ORC, low-pressure saturated R123
participates in exchanging heat with CO2 and
exhaust (isobaric heating process), corresponding to process 12-8-9. After expansion
(9-10), it goes through the condenser CLT before
being boosted to a certain pressure by the pump
PLT.
Fig.2 displays the corresponding thermodynamic processes. CO2 (state 1) is compressed by compressor CPHT (non-isentropic
compression process), it (state 2) then enters
the regenerator RHT and to be heated by the
low-pressure CO2 exits the turbine THT (regeneration process). After that, it (state 3) is further
heated by exhaust at the evaporator HHT (isobaric heating process). Subsequently, it (state 4)

Mathematical modeling and validation

Some assumptions are made for the sake

of simplifying the model: (1) System works under steady states, i.e. both potential and kinetic
energy are ignored. (2) Components pressure
drops and heat losses are not taken into consideration. (3) The isentropic efficiencies of
these two turbines are 0.75, while that of pump
and compressor are 0.8 and 0.78 respectively.
(4) The pinch point temperatures of HHT and
H2,LT are set to be 30K. In the case of Brayton,
CO2 exits the cooler C2,HT in the form of saturated vapour. The exergy at state i is defined as
Ei m[(hi h0 ) T0 (si s0 )] 0 means
ambient state, here T0=293K, P0=0.1 MPa.
In the CO2 Brayton system:
For the compressor CPHT,

WCPHT mHT (h2 h1 )

(1)

ICPHT E1 WCPHT E2

(2)
For the regenerator RHT,
The efficiency of the regenerator, R is expressed as follow:

R
(3)

218

mHT h3 h2
Qmax

I H2,LT E8 E9 +EB EC

I RHT ( E2 -E3 )+( E5 -E6 )

T(

Ref[9]

Calculation

T0

20

20

Error
(%)
0

Q,W
(kJ/kg)
Qw

Ref[9]

Calculation

164.2

T1

114.6

115

0.35

Wc

50.4

50.72

0.63

Ic

3.8

3.777

0.61

T2

370

370.3

0.08

QR

355.5

355

0.14

IR

20.6

20.47

0.63

T3

600

600

QH

283.6

283.3

0.11

IH

15

15.12

0.8

T4

449

449.1

0.02

WT

169.9

169.8

0.06

IT

7.6

7.611

0.14

T5

131.1

131.5

0.31

QR

355.5

355

0.14

IR

20.6

20.47

0.63

(4)

I(kJ/kg)

164.2

Error
(%)
0

Ref[9]

Calculation

Iw

23.6

23.93

(16)
For the turbine TLT,

Where Qmax is the maximum heat exchange

quantity
in
the
process,

WTLT mLT (h9 h10 )

Qmax mHT (h5 h6 ) assuming T6=T2

(17)

For the heater HHT,

Qexh, HT mHT (h4 h3 ) mexh c p (TA TB )

(5)

I H HT ( E3 -E4 )+( EA -EB )

ITLT E9 E10 WTLT

(18)
For the condenser CLT,

Qcond ,CLT mLT (h10 h11 )

(6)
For the turbine THT,

(19)

WTHT mHT (h4 h5 )

Table 3 Comparison between the present calcula

(7)

ICLT .1EMain
engine
1 0 E
1 1 parameters

ITHT E4 -E5 WTHT

(20)
For the combined system:
System total output power

(8)
For the cooler C1,HT (H1,LT),

Wnet ,all Wnet , HT Wnet , LT WTHT WCPHT WTLT WPLT

Qcond ,C1,HT mHT (h6 h7 ) mLT (h8 h12 )

(9)

(
2
1
)

IC1,HT ( E6 -E7 )+( E12 -E8 )

(10)
Here T7 is set to be 30K higher than T12.
For the cooler C2,HT,

Brayton and ORC thermal efficiency

Qcond ,C2,HT mHT (h7 h1 )

(11)

Error
(%)
1.4

th, HT

IC2,HT E7 -E1

Wnet , HT
Qexh, HT

th, LT

(22)

(12)
In the ORC system, most processes are
similar to those of Brayton discussed above.
For the pump PLT,

Wnet , LT
Qexh , LT Qcond ,C1,HT

(23)
System thermal efficiency

WPLT mLT (h12 h11 )

th,all

(13)

I PLT E11 WPLT E12

Wnet ,all
Qexh , HT Qexh , LT

(24)
System total exergy loss

I all ICPHT I R I H HT ITHT IC1,HT IC2,HT I PLT

(14)
For the heater H2,LT,

HT

Qexh, LT mLT (h9 h8 ) mexh c p (TB TC )

(15)

I H 2,LT ITLT I CLT Wnet ,all mexh ( EA EC )

(25)

219

e, a l l

Wn e ,t

perature are 3MPa and 303K.

As for the Brayton system, when other operating parameters have already been fixed, it
can
get
maximum
at
a
particular
high-pressure[13]. Turbine inlet temperature
keeps 750K, and the compressor inlet temperature is set to be 293K as saturated vapour, so
the corresponding low-pressure is 5.73MPa.
Table 5 displays the main operating parameters
of the combined system while high-pressure
varies from 17MPa to 22MPa. Apparently, most
of them show little fluctuations,

all

Ia l l

(26)
Validation of CO2 Brayton model
In order to make sure the accuracy of CO2
Brayton cycle, it is important to validate this
model. In this article, this is conducted by comparing the calculation results with Ref.[9]. For
this part, a particular operation condition is selected to make a comparison, the main operation parameters in Ref. [9] are as follows: isentropic efficiencies of compressor and turbine are
0.9, R=0.95, compressor inlet temperature is
20 as saturated vapour, and maximum cycle
temperature is 600. Energy and
Parameter

Wnet

Unit

[kW]

Results

349.3

take system output power Pnet,all as an example,

its increment is less than 0.3kW in the whole

th
mf
Pcond
Tevp
V3
V4/V3
between
results and Ref[-][8]
[-]Table 4 Comparison
[kg/s]
[kPa] the present
[K] calculated [m3/s]
0.1986

Calculation .1 Main341.5
0.1981
engine parameters
error(%)
2.23
0.25

[kJ/kg]

2.737

19.6

494.5

0.052

107

130.5

2.674

19.66

494.6

0.0511

107.4

130.6

2.3

0.31

0.02

0.37

0.08

1.73

region. This is because at the region near where

Brayton cycle efficiency arrives at maximum,
system performance is not so sensitive about
high-pressure. In the later study, Brayton expansion ratio of 3 (i.e. Pmax is around 17MPa)
is proposed.

exergy analysis results between the present

calculated results and Ref[9] are listed in Table 3.
It shows a good agreement, in fact, the maximum error is merely 1.4%. It proves that the
CO2 Brayton model is accurate.

Table 5 Comparison of system performance und

Validation of ORC model

The ORC model is established on the basis
of material and energy balance. Benzene is
chosen as working fluid, and the exhaust gas
parameters in Ref.[8] are as follows:
Texh=470,mexh=15673kg/h, and the composition of exhaust is 9.1% CO2, 7.4% H2O, 74.2%
N2 and 9.3%O2. Besides that, the isentropic
efficiencies of the corresponding turbine and
pump are 0.7 and 0.8 respectively. There is a
good agreement between the present calculated results and Ref [8] as shown in Table 4. The
error is mainly due to the fact that this paper
uses EES to build the model while REFPROP
Software is used in Ref. [8]. It confirms the accuracy of ORC model.

h3-4

.1 Main engine parameters

Results and discussion

Here we mainly change CO2 Brayton cycle

parameters and the calculation results are presented for a typical saturated ORC whose
evaporation pressure and condensation tem-

220

Pmax(MPa)

17

18

20

21

22

TB(K)

598.7

594.7

591.1

587.9

585

582.5

TC(K)

393.5

Wnet(kW)

29.14

396.8

400.1

403.1

405.5

408.2

29.26

29.34

29.38

29.41

29.4

Wnet,HT(kW)
Wnet,LT(kW)

14.87

15.2

15.47

15.69

15.85

15.98

14.27

14.06

13.87

13.69

13.56

13.42

th,HT(%)
th,LT(%)
th,all (%)
e,all (%)

24.74

24.78

24.78

24.74

24.66

24.56

TA(K)

19
792

16.68
23.79

24.11

24.37

24.6

24.79

24.96

49.3

49.71

50.05

50.33

50.55

50.72

Qexh,HT(kW)

60.12

61.34

62.43

63.4

64.27

65.05

QR,HT (kW)

73.52

70.2

67.11

64.2

61.47

58.89

Qexh,LT(kW)

62.35

60.04

57.93

56

54.34

52.74

Qcond,C1,HT(kW)

23.21

24.25

25.21

26.11

26.95

27.73

T2(K)

379.2

384

388.6

393

397.2

401.2

T3(K)

568.7

564.7

561.1

557.9

555

552.5

T1(K)

293

T4(K)

750

T5(K)

648

642.8

637.9

633.2

628.8

624.6

T6(K)

405.5

409.4

413.2

416.7

420.1

423.4

T7(K)

334.7

v4(m3/s)

0.002322

0.002182

0.002057

0.001945

0.001844

0.001753

v9(m3/s)

0.001482

0.00146

0.00144

0.001422

0.001408

0.001394

T8(K)

363.4

366.7

369.9

337.9

337.9

T9(K)
T10(K)

372.9

375.7

378.3

337.9

337.9

337.9

444.3
337.9

T11(K)

303.2

T12(K)

304.7

mHT (kg/s)

0.2736

0.2718

0.27

0.2682

0.2666

0.2649

mLT(kg/s)

0.3652

0.3598

0.3549

0.3505

0.347

0.3435

The Brayton cycle is coupled to the ORC

via a cooler C1,HT, which is H1,LT at the same time.
The amount of heat transferred in it basically
depends on the performance of regenerator RHT,
as the C1,HT inlet temperature of CO2 is determined by it. Because of this, R is the key parameter to affect ORC performance. In this way,
it has a great influence on the coordination between CO2 Brayton cycle and ORC.
Fig.3 shows the variation of output power,
Wnet,HT depends on the pressure ratio and inlet
temperature of compressor and turbine rather
than R, so the output power of Brayton W net,HT
changes little. When R is small, i.e. under 0.6,
the CO2 flows into the C1,HT with a high temperature, which makes the R123 in H1,LT to be
heated into saturated. In the case, the pinch
point (minimum temperature difference) happens at the

entrance of R123 in the H2,LT, the final exhaust

temperature is limited by it and it keeps constant.
However, as R rises, less heat is used to preheated R123 in H1,LT, as a consequence, R123
is no long saturated after flowing out of it. More
heat is distributed to heat R123 in H2,LT, hence,
final exhaust temperature decreases and the
mass flow rate of R123 grows. W net,LT changes
little when R is under 0.6, otherwise, it increases linearly. Similarly, with the increase of R,
system output power W net,all remains just under
25kW, however, when R is over 0.6, W net,all rises
linearly.

221

30

0.26
0.54
0.24

W net,all

0.52

Exergy Effificeny

W net,HT
W net,LT

20

0.22
0.50
0.20
e,all

0.48

th,HT

15

0.18

th,all

0.46

0.16

10
0.5

0.6

0.7

0.8

0.5

0.9

0.6

0.7

0.8

0.9

Fig4. Variation of exergy efficiency and thermal efficiency

Fig3. Variation of output power

Fig.5 indicates variation of volumetric flow

rate of CO2 and R123 at turbine inlet. Apparently,
volumetric flow rate of CO2 increases gently with
the rise of R, ranging from 0.0022-0.0023m3/s.
That of R123 changes little when R is below 0.6,
and it goes up consistently if over that value. As
the specific volume of both working fluids has no
relevance with R, it keeps constant on the
whole region. While the mass fluid rate of CO2
increases gradually as R grows, while on the
other hand, that of R123 remains stable when R
is small, and shows an upward trend as R is
over 0.6. Overall, volumetric flow rate of CO2 is
much larger than corresponding R123.The
physical size of turbine is mainly determined by
mass and volumetric flow rate of working fluid,
especially the later [13]. In this condition, both
fluids values are small, which contribute to
make the system compact.

Fig.4 indicates the variation of exergy efficiency and thermal efficiency. th,HT ascends
consistently and the increase rate increases as
R goes up. The reason is that with the growth of
R, the exchange heat quantity in the RHT increases, which results in the rise of CO2 temperature when it flows into the HHT. Consequently, less heat is absorbed from the exhaust
gas in the HHT. While on the other hand, as
discussed before, R affects Wnet,HT little.
System thermal efficiency th,all remains
stable at around 25.3% when R is small, it then
goes down linearly. th,LT is mainly determined by
the evaporation pressure and condensation
temperature, it keeps constant at 16.68% in that
condition. When R is smaller than 0.6, as mentioned above, the final exhaust temperature of
CO2 is limited by the pinch point and it remains
constant, consequently, the exhaust dissipates
an invariable amount of heat to the combined
system. While the W net,all is changeless as well,
so does th,all. Whereas in contrast, a higher R
leads to the decline of final exhaust temperature.
Wnet,all also increases, but less steeply. Overall,
th,all shows a downward trend. Conversely,
system exergy e,all experiences a gentle increase. That makes sense in that W net,all ascends more rapidly than that of exergy reduction.

0.0024

V4
V9

0.0020

volumetric flow rate (m /s)

0.0022

0.0018
0.0016
0.0014
0.0012
0.0010
0.5

0.6

0.7

0.8

0.9

Fig.5 Variation of volumetric flow rate of CO2 and R123 at

turbine inlet

Fig.6 shows the irreversibility of each

component in the combined system at R =0.9,
where the exergy efficiency reaches the maximum value. It is obvious that the heat exchanger H2,LT accounts for the biggest item of system

222

Thermal Efficiency

Output Power(kW)

25

maximum Brayton cycle pressure (MPa)

26

W net,HT

24

W net,LT

22

26

20
24

18
16

22

14
12
293

294

295

296

297

298

299

300

301

302

303

304

Fig.7 Variation of maximum output power and corresponding

maximum Brayton cycle pressure

0.0020

V4
V9
0.0018

28

W net,all

compressor inlet temperature (K)

volumetric flow rate (m /s)

Irreversibility(kW)

28

Pmax

20
292

IH2,LT
IRHT
ITHT
ITLT
ICLT
ICPHT
IC1,HT
IHHT
IC2,HT
IPLT

30

30

output power (kW)

irreversibility. Followed by regenerator RHT, this

is because in the CO2-Brayton system, the CO2
after expansion in the THT still has high temperature which contributes to a large temperature
difference in the RHT. It is interesting that the
irreversibility in both turbines show approximately the same value. While the non-isentropic
compression process in pump PLT has a minimal
influence in system exergy performance. One
thing worth mentioning would be that the exergy
destruction in heater HHT does not affect system
irreversibility largely. This is due to the fact that
CO2 flows into HHT with a high temperature after
participating in heat exchanging process at RHT,
which lowers the temperature difference between exhaust and CO2 significantly.

0.0016

0.0014

each component
1
0.0012
292

294

296

298

300

302

compressor inlet temperature (K)

Fig.6 irreversibility of each component

Fig.8 Variation of volumetric flow rate of CO2 and R123 at

turbine inlet

For the combined system, we mainly focus

on its ability to generate power rather than
achieving a high efficiency, as the waste heat is
a no-cost heat resource. When the temperature
of CO2 is under the critical temperature 304.13K,
in order to make sure CO2 is in the vapor phase,
saturated gas is assumed to exit the cooler C2,HT.
Fig.7 shows the maximum output power W net,all
and the corresponding maximum Brayton cycle
pressure Pmax where it occurs at a particular
compressor inlet temperature. The output power
of Brayton W net,HT increases gently with the
compressor inlet temperature, this is mainly
because near the critical point, the compressor
would consume less power. Conversely, W net,LT
declines gradually, which contributes to a slight
increase of W net,all. It is noticeable that the corresponding Pmax grows dramatically from 21.38
to 29.28MPa. High operating pressure will add
burden to the piping system and seal, more
importantly, the increase of Wnet,all is minimal,
therefore, it is not suitable for the whole system.

Both the volumetric flow rates of CO2 and

R123 decrease with compressor inlet temperature increasing, but that of CO2 decreases
more dramatically. As discussed before, the
size of turbine is mainly decided by this parameter, so a lower value is favorable in this
respect.

Conclusions

In this paper, a novel CO2 Brayton-ORC

combined system is used to recover engines
exhaust heat. It enables system to work safely
as CO2 is non-flammable and non-toxic, but
produces additional power as well. Based on
the analysis above, some conclusions are
made as follows:
1. The efficiency of the regenerator, R plays an
important role in the coordination between CO2
Brayton cycle and ORC. When R=0.9, system
output power W net,all is as large as 29.38kW
with a maximum Brayton cycle pressure of
20MPa, accordingly, th,all and e,all are 24.6%

223

304

and 50.33%.
2. Based on the combined system working at
R=0.9, the maximum irreversibility happens at
the H2,LT, while the exergy destruction in HHT is
relatively small.
3. When compressor inlet temperature is under
the critical temperature of CO2, with the increase of it, the systems ability to output power
does not rise obviously, however it contributes
to reducing the appropriate high-pressure, so it
is favorable to work under a low temperature in
this aspect.

namic analysis of a bottoming Organic Rankine

Cycle (ORC) of diesel engine (DE). Energy
2013; 51:281-90.
[8] Vaja I, Gambarotta A. Internal combustion
engine (ICE) bottoming with organic Rankine
cycles (ORCs).Energy 2010; 35: 1084-93.
[9] Y.M. Kim, C.G. Kim, D.Favrat. Transcritical
or supercritical CO2 cycles using both low- and
high-temperature heat sources. Energy
2012;43: 402-15.
[10] J.P. Liu, J.Q. Fu, C.Q. Ren, L.J. Wang, Z.X.
Xu, B.L. Deng. Comparison and analysis of
engine exhaust gas energy recovery potential
through various bottom cycles. Applied Thermal Engineering 2013;50:1219-34.
[11] Emmanuel Cayer, Nicolas Galanis, Martin
Desilets, Hakim Nesreddine, Philippe Roy.
Analysis of a carbon dioxide transcritical power
cycle using a low temperature source. Applied
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Acknowledgments
This work was sponsored by the National Basic
Research
(973)
Program
of
China
(NO.2011CB707201), the National Natural
Science Foundation of China (NO.51206117)
and the Natural Science Foundation of Tianjin
(NO.12JCQNJC04400).
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224

Thermal and Economic Analysis on a Combined Diesel Engine-Organic Rankine Cycle (DE-ORC) System Used in Coolant Heat Recovery of DE
Tian Hua1, Huang ZhiYong1,2, Shu GeQun1*, Jiang Na1, Wei HaiQiao1, Liang XingYu1
1 State

Key Laboratory of Engines, Tianjin University, Tianjin 300072, China;

Engine Research Institute, Tianjin University, Tianjin 300072, China
*Corresponding authors contact email: sgq@tju.edu.cn; thtju@tju.edu.cn

2 Combustion

ABSTRACT
As it is significant to recover the coolant heat of Diesel Engine (DE) (a kind of low grade waste heat,
about one fourth of energy generated from the fuel), an Organic Rankine Cycle (ORC) system used
for the DE coolant heat recovery is proposed and its thermal and economic analysis based on
various working fluids is presented in this paper. The detailed calculation models of ORC include
thermodynamic model, heat transfer model and economical model and the screened and recommended suitable working fluids include 16 traditional fluids. The analyzed and optimized cycle parameters include the thermal efficiency (th), the expansion ratio (v2/v1), the net power output per
unit mass flow rate of heat source (Pnet), the ratio of total heat transfer area to net power output
(A/Wnet), and electricity production cost (Epc). Results show that there exist optimum evaporating
temperatures maximizing the Pnet value and minimizing the A/Wnet and Epc values. The top four
fluids presenting lower Epc values are R600, R245fa, R152a, R123 with values ranging from
0.2957 to 0.3121$/kWh. R245fa and R123 show the better system performance with the optimum
evaporating temperatures of 68C. By integrating the ORC system to DE, the efficiency will be lifted
up to 45.4% by adopting RC318 from 41.8% of the original DE.
Keywords: Organic Rankine Cycle (ORC); Diesel Engine; coolant waste heat; thermal-economy

Introduction

the waste heat of coolant was considered as

an important source for WHR.
Organic Rankine Cycle (ORC) could be using in recovering waste heat from DE coolant.
There are some advantages of ORC as follows.
First, higher thermal efficiency and more net
power are achieved by ORC. Second, organic
fluids often have lower heat of vaporization and
can better follow the heat source, thus reducing temperature differences and irreversibility
at the evaporator, and therefore downsizing
system volume and weight, which is significant
for vehicle applications. Finally, turbine used as
an expansion device in ORC can provide
higher efficiency at part loads as well as at
rated condition and is usually less complex due
to the lower enthalpy drop of the fluid. For the
ORC system used in waste heat recovery of
internal combustion engine coolant, there are
several researches. Oomori et al. [9] developed a Rankine bottoming system, which operates on waste heat of engine cooling, to improve the fuel economy of a passenger car.
The bottoming system used R123 as a working
fluid, and scroll expander as a power conversion unit. The results indicated that energy
recovery, which depends on the ambient temperature, was almost 3% of engine output
power at ambient temperature of 25C. Arias et
al. [8] presented an ORC system using coolant
as the preheating source and exhaust as the

Energy is an important entity for the economic development of any country. Considering the environmental protection and great
uncertainty over future energy supplies, attention is concentrated on the utilization of sustainable energy sources and the energy conservation methodologies. In China, diesel engines (DE) have consumed over 66% of overall
fuel consumption. Since it is difficult to make
the maximum efficiency of DE higher than 42%
[1], the large amount of fuel energy is rejected
from the engine to the surroundings as waste
heat in several forms, with a significant fraction
through the coolant. A recent study estimating
the heat balance of an automotive engine
showed that, the thermal efficiency of the considered
engine ranged around 26% depending on operating conditions, while the remaining 60% to
70% of the fuel energy was rejected as waste
heat to the environment, primarily through the
coolant (about 29%) [2]. Teng et al. [3] calculated the energy balance of a typical truck
diesel engine without EGR at full load. At medium and high engine speeds, the brake power
was about 40%, and the heat rejection from the
radiator was about 18%. In the waste heat
recovery (WHR) systems reported recently by
Shu et al. [4-6], Bauer [7] and Arias et al. [8],

225

evaporating source. The results indicated a

maximum recovered waste heat of 2014W, in
which only 20W was from coolant system. Vaja
et al. [10] considered a simple cycle with the
use of exhaust gases and engine coolant. The
analysis demonstrated that a 12% increase in
the overall efficiency can be achieved compared with the engine without bottoming system; nevertheless the analysis also indicated
that it was observed that ORC can recover only
a small fraction of the heat released by the
engine through the coolant. Alberto et al. [11]
introduced an ORC to recover waste heat from
the coolant in a H2ICE, using R245fa as
working fluid. The results indicated that with the
coolant ORC, neglecting the reduced mechanical efficiency for the coolant back pressure increment, the maximum efficiency increased to 43.4% (42% without ORC), and the
average efficiency increased to 34.6% (32.7%
without ORC). Kalina et al. [12] established two
ORC models. One was a single stage ORC
using coolant as the preheating source, the
other was a double cascade ORC using coolant as the heat source of second stage cycle.
The analysis demonstrated that the double
cascade ORC had a 1.7% increase of system
thermal efficiency compared with the single
stage ORC, whose value was about 13.9%.
Moreover, the net output power and generated
electricity of the double cascade ORC increased significantly.
For the working fluids of the ORC system,
several researches focused on solar energy
harnessing, low-grade waste heat recovery,
and geothermal energy utilization. Yamamoto
et al. [13] estimated the optimum operating
conditions of ORC comparing HCFC-123 with
water as working fluids. Tchanche et al. [14]
comparatively accessed 20 working fluids for
use in low-temperature solar organic Rankine
cycle systems. Hung et al. [15] analyzed the
ORC efficiency using cryogens such as benzene, ammonia, R11, R12, R134a and R113 as
working fluids. Maizza et al. [16] investigated
the thermodynamic and physical properties of
20 unconventional fluids used in ORC supplied
by waste energy sources. Lemort et al. [17]
studied the performance of an ORC system
using R123 as the working fluid, and a scroll
expander instead of a turbine. Angelino et al.
[18] evaluated organic fluid mixtures as working media for Rankine power cycles. Chen et al.
[19] compared a carbon dioxide, trans-critical
power cycle with an ORC using R123 as the
working fluid. Saleh et al. [20] investigated 31
pure component working fluids used in the

sub-critical and supercritical ORCs for geothermal power plants. Liu et al. [21] and Tian et
al. [22] examined the influence of working fluids on the performance of ORC used in waste
heat recovery. The considered performance
parameters were thermal efficiency and total
heat recovery efficiency.
In this study, an ORC system used in the
DEs coolant heat recovery was proposed and
techno-economically analyzed based on various working fluids. The detailed calculation
models including thermodynamic model, heat
transfer model and economical model, have
been established. And then the suitable working fluids have been screened and recommended for the ORC system, among 16 fluids
with boiling point temperature ranging from
-51.6 to 47.6 C analyzed on the rated condition of one popular diesel generator set. The
cycle parameters, including the thermal efficiency (th) , the expansion ratio (v2/v1), the
net power output per unit mass flow rate of hot
exhaust (Pnet), the ratio of total heat transfer
area to net power output (A/Wnet), and electricity production cost (Epc), have also been
analyzed and optimized.

System Description

In this study, a commercial diesel generator

set, which is an inline 6 cylinder 4 stroke supercharged diesel engine is considered as a
topping system. Table 1 shows the main parameters of the engine. As this study aims to
analyze the fluids comparison and parameter
optimization for ORC used in coolant heat recovery of DE, we assume the engine to operate at the rated condition. As the coolant temperature of this engine should not be less than
50C, we assume that the temperature of
coolant returning to engine is 50C, which
means it is 50C after rejecting heat in evaporator of the ORC system.
Table 1. Main parameters of the commercial cogeneration engine
values
Parameter
Electrical power output (kW)
235.8
Torque (N.m)
1500
Coolant outlet temperature ( C)
95
Smoke (FSN)
0.55
Rotate speed (r/min)
1501
Fuel consumption (kg/h)
47.79
Coolant mass flow (kg/min)
163.00
Exhaust mass flow (kg/h)
990.79

Figures 1 and 2 show the proposed bottoming ORC system layout and its corre-

226

sponding T-s diagram (taking R123 for example) respectively. The system is a subcritical
ORC, consisting of turbine-generator, condenser, refrigerant pump, evaporator and other

coolant Tc,in,Pc

DE

1,T
1,P1
Ev
a

Tc,l,Pc

Gen

Tur

T2,P2
2
Con

5 T5,P5
Pre

Tcw,in
mcw

DE-Diesel Engine
Tur-Turbine
Gen-Generator
Con-Condenser
M-Mass flowmeter
Rp-Refrigerant pump
Pre-Preheater
Eva-Evaporater

R123

Tc,out,Pc

Rp

mr
M

T c,l

T c,out

1
DT min

75

50

25

Tcw,out
4 T4,P4

T c,in

100

T [C]

mc

to point 2s, which means the real expansion

process in turbine is closer to the isentropic
expansion process. The vapor (point 2) with
low pressure exits from the turbine and flows

2s

3
DT min

T cw,in

0
1.00

3,T
3,P3

1.25

1.50

s [kJ/kg-K]

test facilities. The hot coolant from DE rejects

heat in evaporator, and then returns to the engine. The temperature of coolant decreases
from Tc,in to Tc,l, then to Tc,out, The ORC
system can be identified as 1-2-3-4-5-1 and
described as follows. The generated saturated
vapor with high pressure (point 1) in the evaporator flows into the turbine, in which vapors
enthalpy is converted into work, and then
converted into electricity by generator. The
process 1 to 2s means isentropic expansion
process, which is ideal and impossible. When
the turbine efficiency is higher, point 2 is closer

into the condenser where it is liquefied and

condensed into the saturated liquid (point 3) by
the supplied cooling water. The saturated liquid
available at the condenser outlet is pumped to
be a liquid with high pressure (point 4) by refrigerant pump, and then flows into the preheater where it is heated to be saturated liquid
at high pressure (point 5) by the coolant. The
saturated liquid at high pressure flows into the
evaporator and is vaporized to be saturated
vapor (point 1) by the coolant. The whole cycle
is complete as shown in Figures 1 and 2.

Figure 1.Schematic diagram of the bottoming ORC system

Figure 2.T-s diagram of the bot-

toming ORC system

Figure 2 shows the heat exchange diagram

during the working fluids heating process and
condensing process. The preheating process
and evaporating process are considered as a
unified heating process. The coolant of engine
supplies the heat needed to heat and vaporize
the working fluid, and the cooling water supplies the cooling capacity. During the heating
process, the temperature (Tc,in) and mass flow
rate (mc) of DE coolant are tested and constant.
During the condensing process, the inlet
(Tcw,in) and outlet temperatures (Tcw,out) of
cooling water are assumed to be 30C and
35C. A minimum temperature difference
(Tmin) at Pinch Point (PP) to meet the heat
exchanger performance is assumed to be 3C.
The heat exchange during the working fluid
heating process is as follows.

Step 1. Assume that an evaporating temperature Te and the PP exist at point 5, which
means Tc,l=T5+Tmin, and this allows writing
the first energy balance, referring to complete
fluid vaporization:

mr ,1

mc cpc ,inl Tc ,in Tc ,l

h1 h5

(1)
wherein, the organic fluid enthalpies are
obtained at the evaporating temperature chosen for ORC and cpc,inl is calculated at the
average temperature between Tc,in and Tc,l.
Step 2. Another two energy balances are
used to determine the coolant outlet temperature (Tc,out) :

227

T cw,out

1.75

Tc ,out Tc ,in

procedure of condensing process, the condensing temperature (Tcond) and mass ratio of
cooling water (mcw) could be obtained.

mr ,1 h1 h4
mc cpc

(2)

where the cpc are calculated at the average

temperature between Tc,in and Tc,out. Therefore, three temperature differences during the
working fluid heating process are as follows:

Organic working fluids used for the ORC

system may have different characteristics in
the T-s diagram and the saturation lines may
be bell shaped, nearly isentropic or overhanging depending on the fluid molecule complexity.
Typically, fluids with simpler molecule have bell
shaped vapor lines and lower critical temperatures, and fluids with more complex molecules
display an overhanging vapor line and higher
critical temperatures. According to the slope of
the saturated vapor curve in the T-s diagram,
organic fluids can be classified as the dry one,
isentropic one and wet one. Types of working
fluids can be predicted by =ds/dTH, which is
the slope of saturated vapor curve. The organic
fluid is a dry type with >0, an isentropic type
with =0, and a wet type with <0 [21]. Meanwhile, there are several general criteria for the
proper working fluids. Stability, non-fouling,
non-corrosiveness,
non-toxicity
and
non-flammability are a few preferable physical
and chemical characteristics. However, in a
cycle design, not all the desired general requirements can be satisfied. Table 2 shows
physical property and environmental data of
fluids considered in this study and the predicted fluid types.

Tin Tc,in T1
(3)

Tl Tc,l T5
(4)

Tout Tc,out T4
(5)
Step 3. Compare the three temperature differences above, choose the point with the
minimum one as the real pinch point, and set
its temperature difference to be the minimum
temperature difference (Tmin), and then repeat establishing energy balances from equation (1) to (2) to determine the true working
fluid mass flow ratio and other parameters.
Step 4. If Tc,out calculated with the equations above is lower than the minimum allowed
temperature for the coolant (50C), the calculation will end.
The heat exchange during the working fluids condensing process is the same as that of
heating process. According to the calculation
Table.2 .Physical and environmental data of working fluids [23-38].
Physical data
Substance
M
Tb
Tcr
(kg/kmol)
(C)
(C)
R143a
84.04
-47.24
72.71
R290
44.10
-42.09
96.68
R22
86.47
-40.81
96.15
R717
17.03
-33.33
132.25
I
R1234yf
114.04
-29.45
94.70
R134a
102.03
-26.07
101.06
R152a
66.05
-24.02
113.26
R124
136.48
-11.96
122.28
R142b
100.50
-9.15
137.11
RC318
200.03
-5.98
115.23
R600
58.12
-0.55
151.98
R114
170.92
3.59
145.68

R245fa
134.05
14.90
154.05
R11
137.37
23.71
197.96
R123
152.93
27.82
183.68
R141b
116.95
32.05
206.81

228

Working Fluids Consideration

Pcr
(MPa)
3.761
4.247
4.990
11.33
3.382
4.059
4.517
3.624
4.070
2.778
3.796
3.257
3.640
4.408
3.662
4.460

Environmental properties*
ALT
GWP
ODP
(a)
(100a)
52
0
4470
20
0.04
0
12
0.05
1810
0.01
0
<1
0.03
0
4
14
0
1430
1.4
0
124
5.8
0.02
609
17.9
0.07
2310
3200
0
10,250
20
0.02
0
300
7.6
45
1.3
9.3

1
0
1
0.02
0.12

10,040
1030
4750
77
725

Fluid Type
Isentropic
Wet
Wet
Wet
Isentropic
Isentropic
Wet
Isentropic
Isentropic
Isentropic
Isentropic
Isentropic
Isentropic
Isentropic
Isentropic
Isentropic

of heat exchangers are defined as the following

equation:

4 Mathematical Modeling

1 U i 1 r ,i l k 1 j

Before establishing the mathematical

model of this system, some general assumptions are made. (1) Neglect the kinetic and
potential energies. (2) Consider each component as a steady-state and steady-flow system.
(3) Neglect the heat and friction losses in each
component and system pipe. (4) Consider the
plate type heat exchangers as the preheater,
evaporator and condenser in this analysis due
to their compactness and high heat transfer
coefficients which result in less heat transfer
area than those when using shell and tube heat
exchanger[39]. The plate type heat exchangers
whose heat transfer plate is about 0.5m long,
0.2m wide and 0.002m thick, are supplied by a
famous European company. Moreover, the
passage interval of hot gas side is about
0.008m, and that of others is all 0.006m. The
detailed mathematical models are described as
follows.

(14)
In equation (14), i means the heat exchanger
such as preheater and j means the coolant or
cooling water. Numerical correlations are used
to calculate the heat transfer coefficients of
working fluids, coolant and cooling water in
these heat exchangers. In condenser, the heat
transfer coefficient (r,suph) of gas phase on
working fluid side can be calculated using the
correlation as follows [40]:

Rev v v Deq ,r v
(15)
Prv cpv v kv
(16)

Nuv 0.122Prv1/3 (v wall )1/6 ( f Rev 2 sin 2 )0.374

(17)

r ,suph Nuv kv Deq ,r

(18)

4.1 Turbine

1 f 0.5 cos (0.18 tan 0.36sin f 0 cos )

Wt mr h1 h2 mr h1 h2 s t

0.5

(1 cos ) (3.8 f1 )0.5

(5)
lg C p ,t K1,t K 2,t lg Wt K 3,t lg Wt

(
19)
When Rev<2000,
f0 64 Rev

(6)
Cbm,t C p ,t Fbm,t
(7)

f1 579 Rev 3.85

When Rev2000,

f0 (1.8lg Rev 1.5)2

4.2 Work fluid pump

f1 39 Rev 0.289

Wrp mr h4 h3 mr h4 s h3 rp

Wherein, subscript v means the properties on

the gas phase condition. Deq,r in equations (15)
and (18) should be the equivalent diameter of
condenser channel.
The condensation heat transfer coefficient
(r,c) of all the working fluids can be calculated
using the correlation as follows [41,42]:

(8)
lg C p , rp K1,rp K 2,rp lg Wrp K 3,rp (lg Wrp ) 2
(9)
lg Fp,rp C1,rp C2,rp lg Prp C3 (lg Prp )2
(10)

Cbm,rp C p,rp Fbm,rp C p,rp ( B1,rp B2,rp Fm,rp Fp,rp )

r ,l 0.2092(kl Deq,r ) Rel 0.78 Prl 0.33 ( wall )0.14

(11)
4.3 Condenser

(20)
Co ( v l )(1 x 1)0.8

Qc mr (h2 h3 )

(21)

Frl G 2 ( l 2 gDeq,r )

(12)
Ac Qc (U c Tm,c )

(22)

Bo q G i fg

(13)

(23)
The overall heat transfer coefficients (Ui)

229

 r ,c r ,l (0.25Co0.45 Frl 0.25 75Bo0.75 )

(kJ/kg.K); k means the conductivity of working

fluid (kW/m.K); means the chevron angle of
plate type heat exchanger (radian); subscripts l
and wall mean the properties on the liquid
phase condition and wall temperature condition
respectively.

(24)
where x means the vapor quality; G means the
working fluid mass flux (kg/m2.s); g means the
acceleration due to gravity (m/s2); ifg means
the enthalpy of vaporization (kJ/kg).
The heat transfer coefficient (cw) of
cooling water is evaluated by the same model
as that of gas phase on working fluid side [40].

Table 3 .Equivalent diameter of each channel

hot coolant
Working fluid
Components
side(m)
side(m)
0.016
0.012
Preheater
Evaporator
0.016
0.012
Condenser
0.012
0.012
Note:Values in the table are obtained by plate type heat
exchanger products from a European company

lg C p,c K1,c K2,c lg Ac K3,c (lg Ac )2

(25)
lg Fp,c C1,c C2,c lg Pc C3,c (lg Pc )2

The heat transfer coefficient (c) of coolant

is evaluated by the same model as that of gas
phase on working fluid side [40].

(26)
Cbm,c C p,c Fbm,c C p,c ( B1,c B2,c Fm,c Fp,c )
(27)

lg C p, preh K1, preh K2, preh lg Apreh K3, preh (lg Apreh )2

4.4 Preheater

(34)

lg Fp, preh C1, preh C2, preh lg Ppreh C3, preh (lg Ppreh )2

Qpreh mr (h5 h4 )
(28)

(35)

Apreh Qpreh (U preh Tm, preh )

Cbm, preh C p, preh Fbm, preh C p , preh ( B1, preh B2, preh Fm, preh Fp , preh )

(36)

(29)

4.5 Evaporator

In preheater, the heat transfer coefficient

(r,preh) of liquid phase on working fluid side
can be calculated using the correlation as follows [43]:

Qe mr (h6 h5 )

(37)
Ae Qe (U e Tm,e )

Rel
l l Deq , r l

(38)

(30)

Prl cpl l kl

In evaporator, the boiling heat transfer coefficient (r,e) for all the working fluids is calculated using the correlation as follows [44,45]:

(31)
Nul (0.0154 0.1298) Rel (0.1892 0.6398)

Prl 0.35 ( l wall )0.14

(32)
r , preh Nul kl Deq ,r

r ,e 1.5 55( Pe Pcr )(0.120.2lg Rp ) (1g ( Pe Pcr ))0.55 q0.67 M 0.5

(39)

(33)

where Pcr means the critical pressure of

working fluid (MPa); Rp means the mean asperity height (m), which is the mean roughness between peak and valley at surface. According to the supplied plate type heat exchangers by an European company, the value
of Rp is 0.3 in this calculation; q means the
heat flux (W/m2) which is evaluated by assuming wall temperature initial, and then using
the iterative method; M means the molar mass
of working fluid (kg/kmol).

where Re, Pr, Nu mean the Reynolds number,

Prandtl number and Nusselt number respectively; means the density of working fluid
(kg/m3); means the velocity (m/s); Deq,r
means the equivalent diameter of channel (m),
which
is
defined
as

Deq

4A 4 d l

2d
Ch
2l

, twice the passage interval to plate type heat exchangers.

Table 3 gives the equivalent diameter of each
channel; means the viscosity (Pa.s); cp
means the specific heat at constant pressure

lg C p,e K1,e K2,e lg Ae K3,e (lg Ae )2

(40)

230

lg Fp,e C1,e C2,e lg Pe C3,e (lg Pe )2

chanical power is the sum of the original diesel

engine power (W0) and the ORC expansion
net power (Wnet).

(41)
Cbm,e C p,e Fbm,e C p,e ( B1,e B2,e Fm,e Fp,e )
(42)

In the equations (5) to (42), Wt means the

turbines power output (kW); mr means the
mass flow rate of the ORC system (kg/s); h
means the specific enthalpy (kJ/kg); t means
the isentropic efficiency of turbine; rp means
the isentropic efficiency of refrigerant pump; P
means pressure (MPa); Q means the heat
capacity in heat exchanger (kW); U means the
overall heat transfer coefficient (kW/m2.K); A
means the overall heat transfer area (m2); Tm
means the logarithmic mean temperature difference (K). K, C, B, F are the coefficients
whose values are presented in Table 4. Subscripts t, rp, preh, e and c mean turbine, refrigerant pump, preheater, evaporator and
condenser respectively. Equations (6), (7),
(9)-(11), (25)-(27), (34)-(36), (40)-(42), which
evaluate the component invest, are referring to
ref. [46].

W net W 0
Q fuel

(47)

4.7 Economic analysis

The electricity production cost (EPC) is defined and obtained by the follow equations:
Cost1996 Cbm,t Cbm,rp Cbm, preh Cbm,e Cbm,c

(48)
Cost2008 Cost1996 CEPCI 2008 CEPCI1996
(49)
CRF i(1 i)time ((1 i)time 1)
(50)
AN , K Cost2008CRF

(51)
EPC ( AN , K f K Cost2008 ) ((Wt Wrp ) h full load )

(52)
4.6 System performance
where Cost2008 is the system cost based on
the price in the year 2008. CEPCI1996 =382,
CEPCI2008 = 575.4 (CEPCI means Chemical
Engineering Plant Cost Index). CRF means the
capital recovery cost. AN,K means the annuity
of the investment obtained using equation (50).
i is the interest rate, whose value is 5%. Parameter time is the economic life time, whose
value is 15 years. fK is the maintenance and
insurance cost factor, whose value is 1.65%.
hfull-load is the full load operation hours,
whose value is 7500h. These values are referring to references [47,48], in which there are
almost the same components as those in our
system. The values are reasonable and obtained by statistic of the related products.

The thermal efficiency can be calculated by

equation (43) as follows:

th (Wt Wrp ) (Qpreh Qe Qsuph )

(43)
The net power output can be calculated
by equation (44). Therefore, the net power
output per unit mass flow rate of hot exhaust
can be defined as equation (45). Wherein, mg
means the mass flow rate of coolant in DE
(kg/s).
Wnet Wt Wrp

(44)
Pnet Wnet mg

(45)
Therefore, the total heat transfer area per
net power output can be defined as equation
(46).

Validation

Numerical calculating solution is validated

with the results of Saleh et al. [20] for various
fluids-based ORC and for the same operating
conditions listed below. The cycle in Saleh et al.
[20] used heat source with 120C available
temperature and the mass flow rate referred to
a net power output of 1MW. The condensation
temperature was 30C, the isentropic turbine
efficiency was 0.85, and the isentropic pump
efficiency was 0.65. The turbine inlet tempera-

A W ( Apreh Ae Asuph Ac ) Wnet

(46)
Efficiency of the DE-ORC combined system
(a) is the ratio of total output mechanical
power to total fuel energy. Total output me-

231

ture was 20C lower than the geothermal

source temperature, i.e. 100C. The temperature difference in pinch point was 10C. As
shown in table 5, the comparison shows a very
good agreement between the present solution
and the results of Saleh et al. [20]. The dis-

crepancies of different parameters shown in

Table 5 mainly derive from the choosing of
equation of state (EOS), the BACKONE EOS
was selected in Saleh et al. [20] while the EES
database is chosen for property in the present
study.

Table 4. Coefficients in equations evaluating investment of system components [46]

K1
K2
K3
C1
C2
Components
Turbine
3.5137
0.5888
0
/
/
Working flu3.5793
0.3208
0.00285
0.1682
0.3477
id pump
Preheater
3.8528
0.4242
0
0
0
Evaporator
3.8528
0.4242
0
0
0
Condenser
3.8528
0.4242
0
0
0

C3
/

B1
/

B2
/

Fm
/

Fbm
3.5

0.4841

1.80

1.51

1.80

0
0
0

1.53
1.53
1.53

1.27
1.27
1.27

2.80
2.80
2.80

/
/
/

Table 5 .Validation of the numerical model with the previously published data [20] for the various fluids-based ORC
Substance
Tt,i
Tt,o
Pcond
Pevap
mr
v2/v1
th
Source
(C)
(C)
(MPa)
(MPa)
(kg/s)
(/)
(/)
R143a
100
51.72
1.44
4.0
56.86
3.01
8.64
[20]
100
54.21
1.435
4.0
57.26
3.1
8.85
present
100
42.70
1.44
4.5
57.44
3.52
9.05
[20]
100
45.52
1.435
4.5
58.8
3.66
9.6
present
100
30
1.44
5.0
70.95
4.85
8.68
[20]
100
36.28
1.435
5.0
74.13
4.5
10.1
present
*Tt,i means the inlet temperature of turbine; Tt,o the outlet temperature of turbine; Pcond the condensation pressure; Pevap
the evaporating pressure; mr the mass flow rate of working fluid; v2 and v1 mean the specific volumes of working fluid outlet and
inlet of the turbine. th means the thermal efficiency of ORC.

Calculated Results and Discussion

Input parameters: mc, Tc,in,
Pc, Tcw,in, Tcw,out, Pcw, Tmin, t, rp,

The engine coolant conditions of a real engine are shown in Table 1 and the calculated
conditions of the ORC system along with the
characteristics of the turbine, pump, etc. are
expressed in sections above. In the following
paragraphs, we present the results of a comparative study for different working fluids-based
ORC system based on the model previously
described. The thermodynamic properties of
fluids and system performance are evaluated
with EES (Equation Evaluation Solution), which
has sufficient accuracy. The condensing temperature of the ORC-based power generation
subsystem can be determined and the evaporating temperature for each working fluid is
optimized according to different criteria discussed in the flow chart of the simulation procedure as shown in Figure 3. The investigated
16 fluids are divided into two groups according
to their normal boiling point temperatures
ranging from -51.6 to 47.6C. They are listed
as follows, Group 1, Tb <-10C; Group 2, Tb >
-10C. Figures 4-13 show performances of
different working fluids investigated for the
based bottoming ORC system on five different
screening criteria, including th, v2/v1, Pnet,
A/Wnet and EPC in this analysis.

g
Variable

parame-

Variable parameter: Tcond

ters
Upre, Ue, Uc, Uc,sup

Apreh, Ae, Ac, Ac,sup, Pnet,

A/Wnet

Cost calculation
Cbm,t, Cbm,rp, Cbm,preh,
Cbm,e, Cbm,c, EPC

Figure 3.Flow chart of the simulation procedure

6.1 Thermal efficiency th

232

/Tcw,out>0.001

Wt, Wrp, Qpreh, Qe, Qc,

Qc,sup, Tcw,outcall, state parame-

Tcw,outcall-Tcw,out

Minimizing EPC

Maximizing Pnet and minimizing A/Wnet

ter:Te

9.0
8.5
8.0
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5

the turbine outlet/inlet volume flow ratio (v2/v1).

The expansion ratio is particularly significant as
it shows how much the fluid volume increases
through the expansion. As shown in Figure. 6
and 7, the curves are increasing as the increase of evaporating temperatures for all the
fluids. In Group 1, R1234yf and R124 outstand
among the considered working fluids. R245fa,
RC318 and R123 show larger v2/v1 value in
Group 2. RC318 presents the highest v2/v1
value of about 4.49. The top three fluids presenting higher v2/v1 values are RC318,
R245fa and R1234yf of 4.49, 4.48 and 4.27
respectively. It should be noted that the expansion ratio v2/v1 can change significantly
depending on the characteristics of the working
fluid, for example several fluids can achieve
values up to 550, but some others values are
smaller than 50. However, the high expansion
ratio is bad for a single stage turbine design.
The pre-research [49] indicates that when the
expansion ratio is smaller than 50, a single
stage axial turbine can be easily designed and
achieve expansion efficiencies higher than 0.8.
4.5

R143a
R290
R22
R717
R1234yf
R134a
R152a
R124

50

55

60
65
70
75
80
Evaporating temperature( )

85

60
65
70
75
80
Evaporating temperature( )

2.5
2.0

90

85

55

60
65
70
75
80
85
Evaporating temperature( )

90

Figure 6 .Variation of expansion ratio with evaporating

temperature (Group 1)
4.5
R142b
RC318
R600
R114
R245fa
R11
R123
R141b

4.0
Expansion ratio (v2/v1)

Thermal efficiency (th)(%)

55

3.0

50

R142b
RC318
R600
R114
R245fa
R11
R123
R141b

50

3.5

1.5

Figure 4.Variation of thermal efficiency with evaporating

temperature (Group 1)
9.0
8.5
8.0
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5

R143a
R290
R22
R717
R1234yf
R134a
R152a
R124

4.0

Expansion ratio (v2/v1)

Thermal efficiency (th)(%)

In Figures 4 and 5, the cycle thermal efficiency is plotted for the considered working
fluids in the range of evaporating temperatures.
Higher th value means that more power output can be obtained with the same heat capacity recovered from engine coolant. As shown in
Figures 4 and 5, the curves are monotonic and
increasing as the increase of evaporating
temperature for all the fluids. The suitable
evaporating temperature ranges from 50C to
88C. In Group 1, R22 outstands at the same
evaporating temperature and R290 has the
highest value of 8.81%. R141b, R11 and R123
outstand among Group 2. With the highest th
value presented by each fluid being compared,
R11 is the highest one of about 8.82% at
evaporating temperature 88C, and the top
high ones are as follows.
R11(8.82%,88C)>R290(8.81%,88C)>R15
2a(8.75%,88C)>R141b(8.71%,88C)>R142b(
8.69%,88C)>R123(8.64%,88C)>R600(8.54
%,88C)>R245fa(8.47%,8C).
If the environmental characteristics are taken into consideration (ODP value <0.20, GWP
value < 1500), the top three fluids presenting
higher th values are R290, R141b, R123 and
R245fa ranging from 8.47% to 8.81%.

3.5
3.0
2.5
2.0
1.5
45

90

50

55

60 65 70 75 80
Evaporating temperature( )

85

90

Figure 7. Variation of expansion ratio with evaporating

temperature (Group 2)

Figure 5 Variation of thermal efficiency with evaporating

temperature (Group 2)

6.3 Net power output per unit mass flow

rate Pnet

6.2 Expansion ratio v2/v1

Figures 6 and 7 report, for each fluid, the
curves referring to the expansion ratio, which is

Figures 8 and 9 present variation of Pnet

values for Groups 1-2 working fluids with vari-

233

Pnet(kJ/kg)

ous evaporating temperatures. Higher Pnet

value means that more power output can be
obtained with the same mass flow rate of engine coolant. As shown in Figures 8 and 9,
Pnet value increases first and then decreases
after reaching its maximum at evaporating
temperature of about 66C except R124 whose
optimum evaporating temperature is 69C. The
investigated evaporating temperatures for
R143a are lower because of its lower critical
temperature value. The maximum considered
evaporating temperature for R717 is 66C
since it presents higher pressure (exceeds 3.0
MPa) at higher evaporating temperature. In
Group 1, R1234yf and R134a outstand. RC318
shows larger Pnet value in Group 2. Fluids in
Group 1 show the lowest Pnet values except
R143a and R134a which present the highest
Pnet values of about 8.88kJ/kg and 7.06kJ/kg
respectively. Among all the considered working
fluids, R143a presents the highest Pnet value
of about 8.88kJ/kg at evaporating temperature
72C. Besides R143a, RC318 presents the
highest Pnet value of about 7.42kJ/kg at
evaporating temperature 66C. Moreover,
R245fa and R114 also present high Pnet values of about 7.08kJ/kg and 7.07kJ/kg, which
are 4.6% and 4.7% lower than RC318 respectively. Also if the environmental characteristics
are taken into consideration (ODP value <0.20,
GWP value < 1500), the top three fluids presenting higher Pnet values are R245fa, R134a
and R123 ranging from 7.08 to 6.93 kJ/kg.

9.0
8.5
8.0
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5

Pnet(kJ/kg)

55

60

65 70 75 80 85
Evaporating temperature( )

90

4
3
2
1

50

55

60
65
70
75
80
Evaporating temperature( )

85

90

Figure 9.Variation of net power output per unit mass flow

rate with evaporating temperature (Group 2)

6.4 Total heat transfer area per net power

output A/Wnet
Figures 10 and 11 report, for each fluid in
Groups 1 and 2, the curves referring to the total
heat transfer area per net power output A/Wnet
values with various evaporating temperatures.
It is noted that lower A/Wnet value expresses
that smaller total heat transfer areas would be
needed in order to achieve the same net power
output which can indicate the heat transfer
performance and reduce the system investment in some aspects. As shown in Figure 10
and 11, the curves decrease first and then increase after reaching their minimum value at
some evaporating temperature which varies
with different working fluids. For Group 1 fluids,
the optimum evaporating temperatures range
from 64 to 82C. For Group 2 fluids, the optimum evaporating temperatures range from 74
to 80C. In Group 1, R152a and R134a show
the lowest values. R142b and R600 show lower A/Wnet value in Group 2. The minimum
A/Wnet values for R152a, R134a, R600,
R142b, RC318 and R245fa are 0.874, 0.893,
0.908, 0.937, 1.019 and 1.054m2/kW corresponding with the optimum evaporating pressure of 76, 78, 80, 80, 80 and 76C respectively. Fluids with better environmental characteristics presenting lower A/Wnet values are
R600, R134a, R245fa and R152a ranging from
0.874 to 1.054m2/kW.

R143a
R290
R22
R717
R1234yf
R134a
R152a
R124

50

R142b
RC318
R600
R114
R245fa
R11
R123
R141b

95

Figure 8.Variation of net power output per unit mass flow

rate with evaporating temperature (Group 1)

234

R143a
R290
R22
R717
R1234yf
R134a
R152a
R124

2.2
2.0

A/W(m /kW)

Electricity production cost(Epc)(dollar/kWh)

2.4

1.8
1.6
1.4
1.2
1.0
0.8

48

52

56

60

64

68

72

76

80

84

88

Evaporating temperature( )

R142b
RC318
R600
R114
R245fa
R11
R123
R141b

2.0
2

A/W(m /kW)

Electricity production cost(Epc)(dollar/kWh)

2.6

2.2

1.8
1.6
1.4
1.2
1.0
0.8

48

52

56

60

64

68

72

76

80

84

R143a
R290
R22
R717
R1234yf
R134a
R152a
R124

0.56
0.52
0.48
0.44
0.40
0.36
0.32
48

52

56

60
64
68
72
76
Evaporating temperature( )

80

84

Figure 12. Variation of Epc with evaporating temperature

(Group 1)

Figure 10. Variation of total heat transfer area per net

power output with evaporating temperature (Group 1)

2.4

0.60

88

Evaporating temperature( )

Figure 11. Variation of total heat transfer area per net

power output with evaporating temperature (Group 2)

0.52

R142b
RC318
R600
R114
R245fa
R11
R123
R141b

0.48
0.44
0.40
0.36
0.32
0.28

45

50

55
60
65
70
75
Evaporating temperature( )

80

85

Figure 13. Variation of Epc with evaporating temperature

(Group 2)

6.5 Electricity production cost Epc

Figures 12 and 13 present variation of the
electricity production cost Epc values for
Groups 1-2 working fluids with various evaporating temperatures. It is noted that smaller
Epc value means more system techno-economy. As shown in Figures12 and 13,
Epc value decreases first and then increases
after reaching its minimum at evaporating
temperatures of about 60-73C. For Group 1,
R152a shows the lowest value of about
0.3085$/kWh. R600, R412b and R245fa show
smaller Epc values in Group 2. Among all the
fluids, the lower ones are as follows:
R600(0.2957$/kWh,68C)<R142b(0.3024$/
kWh,68C)<R245fa(0.307$/kWh,68C)<R152a
(0.3085$/kWh,66C)<R123(0.3121$/kWh,66C
)<RC318(0.3145$/kWh,68C)<R134a(0.3158$
/kWh,68C). If we consider the environmental
characteristics (ODP value <0.20, GWP value<1500), the top four fluids presenting lower
Epc values are R600, R245fa, R152a, and
R123 ranging from 0.2957 to 0.3121$/kWh.

6.6 System efficiency increments

By comparing the efficiencies between
original DE and the combined system DE-ORC
with different working fluid, we could figure out
the biggest potential of waste heat recovery by
applying the ORC bottoming system, as shown
in Figure 14. By integrating the ORC system to
DE, the efficiency will be lifted up to 45.4%
while adopting RC318 from 41.8% of the original DE. Besides, the efficiencies are all above
45% with eight kinds of working fluid selected.
What is more, system efficiencies are slightly
higher with RC318, R245fa, and R114 than
those with other four fluids. In a word, it is significant to improve the system efficiency by
adopting the bottoming ORC system to recover
waste heat in engine coolant.

235

47

This work was supported by the National Natural Science

Foundation of China (Grant No. 51206117)

46

Efficiency[%]

45

44

43

42

41

40

4
DE

DE-ORC
R142b

DE-ORC DE-ORC DE-ORC DE-ORC

RC318
R600
R245fa
R114

DE-ORC DE-ORC DE-ORC

R123
R141b
R11

Figure 14 Efficiency comparisons between DE and

DE-ORC.

Conclusions
6

In this study, an ORC system used in coolant heat recovery of DE is proposed and
techno-economically analyzed. The main results are as follows.
(1) When evaporating pressure varies from
condensation pressure Pcond to critical pressure of each working fluid Pcrit, the curves of
th and v2/v1 are monotonic and increasing.
The top three fluids presenting higher th values are R11, R290 and R152a ranging from
8.82% to 8.75%. However, RC318, R245fa and
R1234yf present higher v2/v1 values.
(2) Pnet value has a maximum value at the
optimum evaporating temperature. The curves
of A/Wnet and Epc decrease first and then
increase after reaching their minimum value.
Fluids with better environmental characteristics
presenting higher Pnet value are R245fa,
R134a and R123 ranging from 7.08 kJ/kg to
6.93 kJ/kg. The fluids presenting lower A/Wnet
values are R141b, R123, R245fa and R152a
ranging from 0.4356 to 0.5722m2/kW. The top
four fluids presenting lower Epc values are
R600, R245fa, R152a, R123 and ranging from
0.2957 to 0.3121$/kWh.
(3) With the integrated screening criteria
taken into consideration, R245fa and R123
always show better performance than the other
fluids and small discrepancy with each other.
The optimum evaporating temperatures for
R245fa and R123 are about 68C.
Moreover, further ORC cycle solutions will
be analyzed in future work and dynamical
model will be introduced to evaluate the behavior of the system in off-design conditions.
Also a detailed exergy analysis will numerically
quantify the entity of losses in the ORC system
used in coolant heat recovery.

7
8

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Engine Combustion With High Efficiency And Low Emissions

238

Research on the Generic Trends of Engine Performances in a Heavy Duty SI

LNG Engine and Application in Simulation based Performance Development
1

Zhang Kongming , Jin Zebing , Zhang Fan , Wang Ke ,

2

Tang Qijun* and Liu Jingping

(1 BeiJing Green Energy Cooperation, Beijing, 100096

2 Research Center for Advanced Powertrain Technologies, Hunan University,Changsha,
410082)
*Corresponding authors contact email: tangqijun293@126.com

ABSTRACT
The engine performance and fuel economy data, as well as related parameters, including
in-cylinder pressure traces of a turbocharged, LNG fuelled, spark ignited engine are measured in a
wide range of engine speed and load conditions. The general variation trends of engine
performance vs. the operational parameters are analyzed and presented in this paper. In-cylinder
burning rate curves are processed from the measured pressure traces. The combustion and
in-cylinder heat release related characteristics, such as the 10-90 burn duration, 50% burning point
location, the shape of ROHR curves, etc

are then associated with engine speed and load (BMEP),

in that way the general characteristics representing the LNG combustion are demonstrated. Results
indicate that, engine BMEP has a strong linearty with the intake air density and the relative AFR of
the mixture; the rate of heat release (ROHR) is influenced more by the relative AFR than the engine
speed and load; the location of the 50% burning points has a strong influence on the thermal
efficiency of the engine; the ROHR curves have very similar shape regardless of engine speed and
load; variations of FMEP vs. engine speed and load are also demonstrated. The results of this
research provide a good base for the performance simulation model setup of this type of engine
and also the optimization guidelines.
Keywords: LNG engine, Performance, Influencing parameters, General trend, Combustion
characteristics.
INTRODUCTION
Natural gas (NG) is in gaseous state and also with lower carbon content which promotes much
easier

air/fuel mixing and therefore is very advantageous over the diesel fuel with regard to the

PM emissions; It also has advantages on gasoline fuel because its higher Octane number which
allows for higher CR to achieve higher thermal efficiency; its gaseous state also promotes better
mixing and therefore lower HC and CO emissions. Therefore NG is usually regarded as a "clean"
energy or "green" energy. Also, the cost to the end customers, on the basis of RMB per BTU, is
about 20-30% lower than gasoline and diesel. Therefore NG is expected a boosted application as
the automotive fuel.
Although China has a large fleet of automobiles fueled by NG, those NG engines are modified
either from their diesel or gasoline engine cousins, and the quantity of the NG engines are much
smaller than their diesel or gasoline counterparties. Because of that, few NG engines were specially
designed for the NG application, very little systematics research work was conducted on revealing
the relationship between the performances vs. the design and operational parameters of the NG
engines, let alone on the design and optimization guidelines.

1
239

Engine performance is influenced by many design and operational parameters[1-4]. Those are all
required to be defined and optimized in the engine performance development stage. Because the
huge number of influencing parameters and the possible combinations of those parameters, the
effort of defining and optimizing those parameters is tremendous, it could take months just to do a
computer simulation based concept study for engine performances. To make the problem worse, at
the early stage of the engine performance concept study many boundary condition data (usually
acquired from engine dyno tests) are not available. Therefore, the baseline data and the generic
trends between the engine performance and operational data, are critically important to establish
and calibrate an accurate engine performance simulation model, and to judge the feasibility of the
simulated engine performance results. Therefore, this paper is focused on the following aspects:

To classify the major and minor influencing parameters to the engine performance and fuel
economy, and their influencing trends, through analyzing the engine dyno test data

To provide boundary conditions on setting up engine performance simulation models,

especially the combustion parameters

To provide guidelines on the procedures and judgement of results for the simulation based
engine performance optimization practice

GENERAL TRENDS OF ENGINE PERFORMANCE AND MAJOR INFLUENCING

PARAMETERS
Engine Dyno Tests
One LNG engine in heavy duty application, as specified in Table 1, was chosen for testing on
the Hunan University AVL AC dyno. The engine was tested for various speed and load conditions,
with the speed interval of 200r/min and load interval of 1 bar BMEP. Parameters measured include
engine speed, torque, air and fuel flowrate, pressures and temperatures at various locations.
Dynamic pressure traces in 2 cylinders are also recorded. Rate of heat release (ROHR) analysis
are conducted from the recorded dynamic pressure traces.
Tab.1 The major specifications of the LNG engines tested
Engine Type

Bore (mm)

Stroke (mm)

Compression ratio

Displacement (L)

In-line 6 cylinder,
turbocharged, water cooled,

126

130

11

9.726

spark ignited, LNG fueled

Engine Performance Related Parameters

First of all, the controlling parameters to the engine performance is derived. By definition, the
engine performance (BMEP) related parameters has the following relationship:

BMEP IMEP PMEP FMEP

NMEP FMEP
(1)
In Equation (1):
IMEP: the Indicated Mean Effective Pressure of the high pressure (power) loop, bar
PMEP: the Indicated Mean Effective Pressure of the low pressure (pumping) loop, bar

2
240

NMEP: the Net indicated Mean Effective Pressure of the entire cycle, including both the high
pressure and the pumping loop, bar
FMEP: the Friction Mean Effective Pressure of the engine, including mechanical friction losses
and auxiliary losses, bar
From the definition of Mean Effective Pressures (XMEP) and the in-cylinder energy balance
rule, i.e. the piston work output during a complete engine cycle equals to the portion of the fuel's
heat energy converted into mechanical work, i.e. :

PXMEP Vh m fuel Hu fuel x

(2)
Here the amount of fuel burnt in-cylinder, m fuel , is related to the amount of fresh air induced
and trapped in cylinder,

m fuel

ma i r in the following equation:

mair
AFR0
(3)

And the amount of fresh air induced and trapped in cylinder,

mair , equals to the intake air

density air and the volumetric efficiency v in the following equation:

mair air V Vh
(4)
Substitute equations (3) and (4) into (2) and after simplifying:

PXMEP

Hu fuel
AFR0

v X

air

(5)

3
241

24
600rpm
1000rpm
1400rpm
1800rpm
2200rpm
Trend line R=

20

IMEP / bar

16
12
8
4
0
0

0.5

1
1.5
Intake parameter (/) / -

2.5

24

NMEP / bar

600rpm
20

1000rpm

16

1400rpm
1800rpm

12

2200rpm

8
4
0
0

0.5

1
1.5
2
Intake parameter (/) / -

2.5

24

BMEP / bar

600rpm
20

1000rpm

16

1400rpm
1800rpm

12

2200rpm

8
4
0
0

0.5

1
1.5
Intake parameter (/) / -

Figure 1 Measured IMEP, NMEP and BMEP vs. intake parameter

2.5

air / , all speed and load points

Equation (5) shows that, the engine's IMEP, NMEP and BMEP are directly proportional to the
volumetric efficiency v, thermal efficiency of x, intake air density of air, and reversely proportional
to the relative AFR of the mixture . Since those 4 parameters are not related individuals, it seems
that the engine performance is determined by a very complicate mechanism with 4 degree of
freedom.
However, the issue can be significantly simplified if the data is organized in typical way.
Depicted in Figure 1 are the measured engine IMEP, NMEP and BMEP of all the engine speed and
load points as a function of the engine intake parameter
although the engine's thermal efficiency

air / . What Figure 1 indicates are that:

x, as well as the volumetric efficiency v would change

from speed to speed and from load to load, the fact that the IMEP, NMEP, and as well as BMEP
has a good linear relationship with the intake parameter

air /

hints that, the influences of

4
242

parameter x and vare of secondary important, they could be treated as constants during the
early stage of concept study, therefore the work effort would not be overwhelmed by too many
variations.
The relationship depicted in Figure 1 is very useful for sizing and pre-matching a turbocharger
to the engine. A compressor can be defined by 2 parameters, i.e. the mass flowrate passing
through and the pressure ratio it has to provide. Once a compressor is defined, the turbine could be
defined based on mass flowrate and energy balance criteria between a turbine and a compressor [5].
From equation (5) and Figure 1, if the MEP target is known, then

PXMEP
P

Cons1 XMEP
Cons 2 PXMEP
Hu fuel
v X
v X
AFR0

air

(6)
The air density in the intake manifold,

air ,

is related to the manifold air pressure and

temperature, Pmap and Tmap as following:

Pmap

air

R Tman
(7)

While on the other end the intake manifold air pressure is associated to the compressor output
pressure as:

pmap p out_ comp pintercooler

8
Here:

pint ercooler is the pressure loss in an intercooler, typical values are known

Assign P0 as the ambient pressure and

pin _ pipe

as the pressure loss in the upstream

components, then the pressure ratio that the compressor has to provide is defined as:

pout _ comp
pin _ comp

pmap Pint ercooler

P0 Pin _ pipe
(9)

The mass flowrate through the compressor (and the engine) can be determined from:
.

mair

mair n air V Vh n

120
120
(10)

Based on equation (6), the required fresh air density at the engine intake manifold is defined to
meet the predefined engine performance target,

PXMEP . The required compressor pressure ratio

and flowrate are defined from Eqution (9) and (10). The suitable compressors and turbines could
then be defined [6].

5
243

Depicted in Figure 2 are the measured peak cylinder pressure as a function of intake manifold
air pressure Pmap. This is to reveal the relationship between the peak cylinder pressure PCP, with
the intake boost pressure. As shown, apart from the 600 and 1000 r/min cases, in which the
combustion occur very late, as shown in Figure 6 , the PCP had demonstrated a very good linearity
with the intake manifold air pressure. Together with the relationship depicted in Figure 1, one could
quickly estimate the PCP level corresponding to the IMEP or BMEP level target.

Peak cylinder pressure / bar

120

600rpm
1000rpm
1400rpm
1800rpm
2200rpm
Trend line R=

100
80
60
40
20
0
0

0.2 0.4 0.6 0.8

1 1.2 1.4 1.6 1.8

Pmap/bar

2.2 2.4

Figure 2 Measured peak cylinder pressure vs. intake manifold air pressure, all speed and load points

Engine Thermal Efficiency and Fuel Economy Related Parameters

The fuel economy of an engine is usually judged by its fuel consumption rate:

XSFC

Cons
H u x
(11)

When the parameter X is assigned to I, N, or B, then the corresponding thermal efficiency x

becomes to i, N and B. XSFC becomes to the high pressure loop Indicated Specific Fuel
Consumption (ISFC) rate, Net indicated Specific Fuel Consumption (NSFC) rate and the Effective
Specific Fuel Consumption (BSFC) rate respectively. The relationship between those three
parameters are:

B N 1

FMEP
PMEP FMEP

i 1

NMEP
IMEP IMEP

(12)

Or:

BSFC

NSFC
ISFC

FMEP PMEP FMEP

1
1

IMEP IMEP
NMEP
(13)

6
244

50

40

40

Thermal efficiency /%

Thermal efficiency /%

50

30
Brake efficiency (1000r/min)
20

Cycle efficiency

10

30
Brake efficiency (1400r/min)
20

Cycle efficiency

10

HP loop efficiency

HP loop efficiency

0
0

12
BMEP / bar

16

20

24

12
BMEP / bar

16

20

24

Thermal efficiency /%

50
40
30

Brake efficiency(1800
r/min)
Cycle efficiency

20

HP loop efficiency

10
0
0

12
BMEP / bar

16

20

24

Figure 3 Influences of pumping and friction losses to the brake thermal efficiency

Depicted in Figure 3 are the influences over the brake thermal efficiency of the pumping and
friction losses for 3 typical engine speeds, i.e. 1000r/min, 1400 r/min and 1800 r/min. It can be
observed that:

The high pressure loop thermal efficiency curves are all very flat, also the curves are close
to each other. This defines the "ceiling" of the indicated thermal efficiency of this engine at
this compression ratio

Pumping losses decreases sharply with increase of engine load. When the BMEP is
greater than about 10 bars where the throttle starts to fully open, pumping losses (the gap
between the HP loop and the cycle efficiency lines) are negligible

Friction losses (the gap between the cycle efficiency with the brake efficiency) plays a
important role on the thermal efficiency of the engine, especially at part loads

The major reasons that cause the engine brake thermal efficiency to drop (BSFC to
increase) sharply are that both the fraction of pumping and friction losses increase with
decrease of engine load (BMEP).

Burning and Heat Release Characteristics

Combustion efficiency: Combustion efficiency is an indicator of the completeness of the
combustion process and the raw emissions of C, HC and CO. It could be obtained from analyzing
the raw exhaust gas components[5], [7]. As shown in Figure 4, the combustion efficiency increases
with increased relative AFR with an almost linear relationship.

7
245

Combustin efficiency /%

100
95
90
85
80
75
Test data

70
65
0.75

0.80

0.85
0.90
0.95
Relative AFR /-

1.00

1.05

Figure 4: Combustion efficiency vs. relative AFR , all engine operating points

Burning Rate: The burning rate of air/fuel mixture in cylinder is usually represented by the
10-90% burning duration. Figure 5 (a) depicts how does the burning duration change vs. the engine
speed and load. The following conclusions could be drawn:

When the engine's high pressure loop IMEP is below approx. 4 bar, the burning duration
increases almost linearly with decrease of engine load, as shown in Figure 5 (a), i.e. the
lower the engine load is, the longer the combustion duration is. This is most likely caused
by the throttling of the engine intake which reduces the air motion in cylinder and the
excessive cooling of mixture, which lowers down the combustion process

However, when the engine load is greater than approx. 4 bar, the 10-90% burning duration
is almost kept constant, except for the engine speed of 600 and 1000 r/min. Careful
examining of the 10-90% burning duration, together with the relative AFR data in Figure
5(b) , it could be concluded that the combustion duration is significantly influenced by the
relative AFR.

Figure 5(c) indicates that, in general the 10-90% burning duration increases when the
mixture becomes leaner. The trend is very strong at low engine speeds but it becomes
weaker with increase of engine speed.

8
246

50

10%_90% duration / deg

40
30
600rpm
20

1000rpm
1400rpm

10

1800rpm
2200rpm

0
0

12

16

20

24

NMEP / bar

Relative AFR

l/-

1.2

1.1
600rpm
1.0

1000rpm
1400rpm
1800rpm

0.9

2200rpm
0.8
0

12
16
NM EP / bar

20

24

(a)

(b)
40

10%_90% duration / deg

35
30
25

600rpm
1000rpm

20

1400rpm
15

1800rpm
2200rpm

10
0.8

0.85

0.9

0.95

1.05

1.1

1.15

1.2

Relative AFR / -

(c)
Figure 5: Combustion duration as a function of engine speed, load and other parameters

Location of 50% burning point. The combustion phasing is usually compared by the 50%
burning point location. The latter affects the in-cylinder thermal to work conversion efficiency
because it affects the effective expansion ratio, and also the compression work consumed during
the compression stroke. The closer the 50% burning point is located to the TDC, the burning
process is closer to the constant volume combustion. From one aspect, it is true that the closer the
combustion process closer to the TDC, the more effective expansion ratio it has for the burnt gas,
but on the other end, since the combustion does not occur instantly, while rather it takes certain
decrees of crankangle, Figure 5, the closer the 50% burning point is to the TDC,

means that the

earlier the combustion starts in the compression stroke which will consume more compress work.
Therefore, there is an optimal 50% burning point location

[8]

from the in-cylinder thermal efficiency

point of view. Both too early or too late 50% burning point location would result in a drop of thermal
efficiency.

9
247

50

1000rpm

40

40

1400rpm
1800rpm

30

i/%

50% comb_ position/ CA

50

600rpm

2200rpm

30

20

20

10

10

600rpm
1000rpm
1400rpm
1800rpm
2200rpm

12
IMEP / bar

16

20

24

12
IMEP / bar

(a)

16

20

24

(b)

Figure 6 50% burning location and indicated high pressure loop efficiency

Figure 6(a)

indicates that, in the 600r/min and the 1000r/min cases the combustion occur too

late, the combustion does not start until at or after TDC, Figure 8,

the effective expansion ratio for

the burnt gas is smaller. These partially explains why the thermal efficiency of the 600 r/min and
1000 r/min cases are obviously lower than the other speeds, as shown in Figure 6(b), other reasons
include lower than 1.0 relative AFR (richer mixture) and more in-cylinder heat loss at lower speeds .
The location of the peak cylinder pressure PCP has an almost linear relationship with the 50%
burning point location, as shown in Figure 7, but the former occurs about 5oCA later.

PCP position / CA

30
25
20
15

600rpm
1000rpm
1400rpm
1800rpm
2200rpm
Trend line: R=

10
5
0
0

10
15
20
50% comb_ position/ CA

Figure 7 Location of PCP vs

25

the 50% burning location

Burning Rate CurveThe shape of the burning rate curves need to be defined in order for
engine performance simulation. The in-cylinder burning and heat release process is usually
modeled using vibe functions[7], the vibe curve can be defined by three parameters, namely the
combustion duration 50% burning point location and the vibe index.

10
248

0.06

0.06

1000rpm

0.04

NMEP=5.19bar

NMEP=10.10bar

ROHR (1/o CA)

ROHR (1/o CA)

NMEP=4.98bar
NMEP=13.54bar

0.02

0.04

0.02

0
-90

-60

-30
0
30
Crank angle /CA

60

-90

90

0.06

-30
0
30
Crank angle /CA

60

90

NMEP=4.79bar

NMEP=9.91bar
NMEP=15.21bar
NMEP=18.88bar

1800rpm

ROHR (1/o CA)

0.04

-60

0.06
NMEP=4.89bar

ROHR (1/o CA)

1400rpm

NMEP=9.73bar
NMEP=14.53bar
NMEP=19.95bar

0.02

0.04

NMEP=9.55bar
NMEP=14.80bar
NMEP=18.90bar

2200rpm

0.02

0
-90

-60

-30
0
30
Crank angle /CA

60

90

-90

-60

-30
0
30
Crank angle /CA

60

90

Figure 8 Processed ROHR curves vs. engine speed and load

Shown in Figure 8 are the processed rate of heat release (ROHR)curves from the measured
cylinder pressure traces. Through analyzing those curves the individual Vibe parameters for each
case could be obtained. What Figure 8 indicates are:

With a fixed engine speed, except for very low engine load, the ROHR curves are very little
influences by the engine load, i.e. the combustion duration, as well as the shape of the
ROHR curves, are very similar regardless of the engine speed and load. This
characteristics are also demonstrated in Figure 5(a)

Visually the different engine speeds produces very similar ROHR curves, in both the
shape (Vibe Index) of the curves, and the combustion duration. The similarity of ROHR
curves under similar load but different speed, or similar speed but different loads, will be
analyzed and confirmed in a later phase.

Figure 8 provides essential information with regards to how to setup the engine's
in-cylinder combustion model.

Friction modelThe FMEP level affects the engine's brake efficiency, as shown in equation (12),
(13) and Figure 3. However, this is a parameter very difficult to determine without actual
measurement. Shown in Figure 9 is the measured FMEP as a function of engine speed and load.
The FMEP was determined from the averaged NMEP (of the two cylinders)-BMEP. Figure 9
indicates:

For the same engine speed, FMEP increases with engine load (BMEP) . Because the
higher the engine load is, the higher the in-cylinder pressure is and the larger forces are
acting on the piston rings, conrods and crankshaft, producing higher friction power
consumption

For the same load, FMEP increases with engine speed. Higher engine speed produces
higher sliding and rotational velocity of the frictional surfaces therefore with higher friction
power consumption.

11
249

Although different engines would produce different FMEP, the difference is not expected to
be big between the same type of engines. Figure 9 would provide references on how to
vary FMEP vs. engine speed and load when conducting engine performance simulations.

3.0
2.5
FMEP / bar

2.0
1.5
1.0
0.5
0.0
0

12
BMEP / bar

600rpm
1000rpm
1400rpm
1800rpm
2200rpm
(600rpm)
(1000rpm)
16
20
24
(1400rpm)
(1800rpm)
(2200rpm)

Figure 9: Measured FMEP as a function of engine speed and load

DISCUSSIONS: APPLICATION OF RESULTS DERIVED FROM THIS STUDY

The wide application of engine performance simulation codes, such as GT-Power, Boost,
Wave, etc. have made it possible and fairly easy to simulate the engine performance and to
optimize for engine's design and operational parameters. However, it is still difficult with regard to

Which are the major and which are the minor influencing parameters

How to set up the close to reality simulation boundary conditions

How to verify if the simulation results are feasible and reasoanble

Figure 10 illustrates how the results from this study could be utilized to guide a simulation
based engine performance concept study.

12
250

Engine full load toque (BMEP) -speed curve defined from vehicle simulation or other means

Using Figure1 and Equation6relationship to define the intake air density and

Turbocharger pre-match based on intake air density required and the

engine displacement, based on Figure 1 and Equations (9) and (10)

Establishment of detailed engine performance simulation model:

Figure 4
Combustion duration based on relationship shown in Figure 5(c)
50% burning point location: baseline from Figure 6(a), variation
for optimal fuel economy, watch for knock and PCP
Vibe index based on on relationship shown in Figure 8
FMEP level based on Figure 9

Simulation

based

optimization

of

design

and

operational

parameters:
Refinement of engine/turbo matching, using Figure 1 relationship
as directional guide
Engine vale timing and manifold geometry optimization study

[9]

Engine performance simulation at part load: Figure 3 results as

references
Variation 50% burning point location for optimal engine/turbo
matching and fuel economy, need to watch for knock tendency
[10]

and PCP locationFigure 7) and PCP value

Results meet
targets?

No, Go back
and continue

Yes, Finish

Figure 10 Flowchart of knowledge based engine performance simulation optimization

CONCLUSIONS
The following conclusions could be drawn from this study:
1. For a boosted engine, engine BMEP or torque output has good linearity with the intake air
density and the reverse of the relative AFR.

Variations of volumetric efficiency and thermal

efficiency is only of secondary importance

13
251

2. The combustion duration (heat release rate) mainly varies with the relative AFR. Engine
speed and load are of secondary influences, except at very low load when the combustion
becomes significantly slower
3. The 50% burning point location has a strong influence to the thermal to mechanical work
conversion efficiency
4. The amplitude of the peak cylinder pressure is controlled by the intake manifold pressure
while the location is determined by the 50% burning point
5. A knowledge based engine performance simulation procedure is proposed.
ACKNOWLEDGMENT
The authors would like to acknowledge the test engineers at Hunan Peteco company to
conduct the engine dyno testing work and the authorities of Beijing Green Energy Cooperation for
authorizing to publish this paper.
REFERENCES
[1]

Henning Kleeberg, Dean Tomazic, Oliver Lang, et al. 2006, Future Potential and Development
Method for high output turbocharged direct injection gasoline engines. SAE Paper
2006-01-0046. (for Conference)

[2]

Ryan J, Wong V, Lyon R, et al. 2014, Engine experiments on the effects of design and
operational parameters on piston secondary motion and piston slap. Internal combustion
engine fundamentals 2014: 01-07.Heywoods J. (for Journal)

[3]

Kesgin U. 2003, Study on prediction of the effects of design and operating parameters on NO<
sub> x</sub> emissions from a leanburn natural gas engine. Energy Conversion and
Management, 44(6): 907-921. (for Journal)

[4]

SHAO Fa-ke, LIAO Cheng, FU Jian-qin,et al. 2013, Study on the Controlling Parameters of
Power Performances in Advanced Turbocharged Direct-injected Gasoline Engines and
Pre-selection of Turbochargers. Journal of Central South University, 44(9). (for Journal)

[5]

Liu Jing-ping. 2013, Numerical Development Technologies of Engine Performances. Beijing:

Science Press, 2013: 108-159. (for book)

[6]

Okiishi T H, Walker G J, Hodson H P, et al. 1997,Boundary layer development in axial

compressors and turbines: Part 1 of 4composite picture. Journal of turbomachinery, 119(1):
114-127. (for Journal)

[7]

Heywoods J. 1988, Internal combustion engine fundamentals. New York: Mc Graw Hill,
1988:42-57. (for book)

[8]

Liu Jing-ping, Xia Xiao-lang, Zhao Zhi-chao, et al. 2012, Study on the in-cylinder heat release
related characteristic parameters and their influences on the indicated high pressure cycle
thermal efficiency of an I.C.E. Journal of internal combustion engine, 3: 010. (for Journal)

[9]

Umesh K S, Pravin V K, Rajagopal K. 2013, Experimental Analysis of Optimal Geometry for

Exhaust Manifold of Multi-cylinder SI Engine for Optimum Performance. International Journal,.
(for Journal)

[10] Wise D M, Olsen D B, Kim M. 2013, Development of a Lean Burn Methane Number
Measurement Technique for Alternative Gaseous Fuel Evaluation//ASME 2013 Internal
Combustion Engine Division Fall Technical Conference: V002T02A014-V002T02A014. (for
Conference)

14
252

NUMERICAL SIMULATION RESEARCH ON CORNSTALK REBURNING IN A

PULVERIZED COAL COMBUSTOR
1,

Xiang Gou *, Zifang Wang , Wei Ji , Liansheng Liu , Jinxiang Wu , Enyu Wang
School of Energy and Environmental Engineering, Hebei University of Technology, Tianjin 300401,
China
2
Chengde Heating Power Supply Co. Ltd., Chengde 067000, China
*Corresponding authors contact email: gouxiang@sina.com

ABSTRACT
Environmental pollution caused by direct coal combustion is increasingly outstanding and the
dominance of coal in power generation is difficult to change in the short time, and NOx is one of the
most hazardous pollutants among these products during the process of coal combustion. The
problem of controlling NOx emissions is imperative. Cornstalk is a kind of typical biomass in rural area
of China. To verify the availability of reducing NOx by using cornstalk as reburning fuel, numerical
analyses of conventional combustion and reburning combustion cases have been performed using
CFD software in a combustor in this paper. The result shows that the temperature and NOx
distribution in the furnace are quite different between the conventional combustion and reburning
combustion. Cornstalk can effectively reduce NOx, and the removal rate of NOx reaches up to 62.74%
when the excess air coefficient of reburn zone is 0.9.

Keywords: NOx, cornstalk reburning, pulverized coal, simulation.

INTRODUCTION
Combustion of coal creates significant atmospheric pollutants. Among them, nitrogen
oxides(NOx) are of great interest as a result of their toxicity(Celso et al., 2004). How to effectively
control the generation of NOx has become general concern for people. Nowadays, measures to
control NOx emissions are roughly divided into two categories. One is the flue gas purification
technology, and the other is low NOx combustion technology. Due to the huge investment and
expensive operating cost of the first one, low NOx combustion technologies, such as decoupling
combustion(Cai et al., 2013 ), oxygen enrichment and SNCR(Daood et al., 2013) and so on, are
particularly important. Among them, fuel staging combustion is one of the most promising and
effective NOx reduction strategies with reduced environmental impact for pulverized fuel
combustors (Dimitriou et al., 2003). Reburning using solid fuel for NOx control has been
discussed by many scholars (Dimitriou et al., 2003; Adams et al., 1998; MARTIN et al., 1998;
Nimmo et al., 2008; Julien et al., 2008; Smoot et al., 1998). Previous test work has shown that
the parameters, particle size (Shen et al., 2013; Casaca et al., 2009), reburn zone stoichiometric
ratio, residence time in the reburn zone and initial NOx concentration are very sensitive to NOx
reduction (Stanley et al., 2000; Ballester et al., 2008).
In this work, cornstalk is introduced as reburning fuel to simulate the denitration effect in a
combustor. The main body of the combustor is 4 meters long with a cross sectional area of 350
2

mm as shown in Fig.1. The primary air inlet and secondary inlet are set on the burner upon the
furnace. The pulverized coal enters at the top of the burner at the primary air flow rate.
Secondary air inlet is set on the side of the burner. There are four cross baffles in the burner to
make the secondary air swirled. The swirled air and the primary air encounter at the bottom of

253

the burner and then mix. They flow into the furnace and burn in the enough space. The reburning
fuel inlets and burnout air inlets are all set on the wall of the furnace. For the reburning case, the
reburning fuel, i.e. cornstalk enters at the reburning fuel inlet at a specific air flow rate. Certainly it
is necessary to add the over fire air from the burnout inlet to make the pulverized coal and
cornstalk combust completely.

Fig.1. Scheme of the combustor

The proximate and ultimate analyses of the coal and cornstalk used in simulations are
summarized in Table 1. Flow parameters for conventional case and reburning case shown in
Table 2 have been chosen with the same overall excess air ratio 1.16. For the reburning case,
the excess air coefficient in the reburn zone is 0.9, which keeps the reburn zone in a reducing
atmosphere.

254

Table 1. Coal and cornstalk analyses.

Ultimate analysis(wt%)

Proximate analysis(wt%)

FC

Coal (ar)

68.04

4.37

9.57

1.43

0.59

4.10

11.90

33.20

50.80

Cornstalk (ar)

36.84

4.81

38.84

0.72

0.09

10.00

8.70

67.48

13.82

Table 2. Characteristic parameters of furnace combustion for calculation.

Parameter

Value

Volume flow rate of primary air for conventional case

16.32(m /h)

Volume flow rate of secondary air for conventional case

63.00 (m /h)

Volume flow rate of primary air for reburning case

16.32(m /h)

Volume flow rate of secondary air for reburning case

48.00(m /h)

Pulverized coal mass flow rate for conventional case

9.90 (kg/h)

Pulverized coal mass flow rate for reburning case

8.87(kg/h)

Cornstalk mass flow rate for reburning case

2.27(kg/h)

3
3

MATHEMATICAL MODEL
Turbulence and combustion modeling
The numerical simulations have been performed with the application of CFD software Fluent.
The SIMPLE algorithm is used for velocity-pressure coupling. As for the boundary conditions,
inlets of the primary air and secondary air inlets are both velocity inlets. Pressure outlet for the
outlet is applied. The air and fuel are injected at 300K. For turbulence model, realizable k
turbulence model with standard wall functions is adopted, and turbulence kinetic energy k and
transmission equations are expressed by Eq.(1) and Eq.(2).
()

( )

[( +

] + + +

()

( )

[( +

] + 1 2

+ 1 3 +

1 = [0.43,

+5

= 2

in which Gk and Gb are the generation of turbulence kinetic energy due to the mean velocity
gradients and buoyancy respectively, YM is the contribution of the fluctuating dilatation in
compressible turbulence to the overall dissipation rate,SK and S are user-defined source terms,
k and are the turbulence Prandtl numbers for k and . For radiation heat transfer, the P1
method is applied to simulate the thermal radiation in the furnace with wsggm-domain-based
model

to

predict

emissivity.

Non-premixed

255

combustion

model

and

two-mixture-fraction/transported probability density function (PDF) model are applied in

simulations (Dong et al., 2010). The discrete phase (coal/cornstalk particles) is modeled using
the Eulerian-Lagrangian approach. Stochastic particle trajectory (SPT) model is used for the
particle-turbulence interaction to simulate the two-phase flow of pulverized coal. Coal
devolatilization is simulated by a two-competing-rates method. The kinetic devolatilization rate
expressions are as follows:

1 = 1 (

/ )

(4)

2 = 2 (

/ )

(5)

where TP is the particle temperature, Z1 and Z2 are competing rates that may control the
devolatilization over different temperature ranges (Dong et al., 2010). The two kinetic rates are
weighted to yield an expression for the devolatilization as

()

= 0 (1 1 + 2 2 )[ 0 (1 + 2 ) ]

(1 , ) ,

(6)

where mv (t) is volatile yielding up to time t, mp,0 the initial particle mass at injection, 1 and 2
the yield factors, ma the ash content in the particle, and fw,0 the mass fraction of
evaporating/boiling material. Char particle combustion is expressed by a kinetic/diffusion-limited
model as elaborated by Baum and Street (Baum et al., 1971) and Field (Field et al., 1969). For
the kinetic/diffusion-limited combustion model, the mass diffusion-limited rate constant K1 ,
kinetic-limited rate pre-exponential factor K 2 and the kinetic-limited rate activation energy E are
expressed as follows:

0 = 1

[( + )/2] .

(
= 2 (/
(

256

NOx formation and destruction modelling

For the formation of NOx, post-processing method is adopted, and the fuel NOx, thermal NOx and
the reburning effect of NOx are considered. For the coal, it is assumed that the fuel nitrogen of
the coal is distributed between the volatiles and the char. Fraction of N in the volatiles and
fraction of N in the char are specified separately. The fuel nitrogen in the volatiles and char
evolves as HCN or NH3 intermediates. The [O] and [OH] model of the thermal NOx are both
equilibrium model. For the fuel NOx, N intermediates are HCN, NH3 and NO.
As for the reburning model, partial-equilibrium model is adopted (Su et al., 2007). In the reburn
zone, the HCN oxidation reaction is suppressed and the amount of NO formed in the primary
combustion zone is decreased by the reduction reaction from HCN to N2. NO concentration also
decreases due to the reactions with CH radicals which are available in significant amounts in the
reburn zone. The reactions shown in Eq.(9-11) are the most important reactions of NO reduction
by CH radicals:
+ 2 +
(9)
+ +
(

+ +
(11)
The momentum equation and energy equation are discreted by second order upwind, while the
turbulent kinetic energy and turbulent dissipation rate are discreted by first order upwind.

257

(a) conventional case

(b) reburning case

Fig.3. Temperature distribution of the cross section of X=0

RESULTS AND DISCUSSION

The temperature distribution of the cross section of X=0 and points on the central axis along
with the height of the furnace are shown in Fig.3 and Fig.4 respectively. There are obvious
differences of the two cases. As the influence of the swirled air mentioned above, temperature
distribution on the cross section is not symmetrical. For the conventional case, with the
reduction of the height in the furnace, temperature is decreasing. While for the reburning case,
the temperature decreases with the decrease of the height of the furnace at first. And when it
reaches to the burnout zone, temperature increases, which is probably due to the fact that in
the burnout zone, fuels unburned in the reburn zone combust with the new air added from the
burnout inlets and release a lot of heat.

258

2100
conventional case
reburning case

2000

Temperature(K)

1900
1800
1700
1600
1500
1400
1300
1200
4.0

3.5

3.0

2.5 2.0 1.5 1.0

Furnace elevation(m)

0.5

0.0

Fig.4. Temperature distribution along with the height of the furnace

NOx distribution of the cross section of X=0 and points on the central axis along with the height
of the furnace are shown in Fig.5 and Fig.6 respectively. For the conventional case, NOx
content decreases very slowly and basically keeps unchanged below the primary zone. While
the reburning case shows a very different trend. In the primary zone, it decreases with the
decrease of the height of the furnace and then decreases sharply when the flue gas arrives at
the reburn zone. And then NOx begins to increase gradually after the flue gas enters the
burnout zone. In the reburn zone, as the injection of the cornstalk and very small amount of the
air, the atmosphere in this stage is reducing, which makes the reduction reaction of the NO x
dominant. Therefore, there is a significant decrease of NOx content. But when entering into the
burnout zone, unburned intermediate products, HCN and NH3, etc, react with the air and
generate new NOx further. From the analysis above, it is found that the NOx content at the
outlet depend not only on the reduction of the reburn zone, but also on the new generation of
the NOx in the burnout zone.
Table 3. NOx emissions at outlet and NOx removal rate of the reburning case
Case

NOx emission at the outlet (ppm)

conventional

967.71

reburning

360.56

(%)
62.74

The parameters of NOx at the outlets of both cases are shown in Table 3. The effect of NO x
[NO]

reduction can be expressed by NOx removal rate, = (1 [NO]c ) 100%, in which,[NO]c is

r

NOx content at the outlet of the conventional case, [NO]r is NOx content at the outlet of the
reburing one. Compared to conventional combustion, 62.74% of NOx removal rate using
cornstalk reburning can be achieved.

259

(a) conventional case

(b) reburning case

Fig.5. NOx distribution of the cross section of X=0

260

conventional case
reburning case

1200

NOx content(ppm)

1000
800
600
400
200
0
4.0

3.5

3.0

2.5 2.0 1.5 1.0

Furnace elevation(m)

0.5

0.0

Fig.6. NOx distribution along the height of the furnace

CONCLUSION
Cornstalk as a reburning fuel combusting in a combustor can effectively reduce NOx emission.
Temperature and NOx distributions in the furnace of the reburning combustion are significantly
different from the conventional combustion. The rate of NOx removal reaches up to 62.74%
when the excess air coefficient of the reburn zone is set to 0.9, which indicates that cornstalk is
a promising reburning fuel and further research will be performed.
ACKNOWLEDGEMENT
This work was financially supported by the Youth Foundation of Hebei Education Department (Grant
No. 2010120), the National Natural Science Foundation of China (Grant No.51276055), Key Project
of College Science and Technology of Hebei Province (Grant No. ZD2010122) and Key project of
Hebei Province Basic Research Program for Application (Grant No. 13964503D).

NOMENCLATURE

density, kg/m

NOx removal rate, %

REFERENCES
Adams B.R., Harding N.S, 1998, Reburning using biomass for NOx control. Fuel Processing
Technology 54:249-263.
Ballester J., Ichaso R, 2008, Experimental evaluation and detailed characterisation of biomass
reburning. Biomass and Bioenergy 32:959-970.
Baum M.M., Street PJ, 1971, Predicting the combustion behavior of coal particles. Combust Sci
Technol 3:231343.
Cai l., Shang X., 2013, Low-NOx coal combustion via combining decoupling combustion and gas
reburning. Fuel 112: 695-703.

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Casaca C., Costa M., 2009, NOx control through reburning using biomass in a laboratory furnace:
Effect of particle size. Proceedings of the Combustion Institute 32: 26412648.
Celso A. Bertran, Carla S.T, 2004, Reburning and burnout simulations of natural gas for heavy oil
combustion. Fuel 83:109-121.
Daood S.S., Javed M.T., 2013, NOx control in coal combustion by combining biomass co-firing,
oxygen enrichment and SNCR. Fuel 105: 283-292.
Dimitriou D.J., N. Kandamby, 2003, A mathematical modelling technique for gaseous and solid fuel
reburning in pulverised coal combustors. Fuel 82:21072114.
Dong C., Yang Y., 2010, Numerical modeling of the gasification based biomass co-firing in a 600
MW pulverized coal boiler. Applied Energy 87: 28342838.
Field M.A., 1969, Rate of combustion of size-graded fraction of char from a low rank coal between
1200K2000K. Combust Flame 13:23752.
Julien Cance`s , Jean-Michel Commandre, 2008, NO reduction capacity of four major solid fuels in
reburning conditions-Experiments and modeling. Fuel 87:274-289.
MARTIN STBERG, PETER GLARBORG, 1998, A model of the coal reburning process.
Twenty-Seventh Symposium (International) on Combustion/The Combustion Institute, 1998.
Pittsburgh, U.S.A.
Nimmo W., Singh S, 2008, The evaluation of waste tyre pulverised fuel for NOx reduction by
reburning. Fuel 87:2893-2900.
Shen Jun, Liu Jiaxun, 2013, NOx emission characteristics of superfine pulverized anthracite coal in
air-staged combustion. Energy Conversion and Management 74:454-461.
Smoot L. D., Hill S. C, 1998, NOx control through reburning. Prog. Energy Combust. Sci
24:385-408.
Stanley N. Harding, Bradley R. Adams, 2000, Biomass as a reburning fuel: a specialized cofiring
application. Biomass and Bioenergy 19:429-445.
Su Sheng, Xiang Jun, 2007, Numerical simulation of nitric oxide destruction by gaseous fuel
reburning in a single-burner furnace. Proceedings of the Combustion Institute 31:2795-2803.

262

A High Efficiency Low Emission Thermodynamics Cycle for Prime Movers

based on Timed Constant Volume Combustion
1

Zhang Kongming , Liang Shixi , Jin Zebing , Wang Ke , Zhang Fan ,

2

Liao Cheng* and Liu Jingping

(1 BeiJing Green Energy Cooperation, Beijing, 100096

2 Research Center for Advanced Powertrain Technologies, Hunan University,Changsha,
410082)
*Corresponding authors contact email: liaocheng@hnu.edu.cn

ABSTRACT
Base on a patent of the primary authors, in this paper a new type of thermodynamics cycle is
proposed, namely the Green Energy Cycle, which has the characteristics of multiply compression
with intercooling, counter-flow heat recuperator, timed constant volume combustion and full
expansion. The concept of multiply compression with intercooling reduced the compression work
consumption. Within the counter-flow recuperator most of the thermal energy of the expanded
exhaust gas is recovered and passed through to the fresh charge, while the latter will be directed to
the expander for mechanical work output. The idea of the timed constant volume combustion
process ensures a well mixed, longer time and lower temperature combustion, which has the
potential to control the raw emissions of HC,CO,PM and NOx at the same time. This
thermodynamics cycle demonstrates a great potential to achieve superior thermal efficiency than
the other typical cycles at very low mechanical compression ratio and therefore with low mechanical
load, smooth combustion, low raw emissions and low combustion noise.
Keywords: Appropriate compression, intercooling, counter-flow recuperator, timed constant
volume combustion, thermodynamics cycle.

INTRODUCTION
Recent years, the frequent occurring smog and dusty skies in the developing country including
China, have exercise a great pressure on energy saving and harmful pollution reduction in the
automotive engines. Recent research work[1-2] indicated that PM2.5 is the main contributor of the
smog and dusty skies, while the exhaust emissions from an automotive engine is one of the
important contributor of PM2.5. On the other hand, nowadays fossil fuel is still the major fuel supply
of automobiles, the concerns on the dried-up and consumed-up of the fossil fuel has forced
researcher to look for technologies and approaches to save energy on one end, and new
energy/alternative energy on the another end[3].
New technologies and approaches[4-6] emerge everyday, focused on energy saving and
pollution reduction in automobiles. However, limited by many constrains in the real application, e.g.
the peak cylinder temperature is limited by the formation rate of NOx as well as the thermal loading
of the combustion chamber; while the peak cylinder pressure is limited by the mechanical loading
and the strength of the material; lean mixture is prohibited by the cost of the aftertreatment system,
etc.; today the energy conversion efficiency of automotive diesel engines are still in the range of
30%, while the thermal efficiency of the automotive gasoline engines is even in the range of 20%. It
is necessary to look back into the fundamental aspects of the thermal to mechanical work

1
263

conversion and to investigate on new thermodynamics cycles which have the potential of not only
to achieve high efficiency and low emissions, but is also practical to realize in hardware.
Presented in this paper is a new type of thermodynamics cycle which focuses on
overcoming the issues of the existing cycles. The proposed cycle has the characteristics of
reduced compression work, exhaust gas energy recovery, perfect mixing and extended time
combustion, as well as full expansion. It has the potential of high thermal efficiency, low
emissions, multi-fuel adaptability and lower combustion noise.

ISSUES LIMITING THE THERMAL EFFICIENCY OF THE

INTERNAL COMBUSTION ENGINES
A typical thermodynamics cycle in an internal combustion engine consists the processes of
compression, combustion, expansion and heat rejection.
The cycle in a gasoline engine can be idealized as the Otto Cycle which has a constant volume
combustion process. The thermal efficiency of the idealized Otto Cycle is

t ,V 1

(1)

c k 1

In contrast to the constant volume combustion process, the thermal efficiency in a constant
pressure combustion cycle can be expressed as:

t , p 1

c k 1

0k 1
k ( 0 1)

(2)

The idealized thermodynamics cycle in a diesel engine is a combination of the constant volume
and constant pressure combustion, which is usually called the limited pressure cycle or the
Seilinger Cycle. The thermal efficiency of this cycle can be expressed as

t , s 1

p 0k 1
c k 1 p 1 k p ( 0 1)
1

(3)

In the above equations:

t ,V : thermal efficiency of the constant volume combustion cycle

Otto Cycle

t, P : thermal efficiency of the constant pressure combustion cycle

t, S : thermal efficiency of the limited pressure cycle or Seilinger Cycle

c : compression ratio
k : ratio of specific heat under constant pressure over the constant volume
0 V3 / V2 : expansion ratio at constant pressure
p3 / p2 : pressure rising ratio under constant volume.
As indicated by equation (1) to (3), the indicated thermal efficiency of the typical
thermodynamics cycles depends all on the compression ratio c . Fig.1 illustrates the thermal
efficiency of those typical cycles as a function compression c . It could be concluded from Fig.1
that:

2
264

Higher thermal efficiency requires larger compression ratio. Fig.1 indicates higher thermal
efficiency requires large compression ratio, which is true for all the typical cycles analyzed.
Larger compression ratio results in higher peak cylinder pressure (PCP) and
temperature (PCT). Fig.1 also indicates that accompanied by the increased thermal efficiency, the
increased compression ratio will also cause the peak cylinder pressure (PCP) and peak cylinder
temperature (PCT) to rise. This will not only increase the engines mechanical and thermal loading,
but also calls for expensive material to use, and produces high NOx emissions and combustion
noise.
Large quantity of thermal energy in the exhaust gas is rejected into the ambient without
utilization. Due to the limited expansion ratio (controlled by the compression ratio), there is still
significant amount of thermal energy (approx. 30-40% of fuel energy[7]) in the form of enthalpy in the
after expanded exhaust gases. The most common approach of utilizing the exhaust gas energy is
through turbocharing the engines, which improves the engine power density but is not really

Thermal efficiency -

effective on improving the thermal efficiency[8].

1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0

Constant V
Constant P
Cannot cycle

Peak Cylinder pressure bar, abs.)

10
12
14
16
Compression Ratio-

18

20

22

350
300
250
200

Constant V

150

Carnot cycle

Constant P

100
50
0
4

10
12
14
16
Compression Ratio-

18

20

22

Peak Cylinder Tempreture(K)

6000
5000
4000
Constant V

3000

Constant P

2000

Carnot cycle

1000
0
4

10
12
14
16
Compression Ratio-

18

20

22

Fig.1 Thermal efficiency, PCP and PCT vs. compression ratio of typical idealized cycles, =2.0

3
265

Rough and incomplete combustion. Due to the nature of the reciprocating working cycle in
an internal combustion engine, the air-fuel has limited time for mixing and combustion, especially in
direct injection engines. The very limited mixing and combustion time duration not only calls for high
pressure and expensive fuel supply systems, but also ends up with inhomogeneous mixture and
incomplete combustion, which produces harmful PM (in diesel engines), HC and CO (in gasoline
engines) . Although homogeneous charge compression ignition (HCCI) combustion mode
demonstrated a potential to solve the NOx and PM problem at the same time, the lack of power
density and difficult in the combustion control of this combustion model made it difficult for practical
application [9-10].
Therefore new thermodynamics cycles which have the potential to overcome the above
disadvantages and to solve the issues are continuously sought. A cycle with reduced compression
work consumption, improved expansion work, improved thermal efficiency, and reduced heat
rejection to the ambient, as well as improved air/fuel mixing and extended combustion time will be
particularly preferred.

FUNDAMENTAL FEATURES OF THE GREEN ENERGY

CYCLE
This paper proposes a new type of thermodynamics cycle, namely the Green Energy Cycle. It
consists of 4 major processes, as illustrated in Fig.2.
Multi-stage compression with intercooling. The purpose of adopting a multi-stage
compression and intercooling is to a) approach a near isothermal compression in order to reduce
the compression work consumption, and b) to achieve a lower end compression temperature to
ensure a higher heat recovery efficiency from the recuperator.
Heat energy recovery in the counter-flow recuperator. In this recuperator the expanded
burnt gas passes its residual heat energy to the compressed fresh charge before the latter enters
into the combustor. A counter-flow type recuperator is utilized in order for lower temperature
difference between the hotter and colder sides of the work media and therefore higher heat energy
recovery efficiency.
Timed constant volume combustion. The fresh charge leaving the recuperator is then
directed into a separated combustor. The combustor is a fixed volume device with controlled valves
at both the entry and the exit when gas exchange (from the recuperator), combustion inside and
exhausting (to the expander) will happen in a sequence with a planed order. The combustor
separates the compression and the expansion devices therefore different compression and
expansion ratios could be used to achieve higher cycle efficiency. More importantly, with the
separated combustor from the expansion device, much longer combustion time, e.g. as long as
210oCA, could be used, which enables to use low cost fueling system, promotes better air-fuel
mixing, and cleaner, more complete combustion for higher combustion efficiency and smoother
combustion, lower emissions.
High expansion ratio and full expansion. After combustion, the burnt gas is directed into the
expansion device where the thermal energy of the high pressure high temperature gas is converted
into mechanical work of the piston. Since the expansion device is separated with the compressor,
the expansion ratio is no longer limited to the compression ratio. Higher expansion ratio can be
utilized and the burnt gas can be fully expanded to as low as the ambient pressure for the maximum
extraction of the expansion work.

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266

Fig.2 Sketch of the system to realize the Green Energy Cycle

Fig.3 P-V diagram of the Idealized Green Energy Cycle

The process described above can be expressed in the P-V diagram depicted in Fig.3 Where
process a-b, c-d, e-f represent the multi-stage compression processes (in the example it is 3
stages), while process b-c and d-e are the intercooling process between the compressions.
Process f-g-h is the constant pressure heat transfer in the recuperator as well as gas exchange in
the combustor. Process h-i is the constant volume combustion in the combustor. I-j is the adiabatic
expansion process in the expander and j-k is the heat transfer process of the after expansion burnt
gas passing its thermal energy to the fresh charge. Process k-j is the heat rejection process of the
expanded burnt gas to ambient.
The advantages of the Green Energy Cycle over conventional thermodynamic cycles could be
illustrated in Fig.4 First all, the multi-stage, intercooled compression process will reduce the amount
of compression work as shown by the area I; The amount of fuel energy saved in the recuperator is
the area represented by ; while the increase expansion work output (by increased expansion ratio)
is represented by area . The reduced compression work, increased expansions work with the
reduced fuel energy input will significantly elevate the thermal efficiency of the this cycle.

5
267

Fig.4 Sketch showing where energy saving and work boost come from in the Green Energy Cycle

ANALYSIS OF THE THERMAL EFFICIENCY OF THE GREEN

ENERGY CYCLE
The thermal efficiency of the Green Energy Cycle can be analyzed and the major influencing
parameters derived as following.
Definition of the indicated thermal efficiency:

Expansion work output Compression work comsumption

GEC

(4)
Fuel heat energy input

While: Expansion work output= c v(i )Ti cv ( j )T j

(5)

Compression work consumption of the n stages of compression=

c p(a)Ta (

ka 1
ka

1) c p(c)Tc (

kc 1
kc

1) c p(e)Te (

ke 1
ke

1)

(6)

Energy input of fuel= c v (i )Ti cv ( h )Th

(7)

Combining (4) to (7):

GEC

(c v (i )Ti cv ( j )T j ) (c p(a)Ta (

Assuming:

k a 1
ka

1) c p(c)Tc (

k3 1
k3

1) c p(e)Te (

ke 1
ke

1) )

(8)

c v (i )Ti cv ( h )T( h )

Th Ti , p j pa

and neglecting all the losses, then

c v (i )Ti cv ( h)Th c v (i )Ti cv ( j )T j

(9)

and

pj
Th T j
( )
Ti Ti
pi

k 2 1
k2

p
( a)
pi

k 2 1
k2

p
( a )
Ti
Ph
Th

k 2 1
k2

6
268

Since

Th
T p
( h a)
Ti
Ti ph

k 2 1
k2

, and

Th
n (1k2 )
Ti

(10)

Substituting (9) and (10) into (8):

cp(a)

k1 1
k1

1)
cv (i )
T
1
a
cv ( h ) n (1 k2 ) Ti
1

cv (i )
n

(11)

where:

k1 : Ratio of specific heat (low temperature compression section)

k 2 : Ratio of specific heat (high temperature expansion section)

: Compression ratio of a single stage

n : Number of compression stages

Ta : Environmental temperature, K
Ti : Temperature after combustion, K
c p (a ) : Specific heat under constant pressure at point a, J/(kgK)
c p (h ) : Specific heat under constant pressure at point h, J/(kgK)
cv (i ) : Specific heat under constant volume at point I, J/(kgK)

What the thermal efficiency formula indicates

The thermal efficiency of the Green Energy Cycle depends on the gap between the combustion
temperature and the environmental temperature, which is very similar to the Carnot cycle. The
higher the combustion temperature is, the higher the thermal efficiency is; the lower the
temperature to reject heat, the higher the thermal efficiency is. Compared in Fig.5 are the thermal
efficiencies as a function of peak cycle temperature across several typical thermodynamics cycles.
As shown, The Green Energy Cycle has very similar thermal efficiency curve as the Carnot cycle,
especially in the high temperature range. The Green Energy Cycle has higher efficiency than the
Otto cycle across the entire temperature range.

Thermal efficiency(-)

100%
80%
60%
40%

Green energy cycle

Carnot cycle
Constant V

20%
0%
0

1000

2000
3000
4000
5000
Peak Cylinder tempretureK

6000

Fig.5 Thermal efficiency vs. combustion temperature, comparison between typical cycles

Unlike the other cycles, the thermal efficiency of the Green Energy Cycle is less influenced by
the compression ratio and certainly the thermal efficiency does not necessarily peak at higher
compression ratio, as shown in Fig.6 It is demonstrated that the peak thermal efficiency occur at a

7
269

single stage compression ratio of around 2. Higher or lower compression ratio would result in a
decrease of thermal efficiency of the Green Energy Cycle.
85%

Thermal efficiency(-)

81%
77%
73%
69%
65%
1

1.4

1.8 2.2 2.6 3 3.4 3.8 4.2

Single-stage compression Ratio(-)

4.6

Fig.6 Thermal Efficiency vs. the single stage compression ratio, 3 stages, Green Energy Cycle
The Green Energy Cycle does not require many stages of compression. Depicted in Fig.7 is
the thermal efficiency vs. the number of compression stages relationship of the Green Energy Cycle.
It is shown that the number of compression stages are not as the more the better, rather the optimal
number of stages is between 1-3. Taking into account the work output capacity of the system, a
three stage compression system will be utilized.
82%

Thermal efficiency(-)

81%
80%
79%
78%
77%
76%
75%
1

3
4
No of compression stage(-)

Fig.7 Thermal Efficiency vs. the number of compression stages, single stage CR=2.5, Green Energy Cycle

Comparison of thermal efficiency across typical cycles

The comparisons of thermal efficiency are conducted under the same conditions, i.e. the same
air intake condition, compression ratio and same relative air/fuel ratio (same fuel energy).
Compared in Fig.8 are the predicted thermal efficiency vs. compression ratio of the 4 typical
thermodynamics cycles. As shown: (1) under the same comparison conditions the Green Energy
Cycle has the highest thermal efficiency, which is because its exhaust gas energy recovery in the
recuperator; (2) The thermal efficiencies of the other three cycles, i.e. the constant volume and
constant pressure combustion cycle, as well as the Carnot cycle, all increase with the increased
compression ratio, while the Green Energy Cycle demonstrates the opposite, the reason is that in
the Green Energy Cycle the larger the compression ratio is, the more compression work is
consumed, the higher the after compression temperature is, therefore less heat is recovered from
the exhaust gas in the recuperator, both decrease the thermal efficiency; (3) In Fig.8 the thermal
efficiency of the Carnot cycle is not the highest, the reason being that, for the same compression
ratio the Carnot cycle has the lowest heating source temperature (which equals to the compression

8
270

temperature). By coincidence the Carnot cycle and the constant volume combustion cycle have the
same efficiency.
1.0
0.9
Thermal efficiency -

0.8
0.7
0.6
0.5
0.4
0.3
0.2

Constant V

Constant P

Green Energy cycle

Carnot cycle

0.1
0.0
6

10

12

14

16

18

Compression Ratio-

Peak Cylinder Pressure bar, abs.)

Fig.8 Thermal efficiency vs. compression ratio, comparison across typical cycles
300
250

Constant P

Green Energy cycle

Carnot cycle

200
150
100
50
0
6

Peak Cylinder Tempreture (K)

Constant V

10
12
14
Compression Ratio-

16

18

3000
2500
2000
1500
1000

Constant V

Constant P

Green Energy cycle

Carnot cycle

500
0
6

10
12
14
Compression Ratio-

16

18

(b)

Fig.9 Comparison of Peak cylinder pressure and temperature across the cycles

Compared in Fig.9 are the peak cylinder pressure and temperature vs. compression ratio of the
4 typical thermodynamics cycles analyzed. Fig.9(a) indicates that the peak cylinder pressures of the
4 cycles all increase with compression ratio. Fig.9(b) shows that, except for the Green Energy Cycle,
the peak cylinder temperature of the other 3 cycles all increase with compression ratio also, the
reason being that, for the same amount of fuel injection quantity, the peak combustion temperature
of the other 3 cycles depends on the end compression temperature, while the peak combustion
temperature of the Green Energy Cycle depends on the heat-up temperature of the fresh charge in
the recuperator while a higher compression ratio results in lower heat-up temperature. What Fig.8
and 9 tell are: unlike the other cycles which has higher efficiency at high compression ratio
therefore results in higher mechanical and thermal loading, the Green Energy Cycle peaks at a
lower compression ratio. This is a very unique feature which very high thermal efficiency could be
achieved with low mechanical load and smooth combustion; (2) The Green Energy Cycle has

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271

higher combustion temperature than the constant volume combustion cycle at the compression
ratio of 8 or lower (and with much higher thermal efficiency). A slightly leaner combustion will bring
down the combustion temperature into the same range (and still have significantly higher thermal
efficiency).
Depicted in Fig.10 is the predicted influence on thermal efficiency of the energy recovery
efficiency in the recuperator. As shown, the thermal efficiency of the Green Energy Cycle is strongly
influenced by the burnt exhaust gas energy recovery efficiency in the recuperator. This emphasizes
the importance of a highly efficient recuperator.

Thermal efficiency(%)

80
76
72
68
64
60
70

76

82

88

94

100

Efficiency of heat exchanging%

Fig.10 Thermal efficiency vs. the energy recovery efficiency in the recuperator, Green Energy Cycle

CONCLUSIONS
The following conclusions could be drawn from the above analysis:
1. A new type of thermodynamics cycle is proposed which has the unique features of achieving
very high thermal efficiency at low working pressure and reasonably low temperature, which is
beneficial for practical application
2. Exhaust gas energy recovery in the counter-flow recuperator is the major contributor of the
higher thermal efficiency
3. The timed constant volume combustor not only enables to adopt different compression ratio
than the expansion ratio, which is in favorable for the cycle efficiency, but more importantly it also
achieve longer time combustion which allows low cost fueling system, promotes improved mixing
and allows to use different types of fuels, and results in cleaner and more efficient combustion,
reduces the NOXHCCOPM at the same time, and with smooth and mild combustion.
4. The multi-stage compression with intercooling not only reduces the compression work
consumption, but also increases the thermal energy recovery efficiency in the recuperator. A
2.0-3.0 single stage compression ratio, and 3 stages system is the optimal.
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[1]

Zheng M, Cass G R, Schauer J J, et al. Source apportionment of PM2.5 in the southeastern

United States using solvent-extractable organic compounds as tracers[J]. Environmental
Science & Technology, 2002, 36(11): 2361-2371.

[2]

Querol X, Alastuey A, Rodriguez S, et al. PM10 and PM2.5 source apportionment in the
Barcelona Metropolitan area, Catalonia, Spain[J]. Atmospheric Environment, 2001, 35(36):

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6407-6419.
[3]

Leung D Y C, Yang Y. Wind energy development and its environmental impact: A review[J].
Renewable and Sustainable Energy Reviews, 2012, 16(1): 1031-1039.

[4]

YANG Shi-chun, Li Jun, LI De-gang, et al. Analysis on Development for Gasoline Direct
Injection Technology[J]. VEHICLE ENGINE, 2007, (5):8-13.(in Chinese)

[5]

Lecointe B. Downsizing a gasoline engine using turbocharging with direct injection[J]. 2003.

[6]

Henning Kleeberg, Dean Tomazic, Oliver Lang, Knut Habermann. Future Potential and
Development Method for high output turbocharged direct injection gasoline engines[C]. SAE
Paper 2006-01-0046.

[7]

Heywoods J. Internal combustion engine fundamentals [M]. New York: Mc Graw Hill,
1988:42-57.

[8]

Sumser S, Finger H, Heinz E, et al. Exhaust-gas turbocharger: U.S. Patent 7,010,916[P].

2006-3-14.

[9]

Stanglmaier R H, Roberts C E. Homogeneous charge compression ignition (HCCI): benefits,

compromises, and future engine applications[J]. Training, 1999: 02-24.

[10] Kokjohn S L, Hanson R M, Splitter D A, et al. Experiments and modeling of dual-fuel HCCI and
PCCI combustion using in-cylinder fuel blending[J]. SAE International Journal of Engines,
2010, 2(2): 24-39.

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273

A LOW PRESSURE DIRECT GAS INJECTION SYSTEM FOR A FOUR STROKE

LPG DIESEL DUAL FUEL ENGINE
Arun Prasath.K., A. Ramesh
IC Engines Laboratory, Dept. of Mechanical Engineering, Indian Institute of Technology Madras,
Chennai - 600036, India.
arunprasath1988@gmail.com, aramesh@iitm.ac.in

ABSTRACT
Internal combustion engines running on gaseous fuels produce low torque because the inducted
gaseous fuel displaces air and reduces the volumetric efficiency. This can be overcome by injecting
the gaseous fuel directly into the cylinder after the intake of air is completed. However, such direct
injection systems are not readily available for small applications. This work is a step in developing
and demonstrating such a cost effective system. A low pressure gas injector was mounted on the
cylinder barrel of a fully instrumented dual fuel engine. Its location is such that the injector will be
exposed to the cylinder gases about 65.5 degrees before bottom dead centre, where the cylinder
pressure and temperature will be relatively low. An electronic controller was also developed to time
the injection process to occur after the intake valve closes and also to control the duration of injection
(quantity). Experiments were conducted with LPG as the primary fuel which was injected with this
new system and diesel as the pilot fuel at the rated speed of 1500 rpm with different amounts of LPG
at 100% load. Comparisons with the conventional manifold injection of LPG were done. The system
resulted in an improvement in volumetric efficiency and no drop in thermal efficiency. Though the HC
levels were elevated due to the stratification of the LPG air mixture on account of late injection the
NOx, smoke and CO values were lower than with manifold injection. The heat release rate showed a
small decrease with the new system with slightly longer combustion duration. The system also
allowed greater amounts of LPG to be used without knock as compared to manifold injection. On the
whole the developed system has potential for application in small dual fuel and spark ignited gas
engines.
Keywords: Gas Direct injection, Alternative fuels, LPG, Dual fuel engines.
INTRODUCTION
Gaseous fuels have several advantages like capability to operate with lean mixtures because of their
high flammability limits and ability to resist knocking in SI engines due to their high self ignition
temperature. Further, they can readily form mixtures with air. Gaseous fuels are generally used in the
spark ignition (SI) mode or in the dual fuel mode. In SI engines, they are generally mixed with air and
then inducted into the cylinder and ignited by a spark. These engines generally use a throttle and
their power output is dependent on the amount of air that they can take in each cycle. In the case of
dual fuel compression ignition (CI) engines the gaseous fuel is mixed with air and inducted into the
cylinder and then compressed. Normal compression ratios used in diesel engines are employed. This
mixture does not ignite as it has a high self ignition temperature. A small amount of diesel generally
called the pilot is then injected towards the end of the compression stroke so that it gets self ignited
thus causing the ignition of the gas air mixture. Here again the amount air that can be taken into the
engine in every cycle determines the power output and also the emission levels. In any internal
combustion engine where a gaseous fuel is mixed with air prior to induction into the cylinder, there is
a loss in the amount of air that is inducted as compared to engines that use liquid fuels. This is
because the inducted gas on account of its low density displaces a considerable volume of air that
can otherwise be inducted. Thus both dual fuel engines and SI engines suffer from the problem of
reduction in volumetric efficiency and hence loss of power when operated with gaseous fuels.
In gaseous fuel operated engines, the loss in volumetric efficiency by the displacement of air in the
inlet manifold can be overcome by directly injecting the fuel after the intake of air is completed. Thus
more fuel can be burnt in the same engine volume so that higher power can be produced or the
same power can be obtained at a lower equivalence ratio. One of the methods to introduce gaseous
fuels into the engine cylinder after the intake valve closes and induction of air is complete is by direct
injection (DI). In gas DI engines a high pressure solenoid based injector is mounted on the cylinder
head and is operated using an electronic circuit. However, gas direct injectors are not common and
are far too expensive to be used in small gas engines. This work is an attempt to demonstrate a cost
effective system for injecting gaseous fuel at the beginning of the compression stroke in an IC
engine. The system uses a conventional solenoid based manifold injector mounted on the cylinder

274

barrel of a dual fuel engine at an appropriate location. The details of this system are explained in a
later section.
BACKGROUND
The properties of some important gaseous fuels are compared with diesel in Table1. It is evident that
gaseous fuels have much higher self ignition temperatures than diesel which make them suitable for
SI engines. Their wide flammability limits favour un-throttled operation. In CI engines because of their
high self ignition temperature, gaseous need a secondary fuel like diesel for ignition. This is the dual
fuel mode. Gaseous fuels also have higher hydrogen to carbon ratios than liquid fuels which lead to
lower HC and carbon based emissions. Gases can readily mix with air and form a homogeneous
mixture which is an advantage in SI and dual fuel engines (E. Porpatham, et. al, 2012). Gaseous
fuels which contain methane are less prone to knocking when compared to gaseous fuels with
propane. This is because methane has a higher self ignition temperature(G. A. Karim, et.al, 1983).
Dual fuel engines where most of the energy is from the gaseous fuel emit very low levels of
particulates (G. A. Karim, 1990).
Table1. Properties of gaseous fuels (E. Porpatham, et.al, 2012)
Property
Self ignition
temperature(C)
Lower Heating
Value(LHV)(MJ/m3)
at 15C
Lower Heating
Value(LHV)(MJ/kg)
at 15C
Flammability
limit(vol.% in air)

CNG

LPG

Hydrogen

Bio-gas

Diesel

540

405-450

585

650

210

39.5

103.282

9.6

20.4

35360

50

45.7

120

17

42.5

5-15

2.15-9.6

4-75

7.5-14

1-6

Use of gaseous fuels in the dual fuel mode is superior to the normal spark ignition (SI) mode
because of the higher compression ratios used in these engines (G. A. Karim, 1983). The
performance of a dual fuel engine is influenced significantly by the amount of the gaseous fuel and
pilot fuel used. At low loads the small amounts of pilot used affect the ignition of the gaseous fuel
particularly when the substitution rates are high. On the other hand at high loads the inducted gas air
mixture along with the pilot quantity that is also relatively high, leads to rapid combustion and knock.
(G. A. Karim, et.al, 1983). LPG has been used in dual fuel engines along with diesel. It is found that
the use of high pilot quantities reduces HC levels at all outputs. Increase in the intake temperature
also reduces HC levels particularly at low pilot injection rates. High pilot quantities cause low CO
levels (M. P. Poonia, et. al.,1999). Combustion in dual fuel engines mainly consists of three stages
namely: premixed combustion of the pilot fuel, premixed combustion of gaseous fuel and diffusion
combustion of the remaining liquid fuel (A. Bilcan, O. Le Corre,et. al, 2001). Induction of LPG lowers
soot levels in dual fuel engines. At full load and various engine speeds a reduction in soot emissions
of 50% up to 70% was observed (A.M.L.M. Wagemakers, et. al, 2012). In LPG dual fuel engines,
the ignition delay in the dual fuel mode is greater than that of the diesel mode. With increase in power
output the pilot quantity has to be reduced to control rapid combustion and knock. (M. P. Poonia, et.
al.,1998). Blends of LPG and Diesel have also been tried with direct injection. Higher equivalent
specific fuel consumption was observed at increased LPG ratios and the power output was also
lower as compared with neat diesel operation. Smoke and NOx levels were however reduced with the
LPG-diesel blend (Qi Donghui, et. al, 2005).
Since gaseous fuels displace air in the inlet manifold of engines there is a reduction of partial
pressure of air. At stoichiometric mixtures the ratio of the partial pressure of air to the total inlet
pressure in case of hydrogen is nearly 0.6 where as in the case of methane it is nearly 0.85 (J.B.
Heywood, 1988). This will result in a reduction in the maximum torque that can be produced. The
reduction in volumetric efficiency will be high in the case of fuels like biogas that have a very low
energy density on the volume basis. The volumetric efficiency of propane fuelled engines is higher
when compared to methane fuelled engines. This is due to the lower displacement of air and
relatively cold vaporised propane.(G. A. Karim, et.al, 1983). In the case of CNG fuelled dual fuel
engines the effect of the gas displacing air on the power output was felt when the substitution went
beyond 20%( Nafis Ahmad I, et.al, 2005). In one attempt to overcome this problem a

275

hydraulically operated gas injector was mounted on the cylinder head. The injector had to be
carefully developed with proper materials and heat treatment to prevent leakage (L.M. Das, 2002).
There have been attempts to inject LPG directly through the cylinder head using solenoid based
injectors in small two stroke SI engines (Horizon Gitano-Briggs, et. al, 2007). However, injectors
for LPG and other gases for CI engines are not readily available. Thus it is attractive to come up
with low cost solutions to inject gas directly into the cylinder for small stationary gas engines.
PRESENT WORK
In this work a conventional medium speed stationary CI engine was modified to operate in the dual
fuel mode with LPG as the primary fuel and the injected diesel as the secondary pilot fuel. Two dual
fuel modes were tried and compared at a constant speed of 1500 rpm. The first dual fuel mode was
conventional wherein LPG was admitted along with the air through the intake manifold. The diesel
was injected at the rated injection timing of the engine (23 deg bTDC). This is called the LPG MI
(Manifold Induction) mode. Here the amounts of LPG and diesel were varied while the BMEP (Brake
mean effective pressure) was maintained at constant level (5.3 bar representing 100% load).
Subsequently the cylinder barrel was modified to accommodate a low pressure electronic gas
injector for the LPG direct injection (DI) mode of operation as shown in Fig.1. For this a hole was
made on the cylinder barrel at a suitable distance along the axis of the cylinder. The location of the
hole was such that it will be exposed by the top of the piston at a crank position where the pressure
in the cylinder would have dropped significantly during the expansion stroke. Thus the injector was
exposed to the cylinder for a small crank angle window equally spaced about BDC (Bottom dead
centre).The cylinder pressure curve during this window which will be open twice; once during the end
of the expansion stroke and once near the end of the suction stroke is shown along with the valve
timing diagram in Fig.1. The window covers a duration of 131about BDC as shown in Fig.1. The
intake valve closes at 35.5 deg aTDC. Thus injection can occur in the window B after the intake
valve closes as shown in Fig.1. The maximum pressure (which occurs in the window C) to which the
injector will be exposed during the expansion stroke is 3.93 bar. During the LPG injection period, the
maximum pressure in cylinder will be 1.5 bar (in window B). An electronic circuit was developed to
control the timing of injection and its duration. This circuit takes a pulse from the crank shaft position
sensor as input. The injection pressure of LPG was also a variable in the experiments. The gas
injector fixed in the engine cylinder barrel is schematically shown in the Fig.2.

Fig.1. Pressure curve and valve timing diagram with the operating window
EXPERIMENTAL SETUP AND EXPERIMENTS
The specifications of the single cylinder 4-stroke air cooled CI engine used for this work are given in
Table 2. The intake manifold was modified to induct LPG along with the inlet air for operating in LPG
MI mode . The cylinder barrel was modified to accommodate the gas injector as explained in the
previous section. An electronic circuit using mono-stable multi-vibrators and drivers was developed to
control the start and duration of injection of LPG. The LPG cylinder, heated in a constant temperature
hot water bath was used. The pressure of LPG was regulated after its outlet from the cylinder. A fuel
surge tank was provided just before the injector to maintain the pressure and eliminate flow
fluctuations in the LPG fuel line for aiding flow measurement. The diesel injector was a conventional
one. The schematic of the setup is shown in the Fig.2. The injection timing of diesel injection was
kept constant at 23bTDC. The start timing of injection pulse in the LPG DI mode was kept constant

276

as 30aBDC i.e. during the compression stroke. Duration of injection was kept as 1.5ms. The speed
of the engine was kept constant at 1500 rpm.
The engine was first run in pure diesel. As diesel quantity was reduced and LPG was admitted while
the torque was maintained constant. The quantity of LPG was increased by increasing the injection
pressure. The maximum injection pressure was 2.7 bar (absolute) in the case of 100% load. Increase
in the LPG flow rate was done till knock or misfire occurred. The experiments were done at 100%
load of the engine. LPG energy ratio is defined as:
LPG energy ratio=(gxCVg)x100/((gxCVg) +(dxCVd))
where,
g
CVg
d
CVd

Mass flow rate of LPG, kg/s

Heating Value of LPG, J/kg
Mass flow rate of diesel, kg/s
Heating Value of diesel, J/kg

Emissions were measured online during the experiment. Smoke measurement was by an AVL filter
paper based Smoke meter. Exhaust emissions(HC, CO, NOx) measurement was by an AVL Digas
Analyser 444.
Table2.Engine Specifications.
KIRLOSKAR TAF1 ENGINE
Bore x Stroke

87.5 x 110mm

Connecting Rod length

232mm

Cubic capacity

662 cc

Comp. Ratio

17.5: 1

Rated Power Output

4.4 kW/ 6hP

Rated Speed

1500 rpm

277

Fig.2. Schematic Diagram of the setup.

RESULTS AND DISCUSSION
The effect of induction of LPG is indicated in Figs. 3-6 at 100% load. In both LPG MI and LPG DI
cases the introduction of LPG (increase in the LPG energy ratio) leads to a drop in the brake thermal
efficiency (BTE) due to the influence of LPG on combustion as will be explained later. We also see
that with LPG DI the BTE is similar or even slightly better than the conventional LPG MI mode at
100% load. It may also be noted that the maximum amount of LPG that can be inducted (energy
ratio) is limited by knock at this high load condition. We find that the maximum energy ratio is higher
with LPG DI as compared to LPG MI which is an advantage. This could be because of the
stratification of the LPG air mixture with LPG MI as the fuel is injected late and has less time to mix
homogeneously with air as compared to LPG MI. The volumetric efficiency shown in Fig.4 based on
the amount of air inducted per engine cycle is also always higher in the case of LPG DI. This is
because the gas is injected in the early part of the compression stroke when the intake valve is
closed and thus the air that has been inducted is not displaced by the injected LPG. The increase in
the volumetric efficiency is about 1.7% on an average and will be much higher with fuels like biogas
and hydrogen which have low densities.
In Fig.5 we see that the HC emissions are always higher in the case of the dual fuel mode (i.e. as
compared to the case where the energy ratio is zero). This is because the inducted LPG air mixture
is the main source of HC emissions. The lean pockets formed and the LPG near the walls and
crevices will contribute towards increased HC levels. LPG DI leads to higher levels of HC as
compared to LPG MI because of the greater stratification of the charge in the former case. The late
injection of LPG with LPG DI leads to this and the too lean and rich pockets formed could be the
main reason for the increased HC levels. This problem needs attention and perhaps better mixture

278

formation strategies like enhanced swirl or multi port injection around the cylinder barrel will help
reduce the HC levels. Since smoke emissions are dependent on the amount of diesel injected and its
mixing with air we see that the levels fall as the energy ratio increases. The smoke with LPG DI is
lower than LPG MI which is again an advantage. The higher volumetric efficiency (more air available
for combustion) and higher BTE (lesser amount of diesel and LPG being used at any energy ratio)
are important reasons for this trend. At an energy ratio of about 46% the smoke level drops from 1.28
FSN to 0.99 FSN with LPG DI. CO level is influenced by the local equivalence ratio which will be
affected by mixture homogeneity and the volumetric efficiency. LPG MI results in lower CO levels
even though the homogeneity of the LPG air mixture is likely to be lower compared to LPG MI.
However, in all cases the levels are very low. NOx levels with LPG DI are lower than LPG MI because
of the lower heat release rates as will be shown later. Further, the stratification of the LPG air mixture
due to late injection, the overall leaner mixtures due to higher volumetric efficiencies and higher BTE
could also influence the reduction of NOx emissions favourably. At the energy ratio of about 46% the
NOx drops from 1428 ppm to 1226 ppm when we move from LPG MI to LPG DI.

Fig.3, 4. BTE Vs LPG Energy Ratio & Volumetric Efficiency Vs LPG Energy Ratio.

Fig.5, 6. HC Vs LPG Energy Ratio & Smoke Vs LPG Energy Ratio.

279

Fig.7, 8. CO Vs LPG Energy Ratio & NOx Vs LPG Energy Ratio.

The heat release rates are shown at two energy ratios in Figs. 9 and 10. In both cases the peak heat
release rate is lower and is also shifted towards later crank angles in the case of LPG DI as
compared to LPG MI. This is because of the higher ignition delay of the injected pilot diesel in the
presence of LPG which has also been reported in literature (M. P. Poonia, et. al.,1998). The higher
ignition delay in the case of LPG DI as seen in Fig. 9 is due to the lower temperatures in the cylinder
due to the higher amounts of air and the lesser amounts of fuel used. It may be noted that the
exhaust gas temperatures in the case of LPG DI were lower by about 25 to 30 C. LPG DI leads to
slightly enhanced combustion durations (Fig.12) due to lower combustion rates probably influenced
by the stratification of the charge.

Fig.9, 10. Heat Release Rate Vs Crank Angle.

Fig. 11, 12. Ignition delay and Combustion duration.

280

CONCLUSIONS
In this work a low cost LPG direct injection (LPG DI) system was developed and demonstrated for
application on a small LPG - diesel dual fuel engine. Experiments were conducted at different energy
ratios of LPG at full load. Based on these results the following are the main conclusions that were
derived:

The system could inject the required amount of LPG with the start of LPG injection set after
the closure of the intake valve. The required injection pressures were as low as 2.9 bar
(absolute).
The brake thermal efficiency was similar or even slightly better than the conventional
method of manifold injection of LPG (LPG MI).
More amount of LPG could be tolerated without knock with LPG DI as compared to LPG DI.
The maximum energy share with LPG DI was 51% as against 46% with LPG MI.
The HC levels were always higher than the conventional diesel mode in both the dual fuel
modes. However, the HC levels were highest with LPG DI due to charge stratification.
The volumetric efficiency with LPG DI was higher by about 1.7% than LPG MI as the
injection occurred after the intake valve was closed.
Smoke and NOx levels were lower by 0.29 FSN and 200ppm with LPG DI as compared to
LPG MI at an energy ratio of 46%.
Significant influences on combustion were not seen with LPG DI.

On the whole the method proposed in this work has potential for application in small gas
based dual fuel and SI engines. Further work to enhance mixture homogeneity is needed to
counter the problem of higher HC emissions.
ACKNOWLEDGEMENT
The authors thank Nithin Joseph Tito, Vishnu Ashok, Arun Das and Varuna Narasimhan for their
great support during experimentation.
NOMENCLATURE
aBDC after Bottom Dead Centre
bTDC before Top Dead Centre
BDC
Bottom Dead Centre
BMEP Brake Mean Effective Pressure, bar
BTE
Brake Thermal Efficiency
CA
Crank angle, degree
CI
Compression Ignition
CNG
Compressed Natural Gas
CO
Carbon monoxide, percentage by volume
CV
Heating Value of the fuel, J/kg
DI
Direct Injection
EVC
Exhaust Valve Closure
EVO
Exhaust Valve Open
FSN
Filter Smoke Number
HC
Hydrocarbons, ppm by volume
IVC
Inlet Valve Closure
IVO
Inlet Valve Open
LPG
Liquefied Petroleum Gas

Mass flow rate, kg/s

MI
Manifold Induction
NOx
Oxides of Nitrogen, ppm by volume
SI
Spark Ignition
SOI
Start Of Injection
TDC
Top Dead Centre
Subscripts
g
Liquefied Petroleum Gas
d
Diesel

281

REFERENCES
A. Bilcan, O. Le Corre , M. Tazerout, A. Ramesh, S. Ganesan, 2001, Characterization of the LPG Diesel Dual Fuel Combustion, SAE Technical Paper, 2001-28-0036.
A.M.L.M. Wagemakers, C.A.J. Leermakers, 2012, Review on the Effects of Dual-Fuel Operation,
Using Diesel and Gaseous Fuels, on Emissions and Performance, SAE Technical Paper , 201201-0869.
E. Porpatham, A. Ramesh, B. Nagalingam, 2012, Effect of compression ratio on the performance
and combustion of a biogas fuelled spark ignition engine, Fuel 95 (2012), Pages 247256.
G.A. Karim, N.P.W. Moore, 1990,Examination of Rich Mixture Operation of a Dual Fuel Engine,
SAE Technical Paper, 901500.
G. A. Karim and I. Wierzba, 1983, Comparative Studies of Methane and Propane as Fuels for
Spark Ignition and
Compression Ignition Engines, SAE Technical Paper, 831196.
G. A. Karim , 1983, The Dual Fuel Engine of the Compression Ignition Type - Prospects,
Problems and Solutions - A Review, 1983, SAE Technical Paper, 831073.
J.B. Heywood, 1988, Internal Combustion Engine Fundamentals, McGraw Hill Book Company.
M. P. Poonia, A. Ramesh, R. R. Gaur,1998, Effect of Intake Air Temperature and Pilot Fuel
Quantity on the Combustion Characteristics of a LPG Diesel Dual Fuel Engine, SAE Technical
Paper, 982455.
M. P. Poonia, A. Ramesh, R. R. Gaur,1999, Experimental Investigation of the Factors Affecting the
Performance of a LPG - Diesel Dual Fuel Engine, SAE Technical Paper,1999-01-1123.
Nafis Ahmad I , M. K. Gajendra Babu, A. Ramesh, 2005, Experimental Investigations of Different
Parameters Affecting the Performance of a CNG Diesel Dual Fuel Engine, SAE Technical Paper,
2005-01-3767.
Qi Donghui, Zhou Longbao, Liu Shenghua, 2005, Experimental studies on the combustion
characteristics and performance of a naturally aspirated, direct injection engine fuelled with a liquid
petroleum gas/diesel blend, Proceedings of the Institution of Mechanical Engineers, Part D:
Journal of Automobile Engineering, 219 : 2: 253-261.
Tuan Anh Le, Truc The Nguyen, 2011, Experimental Study on Performance, Emissions and
Combustion Characteristics of a Single Cylinder Dual Fuel LPG/Diesel Engine, SAE Technical
Paper , 2011-32-0562.

282

Green Building

283

THE COOLING LOAD CALCULATION OF A LARGE SYSTEM IN AN

ENVIRONMENTAL CONTROL SYSTEM AT A SUBWAY STATION INSTALLED WITH
PLATFORM SCREEN DOORS
1,*

Xinshu ZHANG ,Guangcai GONG , Chunwen XU , Jingyuan HUANG , and Zehua LIU
1

College of Civil Engineering, Hunan University, Changsha 410082, China

Shanghai City Construction Technology co.,LTD, Shanghai 200233, China

College of Urban Construction, University of South China, Hengyang 421001, China

*Corresponding email: ahtree2005@163.com

ABSTRACT
At present, the subway construction is in a climax period in China. With the increasing
construction of subways, more energy is needed. The energy consumption of large system
belonging to the environmental control system accounts for a large proportion of the total
subway energy consumption. So the reasonable selection of air conditioning equipments should
be carefully considered according to the cooling load of the large system. The calculation
method of cooling load in large system changes with different environment control system in
different climatic regions. The load calculation method of large system in subway environment
control system in the hot-summer and cold-winter zone is depicted in detail in this paper. Firstly,
five different portions, which constitute the cooling load of large system in environment control
system, are calculated. The proportions of the five different parts are respectively listed. Some
index or parameters, which are obtained according to literatures and actual operating
experiences, have high practicability during calculation process of air conditioning cooling load of
large system. After that, the real air handling process for the air conditioning system in subway
large system is analyzed with the enthalpy-humidity chart. The total supply air volume of station
hall and platform are gained respectively. Finally, the components of air conditioning cooling load
of large system are summarized in the tabulation. The calculation method of cooling load of large
system in environment control system, which is deduced in this paper, is applicative in Mid-South
Region, South China and Eastern China etc.

Keywords: Energy conservation, Subway station, Platform screen door, Large system,
Load calculation
INTRODUCTION
Subways that employ underground spaces, having advantages of fast speed, large capacity
and so on, will become the preferred means of transport in large and medium-sized cities to
release the traffic pressure and reduce the environmental pollution (Fengxing Lei, 1996).
Subway station is a large client of urban energy consumption. The energy consumption of
environmental control system accounts for about 50% of the energy consumption of the total
subway station (Guanghua Tu, 2008). Meanwhile, there are five different climatic regions:
servere cold region, cold region, hot-summer and cold-winter zone, hot summer and warm
winter zone and mild region in China (GB50176, 1993). The design schemes of subway
environmental control system are different in different climatic zones. There are open-type
system, closed system and platform screen door system in environmental control system of
subway station (Qinghe Zhang, 2002). In order to calculate the cooling load of large system of
environmental control system in subway station that installs PSD (Platform Screen Doors), the

284

paper detailedly introduced the calculation process by taking some subway station in
hot-summer and cold-winter zone as an example.
METHODOLOGIES
1 The air calculation parameters and standards (GB50157, 2003)

The calculating parameters of outdoor air

Nanning, which is the provincial capital city of Guangxi province, locats in the hot-summer

and cold-winter zone. The outdoor computational dry-bulb temperature of air-condition in

summer is 32.3. The outdoor computational wet bulb temperature of air-condition in summer
is 27.4.

The calculating parameters of indoor air

Table 1. Calculating parameters of indoor air
Dry-bulb temperature

Relative humidity

()

(%)

Station hall

30.01

40~65

Platform

28.01

40~65

Location

The air-condition supply air temperature difference (T) is 8~10

2 The calculation of humidity load and cooling load in public area

There are five constituent parts in the cooling load in public area: personnel heat load,
calorific value of equipment and lighting, inward and outward infiltration heat load, heat load of
platform screen door and exhaust air heat transfer.
There are personnel moisture load and moisture load of building envelope in the moisture
load of public area.
2.1 The cooling load in the public area
2.1.1 The forward traffic in the public area and heating load, humidity load of people
2.1.1.1 The forward traffic in the public area

The peak hour traffic in 2039.

Table 2. The peak hour traffic
downlink

uplink

Passenger

Passenger

Passenger

Passenger

collecting

distributing

Che

collecting

distributing

volume

volume

Ping station

volume

volume

(P)

(P)

(P)

(P)

25

798

1004

32

Tian

Sojourn time of passengers in the station

Table 3. Sojourn time

Station hall

Platform

(min)

(min)

Getting on

Getting off

1.5

1.5

The computational formula of people who stay in the station at the same time and its
result

285

The computational formula of people who stay in the interchange station at the same time
is:
A1
A2
a1
b1
60
60

Gc

(1)
Gp

A1
A2
a2
b2
60
60

(2)
where G c is the number of people calculated in the station hall, G p is the number of people
calculated in the platform, A1 is passenger flow getting on train per hour in the station which
depend on the forward forecast passenger flow by super peak hour coefficient, A2 is
passenger flow getting off train per hour in the station which depend on the forward forecast
passenger flow by super peak hour coefficient, a1 is sojourn time in the station hall of
passengers who getting on train, a 2 is sojourn time in the platform of passengers who getting
on train, b1 is sojourn time in the station hall of passengers who getting off train and b2 is
sojourn time in the platform of passengers who getting off train.
By getting the peak passenger flow coefficient as 1.4, the number of passengers stay in
the station hall is the same to the platform, which is 77.
2.1.1.2 Cooling load, humidity load of people

Heat dissipating capacity, moisture gain criterions of people

Table 4. Sensible heat, latent heat and Moisture load of people

Temperature

Sensible heat

Latent heat

Moisture load

()

(W)

(W)

(g/h)

Station hall

30

39

142

212

platform

28

52

129

193

Heat dissipating capacity, moisture gain calculations of people

The total sensible heat of people in station hall equals 39 (W) by 77 (P). The total latent

heat of people in station hall equals 142 (W) by 77 (P). The total heat of people in station hall is
13937 W.
The total sensible heat of people in platform equals 52 (W) by 77 (P). The total latent heat
of people in platform equals 129 (W) by 77 (P). The total heat of people in platform is also
13937 W.
2.1.2 Calorific values of lighting and equipments

Lighting load
The lighting calorific value in station hall is: Q1 201446 1000 28.92kW .
The lighting calorific value in platform is: Q2 201120 1000 22.40kW .

The calorific value of advertising signs is 30 kW in station hall. And the value of platform is
20 kW.

Calorific value of automatic ticket machines

Table 5. Total calorific value of automatic ticket machines
Heating indicators

Number

Cooling load of station

(kW/piece)

(piece)

hall

286

(kW)
Ticket vending
machine
Gate
Box office check-in
machine
Ticket barrier machine

1.2

9.6

0.55

22

12.1

0.5

0.13

0.26

Total value (kW)

22.96

Cooling load of escalator, vertical elevator and communication device

Table 6. Cooling load of escalator, vertical elevator and communication device
Communication

Escalator

Vertical elevator

3.7

3.7

2.5

8.2

3.7

2.5

9.2

device

Total value

Heating
indicators
(kW/piece)
Number
(piece)
Cooling load of
station hall
(kW)
Cooling load of
platform
(kW)

2.1.3 Infiltration load of inward and outward

The infiltration load of inward and outward is: Q3 200 (30 30 23.5 30) 1000 22.7kW

2.1.4 Heat transfer between PSD and platform

Table 7. Heat transfer between PSD and platform
Heat
Area of

Heat transfer

transfer

PSD

coefficient

temperature

(m2)

(W/m2)

difference
()

684

10

Capacity of

Capacity

heat

of heat

transmission

dissipating

(kW)

(kW)

20.52

11

Heat gain
of platform
(kW)
31.52

2.1.5 Heat transfer in hot air duct

Heat gain of hot air exhaust duct in station hall

The heat gain of hot air exhaust duct in station hall is: Q4 581.4 1.67 8 1000 7.77kW

Heat gain of hot air exhaust duct in platform

The capacity of heat transmission of rail against the wind in platform is:
Q5 171 3.3110 1000 5.66kW .
The capacity of heat transmission of rail bottom air duct in platform is
Q6 296.4 2.35 8 1000 5.57kW .

287

2.2 Humidity load in the public area

2.2.1 Humidity load of people
The humidity load of people in station hall equals 212 (g/h) by 77 (P). The humidity load of
people in platform equals 193 (g/h) by 77 (P).
2.2.2 Humidity load of building envelope
According to the calculation above, the moisture area of station hall is 1873.5 m2 and the
produce moisture content of wall is 2g/m2h. So the produce moisture content of station hall
equals 2 (g/m2h) by 1873.5 (m2).
3 Calculation of air output
In the figure 1, W is outdoor air design state point, NT is design state point of station
hall, Nt is design state point of platform, O is air supply state point and L is apparatus
dew point. The air from station hall and platform mix to point C , the temperature of point C
rise to C by 1 more, point C air and point W air mix to point H , the temperature of
H is handled to the apparatus dew point L , then rise to air supply state point O by 1

more, finally the supply air reach design state point in station hall by 1 and in platform by 2
respectively.
The hot wet ratio of station hall is: 1 (134.5 20.09) 3600 24101.
The hot wet ratio of platform is: 2 (108.3 14.87) 3600 26212 .
According to figure 1, the values of the h1 , h2 and h3 can be acquired.
The air output in station hall is:
G1 Q7 ( h1) 134.5 [1.2 (65.5 54)] 3600 35086m3 / h .

The air output in platform is:

G2 Q8 ( h2) 108.3 [1.2 (63.2 54)] 3600 35316m3 / h .

So the total air volume of large system equals 70402m3/h.

NT
C
C

95%

Nt

L
Figure 1. H-d chart of large system

288

4 The minimum fresh air requirement and calculation of cooling load from outdoor air
4.1 The minimum fresh air requirement
The minimum fresh air requirement is 4620 m3/h according to the people in the station. It
is 7040 m3/h according to the 10% of the system total air volume of large system. So the latter
is selected in this paper.
4.2 The calculation of cooling load from outdoor air
The cooling load from outdoor air can divide into two types. One in station hall is calculated
as follow: Q9 1.16 3509 (87.8 65.5) 3600 25.21kW . The other in platform is calculated as
follow: Q10 1.16 3532 (87.8 63.2) 3600 27.99kW

5 The heat gain by the temperature rise of supply air fan and exhaust air fan

The heat gain of supply air fan

The heat gain of supply air fan is: Q11 1.16 70402 (54 52.9) 3600 24.95kW .

The heat gain of exhaust air fan

The heat gain of exhaust air fan is: Q12 1.16 63362 (65.4 64.5) 3600 18.37kW .

6 Additional heat
The exchange heat caused by exchange air between inward and outward in station hall
and outdoor air is difficult to analyse and quantify because its influence factors are too many.
The exchange heat caused by exchange air between PSD and station tunnel is also difficult to
analyse and quantify. The exchange heat of the two parts mentioned above is estimated 100
kW (Nanning, 2011).
The additional air output in station hall is:
G3 (100 35086 70402) (65.5 54) 1.2 3600 13000.87m3 / h .

The additional air output in platform is:

G4 (100 35316 70402) (63.2 54) 1.2 3600 16357.61m3 / h .

So the total additional air output is 29358.48 m3/h.

7 The sum of cooling load and humidity load in public area
Table 8. Statistics of calculated results in public area
Name of
station

Station hall
Chetian Ping station

Platform

Sensible

Latent

Sensible

Latent

heat

heat

heat

heat

Heat gain of passengers

3.01

10.94

4.01

9.94

Lighting

28.92

22.4

30

20

Light box of advertisement,

indicate board
Heat gain in

Escalator

3.7

3.7

the public area

Vertical elevator

(kW)

Automatic ticket machines

22.96

Convection heat exchange

22.7

inward and outward

Cooling load of

2.5

289

0
2.5

communication equipment
Heat transfer and calorific
heat of PSD
Heat transfer of exhaust air
way

31.52

7.77

11.23

The whole heat

134.50

108.30

Humidity gain

Humidity gain of passengers

16.34

14.87

in the public

Humidity load of building

area

envelope

3.747

(kg/h)

Total

20.09

14.87

Hot wet ratio (kJ/kg)

24101

26212

Calculated supply air (m3/h)

35086

35316

Fresh

Blast capacity (m3/h)

3509

3532

air

Load (kW)

25.21

27.99

Heat gain by the temperature rise of supply air fan

24.95

(/ kW)
Heat gain by the temperature rise of exhaust air fan

18.37

(/kW)
Calculated cooling load (kW)

339.33

Additional heat (kW)

100

Additional air output (m3/h)

29358.48

The total air output (m3/h)

99760

The total cooling load (kW)

439.33

RESULTS AND DISCUSSION

Various parts constituting the cooling load of large system in environment control system
are inferred. The realization process of large system is analysed by using the
enthalpy-humidity chart in this paper. The following results are summarized:
1. There are five different parts that constitute the cooling load of large system in
environment control system, which are heat gain in the public area, cooling load of fresh air,
heat gain by the temperature rise of supply air fan, heat gain by the temperature rise of
exhaust air fan and additional heat.
2. The proportions of the five different parts mentioned above are respectively listed. Heat
gain in the public area accounts for 55.27% of the total heat. Cooling load of fresh air accounts
for 12.11% of the total heat. Heat gain by the temperature rise of supply air fan accounts for
5.68% of the total heat. Heat gain by the temperature rise of exhaust air fan accounts for 4.18%
of the total heat. Additional heat accounts for 22.76% of the total heat. From the data, the
major influence factors can be concluded.
3. Some index or parameters, which are obtained according to literatures and actual
operating experiences, have high practicability during calculation process of air conditioning
cooling load of large system. According to a large number of analog computations, additional
heat adopts 100 kW. It is applicative in the practical engineering.
4. The calculation methods of cooling load in large systems where install PSDs are the
same. The PSDs are applied in the hot-summer and cold-winter zone, hot-summer and

290

warm-winter zone and mild region. So the calculation method of cooling load of large system in
environment control system has practicability and guidance meanings.
CONCLUSION
The cooling load calculation method of large environment control system, which is
deduced in this paper, is applicative in Mid-South Region, South China and Eastern China etc.
ACKNOWLEDGEMENT
In the process of preparing this paper, the other authors give me a number of suggestion
and information. Thanks for their help.
REFERENCES
Fengxing Lei ,1996, A overview of Chinas subway construction and its development. The
Tunnel, 1, 1-6. (for journal)
Guanghua Tu ,2008, The energy saving research of subway ventilation system and air
conditioning system. Refrigeration & Air-Conditioning, 22, 14-17. (for journal)
China Plan to Press ,GB50176, 1993, Civil Building Thermal Design Code. Beijing, China.
(for criterion)
Qinghe Zhang ,2002, Subway and Light Rail . China Communications Press, Beijing,
China. (for journal)
Guangzhou metro design and research institute co., LTD ,2011, The technical
requirements of the first-stage project in rail transit line 1 in Nanning City. Nanning, China. (for
criterion)
China Plan to Press ,GB50157, 2003, Code for Design of Metro. Beijing, China. (for
criterion)

291

STUDY ON THE INFLUENCE OF ENVELOPE INSULATION MATERIALSON THE

BUILDING ENERGY CONSUMPTION
JunLan Yang*, Li Na Zhao, Guo Wei Miao, Mu Chao Yao
School of Energy and Safety Engineering,Tianjin Institute of Urban Construction
No.26, Jinjing Road, Xiqing District, 300384, Tianjin, Peoples Republic of China
yjlfg@163.com

ABSTRACT
In this paper, an energy analysis model is set up in order to clarify the effect of insulation materials on
the thermal performance and the energy consumption of building envelope. Three types of insulation
materials commonly used in Germany including mineral fiber, polyurethane and vacuum insulation
panel are chosen as the case study. The calculation results show that the energy consumption
increases with the increasing of the insulation thickness while the heat losses decrease. So there
exists an optimum thickness of the insulation to get the lowest total energy consumption. The
ascending order of the total energy consumption of the three materials is mineral fiber, polyurethane
and vacuum insulation panel. While their optimum insulation thicknesses show a reverse orderwith
the increasing of heat transfer coefficients of the base envelope. Moreover, the energy payback time
of each material is analysed at the optimum thickness, which is greatly affected by the heat transfer
coefficient of the base envelope. The longest payback time is up to 21 years for the vacuum
insulation panel if the base envelope heat transfer coefficient is as small as 0.2W/m2.K.
Keywords: building envelope, insulation materials, energy consumption, payback time.
INTRODUCTION
In European Union, the construction and building sector is responsible for about 40% of the overall
environmental burden. Most European governments have introduced new policy instruments, such
as the European Communitys energy performance directive for buildings (EPBD), in order to reduce
the negative impacts of the building sector (Mohamad et al., 2009).Life cycle assessment (LCA) is
widely used to assess the environmental impacts of materials and components(Klpffer, 2006).
Brendon developed and implemented a life-cycle assessment for the building enclosures over a
typical useful life in USA (Brendon, 2006). Robin, etc. proposed a life cycle energy analysis model to
analyze the house energy consumption in Australia (Robin et al., 2002). Carol (Carol, 2007) studied
the real efficiency of walls with high thickness insulation materials in Italy. Roger, etc. (Roger et al.,
2000) presented some of the theoretical issues associated with life-cycle energy analysis and applied
it to an energy efficient residential building. In China, many researchers (Gu et al., 2007; Shi et al.,
2008; Zhang, 2002; Zheng et al., 2009) developed a life cycle assessment framework to evaluate
building energy conservation and environment impact.
In this paper, a simplified approach to investigate the embodied energy of the building insulation
materials and the heat transfer energy losses of the insulation in lifetime is described.
CALCULATION MODEL
A short abstract should state briefly the content, methods and results only.Define abbreviations and
acronyms the first time they are used. Avoid footnotes at the bottom of the page within the frame.
Three types of insulation materials are chosen as the analysis object, as shown in Table 1. The
lifetime of the building insulation materials is assumed to be 30 years. A unit area of envelope is
chosen as the functional unit.
Table 1. Properties and production energy demand of insulation materials
Density
Thermal conductivity
Production energy demand
Materials
(kg/m3)
(W/m.K)
(MJ/kg)
Polyurethane
30
0.025
134
Mineral fiber
25
0.035
36
Vacuum insulation panel 190
0.005
139.4

In this study, the total energy consumption comprises two parts, one is the energy compensating the
heat transfer losses of the building envelope, and the other is the energy for producing the insulation
materials.

292

E
E E
tot
t
in
(1)
where, Etot is the total primary energy,

kWh / m2 ; Et

losses through the building envelope,

kWh / m2 ;

insulation materials,

the primary energy compensating the heat

and Ein the primary energy for producing the

kWh / m2 .

Annual heat loss is assumed to be constant during the lifetime of a building. So the entire energy
demand by heat loss can be calculated by Eq. (2).

Et

k Gt 24

t 1000

N
(2)

where,

is the overall heat transfer coefficient of the building envelope,

heating days,

Kd / a ; N

the lifetime of the insulation materials, and

W / m2 K ; Gt

the annual

the efficiency of heating

system.
For 1m2 envelope surface, the total production energy consumption of insulation material is given by
Eq. (3).

PEin 1000
Ein in in
3600
(3)
where,

in

is the density of the insulation material,

per unit mass of the insulation material,

kg / m3 ; PEin

the production energy demand

MJ / kg .

When the total primary energy consumption of the insulation layer takesthe minimum value, the
corresponding thickness is defined as its optimum thickness.
The Energy Payback Time (EPT) is defined as the ratio of the production energy consumption of the
insulation material to the annual reduced heat loss due to addition of the insulation, as shown in Eq.
(4).

EPT

Ein
Qtb Qtin
(4)

where, EPT is the energy payback time, year; Qtb is the annual heat loss through the base envelope,

kWh / m2a

Qtin

is the annual heat loss through the envelope with insulation material,

kWh / m2 a .
RESULTS AND ANALYSIS
The overall heat transfer coefficient of the base envelope kbw is assumed to be 1.0W/m2K and the
energy consumptions for polyurethane over 30 years are calculated, as shown in Fig.1. It can be
seen thatthe production energy consumptions rise linearly and the heat losses decrease with
increasing the insulation thickness. Fig.1also shows that the total energy consumption firstly
decreases to a minimal value at a certain thickness and then it increases with the thickness.

293

Production of polyurethane
Heat losses
Total energy consumption

Energy consumption (kWh/m )

2000
1600
1200
800
400
0
0

10
20
30
40
Thickness of insulation (cm)

50

Fig. 1 Energy consumption for polyurethane

Total energy consumption (kWh/m )

Fig. 2 plots the total energy consumptions for the three insulation materials. Obviously, the total
energy consumption for the vacuum insulation panel is the largest, and that of mineral fiber is the
lowest. The optimum insulation thicknesses for the three materials all increase slightly with the
increase of kbw, as shown in Fig. 3. It shows that the optimum thickness of the mineral fiberis the
largest, and that of the vacuum insulation panelis the lowest.
4000

Polyurethane
M ineral fiber
Vacuum insulation panel

3500
3000
2500
2000
1500
1000
500
0
0

10
20
30
40
Thickness of insulation (cm)

50

Fig. 2 Comparison of total energy consumption

Optimum insulation thickness (cm)

50
40

Polyurethane
Mineral fiber
Vacuum insulation panel

30
20
10
0
0.2

0.4

0.6

0.8

Overall heat transfer coefficients of base envelope (W/m .K)

294

The energy payback time is plotted in Fig. 4. It is shown that when the heat transfer coefficient of the
base envelope is reduced, the energy payback time increases quickly.
Energy payback time (year)

25
20
15

Polyurethane
M ineral fiber
Vacuum insulation panel

10
5

Fig.0 3 The optimum thickness of the insulation

0.2
0.4
0.6
0.8
1
Overall heat transfer coefficients of base envelope (W/m2 .K)

Fig.4. Change of the energy payback time

CONCLUSIONS
In this paper, the energy analysis model is set up to study the effect of three types of insulation
materials. Vacuum insulation panel is a high density and energy-intensive material, so its total energy
consumption is the largest, while mineral fiber is on the contrary. There is an optimum insulation
thickness for each material to get the lowest total energy consumption. Vacuum insulation panel has
the smallest optimum insulation thickness and mineral fiber has the largest. If the energy payback
time is considered, the vacuum insulation panel needs the longest time. Thus, the total energy
consumption and the envelope structure should be considered comprehensively when choosing
insulation materials, or it will take very long time to pay back the production energy consumption of
the materials.

ACKNOWLEDGEMENT
The authors acknowledge the support by the Natural Science Foundation of Tianjin, China under
Grant 10JCYBJC08300.
REFERENCES
Brendon Burley, 2006, Life cycle assessment of operational energy expenses of building
envelope.http://www.engr.psu.edu/Symposium2006/papers/Burley.pdf.
Carol
M.,
2007,
LCA
of
innovative
http://www.lcm2007.org/paper/318.pdf.

high

energy

performance

envelope.

Gu D.J., Gu L.J. and Zhu Y.X., 2007, A life cycle assessment method for buildings, Proceedings of
Building Simulation, Beijing, China. p. 595-1600.
Klpffer, W., 2006, The role of SETAC in the development of LCA. Int. J. Life Cycle Assess,
11(Supplement 1): 116-122.
Mohamad M.K., Phillip F.G. Banfill and Gillian F. Menzies, 2009, Life-cycle assessment and the
environmental impact of buildings: a Review. Sustainability,1: 674-701.
Robin D., Michael A. and Selwyn T., 2002, Automating building life cycle energy assessment.
International Council for Research and Innovation in Building and Construction CIB w78 conference,
Aarhus School of Architecture, Denmark, p.1-8.
Roger Fay, Graham Treloar and UshaIyer-Raniga, 2000, Life-cycle energy analysis of buildings: a
case study. Building Research & Information, 28(1): 31-41.

295

Shi J.F., Li A.G., Chen S.L., etc., 2008, Research on the thickness of economical insulation layer of
external wall in Xian. Architecture Technology & Design, 9: 78-83.
Zheng Guozhong, Jing Youyin, Huang Hongxia, Zhang Xutao and Gao Yuefen, 2009, Application of
Life Cycle Assessment (LCA) and extenics theory for building energy conservationassessment.
Energy, 34(11):1870-1879.
Zhang Xu, 2002, Assessment Method of Building Energy Consumption Based on LCA. Refrigeration
Air Conditioning & Electric Power Machinery, 23(4):1-3,27.

296

NUMERICAL SIMULATION AND FLAMMABILITY ANALYSIS ON R32 LEAKAGE

OF INDOOR AIR-CONDITIONER
Shengchun Liu1,2,* and Pengxiao Wang1
1. Tianjin Key Laboratory of Refrigeration Technology ,Tianjin University of Commerce, Tianjin, China
2.Key Laboratory of Efficient Utilization of Low and Medium Grade Energy, Ministry of Education
*Corresponding author, email: liushch@tjcu.edu.cn

Abstract:As global warming has raised more critical concerns in recent years, refrigerants with high
global warming potentials (GWP) are facing the challenges of being phased out. R32, with a GWP of
375 has been widely used in residential air-conditioner systems. In this paper, it is analyzed the
potential fire hazard of indoor air-conditioner with R32 by of its flammability.
Numerical simulation on leakage of the R32 is processed with Computational Fluid Dynamics
software FLUENT, considering the influence of operating status and wind speed scale of airconditioner and diametric of leakage hole and mass flow rate.
It is concluded by analyzing the simulation data that mass fraction of R32 is enormous implicated
by different conditions, such as direction of the leakage flow, mass flowed from leakage hole,
functional mode of the air-conditioner, size of the leakage hole and the flammable domain is so small
that can be ignored, and it is concluded that R32 is non-hazardous in the field of indoor airconditioner.
Keywords: R32, leakage, flammability, simulation,air-conditioner
1. Introduction
China is the largest producer of household air conditioner in the world. And
hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs), particularly in
chlorodifluoromethane (R22), has been predominantly used, in the past few decades, in household
air-conditioners due to its preferable characteristics. However, it still contains ozone depleting
chlorine and causes environmental problemsespecially ozone hole and global warming. The
Montreal protocol has made regulations for HCFCs production in the developed countries from 1996
and decided to abandon R22 as well as other HCFCs which are harmful to the environment in 2020
eventually. So researches on finding alternatives to replace R22 have become hot issues.
In the past years, various substitutes have been studied as working fluids in refrigerating devices.
At present, replacements for R22 in household air-conditioners can be categorized into two
approaches: one is to use HFCs and the other is to use hydrocarbon(HC) refrigerants. At the
moment, the most common internationally-applied alternative for household air conditioners is R410A;
however this refrigerant has a high GWP, which is 1730. Given the current concerns and increasing
demands for protection of the climate, high GWP alternatives are facing elimination in the medium to
long-term. Thus for the replacement of HCFCs in air conditioners, R410A is not the perfect
replacement of HCFCs.
At the same time, difluoromethane (R32) is an excellent candidate to replace HCFCs and HFCs
refrigerants. And R32 is more environment friendly than R410A, because its GWP is only 375, much
lower than R410As 1730. Even if the R32 have many advantages, such as excellent system
performance, environmental characteristics, low ODP and GWP,and even cost, it also has
disadvantage of flammable substance, thereby posing additional hazard by a leak in a refrigeration
machine. Many scholars have investigated the performance of R32. Ryuzaburo Yajima et al. have
investigated R32s performance and TEWI of a 16kW prototype with a variable speed compressor
driven by a motor controlled by DC inverter. Willam L.Grosshandler et al. describe an alternative
approach to identify the limits of flammability, using a twin, premixed counter-flow flame, by using the
extinction of an already established flame, the point dividing flammable from non-flammable
becomes unambiguous. Xu Shuxue et al. have experimentally investigated the performance of an
enhanced vapor injection refrigeration/heat pump system using R32. Xing Xu et al. have investigated
the performance difference using R410A and R32 in a vapor-injected heat pump system. Shravan K.
Vudumu et al. develope a buoyancy diffusion computational model to simultaneously solve for the
complete set of equations governing the unsteady flow of hydrogen.
The purpose of this paper is to analyze potential fire hazard of indoor air-conditioner with R32, by
using Computational Fluid Dynamics software FLUENT, considering the influence of operation status
and wind speed scale of air-conditioner and diametric of leakage hole(the shape of the leakage hole
is assumed as circular shape) and mass flow rate.
2. Geometric model of the test domain
A three-dimensional geometry model of the test domain has been developed and shown in Fig. 1.
The leakage hole on the air-conditioner is shown in Fig. 2.

297

Fig. 1. The three-dimensional geometry model

Fig. 2. The partial enlarged detail of air -conditioning

of the studied space

and leakage hole

Three-dimensional grids are established by using code system of gambit, and the superficial
grids of studied space are shown in Fig.3. And the partial grids of the plane of which the leakage
hole in also are shown in Fig. 4.

Fig. 4. The grids on the plane

which the leakage hole located in

Fig. 3. The superficial grids of studied space

3. Mathematical model
The leakage fluid (R32) has been modeled as ideal gas where =f(T,P). Molecular viscosity,
specified heat and thermal conductivity are considered to be constant. The conservation equations
used for mass and momentum in Cartesian coordinate are as below.
Continuity equation:

( u i ) 0
xi
(1)
Momentum equations:

298

______
u u j 2 uk

( ui u j )
[ ( i
)]
( ui'u 'j )

ij
x j
x j
xi x j
x j xi 3 xk

(2)
Energy equation:

1
T

[ui (h ujuj )]
keff
ui (ij )eff

xi
2
xj xj

(3)
The first formula on the left hand side of the energy equation represents the rate of the total
energy lost by convection. The first formula on the right hand side of this equation represents the
energy transfer due to conduction and the second formula involving (ij ) eff represents the
viscous dissipation.
The RNG k- turbulent model in conjunction with law of the wall function is employed to account
for turbulence. The equations involved in RNG k- model for turbulence energy and turbulence
dissipation rate with standard notations are given as
~
eff k
u
u

2
( k )
( u j k
) t ( P PB ) ( t i k ) i
t
x j
k x j
3
xi
xi

(4)

~
eff
u
u

2
( )
( u j
) C 1 [ t P ( t i k ) i ]
t
x j
x j
k
3
xi
xi

C 3

t PB C 2

2
k

C 4

3
ui C (1 / 0 ) 2

xi
1 3
k

(5)
Where C1 , C2 , C3 and C4 , are coefficient factors and given by 1.42, 1.68, 0.0 or 1.42 (if
PB > 0 and 0 otherwise) and -0.387, respectively. C , 0 , , k , h and are empirical
coefficients usually taken as constants. Sij is element of mean strain and is twice of sij.
4. Numerical simulation and flammability analysis
4.1 Boundary conditions

The boundary conditions are as follows:

(1).Outflow boundary condition at the exhaust duct.
(2).Mass flow inlet boundary condition at the leakage hole.
(3).Velocity inlet boundary condition at the air outlet of the air-conditioner.

Unsteady-state calculations are adopted in this numerical simulation.

4.2 Results and analyses
To disclose the results contributed by direction of the leakage flow, mass flux out from leakage
hole, functional mode of the air-conditioner, size of the leakage hole, contours of mass fraction of
R32 in different conditions will be shown in the below.

299

Fig. 5. The change of mass fraction of R32 over time

and the partial enlarged view of the mass fraction in the vicinity of the leakage hole

The change of mass fraction of R32 over time can be seen in Fig. 5. From this series of picture,
the mass fraction of R32 is expanding over time. And in the partial enlarged view, it shows that high
mass fraction of R32 is higher (red color stand for high mass fraction), and this area is so small that it
can be ignored while comparing with the whole test domain.

Fig. 6. The distribution of the detecting position

Fig. 7.The change of mass fraction of R32 along with switching position in the same moment

The change of mass fraction of R32 along with switching position in the same moment can be
seen in Fig. 7. From this series of pictures, the mass fraction of R32 is varying along with switching
position, and it reaches the highest level in the vicinity of the leakage hole.

300

Fig 8. The distribution of directions of the leakage flow

Fig. 9. The change of mass fraction of R32 along with different directions of the leakage flow at the same moment

The change of mass fraction of R32 along with different directions of the leakage flow in the
same moment is shown in Fig.9. From this series of pictures, the distribution of mass fraction of R32
is very different from each other. It can be seen that direction of leakage flow enormously implicates
the mass fraction.

Fig. 10. The change of mass fraction of R32 along with different sizes of the leakage hole at the same moment

The change of mass fraction of R32 along with different sizes of the leakage hole at the same
moment is shown in Fig. 10. From these two pictures, the mass fraction with larger size of the
leakage hole is bigger than the mass fraction with smaller size.

Fig 11. The change of mass fraction of R32 with different mass flowed from leakage hole

301

The change of mass fraction of R32 with different mass flowed from leakage hole is shown in Fig.
11. From this series of pictures, it shows that the mass fraction of R32 is enlarging along with the
masss larger.

Fig.12. The change of mass fraction of R32 along with different functional modes of the air-conditioner

The change of mass fraction of R32 along with different functional modes of the air-conditioner is
shown in Fig.12. From this series of pictures, it is can be seen that the mass fraction of R32 is very
different from each other: the distribution of R32 is the most concentrate when the air conditioner is in
a state of shut down, and it is the most homogeneous when the wind velocity of the air conditioning is
the biggest.
4.3 Flammability analysis
R32(difluoromethane) is a kind of inflammable matter, and its combustion limit is 0.35% in air. A
color contour level is displayed on the left of the contour. The minimum and maximum value in the
contour level respectively are 0 and 0.35%, consequently the domain, that R32 mass fraction is
outside this range, will not be contoured, namely, the domain that hazard-free, without explosion
hazard, is contoured on the contour.
The last two contours of Fig. 5, the contour of the plane which the leakage hole located in at
150s (the finally instantaneousness of this numerical calculation) and its partial enlarged view, vision
the concentrated of R32 in the test domain. There are not some relatively significant differences of
the domain between the last two contours of Fig. 5 and Fig. 4. So, the flammable domain, the domain
that the R32 mass fraction is more than 0.35%, is negligible.
The series of contours from Fig.5 to Fig. 12 are observed and compared to find that the
flammable domain is a very small domain in the vicinity of the air conditioner, negligible. In
consequence, the R32 is non-hazardous in the field of indoor air-conditioner, because of that the
flammable domain is too small to invite danger even if it is inflamed.
5 Conclusion
It is concluded by comprehensive analysing the simulation results as follows:
(1) The mass fraction of R32 is influenced by the factors of direction of the leakage flow, mass
flowed from leakage hole, functional mode of the air-conditioner, size of the leakage hole.
(2) It is reduced by increasing wind speed or shortening the leakage hole or reducing mass flow
rate when the air-conditioner is on the operation;and the mass fraction formed by the shutdown
state will be slight smaller, but the mass fraction of R32 will be larger while air-conditioner at
power-on state when the leakage hole of air-conditioner in the same position.
(3) The flammable domain is a very small area in the vicinity of the air conditioning. Comparing
the flammable domain with the whole domain, it is too small to negligible. So the conclusion of
the flammability analysis is that R32 is hazard-free in the field of indoor air-conditioner.

References
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ceramics on the flame and shock wave of gas explosion[J]. Safety Science, Volume 50, Issue 4,
April 2012, Pages 797-800. (for Journal)
Baisheng Nie, Xueqiu He, Ruming Zhang, Wenxue Chen, Jinfeng Zhang. The roles of foam
ceramics in suppression of gas explosion overpressure and quenching of flame propagation.
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behavior during gas explosions in confined spaces considering flame instabilities, Journal of Loss
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Lei Pang, Tong Wang, Qi Zhang, Qiuju Ma, Lu Cheng, 2013. Nonlinear distribution characteristics
of flame regions from methane-air explosions in coal tunnels. Process Safety and Environmental
Protection, In Press, Corrected Proof, Available online 10 January 2013. (for Journal)
Valeria Di Sarli, Almerinda Di Benedetto, Gennaro Russo. Large Eddy Simulation of transient
premixed flamevortex interactions in gas explosions. Chemical Engineering Science, Volume 71,
26 March 2012, Pages 539-551. (for Journal)
Lewis B, von Elbe G. Combustion, Flames and Explosions of Gases. New York: A cademic Press
Inc, 1951. 644677. (for Conference)
Sun Yijian. Industrial Ventilation . 3rd edition. Beijing: China A rchitecture and Building Press(in
Chinese) , 1994. 5356. (for Conference)
Zhao Hongyang, 1996. Theory of Dust and Gas Explosion . Beijing: Beijing Institute of Technology
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Tian Guansan, Yang Zhao, Ma Yitai et al, 2000. Simulating the leakage processes of flammable
refrigerants from cooling system. Journal of Engineering Thermophysics(in Chinese) , 2000, 21 (4):
401404. (for Journal)

303

THERMAL PERFORMANCE OF USING A PCM SHUTTER IN BUILDINGS

Qian Wang, C Y Zhao

School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai, 200240, China
*Corresponding author, Email: changying.zhao@sjtu.edu.cn

ABSTRACT
In building constructions, windows are considered as a weaker heat link and are responsible for a
large percent of the solar heat gain. In this paper, a technique using PCM (Phase change
materials) shutter inside the window is proposed to reduce the solar heat gain, which utilizes the
high latent heat of fusion to reduce the heat into the indoor space. The thermal effectiveness of the
proposed PCM shutter is evaluated by comparing the heat gain at the indoor space to that of cloth
curtain during typical working hours. The natural convection effect on the heat flux into the indoor
space is evaluated. PCM with different melting temperatures are investigated for design concern.
It is found that the heat flux into the indoor space can be reduced as much as 16% at a certain
melting temperature.
Keywords: window shutter, PCM, heat flux
INTRODUCTION
In the areas of southern China, the electricity consumption increases sharply due to using airconditioning systems during hot summer seasons. It is thus essential to make some efforts to
reduce the heat flow into buildings. The reduction of the energy consumption and the improvement
of the energy conservation in buildings are crucial on promoting energy efficiency and
sustainability of buildings. Reducing the peak air conditioning demand is also essential for
electricity grid stability.

Using PCM in building materials can effectively reduce the cooling or heating loads, due to the
high latent heat of fusion at a low temperature. During the melting and solidification process of
PCM, a large amount of energy can be absorbed or released over a limited temperature range,
which enables PCM to act like an almost isothermal reservoir of heat. The selection of PCM mainly
concerns its melting temperature, latent heat capacity, chemical characteristics and cost, etc. The
melting temperature should be in the range of operating temperature of the thermal system.
Paraffin is a commonly used PCM in buildings due to its proper melting temperature, large latent
heat capacity, stable chemical characteristics, nontoxic and low cost.

Employing PCM in building structure components to conserve energy was pointed out in 1975
by Barkmann and Wessling (Barkmann et al., 1975). The PCM can be integrated to walls, ceilings,
windows and floors. For walls, PCM layer can be enclosed between the external and internal walls
(Ismail et al., 1997), absorbed into a porous concrete (Hadjiena et al., 2000), impregnated in
Gypsum board (Athienitis et al., 1997), or randomly mixed laminated PCM-wall (Kim et al., 2003).
1

304

A research team working in the University of South Australia (Saman et al., 1997) developed a
roof-integrated solar air heating storage system in 1997. The latent heat storage unit, in which an
existing corrugated iron roof sheet is used as solar collector, is to store heat during the day and
supply the heat at night or when sunshine is unavailable. Kondo and Iwamoto (Kondo et al., 2002)
designed a rock wool PCM ceiling board with microcapsulated PCMs for an office building. Floor
heating systems can be charged by using cheap night-time electricity and discharge the heat
stored at the daytime. The shift of electricity consumption from peak periods to off-peak periods
would provide significant economic benefits. Lin et al. introduced an under-floor electric heating
system with shape-stabilized PCM plates and ductless air supply, which really has good
application feasibility (Lin et al., 2007). E. M. Alawadhi numerically investigated the using of a PCM
shutter outside the window to reduce the solar heat gain in summer seasons (Esam et al., 2012).
The heat flux reduction to the building through window can be as high as 23%. Ismail and
Henriquez (Ismail et al., 2001) designed a PCM window with adding a PCM layer between two
glass layers. It is found that the PCM window can reduce 15% to 25% solar heat gain comparing to
the single layer glass window and 3% to 6% for double layer glazing. The width of the PCM layer
has an optimized value to achieve the maximum heat gain reduction. For all the methods
mentioned above, the PCM has shown to be effective in maintaining room temperature within the
human comfort zone for longer periods of time and is more economic in energy cost.

Comparing to the wall structures, windows are considered as a weaker heat link in building
constructions and are responsible for a large percent of the solar heat gain. Particularly, in modern
cities, there are many glass wall buildings, which are affected more seriously by solar heat gain in
summer seasons. Hence, reducing solar heat gain through windows is an effective way to reduce
energy consumption in buildings, especially for buildings with large windows and glass wall
buildings. However, for the buildings with large windows or glass wall buildings, it is not possible to
use PCM walls; even for the sake of appearance, adding shutter outside of the window or glass
wall to modern buildings are not suitable. In this paper, a more flexible method is proposed by
using a PCM shutter inside the window to reduce the solar heat gain.

305

MODEL DESCRIPTION

Fig.1 Schematic representation of the windows PCM system and the boundary conditions
Figure 1 depicts the geometry configuration of windows with curtain containing PCM. The outdoor
surface of the window glass is subjected to a time dependent solar radiation and forced convection
boundary conditions, while the indoor surface of the curtain is subjected to time independent free
convection boundary condition. Based on the outdoor air temperature and solar radiation, the
solar-air temperature is defined as

,
(1)
where To is the outdoor air temperature, is the solar absorptivity of the glass surface, =0.89,
and qs is the solar flux radiation. The highest temperature and maximum solar radiation of a typical
sunny summer day in Shanghai city is 38C to 40C and 800 W/m2 to 900 W/m2 respectively. In
this study, the hottest days are selected as the simulation case, because the electrical power
consumption will reach its peak under such conditions. Thus a sinusoidal function curve is used to
present Ts value approximately, as shown in Fig. 2.

306

Fig. 2 Approximate solar-air temperature variations of a sunny summer day in Shanghai city

The heat transfer in the window with curtain is actually three dimensional. . However the width
of the window is typically large compared to its thickness. The ends effect on the heat transfer can
be neglected. It is thus reasonable to use two dimensional simulations to investigate the heat
transfer characteristics. The natural convection of air in the space between glass and shutter is
considered. The Rayleigh number of the air is in the range of

to

in this

study, with the height as the characteristic length. Chen et al. reported that, for a vertical plate
heated by a uniform heat flux, the transition to turbulence occurs at

(Chen et al.,

2003). Therefore, we model the air flow between the glass and PCM shutter as laminar. Since the
temperature difference in the air domain is not expected to be very high, the usual Boussinesq
approximation is adopted. The two dimensional conservation equations for the air, glass and PCM
shutter can be written as:
Air:

(2)

(3)

(4)

307

(5)
Glass:

(6)
Shutter:

(7)
Initial condition for the entire domain:

where

is the thermal expansion of the air. By making the specific heat of PCM function of

temperature, thermal effect of melting and solidification of PCM can be simulated. In this study, a
fixed grid method is applied to simulate the PCM solidification/melting process, which is more
effective in computing than the front tracking methods. The main advantage of fixed grid methods
is that the geometry of the grid is independent of time and the numerical treatment of the phase
change can be achieved through simple modifications of existing heat transfer numerical methods.
An enthalpy-porosity model is adopted, in which the fraction of the cell volume that is in liquid form
is associated with each cell, named liquid fraction (Voller et al., 1987). The liquid/solid interface is
tracked by the definition of a mushy zone based on a porous medium model, where the liquid
fraction lies between 0 and 1. When the material has fully solidified in a cell, the porosity becomes
0; when fully melted, the porosity becomes 1.

The natural convection of the liquid PCM is

insignificant when the temperature difference between initial condition and the boundary is small
(Aydin, 2006); thus is not considered in this simulation.

The outside of the glass is subjected to a time dependant solar-air temperature as shown in
Fig. 2; and force convection boundary conditions with

. A free convection

boundary condition is applied on the indoor surface of the PCM shutter with

Considering the thermal comfort for people work and living, the indoor air temperature is set
constant at 25

. Both the top and bottom sides of the domain are considered to be isolated. A

rigid no-slip wall condition is imposed on all walls. The average heat flux from the shutter into
indoor area at any instant is calculated to study the effectiveness of PCM shutter in reducing heat
gain, and it is defined as:

308

(8)

The net heat flux flowing into the indoor area during a specific period can be obtained by
integrating the average heat flux:

(9)

The governing conservation equations of mass, momentum and energy are simultaneously
solved using a finite volume solver. The coupling between the momentum and continuity equations
through pressure is based on the SIMPLE scheme (Patankar, 1997), and the second-order upwind
differencing scheme is adopted for the convective terms of the momentum and energy transport
equations. To ensure numerical stability, the discretized equations are iterated with underrelaxation factors. The finite element mesh of the computational domain is shown in Fig. 3. In the
air domain, two-dimensional quadrilateral elements are used to create a structured, non-uniform
mesh with finer grid distribution in the vicinity of vertical wall boundaries. The grid in glass and
PCM shutter domain is created uniformly.

Fig. 3 Close-up view of the mesh distribution in the computational domain

VALIDATION AND VERIFICATION

In order to validate the numerical model, a natural convection and a phase change cases are
simulated separately. The natural convection flow in a square enclosure is simulated using the
present computing method and the results are compared with published results, which are
commonly conducted to validate the numerical model that involves natural convection. The square
enclosure with a width and height of 0.045 m, is simulated with air,

. The left vertical

wall is set at a constant high temperature, while the right vertical wall is at constant low
temperature. The temperature difference is 50

. The Raleigh number under this condition is

. The temperature distribution at the horizontal mid-height of the enclosure in a non6

309

dimensional form is used to compare with the numerical result of Rasoul and Prinos (Rasoul et al.,
1997) and the experimental result of Bajorek and Lloyd (Bojorek et al., 1982). It can be seen from
Fig.4 that current simulation results are in good agreement of the other two. The
melting/solidification model is validated with the analytical solution of a Stefan-type problem from
the reference by Solomon (Solomon, 1979). The PCM is in a container, with all of its faces are
insulated but one. The PCM container is considered as a semi-infinite slab placed along an x-axis,
with the heat transfer surface located at x=0. He analyzed a slab of N-Eicosene paraffin wax with
an initial temperature of 21

. The thermophysical properties are melting temperature of 36.7

latent heat of 247 kJ/kg, density of 840 kg/

,sensible heat of 2200 J/kgK and thermal

conductivity of 0.15 W/mk. The thickness of the slab is 0.15 m. The slab is heated from one side
under a constant temperature of 95

. The melting temperature range is set at 1K. Set the

aforementioned parameters in our simulation and the results have been shown in Fig.5. It can be
seen that the simulation results agree with the analytical value very well.

Fig.4 Comparisons of temperature distribution at the mid-height of the enclosure between current
simulation and published results

310

Fig.5 Comparisons of temperature distribution at the mid-width of the slab between present
simulation results and analytical values
To ensure that a mesh independent solution is obtained, the computational model shown in
Fig. 1 is solved with three finite volume models with different number of elements: 22800, 3000
and 37500. A curtain without PCM is used instead of shutter and its thickness is 2 mm. The
average heat flux at the indoor surface of the curtain is calculated for the three models. The results
indicate that the difference between the second and third models is less than 2%. Hence, the
second finite element model is adopted for the numerical simulations.

RESULTS AND DISCUSSION

In this study, a typical height of the windows, H, is set at 1.5 m. The thickness of the glass, L g, is at
5 mm; the thickness of the shutter Lsh is at 5 mm; the air gap La is set at 50 mm. The
thermoproperties of the air, glass, curtain and PCMs are shown in Table 1. In order to assess the
effect of air natural convection on the heat flux to indoor space, the simulation has been conducted
on the window with cloth curtain, by neglecting or considering the natural convection in the air gap.
From the result shown in Fig.6 it can be seen that the maximum heat flux by only taking air
conduction into consideration is only 34 W/m2K. However, the maximum heat flux calculated with
natural convection is as high as 103 W/m2K, which is almost 3 times of the case without
considering natural convection. Both the maximum values appear around 12 am. The comparison
shows that natural convection has taken a significant role in increasing the heat transferred
through window to indoor space.

Table 1 Thermophysical properties of the air, glass, curtain and PCMs

311

Fig. 6 Natural convection effect on the heat flux to indoor space with cloth curtain
In order to select the appropriate PCM type for the shutter, maximum and minimum
temperature variations are determined by solving the windows with a cloth curtain. The
temperature contours in the glass, air gap and the shutter are presented at eight time steps in Fig.
7. In these figures, the left side is subjected to outdoor boundary condition, while the right side to
indoor. The temperature contours indicate that the temperature varies significantly between 25 C
and 75 C, which are due to high variations of solar radiation and forced convection at the outdoor
boundary during the day. It can also be seen from Fig. 7 that the natural convection of the air has a
strong influence on the temperature contours, especially in the air gap. Due to the density
variations caused by temperature, hot air is accumulated at the upper region, while cold air is
accumulated at the lower region of the air gap. Temperature reaches high values between 9 AM
and 3 PM, where the solar radiation and ambient temperature reaches its peak. At 6 PM, the air
temperature drops dramatically because the solar-air temperature decreased to a low value.

312

Fig. 7 Temperature contours for windows with curtain during one day at different hours
(Air gap is 0.05 m)

The PCM melting temperature must be in the range of temperature variance shown in Fig.7.
By using PCM shutter, the inner surface temperature variation will become smoother. The
temperature difference between the inner surface and room temperature becomes smaller and
thus the heat flux into the indoor surface can be reduced. The energy consumption to keep the
room at a proper temperature can then be saved. Since the temperature of the curtain varies in a
specific range due to the daily solar heat variations, a proper PCM melting temperature must be
chosen carefully. If the PCM melting temperature is too high, the PCM inside the curtain may not
melt during the day cycle; if it is too low, the PCM may be in liquid state for the whole day. In both
cases, the latent heat during melting/solidification cannot be utilized. It is noticed from Fig. 7 that
the temperature distribution in the computational domain is between 25 C and 75 C. Therefore,
the melting temperature of PCM must be within this temperature range. By a first try, the paraffin of
RT28 and n-Eicosane are chose to investigate the indoor heat flux change, which correspond to a
10

313

melting temperature of 28 C and 37 C respectively. The thermoproperties of the PCM has been
listed in Table 1. The comparison of the heat flux into the indoor surface by using curtain or PCM
shutter has been shown in Fig. 8, during working hours from 7 am to 5 pm. It can be seen that with
filling n-Eicosane inside the shutter, the heat flux at the indoor surface is slightly lower than the
case with curtain during 7 am to 1 pm, while it is even higher from 1 pm to 5 pm. By checking the
liquid fraction during the day cycle, it is found that even at noon only a little bit of the n-Eicosane
melts, which means the melting temperature is too high. With filling RT28 inside the shutter, a
reduction of the heat flux into indoor space can be achieved from 7 am to 3 pm. Almost all the
RT28 melts around 1 pm. A small portion of the PCM at the shutter bottom cannot melt because of
the temperature variance in the vertical direction due to natural convection. By changing the
melting temperature to 29 C and 30C respectively, but with other thermoproperties same as
RT28, it is found that RT 29 has the best performance.

Fig.8 Heat flux at the indoor surface of the flass for different types of PCM
The heat flux is integrated using Eq.(9) to obtain the net heat flux during the working hours, 7
am to 5 pm; and the results are presented in Table 2. The net heat flux at the indoor surface
represents heat gain. The heat flux reduction is calculated for all examined PCMs, using the
following equation:

Heat flux reduction=

(10)

It can be seen from Table 2 that RT29 shutter is capable of reducing the net heat flux at the
11

314

indoor surface of the glass by 16.2% during the working hours, while RT28 and RT30 can reduce
by 13.5% and 13.9% respectively. On the other hand, the n-Eicosane almost has no effect on the
heat flux reduction, due to its high melting temperature.
Table 2 The effect of the PCM type on net heat flux during the working hours

CONCLUSION
In this paper, a PCM shutter model is proposed to decrease the solar heat gain through windows.
The model consists of a glass, a curtain/PCM shutter and an air gap in between. The temperature
distribution and heat flux into the indoor space has been investigated with cloth curtain and PCM
shutter under daily changing temperature conditions. It is found that the natural convection of the
air between glass and shutter takes a significant role in transferring the heat into the buildings. It is
noted that the heat flux reduction by using PCM shutter is influenced by melting temperatures. In
this study, a melting temperature of 29 C is found to have the best performance under the defined
parameters, with which the heat flux to indoor space can be reduced by 16.2%. In order to
optimize the design further, the methods either to depress the natural convection in the air gap or
to increase the PCM amount may be adopted.
ACKNOWLEDGEMENTS
This work is supported by the National Basic Research Program of China (973 Project:
2013CB228303).
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experimental investigation of a solar chimney model with uniform wall heat flux. Building and
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13

316

Modelling of Residential Lighting Load Profile Using Adaptive Neuro Fuzzy

Inference System (ANFIS)
*

O.M. Popoola , J. Munda , A. Mpanda

***

and P. Mlonzi

Electrical Engineering department, Tshwane University of Technology, Pretoria 0001, South Africa
***
ESIEE - Amiens Research Centre, 14 Quai de la Somme, 80082 Amiens France
CORRESPONDING author email: walepopos@gmail.com

ABSTRACT: Most practices currently adopted in modelling the presence of people in residential
houses do not reflect the complexity (randomness, non-linearity etc) of the impact occupants of
such buildings have on lighting loads. Hence the needs to contribute a methodology that will be
able look into such characteristics. This study entailed the use of adaptive Neuro Fuzzy inference
system (ANFIS) for estimation and prediction of the lighting load usage profile for energy and
demand side management initiatives. This is due to its ability to address and solve non-linear
issues, ambiguity and randomness of data. Three impact parameters were considered, namely
natural light, occupancy (active) and income level. The trapezoidal membership function was
applied during the training process of the ANFIS model. The ANFIS model development was
based on (i) 70% audit data for training; 30% audit data for checking and (ii) 100% audit data for
training; and metering data for checking. Result obtained showed a better correlation analysis and
root mean square error (RMSE) in contrast to the regression method model. R2 varied from 1.7%
to 24.6% accurately than the regression model. This shows that the ANFIS model has good
prediction accuracy capability than the regression mode and presents its output according to the
complex nature of light usage with respect to the three variables.
Keywords: Energy, ANFIS, Simulation Model Technique. Statistical Analysis, Load Profile
INTRODUCTION
Improper prediction and management of energy produced can result to high consumer demand
and ultimately may result to load shedding. Modelling techniques are quite imperative in the
provision of good estimation and forecast in daily optimal use and management of resources to
ensure consumers (customer) satisfaction. One of the measures for conservation, reduction and
management of electricity is lighting. It is an essential part of human daily activities especially in
households. South Africa has put in place programs along with incentives to encourage the use
and implementation of efficient technologies e.g. compact fluorescent lamps, light emitting diode,
etc. However, the impact of such exercises need to evaluated for daily demand profile, energy
management and power generation.
Lighting demand usage and impact evaluation of lighting technologies largely have been based
on fixed conditions where the presence of people and interactions of people are handled in an
entirely deterministic way in some simulation programs. several other practices currently adopted
in modelling lighting load in residential homes do not reflect the complexity of the occupant(s)
behaviour and environmental factors have in such buildings.
Methodology that have been used for prediction or estimation of energy usage and lighting load
include statistical methods, analytical methods, empirical methods and modelling methods. Studies
conducted using such methodologies include, modelling of household lighting related load (lighting,
heating, medium level household appliances-washing machine, refrigerator, etc) (Frackowiak &
Tomczykowski, 2007). The model development is inclined on the energy receivers at the
consumers ends being switched ON and OFF as a result of the sunrise and sunset hours. Other
factors included in the development are the way of living of the population, hours of waking up and
going to sleep. The work excluded non-energy receivers lighted related household (households
without ripple control or sensory devices) and was based on daily load waveforms in the MV/LV
transformer feeding the household-type consumers. The study does not articulate the behavioural
pattern of the consumers; neither was the model based on individual household appliances usage.
Aydinalp et al. in their work used the neural network (NN) to model residential energy consumption
that includes appliances, lighting, space heating etc(Aydinalp, Ugursal & Fung, 2002). The study
input determinants of the predictive model includes the effect of cooling degree-days, heating
degree-days, house construction and some social economic characteristics of the occupants. The
output of the study showed that the model was able to predict the average electricity consumption
of appliances such as fans/boilers pumps using natural gas or oil and propane-heated households,

317

central air conditioners and boiler pumps. However appliance, lighting and space cooling model
failed to give a rational estimate use to a higher degree of saturation.
A weighted evolving fuzzy neural network for monthly electricity demand forecasting was also
developed (Chang, Fan & Lin, 2011). This approach gave a better forecasting accuracy than the
other approaches (evolving neural network model, multiple regression analysis model, back
propagation model and winters exponential smoothing method. A methodology to consider the
behavioural factors in the usage conditions of certain electrical equipment in order for estimation of
electricity savings has been presented (Apolinrio et al., 2009). This paper focused on the relation
between energy savings and consumers behaviour. Gago, Garcia & Estralla, 2011 in their study
describe the design, development and application of a model capable of calculating electricity
consumption for lighting in the residential housing sector in Spain. This model use deterministic
and surveyed data to estimate the electricity consumption in different type of residential units in
Andalusia, Spain. This was to show the effectiveness of national policies in the improvement of
lighting efficiency in the residential building sector
Richardson et al, 2009 in their study developed a model capable of generating high-resolution
synthetic lighting demand. This switch on probability model is base on two physical input factors
namely outdoor irradiance and active occupancy within a dwelling.
Other studies include modelling of domestic lighting using stochastic bottom-up model based
on domestic occupancy patterns and daylight availability data (Widen, Nilsson & Wackelgard, 2009).
There were shortcomings in this approach, such as night time demand reproduction. Other
stochastic approaches for modelling domestic lighting demand include Stokes, Ryat and Lomas,
2004 model. The model was based on an half hourly data measured using 100 United Kingdom
homes and has the capability of generating load data of 1-min resolution (Stokes, Rylatt & Lomas,
2004).
In South Africa, the utility service company (Eskom) uses Measurement and Verification
lighting load program base on the International Performance Measurement and Verification
Protocol (IPMVP) for estimation of demand and quantification of savings realized from energy
efficiency investments (program). Purpose of the approach is to provide an agreeable impact level
of accuracy that a project has on the electricity usage of a client [Engelbrecht et al., 2008].
Due to human beings unpredictability, consumption routines, societal lifestyle as well as cost of
metering, lighting load model development have been relatively studied. This may be as a result of
electricity consumption being inevitably influenced by random factors, while demand time series
experiences highly non-linear characteristics (Zhu et al., 2011). Having this as a background, there
is the need to evolve a modelling technique that predict and estimate lighting load profile with such
characterization and factors (e.g. like occupant presence and effect on light usage, income and
comfort level , etc.).
A methodology that is capable of having such characterization such as non-linearity, variability
and probable in nature is the adaptive network-based fuzzy inference system (ANFIS). Studies
using ANFIS for good predictability include, discharge forecasting of the amount of water by a
stream water (River Kaduna)using these variables - rainfall, temperature, stage height and relative
humility (Folorunsho et al., 2012). Shibendu, 2005 in his study used ANFIS for prediction of surface
roughness in turning operation. The set of parameters were namely cutting speed, feed rate and
depth of cut. The bell shaped membership function achieved a slightly prediction accuracy than the
triangular membership function apart from their satisfactory prediction capability. A prediction
model for water reservoir management using ANFIS has been presented (Chang & Chang, 2006).
Result obtained showed that the ANFIS model is capable of high prediction accuracy and reservoir
water level forecasting for next three steps (hour) duration with a correlation coefficient of 0.99.
Another study using ANFIS was forecasting regional electricity loads which are very importance for
the management performance of the electricity industry (Ying & Pan, 2008). Using the mean
absolute percentage errors and other statistical results obtained ANFIS model has a better
forecasting performance in comparison to the regression model, support vector machines with
genetic algorithms, artificial neural network (ANN) model, recurrent support vector machines with
genetic algorithms (RSVMG) model and the hybrid ellipsoidal fuzzy systems for time series
forecasting (HEFST) model.
Studies carried out as discussed above have shown that human behaviour and environmental
climate could significantly change lighting usage in a residential dwelling within over a period monthly or yearly basis.
To demonstrate the applicability of the ANFIS in such instances (human and climatic activities),
a model for middle income lighting load having three input structures will be investigated. The
outline of the study consists of the ANFIS main network structure, the parameter estimating
algorithms, description of the main study group (middle income earners), available data, model
process design and strategy / development. Lastly, the result obtained is discussed and model
impact evaluated.

318

Adaptive neural fuzzy inference system

Due to the complexity of human behaviour and non-linearity of lamp usage; and climatic condition
activities, the prediction model will use a methodology known as the adaptive neuro fuzzy
inference system modelling which is well suited to mathematical analysis. ANFIS is a combination
of fuzzy and neural network. Neural networks (NN) are computational structured that perform well
when dealing with raw data and has the ability to learn its structure and adapt itself in an adaptive
manner however it is ambiguous to users (Firat & Gungor, 2007). Fuzzy logic approach on the
other hand is an artificial intelligence technique that deals with reasoning, using linguistic
information acquired from domain experts rather than numerical uncertainty but lacks the ability to
learn and finds it difficult to adjust to a new environment. ANFIS has the ability to learn and are
more transparent; organize network structure itself and adapts the parameters of the fuzzy system
to solve engineering problems such as estimation of a controlled reservoir water level (Chang &
Chang, 2006, Firat & Gungor, 2007]. ANFIS can simply be defined as a set of fuzzy 'ifthen' rules
with appropriate membership functions to generate the stipulated inputoutput pairs in the solution
of uncertain and ill-defined systems (Jang, 1993). The process of fuzzy inference involves
membership functions, fuzzy logic operators, and if-then rules. The procedure for mapping
computing consists of three sub-processes, fuzzification, aggregation, and defuzzification - Fig.1.

Determines how the

rules are activated and
combined

Output fuzzy set

fuzzification

Aggregation

Defuzzification

Fuzzy set of input variable

Activates the
linguistic rules

Interpretation of the
membership degrees of the
sets into specific decisions
or real values

Fig.1: ANFIS mapping

Structure of the ANFIS
This rule-based system consists of the three conceptual components namely (i) a rule base,
contains fuzzy if-then rules, (ii) a database which defines the membership function (MF) and (iii) an
inference system, combines the fuzzy rules and produces the result (Firat & Gungor, 2007).
Backward propagation algorithms and hybrid-learning algorithms methods are use for
determination of the membership functions, learning provision of the ANFIS and construction of the
rules.
ANFIS is a five layer structured architecture, with all five layer having a function in the
development of the model. In general ANFIS system has input layer, output layer, and hidden
layers that represent membership function and fuzzy rules. A typical three rule systems is shown
as follows:
Rule 1: if is A1, is B1 and is C1,
then
Rule 2: if x is A2, is B2 and z is C2,
then
Rule 3: if x is A3, is B3 and z is C3,
then
General rule being

Where , and represents our inputs which are fuzzy sets Ai, Bi, and Ci representing natural
lighting, occupancy and income. p, q, and z are the design parameters that will be determined
during the training process. For instance the input nodes i.e. first layer (
) has the following
inputs with a node function output.
( ) for

( )for

(1)

319

( ) for

is the input to node , and

is the linguistic label (high, middle, and small) associated with this
node function.
are the appropriate membership functions of
fuzzy sets.
Nodes in this layer represent the MF associated with each linguistic term of input variables. A
trapezoidal membership curve was chosen due to human behavioural inclination (occupancy and
natural lighting patterns) and historical lighting load metering profile for this investigation. The
trapezoidal membership is a function of a vector , and depends on four parameters a, b, c, and d,
as given by equation 2. a and d parameters locate the feet or base of the trapezoidal and b and c
the parameters locate the shoulder.
(
)
(
(
) )
(2)
The output nodes (fifth layer ( ))compute the overall output as the summation of all incoming
signals. The defuzzification process is used to transform each fuzzy rule results into a crisp output
as shown below. N represents the number of rules, i.e. 27 for three variables.

(
)

( )

( )

( )

(3)
The other layers include: second layer outputs is the firing strength ; third layer calculates the
ratio of ith rules firing strength to the sum of all rules firing strengths while the fourth layer
computes the ration of the firing strength and consequent parameters.

Model Process Design Strategy and Evaluation

The process design strategy shown in Fig.2 was applied in the model development strategy. For
the fuzzy light usage output design, three input variables natural light level, effective occupancy
(Active/Awake occupancy) and income of a household were applied
Usage Of light
Metering of
data

Acquired
data

Input
Fuzzy logic
controller

Analysing
of data

Natural light level

Active occupancy
Income

Acquired
data

Survey
Forms

Data
Collection

Fuzzy
membership
function
Extraction

Fuzzy rule
Extraction

Active Occupancy

Output

Controlling
of output

(a) Development strategy

Switch on events
Natural lighting level

Usage of Light
On/off

(b) Fuzzy Logic Lights Usage Output Design

Fig.2: Model development strategy and design

INVESTIGATION MATERIAL AND METHODOLOGY
ANFIS was applied to model a middle income earner 24 hour lighting usage profile in a locality in
Gauteng province, South Africa. A survey data of 102 buildings carried out within the locality in the
year 2010 as the input variables were used for both training and checking database (70%:30%
ratio). Logging database for a month period in November 2013 in two homes will also be used as
checking data to enhance the validation of the model development in this investigation. Three input
variables natural lighting (irradiance level), occupancy (active), and income earning were
considered in relation to environmental factors, daily activities and its social status within the
society.
The survey data gathered are mainly historical obtained during the Eskom M&V Compact
Fluorescent initiative (CFL) implemented in the country using physical door to door exercise. The
questionnaires format included the following key points: (i) Daily wake up time; switching ON lights
and room involved; (ii) Occupant(s) departure time - from home; (iii) Time the occupant returned

320

back home ; (iv) Food preparation time and room lights that are ON in the evening; (iv) Sleeping
time, (v) Bathing time (morning and /or evening).
The information gathered were interpreted using 0 or 1 format. These are then be weighted
between 0 and 1 for the input variables in respect of each houshold.
Metering (logging)
Onset Hobo UX90-005/-006 or UX90-005M/-006M loggers were attached to each indoor
luminaries, or set of luminaries on separate switch at the residential dwellings for the metering
aspect. These loggers monitors room occupancy up to 5 or 12 meters away as well as indoor light
changes with its integrated sensors. The data was downloaded and interpreted using the same
format interpretation as the survey data.
Sample size
This investigation was carried out using data sample size of 125 within the locality. However due to
incomplete information and the level of certainty that the characteristics of the data collected will
represent the characteristics of the population, only 102 buildings were used for this investigation.
Metering and Investigation Analysis
Occupancy
Results obtained from the data loggers installed in different rooms within the household dwellings
in relation to average lighting usage and occupancy is shown in Fig.3. Time of occupancy differs
as shown by the switch-on event occurrences. Most dwellings were occupied during the evening
period while there was little or no occupancy during the daytime. The findings were collaborated
by the historical survey questionnaires.
From the historical data and logged data, occupancy was represented using active room
occupancy in the model development. The assigned weights to reflect the active occupied room
within the dwelling which is expected to be variable throughout the day is shown in Table 1. This is
expected to contribute to effectual determination of the light usage / power demand at specific
intervals.
Natural Lighting
As the level of natural lighting (irradiance) changes during the day, the impact becomes visible on
lighting usage pattern (6). This shows that the use of artificial lighting in a dwelling relatively
depends on the level of natural lighting coming from outdoors. It can naturally be deduced that
there exist an inversely relationship between natural lighting irradiance and light usage in a
dwelling.
To simplify the investigation further, natural lighting was assigned weights as occupancy.
Different weights were assigned according to the level of natural lighting (irradiance level) within
24-hours period as follows: No Natural lighting = 0; Natural Lighting low = 0.3; Natural Lighting
medium = 0.7 and Natural Lighting high = 1.
Income
University of South Africa bureau of market research (2012) was used to group the range of
income within the middle income class. However as a result of occupants not been keen to provide
their earning, the buildings in terms of rooms were used to deduce their earning and social status
within the locality. The following group postulation was used:
Group 1 : Emerging Middle Income earners (EM) : 1- 6 rooms*
Group 2 : Realised Middle Income earners (RM) : 7 - above rooms*
*these is the total rooms within a dwelling and not the active room; this is quite different from the
occupancy weight ratio in Table 1.
For the income weight, the ratio of the two group in respect of the 102 historical data was use as
their weighting e.g. Group EM - 0.3; Group RM 0.7.

321

Fig.3: Occupancy and light usage; impact of natural lighting

Table 1: Rooms occupancy weights

Weight

No
room
occupi
ed

one
room
occupi
ed

Two
rooms
occupi
ed

Three
rooms
occupi
ed

Four
rooms
occupi
ed

Ho
use
fully
occ
upi
ed

Room(
s)

0.2

0.4

0.6

0.8

DEVELOPMENT OF THE ANFIS ESTIMATION MODEL

The model development was based on the following criteria as shown in Table 2.

S/No
1.
2.
3.
4.
5.
6.
7.

Table 2: ANFIS based modeling measure

Custom ANFIS
Variables
Membership Function
Trapezoidal Membership Function
Membership Function Number
Three
Hybrid Learning (gradient descent
Learning algorithms
and least square estimate)
Epoch size
40
Data size
102
Surgeon type system
First Order
Output (consequent parameter)
Linear

The modelling criterion implemented is expected to effectively tune the membership functions in
order to maximize the performance index and minimize error. Matlab version 7.10.0499 (R2010a)
Adaptive Neuro-Fuzzy Inference system (ANFIS) toolbox was employed. The model development
at the graphical user interface entailed, obtaining training and checking data, data sizing, data
partitioning and weighting , data set loading etc.
Using the procedures and investigative process, the information gathered in respect of the
training and checking data were interpreted using between 0 and 1 weight values on excel and
imported into the MATLAB m-files spreadsheet. The first three columns in the data set represent
the input variables while the fourth column indicates the output column for both the training and
checking data. The input variables as indicated above are the natural light (irradiance level),
occupancy (active room(s)) and income while the output is the light Usage. The data were inputted
as time series over a 24hr 1- minute interval. The model development is trained by loading the
training data containing the average usage pattern of the 102 buildings into the ANFIS Editor
graphical interface (GUI) from the MATLAB workspace. These data are arranged as column
vectors and the output data in the last column. This is expected to give an inference system. The
inference system generated consisted of the Fuzzy Inference System (FIS) editor, the Membership
editor, the Rule editor, Rule viewer and the surface Viewer (Fig 6 - Dialog box).

322

Fig.4: Surface Viewer Editor dialog box

With the use of the Matlab tool box ANFIS command lines, the estimated output values were
obtained and were tested using statistical evaluation such as Root Mean Square Error (RMSE),
Correlation coefficient (r) and Coefficient of determination (R2) analysis) in the Microsoft Excel
Statistical environment. Root Mean Square Error was deduced using equation 4 and 5.

(4)

While

(5)
The RMS and r value indicate the closeness one data series is to another in this case; R 2 is
referred to as the goodness of fit - certainty of prediction. The target (actual) output values and the
corresponding estimated output generated by the model are represented by the data series in this
investigation.
The employed training errors for the ANFIS are the mean squared error (MSE) of the training
data set at each epoch and the mean absolute percentage error (MAPE) of the checking data set
at each time. If yt is the actual observation for time period t and Ft is the forecast for the same
period, then MSE and MAPE are defined as in the equation below. These equations are also
employed for actual output and predicted output analyses.
(
)
(6)

(7)
VALIDATION OF THE MODEL
Model performance validation involves the consideration of the estimated output (predicted outputs)
performance with respect to the logged data (actual) using statistical analysis / inferences and
graphs plot.
RESULTS AND DISCUSSION
On completion of the fuzzy inferences procedures using the graphical user interface, the reliability
of the model needed to be examined. This was demonstrated using the procedural and statistical
measures for ten buildings (five buildings each for both EM and RM group) and the metering data.
The result obtained for the different household buildings are shown in Table 3. The accuracies of
the results were analyzed using statistical measures such as Correlation of determination (R2),
Root Mean Square (RMSE), Mean Absolute Error (MAE), Mean Absolute percentage Error (MAPE)
and the Pearson Coefficient.
From the result obtained/analysis carried out, it was observed that the ANFIS based model
predicted much better (R2 varied from 1.7% to 24.6% accurately than the regression model) in
terms of the applied factors - human behavioural tendency as shown in Table 3 for different
households and supported much widely by the metering data analysis. The error level (RMSE) and
MAE were lower than the Regression model analysis.

323

Table 4 shows the estimator output for the various models in comparison with the actual output
for the income groupings (EM & RM). The MAPE for EM estimator at morning standard/ peak
period, evening peak period and daily TOU period are as follows: 2.31%; 2.38% and 5.93% while
that of the regression model are 19.30%, 13.93% and 7.04% in comparison with the actual value
output. For RM estimator the values are 2.69%, 5.17% and 13.45% while the regression model of
17.15%, 12.71% and 25.73% in comparison with the actual value output. Fig. 7 and 8 gives an
insight into the correlation of determination of the EM and RM light usage estimator in comparison
with the actual output.
These results shows that the ANFIS model has the capability to estimate / predict load demand
profile of lighting usage (TOU) in middle income earner; and for savings evaluation or load
reduction. Furthermore, has a good prediction capability of middle income earner household
lighting usage pattern than the regression analysis as shown by the result obtained using metering
data as the checking or testing data Table 3.
In terms of data volume, the ANFIS computational (simulation) time was much better (relatively
5 minutes for 3 epochs) in comparison with the regression model analysis which takes close to 18
hours for 146880 one minute interval data.

Table 3: ANFIS and Regression performance comparison using statistical evaluation

Gro.
1.
RM

2.
RM

3. EM

4.
RM

5. EM

6. EM

No.
Building 1
ANFIS
Building 1
Regression
Model
Difference
Building 2
ANFIS
Building 2
Regression
Model
Difference
Building 24
ANFIS
Building 57
Regression
Model
Difference
Building 57
ANFIS
Building 57
Regression
Model
Difference

R2

RMSE

MAE

Pearson
Coeffici
ent

0,82

0,088

0,019

0,909

0,799

0,093

0,05

0,894

0,021

-0,005

-0,031

0,015

0,995

0,012

0,002

0,997

0,948

0,047

0,036

0,974

0,047

-0,035

-0,034

0,024

0,937

0,112

0,041

0,968

0,92

0,111

0,057

0,959

0,017

0,001

-0,016

0,009

0,83

0,092

0,022

0,911

0,762

0,104

0,055

0,873

0,067

-0,012

-0,033

0,038

Building 57
ANFIS

0,837

0,113

0,025

0,916

Building 57
Regression
Model

0,794

0,124

0,062

0,891

Difference

0,043

-0,011

-0,037

0,025

Building 63
ANFIS

0,982

0,04

0,014

0,991

Building 63
Regression
Model

0,779

0,14

0,069

0,883

Difference

0,203

-0,1

-0,054

0,108

%
Diff.(Pe
rforma
nce)

2,10%

4,70%

1,70%

6,70%

4,30%

20,30%

No.

7. EM

8.
RM

9.
RM

10.
RM

11.
EM

12.
RM

Building 87
ANFIS
Building 87
Regression
Model
Difference
Building 90
ANFIS
Building 90
Regression
Model
Difference
Building 91
ANFIS
Building 91
Regression
Model
Difference
Building101
ANFIS
Building101
Regression
Model
Difference
Metering
Data 1
ANFIS
Metering
Data 1
Regression
Model
Difference
Metering
Data 2 ANFIS
Metering
Data 2
Regression
Model
Difference

R2

RMSE

MAE

Pearson
Coeffici
ent

0,992

0,029

0,012

0,996

0,818

0,119

0,074

0,905

0,174

-0,09

-0,062

0,092

0,836

0,069

0,014

0,914

0,792

0,074

0,044

0,89

0,044

-0,005

-0,03

0,024

0,856

0,07

0,019

0,926

0,829

0,077

0,048

0,911

0,027

-0,006

-0,028

0,015

0,82

0,077

0,018

0,906

0,78

0,079

0,047

0,884

0,04

-0,002

-0,03

0,022

0,506

0,194

0,119

0,724

0,26

0,243

0,161

0,51

0,246

-0,049

-0,042

0,214

0,454

0,183

0,138

0,674

0,481

0,18

0,13

0,694

0,027

0,003

0,009

-0,02

Polyn
omial
R2

11.
EM
12.
RM

324

Metering
Data 1
ANFIS
Metering
Data 1
Regression
Model
Difference
Metering
Data 2 -

%
Diff.(Pe
rforma
nce)

17,40%

4,40%

2,70%

4,00%

24,60%

-2,70%

%
Diff.(Pe
rforma
nce)

0,61

0,261

34,90%

0,349
0,551

4,70%

ANFIS
Metering
Data 2
Regression
Model
Difference

0,504
0,047

CONCLUSION
Adept estimation of load profiles (lighting) is essential for demand side management and energy
efficient initiatives. Studies have shown that behavioural tendency in an environment as well as
income will bring about better prediction and estimation of load profile. Using the Matlab
V7.10.0499 (R2010a) environment, an ANFIS model based on three variables namely natural light,
income and occupancy (active) is presented
Results obtained as well as the application of statistical analysis statistical in terms of
performance and computational time shows that the ANFIS model has good prediction accuracy
than the regression model. R2 varied from 1.7% to 24.6% accurately than the regression model.
The model related to issues such as decrease in the number of occupancy in a household or
rooms un- occupancy do not specifically result to decrease artificial lighting using demand or vice
versa as shown by the output obtained by the estimators around occupancy. It has the ability to
learn from behaviour which often are non linear in nature and predict accordingly. This lay
credence that the variety of ways people occupy and interact with building(s) is needed for good
assessment of load usage and profile development.

0,8

0,7

0,7

0,6
y = 1,021x - 9E-05
R = 0,961

0,5

Weighting Output

Weighting Output

0,6

0,4
0,3
0,2

y = 0,909x + 0,011
R = 0,917

0,1

R = 0,929

y = 0,997x + 0,022
R = 0,908

0,4
0,3

y = 0,859x + 0,020
R = 0,925

0,2
0,1
0

0
-0,10,00

R= 0,939

0,5

0,10

0,20

0,30

0,40

0,50

0,60

0,70

-0,1 0,00

0,10

Actual weight Output

ANFIS

Regression

Linear (ANFIS)

0,20

0,30

0,40

0,50

0,60

Actual weight Output

Linear (Regression)

ANFIS

Regression

Linear (ANFIS)

Fig.6: RM Correlation Analysis

Fig.5: EM Correlation Analysis

Another issue around demand profile are the standard and peak periods (notably the morning
and evening standard). ANFIS is able to give better prediction accuracy as shown by the result
achieved. This will assist power generation and distribution planner in the management of energy
resources.
Based on the result obtained from the research work, it can be deduced that the ANFIS model
is a better modelling tool for the estimation / prediction of lighting load demand profile DSM & EE
(energy efficiency) project - middle income earner category, other income groups investigation
such as low income are is still on-ongoing.
ACKNOWLEDGEMENTS
This work was supported by Eskom, South Africa and Centre for Energy and Electric Power,
Tshwane University of Technology.
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APPENDIX
Table 4: EM & RM Light Usage Output TOU Estimator
Time,
GMT+01:00
12:00:42 AM
12:15:42 AM
12:30:42 AM
12:45:42 AM
01:00:42 AM
01:15:42 AM
01:30:42 AM
01:45:42 AM
02:00:42 AM
02:15:42 AM
02:30:42 AM
02:45:42 AM

NL
0
0
0
0
0
0
0
0
0
0
0
0

Emerging Medium (EM) Estimator; Weight @ 0.3

IN
@
Ac
ANFIS
Regression
Occ
EM
Output
Output
Output
0
0,3
0
-0,00043
0,02935
0
0,3
0
-0,00043
0,02935
0
0,3
0
-0,00043
0,02935
0
0,3
0
-0,00043
0,02935
0
0,3
0
-0,00043
0,02935
0
0,3
0
-0,00043
0,02935
0
0,3
0
-0,00043
0,02935
0
0,3
0
-0,00043
0,02935
0
0,3
0
-0,00043
0,02935
0
0,3
0
-0,00043
0,02935
0
0,3
0
-0,00043
0,02935
0
0,3
0
-0,00043
0,02935

326

Realised Medium (RM) Estimator; Weight @ 0,7

IN
@
Actual
ANFIS Regression
NL
Occ
RM
Output Output
Output
0
0
0,7
0
0,00125
0,03793
0
0
0,7
0
0,00125
0,03793
0
0
0,7
0
0,00125
0,03793
0
0
0,7
0
0,00125
0,03793
0
0
0,7
0
0,00125
0,03793
0
0
0,7
0
0,00125
0,03793
0
0
0,7
0
0,00125
0,03793
0
0
0,7
0
0,00125
0,03793
0
0
0,7
0
0,00125
0,03793
0
0
0,7
0
0,00125
0,03793
0
0
0,7
0
0,00125
0,03793
0
0
0,7
0
0,00125
0,03793

03:00:42 AM
03:15:42 AM
03:30:42 AM
03:45:42 AM
04:00:42 AM
04:15:42 AM
04:30:42 AM
04:45:42 AM
05:00:42 AM
05:15:42 AM
05:30:42 AM
05:45:42 AM
06:00:42 AM
06:15:42 AM
06:30:42 AM
06:45:42 AM
07:00:42 AM
07:15:42 AM
07:30:42 AM
07:45:42 AM
08:00:42 AM
08:15:42 AM
08:30:42 AM
08:45:42 AM
09:00:42 AM
09:15:42 AM
09:30:42 AM
09:45:42 AM
10:00:42 AM
10:15:42 AM
10:30:42 AM
10:45:42 AM
11:00:42 AM
11:15:42 AM
11:30:42 AM
11:45:42 AM
12:00:42 PM
12:15:42 PM
12:30:42 PM
12:45:42 PM
01:00:42 PM
01:15:42 PM
01:30:42 PM
01:45:42 PM
02:00:42 PM
02:15:42 PM
02:30:42 PM
02:45:42 PM
03:00:42 PM
03:15:42 PM
03:30:42 PM
03:45:42 PM
04:00:42 PM
04:15:42 PM
04:30:42 PM
04:45:42 PM
05:00:42 PM
05:15:42 PM
05:30:42 PM
05:45:42 PM
06:00:42 PM
06:15:42 PM
06:30:42 PM
06:45:42 PM
07:00:42 PM
07:15:42 PM
07:30:42 PM
07:45:42 PM
08:00:42 PM
08:15:42 PM
08:30:42 PM

0
0
0
0
0
0
0
0
0
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
0,3
0,3
0
0
0
0
0
0
0
0
0

0
0
0
0
0
0
0
0
0
0
0,2
0,2
0,4
0,4
0,4
0,4
0,4
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0,4
0,2
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0
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0,8
0,8
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0,8
0,6
0,6
0,6

0,3
0,3
0,3
0,3
0,3
0,3
0,3
0,3
0,3
0,3
0,3
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0,3
0,3
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0,3
0,3
0,3
0,3
0,3
0,3
0,3
0,3
0,3
0,3
0,3
0,3
0,3
0,3

0
0
0
0
0
0
0
0
0
0
0,2
0,2
0,4
0,4
0,4
0,4
0,4
0,4
0,4
0,2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0,2
0,2
0,2
0,2
0,6
0,6
0,6
0,6
0,6
0,6
0,6
0,6
0,6
0,6
0,6

-0,00043
-0,00043
-0,00043
-0,00043
-0,00043
-0,00043
-0,00043
-0,00043
-0,00043
-0,00043
0,181
0,181
0,394
0,394
0,394
0,394
0,394
0,394
0,394
0,181
-0,00022
-0,00022
-0,00022
-0,00022
-0,00022
-0,00022
-0,00022
0,000249
0,000249
0,000249
0,000249
0,000249
0,000249
0,000249
0,000249
0,000249
0,000249
0,000249
0,000249
0,000249
0,000249
0,000249
0,000249
0,000249
0,000249
0,000249
0,000249
0,000249
0,000249
0,000249
0,000249
0,000249
-0,016
-0,016
-0,016
-0,016
0,0739
0,0739
0,361
0,0739
0,616
0,616
0,614
0,614
0,614
0,614
0,614
0,614
0,614
0,614
0,614

327

0,02935
0,02935
0,02935
0,02935
0,02935
0,02935
0,02935
0,02935
0,02935
-0,006468
0,151
0,151
0,313
0,313
0,313
0,313
0,313
0,313
0,313
0,151
-0,011978
-0,011978
-0,011978
-0,011978
-0,011978
-0,011978
-0,011978
-0,02969
-0,02969
-0,02969
-0,02969
-0,02969
-0,02969
-0,02969
-0,02969
-0,02969
-0,02969
-0,02969
-0,02969
-0,02969
-0,02969
-0,02969
-0,02969
-0,02969
-0,02969
-0,02969
-0,02969
-0,02969
-0,02969
-0,02969
-0,02969
-0,02969
0,133
0,133
0,133
0,133
0,296
0,2958
0,458
0,296
0,5
0,5
0,518
0,518
0,68
0,68
0,68
0,68
0,518
0,518
0,518

0
0
0
0
0
0
0
0
0
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
0,3
0,3
0,02
0
0
0
0
0
0
0
0

0
0
0
0
0
0
0
0
0,2
0,2
0,2
0,2
0,4
0,4
0,4
0,4
0,4
0,4
0,4
0,2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0,2
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0,2
0,4
0,4
0,4
0,4
0,6
0,6
0,6
0,6
0,6
0,6
0,6
0,6
0,6
0,6
0,6

0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7

0
0
0
0
0
0
0
0
0,2
0,2
0,2
0,2
0,4
0,4
0,4
0,4
0,4
0,4
0,4
0,2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0,2
0,2
0,2
0,2
0,6
0,6
0,6
0,6
0,6
0,6
0,6
0,6
0,6
0,6
0,4

0,00125
0,00125
0,00125
0,00125
0,00125
0,00125
0,00125
0,00125
0,441
0,2
0,2
0,2
0,402
0,402
0,402
0,402
0,402
0,402
0,402
0,234
0,00078
0,00078
0,00078
0,00078
0,00078
0,00078
0,00078
0,00014
0,00014
0,00014
0,00014
0,00014
0,00014
0,00014
0,00014
0,00014
0,00014
0,00014
0,00014
0,00014
0,00014
0,00014
0,00014
0,00014
0,00014
0,00014
0,00014
0,00014
0,00014
0,00014
0,00014
0,00014
0,134
0,134
0,134
0,134
0,274
0,274
0,274
0,274
0,569
0,569
0,569
0,569
0,569
0,569
0,569
0,569
0,569
0,569
0,569

0,03793
0,03793
0,03793
0,03793
0,03793
0,03793
0,03793
0,03793
0,20065
0,15932
0,15932
0,15932
0,32205
0,32205
0,32205
0,31923
0,32205
0,32205
0,32205
0,15862
-0,0034
-0,0034
-0,0034
-0,0034
-0,0034
-0,0034
-0,0034
-0,02111
-0,02111
-0,02111
-0,02111
-0,02111
-0,02111
-0,02111
-0,02111
-0,02111
-0,02111
-0,02111
-0,02111
-0,02111
-0,02111
-0,02111
-0,02111
-0,02111
-0,02111
-0,02111
-0,02111
-0,02111
-0,02111
-0,02111
-0,02111
-0,02111
0,14161
0,14161
0,14161
0,14161
0,30434
0,30434
0,30434
0,30434
0,50839
0,50839
0,52492
0,5261
0,5261
0,5261
0,5261
0,5261
0,5261
0,5261
0,5261

08:45:42 PM
0
0,6
0,3
0,6
0,614
0,518
0
0,6
09:00:42 PM
0
0,2
0,3
0,2
0,432
0,192
0
0,2
09:15:42 PM
0
0,2
0,3
0,2
0,432
0,192
0
0,2
09:30:42 PM
0
0
0,3
0
-0,00043
0,02935
0
0,2
09:45:42 PM
0
0
0,3
0
-0,00043
0,02935
0
0,2
10:00:42 PM
0
0
0,3
0
-0,00043
0,02935
0
0
10:15:42 PM
0
0
0,3
0
-0,00043
0,02935
0
0
10:30:42 PM
0
0
0,3
0
-0,00043
0,02935
0
0
10:45:42 PM
0
0
0,3
0
-0,00043
0,02935
0
0
11:00:42 PM
0
0
0,3
0
-0,00043
0,02935
0
0
11:15:42 PM
0
0
0,3
0
-0,00043
0,02935
0
0
11:30:42 PM
0
0
0,3
0
-0,00043
0,02935
0
0
11:45:42 PM
0
0
0,3
0
-0,00043
0,02935
0
0
*NL=Natural Light; Occ=Active Occupancy; IN @ EM = Income &EM; IN @ RM = Income @ RM

328

0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7
0,7

0,4
0,2
0,2
0,2
0,2
0
0
0
0
0
0
0
0

0,569
0,441
0,441
0,441
0,441
0,00125
0,00125
0,00125
0,00125
0,00125
0,00125
0,00125
0,00125

0,5261
0,20065
0,20065
0,20065
0,20065
0,03793
0,03793
0,03793
0,03793
0,03793
0,03793
0,03793
0,03793

OPTIMAL APPLIANCE SCHEDULING FOR HOUSEHOLD ENERGY

MANAGEMENT
Ditiro Setlhaolo and Xiaohua Xia
Centre of New Energy Systems
Department of Electrical Electronic and Computer Engineering
University of Pretoria
South Africa

ABSTRACT
This paper explores a household appliance scheduling problem with a battery as an energy
storage system. A nonlinear integer optimization problem is formulated taking into account
appliance coordination constraints, scheduling inconvenience and is solved with Solving Integer
Constraint Problems (SCIP) solver from Matlab OPTI tool box. The results show that by optimally
scheduling appliances taking into account coordination, a cost saving is achieved through load
shifting and curtailment. The battery bank system promotes peak shaving and valley filling. By use
of the weighting factor, a consumer can choose how they favour inconvenience over the cost.
Keywords: Time of use, nonlinear integer optimization, Solving Integer Constraint Problems
(SCIP), Household appliance scheduling, Battery energy storage system.
INTRODUCTION
Energy consumption in the residential sector accounts for more than 18% of total electricity demand
in South Africa (Krueger, 2009; Greenpeace report 2012). This situation has an impact on the
environment, and on the user's budget. Residential Demand Response (RDR), a topic of increasing
importance to South Africa particularly in urban household, is an energy cost minimization appliance
scheduling problem. The literature extensively covers the definition and different types of demand
response programs and the reader is referred to the references (Xia et al., 2012; FERC report, 2010).
In this work we consider a time of use tariff structure used in South Africa. Deriving cost optimal
household scheduling model is a very involving task because it has to take into account dynamic
electricity prices, demand prediction, physical model of appliances and comfort constraints if any
(Saad al-sumati et al., 2014). The scheduling inconvenience which measures the disparity between
the baseline schedule and the optimal schedule, practical uncertainties involved and proper
coordination of appliances may also be taken into account. Literature provides basic household
appliance scheduling models (Rasteger et al., 2012; Chen et al., 2012; Wang et al., 2013; Sou et al.,
2011) as a mixed integer linear problem. In this work, we present this problem as an nonlinear integer
problem which is an improvement of our previous work (Setlhaolo et al., 2014).
Battery energy storage systems (BESS) are an option to provide peak shaving and valley filling of the
residential load profile (Chen Haiseng, et al., 2009; Leadbetter, et al., 2012). Other storage
technologies at distribution-grid such as systems and super-capacitors are mainly for peak power
supply/storage (Purvins, et al., 2013). Hydrogen based storage are known to have relatively high cost
and low energy storage efficiency hence adoption of this is comparatively low as compared to
conventional batteries. Electric vehicles and conventional batteries have over the years been used as
residential energy storage devices. Conventional batteries are a widely adopted technology both in
residential sectors and commercial application (Purvins et al., 2013). In this work a conventional
battery is used as an energy storage device because their modularity make them easily applicable to
installations at household level (Divya, et al., 2009). An additional benefit of energy storage is to
reduce peak-usage charges on the bill. Price-based demand response such as real-time pricing
(RTP), critical-peak pricing (CPP) and time-of-use (TOU) tariffs, give customers time-varying rates
that reflect the value and cost of electricity in different time periods. Armed with this information,
customers tend to use less electricity at times when electricity prices are high. During peak times
when electricity rates are high, a storage system may help save more money by supplying power
instead of the grid. Battery can be recharged during lower rate, off-peak hours (Chen et al., 2009).
Literature on micro grids consider the use of battery in conjunction with renewable energy and less
has been done on its use with the grid only at household level. The motivation of this study is the

329

need to optimally schedule household appliances in order to contribute towards reduction of energy
during peak times. Demand response programs are designed to be both fiscally and environmentally
responsible ways to respond to occasional and temporary peak demand periods. This paper presents
household energy cost minimization through appliance scheduling with battery as a grid connected
storage device in order to promote energy balance in the system network. The effect of using the grid
connected battery is analyzed.
PROBLEM DESCRIPTION
We consider a household under a time of use tariff with a grid connected battery as storage. The
layout of the problem is shown in Figure 1. The power flows are indicated by the arrows. The reader
will notice that the battery bank consumes power from the mains, this will happen during off-peak
times while it feeds the load during peak times.

Household appliances

Ac mains + battery bank

AC mains

Pm
Pd

Pb

Pb

Figure 1: System layout.

The optimal control problem of the household appliance scheduling with storage has control inputs as
the energy demand, the desired time of starting and completing tasks, appliance rated power, the
baseline schedule, time of use tariff price, battery input and output efficiencies as well as capacity.
The control decisions are the scheduling status of appliances, power from the mains and battery state
of charge which has battery charging and discharging power as control variables. The main objective
is to determine the minimum cost of scheduling these appliances during a time of use tariff taking into
account the appliance coordination and inconvenience level. This problem is of great importance
because worldwide research on demand response which main purpose is to reduce energy
consumption particularly during peak times, has opened new possibilities for advanced planning and
control of the supply and demand especially at residential level where appliance scheduling plays a
major role. A major benefit of scheduling is that users can compare the cost benefit among different
inconvenience levels that come with optimal solution against baseline schedule.
OPEN LOOP OPTIMIZATION MODEL
In this section, we formulate the mathematical model as an open loop optimization problem for
household appliance scheduling during a time of use tariff with battery as a storage. First we present
the energy cost model, then the battery model and finally we formulate the problem's overall objective
function incorporating the battery and scheduling inconvenience.
An electricity consuming household's objective is to minimize their electricity cost during a dynamic
price tariff. We have adopted this part of the model from our previous work (Setlhaolo et al., 2014).

330

min J e =

P u

t i ,t t

t 1 i 1

Pi 0, t 0, i 1,..., A, t 1,...T .
1, when appliance i is on at t;
ui ,t
0, when appliance i is off at t;
(1)
where the notations are listed and described in the nomenclature.
In a household scheduling problem there are three main types of constraints. These are; appliance
operation time, continuous operation, maximum cost or maximum energy constraint. Additional
constraints can be added such as coordination and comfort constraints if there are any (Setlhaolo
et al., Chen et al., 2013). Most literature leaves out the coordination and continuous operation to
reduce the complexity of the problem since they are nonlinear which we have included in our
model. The following constraints are formulated to the objective function (1).

a) Maximum cost.
A

P t C
i t

i 1 t 1

(2)
b) Appliance operation time
ei

i ,t

Ni , i

t di

(3)
b) Continuous operation
t ( ei Ni )

t di

ui ,t ui ,t 1 ui ,t Ni 1 1, i

(4)
b) Coordination constraint

i2 is off when i1 is on; ui1,t ui 2,t 1, 1 t T .

(5)
The coordination is between the dryer and washing machine.
The above model has been adopted from our previous work (Setlhaolo et al., 2014).
Battery model
In this work it is assumed that the household under study has a battery bank as storage device.
The battery is charged during off peak times and acts as energy source during peak hours. The
battery state of charge at any given hour is given by;

Et Et 1 c Pint t d Poutt t , 1 t T .
(6)
The battery dynamics are presented by (Durr et al., 2006; Tazvinga et al., 2013; Lu et al., 2005);

Et E (0) c

k 1

Pint t d

Pou t, 1 t T ,
t

k 1

(7)
where Et is the energy state variable, Et 1 is the state of charge in the previous time step,

E (0) E0 is the initial state of charge whereas c and d are the battery charging and discharging

efficiency.

t
k 1

Pint t is the battery energy during the charging period and

battery energy during the discharge period.

331

t
k 1

Poutt t is the

The objective is to minimize the cost of charging the battery. Therefore the cost objective function
for the battery is as follows;
T

min Jb

Pin t
t t

t 1

(8)
with continuous control variable Pint as the battery power during the charging period. The battery
is subjected to the following constraints.
Battery power capacity limits
The battery capacity limits provide the upper and lower bounds to the battery capacity.

E min Et E max , t 1,..., T .

(9)
Where the final state of charge;

E min (1 DOD) E max ,

(10)
DOD is the depth of battery discharge which literature gives a range of 30-50% of the battery
capacity.
To allow battery charge or idle when not discharging
In this work we include two additional constraints to the battery model. These two constraints
prevent the battery from attempting to charge while discharging and also allows the state of battery
the battery to be idle or discharge while not charging.

ub,t 1; ub,t 0
(11)
ub,t 0; ub,t 0 /1
(12)
Power balance
The power demanded by the load at time t should be met by both the battery during discharge
and the mains supply.

Pout ,t Pm,t PD,t , t 1,..., T .

(13)

Pout ,t is the battery power during discharge, Pm,t is the power from the mains and PD,t is the
aggregated power demanded by the appliances at time t . Without the battery, the supplied power
is equivalent to the energy consumed by the aggregated household load, Pm,t PD,t . The grid
power is also variable since it is dependent on the consumption and it lies within bounds,

Pmmin Pm Pmmax , t 1,..., T .

Inconvenience level
The inconvenience level is taken to be as the disparity between the baseline and the optimal
switching state which the consumer also seeks to minimize.
T

I :

(u

bl
i ,t

ui ,t )2 .

t 1 i 1

(14)
The overall objective

min

ui ,t , Pint , Poutt

J ( Je Jb ) I ,

(15)

332

where J e is the energy cost function as in (1), J b is the battery cost function during the charging
period, I is the scheduling inconvenience as in (14) and is a weighting factor which represents
how the consumer favors the scheduling inconvenience. The objective function (15) is subjected to
constraints (2)-(7) and (9)-(12).
The model obtained in (1)-(14) is a nonlinear integer open loop control model with control variables;
ui ,t as binary integer, Pint and Poutt as continuous variables. This problem is solved with
Solving Integer Constraint Problems (SCIP) solver from OPTI tool box. OPTimization Interface
(OPTI) Toolbox is a MATLAB toolbox for constructing and solving linear, nonlinear, continuous and
discrete optimization problems. SCIP is currently one of the fastest solvers for mixed integer
programming (MIP) and mixed integer nonlinear programming (MINLP). It allows for total control of
the solution process and the access of detailed information (SCIP n.d.).

A * x b, Aeq * x beq (linear constraints)

C ( x) 0, Ceq( x) 0 (nonlinear constraints)

min f ( x), s.t.,

lb x ub (variable bounds)
x

xi , x j 0,1

xi are the integer decision variables, x j are the binary decision variables and i j .
CASE STUDY
The case study of an urban household in South Africa with baseline scheduling obtained from a
one month week days collected data of appliance usage as in Table 1 for the considered
appliances with their rated power, average operation time and baseline switching status.
The tariff used is based on South Africa's TOU Homeflex structure for residential consumers. The
Homeflex 1 tariff has five charge components (Eskom, 2013) but for illustration purposes the
hourly charge is discretized into 10 minutes and only the energy charges for high demand period
are used for calculations as they are variable. The TOU tariff peak and off-peak data are;
t ( peak) )=R1.4452, t [7,10) [18,20) and t (off peak) = R1.4452, t [0,7) [10,18) [20,24).
Table 1: Appliance data
No. Appliance, i
1
2
3

Washing machine
Clothes dryer
Stove

Power
rating, Pi
3.0
3.3
3.0

Load type
Flexible
Night

Inflexible

Duration,
Ni (min)

Baseline
ui,tbl

50
50
30,50

107-112
113-118
37-40,106-111

Most literature states the lead acid battery as commonly used in households with discharge
efficiency of 100% and charging efficiency in the range 65-85% (Purvins, et al., 2013; Durr et al.,
2006). A point to note about the battery is that for it to work with an ac network, conversion and
inversion from ac to dc and dc to ac is required. It is acknowledged that there are some losses
within these electronics modules. However in this work the net efficiency has been used, that is,
converter/battery as charging efficiency and battery/inverter as discharging efficiency. The battery
bank maximum power output capacity is set by rule of thumb to meet 50% of the maximum load.
The minimum discharge capacity of 50% has been shown to sustain the lifespan of the battery
(Purvins, et al., 2013; Durr et al., 2006).
Table 2: Battery data
Battery capacity
c
d
DOD
Pout_max
Table 3: Other data
Daily maximum bill (C)

3.12kWh
75%
100%
50%
3.2kW

R50

333

Maximum
(Pm_max)

Power

from

mains

230V*60A*0.70=9.66kW

SIMULATION AND RESULTS

The first results are for the optimal commitment of appliances without the battery. These are
shown in Figure 2 and Table 4. Figure 2 shows optimal schedule of the three considered
appliances which results in a cost saving of 40% against the baseline cost. This is due to the load
shifting which results in peak reduction as shown in Figure 2 baseline load profile (L1) and optimal
load profile L2. The use of battery as a storage device shows a further reduction of energy cost by
4.8% as shown in Table 4. Figure 3 shows the battery SOC showing the charging, idling and
discharging phase. These are supported by the batterys power input and output. The input power
is indicated as positive while the discharging power is negative. The battery charged during off
peak and discharged during the evening peak. The load profiles in Figure 3 show the load profile
of the appliances only (L1) and appliances with battery (L2). A shaved evening peak is shown by
the difference in L1 and L2. The battery during charging periods adds to the household
consumption as shown in Figure 3 and promotes valley filling. Peak shaving and valley filling
balances the power system and thin in turn promotes system stability. The inconvenience with
=0.1 is 20.
.

On/Off status

1.5
Dryer
Washing machine
Stove

0.5

10

15

20

25

Time(hours)

Load profiles(kW)

8
L1
L2

6
4
2
0

10

15
Time(hours)

Figure 2: Simulation results of appliances without battery

334

20

25

SOC (kWh)

3.5

2.5

10

On status

1.5

20

25
Dryer
WashingM
Stove

1
0.5
0

Battery power (kW)

15
Time(hours)

10

15

20

25

Time(hours)

10

Pin
Pout

0
-10

10

15

20

Load profiles (kW)

Time(hours)

25

Shaving

4
L1
L2

Filling
2
0

10

15

20

25

Time(hours)

Figure 3: Simulation results with battery

Table 4: Energy cost saving
Baseline
Without battery
With battery

Actual cost (ZAR)

9.58
5.75
5.29

Cost saving (ZAR)

3.83
4.29

CONCLUSIONS AND FURTHER STUDY

In this study appliance scheduling optimization under a TOU tariff with battery as storage has been
studied. It is found out that the net energy cost realized by incorporating the battery is less than the
cost without the battery. This shows the potential of battery storage to help in daily energy cost
saving. The energy realized by optimal scheduling for this problem is 9.75%, from 10.25kWh to
9.25kWh whereas there is no energy saving by employing the battery; hence the battery promotes
system balance. More study involving the actual sizing and economic analysis of this battery needs
to be carried to obtain a more in-depth analyses. The model of the converter/inverter modules need to
be considered.

NOMENCLATURE

appliances index

Ni

duration of appliance

index of the time period

battery charging efficiency

total number of appliances

battery discharge efficiency

the price incentive at time t.

Time of use electricity price at time

the control horizon

sampling time

Pi

rated power of appliance

i kW

335

being on

t , R.

The maximum cost the consumer is willing to

incur, R.

di

the on time start of appliance

i.

ei

the on-time end of appliance

i.

u b ,t

battery switching status during discharge

EDt
time

soc

the initial state of charge of the battery at time

the minimum allowable battery bank capacity

kWh.

i at time

Emax

the maximum allowable battery bank in kWh.

ui , t

the switching status of the

at time interval

battery switching status during charging

period at time

E0

Emin

baseline on/off status of appliance

ub ,t

state of the battery at time

t.

ubbl,t
t

period at time

Et

energy consumed by aggregate appliances at

t.

i th appliance

t.

Pint

the battery charging power.

Poutt

the battery discharging power.

ac

alternating current

dc

direct current

state of charge of the battery

REFERENCES
Chen H., Cong T.N., Yang W., Tan C., Li Y. and Ding Y., Progress in electrical energy storage
system: A critical review, Progress in Natural Science 19(3)(2009)291-312.
Chen Z., Wu L. and Fu Y., Real-time price-based demand response management for residential
appliances via stochastic optimization and robust optimization, IEEE Trans., Smart Grid
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Durr M., A. Cruden, Gair S. and McDonald J.R., Dynamic model of a lead acid battery for use in a
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Morari M. and Lee J. H., Model predictive control: past, present and future, Computers & Chemical
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household-demand smoothening in electricity-distribution grids, Energy Conversion and
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Rasteger M., Firuzabad M. and Aminifar F., Load commitment in a smart home, Appl. Energy
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Setlhaolo D., Xia X. and Zhang J., Optimal scheduling of household appliances for demand
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Sou K., Weimer J., Sandberg H. and Johansson K., Scheduling smart home appliances using
mixed integer linear programming, in 50th IEEE, Decision and Control and European Control
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pp.1-6, 9-13 July 2012.

337

INDOOR HUMAN THERMAL COMFORT OPTIMAL CONTROL WITH SOLAR AIR

HEATER DRIVEN DESICCANT COOLING SYSTEM
Nan Wang *, Xiaohua Xia
Centre of New Energy Systems
Department of Electrical, Electronic and Computer Engineering
University of Pretoria, Pretoria 0002, South Africa
*wangnan@tuks.co.za

ABSTRACT
Human thermal comfort is an important concern in the energy management of commercial
buildings. The conventional desiccant cooling system can be used to maintain the required human
thermal comfort and consume abundant energy due to the utilization of electric heater. The
desiccant cooling system can be driven with a low temperature heat such as solar heat instead of
electricity. In this paper, an optimal human thermal comfort control model (OHTCM) for a solar air
heater driven desiccant cooling system is presented for the dehumidification and cooling of a
commercial building in summer seasons. The OHTCM has two objectives. The first objective of the
OHTCM is to minimize the predicted percentage of dissatisfied (PPD) which is the human thermal
comfort index, and the second objective is to minimize the energy consumption of the desiccant
cooling system. Model predictive control (MPC) strategy has the ability to handle constraints, being
able to use simple models and to change controls dynamically in terms of temperature, humidity
and air velocity changes, which makes it very practical to use in indoor human thermal comfort
control problem. Therefore, MPC strategy is applied to implement the optimal operation of the
solar desiccant cooling system during working hours of the commercial building. The OHTCM is
revised to apply the MPC strategy. To illustrate the practical applications of the MPC strategy, the
optimization of the desiccant wheel cooling system in a commercial building of South Africa is
studied. To show the benefit of MPC strategy, the comparison between MPC strategy and an
open loop control approach is studied in this paper.
.
Keywords: Human thermal comfort, Model predictive control, Solar air heater.
1. INTRODUCTION
In modern society people spend more than 90% of their time in the indoor environment, such as
commercial building. Indoor conditions have therefore significant implications for their health and
performance. Numerous studies have explored how building users perceive the indoor environment
and which conditions are considered to be comfortable. In the indoor environment, the human thermal
condition has been identified as a great influence on the comfort of building occupants. Therefore,
keeping indoor human thermal comfort steady at the correct level is very important to ensure peoples
health and performance in commercial buildings. Thermal comfort is that condition of mind which
expresses satisfaction with the thermal environment. When thermally comfortable, a building
occupant will wish to feel neither warmer nor cooler. Standard ISO 7730 provides the indices
predicted mean vote (PMV) and predicted percentage dissatisfied (PPD), which make it possible to
predict the mean thermal sensation and mean satisfaction with thermal conditions of a group of
people. To keep the correct level of thermal comfort of the commercial building in summer, the air
conditioning system will be used to supply the dehumidified and cooled air to the indoor environment.
For the dehumidification and cooling of commercial buildings in summer, existing research focuses
on developing new energy efficient equipment, applying different control strategy in traditional air
conditioning, or changing design parameters of dehumidifier. A model is presented to study the
humidity control effects of different control strategies in traditional air conditioning system during the
part-load condition (Chua KJ et al., 2008). The results show that some strategies are more effective
than others in sustaining acceptable indoor humidity and temperature under part-load condition, but
none of these strategies provides the best performance under full load conditions. The principles of
dehumidifier are studied (Mazzei P et al., 2005). The one class of chemical dehumidification is the
solid desiccant system, such as desiccant wheel. An optimal design problem of the desiccant wheel
is illustrated to maximize the performance of the desiccant wheel (Antonellis SD et al., 2010). The
optimal wheel speed and area ratio of dehumidification section to regeneration section are
determined under a range of regeneration temperatures from 60C to 150C. Subramanyam presents
a model of a desiccant wheel used for dehumidifying ventilation air (Subramanyam N et al., 2004).
The simulation result shows that the model has good accuracy in certain working conditions.
Panarasa presents an experimental validation of a simplified approach for a desiccant wheel model
(Panarasa G et al., 2010). This approach can be used to design the desiccant wheel and analyze its

338

performance easily. In the traditional desiccant wheel system, the electric heater is used to heat the
regeneration air, which consumes abundant energy. To reduce the energy consumption of the
desiccant wheel system, the renewable energy is used to replace the electric heater. Fong presents
six solar desiccant wheel cooling systems for the buildings in Hong Kong (Fong K.F. et al., 2010).
Compare to the conventional air conditioning system, up to 35.2% saving of year-round energy
consumption is obtained with the solar desiccant wheel cooling systems. Zahra H illustrates an
optimal design problem for the solar desiccant wheel cycle (Zahra H et al., 2012). The optimal solar
collector surface is determined by taking into account of design parameters and operating condition.
Model predictive control (MPC) strategy has the ability to handle constraints, being able to use
simple models and to change controls dynamically in terms of system changes, which makes it very
practical to use in various energy problems. Zhang J proposes an MPC approach to the periodic
implementation of the optimal solutions of a class of resource allocation problems (Zhang J et al.,
2011). Privara S presents the MPC strategy applied to the temperature control of a building (Privara S
et al., 2011). None of the existing research applies MPC strategies in the solar desiccant wheel
cooling system of commercial buildings to maintain a required indoor human thermal comfort.
In this paper, an optimal human thermal comfort control model (OHTCM) for a commercial building
with a solar desiccant wheel cooling system is presented. MPC strategy is applied to implement the
optimal operation of the solar desiccant wheel cooling system during working hours of the commercial
building. To illustrate the practical applications of the MPC strategy, the optimization of the solar
desiccant wheel cooling system in a commercial building of South Africa is studied. To show the
benefit of MPC strategy, the comparison between MPC strategy and an open loop control approach is
studied.
The layout of the paper is as follows. In Section 2, the backgrounds of the solar desiccant wheel
cooling system model, indoor thermal comfort model and power consumption model are recalled. The
formulation of OHTCM and the procedure of the MPC strategy can be found in Section 3. Section 4
illustrates the MPC strategy by a case study. The last section is concluding remarks.
2. BACKGROUND
The solar desiccant wheel cooling system to be considered in this paper is shown in Fig. 1. The
desiccant wheel is driven by an engine and moves at a given rotary velocity. The desiccant wheel is
divided into two sections: dehumidification section (position 1 to 2) and regeneration section (position
6 to 7). Water vapour of outdoor air is absorbed by the desiccant wheel when the outdoor air is
moving from position 1 to 2. After the indoor hot air is heated up by the heat exchanger (position 4 to
5) and solar air heater (position 5 to 6), the heated air is flowing through the desiccant wheel. Then
the water is desorbed out from the desiccant and the desiccant material is regenerated (position 6 to
7). The dehumidified air is pre-cooled through the heat exchanger. The pre-cooled air is cooled by the
cooling system when the pre-cooled air is flowing through the evaporator (position 2 to 3) and sent to
the building.
1
Outdoor air

3 Cooling 2
System
Building

DW

HX
4

Solar 6
Air
Heater

Figure 1 Typical desiccant wheel cooling system set-up

2.1 Desiccant wheel model
The temperature and humidity ratio of outlet air from the dehumidification section of the desiccant
wheel is calculated by using a mathematical model. The model is achieved by solving heat and mass
transfer equations as follows (Esfandiari Nia et al., 2006):

Has Hap Hap ,

(1)

f1 (ud ) f2 (Tap ) f3 (L) f4 (Tar ) f5 (Hap ) f6 (Dh ) f7 (uap ),

(2)

Tao g1 (ud )g2 (Tap )g3 (L)g4 (Tar )g5 (Hap )g6 (Dh )g7 (uap ),
(3)

339

where fi and gi are functions of desiccant wheel parameters that are as follows:

f1 (ud ) 0.0001ud2 0.0042ud 0.4474,

(4)

f2 (Tap ) 0.0001Tap2 0.0031Tap 0.8353,

(5)

f3 (L) 21.67L2 6.93L 1.34,

(6)

f4 (Tar ) 0.0001Tar2 0.0355Tar 0.4924,

(7)
2
f5 (Hap ) 592.77Hap
41.23Hap 1.283,

(8)

f6 (Dh ) 0.0572Dh3 0.0933Dh2 0.6139Dh 0.0922,

(9)

f7 (uap ) 0.0611uap 0.8376,

(10)

g1 (ud ) 0.0002ud2 0.0112ud 0.4201,

(11)

g2 (Tap ) 0.0001Tap2 0.0275Tap 0.7993,

(12)

g3 (L) 18.79L2 7.92L 1.75,

(13)

g4 (Tar ) 0.0004Tar2 0.1255Tar 0.6757,

(14)
2
g5 (Hap ) 594.48Hap
26.76Hap 3.79,

(15)

g6 (Dh ) 0.039Dh3 0.026Dh2 0.603Dh 0.0912,

(16)

g7 (uap ) 0.06uap 0.7973.

(17)
The effect of heat exchanger on the outlet air of heat exchanger must be calculated (point 2
and point 5). For this purpose a heat exchanger with effectiveness h can be used. The
effectiveness of heat exchanger can be written as:

Tao Tah
,
Tao Ti

(18)

Tac Ti
.
Tao Ti

(19)

340

The performance of solar air heater can be calculated as follows (Zahra H et al., 2012):

h 1.006T H(2501 1.805T ),

(20)

Asolar Sra mr (hpost hpre ),

(21)

Tah Ti
(T T )2
) 0.00053 ah i ,
Sra
Sra

0.514 6.31060(
(22)

2.2 Cooling system model

In this paper the cooling system consists of four components: Cooling tower, Evaporator, Watercooled condenser and Compressor. The schematic of the cooling system is shown in Fig. 2.
Dehumidified
Air
Water

Cooling
Tower

Condenser

Refrigeration
liquid

Evaporator
Dehumidified
and cooled
Air

Compressor

Figure 2 Typical water-cooled cooling system

The temperature of supply air from cooling system is determined by the performance of the
condenser and evaporator. To predict the performance of the condenser, the following equations are
used (Lee WL et al., 2008):

Qcond Cvl mw (Twl Twe ),

(23)

Qcond Qevp Wcomp ,

(24)

RNG (Twl Twe )

Qevp Wcomp
Cvl mw

(25)

Wcomp WR (b0 b1Ti b2Twe ),

(26)
2
2
2
Twe c0 c1toa c2toa
c3RNG c4RNG2 c5toaRNG c6toa
RNG c7toaRNG2 c8toa
RNG2 .

(27)

The performance of evaporator is expressed by the following energy balance equations:

Qevp aQsa (hao has ),

(28)

Qevp QR (a0 a1Ti a2Twe ).

(29)

341

Use Eqs (20) and (23)-(29), the temperature of outlet air from the cooling system is determined as
follows:

Tsa

has 2501Has
.
1.006 1.805Has

(30)
2.3 Human thermal comfort model
The human thermal comfort index PPD model includes four physical variables (indoor temperature,
air velocity, mean radiant temperature, and indoor humidity ratio), and two personal variables (clothing
insulation and activity level). In this paper only the indoor temperature and humidity ratio is calculated
based on the energy balance model. The rest variables of PPD model are assumed as the constant
values.
Humidity in the building comes from three sources. The first source is the water vapour of air
generated by infiltration from outdoor to indoor. Infiltration is the flow of outdoor air into a conditioned
space through doors, windows, cracks, etc. Infiltration is also known as air leakage into a building.
The second source is the water vapour of air generated by the human skin. The third source is the
water vapour added by the ventilation of solar desiccant wheel cooling system. Therefore, the
variation of humidity in the commercial building is given as follows (Diasty R et al., 1992):

dHi Qsa
Q
G

(Has Hi ) I (Ho Hi )
.
dt
V
V
aV
(31)
The variation of humidity in the commercial building without the ventilation of solar desiccant wheel
cooling system is calculated as

dHi QI
G
(Ho Hi )
.
dt V
aV
(32)
Eqs (31) and (32) are subject to the initial condition Hi (0) Hin (0), and solved by Matlab function
Ode23 with 360s step size.
The cooling load in the building comes from four sources. The first source is the heat gain due to a
temperature difference across the building elements. The second source is the heat gain due to the
infiltration from outdoor to indoor. The third source is solar heat gain. The fourth source is the internal
heat gain. Therefore, the cooling load in the commercial building during working hours is given as
follows.

Qcooling US(To Ti ) Qi aCa (To Ti ) Aw SoE Qlight Qpeople .

(33)
The cooling load in the commercial building during non-working hours is given as follows.

Qcooling US(To Ti ) Qi aCa (To Ti ) Aw SoE.

(34)
According to Eqs (20), (32) and (33), the indoor air properties at time t n are calculated as follows.

Mhindoor (tn ) Mhindoor (tn1 ) (Qcooling Qsa aCa (Tsa Ti ))(tn tn1 ),
(35)

Ti

hindoor 2501Hi
.
1.006 1.805Hi

(36)

342

2.4 Power consumption model

The primary power consumption of the traditional desiccant wheel cooling system includes the power
consumption of electric heater and the cooling system. In the solar desiccant wheel cooling system,
the electric heater is replaced by the solar air heater. Therefore, the primary power consumption of
the solar desiccant wheel cooling system includes the power consumption of the cooling system only,
which can be calculated as follows:

Pd (Wcomp

Qcooling
Qevp

wF )WR ,

(37)
3. OPTIMAL HUMAN THERMAL COMFORT CONTROL MODEL AND MPC STRATEGY
3.1 Optimal human thermal comfort control model
The commercial building to be studied in this paper has several storeys and each storey has the
same height, single glazing glass windows and concrete walls. The building has no other devices for
indoor moisture generation except the desiccant wheel cooling system. None of chimneys or any
other natural ventilation devices is applied in the building. It can be assumed that all the rooms of the
building have the same humidity ratio. The water absorbed and desorbed by walls and furniture are
ignored.
To keep the indoor human thermal comfort steady at the required level, the solar desiccant wheel
cooling system will remove the water vapour of air generated by infiltration and occupants and cool
the air. Therefore, the optimal human thermal comfort control model (OHTCM) has two objectives.
The first objective of the OHTCM is to minimize the PPD index and the second objective is to
minimize the power consumption of the solar desiccant wheel cooling system. Consider a fixed
time interval [t0 , tN ] , for example, five hours, one day or one week. The objective function of the
OHTCM is defined as follow:
N

min (1 )PPD(tm )2 Pd (tm )2 ,

m1

(38)
where [0,1]. is the weight factor that indicate the importance of sub objective. The following
constraints are used in the OHTCM.
(1) Indoor humidity ratio constraints: According to the solution of ordinary differential equation
(31), the indoor humidity ratio at time t m is given by

Hi (tm ) F1 (Hsa (tm ),Hin (tm ),Qsa (tm ),QI ,Ho (tm ),G).
(39)

(2) Indoor temperature constraint: For m [1,N], the indoor temperature at time t m should be
calculated by Eq (36).
(3) Initial indoor humidity ratio constraints: For m [1,N], the initial indoor humidity ratio at
time t m should be equal to the indoor humidity ratio at time tm-1 .
(4) Desiccant wheel constraints: The temperature of inlet air in the regeneration section at
time t m must be between the maximum and minimum specified temperature. The velocity of
inlet air in the dehumidification section at time t m must be between the maximum and
minimum specified velocity. The wheel speed at time t m must be between the maximum and
minimum specified speed. The temperature of regeneration air should be calculated by Eqs
(20) and (21).
(5) Cooling system constraints: The velocity of outlet air from the cooling system at time t m must
be between the maximum and minimum specified velocity. The water flow rate at
time t m must be between the maximum and minimum specified flow rate.

(6) PPD constraints: The PPD index at time t m should be calculated as follows:

PPD=100 95 exp(0.03353 f (Ti (tm ),Tmrt (tm ),v ,Hi (tm ),Ma ,Icl )4 0.219 f (Ti (tm ),Tmrt (tm ),v ,Hi (tm ),Ma ,Icl )2 ).
(40)

343

According to the description in Section 2, it can be assumed that Hap Ho . Therefore, the OHTCM is
defined as
N

min

uap ,ud ,mw ,Qsa

(1 )PPD(t
m1

)2 Pd (tm )2

s.t. Hi (t m ) F1 (Has (t m ), Hin (t m ),Qsa (t m ),QI , Ho (tm ), G),

PPD(tm )=100 95 exp(0.03353 f (Ti (tm ),Tmrt (tm ), v , Hi (tm ), Ma , Icl )4 0.219 f (Ti (t m ),Tmrt (t m ),v ,Hi (t m ),Ma ,Icl )2 ),
Pd (tm ) (Wcomp (tm )

Qcooling (tm )
Qevp (tm )

wF )WR ,

hindoor (tm ) 2501Hi (t m )

,
1.006 1.805Hi (tm )
hindoor (tm ) hini (t m ) (Qcooling (t m ) Qsa (t m )aC a (Tsa (t m ) Ti (t m )))(t m t m1 ) / M ,

Has (tm ) Ho (tm ) Ho (tm ),Ti (tm )

hini (tm ) hindoor (tm1 ), Hin (tm ) Hi (tm1 ),

uap ,lb uap (tm ) uap ,ub ,ud ,lb ud (t m ) ud ,ub ,Qsa ,lb Qsa (t m ) Qsa ,ub ,
mw ,lb mw (tm ) mw ,ub ,1 m N , [0,1].
(41)
The above OHTCM is a quadratic linear programming problem. It is solved by Matlab genetic
algorithm (GA) toolbox in this paper. The population size of the GA method is set as 100, and the
number of generations is chosen as 2000.
3.2 MPC strategy
In a commercial building, it is important to maintain the required human thermal comfort during daily
working hours, while the human thermal comfort at non-office hours is often ignored. Assume that the
period of daily working hours is from 8:00 to 18:00. Then the period of daily working hours is 10 hours,
and (38) can be rewritten as follow.
10

min (1 )PPD(tm )2 Pd (tm )2 ,

m1

(42)
The closed-loop objective function of MPC strategy is defined as follows.
10k

min

(1 )PPD(t

m1k

)2 Pd (tm )2 ,

(43)
Assume that the MPC strategy is applied in two days. When k 1, the control horizon of the MPC
strategy is over [t2 , t11 ]. The control interval [t2 , t10 ] is the working hours of the first day which is from
9:00 to 18:00, and the control interval [t10 , t11 ] is the first working hour of the second day. The whole
system is switched off during the nonworking hours. Therefore,

Hin (t11 ) F2 (Hi (t10 ),Qi ,G,Hu1 ),

(44)

hini (t11 ) F3 (Hi (t10 ),Ti (t10 ),Te1 ),

(45)
where F2 (Hi (t10 ),Qi ,G,Hu1 ) is given by the solution of ordinary differential equation (32),

F3 (Hi (t10 ),Ti (t10 ),Te1 ), is given by the solution of Eqs (34)-(36), Hu1 and Te1 are the vector of outdoor
humidity ratio and temperature during the first period of nonworking hours respectively. To apply the
MPC strategy, the OHTCM is revised as follows

344

10k

min

uap ,ud ,mw ,Qsa

(1 )PPD(t

m1k

)2 Pd (tm )2

s.t. Hi (t m ) F1 (Has (t m ), Hin (t m ),Qsa (t m ),QI , Ho (tm ), G),

PPD(tm )=100 95 exp(0.03353 f (Ti (tm ),Tmrt (tm ), v , Hi (tm ), Ma , Icl )4 0.219 f (Ti (t m ),Tmrt (t m ),v ,Hi (t m ),Ma ,Icl )2 ),
Qcooling (tm )
Pd (tm ) (Wcomp (tm )
wF )WR ,
Qevp (tm )
hindoor (tm ) 2501Hi (t m )
,
1.006 1.805Hi (tm )
hindoor (tm ) hini (tm ) (Qcooling (t m ) Qsa (t m )aC a (Tsa (t m ) Ti (t m )))(t m t m1 ) / M ,

Has (tm ) Ho (tm ) Ho (tm ),Ti (tm )

H (t )
m 11 0,
Hin (tm ) i m1
F2 (Hi (t m1 ),Qi , G , Hu j ) others ,
h
(t )
m 11 0,
hini (tm ) indoor m1
F3 (Hi (t10 ),Ti (t10 ),Te1 ), others ,
uap ,lb uap (tm ) uap ,ub ,ud ,lb ud (tm ) ud ,ub ,Qsa ,lb Qsa (tm ) Qsa ,ub ,
mw ,lb mw (tm ) mw ,ub ,1 k m 10 k , j m / 11, [0,1].
(46)
Now the following MPC strategy is obtained.
(1) Initialize the conditions of desiccant wheel cooling system and indoor environment at time
instant t 0 , and let k 0.
(2) Measure the outdoor temperature and humidity ratio at time instant t k , and solve the revised
OHTCM over time interval [tk1 , tk10 ] to find its optimal solution.
(3) The optimal solution of the revised OHTCM at time instant tk1 , is denoted by k1 Implement

k1 to control the solar desiccant wheel cooling system, let k k 1 and go to Step (2).
4. RESULTS AND DISCUSSION
Consider a commercial building in South Africa, the volume of the building is 500 m3 . During the
period
of
working
hours
and
nonworking
hours
it
can
be
assumed
that G 0.0060479 and G 0 respectively. The settings of the OHTCM are given in Table 1. The
properties of desiccant wheel cooling system are shown in Table 2.

Ma

Table 1 Settings of the OHCM

Value
1.0

Icl

1.2

QI

0.833

Qlb

Qub

uap ,lb

uap ,ub

ud ,lb

ud ,ub

15

mw ,lb

mw ,ub

0.5

0.8

Settings

Table 2 Properties of solar desiccant wheel cooling system

Parameters Value
70
Asolar

345

Ca

1007

Cvl
L
Dh

4186

QR

5.3

WR

1.256

a0

0.3167

a1

-0.0072

a2

0.0331

b0

0.3167

b1

-0.0072

b2

0.0331

c0

2.5264

c1

0.8566

c2

0.0028

c3

2.1849

c4

-0.0604

c5

-0.0745

c6

0.0004

c7

24.9447

c8

-0.00002

0.9

0.2
2.33

To illustrate the practical applications of the MPC strategy, the optimization of the solar desiccant
wheel cooling system in this commercial building during the two days is studied. In this case study,
assume that k1 in Step (3) of MPC strategy is replaced by k1 w[k] where w[k] is a noise vector
and each of its components is generated randomly by the Matlab uniform distribution function
rand(1)/20. The simulation results are shown in the Fig. 3 and 4. The indoor environment is varied
due to the variation of outdoor environment and the added noise in the optimal solution. The variation
of PPD during working hours of the two days is shown in Fig. 3.

Figure 3 Variation of PPD during working hours of the two days

As shown in Fig. 3, the maximal value of PPD is 9.99%. The minimal value of PPD is 5.19%. All the
values of PPD during working hours are less than the 10%, which mean that less than 10% people
feel uncomfortable in the building. Fig. 4 shows the variation of power consumption during working
hours of the two days.

346

Figure 4 Variation of power consumption during working hours of the two days
The blue line shows the variation of power consumption of solar desiccant wheel cooling system
under optimal human thermal comfort control. The red line shows the variation of power consumption
of solar desiccant wheel cooling system under MPC strategy with constant temperature and humidity
set point. As shown in Fig. 4, the power consumption of solar desiccant wheel cooling system can be
reduced while the optimal human thermal comfort control is implemented. To show the benefit of MPC
strategy, the comparison between MPC strategy and an open loop control approach is shown in Fig.
5.

Figure 5 Comparison between MPC strategy and the open loop control approach
In this comparison, assume that the control solutions of MPC strategy and the open loop control
approach at each hour are replaced by the control solutions plus a same noise vector respectively.
Each of components of the noise vector is generated randomly by the Matlab uniform distribution
function rand(1)/10. In Fig. 5, the solid line is the profile of indoor humidity ratio and temperature by
using MPC strategy. The blue dash line is the profile of indoor humidity ratio and temperature by
using open loop control approach. The red dash line is the profile of the humidity ratio and
temperature set point. As shown in Fig. 5, the control results of MPC strategy are better than the
results of the open loop control approach, which implies that MPC strategy can handle the variation of
the indoor environment better than the open loop control approach.
5. CONCLUSION
This paper presents an optimal human thermal comfort control model and provides the
corresponding MPC strategy to implement the optimal operation solution of the solar desiccant wheel
cooling system during working hours for commercial buildings. The optimization of the solar desiccant
wheel cooling system control in a commercial building of South Africa is studied to illustrate the
practical applications of the MPC strategy. The results show that the power consumption of solar
desiccant wheel cooling system can be reduced and the most of occupants can feel comfortable
while the optimal human thermal comfort control is implemented. The OHTCM established in this
paper considers only primary power consumption of solar desiccant wheel cooling system. A total
power consumption model and COP of solar desiccant wheel cooling system will be considered in the
future work.
NOMENCLATURE
Area of windows [m2]
Aw
Area of solar collector [m2]
Asolar

347

Ca
Cvl
Dh
E
G

h
hao
has
hindoor
hini
hpre
hpost
H

Hap
Has
Hi
Hin
Ho

Icl
L
mw
mr
M
Ma
Pd
Qcond
Qcooling
Qevp
Qi
Qlight
Qpeople
QR
Qsa
RNG
S

So
Sra

t
toa
Tac
Tah
Tao
Tap
Tar
Ti
To
Tsa
Twl
Twe

Specific heat of air [J kg-1 C -1]

Specific heat of water liquid [J kg-1 C -1]
Hydraulic diameter of the desiccant wheel channels [mm]
Irradiance of the direct solar beam [W m-2]
Moisture generation rate [kg s-1]
Enthalpy of air [kJ kg-1]
Enthalpy of outlet air in the dehumidification section [kJ kg-1]
Enthalpy of supply air [kJ kg-1]
Enthalpy of indoor air [kJ kg-1]
Initial enthalpy of indoor air [kJ kg-1]
Enthalpy of inlet air of solar air heater[kJ kg-1]
Enthalpy of outlet air of solar air heater[kJ kg-1]
Humidity ratio of air [kg kg-1]
Humidity ratio of inlet air in the dehumidification section [kg kg-1]
Humidity ratio of outlet air in the dehumidification section [kg kg-1]
Indoor humidity ratio [kg kg-1]
Initial indoor humidity ratio [kg kg-1]
Outdoor humidity ratio [kg kg-1]
clothing insulation [col]
Thickness of the desiccant [mm]
Mass flow rate of water [kg s-1]
Mass flow rate of air [kg s-1]
Mass of indoor air [kg]
Activity level [met]
Power consumption of solar desiccant wheel cooling system [kW]
Condenser heat transfer rate[kW]
Total cooling load [kW]
Evaporator heat transfer rate [kW]
Air flow rate of infiltration [m3 s-1]
Cooling load from lighting [kW]
Cooling load from people [kW]
Rated cooling capacity [kW]
Flow rate of supply air [m3 s-1]
Cooling tower temperature range [C]
Transmission area [m2]
Solar heat gain coefficient
Solar total irradiance [W m-2]
Time [s]
Wet-bulb temperature of outdoor air [C]
Temperature of inlet air of cooling system [C]
Temperature of inlet air of solar air heater [C]
Temperature of outlet air in the dehumidification section [C]
Temperature of inlet air in the dehumidification section [C]
Temperature of inlet air in the regeneration section [C]
Indoor temperature [C]
Outdoor temperature [C]
Temperature of supply air [C]
Temperature of condenser leaving water [C]
Temperature of condenser entering water [C]

348

uap
ud

U
V
v
Wcomp
WR
wF

Velocity of inlet air in the dehumidification section [m s -1]

Wheel speed [rph]
Heat transfer constant [W m-2 C-1]
Volume of building [m3]
Velocity of air close to body [m s-1]
Power input of compressor [kW]
Rated power input of compressor [kW]
Normalized fixed power inputs [kW]

Greek Letters
Weight factor

Desiccant wheel efficiency

h Heat exchange efficiency

Solar collector efficiency

-3
a Density of air [kg m ]
Subscripts
lb Lower bund
ub Upper bund
REFERENCES
[1] Antonellis SD, Joppolo CM, Molinaroli L. Simulation, performance analysis and optimization of
desiccant wheels. Energy and Buildings 2010; 42:1386-1393.
[2] Chua KJ, Chou SK, Ho JC. A model to study the effects of different control strategies on space
humidity during part-load conditions. Building and Environment 2008; 43:2074-2089.
[3] Diasty R, Fazio P, Bundaiwi I. Modelling of indoor air humidity: the dynamic behaviour within an
enclosure. Energy and Buildings 1992; 19:61-73.
[4] Esfandiari Nia F., Paassen D.V., Saidi M.H., Modeling and simulation of desiccant wheel for air
conditioning, International Journal of Energy and Buildings 38 (2006) 12301239.
[5] Fong K.F., Chow T.T., Lee C.K., Lin Z., Chan L.S., Advancement of solar desiccant cooling system
for building use in subtropical Hong Kong, International Journal of Energy and Buildings 38 (2006)
12301239.
[6] Lee WL, Chen H, Yik FWH. Modeling the performance characteristics of water-cooled airconditioners. Energy and Buildings 2008; 40:1456-1465.
[7] Mazzei P, Minichiello F, Palma D. HVAC dehumidification systems for thermal comfort: a critical
review. Applied Thermal Engineering 2005; 25:677-707.
[8] Panarasa G, Mathioulakisa E, Belessiotis V, et al. Experimental validation of a simplified approach
for a desiccant wheel model. Energy and Buildings 2010; 42:1719-1725.
[9] Privara S, Siroky J, Ferkl L, et al. Model predictive control of a building heating system: the first
experience. Energy and Buildings 2011; 43:564-572.
[10] Subramanyam N, Maiya MP, Murthy S. Application of desiccant wheel to control humidity in airconditioning systems. Applied Thermal Engineering 2004; 24:2777-2788.
[11] Zhang J, Xia X. A model predictive control approach to the periodic implementation of the
solutions of the optimal dynamic resource allocation problem. Automatica 2011; 47:358-362.
[12] Zahra H, Mohammad HS. Optimization of solar collector surface in solar desiccant wheel cycle.
Energy and Buildings 2012; 45:197-201.

349

Renewable And Clean Energy Technologies

350

PERFORMANCE ANALYSIS OF DIRECT METHANOL FUEL CELLS BY COATING

DIFFERENT PROPORTIONS OF CATALYSTS ONTO FUEL CHANNELS
a

Kao-Feng Yarn , Win-Jet Luo

b,*

, Yi-Hua Kuo , Guan-Chen Cheng and Chun-Nan Chen

Department of Electronic Engineering, Far East University of Technology, Tainan 744, Taiwan
Graduate Institute of Precision Manufacturing, National Chin-Yi University of Technology, Taichung
411, Taiwan
c
Department of Refrigeration, Air Conditioning and Energy Engineering, National Chin-Yi University of
Technology, Taichung 411, Taiwan
d
Department of Physics, Tamkang University, Taipei, Taiwan
*
email:wjluo@ncut.edu.tw
b

ABSTRACT
In this study, different proportions of catalysts including Pt, active carbon and Se were respectively
added onto anode and cathode channels made of PDMS (Polydimethylsiloxane) in order to
promote the fuel decomposing reaction in the fuel channels, and further enhance the output of the
DMFCs under various operating temperatures. The experimental results indicated that under the
same operating conditions, the performances of the DMFCs with catalysts added onto their
channels are always superior to that of DMFCs without catalyst added. It is found that there exists
a critical value of the adding proportions for every catalyst. While the adding proportions of catalyst
are less than the value, with the increase in the adding proportion of the catalyst on the fuel
channels, the output of the DMFCs can be greatly enhanced. However, while the adding
proportions exceed the value, the efficiency enhancements become unapparent. The
enhancement of 2% to 119% for the DMFCs with different proportions of catalysts added onto the
channels can be achieved under the operation conditions investigated.
Keywords: DMFCs, Polydimethylsiloxane fuel channel, Pt, Active carbon, Se.
INTRODUCTION
Direct methanol fuel cell (DMFC), which utilizes the methanol solution as a fuel, has been
considered as a promising power source for portable electronic devices. Methanol has high energy
density and specific, superior chemical stability, which are important for transport and storage.
Thus, compared with other fuel cell systems, the DMFC is a simple and compact system and
also a potential power source for portable applications. However, the major drawbacks of DMFC
including high production cost, catalyst and methanol crossover poisoning have motivated
researchers and industry engineers all over the world to study the DMFC. Finding and prepare
suitable catalysts to enhance the performance of DMFC and methanol tolerance is a crucial issue
for the development of DMFC.
For the studies of catalyst in DMFC, Wei et al. [1] developed a new electrode structure includes
a hydrophilic thin film and a traditional catalyst layer for direct methanol fuel cells. Their results
showed that the performance of a cell with the hydrophilic thin film was obviously enhanced and
the stability of the cell in a short-term life operation was also increased. Baranton et al. [2]
developed new electron conductive polymers stable under oxidative environment and with a high
doping capacity for using platinum alternative cathode catalysts in DMFC technology. Qiao et al.
[3] developed a new plating process for the formation of the cathode catalyst of a micro tubular
direct methanol fuel cell. By using this method, a thin porous layer of Pt electrocatalyst was firstly
bonded onto a tubular polymer electrolyte membrane by chemical reduction of Pt complex
impregnated in the membrane. Guo et al. [4] investigated the structural and surface features and
electrocatalytic properties of bimetallic PtRu/OCNF and PtRu/RCNF. The OCNF supported
catalysts give better performance than commercial catalysts when current density is higher than 50
mA cm-2 in spite of low methanol oxidation peak current density. Baglio et al. [5] used a low
temperature preparation procedure to modify the Pt catalyst with transition metals (Fe, Cu and Co).
Through adsorbed methanolic residues stripping analysis, the case of the PtFe system presented
a better methanol tolerance and an enhanced activity towards oxygen reduction. An improvement
of the DMFC single cell performance was also observed in the presence of PtFe catalysts. Wang
et al. [6] used Ketjen Black EC 300Jas an additive in the cathode catalyst layer to improve the
DMFC performance. The cathode catalyst layer with Ketjen Black EC 300J additive showed a
greater single cell performance than the cathode catalyst layer without any additive, especially in
the air-breathing mode. Choi et al. [7] developed a new type of Se/Ru catalyst called Se/Ru(aq)
and studied the methanol tolerance and the performance of the direct methanol fuel cell for the

351

catalyst. They indicated that the catalyst of Se/Ru(aq) was highly tolerant to methanol crossing
through the membrane (from the anode side) up to a feed concentration of 17 M. Compared to Pt
cathodes, the performance of Se/Ru(aq) is significantly better at high methanol concentrations.
Yao et al. [8] used a magnetron sputtering (MS) and metal-plasma ion implantation (MPII)
technique to prepare PtM/C catalyst. They indicated that the membrane electrode assembly for
PtNi/C, PtFe/C and PtCr/C catalysts can enhance DMFC cell performance, compared with
traditional Pt/C and PtRu/C.
This study aimed to investigate the output efficiency of DMFCs by coating different catalysts
on the fuel channels in order to promote the fuel decomposing reaction within the channels and
further enhance the output of the DMFCs. At present, the platinum is often used as catalyst in
MEA, but it is still expensive. In order to reduce the cost, this study used the catalysts of active
carbon and Se as the substitute added onto fuel channels, which have the similar effect and lower
price. The effect of adding proportions of the catalysts on the output efficiency of DMFCs was
investigated under different operating temperatures.

EXPERIMENTAL
Channel fabrication
In this study, the channel for DMFCs uses PDMS as substrate. The related injection molding
processes are described below:
(1) PDMS preparation: the silicone resin (Agent A) and the hardener (Agent B) are mixed in
weight ratio of 10:1, and then the mixture is uniformly mixed with different weight ratios of
catalysts; the total weight is 35 g. The PDMS is mixed with catalysts at different concentrations.
For the weight proportions of 0.03%, 0.06%, 0.09%, 0.29% and 0.34%, the additive weight
accounts for 0.01 g, 0.02 g, 0.03 g, 0.1 g and 0.12 g of total weight, respectively.
(2) Vacuum treatment: since the mixing of A and B agents in the previous step produces a
large amount of bubbles, the mixed PDMS is placed in the vacuum chamber for vacuum treatment
to completely eliminate the bubbles.
(3) Injection mold solidification and catalyst coating: the master mold is placed on a balanced
stage, and then the vacuumized PDMS is injected into the master mold (8cm x 8cm). The channel
area (3.5cm x 3.5cm) of the master mold is isolated by the self-made square glass plate before
injection, and then the PDMS with catalyst is injected into it. The PDMS without catalyst fills up the
exterior of the mold, and then the glass plate is taken out placed on the hot plate and baked at
70for 30-40 min, so as to complete the solidification of PDMS.
4) Turning mold: the solidified PDMS is removed from the master mold. The fabrication
channels of active carbon catalysts at different concentrations are shown in Fig. 1.

Figure 1 Channels of catalysts at different concentrations

Transparent cell
Fig. 2 shows the exploded view of the transparent DMFC test fixture designed and fabricated
for the visualization study in this paper. The MEA, which is detailed in the subsequent paragraph,
was sandwiched between two bipolar plates with a gasket onto either side of the MEA. This
assembly, including the bipolar plates and MEA, was clamped between two enclosure plates by
using eight M8 screw joints (each having a torque of about 12 KGF-CM). The active area of the
MEA adopted in this paper is 3.5cm3.5 cm, which consisted of two single-side ELAT electrodes
from E-TEK and a NafionR membrane 117. Both anode and cathode electrodes used carbon cloth
(E-TEK, Type A) as the backing support layer with 30% PTFE wet-proofing treatment. The catalyst
loading on the anode side was 4.0mgcm-2 with unsupported [Pt:Ru] Ox (1:1 a/o), while the catalyst
loading on the cathode side was 2.0mgcm-2 with 40% Pt on Vulcan XC-72. Furthermore, 0.8mgcm2
NafionR was applied to the surface of each electrode. The bipolar plates (shown in Fig. 2) were

352

made of 316 stainless steel plates with a thickness of 2.0mm in order to avoid corrosion. As shown
in Fig. 2, the rectangular bipolar plate consisted of two portions: the channel area and the
extension area. The channel area acted as the distributor for supplying fuel and oxidant to the
MEA. The parallel serpentine channels, having an area of 2.0mm2.0mm, were machined using
the wire-cut technology. The width of the ribs was 2mm.

Figure 2 Exploded view of the transparent DMFC test fixture.

Experimental procedure
The schematic of the experimental setup is shown in Fig. 3. Methanol solution was driven by a
squirm pump, which can precisely control the liquid flow rate from 3 to 15ml/min with an error of
2%. Before entering the cell, methanol solution was pre-heated to a desired temperature by
placing the methanol solution tank in a temperature controllable water bath. The mixture of gas
CO2 and unreacted methanol solution was drained from the cell and cooled down when passing
through a cooling system. The gas (CO2) produced at anode was separated from the methanol
solution tank and released to the atmosphere, while the unreacted methanol solution was recollected into a chemical liquid tank. Simultaneously, the ambient air with almost 80% oxygen as
oxidant was provided to the cathode side of the cell without humidification. The flow rate of oxygen
was controlled by an air mass flow regulator, which has an error of 5% of the full scale.
As shown in Fig. 3, when the MEA is activated, the electronic DC loader is connected to the
fuel cell by connecting the anode to the negative terminal and connecting the cathode to the
positive terminal. The 0.6V~0.2V load is given in constant voltage mode, the time for each interval
of 0.05V is several minutes, and the voltage and current are recorded. The I-P curve and I-V curve
are drawn, and the current density and power density distribution curves are worked out. All the
measurements of the DMFCs investigated were tested in an experimental chamber in which the
temperature and humidity can be controlled.

353

Figure 3 Schematic diagram of experimental apparatuses

RESULTS AND DISCUSSION

In the experiments, 10% of the methanol-water fluid concentration was injected into the
DMFCs with a flow rate of 10cc/min. Different weight percentages of catalysts were added onto the
PDMS channels of 2cm width, and the performance of DMFC was tested under different operating
temperatures (30, 40, 50, 60, 70), respectively
.
Performance of DMFCs with different weight percentages of Pt catalyst added onto fuel
channels
Table 1 indicates the maximum power densities and corresponding increment percentages of
the maximum power densities for the DMFCs with different adding percentages of Pt (platinum)
catalyst under different operating temperatures. From the table, it can be seen that the maximum
power densities of the DMFCs increase with the increase in the operating temperature at the same
adding percentage. At the same operating temperature, with a little adding Pt catalyst percentage
of 0.03% onto the fuel channels, the maximum power densities can be greatly enhanced,
especially at lower operating temperature of 30 and 40. The output enhancements of the
DMFCs result from promotion of the fuel decomposing reaction by the additive catalyst on
channels. Furthermore, from the table, it can be observed that there exists a critical value of
adding Pt catalyst percentage of 0.06%. While the adding percentages are greater than 0.06%, the
enhancements of the maximum power densities of the DMFCs become unapparent, because the
fuel decomposing reactions by the additive catalyst reach the toleration of MEA, which may cause
the performance deterioration of the DMFCs. For the DMFCs, the maximum power density can
reach a highest value of 21.5 mW cm-2 by adding Pt percentage of 0.09% at the operating
temperature of 70. In table 1, it also indicates the maximum power density increments of the
DMFCs in comparison to those of DMFCs without additive catalyst on the channels at the same
operating temperature. It can be seen that the maximum power density increment of 145.9% can
be attained in the case with 0.09% catalyst adding percentage at the operating temperature of 30
. Figure 4 illustrates the power density distributions of DMFCs with different percentages of Pt
catalyst added onto fuel channels at operating temperature of 70. It can be seen that the power
densities of the DMFCs with Pt catalyst added on fuel channels under various current densities are
always superior to those of the DMFC without catalyst added on channels. Furthermore, it can be
seen that while the adding Pt percentages are greater than 0.06%, the power density distributions
get close to each other. This can demonstrate that there exists a critical value of catalyst adding
percentage for performance enhancement.

Table 1 Maximum power densities and corresponding increment percentage of DMFCs with
different percentages of Pt catalyst added onto channels at different temperatures.
Temperature
30
Maximum
power
density
Percentage (mWcm-2)

40

50

60

70

Increment
percentage
(%)

Maximum
power
density
(mWcm-2)

Increment
percentage
(%)

Maximum
power
density
(mWcm-2)

Increment
percentage
(%)

Maximum
power
density
(mWcm-2)

Increment
percentage
(%)

Maximum
power
density
(mWcm-2)

Increment
percentage
(%)

0%

6.358

7.483

8.348

9.364

10.402

0.03%

13.356

110.1

15.208

103.2

16.505

97.7

18.274

95.2

19.658

88.98

0.06%

13.365

110.2

15.571

108.1

18.404

120.5

19.896

112.5

20.956

101.46

0.09%

15.636

145.9

16.89

125.7

18.81

125.3

20.13

114.9

21.5

106.7

Power density increment is defined as E X E P / E p 100 % , where E X is the maximum power density of a DMFC with
different percentage catalyst added on to channels, E P is the maximum power density without additive catalyst on channels at
the same operating temperature.

354

Power density / mW cm-2

Electrical potential / V

Current density / mA cm-2

Figure 4 Power density of DMFCs with different percentages of Pt catalyst added onto channels at
operating temperature of 70.

Performances of DMFCs with different weight percentages of active carbon catalyst added
onto fuel channels
In the cases of active carbon catalyst added onto fuel channels, as shown in Table 2, the
maximum power densities of DMFCs also increase with the increase in the operating temperature.
As shown in table 2, the performances of DMFCs with active carbon added are improved greatly
compared with those without catalyst added on channels. In the cases of 0.29% and 0.34% weight
percentages of active carbon catalyst added, the maximum power densities of the DMFCs can
reach 21.7 mWcm-2 and 21.61 mWcm-2 at 70, respectively. From table 2, it also can be seen
that, with the increase in the adding catalyst percentage, the performances of the DMFCs also
gradually increases due to promotion of the fuel decomposing reaction by the additive catalyst on
channels. However, while the adding percentages are greater than 0.29%, the maximum power
densities of the DMFCs decrease slightly, because the fuel decomposing reactions by the additive
catalyst exceed the toleration of MEA, which cause the cross over phenomenon and performance
deterioration of the DMFCs. Thus, there exists a critical value of 0.29% adding percentage for
active carbon catalyst. While the added percentages of the catalyst are less than the value, with
the increase in the adding percentage on the fuel channels, the output of the DMFCs can be
greatly enhanced. However, while the added percentages exceed the value, the efficiency
enhancements become unapparent, even deteriorating. From table 2, it also can be seen that at
the catalyst adding percentage of 0.29%, the maximum power density increment percentages of
the DMFC always superior to those of DMFCs with other adding percentages under the same
operating temperature. The maximum power density increment of 119.4% can be attained in the
case with 0.29% catalyst adding percentage at the operating temperature of 40 . Figure 5
illustrates the power density distributions of DMFCs with different percentages of active carbon
catalyst added onto fuel channels at operating temperature of 70. It can be seen that the power
densities of the DMFCs with active carbon catalyst added on fuel channels under various current
densities are always superior to those of the DMFC without catalyst added on channels.
Furthermore, it can be seen that while the adding active carbon percentages are greater than
0.29%, the power density distributions almost overlap to each other. This also demonstrates that
there exists a critical value of adding percentage for performance enhancement.

355

Table 2 Maximum power densities and corresponding increment percentage of DMFCs with
different percentages of active carbon catalyst added onto channels at different temperatures.
Temperature

30

Maximum
power
density
Percentage (mWcm-2)

40

50

60

70

Increment
percentage
(%)

Maximum
power
density
(mWcm-2)

Increment
percentage
(%)

Maximum
power
density
(mWcm-2)

Increment
percentage
(%)

Maximum
power
density
(mWcm-2)

Increment
percentage
(%)

Maximum
power
density
(mWcm-2)

Increment
percentage
(%)

0%

6.358

7.483

8.348

9.364

10.402

0.03%

6.747

6.12

8.023

7.22

8.694

4.14

9.667

3.24

10.64

2.29

0.06%

11.526

18.37

13.456

13

14.321

11.66

15.078

7.62

15.986

5.61

0.17%

8.91

40.1

11.873

58.7

13.538

62.2

13.819

47.6

14.598

40.3

0.2%

9.299

46.3

12.003

60.4

13.927

66.8

14.1

50.6

14.9

43.2

0.23%

10.489

65

11.592

54.9

12.651

51.6

14.014

49.7

14.468

39.1

0.29%

12.392

94.9

16.414

119.4

18.188

117.9

19.983

113.4

21.734

108.9

0.34%

11.267

77.21

13.408

79.18

16.371

96.12

18.728

100

21.605

107.7

Electrical potential / V

Power density / mW cm-2

Power density increment is defined as E X E P / E p 100 % , where E X is the maximum power density of a DMFC with
different percentage catalyst added on to channels, E P is the maximum power density without additive catalyst on channels at
the same operating temperature.

Current density / mA cm-2

Figure 5 Power density of DMFCs with different percentages of active carbon catalyst added onto
channels at operating temperature of 70.

Performances of DMFCs with different weight proportions of Se catalyst added onto fuel
channels
Table 3 indicates the maximum power densities and corresponding increment percentages of the
maximum power densities for the DMFCs with different adding percentage of Se catalyst under
different operating temperature. From the table, it can be seen that the maximum power densities
of the DMFCs also increase with the increase in the operating temperature. At the same operating

356

temperature, there still exists a critical value of adding Se catalyst percentage of 0.29%. While the
adding percentage of Se catalyst are less than 0.29%, the maximum power density of the DMFCs
also gradually enhance with the rising of catalyst adding percentage. While the adding
percentages are greater than 0.29%, the maximum power densities of the DMFCs decrease
severely due to cross over phenomenon of the DMFCs. For the DMFCs, the maximum power
densities can reach a highest value of 19.16 mWcm-2 by adding Se percentage of 29% at the
operating temperature of 70. From table 3, it also can be seen that at the catalyst adding
percentage of 0.29%, the maximum power density increment percentages of the DMFC always
superior to those of DMFCs with other adding percentages under the same operating temperature.
The maximum power density increment of 182.3% can be attained in the case with 0.29% catalyst
adding percentage at the operating temperature of 30. Figure 6 illustrates the power density
distributions of DMFCs with different percentages of Se catalyst added onto fuel channels at
operating temperature of 70. It can be seen that the power densities of the DMFCs with Se
catalyst added on fuel channels under various current densities are always superior to those of the
DMFC without catalyst added on channels. Furthermore, it can be seen that while adding
percentage of 0.29%, the output of the DMFC possesses a superior performance in comparison to
those with other adding catalyst percentages. This also demonstrates that there exists a critical
value of adding percentage for performance enhancement. Figure 7 illustrates the comparison of
power densities of DMFCs with corresponding critical values of adding catalyst percentages at
operating temperature of 70. The performance of the DMFCs with adding appropriate catalyst
percentages can be effectively enhanced. The DMFC with adding Pt catalyst possesses the best
performance among the DMFCs, but the differences between the DMFCs with Pt and active
carbon catalysts are not large. Owing to high price of the platinum catalyst, the substitute catalyst
of active carbon is recommended to be added on fuel channels for further performance
enhancement.

Table 3 Maximum power densities and corresponding increment percentage of DMFCs with
different percentages of Se catalyst added onto channels at different temperatures.
Temperature

30

Maximum
power
density
Percentage (mWcm-2)

40

50

60

70

Increment
percentage
(%)

Maximum
power
density
(mWcm-2)

Increment
percentage
(%)

Maximum
power
density
(mWcm-2)

Increment
percentage
(%)

Maximum
power
density
(mWcm-2)

Increment
percentage
(%)

Maximum
power
density
(mWcm-2)

Increment
percentage
(%)

0%

6.358

7.483

8.348

9.364

10.402

0.09%

11.03

73.5

13.18

76.2

14.29

71.2

14.954

59.7

15.351

47.6

0.14%

14.464

127.5

15.312

104.6

15.83

89.6

16.122

72.2

16.023

54

0.29%

17.95

182.3

18.19

143.1

18.77

124.9

18.92

102

19.16

84.2

0.43%

10.49

65

11.59

54.9

12.65

51.6

14.0138

49.7

14.468

39.1

0.57%

8.91

40.1

10.873

45.3

11.54

38.2

12.82

36.9

13.6

30.7

Power density increment is defined as E X E P / E p 100 % , where E X is the maximum power density of a DMFC with
different percentage catalyst added on to channels, E P is the maximum power density without additive catalyst on channels at
the same operating temperature.

357

Power density / mW cm-2

Electrical potential / V

Current density / mA cm-2

Electrical potential / V

Power density / mW cm-2

Figure 6 Power density of DMFCs with different percentages of Se catalyst added onto channels
at operating temperature of 70.

Current density / mA cm-2

Figure 7 Comparison of power densities of DMFCs with corresponding threshold percentage
values of catalysts added on fuel channels at operating temperature of 70.

CONCLUSIONS
This study investigated the enhancement effect of the output performance of DMFCs by
adding different weight percentages of catalysts onto fuel channels under different operating

358

temperatures. Three different kinds of catalysts, Pt, active carbon and Se, were respectively added
on the fuel channels made by PDMS material. It is found that the performances of the DMFCs can
be greatly enhanced by adding appropriate percentages of catalysts on the channels due to
promotion of the fuel decomposing reaction within the channels. However, there exist critical
values of the catalyst adding percentage for every DMFC investigated in this study. While the
adding percentages are greater than the corresponding critical value, the maximum power
densities of the DMFCs may decrease due to the limited toleration of MEA. In this study, the
highest maximum power density of 21.734 mWcm-2 can be obtained for the DMFC with 0.29%
active carbon catalyst at operating temperature of 70. In comparison to the maximum power
densities of the PDMS channel without catalyst at various operating temperature, the highest
maximum power density increment can be attained in the case of the DMFC with 0.29% Se
catalyst added on the channels at the operating temperature of 30. In this study, it is also found
that, in the cases of the DMFCs with the same adding catalyst percentage, higher maximum power
density increments usually can be obtained under lower operating temperatures, because lower
temperatures can retard the cross over effect in the DMFCs. The experimental results suggested
that adding appropriate percentage of catalyst in the channel is helpful to increase the efficiency of
DMFC. At present, the platinum catalyst is still expensive. In order to reduce the cost, catalyst with
the same effect but at lower price can be used as a substitute.
ACKNOWLEDGEMENT
This study is financially supported by the National Science Council under grant No. NSC 1012221-E-167-010.
REFERENCES
[1] Wei, Zhaobin, Suli Wang, Baolian Yi, Jianguo Liu and Likang Chen, 2002, Influence of
Electrode Structure on the Performance of a Dircet Methanol Fuel Cell. Journal of Power
Sources 106364-369.
[2] Baranton, S., C. Coutanceau, J.-M. Leger, C. Rouxb and P. Capron, 2005, Alternative cathodes
based on iron phthalocyanine catalysts for mini- or micro-DMFC working at room temperature.
Electrochimica Acta 51517525.
[3] Qiao, H., M. Kunimatsu and T. Okada, 2005, Pt catalyst configuration by a new plating process
for a micro tubular DMFC cathode. Journal of Power Sources 1393034.
[4] Guo, Junsong, Gongquan Sun, Qi Wang, Guoxiong Wang, Zhenhua Zhou, Shuihua Tang,
Luhua Jiang, Bing Zhou and Qin Xin, 2006, Carbon nanofibers supported PtRu
electrocatalysts for direct methanol fuel cells. Carbon 44 152157.
[5] Baglio, V., A. Stassi, A. Di Blasi, C. DUrso, V. Antonucci and A. S. Aric`o, 2007, Investigation of
bimetallic PtM/C as DMFC cathode catalysts. Electrochimica Acta 5313601364.
[6] Wang, Guoxiong, Gongquan Sun, Qi Wang, SuliWang, Junsong Guo, Yan Gao and Qin Xin,
2008, Improving the DMFC performance with Ketjen Black EC 300J as the additive in the
cathode catalyst layer. Journal of Power Sources 180176180.
[7] Choi, Jong-Ho, Christina M. Johnston, Dianxue Cao, Panakkattu K. Babu and Piotr Zelenay,
2011, Se-modified Ru nanoparticles as ORR catalysts Part 2: Evaluation for use as DMFC
cathodes. Journal of Electroanalytical Chemistry 662267273.
[8] Yao, Kuo-Shan, Ya-Chi Chen, Ching-Hsun Chao, Wei-Fan Wang, Shui-Yang Lien, Han Chang
Shih, Tien-Lai Chen and Ko-Wei Weng, 2010, Electrical enhancement of DMFC by PtM/C
catalyst-assisted PVD. Thin Solid Films 51872257228.

359

A Test Study On The Efficacy Of Four Times Series Models Involving Short
Memory, Long Memory And Harmonic Phenomena in Modelling And
Forecasting Solar Radiation Data
Edmore Ranganai
a

University of South Africa, Department of Statistics, Florida Campus, Private Bag X6, Florida 1710,
Roodepoort, Johannesburg, South Africa (Corresponding Author)
email: rangae@unisa.ac.za

ASTRACT
It is well-known that the radiation recorded at the earths horizontal surface is a mixture of
deterministic (extra-terrestrially) and stochastic components. Short memory and long memory
stochastic models have been used extensively at various sites in the world to describe, monitor,
forecast and generate solar radiation data series with some degree of success. These include the
Box-Jenkins Seasonal/Non-seasonal Autoregressive Integrated Moving Average (S/ARIMA)
stochastic models and the autoregressive fractionally integrated moving average (ARFIMA),
respectively. The other two classes of models which have not been employed, perhaps to the
same extent, are the extensions of the above two classes of models. These are harmonically
coupled SARIMA (HCSARIMA) models and seasonal autoregressive fractionally integrated moving
average (SARFIMA) processes, respectively. SARIMA models are coupled with a sinusoidal
predictor at determined harmonic (Fourier) frequencies to form harmonically coupled SARIMA
(HCSARIMA) models which capture the inherent periodicities (seasonalities) due to the diurnal
cycle. ARFIMA models are extended to seasonal autoregressive fractionally integrated moving
average (SARFIMA) processes so as to cater for the possibility of long range dependence in the
diurnal cycle. We carry out a test study on the efficacy of these models.
Key Words: Irradiance, Short memory, Long memory, Seasonality, Harmonic
1

Introduction

It is well-known that the global horizontal irradiance (GHI) data series recorded at the earths
surface is a mixture of deterministic (extra-terrestrially) and stochastic components due to the
unpredictability of the prevailing atmospheric conditions. Furthermore, these data series are also
dominated by the diurnal cycle. Due to the unpredictability of the solar resource, assessment and
forecasting of GHI for operational planning, switching sources, programming backup, and shortterm power purchases, planning for reserve usage, and peak load matching is of paramount
importance. The successful models used in this regard include the short memory Box-Jenkins
Seasonal/Non-seasonal Autoregressive Integrated Moving Average (S/ARIMA) (see e.g. Box and
Jenkins 1976) and long memory autoregressive fractionally integrated moving average (ARFIMA)
stochastic (see e.g. Tsekouras and Koutsoyiannis, 2014) amongst others.
The other two classes of models which have not been employed, perhaps to the same extent, are
the extensions of the above two classes of models. These are harmonically coupled SARIMA
(HCSARIMA) models and seasonal autoregressive fractionally integrated moving average
(SARFIMA) processes (see e.g. Palma, 2007), respectively. SARIMA models are coupled with a
sinusoidal predictor at determined harmonic (Fourier) frequencies to form harmonically coupled
SARIMA (HCSARIMA) models. The deterministic (sinusoidal predictor captures the inherent
periodicities (seasonalities) due to the diurnal cycle while the stochastic SARIMA models captures
the random fluctuation. The extension of ARFIMA to SARFIMA models caters for the possibility of
long range dependence in the diurnal cycle.
The ranges of the data series under study vary from about 5 minutes to as long as a day. Recently,
high resolution data series has (from about 1 minute to 60min) generated more interest amongst
researchers (see e.g. Badescu et al., 2008; Reikard 2009).
We carry out a test study on the efficacy of the above models on the GHI (from the PSP instrument)
data
from
the
Solar
Radiation
Research
Laboratory
(SRRL)
(see
http://www.nrel.gov/midc/srrl_bms ), recorded in W/m2 from January 1, 2011 to February 11, 2012.
The data series are averaged into hourly, 30-minutely and 10-minutely. In the next section a brief
overview of SARIMA models is given. In section 3 some frequency domain analysis techniques are
elaborated on leading to the construction of the HCSARIMA model. Some long memory aspects

360

and related models, i.e., ARFIMA and SARFIMA models are given in section 4. Analysis and
results are given in section 5 while conclusions are given in the last section.

SARIMA MODELS

In general a multiplicative

. model is specified as
,

(2.1)

(see e.g., Cryer and Chan, 2008), where

,
,
, and
,
are the seasonal AR, non-seasonal AR, seasonal MA and non-seasonal MA factors, respectively.
The operator, L is the backward shift operator such that LkYt = Yt - k , d and D are the integer
non-seasonal and seasonal order differences such that
and
for d D 1 , respectively where
is the seasonality. The
powers, PS , p , QS and q denote the seasonal AR, non-seasonal AR, seasonal MA and nonseasonal MA orders, respectively while the parameters
,
,
,
, ,
and ,
are real numbers. It is assumed that the error terms are white noise,
i.e.,
.
To apply the Box-Jenkins SARIMA model building procedure the data series must be weakly
(second-order) stationary, i.e., the mean and variance (auto-covariance) must be approximately
constant. The main tool used to establish the aspects of stationarity and to identify the short
memory Box-Jenkins SARIMA models is the sample auto-covariance function (ACVF) or its scaled
version, the sample auto-correlation function (ACF). In the Frequency Domain analysis models
spectral methods are used.

TIME SERIES IN THE FREQUENCY DOMAIN

In the Frequency Domain Analysis, the complementary function of the ACVF/ACF, the spectral
density function (spectrum) which is the Fourier transform of the ACVF (ACF) is the analytical tool.
Its sample estimator, the periodogram (Schuster, 1898), is used in practice, to study periodicities in
data. The periodogram can be computed efficiently using the Fast Fourier transform (FFT) (see e.g.
Chatfield, 2003). For a realization of a time series,

I ( p )
where

1
n

2 p
n

X ( p ) t 1 X t e
n

f p p 2

X t 1n , the periodogram is defined as

2
1
it p 2
n
X
e

X
(

)
,
t
k
t 1
n

it p

p 1,...,[n 2]

are

is the FFT and

[.]

Fourier

(3.1)

(harmonic)

frequencies

and

denotes the integer part. The frequency

is the number of cycles per unit time.

If a determined periodogram ordinate,

I ( p )

is statistically significant, then it accounts for

substantial variability in the data series. To account for this variability a sinusoidal function
evaluated at

p has to be included.

In the next subsection a brief overview on searching for periodicities in data using these frequency
domain techniques leading to the development of a model that describes the harmonic variation
and stochastic variation, viz., harmonically coupled SARIMA (HCSARIMA) model is outlined.

361

3.1 Determination of Periodicities and Construction of the HCSARIMA Model

If a time series is dominated by a periodic sinusoidal component with a known wavelength. Then
the natural model is
(3.2)
X t t R cos( pt ) t ,
where

variation ,

is the harmonic frequency of the sinusoidal variation,

is the phase and

{Zt } denotes

2 p
2
(equal to
) Eq.(3.2)
n
S
2
2
X t cos
t sin
t t ,
S
S

ordinate

where,

R sin

and

is the amplitude of the

a white noise process. At a significant periodic

can equivalently, be expressed as

(3.3)

R cos , t 0

and

S the seasonality. In practice a series may

contain multiplicities of periodicities and the generalized form of (3.4) becomes

Xt

(k cos k t k sin k t ) t .

(3.4)

k 1

Remark: Note that

has to be a harmonic (Fourier) frequency since ordinary least squares

(and maximum likelihood under the Gaussian assumption) estimators at different general
frequencies k and j are not independent because the sine-cosine and complex exponential
systems are complete and orthogonal only over Fourier frequencies
For the model (3.4), if in a periodogram analysis a particular intensity
test the hypothesis whether the parameters

and

I (g )

is largest one, we can

are indeed zero, at this frequency i.e.

H0 : 0 ({ X t }1n is white noise)

vs
H1 : 0 or 0 ({X t }1n contains a periodic component )
by making use of The Fisher's Kappa statistic (see e.g., Davis 1941) or the usual F-test statistic.
The Critical values for the Fisher's Kappa statistic can be found in Fuller (1976).
Thus combining Eq.(3.3) or (3.4) with a trend component, and Eq.(2.1) or Eq.(2.2) gives a
harmonically coupled SARIMA (HCSARIMA) model, viz.,

X t t cos pt sin pt P ( LS ) p ( L)(1 LS ) D (1 L)d Yt Q ( LS )q ( L) t .

(3.5)
At the strongest intensity (largest ordinate) the variability in the data series is described by a
sinusoidal function determined at p while that at minor seasonalities are allowed to be
described by a stochastic SARIMA model. In practice, these determined seasonalities might be
persistent, i.e., exhibit long range dependency. The class of models in the next section caters for
this phenomenon.
4

LONG MEMORY PROCESSES

The autoregressive fractionally integrated moving average (ARFIMA) process generalizes the
usual Box-Jenkins ARIMA models by allowing non-integer (fractional) values of the differencing
parameter and are useful in modelling time series with inherent long-range dependence (see e.g.
Granger and Joyeux, 1980; Hosking, 1981). In such series the rate of decay of the inherent
statistical dependence is much slower than the exponential decay typified by short memory (Box-

362

Jenkins) processes. Actually, the ACF of a long memory process typically decays at a hyperbolic
rate (Haslett and Raftery, 1989).
The general ARFIMA
process is defined by
(
)
(4.1)
where
and
are the autoregressive and moving-average operators, respectively with no
common roots and
is a white noise process. Then we can, of course, define
so that
is an ARMA
process. The ARFIMA process has the following
properties; it is stationary and invertible for
,0.5), for
, the ACF decays very slowly
and the spectrum typically diverges to infinity at frequency
, i.e.
indicating
strong long-range dependence, for
, the spectrum of the series is equal to zero at
indicating intermediate-range dependence and
is indicative of short memory.
Various techniques for the estimation of the long memory parameter have been developed in the
literature. These include use of the Hurst coefficient coefficient,
(Beran et al., 1994), i.e.,
, where
and Geweke and Porter-Hudaks 1983 semi-parametric procedure
based on frequency domain analysis, amongst others. It is on the later procedure that many later
techniques were based on (see e.g., Reisen, 1994 and Chen et al., 1994). The long memory
phenomenon might be persistent at seasonal lags. The remedy for this is the class of models
described in the next subsection.

4.1

Seasonal Fractionally Integrated Processes

The seasonal autoregressive fractionally integrated moving average process, denoted by

, is an extension of the
model (4.1) applied to a series
with seasonality of length
(see e.g. Brietzke et al., 2005 ). In a particular case where
, for a fractional values of the long memory parameter vector
,
the process is expressed as follows,
,
where

(4.1)

For all
both non-seasonal and seasonal filters can be computed via the binomial
expansion as follows,

( )

where
( )
and

is the gamma function. In general, the SARIMA model can be expressed as

,

where

(4.1)

d (1 L)d (1 Ls ) D .

called memory vector parameter,

| d D | 0.5 and | D | 0.5 , then X t is a stationary and invertible process with seasonal
frequency s [ , ]. The spectral density becomes unbounded and behave as
If

f X ( s ) 2 | s |2 D | 2sin

ANALYSIS AND RESULTS

363

|
s
2

2 d

,
0.

The PSP GHI (in W/m2) day time data series recorded from January 1, 2011 to February 11, 2012
was obtained from SRRL (see http://www.nrel.gov/midc/srrl_bms ). The hourly data series was
obtained as is, while the minutely recorded was averaged into 30-minutely and 10-minutely. Time
series plots of the data series show a slowly changing variance which warrants the logarithm
transformation. A negligible proportion of the 30-minutely and 10-minutely averaged series had
negative values. These were replaced with ones so to obtain zero values under logarithm
transformation.
5.1

Data Exploration

Variance non-stationarity in the data series can be easily deduced from a time series plot. Time
series plots of the raw data series with their logarithm transformed counter-parts are given in Fig. 1.
Hourly log transformed GHI

log of GHI

-5

400
0

GHI

800

Hourly raw data, GHI

1000

2000

3000

4000

1000

2000

3000

time, hourly

time, hourly

Ten minutely raw data, GHI

Ten minutely log transformed GHI

4000

4000

6000

4
2

log of GHI
2000

8000

2000

4000

6000

Thirty minutely raw data, GHI

Thirty minutely log transformed GHI

log of GHI

-4

400

8000

0 2 4 6

time, ten minutely

800 1200

time, ten minutely

GHI

-2 0

800
400
0

GHI

5000

10000

15000

20000

25000

time, thirty minutely

5000

10000

15000

20000

time, thirty minutely

Figure 1: Time series plots of hourly, 10-minutely and 30 minutely GHI respectively: RHS,
raw data series; LHS, log of GHI (in W/m2)
The plots show that the raw data series exhibit changing variance over time, hence a natural
logarithm transformation was applied. The resulting series are now covariance stationary.
The ACF of the now stationary logarithm transformed are shown in Fig. 2. Clearly, the ACFs are
statistically significant at far distant seasonal lags indicating inherent long-range dependence (long
memory) at these lags.

364

25000

0.4
0.0

ACF

0.8

Hourly log transformed GHI

50

100

150

200

300

400

Lag

ACF

-0.2 0.2

0.6

1.0

Thirty minutely log transformed GHI

100

200
Lag

ACF

-0.2 0.2

0.6

1.0

Ten minutely log transformed GHI

200

400

600

800

1000

Lag

Figure 2: ACF plots of hourly, 10-minutely and 30 minutely of log transformed GHI
respectively
The periodogram plots given in Fig. 3 also show larger spikes periodically indicating presence of
the long memory in the data series.

1e-02
1e-06

Periodogram

1e+02

Raw periodogram of log of Hourly GHI

0.0

0.1

0.2

0.3

0.4

0.5

0.4

0.5

0.4

0.5

frequency, f cycles per unit time

1e-02
1e-06

Periodogram

1e+02

Raw periodogram of log of Thirty minutely GHI

0.0

0.1

0.2

0.3
frequency, f cycles per unit time

1e-01
1e-04
1e-07

Periodogram

1e+02

Raw periodogram of log of Ten minutely GHI

0.0

0.1

0.2

0.3
frequency, f cycles per unit time

Figure 3: Periodogram plots of the log of hourly, 30-minutely and 10-minutely GHI,
respectively. Note that the periodicities are more visible in the hourly data as it has the
least number of observations.
The determined harmonics corresponding to these spikes (seasonalities) are given in Table 1. All
the three data sets exhibit strong long-range dependence as
.

365

Table 1: Some periodogram analysis for all three data sets

Period,

I (k )

60-min

0.100

0.628

10

1436.270

0.487

30-min

0.491

0.313

20

126.224

0.116

10-min

0.011

0.071

89

1148.720

0.200

The seasonalities were used in fitting seasonal models, i.e., all the models as all the models fitted
here have seasonality aspects.

5.2

Model Diagnostics

The models are assessed with respect to good description of the underlying data generating
process as well as prediction. Two Information Criteria, viz., Akaikes information criterion ( AIC )
and the Schwarzs Bayesian criterion ( SBC ) (Akaike, 1983; Schwarz, 1978) also known as the
Bayesian information criterion ( BIC ) are used to assess the former aspect. The lower the values
of these statistics the better the model is. The later aspect (prediction) is assessed using the Mean
Bias Error (MBE) in W/m2, and Root Mean Squared Error (RMSE) in W/m2. The formulations of
these forecasting measures are:

(Yt (l ) - Yt +l ) W / m2 ,

where

Yt +l

(Yt (l ) - Yt +l )2 } 1 2 W / m2
and

Yt (l )

are the actual and forecasted

l -steps ahead forecasted values,

respectively.
Both model description and model prediction accuracy measures are given in Table 2.

Prediction accuracy measure

MODEL

AIC

BIC (SBC)

MBE(in W/m2)

RMSE(in W/m2)

SARIMA

5230.855

5268.708

-0.222

0.597

HCSARIMA

5233.004

5308.741

-0.247

0.609

SARFIMA

-6157.571

18250.411

-0.195

0.547

SARIMA

21789.163

21853.161

HCSARIMA

27032.372

27117.716

-0.086

0.957

SARFIMA

-2557.253

51808.712

0.156

0.899

30-minutely

Scale
60-minutely

Table 2: Prediction errors for the fitted models

Model description measure

366

-0.287

1.457

10-minutely

SARIMA

31151.691

31217.350

-0.140

1.162

HCSARIMA

30766.654

30865.173

-0.433

1.398

SARFIMA

-5375.000

62595.000

-0.001

0.987

SARIMA models outperform HCSARIMA models with respect to the AIC and BIC criteria for both
60-minutely and 10-minutely series but the reverse is true for the 30-minutely series. SARFIMA
models are the best with rest to AIC but worst with respect to BIC in all cases.

The prediction picture is somewhat different. For the 60-minutely data series the SARFIMA model
is the best model with respect to both AIC and BIC followed by the SARIMA model. The SARFIMA
model remains the best model for the 30-minutely data series followed by the HCSARIMA model.
The 10-minutely data series gives a similar picture to the 60-minutely.

ACTUAL
SARIMA

SARFIMA

HCSARIMA

log of GHI

10 12

Hourly daytime GHI from 12 to 13 Feb 2012 2-days ahead forecasts

12 Feb 2012

13 Feb 2012
Hourly, daytime

8
6
4
0

log of GHI

10 12

30-minutely daytime GHI from 12 to 13 Feb 2012 2-days ahead forecasts

12 Feb 2012

13 Feb 2012
30-minutely, daytime

8
6
4
0

log of GHI

10 12

10-minutely daytime GHI from 12 to 13 Feb 2012 2-days ahead forecasts

12 Feb 2012

13 Feb 2012
10-minutely, daytime

Figure 4: Hourly, 30-minutely and 10-minutely 2-days out of sample forecasts, respectively
The graphical display of prediction picture shows HCSARIMA to follow a similar pattern.
6

Conclusions

Overall, there is no clear winner with respect all diagnostics. However, it is noteworthy that the
HCSARIMA and SARFIMA models outcompeted the already known to be successful SARIMA (see
e.g., Reikard, 2009) models in some respects. The inclusion of a sinusoidal (deterministic)
predictor seems to inflate the AIC and BIC criteria. Using just the major harmonic frequency in the
sinusoidal function helps to minimize this undesirable effect. The fact that the SARFIMA model
outperforms the other two models with respect to AIC and BIC is welcome. Further, graphically the
HCSARIMA and SARFIMA more or less follow a similar pattern. So these two models are likely to
be plausible proposals for distant ahead forecasts, a short coming of the short memory BoxJenkins SARIMA models as they give unacceptable errors for distant horizon forecasting such as
for more than 2 hours in the hourly case and 2 days in the daily case (Voyant et al., 2013). This
competitive advantage may come from the fact that these two models are able to capture the
diurnal cycle better. Further, building HCSARIMA models via frequency domain analysis (not used
in Box-Jenkins SARIMA methodology) enables seasonalities to be known apriori.

367

ACKNOWLEDGEMENT
Special thanks go to the Solar Radiation Research Laboratory for providing data.

NOMENCLATURE
GHI

global horizontal irradiance, W/m2

SARIMA

seasonal autoregressive integrated moving Average

HCSARIMA

harmonically coupled SARIMA

ARFIMA

autoregressive fractionally integrated moving average

SARFIMA

seasonal ARFIMA

ACVF

auto-covariance function

ACF

auto-correlation function

FFT

fast fourier transform

AIC
BIC
MBE
RMSE

Akaikes information criterion

Bayesian information criterion
mean bias error, W/m2
root mean squared error, W/m2

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369

THE SOLAR ENERGY POTENTIAL OF SOUTH EASTERN ANATOLIA REGION IN

TURKEY AND THE POTENTIAL USE OF DEGREE
Dilan ALP
Energy Systems Engineering Department, University of rnak
73000 rnak, Turkey
dilanalp79@gmail.com

ABSTRACT
The energy consumption and environmental pollution have turned out to be a serious
problem. Thus, the sustainable energy development of the renewable energy sources such as
solar, wind and solar-hydrogen are accepted as one of the most fruitful and effective solution
to prevent environmental pollution. Therefore, it is of great importance for Turkey to make use
of its local energy resources more effectively, including its solar energy potential.
Turkey is geographically located (36-42N latitudes) in a useful position for the solar power in
the South Eastern of Europe and the Mediterranean. South eastern Anatolia regions
geographical location is highly favourable for the utilization of solar energy and the highest
average sunshine duration along with the highest average solar radiance total followed by the
Mediterranean and the Eastern Anatolian regions. In addition Southeast Anatolia Region has
a significant renewable energy potential particularly in solar energy field. However, the
potential of this region have, thus far, not been used efficiently.
In the present article gives an overview of solar energy potential to improve the
competitiveness of the Southeast Anatolia Region in a sustainable and socially equitable
manner by improving the capacity for better utilization of solar energy resources and by
increasing the energy efficiency in the Southeast Anatolia Region.
Keywords: Solar Energy, Energy Efficiency, South East Anatolia Region.
INTRODUCTION
Energy is therefore essential to life, and the quantity of energy consumed per capita can be
used as one indicator of a country s level of development (Kaygusuz et al., 1999). Solar
energy, being the oldest energy source used by mankind, is the cleanest and most abundant
one among others. Solar power is one of the most promising and more predictable than other
renewable sources and less vulnerable to changes in seasonal weather. Whereas, generation
of power from other renewable sources is limited to sites where these resources exist in
sufficient quantities and can be harnessed, solar energy can produce power at the point of
demand in both rural and urban areas (Rizwan et al., 2010).
Turkey is an energy importing country; more than half of the energy requirement has been
supplied by imports (Bilgen et al.,2008, Kaygusuz 2009). Oil, coal and gas have the biggest
share in total primary energy consumption. Turkey, with its young population and growing
energy demand per person, its fast growing urbanization, and its economic development, has
been one of the fast growing power markets of the world for the last two decades. It is
expected that the demand for electric energy in Turkey will be 573 billion kW h by the year
2020 and 760 billion kW h by the year 2030 (IEA, 2009, DPT., 2006). Turkeys electric energy
demand is growing about 4%6% yearly due to fast economic growing.
The South-Eastern Anatolia Region has political, economic, commercial and strategically
importance as well as religious due to the fact that it has been used as settlement, and hosted
for divine religions. This region is on the historical Silk Road, and Turkey part of the
Mesopotamia, which means to the land between two rivers in Latin, composed of fertile soil
and located in a geographical place where the energy resources roads crosses. (A. Akpnar et
al., 2013) This (GAP) region comprises nine provinces (Adiyaman, Batman, Diyarbakir,
Gaziantep, Mardin, rnak, Siirt, Sanliurfa and Kilis) in South-eastern Turkey, bordering Iraq
2
and Syria, and covers about 75193 km of land which corresponds to about 10% of the total
area of Turkey. The GAP region is the richest region of the country in terms of its coal as well
as its, oil, asphalt, asphaltites reserves. in this region at the beginning of renewable energy

370

sources of solar energy as well as hydro energy potential is highest in the country. In this
study, the solar energy potential of this region will be presented.
Turkeys Geographical Location And Solar Energy Potential
Turkey has abundant solar energy resources, as it is located in a sunny belt between 36 and
42N latitudes. The natural energy potential of the country is estimated to be 1.3 billion tons of
oil equivalents (15,120 TWh) .Most of these areas are suitable for developing solar energy
power systems. The annual average solar radiation of Turkeys larger part and the total yearly
radiation period have enough potential for solar energy applications. (General Directorate of
EIE)
Turkeys average annual sunshine duration is 2640 h (7.2 hours/day) and average solar
intensity 3.6 kWh/mday (Table 1.). Despite this potential, in todays Turkey, the solar energy
is generally used for heating, cooling and to get hot water for buildings. The usage for getting
hot water is the most common form of benefiting from solar energy.
Table 1. Monthly Average Solar Potential of Turkey (General Directorate of EIE)
Months
Monthly Total Solar Energy Sunshine Duration
2
2
(Kcal/Cm -Month) (Kwh/M -Month)
(Hours /Month)
January
4,45
51,75
103,0
February
5,44
63,27
115,0
March
8,31
96,65
165,0
April
10,51
122,23
197,0
May
13,23
153,86
273,0
June
14,51
168,75
325,0
July
15,08
175,38
365,0
August
13,62
158,40
343,0
September 10,60
123,28
280,0
October
7,73
89,90
214,0
November
5,23
60,82
157,0
December
4,03
46,87
103,0
TOTAL
112,74
1311
2640
2
2
AVERAGE
308,0 cal/cm - 3,6 kWh/m -day
7,2 hours/day
day
Turkey is a well-suited market for the usage of photovoltaic energy. (Dundar et al., 2002,
General Directorate of EIE)The main solar energy utilization in Turkey comes from flat plate
collectors in the domestic hot water systems. Flat plate solar collectors can be seen at the top
of a residential buildings roof with a water tank almost in every region especially in the
southern and western regions even in the villages. The electricity generation from the solar is
realized by photovoltaics (PV) and solar collectors. Unfortunately, PVs have high installing
costs; hence, an economical usage of them is not available today. In Turkey, only the Ministry
of Environment and Forestry (forestry observation towers), Turkish Telecommunication
Companies (transfer stations), the Highway Board Department (emergency calling, traffic
management systems), Electrical Power Resources Survey and Development Administration
(EIE) and various research associations (most of them are off-grid) have a common installed
PV capacity of 300 kW (zgr, 2008) PV cells are produced in various research
establishments in order to study the feasibility of local manufacturing. So far none of these
studies yielded a positive result in order to justify a mass production facility in Turkey. There
are more than 30,000 small residential areas where solar powered electricity would likely be
more economical than grid supply. Another potential for PV market is holiday villages at the
long coastal areas. These facilities are frequently far from the main grid nodes and require
additional power when solar insolation is high. (C. Ilkl, et al.,2011)
RESULTS AND DISCUSSION
Solar Energy Potential Of South East Anatolia Region

371

Turkey, which has 81 administrative provinces, is divided into seven geographical regions,
and one of them is southeastern Anatolia region which is generally called the Southeastern
Anatolia Project (SAP, Turkish initials GAP) Region (Fig. 1). The Southeastern Anatolia
Project (SAP) is Turkeys largest and most multifaceted development project, and also, one of
the largest development Project of its kind in the world (Kaygusuz, 1999). The project area
covers nine provinces (Adyaman, Batman, Diyarbakr, Gaziantep, Kilis, Mardin, Siirt,
anlurfa and rnak) of the Southeastern Anatolia Region, which is a relatively
underdeveloped region in Turkey (Fig. 1.). The Project covers such sectors as irrigation,
hydroelectric power production, agriculture, urban, rural and agricultural infrastructure,
transportation, industry, forestry, tourism, education and health. Its water resources program
envisages the construction of 22 dams and 19 power plants and irrigation schemes on an
area extending over 1.7 million hectares Parallel to this development, an intensive investment
activity is expected to be undertaken in the region. Modern buildings and many new industrial
establishments, etc., demanding considerable extra energy, will be installed. Therefore, new,
reliable and detailed weather data for solar energy systems would be required, because
energy analysis and simulation is of great importance for the region. (Bulut, 2004)

Fig.1. The South East Anatolia Region and Provinces

Southeastern Anatolia has the highest average sunshine duration along with the highest
average solar radiance total followed by the Mediterranean and the Eastern Anatolian
regions.
Turkey has high solar radiation along with high sunshine duration due its geographical
location. According to research conducted by the General Directorate of Renewable Energy,
Turkeys annual sunshine duration is 2,640 hours and average annual solar irradiance is
2
recorded as 1,311 kWh/m . South East Anatolia region receives the highest solar energy
resource followed by the Mediterranean Region. The table below demonstrates the average
solar energy intensity and average sunshine duration for seven main regions of Turkey.

372

Southe astern Anatolia is also one of the richest regions of Turkey as far as theoretical solar
energy potential in Table 2.
Table 2. Regional distribution of solar energy potential in Turkey (General Directorate of
Renewable Energy)
Region of Turkey
Total average Solar Energy
Average sunshine duration
2
(kWh/m -year)
(hour/year)
Marmara
1168
2409
Black Sea
1120
1971
Aegean
1304
2738
Central Anatolia
1314
2628
Mediterranean
1390
2956
East Anatolia
1365
2664
Southeast Anatolia
1460
2993
2

The country has an average 3.6 kWh/m -day irradiation and 7.2 hours insolation time per day.
In the southern parts of Turkey, there are about 3000 sunshine hours per year . Figure 2.
shows the solar map of South East Region. Southeastern Anatolia and Mediterranean regions
of Turkey are in the highest levels with closing to 1500 kWh/m-year. Solar energy is widely
used in Turkey. The main solar energy utilizations in Turkey are the flat-plate collectors in
2
domestic hot water systems. The hot water heating system installations exceeds 10 million m
area having with a total installed capacity of 7.8 GWth in 2008.

Fig. 2. Shows the solar map of South East Region. (General Directorate of EIE)
High solar energy potential in the region, as well as the low level of use of solar energy is a
fact. Number of solar panels for heating water used in homes is very little indication of the
largest solar energy utilization rate is low. This is increasing the number of panels with small
businesses and projects supported by the province aimed to bring the solution to the problem
of illegal electricity usage.
2

Table 3. 100 m area of energy that can be produced (kWh/year) (General Directorate of EIE)
Crystalline silicon Thin copper
Cadmium amorphous
film strip
tellurium
silicon
Mono
Poli
Turkey
25.000 22.000
13.000
11.000
10.000
(Avarage)
Southeast Anatolia 26.333 23.222
13.778
11.889
10.278
(Avarage)
Adyaman
27.000 24.000
14.000
12.000
10.500

373

Batman
Diyarbakr
Gaziantep
Kilis
Mardin
Siirt
anlurfa
rnak

27.000
25.000
26.000
26.000
26.000
27.000
26.000
27.000

23.000
22.000
23.000
23.000
23.000
24.000
23.000
24.000

14.000
13.000
14.000
13.000
14.000
14.000
14.000
14.000

12.000
11.000
12.000
12.000
12.000
12.000
12.000
12.000

10.500
10.000
10.000
10.000
10.500
10.500
10.000
10.500

Southeastern Anatolia is the richest region of Turkey in terms of solar energy production.
2
Tables 4. and 5. give the monthly averaged daily total solar energy values in (kWh/m -day)
and monthly averaged daily bright sunshine hours in the GAP region, respectively. This region
is formed by a low-altitude desert plateau extending to the Arabian peninsula. Because of the
semiarid climatic features prevailing in this region, contour lines have the form of concentric
circles from June to September. For July, 13 hours and 26 min of maximum bright sunshine
2
was observed. About 6.6 (kWh/m -day). of maximum total solar radiation is also observed in
June. The solar radiation value s are sufficient for heating and hot water purposes in the
region. In order to estimate of total solar radiation from bright sunshine hours given by the
State Meteorological Station for the GAP region, we used the following equation given
(Ogelman et al. 1984, Kaygusuz, 1999), and obtained results are given in
0 = 0.195 + 0.676() 0.142()2
where H /H0 is the ratio of the monthly average daily terrestrial radiation of extra terrestrial
radiation and n /N is the ratio of the monthly average daily bright sunshine hours to the
monthly average day length.

Table 4. Monthly mean of long-term daily global solar radiation for provinces of GAP region.
(General Directorate of EIE)
2
(kWh/m - Jan.
Feb.
Mar.
Apr. May Jun. Jul. Aug.
Sep.
Oct.
Nov.
day)
Adyaman 1.95
2.51
4.16
5.12 6.23 6.82 6.54 5.97
5.06
3.80
2.40
Batman
1.80
2.45
4.04
5.07 6.22 6.78 6.62 5.91
5.02
3.79
2.34
Diyarbakr 1.69
2.47
3.75
4.74 6.01 6.35 6.32 5.71
4.70
3.25
1.97
Gaziantep 2.02
2.49
4.13
5.04 6.14 6.78 6.56 5.92
4.98
3.77
2.40
Kilis
2.08
2.55
4.10
4.95 6.10 6.76 6.49 5.89
4.93
3.70
2.40
Mardin
1.91
2.52
4.07
5.08 6.23 6.83 6.62 5.92
5.04
3.80
2.41
Siirt
1.89
2.54
4.09
5.10 6.27 6.78 6.71 5.93
5.07
3.79
2.37
anlurfa
1.94
2.48
4.09
5.08 6.18 6.83 6.58 5.94
5.02
3.79
3.42
rnak
1.95
2.63
4.14
5.12 6.29 6.78 6.73 5.93
5.10
3.74
2.44
Turkey
1.79
2.50
3.87
4.93 6.14 6.57 6.50 5.81
4.81
3.46
2.14

374

Dec.
1.80
1.77
1.47
1.80
1.81
1.80
1.79
1.80
1.81
1.59

Turkey

Solar radiation (kWh/m -day)

8
6
4
2
0

Turkey

Adyaman
8
6
4
2
0

Adyaman

Batman
8
6
4
2
0

Batman

Diyarbakr
8
6
4
2
0

Diyarbakr

375

Gaziantep
8
6
4
2
0

Mounth

Gaziantep

Mounth

Kilis

8
6
4
2
0

Kilis

Mardin

Mardin

Solar radiation (kWh/m -day)

8
6
4
2
0

Siirt
8
6
4
2
0

Siirt

376

anlurfa
8
6
4
2

anlurfa

rnak
8
6
4
2

rnak

Mounth

Mounth

Fig. 3. Monthly mean of long-term daily global solar radiation for provinces of South East
region.
In the provinces of the South East regions, Monthly long-term daily global solar radiation
(Fig.3.) and Sunshine Duration (Fig. 4.) values are seen that on average in Turkeys value.
Table 5. Sunshine Duration (General Directorate of EIE)
Hour

Jan.

Feb.

Mar.

Apr.

May

Jun.

Jul.

Aug.

Sep.

Oct.

Nov.

Dec.

Adyaman
Batman
Diyarbakr
Gaziantep
Kilis
Mardin
Siirt
anlurfa
rnak
Turkey

4.51
3.92
3.73
4.60
4.70
4.35
3.84
4.68
4.32
4.11

5.43
5.02
4.89
5.78
5.92
5.45
5.00
5.62
5.52
5.22

6.74
6.16
6.16
6.82
6.80
6.74
5.04
6.92
6.65
6.27

8.08
7.64
7.21
8.10
8.12
7.90
7.38
8.14
7.61
7.46

8.70
9.71
8.76
9.93
10.15
10.01
9.64
9.96
9.87
9.10

11.78
11.72
10.21
11.63
11.48
12.52
11.52
12.24
12.12
10.81

12.25
11.09
11.06
11.74
11.43
12.84
11.78
12.42
12.42
11.31

11.52
11.34
10.45
11.07
10.86
12.03
11.07
11.66
11.67
10.70

10.17
10.05
8.83
10.03
9.81
10.07
9.99
10.11
9.90
9.23

7.56
7.33
6.48
7.80
7.86
7.59
7.19
7.71
7.38
6.87

5.56
5.48
4.73
5.98
6.14
5.83
5.53
5.87
5.86
5.15

4.01
3.92
3.35
4.38
4.58
4.43
4.02
4.40
4.50
3.75

377

Turkey
15
10
5
Turkey

Adyaman
15
10
5
Adyaman

Batman
15
10
5
0

Batman

Diyarbakr
15
10
5
0

Diyarbakr

378

Sunshine Duration (Hour)

Gaziantep
15
10
5
Gaziantep

Kilis
15
10
5
Kilis

Mardin
15
10
5
0

Mardin

Siirt
15
10
5
0

Siirt

379

anlurfa
15
10
5
0

anlurfa

Mounth

rnak
15
10
5
0

rnak

Fig. 4. Sunshine Duration for provinces of South East Anatolia region.

Mounth

In the South East Anatolia, among the three applications of solar energy (i.e. photovoltaic,
thermoelectricity and thermal), thermal is the most commonly used one for producing hot
water. Some other applications, such as irrigation pumps, lighting of various places and
cathodic protection against corrosion, are negligible when compared to applications for
heating purposes.
COCULISION
In The South East Anatolia region has a considerably high level of renewable energy
resources that can be utilized to satisfy a part of the total energy demand in the country,
especially solar energy have large potential in the region of South East Anatolia.
This study was made for suitability of investments in order to determine of existing solar
energy potential in South East Anatolia region. Even if the solar energy systems have high
investment costs today, they will provide significant contributions in terms of meeting future
energy needs by the help of studies and supports. Solar energy potential in this region
provides an important alternative for the future. Moreover, the private sector is related to
renewable energy development according to its capacity to mobilize funds. To support
gradually rising renewable energy applications, requesting procedures should be
implemented. The aim of renewable energy policies is to reduce greenhouse gases emissions
by generalizing green technologies. Collaboration between the government, the private sector
and consumer is led to Research and Development studies for decreasing cost of energy
World's most important energy source, the sun, the main source of energy on earth that affect
the physical formations. From solar energy, in turn into different types of energy used. Mostly
in this region, they are utilized in solar water heating systems. Different intended use of the
solar energy potential should be increased for example, variations of solar irradiance are
known to have a significant influence on electric power generation by solar energy systems.

Acknowledgements
The author would like to acknowledge conference organizer for their kind invitation and
acceptation of this paper, as well as excellent organization. Thank you for graph drawing to
staff Mjdat Kl in University of Sirnak, Engineering Faculty.

380

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University, Tirana,974-982.
Bilgen S., S. Keles , A. Kaygusuz, A. Sar, K. Kaygusuz, 2008, Global warming and renewable
energy sources for sustainable development: a case study in Turkey. Renewable and
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Bulut, H., 2004, Typical solar radiation year for southeastern Anatolia, Renewable Energy 29
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Dundar C., M. Canbaz, N. Akgun and G. Ural, 2002, EIE&DMI (Turkish State Meteorological
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DPT, State planning organization, Ninth development plan 20072013, DPT, Ankara, Turkey,
2006.
Ilkl C., H. Aydn, R. Behet, 2011, The Current Status of Wind Energy in Turkey and in the
World, Energy Policy, vol. 39, pp. 961967.
International Energy Agency (IEA), Energy policies of IEA countries: Turkey 2009 review.
Kaygusuz, K., 1999, Energy and Water Potential of the South eastern Anatolia Project (GAP),
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gelman, H., A. Ecevit, and E. Tademirolu. 1984, A new method for e stimating solar
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Power Resources Survey and Development Administration, Solar energy in Turkey (EIE))

381

HYGROSCOPIC EFFICIENCY ANALYSIS OF DESICCANT COATING HEAT

EXCHANGERS WITH DIFFERENT SOLID DESICCANTS
Win-Jet Luo, Chi-Wun Lu, Wei-Jyum Liao and Zhi-Hua Lin
Department of Refrigeration, Air Conditioning and Energy Engineering
National Chin-Yi University of Technology, Taichung City, 41170, Taiwan
wjluo wjluo@ncut.edu.tw

ABSTRACT
This study used desiccants of silica gel and sodium polyacrylate coated on fin and tube heat
exchangers to enhance the absorption of vapor in the air. The experimental results show that, while
the temperature and relative humidity of the inlet air are 25 and 85% RH, respectively, the vapor
absorbent capacities of the two desiccants are better than that of the conventional cooling and
dehumidification method with supplied chill water of 7. The enhanced dehumidification efficiencies
of sodium polyacrylate and silica gel are 64% and 42.8%, respectively, as compared to that of the
conventional method. The two desiccant coating heat exchangers are also operated periodically in
mass equilibrium states between the absorption and regeneration processes. While hot water of 60
was supplied during the regeneration process, after reaching an equilibrium state in periodic cycles,
the average vapor absorption rates per unite desiccant are 0.0018gvapor/(g min) for silica gel and
0.004gvapor/(g min) for sodium polyacrylate. For the desiccant of sodium polyacrylate, the period of
absorption process could be much longer, and the vapor could be discharged in a shorter period of
the regeneration process. Thus, the dehumidification efficiency of sodium polyacrylate in DCHE has
much better performance than that of silica gel.
Keywords: silica gel, sodium polyacrylate, solid dehumidification, dehumidification efficiency.
INTRODUCTION
During operation of air conditioning systems, air dehumidification is a high energy consumption
process, which accounts for 20%-40% of the total consumption of the air conditioning (Wu 2001). In
the past, to minimize energy consumption, inefficient energy-saving measures were taken in the
design of air conditioners, such as reducing the induction of fresh air into conditioning room.
However, the inefficient energy-saving measures cannot effectively control or discharge indoor
pollutants, which may increase pollutants in the air and decline air quality. Thus, the public has
become interested in IAQ (indoor air quality) and has begun to seek methods or measures to ensure
IAQ in order to maintain human health and improve work efficiency. In order to maintain a high indoor
air quality, a effective way is introducing outdoor fresh air into conditioning room for diluting the indoor
air and removing the pollutant indoor air from the room. However, the outdoor fresh air is often with
high temperature and humidity, which may require lots of energy consumption on the cooling and
dehumidification of the introducing fresh air.
Currently, Taiwan often uses coolers for temperature reduction and dehumidification in order to
meet the comfort needs of maintaining suitable indoor temperature and humidity. For the purpose of
dehumidification, the evaporate temperature of refrigerant must be reduced to a very low temperature
less than the corresponding temperature of dew point, and vapor can be condensed to achieve the
dehumidification effect. In some cases, dehumidified air must be reheated to reach the preferred
environmental conditions, which may waste lots of energy. In recent years, air conditioners have been
developed towards separating dehumidification from cooling. Air can be supplied by using a hightemperature cold source, which can improve the efficiency of the chiller unit or cooling equipment,
reduce energy consumption, and increase indoor comfort. In view of this, the development of more
efficient dehumidification technology is significant for effective utilization of energy and environmental
protection.
In the researches on solid dehumidification, Zhang et al (2007) used different desiccants and
electroosmosis dehumidification for experimental analysis, and indicated the relations between
current and voltage, as well as between water discharge and desiccants. The water discharge rate
was proportional to the voltage, and water discharge curve was consistent with the current variation
curve. Zhang et al (2007) conducted experimental analysis on SiO2 coated on fin and tube heat
exchangers, and the findings show that air temperature and air speed have significant impact during
absorption. Jia et al (2006) compared the dehumidification performance of silica gel with lithium
chloride wheels, and discussed the impact of operation conditions (inlet humidity and temperature of
handling air, regenerative temperature and handling air amount) on the dehumidification performance
of wheels. Li et al (2005) used five methods to analyze wheel dehumidification systems, and these
methods can reduce requiring capacity of dehumidification wheels and regenerative air flow rate in

382

order to reduce energy consumption and operation costs. Inaba et al (2007) applied the organic
absorbent of sodium polyacrylate to heat exchangers. The experimental results show that air speed
and temperature of water in the heat exchangers affect the absorption efficiency of water vapor. T.S.
Ge et al (2011) found that the regenerative temperature of heat exchangers with silica gel coating had
better performance than that of polymer under the given conditions, and analyzed the impact of inlet
temperature and humidity on the average vapor absorption amount and the heat performance
coefficient. C.E.L. Nobrega et al (2012) conducted a comparison between heat transfer and mass
transfer of passive and active air absorption and dehumidification, and discussed the definition of
desiccant wheel effectiveness. In the research of Mihajlo N. Golubovic et al (2010), the sorption
properties for different types of molecular sieves (synthetic zeolites) are presented in equation form.
Using the numerical model, the influence of different assumptions for the heat of sorption and
equilibrium equation of a molecular sieve on the predicted optimum performance of the rotary
dehumidifier is evaluated. Yuan Weixing et al (2008) proposed the newly modified Cross-Cooled
Compact Solid Desiccant Dehumidifier (CCCD), and used a mathematical model to describe the
media transfer process between hot/wet air and desiccants, and simulated the dehumidification
performance and experimental results, which indicated the agreed better error was 7%. In this study,
desiccants of silica gel and sodium polyacrylate coated on fin and tube heat exchangers were used to
enhance the absorption of vapor in the air. The operation parameters including inlet air temperature,
dehumidification and regeneration time, and supplied water temperatures in absorption and
regeneration processes were investigated in order to evaluate dehumidification efficiency under
different dehumidification conditions.
RESEARCH METHOD AND EXPERIMENTAL FRAMEWORK
Solid desiccants coated on fin and tube heat exchangers are called DCHE, which accomplish
dehumidification using solid desiccants to absorb the vapor from wet air. In this study, a supply
chamber is used to supply inlet air with constant temperature and humidity to the experimental
chamber with a desiccant-coated heat exchanger. In order to ensure adequate humidity is provided
by the chambers, additional humidifiers are installed to compensate the humidity deficiency of the
supplied air. The experiment is performed at a suitable inlet air speed of 0.25m/s, as mentioned in
literature [3]. An air fan is installed on the back end of the experimental chamber for forced draft, and
then, air speed is calculated using the static pressure difference. The supplied air flow in the
experimental chamber is 0.048m3/min. Two tanks with constant temperature cold and hot waters are
used to alternately supply waters to the desiccant-coated heat exchanger during the absorption and
regeneration processes.
Aluminum hollow plates are fixed on the front and back ends of the desiccant test chambers, and
air evenly flows through the desiccant coated heat exchanger. The distance between the front-end
hollow plates and desiccant-coated heat exchanger is 300mm. The temperature and humidity meters
are installed on the front and back of the heat exchanger to record changes of temperature and
humidity of the inlet and outlet air of the heat exchanger. Nozzles are installed in the chambers to
generate static pressure difference. A differential pressure gauge is used to measure the static
pressure difference, through which air speed and air flow rate are calculated.

383

Fig.1. Experimental device.

EXPERIMENTAL RESULTS AND DISCUSSION
Dehumidification amount of heat exchangers coated with different desiccants
The heat exchangers coated with silica gel and sodium polyacrylate were used for cooling
dehumidification, while the relative humidity of the supplied inlet air was 85% RH. Furthermore, chill
water with temperature of 7 was introduced into coils of the heat exchanger in order to reduce the
temperature of the passing air flow and remove the absorption heat from the dessicants during
dehumidification process. The absolute humidity differential value of the air between the inlet and out
a were used to calculate mass
of the heat exchangers and the corresponding air mass flow rate m
transfer rate of vapor Mvap, as shown in Eq. (1). Mass transfer rate of vapor is defined as

M vap m (Wa ,out Wa ,in ) ,

(1)

where W a,out and W a,in are the absolute humidities of the air at the outlet and inlet of the heat
exchanger, respectively. From the distributions of mass transfer rate Mvap in the cooling
dehumidification process, as shown in Fig. 2, it can be seen that, the sodium polyacrylate-coated
heat exchanger at inlet air temperature of 25 has the best enhancement of dehumidification
efficiency. As shown in the fig. 2, the mass transfer rates of vapor increase apparently within 5 min of
cooling absorption. After 20 minutes of the absorption experiments, all of the mass transfer rates of
the three dehumidification methods gradually reach to stable values. At inlet air temperature of 25,
it can be seen that a difference exists in the dehumidification amount of different desiccants.

Fig.2. Cooling absorption of Mvap at inlet air temperature of 25

The enhancements of dehumidification efficiencies of the desiccant heat exchangers at different
inlet air temperatures in comparison to that of conventional cooling method are as shown in Fig. 3.
The dehumidification amount of conventional cooling method is used as the benchmark to calculate
the enhanced percent of the silica gel-coated heat and sodium polyacrylate-coated heat exchangers.
It can be seen that the enhancement of desiccant heat exchangers at inlet air temperature of 25
and 85% RH is more significant. The enhancement of dehumidification efficiencies, of silica gelcoated heat and sodium polyacrylate-coated heat exchangers are 42.8% and 64%, respectively. With
the increase in the inlet temperature, due to the reduction of the vapor amount containing in the air,
the dehumidification efficiencies of the desiccants also gradually decrease.

384

Fig.3. Enhancement of dehumidification efficiencies of the desiccant heat exchangers at different

inlet air temperature.
Effect of hot water temperature on regeneration efficiency of desiccant coated heat
exchangers
In the regeneration experiments of the silica gel-coated heat exchanger and the sodium
polyacrylate-coated heat exchanger, the mass transfer distributions of Mvap at different hot water
temperatures are as shown in Fig. 4 and 5. The regeneration time is defined as the required time for
the mass transfer rate approaching to zero after hot water is introduced into the coils of the heat
exchanges. For the silica gel-coated heat exchanger, the regeneration curve has no great difference
at the hot water temperature of 60and 70. However, the regeneration time was increased from 9
minutes to 15 minutes, and the regeneration amount also increased when the hot water of 60 was
introduced. When the hot water temperature was 50, regeneration efficiency declined greatly. The
required energy consumption per unit of absorbed or discharged vapor is defined as

Q d
Qave 0 b
,
0 M vap d
(2)

b C p,b Tb,out Tb,in , m b is the supplied water flow rate in the absorption or
where Qb m
regeneration processes. Tb,out and Tb,in are the water temperatures flowing into and out of the heat
exchanger, respectively. The vapor desorption ability per unit of desiccant, Cw, can be determined
by dividing the regenerated amount by the weight of the desiccants, as shown in Eq. (3). The
vapor desorption ability per unit of desiccant is defined as

Cw

M vap d

M desiccant

(4)
where Mdesiccant is the mass of the desiccant coated on the heat exchanger, and is the vapor
absorption or discharge time. In terms of the above experimental data, the silica gel-coated heat
exchanger had a higher regeneration amount when hot water of 60was introduced. As the
regeneration time is longer, the absorption ability at the hot water temperature of 60 is better
than other hot water temperatures.

385

Fig.4. Regeneration of Mvap of silica gel-coated heat exchanger at different hot water temperatures

Fig. 5 Regeneration of Mvap of sodium polyacrylate-coated heat exchanger at different hot water
temperatures.
As shown in Table 1 for silica gel-coated heat exchangers, when the regeneration time is
longer, the energy consumption of regeneration and average vapor energy consumption Qave are
higher. The desorption ability Cw of the desiccants can be determined by dividing the regenerated
amount by the weight of the desiccants. In terms of the above experimental data, the silica gelcoated heat exchanger had better desorption ability when the hot water temperature is 60.
As shown in Table 2 for sodium polyacrylate-coated heat exchangers, the regenerated amount
of the sodium polyacrylate-coated heat exchanger increased significantly as the hot water
temperature increased. When the hot water temperature is 50 and the required regeneration
time is more than 28 min, in the case, the regeneration amount is higher than those of other hot
water temperatures. However, the energy consumption for regeneration reaches 69.9kW. Thus,
the sodium polyacrylate coated heat exchanger (DCHE) is not recommended for regeneration
when the hot water temperature is 50. By comparison, the desorption abilities of the sodium
polyacrylate coated heat exchanger (DCHE) at the hot water temperature of 60 is better than
that at 70, and the average energy consumption of vapor is lower, thus, this study considers the
suitable temperature for sodium polyacrylate as 60. In comparison to Cw, Qave and requiring
regeneration time of the desiccants of silica gel and sodium polyacrylate, the sodium polyacrylate
can discharge more vapor water with lower energy consumption at the same influence of hot water
temperature.

386

Table 1 Regeneration test records of silica gel-coated heat exchangers at different hot water
temperatures.
Experiment conditions
Weight of silica gel (g)
Regeneration amount (gvapor)
Regeneration time of silica gel (min)
Energy consumption of regeneration
using silica gel (kw)
Qave(kJ/ gvapor)
Cw (gvapor/gdesiccant min)

70
6.2812
9

60
143g
6.802
15

50
5.0309
10

22.35

27.7

14.98

3.56
0.0439

4.07
0.0476

2.97
0.00352

Table 2 Regeneration test records of sodium polyacrylate-coated heat exchangers at different hot water
temperatures.
Experiment conditions
Weight of sodium polyacrylate (g)
Regeneration amount (gvapor)
Regeneration time of sodium polyacrylate
(min)
Energy consumption of regeneration of
sodium polyacrylate (kw)
Qave(kJ/ gvapor)
Cw (gvapor/gdesiccant)

70
9.7925

60
70g
15.1199

50
20.425

10

17

28

31.65

44.33

69.9

3.23
0.14

2.93
0.216

3.42
0.292

Periodic equilibrium switch between regeneration and dehumidification Processes

As shown in previous section, the required regeneration time of the silica gel-coated heat
exchanger and sodium polyacrylate-coated heat exchanger is 15 minutes and 17 minutes,
respectively, when the hot water temperature of 60 is applied. Based on the known regeneration
amount of the silica gel-coated heat exchanger and the sodium polyacrylate-coated heat
exchanger, we can determine the corresponding cooling absorption time during the cooling
dehumidification process with supplied chill water of 7 at an inlet air conditions of 25and 85%
RH. In order to reach the discharging vapor amounts during the regeneration processes, the
required absorption times for the silica gel-coated and sodium polyacrylate-coated heat
exchangers are 33 minutes and 63 minutes, respectively. As shown in Fig. 6, the silica gel-coated
heat exchanger has 7 cycles within five hours of operation. The stabilized regeneration time for
each cycle is 14 min, the time error in dehumidification processes is about 6 minutes, and the
average dehumidification time of the silica gel-coated heat exchanger is 27 minutes.

Fig.6. Regeneration and absorption of silia gel-coated heat exchanger for 5 hours.

387

For the desiccant of sodium polyacrylate, the average dehumidification time is 51 minutes
during the five hour of cycle experiment. The mass transfer rate during the 51 minutes of
dehumidification is higher than that during the equilibrium switch time. As shown in Table 3, the
average vapor absorption rates per unite desiccant are 0.0018gvapor/(g min) for silica gel and
0.004gvapor/(g min) for sodium polyacrylate. The mass transfer rate per unit desiccant of sodium
polyacrylate in the regeneration process is 0.0127gvapor/(g min), which is much larger than that of
silica gel. Furthermore, the sodium polyacrylate-coated heat exchanger has longer
dehumidification time, and can absorb vapor within a shorter time. In terms of the abilities of the
desiccants, the sodium polyacrylate-coated heat exchanger has better performance in the amount
of dehumidification and regeneration, as compared to the silica gel-coated heat exchanger, as
shown in Table 3.

Fig.7. Regeneration and absorption of sodium polyacrylate-coated heat exchanger for 5 hours.
Table 3 The dehumidification and regeneration efficiencies of the desiccants during absorption and
regeneration process.
silica gel
sodium polyacrylate
Weight of desiccants(g)
143
70
Dehumidification time (min)
27
51
Absorption amounts (g)
7.05
15.15
Dehumidification rate (gvapor/min)
0.26
0.30
Dehumidification rate per unit of desiccant
0.0018
0.004
(gvapor/g min)
Regeneration time (min)
14
17
Regeneration rate(gvapor/min)
0.50
0.89
Regeneration rate per unit desiccant
0.0035
0.0127
(gvapor/g min)

CONCLUSIONS

This study used desiccants of silica gel and sodium polyacrylate to improve the efficiency of
conventional cooling and dehumidification. From experimentation, it can be found that the silica gel
coated heat exchanger and the sodium polyacrylate coated heat exchanger can increase the
efficiency of conventional cooling and dehumidification. In the cooling and dehumidification
experiment, it can be seen that the enhancement of dehumidification efficiencies of sodium
polyacrylate and silica gel are 64% and 42.84%, respectively, when the inlet air temperature is
25 and relative humidity is 85%. The dehumidification amount depends on the pore size of the
desiccant, thus, it is not necessary to lower the cold water temperature to improve the efficiency of
cooling and dehumidification.
For other highly efficient dehumidification facilities, such as dehumidification wheels and
solutions, the regeneration process occurs when the facilities are heated to produce high
temperatures. This experiment used 60 hot water to regenerate the vapor absorbed by the
desiccants, which can reduce energy consumption, as compared to other dehumidification
facilities. Based on the experimental data, this study obtained suitable operating periods of

388

absorption and regeneration process for silica gel and sodium polyacrylate coated heat
exchangers. Next, with reference to the operation time, automatic dehumidification facilities with
different desiccants can be developed.
ACKNOWLEDGEMENT
The authors gratefully acknowledge the financial support provided for this study by the National
Science Council of Taiwan under Grant Nos. NSC 102-2221-E-167 -021 -MY2 and NSC 1022622-E-167 -010 -CC3.
REFERENCES
[1] Wu, K.L., 2001, Effect of Humidity on Health in Winter. Health & Life Guide t, December 3.
[2] Zhang, Y.Q, 2007, Study on Dehumidification Methods of Air Conditioning based on Electrodialysis
Principle, masters thesis. Beijing University of Technology, China.
[3] Zhang l,Ssaikawa M, Fujinawat, Kaidat, Hashimoto K., Experimental analysis of adsorption and
desorption characteristics of a meso-porous silica coated fin-tube heat exchanger, Japan.
[4] Jia, C.X., Wu, J.Y., Dai, Y.J., 2006, Study on Dehumdification Efficiency of Desiccant Wheels,
Institute of Refrigeration and Cryogenics, Shanghai Jiao Tong University, China
[5] Li, C.Y., Chang, K.Y., Wu, T.C., Wang, W.P., 2005, Performance Analysis of Honeycomb Rotor
Dehumidifier of Air Conditioning System, National Taipei University of Technology, Chinese Water,
Electrical, Frozen and Air-Conditioning Monthly, Taiwan
[6] Inaba, H., Komatsu, F., Horibe, A., Haruki, N., Machida, A., 2007, Sorption Characteristics of
Organic Absorbent Coated on Tranfer Surface of Heat Exchanger, Thermal Science &
Engineering , 15 141-150,Japan.
[7] T.S.Ge, Y.J.Dai,R.Z.Wang, 2011, Performance study of silica gel coated fin-tube heat exchanger
cooling system based on a developed mathematical model, Energy Conversion and Management,
52 2329-2338, China
[8] C.E.L.Nobrega, N.C.L. Brum, 2012, An analysis of the heat and mass transfer roles in air
dehumidification by solid desiccants, Energy and Buildings, 50251-258, Janeiro, Brazil.
[9] Mihajlo N. Golubovic, H.D.M. Hettiarachchi, William M. Worek, 2010, Sorption Properties for
Different Types of Molecular Sieve and Their Influence on Optimum Dehumidification Performance
of Desiccant Wheels, University of Illinois at Chicago, 49 2802-2809, United States.
[10] Yuan Weixing, Zheng Yi, Liu Xiaoru, Yuan Xiugan, 2008, Study of a new modified cross-cooled
compact solid desiccant dehumidifier, Thermal Engineering, 28 2257-2266.

389

The mechanical analysis and experimental verification of screen-printed front

electrode for crystalline silicon solar cells
Hong Yang, He Wang*,Chuanke Chen, Dingyue Cao
Institute of Solar Energy, MOE Key laboratory for Nonequilibrim Synthese and Modulation of
Condensed
Matter, Xian Jiaotong University
Xian 710049, Peoples Republic of China
E-mail: hw69cn@126.com

ABSTRACT
The daily thermal cycling of modules deployed outdoors results in a gradual increase in series
resistance and power degradation because of the difference in coefficient of thermal expansion
(CTE) between the metal electrode and the silicon wafer. The mechanical property of metal
electrode /Si contact structure is one of the key factors for 25 years useful lifetime crystalline silicon
solar module. So it is very important to give a thorough investigation for the mechanical properties
of the front electrode structure. In this paper, we established, for the first time, the relationship
between the shear force and the width of bus-bar which based on material mechanics. The
experimental results prove validation of the theoretical analysis. The conclusions we get in this
paper provide a theoretical basis for the mechanical properties of front electrode for crystalline
silicon solar cells.
Keywords: solar cells; electrode; mechanical properties; silver paste
1. INTRODUCTION
The crystalline silicon solar cell is a workhorse for regenerative energy techniques. The
screen-printed silver front electrode is a predominant technique in the photovoltaic (PV) industry to
establish an ohmic contact to an n-type emitter of a crystalline silicon solar cells (Green, 2011;
Schubert, et.al, 2006). The adhesional strength of front electrode is one of the key factors which
affect the reliability of solar cells and solar modules. Many researchers thought that the power
degradation of solar modules was correlated with the loss of adhesion because of the difference in
coefficient of thermal expansion (CTE) between the metal and the silicon wafer. Poor mechanical
property of front electrode will cause a high contact resistance and heavy power degradation, which
will lead the solar cells and solar modules to failure ahead of time ( Yang, et al, 2013). Although many
works that the electrical property of the interface microstructure between screen-printed silver
thick-film and silicon solar cells emitter has been studied by some scientists, in view of the
complexity of Ag paste/Si contact system, few people investigated the quantitative relationship
between shear force and width of bus-bar (Zhang, et al, 2008; Cabrera, et al, 2013; Hilali, et al, 2006). A
popular method for quality control in photovoltaic industry is the so-called Ribbon-Pull-Test. Pull
tests are well known and standardized in the semiconductor and microelectronic packaging
industries, but the method is not simply transferable for soldered solar cells with the available
standard test equipment. Different test conditions like pull angle and test velocity implicate
difficulties concerning comparability between different users (Wendt, et al, 2010). For a natural load
case, the main direction of applied force is longitudinal to the solder ribbon. For that reason, a pull
angle of 180may seem to be more realistic. However it is more peeling than pulling. The shear
1
390

force test used in microelectronic industry is more accurate method for evaluating the reliability of
the screen-printed front electrode, so exploring the shear force of front electrode is very important
for photovoltaic science. In this paper, a thorough investigation for the mechanical properties of the
front electrode is conducted. The relationship between the shear force and width of bus-bar which
based on material mechanics is established for the first time. The experimental results prove
validation of the theoretical analysis, and also provide a theoretical basis for the front electrode
mechanics of crystalline silicon solar cells with fine finger and high sheet resistance emitters.
2. THEORETICAL ANALYSIS
Before starting the derivations, we made the following assumptions for simplicity (Tljsten, 1996;
Tljsten, 1997; Her, 1999).

Adherends are homogeneous and linear elastic, and the adhesive layer is exposed only to
shear force.

Normal stresses are uniformly distributed over the cross-section, and the thickness and
width of the adherend are constant throughout the bondline.

Glass layer is the only binder phase at Ag paste/Si contact interface, and the all bonding
interfaces is effective.

According to the design of the experiments, the Ag paste/Si contact structure for crystalline silicon
solar cells can be analysized as shown in Fig.1. The thickness, width and Youngs modulus of the
ribbon (adherend 1) are t1 ,

b1

and E1 ;

t2 , b2

and

E2

for Si substrate; and t, b and E for

bus-bar respectively, L is the bond length.

Fig.1 Ag paste/Si contact structure of crystalline silicon solar cells

As shown in Fig.1, when a shear load F is exerted on the ribbon from one side, the bus-bar
produces a micro-deformation under the effect of shear force F and generates a slip deformation .
According to the mechanical analysis of this system shown in Fig.2, the equilibrium equation can be
written as follow:

d 1
fV 0
dx
(1)

1t1l1 2t2l2 k ' F

(2)
2
391

Fig.2 Deformation and stresses analysis of Ag paste/Si contact structure

fV

where

represents the volume force, F represents the shear force and

relevant to the Ag paste-Si contact area,

and

k'

is a parameter

are the normal stresses for the adherends 1

and 2, respectively.

fV

t1

(3)

F k
(4)

EA
b0

(5)
where is local shear stress, E is the youngs modulus, A is the initial cross-sectional area,

b0

is

the initial length and k is the stiffness factor.

Base on the above assumptions, considering that the adhesive layer shows brittle fracture during
the process of suffering from shear force, so there is almost a linear relationship between the shear
stress and the slip deformation.
According to the linear relationship between the simplified shear stress and the slip deformation, we
can get the f ( ) - model as follow:

f m2
, m

f ( ) 2G f
0,
m

(6)
in which

f ( )

is the actual shear stress applied on the Adherend 1,

Gf

is the interfacial

fracture energy, which defined as the energy required to bring a local bonding element to shear
fracture,

fm

is the local bond strength and

is the corresponding maximum slip deformation,

3
392

as illustrated in Fig.3.

Gf

1
f m m
2

(7)

Fig.3 Simplified shear stress-slip deformation model

Under the effect of shear force, it generates a relative displacement between Adherend 1 and
Adherend 2. Using X 1 ( x) as the displacement of Adherend 1 and

X 2 ( x)

as the displacement of

the Si substrate, we can write the slip deformation as follow:

X 1 ( x) X 2 ( x)
(8)
The constitutive equations for the adhesive layer and the two adherends are expressed as:

f ( )
(9)

1 E1

dX 1 ( x)
dX 2 ( x)
, 2 E2
dx
dx

(10)
Equation (8) can be written in the form of the follow differential equation:

d dX 1 ( x) dX 2 ( x)

dx
dx
dx
(11)
By solving simultaneous equations (2), (10) and (11), we get the equation as follow:

d 1 1t1l1 k ' k

dx E1 E2t2l2 E2t2l2
(12)
4
393

Therefore,

1 (

tl
d k ' k
1

)/( 11 )
dx E2t2l2
E1 E2t2l2

(13)
Equation (13) can also be written in the form of the follow differential equation:

d 1
tl
d 2
k ' k d
1
( 2
)/( 11 )
dx
dx
E2t2l2 dx
E1 E2t2l2
(14)
m can be denoted as

m 1/ (

tl
1
11 )
E1 E2t2l2

Thus equation (14) can be written as follow:

d 1
d 2
k ' k d
m( 2
)
dx
dx
E2t2l2 dx
(15)
Substituting equations (3), (6), (9) and (15) into equation (1) gives:

f m2
d 2
k ' k d

0
dx 2 E2t2l2 dx 2G f mt1
(16)
a and c can be denoted as

f m2
k 'k
a
,c
E2t2l2
2G f mt1

, equation (16) can be written as follows:

d 2
d
a
c 0
2
dx
dx
(17)
For solving equation (17), the relative shear displacement can be written in the following form:

a
x
2

(18)
Equation (18) can be written in the form of the follow differential equation:
a
x
d
a a x
e 2 g e 2 g'
dx
2

(19)
a
a
x
x
d 2 a 2 a2 x
2
2

e
g

ae
g
'

e
g ''
dx 2
4

(20)
5
394

By Substituting equations (19) and (20) into equation (17), the follow equation is obtained:

a
x
2

g '' (

a
x
a2
c )e 2 g 0
4

(21)
That is,

g '' (

a2
c) g 0
4

(22)
Making that

a2
c
4

(23)
The solution of equation (22) can be expressed as:

g [ A sinh( x) B cosh( x)]C1 C2

(24)
Substituting equation (24) into equation (18) gives:

a
x
2

{[ A sinh( x) B cosh( x)]C1 C2 }

(25)
Substituting the boundary conditions x 0,

into equation (25) gives:

C2 BC1
The derivation of the equation (25) is
a
x
aBC1
d
a
a
e 2 {[( B A)sinh( x) ( A B) cosh( x)]C1
}
dx
2
2
2

(26)
Therefore

1 m(

a
x
aBC1
a
a
d k ' k
}

) me 2 {[( B A)sinh( x) ( A B) cosh( x)]C1

2
2
2
dx E2t2l2

(27)
By solving equations (6), (7) and (25), we get the equation as follows:

f m2 a2 x

e {[ A sinh( x) B cosh( x)]C1 C2 }

2G f
(28)
Substitute the boundary conditions as follows into equation (27),
6
395

x 0, 1 0

F k ' k m

x
b
,
1

l1t1
l1t1

(29)
We can get the unknown constants A and B

A0
(30)

B
e

a
b
2

k ' k m
a
a
mt1l1[ sinh(b) cosh(b) ]C1
2
2

(31)
By Substituting equations (30) and (31) into equation (25), (27) and (28), the following simplified
results are obtained:

k ' k m

a
b
2

a
a
mt1l1[ sinh(b) cosh(b) ]
2
2

a
x
2

[cosh( x) 1]

(32)

k ' k m

1
e

a
b
2

a
a
mt1l1[ sinh(b) cosh(b) ]
2
2

me

a
x
2

a
a
[ sinh( x) cosh( x) ]
2
2

(33)

k ' k m

f m2 a2 x
a
e [cosh( x) 1]
b
a
a 2G f
2
e mt1l1[ sinh(b) cosh(b) ]
2
2
(34)
The material parameters used in calculation are shown in Table 1.
Table 1 Main parameters of the materials used
Ribbon
Youngs modulus, E (MPa)
Thickness, t (um)
Length, l (mm)

Bus-bar

103000
180
5

Si

71700

128000

20

180
5

156

7
396

F bl
(35)
From equations (34) and (35), the relationship between the shear force and width of busbar is given
as:

k ' k mbl
f m2 a2 x
e [cosh( x) 1]
a
b
a
a 2G f
2
e mt1l1[ sinh(b) cosh(b) ]
2
2

(36)
3. EXPERIMENTAL PROCEDURE

Fig.4 The experimental samples

Some of 156 mm 156 mm boron-doped single crystalline silicon wafers were used for our
experiments. These wafers were treated by chemical iso-texture for saw damage etch and light
trapping. And then were diffused using liquid POCl3 as the dopant source to form an emitter with a
sheet resistivity of 60-65/square. After POCl3 diffusion, Edge isolation was performed by plasma
etching. The SiNx:H thin films were prepared by plasma enhanced chemical vapour deposition
(PECVD) using SiH4 and NH3. The metallization was carried out in a conventional way, silver and
aluminum pastes were screen printed to top and back surface of wafers, which then formed electric
contact of solar cells through a rapid thermal processing at about 760 for a short time. In the
process of screen printing, DuPont 17F silver paste was used, and different busbars with1.0mm,
1.2mm, 1.4mm, 1.6mm and 1.8mm width are printed respectively. The tabbing was carried out by
manual welding. A 5-mm-long ribbon was soldered on the busbar of crystalline silicon solar cells. In
order to avoid fragmentation during the shear force measurement, the experimental samples were
laminated on a tempered glass in this experiment. The shear force measurement was carried out by
a Dage4000, Fig.4 gives out the samples used in this experiment. The microscopic structure of Ag
paste-Si interfaces and the fracture surface were analyzed with scanning electron microscopy
(SEM).
4. RESULTS and DISCUSSION
8
397

Because the shear force is also related with firing -through and soldering process, the SEM of the
microscopic structure of Ag paste/Si interfaces and the fracture surface are shown in Fig.5. Fig.5 (a)
gives out SEM of the microscopic structure of Ag paste/Si interfaces, Fig.5 (b) gives out SEM of the
fracture surface. From Fig.5(a), we found that the interface microstructure between silver thick-film
and silicon substrate is in optimally fired contacts (Li, et al, 2011;Cabrera, et al, 2011) According to
Fig.5 (b), it was found that some silver was left on the surface of silicon, this shows that soldering
process is proper for the experiment (Nieland, et al, 2007). So the shear force measured in this
experiment should be the true state.

(a)SEM image of Ag paste/Si interface

(b) SEM image of the fracture surface

Fig.5 SEM images of Ag paste-Si interfaces and the fracture surface

The measured and calculated shear forces are shown in Fig.6 for comparison. From Fig.6, the
theoretical values calculated by equation (36) are linear with width for a 5-mm-long busbar, the
measured shear forces agree with the theoretical data nearly. But all the data measured are lower
than the theoretical values, this is because that glass layer is a binder phase, cross-sectional area
between silver paste and silicon is thought as binder area. In fact, there exists three kinds of contact
for the silver paste/Si contact, one is a direct contact between crystal and silver, another is indirect
contact by a very thin glass layer by tunneling, and the third is an indirect contact by thick glass
layer which contains some discontinuous metal precipitates. A direct contact between crystal and
silver is beneficial to ohmic contact formation, but the adhesion force of this contact is weaker than
glass layer. So the measured data should be lower than the theoretical values.

9
398

320
300
280
260
240

Shear force (N)

220
200

Measured data
1.0 mm
1.2 mm
1.4 mm
1.6 mm
1.8 mm

Calculated data

180
160
140
120
100
80
60
40
20
0
1.0

1.2

1.4

1.6

1.8

Busbar width (mm)

Fig.6 Relationship between shear force and bus-bar width for solar cells
5. CONCLUSIONS
The long term reliability of crystalline solar modules is critical to the cost effectiveness and the
commercial success of photovoltaic. The mechanical property of Ag paste/Si contact structure is
one of the key factors which affect the reliability of solar cells and solar modules. In this study, the
theoretical relationship between the shear force and width of busbar which based on material
mechanics is established for the first time, and the experimental results prove validation of the
theoretical analysis. The conclusions we get in this paper lay a foundation for studying the
mechanical performance of front contact metallization system for screen-printed crystalline silicon
solar cells with fine finger and high sheet resistance emitters.

ACKNOWLEDGEMENTS
The authors would like to thank the support of the Fundamental Research Funds for the Central
Universities and Natural Science Foundation of China (Grant No. 61274050 and 61376067). This
study was also supported by the Bureau of Science and Technology (2013k11-02 and
CXY1347(6)).
REFERENCES
Cabrera E, Olibet S, Reichenbach JG. Current transport in thick film Ag metallization: direct
contacts at silicon pyramid tips. Energy Procedia 2011, 8:540545.
Cabrera E, Olibet S, et al. Experimental evidence of direct contact formation for the current
transport in silver thick film metallized silicon emitters. J. Appl. Phys. 2011, 110: 114511.
Green MA. Ag requirements for silicon wafer-based solar cells. Progress in photovoltaic: research
and applications 2011, 19:911-916.
Her SC. Stress analysis of adhesively-bonded lap joints. Composite structures, 1999, 47: 673-678.

10
399

Hilali MM, Sridharan S, Khadilkar C, et al. Effect of glass frit chemistry on the physical and electrical
properties of thick-film Ag contacts for silicon solar cells. Journal of electronic materials 2006, 35:
2041-2047.
Li ZG, Liang L, et al. Microstructural comparison of silicon solar cells front-side Ag contact and the
evolution of current conduction mechanisms. J. Appl. Phys. 2011, 110:074304.
Nieland S, Baehr M, et al. Advantages of microelectronic pachaging for low temperature lead free
soldering of thin solar cells, 22nd European Photovoltaic Solar Energy Conference, Milan, Italy, 3-7
September 2007.
Schubert G, Huster F, Fath P. Physical understanding of printed thick-film front
contacts of crystalline Si solar cellsReview of existing models and recent developments. Solar
Energy Materials & Solar Cells 2006,90: 33993406.
Tljsten B. Strengthening of concrete prisms using the plate-bonding technique. International
journal of fracture 1996, 82: 253-266.
Tljsten B. Strengthening of beams by plate bonding. Journal of Materials in Civil Engineering, 1997,
9: 206-212.
Wendt J, Trager M, et al. Improved quality test method for solder ribbon interconnects on siliocn
solar cells, 35th IEEE Photovoltaic Specialists Conference, IEEE: Honolulu, 22-25 June 2010.
Yang H, Wang H, Chen CK, et al. Effect of binding force between silver paste and silicon on power
degradation of crystalline silicon solar module. Microelectronics Reliability 2013, 54:188-191.
Zhang YP, Yang YX, Zheng JH. Investigation of Ag-bulk/glass-phase/Si heterostructures of printed
Ag contacts on crystalline Si solar cells. Solar Energy Materials & Solar Cells 200892:1011-1015.

11
400

DESIGN AND FABRICATION A DIRECT METHANOL FUEL CELL WITH THE

THERMO ACTUATION BUBBLE REMOVAL MECHANISM
1

Yean-Der Kuan ,* and Min-Shiang Huang , Fong-Hao Wu , Min-Feng Sung

1

Department of Refrigeration, Air Conditioning and Energy, National Chin-Yi University of Technology,
Taichung, Taiwan
Kenda Tires, Changhua County, Taiwan
*ydkuan@ncut.edu.tw

Abstract
This paper proposes a bubble removal mechanism for the direct methanol fuel cell (DMFC) via
embedding a thermo actuation micropump into the DMFC anode flow board. A heating thin film is
fabricated by micro electro mechanical systems (MEMS) technique. The silicon oil is adopted as the
expansion media and filled in the liquid cavity between the heating film and the flow channel which is
made by the polydimethylsiloxane (PDMS). When the electricity is sent to the heating plate, the silicon
oil is heated and expanded, and further squeeze the PDMS flow channel. Then the anode liquid fuel is
compressed and carbon dioxide bubbles produced by the electrochemical reaction are forced to
move toward to the outlet. Such that the mechanism proposed in this paper is able to improve the
bubble retarded problem and enhance the cell performance.
Keywords: Direct Methanol Fuel Cell, Polydimethylsiloxane, Micro Electro Mechanical Systems,
Bubble Removal Mechanism, Thermo Actuation.

Introduction
In recent years, due to energy shortage, many countries are developing alternative energy actively,
and promoting public awareness in green energy. Hence, developing emerging alternative energy has
become a topical subject. Among numerous alternative energy sources, the fuel cell has attracted
wide attention. Proton Exchange Membrane Fuel Cell (PEMFC) is applicable to mobile power supply
for its high conversion efficiency, low noise and short starting time, especially to vehicles. The direct
methanol fuel cell (DMFC) of PEMFC is characterized by simple system, easy fuel refreshment and
approximately ambient operation [1]. It is regarded as most applicable to different portable powers. In
addition, the DMFC system has higher energy density and battery life than lithium ion battery [2], so it
is a promising alternative energy for 3C and peripheral products. The basic working principle of DMFC
is briefly introduced below. The DMFC uses methanol as fuel source. The water methanol enters the
anode flow channel, and a part of water methanol water methanol diffuses via the diffusion layer to the
activated catalyst layer to decompose six positively charged hydrogen ions (H+) and six electrons (e-).
The hydrogen ions are transferred via polymer film to the cathode catalyst layer; and the electrons are
led out of the anode terminal, transferred via the external circuit to the load and reach the cathode
terminal after applying work. The oxygen enters the cathode diffusion layer through the cathode flow
channel, and diffuses to the cathode catalyst layer. Then the oxygen has electrochemical reaction with

401

the hydrogen ions and electrons resolved from the anode side, producing a small amount of CO2,
water and electric energy [3].
In order to enable the DMFC to have higher and stable output, the active supply of liquid and gas is
usually adopted. However, the anode terminal produces CO2 as byproduct after electrochemical
reaction. If the bubble CO2 cannot be removed effectively, the anode flow channel will be blocked, so
that the feed of fuel is obstructed [4]. In view of this, a DMFC with thermal actuated active bubble
removal should be developed, and the fuel cell output is stabilized by active bubble removal.

Research Method
Design concept of thermal actuated bubble removal mechanism
This study refers to the design and production methods in recent studies. Kim et al. used indium tin
oxide (ITO) and Pr on silicon substrate to make heater, and used air as the heated medium, so as to
extrude the valve passage of poly-dimethysiloxane (PDMS) to drive the liquid flow. The results
showed that the flow rate was 78nl/min under DC voltage 55V, 6Hz [5]. Jang et al. used the plasma
enhanced

chemical

vapor

deposition

(PECVD)

and

gas-phase

etching

(GPE)

in

microelectromechanical process to make thermal actuated micropump. The flow rate was 3.1ul/min
under 25V, 5Hz [6]. Jun et al. used Ti and Au as heater, and used air as heated medium to extrude the
flow channel of PDMS, the flow was 116nl within four seconds of operation under 3.5V [7].
Based on the above, the thermal actuated bubble removal mechanism designed in this study uses the
principle of thermal expansion and contraction and flexible PDMS flow channel. Te flow channel is
stressed, so that the bubbles are removed out of the outlet smoothly. The designed source of heat is
that the electrodes heat the metal wire, and the wire transfers heat to the liquid medium. The liquid
expands with heat, so that the left PDMS flow channel is deformed. The fuel in the flow channel is
extruded, compelling the bubbles to move out of the flow channel. When heating is stopped, the flow
channel is restored to the original depth gradually, so that the fuel passes smoothly. The operating
principle is shown in Figure 1.

Figure 1: Operating principle of thermal actuated bubble removal mechanism

Production method
According to the above concept, this work is divided into two major parts. One is to make flexible
PDMS flow channel, the other one is to use micro-electromechanical process to make lightweight

402

heating plate. First, the process starts from the PDMS flow channel, as shown in Figure 2. For
convenient mold processing, the polymethacrylate (PMMA) is used as substrate. The required pattern
is drawn by AutoCAD, and then the pattern is imported into the processing software. The processing
range is selected, and saved as NC code. The CNC engraving machine is used for processing. The
liquid PDMS and hardener are mixed uniformly in ratio of 10:1, rested for 20 minutes, until the air
bubbles dissipate. The liquid PDMS is poured into the mold, placed in the spin coater, rotated at
100rpm for 1 minute, so that the PDMS fills up the mold. After coating, it is put in the vacuum drying
oven, vacuumized to vacuum degree of 30cm-Hg before breaking vacuum. This action is repeated
until the PDMS residual bubbles are removed out of the mold completely. Finally, it is dried at 85
and 50cm-Hg for two hours, hardened and taken out of the mold to obtain the PDMS flow channel
shown in Figure 3.

Figure 2: PDMS flow channel production process

Figure 3: PDMS flow channel

Afterwards, the microelectromechanical system is used to make the heating plate. The process is
shown in Figure 4. First, the epoxy-glass fiberboard is cut to 6" wafer, cleaned to make sure that the
surface is free of smudge. The substrate is spin coated with hexamethylene disiloxane (HMDS) to
enhance the adhesiveness between plate and photoresist, and then it is coated with 5m thick
positive photoresist AZ4620. The panel heater is used for soft bake to remove the excess organic
solvent from the photoresist surface. The substrate is covered with the designed pattern mask. The
exposure machine defines the pattern on the photoresist, and it is put in the developer after exposure.

403

Due to the characteristics of positive photoresist, the photoresist irradiated by UV will be removed. An
apparent pattern appears on the substrate after development, and then the developer is cleaned off
with deionized water, put on the panel heater to remove surface moisture. The microscope is used to
check whether the pattern is identical with design or not, and to check whether there is any residual
water vapor or developer on the surface. After confirmation, it is put in the thermal coater to form the
metal layer. The operating principle of the thermal coater used in this study is that the article to be
coated is put in the upper part inside the chamber body, the tungsten boat is put in the lower part,
holding metal ingot. In order to avoid the foreign matter affecting the purity of metal layer, the chamber
body shall be vacuumized by pump to 5e-5torr before coating, and then the tungsten boat is supplied
with high current, and the metal plating rate is controlled by changing the current. The metal ingot
inside the tungsten boat is molten with high heat, and then evaporated into gas. The metal gas floats
upwards adhering to the surface of article to be coated. The required metal layer is obtained on this
principle. After coating, the substrate with metal is soaked in acetone to lift off the excess metal
outside the pattern, and the ultrasonic oscillator accelerates lift off. Finally, it is cut to the required
appearance and the microelectromechanical heating plate is completed, as shown in Figure 5.

Figure 4: Production process of microelect-romechanical heating plate

Figure 5: Microelectromechanical heating plate

When the above two devices are completed, they are integrated into the single cell fixture. The
exploded diagram of the single cell with thermal actuated bubble removal mechanism developed in

404

this study is shown as Figure 6. The anode terminal has end plate, heating plate, medium storage
chamber and PDMS flow channel; the cathode terminal has end plate and PMMA flow channel. The
membrane electrode assembly (MEA) adopted is Nafion-117 (180m) made by DuPont company.
The effective reaction area is 35mm35mm. The collector plate is made of SUS316 stainless steel,
and its surface is nickel plated to enhance its corrosion resistance. In order to make the MEA stressed
uniformly in the fixture, the cell is locked by 3mm screws. The assembly follows the exploded diagram,
and the screws and nuts are locked by torque wrench to 8kgf-cm. The completed single cell is shown
in Figure 7. After assembly, the heated medium silicone oil is injected into the chamber at the end
plate before test.

Figure 6: Exploded diagram of single cell with thermal actuated bubble removal mechanism
(a. end plate, b. heating plate, c. storage chamber, d. PDMS flow channel, e. collector plate, f. waterproof spacer, g. MEA, h.
waterproof spacer,
i. collector plate, j. cathode channel plate, k. end plate)

Figure 7: Stereogram of single cell with thermal actuated bubble removal mechanism

405

Test platform and method

In order to test the performance of the self-made DMFC fixture, this study designs a test platform
system. This system is divided into experimental apparatuses and equipments and performance
measurement and capture system. The experimental apparatuses and equipments include constant
temperature water tank, peristaltic pump, air pump and float-type flow meter. The DMFC can be
tested under controllable operating conditions. The performance measurement and capture system
consists of DC loader, cell internal resistance meter, computer and data acquisition software. The
software captures data automatically to reduce the experimental errors caused by manual operation.
The platform layout is shown in Figure 8.

Figure 8: Test platform architecture

This study developed a DMFC with bubble removal mechanism, and tests the performance of general
DMFC in the same operating environment and works out their difference. In order to reduce
experimental errors and check whether the MEA is damaged in experiment, a 90mm long, 50mm
wide and 90mm high graphite jig is used as test criterion. The test process is shown in Figure 9. First,
the graphite jig is used for activation and a set of base polarization curve is measured. The designed
fixture is used for test, and it is replaced by graphite jig again to measure the polarization curve,
compared with previous base curve. The next experiment is conducted if the difference value is within
5%, and the difference exceeds the value, the cell is reactivated and compared. This process is
repeated till the end of the experiment.

406

Figure 9: Test process

Results and Discussion

he heat expanded medium used in this study is silicone oil. First, the effect of thermal expansion of
silicone oil on extruding PDMS flow channel is discussed. Clearer results can be observed through
high-speed camera. Figure 10 shows that the PDMS flow channel has swelling deformation at 40 sec,
and it is more apparent at 70 sec. It is observed that when the silicone oil is operated at 5V@0.25A,
the bottom PDMS tends to deform at 20 sec, and then the aforesaid parameters are used to test the
performance.

Figure 10: PDMS flow channel deformation observations

According to the experimental process in Figure 9, the testing environment parameters include indoor
temperature 26, fuel temperature 55, anode flow velocity 5cc min-1, cathode 1L min-1. The
heating plate starting frequency is 5v@0.25A, 20 sec, stop power heat sinking 20 sec, and this
process is repeated. The differences between the single cell with thermal actuated bubble removal
mechanism and general PMMA single cell are shown in Figure 11. It is observed that when the single
cell is in 0.4V operation, the performance difference occurs, the quantity of bubbles increases with the
load, and the effect of bubble removal mechanism becomes more apparent.

407

Figure 11: I-V-P Polarization curves (bubble removal mechanism, general)

As shown in Table 1, the two performances are close to each other when the formation of bubbles is
small under low load. At the maximum power density, the performance of the single cell with bubble
removal mechanism can be increased by 6.4%.

Table 1: Performance sorting table

Conclusion
This study developed a DMFC, which uses thermal actuation to remove bubbles, and uses
micro-electromechanical process to make lightweight heating plate with flexible PDMS flow channel
and silicone oil, so that the byproduct CO2 bubbles are removed out of the outlet smoothly. The
performance of single cell under high load can be increased by 6.4% effectively by using this
mechanism. It may be applied to multi-cell module in the future, so as to further stabilize the
performance output of DMFC.

408

Acknowledgements
This study is financially sponsored by the National Science Council under grant No. NSC
101-2628-E-167-001-MY3.
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G. Aydinli, N. S. Sisworahardjo and M. S. Alam, Reliability and Sensitivity Analysis of Low Power
Portable Direct Methanol Fuel Cell, The International Conference on Computer as a Tool, 2007,
pp. 1457-1462.

J. J. Hwang, FUEL CELL, Third Edition, Taiwan, Sea Bookstore, 2008

G. Q. Lu, and C. Y. Wang, .Electrochemical and flow characterization of a direct methanol fuel cell,
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J. H. Kim, K. H. Na, C. J. Kang

and Y. S. Kim, A disposable thermopneumatic actuated

micropump stacked with PDMS layers and ITO-coated glass, Sensors and Actuators Vol.120,
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W. I. Jang, C. A. Choi, C. H. Jun, Y. T. Kim, M. Esashi, Surface micromachined thermally driven

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D. H. Jun, W. Y. Sim, S. S. Yang A novel constant delivery thermopneumatic micropump using

surface tensions, Sensors and Actuators, Vol. 139, 2007, pp.210215.

409

REPOWERING OF AN EXISTING POWER PLANT BY MEANS OF GAS

TURBINES AND SOLID OXIDE FUEL CELL
Masoud Rokni
Technical University of Denmark, Dept. of Mechanical Engineering, Thermal Energy Section
Building 403, 2800 Kgs, Lyngby, Denmark
e-mail: MR@mek.dtu.dk

ABSTRACT
Repowering is a process consisting in a transformation of an old power plant in order to have a
greater nameplate capacity or more efficiency, which result in a net increase of power generated. As
a consequence of the higher efficiency, the repowered plant is characterized by higher power output
and less specific CO2 emissions.
Usually, a repowering is performed adding one or more gas turbines to an existing steam cycle
which was built decades ago. Thus, traditional repowering results in combined cycles (CC). High
temperature fuel cells (such as SOFC) could also be used as a topping cycle, reaching global plant
efficiency even higher and specific CO2 emissions even lower. Decreasing the operating temperature
in a SOFC allows the use of less complex materials and construction methods, consequently
reducing plant and the electricity cost. A lower working temperature makes it also suitable for topping
an existing steam cycle, instead of gas turbine on the top. This is also the target of this study,
repowering of an existing power plant with SOFC as well as gas turbines.
The plant used here for repowering is the Kyndby power station is an emergency and peak load
facility for Zealand in Denmark. This means the facilities at the station can be started up within
minutes if operational irregularities occur in the high voltage electricity grid or problems arise at other
power stations. Nowadays this station is repowered with two gas turbines but the current study is
about the original steam plant before repowering.
Different repowering strategies are studied here, repowering by one gas turbine with and without
supplementary firing, repowering by two gas turbines with and without supplementary firing and
repowering using SOFC. Plant performances and CO2 emissions are also compared for the
suggested repowering plants.
INTRODUCTION
Due to the ever-increasing demand for more efficient power production and distribution, the main
topics of research and development in the field of electricity production are improving efficiency and
reducing pollutant emissions. Converting existing steam power plant into combined cycle (CC) is
though known as repowering. It would be ideal for an old steam plant in which steam turbine after
many years of operation still has considerable service life expectancy but for example the boiler is
ready to be replaced. The boilers are normally replaced or supplemented with gas turbines and heat
recovery steam generators (HRSG) see e.g. (Kehlhofer et al. 2009). Thus there is an increased
interest in developing an old coal fired steam plants into a CC plant and increase their power output
and efficiency, and at the same time decrease their emissions, see e.g. (Termuehlen 1994), (Kovacik
and Stoll, 1990).
Currently repowering of steam plants can be achieved in two ways; feed water repowering and
boiler repowering, see e.g. (Carapellucci and Milazzo, 2006). The first option uses heat from the
turbine exhaust to raise the feed water temperature instead of bleeding steam. This means that
increased steam flow has to be managed by the low pressure section of the original steam turbine,
requiring either extensive modification of the steam turbine or impairing the repowered plant
performance. The other option, boiler repowering, entails major steam generator redesign or
replacement. Gas turbine exhaust gas is used as heat source for the existing steam cycle. This
increases plant efficiency close to that of new combined cycle plants. Such repowering has been
performed on various old steam plants, see e.g. (Chellini, 1986), (Donatelli, 1990), (Walter et al.,
1996). The second option is widely used across developed countries in which many steam plants are
relatively old and are coal fired, which is also used in this study.
Steam turbine units in older power stations generally have relatively low steam data and can
easily be adapted for use in combined cycles as bottoming cycle for a gas turbine (gas turbines).
Depending on the steam plant data such as live steam temperature, pressure and mas flow, one
needs to screen available gas turbines in the market and choose one which can easily be adapted in
the basic steam plant without changing its original configurations. If one gas turbine cannot supply the
required heat and temperature then one may complement the repowering with a supplementary firing
or two gas turbines. In this study both options will be used.

410

In this study it is also suggested to use a third option which is repowering with SOFC. Solid oxide
fuel cell (SOFC) stacks will soon enter the commercialization phase and therefore it would be
interesting to integrate such technology into repowering of old steam plants.
SOFCs are one of the most promising types of fuel cells, particularly regarding energy production.
They are expected to produce clean electrical energy at high convention rates with low noise and low
pollutant emissions (Calise et al., 2006). The exhaust temperatures of SOFCs are high due to the
high operating temperature of the cells. Additionally, because the fuel utilization in the fuel cell is less
than 100 percent, the unreacted fuel needs to be combusted in a burner. This combustion in turn
produces even hotter off-gases that are perfectly suited for use in a steam generator to produced
steam for the bottoming steam cycle.
Numerous studies have investigated SOFC-based power systems and suggested high thermal
efficiencies in the literature. However, the majority of these studies use gas turbines as the bottoming
cycle, see, e.g., (US Department of energy, 2004), (Riensche et al., 2000) and (Haseli et al. 2008). A
steam turbine has also been used as a bottoming cycle (Rokni 2010a and Rokni 2010b), resulting in
high plant efficiency. At present, using the Brayton and Rankine cycles as bottoming cycles for SOFC
seems to be the most practical because of the maturity of these technologies. Given that the
development trends suggest that the operating temperature of the SOFC will decrease, using gas
turbine as bottoming cycle will become less beneficial over time.
The present work is an analytical study that conducts a thermodynamic investigation of
repowering of old steam plants with SOFC that also functions as a topping cycle for a steam plant
using the heat from the off-gasses exhausted from the topping cycle. The results will be compared
with the traditional repowering strategies using gas turbine as the driving heat. One gas turbine with
supplementary firing, two gas turbines as well as two gas turbines with supplementary firing will be
used. The comparison will be studied in terms of plant thermal efficiency and CO2 emission. The
SOFC is based on a theoretical model with empirical coefficients calibrated from experimental data.
The Stirling engines parameters are chosen by fitting these parameters to a validated feasible
engine.
No investigation on steam plants repowering with SOFC has been found in the open literature,
and therefore, the current investigation seems to be completely novel and might bring up new ideas
on designing new energy system configurations for future applications. It should also be noted that
the system presented here was studied thermodynamically and that the objective of this study was
not to present or discuss the associated costs. The performances of the various plants are compared
in terms of efficiency, fuel consumption and other related parameters.
ORIGINAL PLANT MODEL
The principal components of the plant are the burner, steam generator, high pressure turbine (HP),
two intermediate pressure turbines (IP), low pressure turbine (LP), condenser and deaerator. The coal
burner provides the heat needed for generating steam in a single pressure level steam generator
through economizer (Eco), evaporator (Eva) and super heater (SH). Three steam extractions from the
steam turbines are used to preheat (PH) the sub-cooled water after the condenser. Coal is supplied at
point 61 in the figure while ash is removed from the burner at point 62 in the figure. The coal
composition (mass based) is assumed to be 0.7818 C (solid form), 0.0489 H2, 0.0603 O2, 0.0171 N2,
0.0102 S (solid form) and 0.0817 water (liquid form). The net calorific and gross caloric values are
31120 kJ/kg and 32380 kJ/kg, respectively, with a mean mole mass of 10.34 kg.

411

53
Eva

SH
16

15

54
52

7
EG3

EG1
HP

IP1
2

EG2

EG4

IP2

LP
6

30
8
61

Burner

Eco

20

40
12

51

Condenser

I-1

14
62
55

Deaerator

56

Preheat
13
11

40 10

Air PH
Pump

50

Preheat2
Air Comp

31

41

Throttle1

Con. pump

Throttle2

49

Figure 1. Kyndby original coal steam plant.

The plant net output power is 264MW with an efficiency of about 33% (LHV).Live steam
temperature, pressure and mass flow (point 1 in the figure) is 500C, 80 bar and 280 kg/s,
respectively. The power required to generate such steam is about 756.168 MW, which can be
calculated from enthalpy difference between economizer inlet and super heater outlet (live steam)
multiplying with mass flow rate. This of course is lower than coal power input due to losses through
air preheating and air compressor for the boiler. Main parameters for the turbines are summarized in
Table 1.
Table 1. Turbines parameters.
Turbine
Isentropic efficiency
High pressure turbine
0.885
Intermediate pressure turbine 1
0.878
Intermediate pressure turbine 2
0.811
Low pressure turbine
0.7565

Turbine constant
97.75
766.3
2467
11140

Turbine constant is a parameter that depends on the turbine mass flow, the inlet temperature as well
as inlet and outlet pressure defined as,

CT

m T

(1)

2
p in2 p out

Ambient conditions are assumed to be 25C and 1.01 bar, both for air (point 49 in Fig. 1) and coal
(point 61 in Fig. 1). Other important data are shown in Table 2.
Table 2. The main plant parameters.
Parameter
Value
Coal
Fuel consumption (mass flow), (kg/s)
Fuel consumption (mass flow), (MW)
Burner
Air fuel ration,
Exhaust
Temperatures (C)
Pressure (bar)
Other conditions
Maximum pressure, (bar)
Minimum pressure, (bar)

412

Node in Fig.1
61

25.75
801.146
600
1,2
56
140
1.01
100
0.081

14
9

Others
Air preheater effectiveness, (%)
Generators efficiency, (%)
Power output, (MW)
Plant efficiency based on LHV, (%)

80
97
263.932
32.94

MODELLING
The modeling for SOFC and gas turbine will be briefly explained below while modeling of other
components will be referred to previous publications.
SOFC Modeling
The SOFC model developed in (Bang-Mller and Rokni, 2010) is used in this investigation, which
were calibrated against experimental data for planar SOFC type. For the sake of clarity, it is shortly
described here. In such modeling one must distinguish between electrochemical modeling,
calculation of cell irreversibility (cell voltage efficiency) and the species compositions at outlet. For
electrochemical modeling, the operational voltage (Ecell) was found to be

Ecell E Nernst Eact Eohm Econc

(2)

where ENernst , Eact , Eohm and Econc are the Nernst ideal reversible voltage, activation polarization,
ohmic polarization and concentration polarization. Assuming that only hydrogen is electrochemically
converted, then the Nernst equation can be written as

g f 0
RT p H 2 ,tot pO2

ln
ne F
ne F
p H 2O

p H2 pCO 4 pCH4

E Nernst
pH2,tot

(3)
(4)

where gf0 is the Gibbs free energy (for H2 reaction) at standard pressure. The water-gas shift
reaction is very fast and therefore the assumption of hydrogen as only species to be
electrochemically converted is justified, see (Holtappels et al., 1999) and (Matsuzaki and Yasuda,
2000). In the above equations pH2 and pH2O are the partial pressures for H2 and H2O respectively.
The activation polarization can be evaluated from the ButlerVolmer equation (Keegan et al.,
2002), which is isolated from other polarizations to determine the charge transfer coefficients and
exchange current density from the experiment by the curve fitting technique.
The ohmic polarization (Zhu and Kee, 2003) depends on the electrical conductivity of the
electrodes as well as the ionic conductivity of the electrolyte. This was also calibrated against
experimental data for a cell with anode thickness, electrolyte thickness and cathode thickness of 600
m, 50 m and 10 m respectively.
The concentration polarization is dominant at high current densities for anode-supported SOFCs,
wherein insufficient amounts of reactants are transported to the electrodes and the voltage is then
reduced significantly. Again the concentration polarization was calibrated against experimental data
by introducing the anode limiting current, (Costamagna et al., 2004), in which the anode porosity and
tortuosity were also included among other parameters.
The fuel composition at anode outlet was calculated using the Gibbs minimization method as
described in (Smith et al., 2005). Equilibrium at the anode outlet temperature and pressure was
assumed for the following species: H2, CO, CO2, H2O, CH4 and N2. Thus the Gibbs minimization
method calculates the compositions of these species at outlet by minimizing their Gibbs energy. The
equilibrium assumption is fair because the methane content in this study is very low.
To calculate the voltage efficiency of the SOFC cells, the power production from the SOFC (PSOFC)
depends on the amount of chemical energy fed to the anode, the reversible efficiency (rev), the
voltage efficiency (v) and the fuel utilization factor (UF). It is defined in mathematical form as

PSOFC LHVH 2 n H 2 ,in LHVCO n CO,in LHVCH4 n CH4 ,in rev v U F

(5)

where UF was a set value and v was defined as

E cell
E Nernst

(6)

413

The reversible efficiency is the maximum possible efficiency defined as the relationship between the
maximum electrical energy available (change in Gibbs free energy) and the fuels LHV (lower heating
value) as follows, (see e.g. Winnick, 1997)

rev

g f fuel

(7)

LHV fuel

Additionally, equations for conservation of mass (with molar flows), conservation of energy and
conservation of momentum were also included into the model. Table 3 displays the main parameters
for the SOFC stacks used in this study.
Table 3. The main SOFC parameters used in this study.
Parameter
Value
Fuel utilization factor
0.8
Current density, (mA/cm2)
300
Cathode pressure drop ratio (bar)
0.1
Anode pressure drop ratio (bar)
0.05
Cathode inlet temperature (C)
600
Anode inlet temperature (C)
650
Outlet temperatures (C)
780
DC /AC converter efficiency
0.97
Modeling of Other Components
Modeling of other components such as heat exchangers, pumps, desulfurization reactor, etc. are
adopted from the study of (Rokni, 2013a), in which the reliability of the components modeling was
justified by building a benchmark system consisting SOFC, methanator, heat exchanger, etc. and fed
with different fuels such as natural gas, ethanol, methanol and di-methyl ether (DME). The obtained
results agreed well with the corresponding data obtained by other researchers in the open literature
for all cases studied.
Modeling of Selected Gas Turbine
In (Gas turbine world, 2007) the specification of all gas turbines currently available in the market is
specified. All gas turbines in the data sheet are screened and based on the required temperature as
well as heat for the steam cycle, the gas turbine chosen here is Siemens SGT5 4000F. The
specifications in the specs 2007 are slightly different from the one in Siemens website, which could
depend on improvement. Therefore, an average data is chosen which is summarized in Table 4. A
gas turbine model based on these data is then developed here to capture all important specifications
such as power output, efficiency, etc.
Table 4. Comparison between Siemens SGT5 4000F and the model developed here.
Parameter
Datasheet value
Model
Error (%)
ISO base rating, (MW)
288
290.95
1.0
Heat rate, (kWh)
9114
9111.4
0.0
Efficiency LHV, (%)
39.5
39.5
0.0
Pressure ratio
18
18

Exhaust mass flow rate, (kg/s)

688
688

Turbine speed, (rpm)

3000

Exhaust temperature, (C)

580
580.0

As seen in the exhaust gas temperature if this gas turbine is well above live steam temperature of
500C, allowing for a large terminal temperature and consequently lower HRSG cost. In fact that the
exhaust temperature of the gas turbine must be above 500C, eliminates the choice of many gas
turbines listed in the screening process.
As mentioned above, the minimum power (heat) required for the steam plant is about 756 MW.
From the gas turbine specifications one can calculate its exhaust power by

1
Qexhaust,GT Qin,GT PGT PGT

GT

(8)

414

which gives about 441 MW. This in turn means that one gas turbine alone will not be enough to
generate the required steam and supplementary firing will be necessary. Another option would be
using two gas turbines either without supplementary firing or including supplementary firing.
In modeling ambient temperature and pressure are assumed to be 25C and 1.01 bar,
respectively. Generator efficiency is assumed to be 97% which is typical value. The calculated fuel
mass flow and fuel consumption (based on LHV) are 16.08 kg/s respective 736.7 MW.
The turbine inlet temperature set in the model does not correspond to the inlet temperature of the
real gas turbine. In reality, during the expansion both gases and air cooling are mixed and results in a
lower average temperature. However, in modeling cooling air is neglected and therefore the inlet
temperature would be higher than the reality. Thermodynamically, the most important parameters
would be gas turbine exhaust temperature, exhaust mass flow, fuel consumption, power production
and efficiency which all are calculated correctly.
SUGGESTED REPOWERING CONFIGURATIONS
As mentioned above, the idea is to maintain the steam cycle as it is and replace the burner with a
HRSG. Adding a gas turbine (or gas turbines) on the top of the steam and designing CC is not new
but will be studied here for comparison with the new suggested plant.
Combined Cycles
The first option for CC plant is to use one GT with supplementary firing as shown in Fig. 2. In the
configuration, the HRSG is designed with one drum connected to the evaporator. The off-gases are
sent out at point 55 in the figure. The components settings are not changed for the steam plant at all,
allowing less cost associated for repowering.
61
49

16

50
Combustor

15

EG5
Eva

Compressor

Turbine
51

55

52

48
SuppFiring

53

54

SH
63

HRSG

Eco
1

EG1
HP

7
EG3

IP1

EG4

IP2

LP

EG2
2

30
8

20

40

14
12
Condenser
I-1
Deaerator
Preheat
13
11

40 10

Pump
Preheat2

Con. pump
31
Throttle1

41
Throttle2

Figure 2. Natural gas fired CC plant with one GT and supplementary firing.
As shown in the figure, the fuel (NG) shall be supplied to the gas turbine chamber at point 61 as well
as supplementary firing at point 63. With the estimations shown above the minimum power required
from the supplementary firing will be about 315 MW, which in turn requires a large size burner as
supplementary firing. Another option is to have two gas turbines with or without supplementary firing
as displayed in Fig. 3.
Generally, including a supplementary firing has the pros for allowing
shutting down one gas turbine to undergo service without shutting down the entire plant. In this
configuration, fuel is only supplied to the gas turbines combustion chambers at points 61 and 62, if
no supplementary firing is used. By included supplementary firing then fuel must be supplied to point
63 in addition to the gas turbines combustion chambers (points 61 and 62 in the figure). The HRSG
design is similar to case with one gas turbine, allowing for fair thermodynamic comparison. It should

415

be noted that in the case with two gas turbines the repowering cost is substantially higher than the
corresponding case with one gas turbine.
16
61
49

15

48
Compressor

Eva
Combustor

EG5
55

Turbine

53
52

47

Eco

HRSG

50

54

SH
1

FlueMix
51
43

46
Turbine2

SuppFiring

EG1

63

HP

IP1

IP2

EG3
7

EG4
LP

EG2

EG6

30

Combustor2
Compressor2

14

8
20

44

40

45
12
62

Condenser
I-1
Deaerator
Preheat
13
11

40 10

Pump
Preheat2

Con. pump
31
Throttle1

41
Throttle2

Figure 3. Natural gas fired CC plant with two gas turbines and with or without supplementary firing.
New Hybrid Cycle
The new system suggested here for repowering is presented in Fig. 4, which uses a natural gas fired
SOFC system functioning as a topping cycle, while the steam cycle comprises the bottoming cycle.
For the topping SOFC cycle, the ambient air at 25C is compressed to the working pressure of the
SOFC (normal pressure) and then heated in the cathode air preheater (Cathode PH in the figure) to
600C before entering the cathode side of the SOFC stacks. For the anode side, the fuel was
preheated in a heat exchanger (NG PH in the figure) before it was sent to a desulfurization unit to
remove the sulfur content in the NG. This unit was assumed to be using a catalyst and operated at
temperature of 200C. The heavier carbon contents in the desulfurized gas are cracked down in a
CPO (Catalytic Partial Oxidation) type pre-reformer. Before that, the fuel must be preheated again to
reach the operational temperature of the CPO catalyst, which is accomplished in the reformer
preheater (Ref PH in the figure). The temperature of the pre-reformed gas is supposed to reach
650C which is high enough to be sent to the anode side of the SOFC. The off-fuel out of the fuel cell
is used to preheat the fuel during its paths. The operating temperature of the fuel cell is assumed to
be 780C which is enough to preheat the incoming gas. The entering temperatures mentioned above
are the minimum entering temperatures and are essential requirements for the proper functioning of
SOFC stacks, not only to initiate the chemical reactions but also to avoid cell thermal fractures. The
burner is implemented because all of the fuel will not be reacted in the fuel cell stacks due to SOFC
fuel utilization factor.
The off-gases from the burner have a high heat quality, which can be used to generate steam in a
HRSG through economizer, evaporator and super heater. As discussed in (Rokni, 2010a) and (Rokni,
2012), the off-gases out of HRSG maintains a high quality heat, which can be used to preheat the air
after the compressor in the SOFC cycle. In other words, heat is recycled back to the topping cycle,
and therefore, this technique is called hybrid recuperation. Such hybrid recuperator (HR) is shown to
be very efficient and can increase the plant efficiency significantly. It increases the energy supplied to
the SOFC cycle which in turn decreases the duty of the cathode pre-heater. Therefore, the energy
from the SOFC off-fuel will be higher, allowing for more heat to be available after the burner. Other
parameters assumed for the SOFC plant are summarized in Table 5.
Table 5. System operating input parameters.
Air compressor isentropic efficiency
0.8
Air compressor mechanical efficiency
0.95
Heat exchangers air side pressure drops, (bar)
0.08

416

Hybrid recuperator gas side pressure drop, (bar)

Hybrid recuperator effectiveness
Heat exchangers fuel side pressure drops, (bar)
Reformer compressor isentropic efficiency
Reformer compressor mechanical efficiency
Desulfurizer pressure drop, (bar)

0.1
0.9
0.05
0.85
0.95
0.05

98

Air Comp
99

EG8

De-sulphuriser

83
36

82

86

81

84

80
Ref PH

NG PH

CPO Reformer
56

Cathode PH

95

87

35
85
SOFC
34

37
38
16
15
EVA

55
Hybrid
Recuperator

54

ECO

53

52

89

SH

Burner
88

33
1
FC Air Comp

EG1
HP

IP1

EG3
IP2

EG4

LP

EG2
2
32

30

14
8
20

40
12
Condenser

I-5
Deaerator
Preheat 1
13
11

10

Pump
Preheat 2

Con. Pump
31
Throttle 2

41
Throttle 1

Figure 4. Natural gas fired SOFC steam hybrid plant.

RESULTS AND CONCLUSIONS
Natural gas is assumed to be pressurized and have the following compositions; CH4 = 0.87, C2H6 =
0.081, C3H8 = 0.01, C4H10-N = 0.006, CO2 = 0.02925, H2S = 0.00375.
The calculations show that the heat required from the steam cycle is not enough to use of two gas
turbines without supplementary firing. The exhaust gases out of the gas turbines are mixed but the
total heat provided in the exhausts is still not enough to satisfy the request from the steam cycle and
small amount of supplementary firing is in fact needed. Due to the high excess air in the gas turbines,
the oxygen necessary for the supplementary firing is already bounded in the off gases. Since two gas
turbines are able to provide more than 90% of the heat needed by the steam cycle, then it is possible
to modify the topping cycle in order to avoid the use of supplementary firing. This can be done by
increasing the turbine outlet temperature (TOT) and therefore, in the calculations such option is also
included. Higher gas turbine outlet temperature can be achieved by decreasing the efficiency of the

417

turbine. A simple energy balance shows that the turbine outlet temperature must be about 671C so
that the gas turbines can provide the required heat demand for the steam cycle. Adding 1C margin
then, 672C can be chosen as the optimum turbine outlet temperature. Thus, the calculations for the
CC with 2 gas turbines but without supplementary firing are carried out with outlet temperature of
672C.
The performance comparison among repowering plants presented above is shown in Fig. 5, in
terms of plant net power output. As can bee seen, already with one gas turbine and supplementary
(CC - 1 GT + SF in th efigure) firing the net power can be incaresed by more than 210% compared
to the base case (original steam plant). Adding 2 gas turbines without supplementary firing (CC - 2
GT in the figure) incareses the net power by about 270% while including a supplememntary firing
(CC - 2 GT + SF in the figure) further increases the net power by additional 50% (320% in total).
So far, all such repowering lies withing the CC plants category. The suggetsed repowering with
SOFC without supplementary firing (SOFC in th efigure) incareses the net power more than 375%
(almost 4 times larger). Thus the suggested hybrid SOFCST plant perfoms far better than the CC
plants.

Figure 5. Comparison performance of the repowering plants in terms of power.

Another interesting performance comparison could be plant thermal efficiency and CO2 emissions.
These are displayed in Fig. 6. As demonstrated in the figure, among CC category, repowering with 2
gas turbines and supplementary firing has the best efficiency which is about 53%. This is of course
lower than a new designed CC plant which reaches to about 59%. The reason is that the steam plant
is not designed for the gas turbines but instead the gas turbines are fitted with an existing steam
plant. The CC - 1 GT + SF (CC plant with 1 gas turbine with supplementary firing) as well as CC 2GT (CC plant with gas turbines without supplementary firing) cannot achieve 50% plant efficiency.
However, repowering with SOFC results in plant efficiency more than 60% and can compete with a
new designed CC plant. Again, the efficiency of repowering with SOFC is well below a new designed
SOFC-ST (cf. Rokni, 2010a).
Here, the specific CO2 emission is defined as

eCO2

m CO2
Pel

kg CO2 /kWhel

(9)

which is the mass flow of CO2 per net power output (electricity). As seen in Fig. 6, the specific
emission of CO2 for the base case (coal fired steam plant) is about 1.01 kg/kWh. The results
clearly demonstrate that the higher the efficiency is the lower CO2 emission will be. For the CC
category the combined cycle with two gas turbines and supplementary firing (CC - 2GT + SF) has
the lowest CO2 emission which is about 0.39 kg/kWh which is only about 40% of the original plant.
This of course is much lower than base case, but all the decrease is not only due to plant
efficiency but also because the fuel is changed from coal to natural gas. Therefore, another case is
included in the figure which is steam plant fired with natural gas instead of coal (NG SC in the
figure). Natural gas fired steam plant has an emission which about 60% of the coal fired plant.

418

Figure 6. Comparison performance of the repowering plants in terms of plant thermal efficiency and
CO2 emission.
The suggested repowering with SOFC plant performs best with an emission of about 35% compared
to the original plant, but also about 60% of the original plant fired when natural gas instead.
Other plants calculated data are shown in Table 6, in terms of fuel consumption, total fuel rate,
auxiliary power and supplementary fuel mass flow. As can be seen the auxiliary power consumption
for CC category plants are much higher which is due to compressor of the gas turbines. The auxiliary
power consumption for the presented SOFC plant is relatively very low compared to the CC plants,
which is due to the non-pressurized SOFC stacks. Supplementary fuel consumption for the CC plant
with 2 GT and with supplementary firing is only 3.34 kg/s which is very low, explaining that the two
gas turbines can generate about 90% of the heat required by the original steam plant.
Table 6. Plant performance for different configurations.
Parameter/Configuration
Base
CC - 1GT
CC - 2GT
CC - 2GT
+ SF
+ SF
Fuel consumption, (kW)
801.147
1191.346
1473.322
1626.379
Total fuel flow rate, (kW)
25.75
26
32.16
35.5
Auxiliary power, (kW
17.639
297.254
590.993
590.993
Supplementary fuel rate,

9.92

3.34
(kg/s)

SOFC
1655.807
36.14
118.014

T Q Diagram
To study the reason why the presented repowering with SOFC (SOFC ST hybrid) is superior on CC
plants in terms of plant efficiency, one need to analyze the temperatureheat diagram for HRSG
among others. Such diagram for repowering with SOFC is shown in Fig. 7, in which the temperature
and heat of each components in the HRSG is shown with corresponding node number appear in Fig.
4. For all case the pinch temperature (difference between nodes 54 and 15) is set to 10C. The
terminal temperature difference (difference between node numbers 52 and 1) is about 93C and the
gases leave the HRSG at temperature about 113C. Significant energy has been recovered by hybrid
recuperation, from 218C to 113C, which corresponds to 20% of total energy recovered in the HRSG.
As also seen, both the super heater and economizer uptakes each 20% of the total energy recovered
by HRSG. About 40% of the total energy in the HRSG is allocated by evaporator.

419

Figure 7. The heat - temperature diagram for HRSG of the SOFC ST hybrid system.
Similar temperatureheat diagram is shown for the combined cycle with 2 gas turbines and with
supplementary firing. The reason that CC - 2GT + SF is chosen is that this combined cycle performs
best among all combined cycles studied here. The gases leave the HRSG at a temperature of about
164C which is significantly higher than the case with SOFC repowering. Thus lower energy has been
recovered in HRSG for the CC case compared with SOFC case. The terminal temperature is about
165C which is also higher in this case when compared with previous case. Here both super heater
and economizer uptake each about 25% of the energy in the HRSG, which is slightly higher than the
SOFC case. Evaporator absorbs about 50% of the energy from HRSG, which is also higher when
compared with SOFC repowering. All these together make the area between the off-gases
temperature line (red line) and the water-steam temperature line (blue line) to be larger than the case
with SOFC repowering. This in turn means that less exergy has been wasted in HRSG when SOFC
repowering is used. In other word, for the case with SOFC repowering, the off-gases temperature line
approaches the corresponding line for water-steam and therefore resulting in less exergy loss and
higher effectiveness loss for HRSG. The effectiveness of HRSG can be defined as (see e.g. Rokni,
2012);

HRSG

T gas,in T gas,out

(10)

T gas,in Tambient

then the HRSG effectiveness can be calculated as 78.4% and 84.5% for the CC - GT + SF combined
cycle respective SOFC - ST hybrid system.

420

Figure 8. The heat - temperature diagram for HRSG of the CC - 2G + SF combined cycle.
Effect of SOFC Current Density and Operating Temperature
As discussed in (Rokni, 2012), increasing SOFC current density decreases plant efficiency, while
increasing SOFC operating temperature is in favor for plant efficiency. Similar study can also be
carried out here, which is presented in Fig. 9. Generally, increasing SOFC current density decreases
power generated by SOFC and thereby decreases plant efficiency as well. This is of course also true
for SOFC powering, see Fig 9a. Decreasing current density below 100 mA/cm2 will not be realistic
since the cell voltage reaches to a very high value, 0.9374V, close to open circuit voltage. At this
current density plant efficiency reaches to 67.4% which is significantly higher than the corresponding
efficiency at 300 mA/cm2.
On the other hand, increased SOFC operating temperature is not always in favor for plant
efficiency as established in Fig. 9b. In fact, there exists an optimum operating temperature at which
the plant efficiency is maxima, which is in contrast with the study of (Rokni, 2012). Note that in the
study of (Rokni, 2012) steam plant is designed based on the SOFC topping cycle while here the
topping SOFC cycle is designed to provide required heat for the existing steam plant. This maximum
efficiency is calculated to be about 62% at temperature of 740C, when current density is set to 300
mA/cm2. This temperature is lower than the current temperature technology of 780C, which in turn
means companies endeavor to decrease the SOFC operating temperature, is in favor for such
repowering system if this is decreased slightly.
68

63
62
61

Plant Efficiency [%]

Plant efficiency [%]

66
64
62
60
58

60
59
58
57
56
55

I = 300 mA/cm2

54

56

53
54
100 150 200 250 300 350 400 450 500

52
650 675 700 725 750 775 800 825 850
SOFC operating temperature [ C]

SOFC current density [mA/cm2]

a)
b)
Figure 9. Effect of SOFC current density (a) and operating temperature (b) on plant efficiency of
repowering with SOFC.
CONCLUSIONS

421

Repowering of an existing coal fired power plant is studied and different repowering design is
analyzed. In addition, a new repowering with SOFC plant is also suggested. CO2 emission from
different plant design are calculated and compared with each other. The following conclusions can be
drawn;
Repowering with SOFC produces the highest power
Repowering with SOFC have the highest plant efficiency which is about 60% and competes
with a new CC plant in terms of efficiency
CO2 emission from the SOFC repowered plant is far less than the original coal fired plant
but also much lower than if the original plant was powered with natural gas instead of coal.
Among CC plants, the combined cycle with two Siemens SGT5 4000F gas turbines with
small supplementary firing has the best performance with an efficiency of 53% which is
considerably lower than a new designed CC plant.
It is possible to use two Siemens SGT5 4000F gas turbines without supplementary firing if
gas turbines outlet temperature is increased by reducing expander efficiency.
There exists an optimum SOFC operating temperature at which plant efficiency is maxima.
This temperature is calculated to be 740C for 300 mA/cm2.
It is possible to reach plant efficiencies above 65% if current density is low enough.
NOMENCLATURE
cp
Specific heat, J/kgC
CT
Turbine constant
E
Voltage, V
F
Faradays constant, C/mol
e
emission, kg/kWh
g0
Standard Gibbs free energy, J/mol
gf
Gibbs free energy, J/mol
m
Mass flow, kg/s
Molar reaction rate, mol/s
n
ne
Number of electron
P
Power, W
p
pressure, bar
T
Operating temperature, K
Q
Heat, J
R
Universal gas constant, J/mol K
UF
Fuel utilization factor
Greek Letters
difference
efficiency

Subscripts
act
activation
conc
concentration
ohm
ohmic
rev
reversible
v
voltage
Abbreviations
AP
Anode pre-heater
CC
Combined cycle
CPO
Catalytic partial oxidation
CP
Cathode air pre-heater
EG
Electric generator
Eco
Economizer
Eva
Evaporator
FC
Fuel cell
GT
Gas turbine
HHV
Higher heating value
HP
High pressure
HR
Hybrid recuperator
HRSG Heat recovery steam generator
IP
Intermediate pressure
LHV
Lower heating value

422

LP
NG
PH
SH
SOFC

Low pressure
Natural gas
Preheater
Super heater
Solid oxide fuel cell

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51(12):233039.
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analysis of a hybrid solid oxide fuel cell (SOFC)Gas turbine system. Energy 31:327899.
[3] Carapellucci R. and Milazzo A. 2006. Repowering combined cycle power plants by a modified
STIG configuration. Energy Conversion and Management 48(5):15901600.
[4] Chellini, 1986. Repowering a steam power plant with a gas turbine. Diesel and Gas Turbine
Worldwide 18(8):2830.
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integrated planar solid oxide fuel cell (IP-SOFC). Chemical Engineering 102(1):6169.
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International Gas Turbine Institute (Publication) IGTI 5:201206.
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of Energy, Office of Fossil Energy, National Energy Technology Laboratory.
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2000. Clean combined-cycle SOFC power plantcell modeling and process analysis. Power
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423

GEOTHERMAL ENERGY SOURCES IN SIRNAK REGION-TURKEY

Oyku BILGIN
Sirnak University, Mining Engineering Department, 73000, Sirnak, Turkey
ykbilgin@yahoo.com, ykbilgin@atauni.edu.tr

ABSTRACT
Geothermal energy is defined as hot water and steam which is formed by heat that accumulated in
various depths of the Earth's crust; with more than 20 oC temperature and which contain more than
fused minerals, various salts and gases than normal underground and ground water. Geothermal
energy is clearly distinguishable with its low cost, clean, safe and natural properties. Geothermal
energy depending on temperature is used in various areas such as particularly electric power
generation, house heating, greenhouse heating, thermal tourism-treatment and industry. The main
purpose of this study is to investigate the status of South-East Anatolian the geothermal resources
regarding all the spa and hot waters of Turkey in comparing bathing and curing qualities. Turkey has
many thermal tourism areas. This thermal springs temperature is between 45-100 oC. The main
purpose of this study is to investigate the status of South-East Anatolian the geothermal resources
regarding all the spa and hot waters of Turkey in comparing bathing and curing qualities. As
regarding chemical analysis from collected hot waters, it is determined that various salts as well as
the high content of non-clay minerals and exchange capacity of the muds, make them suitable for
therapeutic and aesthetic applications. Eastern Anatolia Region because of geological structure has
many but low temperature geothermal resources. In this study, is investigated recommendations
about Eastern Anatolia-Sirnak region geothermal resources study area, usage areas, assessment
with the Aquachem Software programme application. In here, they have geothermometers reservoir
temperature, ion contained in the water, gas and the temperature at which thermal isotope ion
exchangeability or comes to have solubility in water is based on the determination.
Keywords: Aquachem, Software Programme, Geothermal waters, Geothermometer, Sirnak,
Turkey.
INTRODUCTION
Geothermal water reservoir (aquifer rock) while staying in the chemical composition of the water rock
interaction becomes. Thermal waters in the depths of the earth geothermometer equations gained by
using these chemical ingredients can be calculated reservoir temperatures. The temperaturedependent thermal water geothermometers water and mineral balance in the application of basic
assumption is that the deep reservoir rock provided. Many studies even at low temperatures of 50100 C, such as water and mineral balance in terms of many of the main ion component of the show
provided it [1]. Measured surface temperatures of the thermal waters from the geothermal reservoir
rocks in the lower temperatures. Decrease in temperature during the thermal waters rise to the
surface in contact with the reservoir rocks rocks heat exchange with a cold mixture of groundwater,
reservoir rock, breaking with the atmosphere impermeable rocks (rock cover) or the absence of
factors such as the fact that a very fine cause [2]. Reservoir water temperature, yields the true
information about the chemical properties of the reservoir is obtained by examining the far reaching
wells. However, for the determination of the temperature of the reservoir opening of the deep drilling
is quite laborious and expensive process. Therefore, the source or shallow geothermal boreholes
located in the area of chemical content obtained using thermal waters, many researchers have tried
to be calculated by the temperature of the reservoir, which is derived Geothermometers.
Geothermometers reservoir temperature or in other words, the calculation of the temperature of the
primary thermal water, ion contained in the water, gas and / or the temperature at which thermal
isotope ion exchangeability or comes to have solubility in water is based on the determination. Two
major classes of chemical reactions in terms of the equations used Geothermometer:
Based on the temperature-dependent solubility of a mineral geothermometers (silica
geothermometer)

424

Fig. 1. Solubility of a mineral in silica geothermometers [3], [4].

Fig.1 shows, solubility of quartz (curve A) and amorphous silica (curve C) as a function of
temperature at the vapour pressure of the solution. Curve B shows the amount of silica that would be
in solution after an initially quartz-saturated solution cooled adiabatically to 100 C without any
precipitation of silica. At low T (C) C qtz less soluble amorph. silica more soluble. Silica solubility is
controlled by amorphous silica at low T (C) quartz at high T (C).
Depending on the temperature of ions dissolved in ion-exchange reactions based on the cation
geothermometers (Na-K, Na-Ca, Na-K-Ca, K-Mg, Li-Na etc.) [1]. The equations used to calculate the
temperature of the geothermal reservoir studies chemical parameters (SiO2, Na, Ca, Mg, K, Li, etc.).
Sampling and analysis to be more easily identified because of silica and are preferred cation
geothermometers. Mainly used to determine the temperature of the reservoir is as follows
Geothermometers: Silica geothermometers, Na-K geothermometers, Na-K-Ca geothermometers,
Na-Li geothermometers, K-Mg ve Li-Mg geothermometers, Na-K-Mg geothermometers.

Fig. 2. Na/K atomic ratios of cation temperatures [3], [5].

Na/K atomic ratios of well discharges plotted at measured downhole temperatures in Fig. 2. Curve A
is the least square fit of the data points above 80 C. Curve B is another empirical curve. Curves C
and D show the approximate locations of the low albite-microcline and high albite-sanidine lines
derived from thermodynamic data.

EASTERN REGIONAL GEOLOGY

In south eastern anotolian region primer time to present different rock types at different ages are
shown on site. Young basalts as heating rocks are coming up to the surface with widely covering
surface as widened the landfill near Diyarbakir. At north site of Batman those are remaining in deep
providing the heating rock for geothermal waters. Cretaceous Mardin limestones are reservoir rocks
for raw patrol and geothermal energy recourses. Those micrinitic and high porous structures
limestone rocks. there are also some rarely sub dolomitic levels among them. Geological units in
south eastern Anatolia is Zagros suture zone and the Arabian plate and sometimes in north part that
suture zone. At the north side of thrust zone is formed by allochthonous masses and at the south

425

rock formation is autochthonous. at south autochthonous rocks of Suture Zone are reservoir
carbonaceous rocks for geothermal energy and oil. The oldest of those rocks are Cretaceous aged
(early and mid) old dolomite and limestone. Over that formation, rocks are irregularly covering Sirnak
Formation (Late Cretaceous Pliocene). Upper zone is limestone and dolomite and horizontal
evaporites are crossing. Over Sirnak formation irregular Eocene - Oligocene aged evaporites
(gypsium) consecutive bands of Midyat Formation. Midyat formation is covering with regular
Neocene sediments. Neocene sediments are clayish limestones and evaporites. From that lithology,
carbonaceous rocks are reservoir rocks for geothermal energy. in Taldere site at the north of
Batman, an oil drill has reached 2400 m. depth. At that depth, as told lithology, Mardin formation is
observed. The reservoir rocks of Taslidere geothermal water is formed with Mardin Formation.
dolomites and limestones of Mardin formation are very porous and highly permeable lithological form.
That formation is the reservoir rock of Taslidere spa waters. At deeper depths, basalt formation is
forming heating source of water. Taslikonak and Germav spas are similar to Taslidere.

Fig. 3. Geological map of Sirnak Region (Scale: 1/100.000) [6].

GEOTHERMAL WATER OF SOUTH EASTERN ANATOLIAN REGIONS

According to Tectonic and stratigraphical structure of South east anotolian region, there is required
reservoir rocks and earth rocks properties for geothermal energy and producing proper fluids for
geothermal energy with suitable fault systems, especiallly flowing waters through deep fissures [7]. In
the general site of the region North-South oriented compression earth crust have subjected to eastwest directed tension and on the direction of occurred tension stress cracks asthenosphere olivine
basaltic magma raised. Among Diyarbakir-Sanliurfa-Mardin Karacadag site, Gaziantep Yavuzeli site
and Idil-Cizre site basaltic magma reaching earth surface by flowing in some periods has left spread
lava flows. At the North of Batman unreached magma to surface have impregnated in some locations
and resulted in hot sites. This situation is clearly seen on the regional hot flow map made by Mine
Technical Research Institute [7]. As Geothermal energy resources of South east region has a great
importance. In the region, Diyarbakir -Cermik, Batman - Taslidere, Siirt - Billoris, Sirnak - Hista,
Sanliurfa - Karaali, Mardin - Dargecit-Germav, Adiyaman Tilek ve Gaziantep - Kartalkoy sites are the
hot spring sites (Fig. 4).

426

Fig. 4. Geothermal water map of study areas

There is a hot spring well at pumping 510 oC hot water to pensions and Physical Rehabilitation
Center of Dicle University in Diyarbakir. There are those hot springs such as 270 oC hot spring water
benefited as spa in Gaziantep Kartalkoy, 63.5 oC hot spring water collected two pools and used as
spa in Mardin, five different hot springs 30-35 oC warm water used as spa in Billoris Siirt, 39-49 oC
five hot springs water used as spa in Karaali Site-Sanliurfa, 51 oC hot waters used for greenhouse
heating and spa rheumatism cure [8]. In addition, there are other spa hot waters such as 83 oC hot
water used as spa and greenhouse warming in Kozluk-Taslidere-Batman, 67 oC hot water used as
spa in Hsta geothermal site in Guclukonak-Sirnak, and 51 oC hot water at 21l/s flow rate used as
spa in Cermik Town, Diyarbakir. There are Hista, Zumrut Dag, Besta ve Nasfaran geothermal sites
in Guclukonak Town of Sirnak City of among 9 cities in the region of South East Region of Turkey in
the cast of South East Anotolia Project. Hista spa is located in Guclukonak town. The hottest spring
water in the field is at 67 oC. Spa water of hot spring mainly contains calcium and sulphite ions. It is
determined that spring water is at 7 l/s flow rate and at 7.15-7 pH. It is thought that flowrate may
increase regarded hydro geological conditions in the field. Spa bath water of the field is mainly
benefited in curing rheumatism and gynecological treatments. Zumrut mountain spa is 7 km. far to
Ilicak village in Beytebap town and at near 1 l/s flowrate and 39 oC temperature. This spa water is
used in dermatological, kidney and rheumantal curing. Besta spa is located near 30 km far in NorthEast side of Sirnak City and has two different spa, of which one is used water bath spa and the other
one is benefited in dermatological, rheumatism gynecological curing. Nasfaran spa is a few kms
away from Kumcati village and have two baths, of which one is mud bath spa and other is water bath
and even as clean water. It is commonly known that mud bath spa for curing of acne, eczema and
fungus is preferred [9], [10].
GEOTHERMAL WATER OF SIRNAK
Guclukonak-Hista Geothermal Site; At the bottom of site, Late Cretaceous-Early Paleocene aged old
Germav formation with grayish, greeny colored shales, marn sandstone, mudstone stripes is layering.
Up this layer, Paleocene- Early Eocene aged old Gerc formation with winy colored marn, sand
stone, pebble stone, rarely contained limestone mid layers. Over this formation, Eocene aged Midyat
formation is occurred with limestones at the bottom chalky stones. As young unite Quaternary aged
alluvia is observed with unbound sand, clay, pebbles. Geothermal sources in Guclukonak Hista Site
was at 63.5 oC at 2 l/s flow rate. Chemical analysis of hot spring specimens obtained from hot water
of Sirnak City are given in Table 1. In this region, hot water collected is used in spa centers.
Table 1. Chemical analyses of hot springs in Sirnak [11].
(oC)

pH

K+

Na+

NH4

Ca++

Mg++

SiO2

CO2

63.5

7.3

18

69.4

0.1

324

15.7

(mg/l)
37
14.4

427

HCO3-

CO3

SO4--

CI-

180

<10

926

93

Belong to studying area of the determination of the temperature of the reservoir rock, the Na / K
geothermometers benefited from them. Reservoir rocks temperature of the study area was
calculated by with the help of Aquachem the software program. Analysis values of the calculations
made by the program according to the values in Table 1 and Table 2 were submitted.
Table 2. Properties of hot waters in Sirnak.
Sodium Adsorption Ratio
Sample ID
Waterytpe
(SAR)
SIRNAK

Ca-SO4

Exchangeable Sodium Ratio

(ESR)

Magnesium hazard
(MH)

0,17

7,40

1,02

This account geothermometres graph of the program according to the values presented in Fig. 5. Fig.
5 anion-cation values of analyzed water samples of the study area see that some low some high.
Geothermometer temperatures read by the program for the source of Sirnak 1973 Fourner Na / K
reservoir temperatures as are presented 331 C.

Fig. 5. Na/K Geothermometer diagram.

CLASSIFICATION OF GEOTHERMAL WATERS in SIRNAK

Volcanic and tectonic belts contain high-temperature waters are classified as follows according to the
dominant anions [12]. These are chloride waters, sulphate waters acid Sulfate-Chlorine waters,
bicarbonate waters and dilute chlorine-bicarbonate waters. Thermal springs in the area, with the help
of Aquachem the software program using the program are classified. For ease of visualization
diagram collectively ions diagrams are used quite often one of the Piper diagram of hydrogeology.
Piper diagram of the anions and cations (%meq / 1terms) separately shown in the triangle and all the
ions in two separate joint consists of a rectangle as shown Fig. 6 Triangular facies types of diagrams,
the incidence of water, the water classification and comparison of the rectangle facilitate [12]. Durov
diagrams, EC and pH characteristics of the water next to the main ions are taken into consideration
(Fig. 7).

428

Fig. 6. Belong to hot water sources Piper Diagram

Durov Diagram

Fig. 7. Belong to hot water sources

Fig. 8. Belong to hot water sources H. Schoeller Diagram

sources Stiff Diagram

Fig. 9. Anion-cation showing the sources of hot

By using Anion-cation concentrations of each water samples caan be classified. The most commonly
used method of classifying Mg2+, Ca2+, Na+, K+, Cl-, HCO3 and SO42- ions concentrations in
semi-logarithmic paper milliequivalents with draw Schoeller Diagram obtained. For each water
sample obtained by combining the values of the different ions concentration profile, differences in
water samples and provides easily viewed. Concentrating ions of hot waters in studying area shown
in Fig. 8.

429

CONCLUSIONS
Geothermal energy has the potential to play an important role in the future energy supply of Turkey.
The main uses of geothermal energy cover a wide range of applications such as space heating and
domestic hot water supply, greenhouse heating, swimming and balneology, industrial processes,
heat pumps and electricity generation. Based upon the current status, the majority of geothermal
applications in Turkey have been realized in district heating systems. However, natural thermal spas
are found almost in every location in Turkey. The hot springs are rich in calcium and magnesium
salts with water temperatures ranging from 25 degree centigrade to 140 degree centigrade and are
said to cure a wide range of ailments like rheumatism, dermatological, gynecological and
neurological diseases. Physical exhaustion and digestive disorders are also said to be cured. In
Middle and Eastern Regions, geothermal resources have rich variety about minerals. So they used
for spring and thermal tourism.The use of spring water in therapy and spa is as old as the whole
history. Since Roman times, there has been a strong tradition of water cures. Especially, and
significantly the curing value and the contents of thermal spring waters were related to its ion
composition and mineral salt concentrations and muddy content and the temperature of the water.
Thus, different spas are recommended for various medical disorders of the gastrointestinal tract, of
the respiratory system or for ear, nose, throat, skin, and gynecological or rheumatological disorders.
All spas, however, seem to be recommended for rheumatological diseases and osteoarticular
disorders, independent of whether the water is high sulfur, bicarbonate, sodium chloride,
bicarbonate-chloride, or other mineral salt. The current study investigates on the effects of general
chemical compasition aspects to soud easten anatolian spas and in general region of easten
anatolian regarding defined curing. Short-term and long-term effects of curing are changing
regionally and disorder types. The clay contents of mud related hot water resources was affected the
ion-change depending on calcium and other alcali contents improving healing muscle and
rheumethical disorders. Hence eastern regional spas are more advantageous rather than south
eastern spa waters. Salt mineral contents of hot water resources affected insentual curing treatment
such as sulphate bicarbonate and carbonate ion concentrations are beneficial healing kidney other
pain disorders. Hence eastern regional spas have similar advantageous to south eastern spa waters
and while similar chemical contents was observed. pH and temperature parameters of hot water
resources affected insentual curing treatment such as physical therapy, dermitalogical curing are
beneficial healing phsical disorders. Hence eastern regional spas have similar advantageous to
south eastern spa waters and while similar chemical contents was observed.

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430

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431

PROPOSAL AND ANALYSIS OF MID-TEMPERATURE SOLAR

THERMOCHEMICAL HYBRIDIZATION POWER SYSTEM FOR IMPROVING OFFDESIGN PERFORMANCE
a

a,b

Hui Hong *, Xiufeng Liu

Institute of Engineering Thermophysics, Chinese Academy of Sciences (IET, CAS),
Beijing, China, honghui@iet.cn
b
University of Chinese Academy of Sciences, Beijing, China, liuxiufeng@iet.cn
*Corresponding author: honghui@iet.cn

ABSTRACT
In our previous research, we proposed a mid-temperature solar hybridization power system with
methanol decomposition. This kind of solar thermochemical hybridization process enables to use the
solar heat below 300C which provides the reaction heat to drive methanol decomposition for
producing solar fuel with CO and H2. Our previous results showed that the peak net solar-to-electricity
efficiency was about 35%, whereas the annually net solar-to-electricity efficiency was less than 28%.
Consequently, there is an important problem of poorly annual solar-to-electricity efficiency, further
sharpening the development predicament of the cost-effective concentrating solar energy use. Based
on our manufactured 15kW mid-temperature solar thermochemical power prototype, a new system is
proposed. According to the energy level concept, the thermodynamic performance is also analyzed.
Both of the solar-driven methanol decomposition and the solar-driven methanol steam reforming are
synergistically integrated for producing solar fuel(CO and H2), which is combustioned to drive an
internal engine for generating electricity. In this way, in contrast to priviously individual solar-driven
methanol decomposition, the proposed system can make it possible to obtain more annual production
of solar fuel, increasing the annual solar-tochemical efficiency. In addition, the interaction between the
solar irradiation and the flow rate of reactants on thermodynamic performance is revealed. As a result,
the annual solar-to-chemical effciency would be increased by more than 2.5%, the annually net solarto-electricity efficiency would expected to be improved by 4.5 percentage points. The results here
would provide an approach to improve the annually thermodynamic performance for concentrating
solar power generation, leading to the reduction in the solar field size per kilowatts of electricity.
Keywords: Mid-temperature solar thermochemical hybridization, Off-design Thermodynamic
performance, Concentrating solar energy power generation
1.INTRODUCTION
Solar thermochemical process is based on the use of concentrated solar thermal energy for
driving an endothermic chemical transformation. More recently, solar thermochemical process has
attracted much attention worldwide and abundant research is available. Steinfeld et al proposed a
high-temperature solar process for co-production of zinc and synthesis gas (Steinfeld et al.,1995)
and designed a novel solar chemical reactor to perform the combined ZnO reduction and CH 4reforming processes(Steinfeld et al.,1998). Rodat et al performed the hydrogen production from
the solar thermal decomposition of natural gas in a high-temperature solar chemical reactor and
experimentally studied the reactor performances (Rodat et al., 2009). Tamme et al developd and
demonstrated a novel process with solar steam reforming of methane, which resulted in a fuel
saving of about 30% compared to the conventional natural gas-fired combined process (Tamme et
al., 2001).
So far, most of solar thermochemical processes focus on the utilization of solar thermal
energy concentrated at above 800C or moderate upper temperature under a fixed solar irradiation,
solar thermal energy at around 200-300C has not been paid more attention. In our previous
studies, we originally proposed a new solar thermal power cycle which integrates methanol
decomposition and middle-temperature solar thermal energy at around 150300C (Hong et al.,
2005). the net solar-to-electricity efficiency of the proposed cycle could reach 35%. Mechanism of
upgrading the energy level of solar thermal energy at around 200C was revealed based on the
second law of thermodynamics (Hong et al., 2008). A 5 kW middle-temperature solar
receiver/reactor was originally proposed and manufactured for the first time (Jin et al., 2007).
Based on the receiver/reactor, a series of experiments of solar-driven methanol decomposition and
methanol steam reforming were conducted from 150C to 300C (Hong et al., 2009; Hong et al.,
2012). The results indicated that the application of integrating solar thermal energy at around 150300C with methanol decomposition or methanol steam reforming is a feasible and promising
approach and could lead a new direction and high-efficiency utlization of middle-temperature solar
thermal energy.
Recently, we studied the thermal performance of solar-driven methanol decomposition system
for power generation with internal-combustion engine. For this kind of solar thermochemical

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hybridization power system, the peak net solar-to-electricity efficiency would be expected to be
about 35%, whereas the annually net solar-to-electricity efficiency would be less than 28% due to
instant solar irridiation, resulting in a poor thermodynamic performance. In this paper, We propose
a new solar thermochemical hybridization power system for improving the annually net solar-toelectricity efficiency. In the new system, methanol decomposition and methanol steam reforming
are synergistically integrated under varied solar irradiation.
The objective of this paper is (1) to propose a new solar methanol hybridization
thermochemical power system. (2) to disclose the thermodynamic performance of this new system
at design and off-design condition. (3) to investigate the new systems potential for reduce the
exergy destruction with the aid of energy level concept.
2.DESCRIPTION OF THE REFERENCE SYSTEM AND THE NEW SYSTEM
2.1.Configuration of the reference system

CH3OH 4

CH3OH

5 CO, H2

CO+2H2

Fig.1(a) Schematic diagram of endothermic reaction in the reference system

HE1

CH3OH

HE2
3

4
5

V1

14

6
Air

9
7

LVS

ICE

10
11

12

13

V1,2,3,4 Valve 1,2,3,4 P Pump HE1,2 Heater Exchanger 1,2 C Collector

LVS Liquid-Vapor Separator ICE Internal-Combustion Engine G Generator
Fig.1(b) Configuration of the reference system

In this study the solar driven methanol decomposition power system is chosen as the
reference system. Fig.1(b) shows the configuration of the reference system. It can be roughly
divided into two processes: the mid-temperature solar-driven methanol decomposition process (12-3-4-5-6-7) and solar fuel combustion process (8,9-10-13,11-12).
In the solar-driven methanol decomposition process, the liquid methanol (1) is pumped up to
about 5 bar (2) by the pump, and enters the heat exchanger 1 (HE1), where the methanol is
preheated by heat recovery from the hot reaction products. In order to keep the methanol (4) at a

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constant pressure and temperature of 4 bar and 150C, respectively, The preheated methanol (3)
need to flow through HE2, absorbing heat (14) from the engine exhaust gas (11-12). A parabolic
trough solar concentrator in an east-west direction is used to concentrate solar thermal energy at
200~300C. The receiver/reactor is directly heated by the concentrated solar thermal energy. In
the solar receiver/reactor (4-5), the methanol decomposition reaction (CH3OHCO+2H2,
H0298K=90kJ/mol) takes place, yielding syngas containing CO and H2. The reaction products (6)
enter into the liquid-vapor separator (LVS) after condensed in HE1. In the LVS, the unreacted
liquid methanol (7) is recycled, the syngas flows into the ICE.
The fuel of combustion process is syngas. Syngas as engine fuel has been studied by many
researchers (Boehman et al., 2008; Hemmings et al., 2012; Sahoo et al., 2011). The combustion
of H2 could improve the internal-combustion engines thermal efficiency and power output.
Syngas(8) is combustioned with air(9) in the Internal-combustion engine for generating electricity .
The exhaust gas is divided into two streams by a splitter: stream (12) is used to provide heat for
HE2 (11-12), the other stream (13) is sent to the environment.
2.2.Configuration of the new system
Although the performance of solar-driven methanol decomposition system is very well on
design condition, when solar irradiation is low, the net solar-to-electricity efficiency is very low.
Therefore, the annually net solar-to-electricity efficiency is much lower than that on design
condition. To solve the problem , a new solar thermochemical hybridization system is proposed, as
shown in Fig.2. In this study, we use mean solar irradiation Im (Jin et al., 2007), which is obtained
by multiplying the solar beam irradiation and cos(), the is the incidence angle and cos() can be
calculated. The annual average mean solar irradiation Im is 366 W/m2. The new system is divided
into two processes: the hybridization thermochemical process and the solar fuel combustion
process. In the hybridization thermochemical process, the solar-driven methanol steam reforming
is integrated with the solar driven methanol decomposition. When mean solar irradiation is below
366W/m2, the solar-driven methanol steam reforming is used; when mean solar irradiation is
above 366W/m2, the solar driven methanol decomposition is used.
When the mean solar irradiation is below 366W/m2, liquid methanol (1r) and water (15r) is
introduced into the mixer in the mole radio of 1:1.2. The mixture is then pumped into HE1 (2-3),
preheated by heat recovery from the hot reaction products (5-6). A part of engine exhaust heat (14)
is used to reheat the mixture. The mixture (4) then can be introduced into the solar receiver/reactor
in a constant pressure and temperature of 4 bar and 150C, respectively. In the solar
receiver/reactor (4-5), the methanol steam reforming reaction (CH3OH+H2OCO2+3H2,
H0298K=50kJ/mol) is drived by the solar thermal energy concentrated at around 150~223C.
Subsequently, the reaction products (6) are condensed in HE1 and enter into the LVS. The liquid
methanol outflow (7) enters into the mixer for recycle. The gaseous solar fuel (8) containing CO2
and H2 enters into the internal-combustion engine and is combustioned for generating electricity.
When solar irradiation is above 366W/m2, Valve 1 and 2 would be turned off , and the process
turns to be the solar-driven methanol decomposition process described before.
The solar fuel combustion process is the same as the combustion process of solar-driven
methanol decomposition system, except that stream (8) is composed of H2 and CO2 with mole ratio
of 3:1. CO2 dilution could reduce the combustion temperature and then remarkablely decrease the
NOx emission with little decrease in brake thermal efficiency (Chen et al., 2012).

CH3OH 4

CH3OH+H2O
CO2+3H2
(When Im<366W/m2)
CH3OH

H 2O

CO, H2 (When Im>366W/m2)

CO2, H2(When Im<366W/m2)

CO+2H2

(When Im>366W/m2)
Fig.2(a). Schematic diagram of endothermic reaction in new system

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CH3OH

1d

1r

P 2

V1
16r

M
15r
H2O

HE1

V3

V2

4
5

7d

7r

HE2

6
14

Air

V4

9
7

LVS

ICE
10

12

11

13

Fig.2(b). Configuration of the new system

3.SIMULATION AND SYSTEM PERFORMANCES

3.1.Simulation
The location selected for the present analysis is Beijing in China at a latitude of 39.5N.
NRELs standard SAM library database provides all the required solar data. Four typical days are
chosen for each season. The solar direct normal irradiance (DNI) of four typical days are shown in
Fig.3.

Fig.3. DNI of four typical days

The system was simulated by using the ASPEN PLUS code. RedlichKwongSoave equation
was applied to calculate the thermodynamic properties. In the simulation, the heat loss of
receiver/reactor was given by (Gong et al., 2010): Qloss=0.1405 Tabs(C)+1.16E-8T4abs(C) . The solar
thermochemical reactor temperature was the same as that of the concentrated solar thermal
energy and there was no side-reaction. The work for pumping the liquid methanol was negligible.
The engine was a constant-speed, watercooled, four-stroke, single-cylinder, direct injection, and

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compression-ignition engine (Sahoo et al., 2011). The engine fuel is syngas or mixture of H2 and
CO2 with a mole ratio of 3:1. The most relevant assumptions of the simulation are summarized in
Table 1.
Table 1. Main assumptions for simulation
Parameter

Specification
Concentrator

Concentration ratio

70

Concentrator length (m)

Concentrator width (m)

2.5

Aperture area (m )

10

Optical efficiency

0.73

Mirror reflectivity

0.92

Heat loss (W/m)

30~90
Receiver/reactor

Inner diameter (mm)

31

Outer diameter (mm)

35

Length (m)

4.7
-1

-1

Heat conductivity (Wm K )

390

Coating emissivity

0.085

Coating absorptivity

0.85

Glass envelope inner diameter (mm)

51

Glass envelope outer diameter (mm)

54

Glass envelope transmittance

0.95

Glass envelope emissivity

0.88
-1

-1

Glass envelope heat conductivity (Wm K )

1.2

Catalyst bed length (m)

4
Engine

Number of cylinder

Bore (mm)

78

Stroke (mm)

84

Connecting rod length (mm)

180

Engine compression ratio

17.5:1

Engine rated power

10kW

Engine speed

1500rpm

3.2.Performance of the reference and new system

Like other solar thermochemical hybridization power systems, The solar-to-chemical efficiency
and net solar-to-electricity efficiency, as two important indicators, are considered to evaluate the
system performance (Pitz-Paal et al., 2011). The solar-to-chemical efficiency is defined as the
portion of solar energy converted into chemical energy:

solar to chemical

time

v(t )*x(t )*H r (t )dt

I *S A dt

time m

Where v(t) denotes the mole flow rate of liquid methanol, x(t) denotes the conversion of
methanol in thermochemical reaction. Hr(t) is the enthalpy of thermochemical reaction
corresponding to per mole of the reactant at a temperature of Treactor. SA refers to the effective area
of the parabolic trough concentrator.

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The net solar-to-electricity efficiency is defined as the ratio of concentrated solar energy into
work output:

net , sol to elec

time

(W Wref )dt

Qsol ,th dt

time

Where W and W ref are, respectively, resprenting the work output of the solar thermochemical
hybrid power system and the reference work output of methanol combustion in a same internal
combustion engine. Qsol,th represents the solar thermal energy reached to the receiver/reactor.
We choose 550W/m2 as the design solar irradiation. In the design condition, the solar driven
methanol decomposition process is used by both of the reference and the new system. Simulation
results on the design condition and the fixed condition are shown in Table 2. The net solar-toelectricity efficiency on design condition is 34.4%. On the fixed solar irradiation of 366 W/m2, the
new systems net solar-to-electricity efficiency is 11 percentage points higher than the reference
system.
Table 2. Simulation results of design irradiation and setted irradiation
2
2
550W/m
366W/m
Parameters
Reference
New
Reference
New
system
system
system
system
Input energy(W)
Methanol
25671.4
25671.4
25671.4
25671.4
Solar energy
4015
4015
3660
3660
Output energy (W)
Methanol recovery
3012.4
3012.4
11348.6
1049.7
Power
9220
9220
5520
9877
Loss(W)
Opitical and heat loss
309
309
1326
1112.3
Engine cool water loss
11486
11486
8157.4
11203.9
Engine exhaust loss
5659
5659
14328
7138.2
Efficiency (%)
System power efficiency
34.6
34.6
30.7
34.9
Solar-to-chemical efficiency
63.3
63.3
59.2
60.3
Net solar-to-electricity efficiency
34.4
34.4
22.2
33.2

The annual performance of the reference system and the new system are summarized in Table
3. In comparison with the reference system, the new sytems annual power efficiency increases
1.3 percentage points. The annual solar-to-chemical efficiency increases 2.5 percentage points
and the annually net solar-to-chemical efficiency increases 4.6 percentage points.
Table 3. Annual performance of the new system and the reference system
Annual performance
Parameters
Reference system
New system
Input energy(MJ)
Methanol
329467
338747
Solar energy
65182
65182
Output energy
Methanol recovery(MJ)
133041
102577
Power(MW.h)
80066
96072
Efficiency (%)
System power efficiency
30.6
31.9
Solar-to-chemical efficiency
42.7
45.2
Net solar-to-electricity efficiency
27.4
32.0

4. DISCUSSION
4.1. Comparison of solar-to-chemical efficiency

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Fig.4. Comparison of solar-to-chemical efficiency on four typical days

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Fig.4 illustrates the comparison of solar-to-chemical efficiency on four typical days between the
new systwm and the reference system. A relatively higher solar-to-chemical efficiency of new
system can be obtained when Im is below 366W/m2 on each typical day. This is due to the fact that
the methanol conversion of methanol steam reforming reaction is higher than that of methanol
decomposition reaction when Im is below 366W/m2. The results illustrate that the new system could
convert more solar energy to chemical energy.
4.2. Comparison of combustion irreversibility loss with energy level concept
Energy level proposed by Ishida (Ishida and Kawamura,1982) is used as the property that
represents the quality of released or accepted energy for a given process. It is defined as the ratio
of exergy change to energy change H, namely, A=/H =1-T0S/H. Energy level of Gibbs
free energy is defined as the ratio of Gibbs free energy change G of a chemical reaction to
energy change H, namely, B=G/H.
In the solar thermochemical hybridization process, the methanols energy level of Gibbs free
energy can be described as B1=G1/H1, the reaction products energy level of Gibbs free energy
can be described as B2=G2/H2. Where G1, G2 denotes the Gibbs free energy change of
methanol and endothermic reaction products, respectively. H1, H2 denotes the energy change of
methanol and endothermic reaction products, respectively. A description of the equation of energy
level for fuel combustion is given in Appendix. According to Eq. (A5), when the energy level of
Gibbs free energy decreases, the exergy destruction in the combustion reaction is also decrease.

Fig.5. Comparison of energy level of Gibbs free energy with Im

Fig.5 shows comparison of energy level of Gibbs free energy with mean solar irradiation Im. In
the reference system, B2 decreases with the rise of Im. This means that by converting methanol to
solar fuel through the methanol decomposition process, the combustion irreversibility loss
decreases. When Im is below 366W/m2, B2 of the new system is much lower than that of the
reference system at the same mean solar irradiation, which means that through the integration of
solar-driven methanol steam reforming, combustion irreversibility loss of methanol can be utilized
more effectively. The comparison of combustion irreversibility loss on four typical days can be
illustrated in Fig.6.

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Fig.6 Comparison of combustion irreversibility loss on four typical days

4.3. Comparison of energy upgrading of mid-temperature solar thermal energy

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In the solar thermochemical process, solar heat drives the endothermic reaction and be
converted into chemical energy of solar fuel. The low grade energy level of solar thermal energy
can be upgraded to high grade chemical energy. That is to say, the upgrade of solar thermal
energy level Asolar is dependent on the degradation of methanols Gibbs free energy level B. The
relative upgrade in energy level of solar thermal energy (Jin et al., 2005) can be defined as Aru
=(A2-A1)/A1, where A1 denotes the energy level of solar thermal energy and A2 denotes the energy
level of endothermic reaction products.
Fig.7 illustrates the comparison of Aru on four typical days between new system and reference
system. In the reference system, Aru increases with the increase of Im when Im is below 366W/m2.
The reason is that the decrease of B2 offers the driving force to increase Aru. The decrease of B2
has been illustrated in Fig.5. Aru in the new system is much higher than that in the reference
system when Im is below 366W/m2, which is showed in Fig.8. This is because the decrease of B2 in
the new system is much larger than that in the reference system. Therefore, more chemical exergy
of methanol can be used to increase the low grade energy level of solar thermal energy.

Fig.7. comparison of solar thermal energy level upgrade with Im

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Fig.8. Relative upgrade of solar energy level on four typical days

4.4. Comparison of net solar-to-electricity efficiency

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Fig.9. Comparison of net solar-to-electricity efficiency on four typical days

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Fig.9 illustrates the comparison of net solar-to-electricity efficiency on four typical days
between the new system and the reference system. As shown in Fig.9, the net solar-to-electricity
efficiency of the new system is much higher than that of the reference system at time when Im is
below 366W/m2. The annually net solar-to-electricity efficiency of the reference system and the
new system are 27.4%, 32%, respectively, The new systems net solar-to-electricity efficiency is
4.6 percentage points higher. Besides, the new systems net solar-to-electricity efficiency is more
stable than reference system.
There are mainly two reasons for the increase of net solar-to-electricity efficiency. First, the
increase of solar-to-chemical efficiency means that more solar energy were converted to the solar
fuels chemical energy in the new system. Second, the increase of relative upgrade in energy level
of solar thermal energy means that more chemical exergy of methanol is converted to solar
thermal energy through the chemical reaction. Therefore, the annual net solar-to-electricity
efficiency is higher in the new system.
5. CONCLUSION
A new solar hybridization power system integrating methanol decomposition and methanol
steam reforming was proposed. The new and reference systems irreversibility was analysisd with
the energy level concept, the thermodynamic performance is also analyzed. As a result, the annual
solar-to-chemical efficiency of the new system increases 2.5 percentage points. The annally net
solar-to-electricity efficiency increases 4.6 percentage points and becames more stable. The new
system provide an approach to improve the annually poor thermodynamic performance for
concentrating solar power generation.
APPENDIX A
In a chemical reaction process, the Gibbs free energy change dG and exergy change dE in at
a given temperature T are respectively:
(A1)
dG dH TdS
(A2)
dE dH T0 dS
where dH (kJ/mol) is the total enthalpy change in a process, TdS (kJ/mol) is the heat equivalent
energy in a process, and dS (kJ/Kmol) is the entropy change in a process, T refers to reaction
temperature (K) and T0 denotes the environment temperature (K).
For the energy conversion in a combustion process, the heating value of fuel Hf is
completely converted into thermal energy because there is no work produced. A combustion
process can be divided into an exothermic reaction at a given temperature T and a heat transfer
process without work (Jin et al., 2005). Based on the functions of Gibbs free energy and exergy,
the exergy of fuel E f and Gibbs free energy change G are respectively:

E f H f T0 S

(A3)

(A4)
G H f T S
Where S denotes the entropy of this process. The Carnot cycle efficiency is c =1 T0 / T .
Thus, Eq.3 can be rewritten as
E f H f c G(1-c ) (A5)
Eq.(A5) states that the exergy of fuel in combustion ( E f ) is composed of two parts: workequivalent energy of G(1 c ) , associated with chemical exergy, and thermal exergy of H f c .
Traditionally, G(1 c ) is often regarded as an exergy destruction in the combustion reaction.
It may be also found that E f on the left-hand side of Eq.(A5)represents the exergy input;

G(1 c ) on the right-hand side of Eq.(A5) stands for the exergy destruction, and
correspondingly H f c refers to the exergy output of thermal energy. An important thing to be
emphasized here is that a part of G(1 c ) should be considered as usable chemical exergy,
which is not simply destroyed. Dividing both sides of Eq.(A5),we have :
Af c B(1 c ) (A6)
Eq.(A6) is the specific equation of the energy level for the combustion of fuel. It states that
during the energy conversion in combustion, the energy level of fuels ( A f ) is the sum of the
Carnot cycle efficiency c and the product of B and (1 c ) .

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In eq.(A6), the utilization of the energy level of fuels ( A f ) in combustion is closely related to
the B(1 c ) and the Carnot cycle efficiency of c .Since the chemical energy of G(1 c ) in the
exergy of fuel ( E f ) could not be converted into useful work in the combustion reaction,

B(1 c ) as an unavoidable degradation of energy level is destroyed.

NOMENCLATURE
Im

mean solar irradiation, W /m2

DNI

direct normal irradiance, W /m2

Qloss

heat loss of receiver/reactor, W

Tabs

temperature of receiver/reactor, C

v(t)

mole flow rate , mol/s

methanol conversion

Hr

reaction heat, kJ/mol

SA

effective area of concentrator, m2

work output of solar hybridization power system, kW

W ref

work output of methanol combustion, kW

Qsol,th

solar thermal energy reached to the receiver/reactor, W

energy level

energy level of Gibbs free energy

Aru

relative upgrade in energy level of solar thermal energy

carnot cycle efficiency

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SYNTHESIS OF A NOVEL HUMIC ACID-BASED POLYCARBOXYLIC

DISPERSANT FOR COAL WATER SLURRY
Shaobo Deng

Qing Cao Li e Jin

Cungui Zhong

(College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan

030024, China)
Corresponding e-mails: qcao2000@163.com(Qing Cao);
dengshaobo1987@163.com(Shaobo Deng)

Tel: 86-0351-6014476

ABSTARCT
Using humic acid as a raw material, acrylic acid and maleic acid as graft monomer, potassium persulfate
and sodium bisulfite as an initiator, a novel humic acid-based polycarboxylic-type (HAP) dispersant for
1

coal water slurry (CWS) was synthesized. The product was characterized by TGAIR and H-NMR. With
the single factor experiment, the optimized conditions of synthesis were as following: the mass ratio of
o

humic acid and monomer was 1:1.08, the initiator dosage was 5%, the reaction temperature was 75 C,
the reaction time was 3 h. The product has been applied to prepare CWS with Linfen coal in Shanxi
province. It showed that the product performed excellent dispersivity and stability for CWS. When the
contents of dispersant is 0.5 w %, the apparent viscosity of CWS prepared is 505 mPas. Comparing with
humic acid as a dispersant, the penetration ratio is 12.87% higher than the latter. And the dehydration
rate was reduced by 1.85% and the concentration of CWS increased by approximately 2.0 wt%. This
work found a new route for utilizing humic acid and enlarged the selecting range of the dispersant for
CWS. It has a positive significance for protection of environment.

Keywords: coal water slurry; dispersant; humic acid; synthesis

1. INTRODCUTION

It is estimated that the combustion of fossil fuels is still a main way of energy use in the
world, about 70-80% of which is supplied by coal. In other words, the pollutants caused are
contributed mainly by combustion of coal. Therefore, cleaning utilization technology of coal
has been developed widely, such as gasification, integrated gasification combined cycle
(IGCC) and coal water slurry (CWS). The strict environmental legislation urged researchers to
develop a new utilizing way of coal to replace conventional combustion technology. Since
CWS has higher combustion efficiency, thermal efficiency and lower emissions of SOx, it has
been paid more attention. However, many factors such as type of dispersant and coal affect its
properity [1-3]. Normally, the concentration of coal for CWS arrived at 60-70 wt% and the
amounts of dispersant was about 1.0 wt% The formation of CWS is greatly influenced by
dispersant although the dosage is low. So far, many commercial dispersants have been
developed [4-5], categorized as sodium naphthalene sulphonate and polyolefin series, but the

447

price is expensive and some sediments appears in CWS [6-7]. In addition, the existence of
atomic sulfur and nitrogen in dispersant severely affects the environment. Therefore, it is very
necessary to develop a new dispersant, which is efficient and environmental.
Humic acid (HA) is an organic matter being macromolecule, existing widely in nature.
Its basic structure composes of lots of aromatic rings, some aliphatic rings and heterocyclic. It
is very similar with the structure of the coal [8], thus it performs a good adsorption between
coal particle and HA. In this paper, we aimed at fabricating a novel humic acid-based
polycarboxylic (HAP) dispersant, which possess a good dispersion performance and stability,
and have environmental and economic benefits.
2. EXPERIMENTAL
2.1 Experimental materials

The commercial products of humic acid sodium, acrylic acid (AA), maleic acid (MA),
potassium persulfate (KPS), sodium bisulfate, sodium hydroxide was freshly dissolved into
20wt% solution before use, hydrochloric acid was diluted to 20wt%.The above mentioned were
analytical reagent.
Linfen coal taken from China was used in this investigation. The proximate and ultimate
analyses of coal sample are listed in Table 1.The coal was first crushed in a jaw crusher, then
was dried in vacuum at 105for 24 h [9], finally through the national standard screener.

Table 1 Proximate analysis and ultimate analysis of Linfen coal

Proximate analysis / w% (ad)

Ultimate analysis / w% (ad)

FC

1.05

7.07

33.22

58.66

79.80

4.83

6.49

1.39

0.41

2.2 Synthesis of humic acid-based polycarboxylic (HAP) dispersant

Ensure the quality of humic acid sodium and sodium hydroxide ratio is 5:1, adding
appropriate distilled water to dissolve and standing for 24 h, then centrifuged the supernatant
fluid and removed residue. The residue was neutralized with aqueous hydrochloric acid at
pH=3, then continue centrifuged to remove hydrochloric acid solution, the precipitate was
neutralized with appropriate amount of sodium hydroxide at pH=8. Finally, the products was
o

dried below 80 C, repeat the above operation two times can obtained pure humic acid sodium.
Using solution polymerization method, appropriate amounts of distilled water and the
above obtained were placed in a 250ml three-necked flask equipped with a reflux condenser,
feeding inlet and thermometer, the quantitative monomer( AA and MA) were added slowly by
constant-voltage funnels within 30 minutes, then sodium bisulfite and KPS as initiator were
added. Afterward they were stirred with 400rpm and heated at a certain temperature for a

448

period of time to obtain black polymer solution, finally the mixed solution were neutralized with
sodium hydroxide at pH=8, dried and achieved the dispersant.
2.3 Infrared spectrum analysis, Thermogravimetric analysis and 1H-NMR spectra

Table 2 Particle size distribution of Linfen coal

Coal particle size mesh

Distributionwt %

20-40

40-120

42

120-200

200-300

Fourier transform infrared (FTIR) in the range of 500-4000cm

-1

were recorded on

German Bruker Tensor-27 FTIR spectrophotometer; Thermo gravimetric analysis (TGA) of

1

WCT-2D (China, Beijing)was used. The H-NMR spectrum was measured on a 600 MHz
spectrum (BRUKER-600 spectrometer, Germany) using D 2 O as the solvent and the
probe temperature of 25.
2.4 CWS preparation and viscosity measurements

The coal power was mixed slowly in a pot containing known quantities of
dispersant and deionized water. The dispersant was stirred for 10 min at 1200rpm with
the amount of pulp water required for solids ratio calculation to ensure homogenization
of the CWS. The slurry was left for study of its properity. According to the multi-peak
grade blending technology of Texaco [10], the particle size distribution of Linfen coal
sample is shown in Table 2.
The apparent viscosity of CWS was tested by rotating viscometer (China,
Shanghai, and NDJ-79), The temperature was kept at 251 and the shear rate of
-1

100s .

449

<325

35

2.5 CWS stability measurements

The stability of CWS was evaluated by the glass rod penetration test[11-12] (penetration
ratio,%)and the storage time was 72 h, the manner was similar to that in the studies described
by Dincer H and co-workers. After the CWS preparation, it was stored in a glass cylinder(3 cm
in a diameterCWS layer 15 cm in height)at room temperature for a definite period. A glass rod
(5mm in diameter, 20g in weight) was spontaneously dropped down from the CWS surface to
the cylinder bottom, and it stopped when the tip got in contact with the hard sediment. The
penetration ratio was calculated as follows:
Penetration ratio (%) =d t /d m 100 %
Where d t is the distance of rod travel (cm) and d m is maximum distance of rod
travel (cm).
Dehydration rate test [13]: the free moisture was exsuction by a pipette from CWS surface
every 12 h, weighted and calculated the proportion.
3. RESULTS AND DISCUSSION
3.1 Chemical structure

The infrared spectrum was used to analyze the chemical structure of the dispersant. Fig.1
shows the infrared spectrum of the products. The adsorption peak in 1377cm

-1

is the

-1

carboxylate group of humic acid;1235cm is the stretching vibration of -O- of ether linkage, the
-1

-1

adsorption peaks in 1712cm and 1610cm are the stretching vibration of the carboxylic acids,
those proved the existence of C=O and COO-.the above analysis results shows that the
dispersant was synthesized.
As shown in Fig.2the peaks at 5.85 ppm were attributed to the H related to the double
boundsthe ring structure of benzene of HA, the peak at 2.0 ppm and 1.3 ppm proved the
existence of CH and CH2.The reagent made active hydrogen transfer to the D2O, so the
peak about carboxylic acid groups disappeared
3.2 Thermogravimetric analysis

Fig.3 is the weightlessness curve of the product at 0-800.We can find that the small
molecule of polymer and water were decomposed before 100, the maximum decomposition
level is 497, confirmed that the dispersant suitable in high temperature environment.
1.05

HAP
H A

1.00
0.95

450

Mass fraction/%

0.90
0.85
0.80
0.75
0.70

HAP
H A

ppm
1

Fig.2 H-NMR spectrum of HAP

3.3 Influences of reaction conditions on the apparent viscosity of CWS

3.3.1 Mass ratio of HA and monomer

The main influence factor is the mass ratio of HA and monomer on the polymerization
process. It is seen from Fig.4 that the apparent viscosity of the CWS decreases constantly
before the mass ratio of 1.08 and then increases. When the mass ratio of HA and monomer is
1:1.08, the apparent viscosity of CWS achieves the minimum. It is due to the contents of
carboxylic groups in the modified products improves with the increase of monomer. If the mass
ratio of HA and monomer exceed 1.08, the contents of carboxylic groups never continues to
increase significantly. Meanwhile, the hydrophilic groups and hydrophobic groups attained an
appropriate proportion, and hindered dispersant to form adsorbed film on the surface of coal

451

particles. Therefore, the optimum ratio of HA and monomer is 1:1.08.

3.3.2 Dosage of initiator

The effect of initiator dosage on the apparent viscosity of CWS is shown in Fig.5.With the
increase of the dosage of initiator, the apparent viscosity of CWS decreases first and then
increases sharply. When the dosage of initiator is 5%, apparent viscosity reaches the
minimum. Because the dosage of initiator have a great influence on the polymerization rate
and the relative molecular mass. When the content of initiator exceeds 5%, the active sites of
reaction increases, meantime the molecular mass of dispersant reduces. Consequently, the

1600

1100

1400

1000

viscosity/mpas

viscosity/m Pa s

apparent viscosity of CWS is higher.

1200
1000
800
600

3.3.3 Reaction temperature

900
800
700
600
500

400

0.4
Ensure
the 0.6mass 0.8ratio 1.0of HA1.2 and monomer and
of initiator
constant,
2% the dosage
3%
4%
5%
6%

m (HA) / m (m onom er)

content of initiator

meanwhile the reaction time remains steady. The influence of reaction temperature on the
Fig.4 Effect of m (HA) / m (monomer) on

apparent viscosity of CWS is observed in Fig.6.With the increase

of the
reaction
Fig.5 Effect
of content
of temperature,
initiator on
viscosity of coal water slurry

the viscosity
of coal
water slurry
the apparent viscosity of the CWS decreases slightly at first
and then
increases
abruptly.

Around the 75, the CWS reaches the minimum viscosity, because the low temperature can
not initiate polyreaction, eventually affect the molecular weight. While the high temperature will
accelerate consume of initiator and can not supply sufficient initiator to keep the appropriate
rate of polymerization, finally lead to the low molecular weight. So the best reaction
temperature is 75.
1200
1100
Viscosity/mpas

Viscosity/mpas

825

750

675

600
525 3.3.4
60

Reaction time

1000
900
800
700
600
500

Ensure the mass ratio of HA and monomer and the dosage of initiator constant,
65

70

75

2.0

80

2.5

3.0

3.5

4.0

Reaction temperature
/ reaction temperature. The influence
meanwhile maintain
a certain
of/hreaction time on the
Reaction time

Fig.6 Effect of reaction temperature on

Fig.7 Relationship between reaction time and the

the viscosity of coal water slurry

viscosity of coal water slurry

452

apparent viscosity of CWS is observed in Fig.7.The CWS has the lowest viscosity when
reaction time keep 3 h. It can be explained that the short time can not made the polyreaction
adequately and affect the degree of polymerization. With the increase of reaction time, the
density of monomer and dosage of initiator reduced, and the graft site also reduced.
In summary, the synthesis optimized conditions were obtained: the mass ratio of HA and
monomer was 1:1.08, the initiator dosage was 5%, the reaction temperature was 75 , the
reaction time was 3 h.
3.3.5 Influence of dosage of dispersant on viscosity of CWS

The relationship between viscosity and dosage of dispersant was observed in Fig.8 under
the condition of 67wt% CWS. With the increase of dispersant, the apparent viscosity
decreased slowly. However, when the dosage of dispersant exceeds 0.5%, the apparent
viscosity increased suddenly. This is due to the hydrophilicity of coal surface enhanced with
the increase of dosage of dispersant, at the meantime, the negative charge of coal surface and
steric hindrance reinforced, finally the viscosity of CWS decreased.
3.3.6 Static stability of CWS

The purpose of this study was to investigate the stability properties of the product and HA
for use in CWS formulated from the Linfen coal. All the CWS were prepared at dispersant
dosage of 0.5wt %( on dry coal basis) and coal contents were 67wt%.
100

1000

96
92

Penetration/%

Viscosity/mPas

900

800

700

600

500

88
84
80
76
72

0.3

0.4

0.5

Dosage of dispersant

0.6

0.7

12

24

36

48

60

Storage time/h

72

84

96

Fig.8 Relationship between viscosity

Fig.9 Relationship between storage time

and dosage of dispersant

and penetration rate

As seen in Fig.9, within the first 24 h, the penetration ratio of CWS prepared from HA
slightly high than prepared from HAP, after 4 d the penetration ratio was 85.45%, but from the
36th h, the former is higher than the later, the maximum penetration ratio differ 12.87%, and at

453

this time the later still has a downtrend, while the former remained inerratic. Fig.10 shows the
influence of the storage time and dewatering rate, within the storage time, the dewatering rate
of CWS prepared from HAP lower than prepared from HA, the dewatering rate up to 2.53% in
the 24h,at the end of observation, the former has 1.85% lower dehydration rate than the latter.
As to the reason, the hydrophilic -COOH groups bring down the surface tension of water,
enhanced the negative charge of coal surface and increases the electrostatic repulsion, thus
the CWS have a better dispersity.
3.3.7 The determination of the highest concentration of CWS

According to the requirement of CWS about GB/T18855-2008, the concentration of CWS

in the range of 65%-70% were made, as seen in Fig.11, with the increase of concentration, the
viscosity is gradually increased. When the concentration was 70%, the viscosity of CWS
prepared from HA is 1424 mPas, but CWS prepared from HAP is 1095 mPas. thus the HAP
can reduce the viscosity significantly and improve the concentration of CWS about 2%.
9

2000

1800
1600

Viscosity/mPas

Dewatering rate/%

H A
HAP

5
4
3
2

1400
1200
1000
800
600

400

40 CONCLUSIONS
12

24

36

48

60

72

200
A novel humic acid-based polycarboxylic dispersant of
coal
65 water
66 slurry
67 was 68synthesized
69
70
Storage time/h
/%ratio of
by solution polymerization, the synthesis optimized conditions were obtained: Coal
theloading
mass

Fig.10and
Relationship
storage the
timeinitiator dosageFig.11
Relationship
between
viscosity and
humic acid
monomerbetween
was 11.08,
was 5%,
the reaction
temperature
and dewatering
rate3 h. The HAP obtained from optimized
coal concentration
was 75 , the reaction
time was
process is used to

prepare CWS, and the HA is used as dispersants for comparison. The results show that HAP
has far better dispersing effect than HA. The static stability also proves that HAP is an effective
dispersant. Meanwhile, the research enhances the utilization value of humic acid, enlarges the
selection range of the dispersant of coal water slurry, and has potential applications for
improve energy utilization efficiency.

REFERENCES
[1] Zhou, M.S. Kong, Q. Pan, B. Qiu, X.Q. Yang, D.J. Lou, H.H. 2010,Evaluation of treated black
liquor used as dispersant of concentrated coalwater slurry. Fuel 89:716723.
[2] Zhou, M.S. Qiu, X.Q. Yang, D.J. 2008, Influence of dispersant on bound water content in

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71

coalwater slurry and its quantitative determination, Energy Conv Manag 49:30633068.
[3] Toshio, K.K. Hidehiro, K. 2004,Effect of sodium aromatic sulfonate group in anionic polymer
dispersant on the viscosity of coalwater mixtures, Energy Fuels 18:652-654.
[4] Wang, R. K,Liu, J. Z,Yu,Hu, Y. X,Zhou, K, Cen, K. F, 2011, The slurrying properties of coal water
slurries containing raw sewage sludge, Energy Fuels 25:747752.
[5] Boylu, F. Atesok, G. Dincer, H. 2004, Effect of coal particle size distribution, volume fraction and
rank on the rheology of coalwater slurries, Fuel ProcessTechnolpgy 85:241250.
[6] Sayeda,G.H. Ghuibab, F.M, Abdoub, M. I. Badrb,E.A.A.Tawfikb,S.M. Negmb,N.A.M.
2012,Synthesis surface and thermodynamic parameters of some biodegradable nonionic
surfactants derived from tannic acid, Colloids Surf. A, Physicochem. Eng. Aspects 393: 96104.
[7] Guo, Z. Z,Feng R,Zheng Y F,Fu X.R.2007,Improvement in properties of coal water slurry by
combined use of new additive and ultrasonic irradiation.Ultrasonics Sonochemistry 14:583-588.
[8] Li, J.G. Zhang, G.H. Liu,L, Zhao, F.2012,Synthesis and Evaluation of Sulfonated Humic
Acid-Acryli Acid Graft Copolymer Applied as Dispersant in Coal-Water Slurry. Advanced
Materials Research334: 581-582.
[9] Zhou, M.S. Qiu, X. Q. Yang, D. J.Lou, H. M,Ouyang, X. P.2007,High-performance dispersant of
coal water slurry synthesized from wheat straw alkali lignin, Fuel ProcessTechnolpgy
88:375-382.
[10] Zhu, J. F, Zhang, G. H, Zhuo, M. Shang, T. 2012, Synthesis and performance of a comblike
amphoteric polycarboxylate dispersant for coal-water slurry. Colloids and Surfaces A
412:101-107.
[11] Boylu, F, Atesok, G, Dincer, H. 2005, The effect of carboxymethyl cellulose (CMC) on the
stability of coal-water slurries. Fuel 84:315-319.
[12] Qiu. X. Q, Zhou M. S, Yang. D. J,Lou, H. M,Ouyang, X. P,Pang, Y, X. 2007,Evalution of
sulphonated acetone-formaldehyde(SAF) used in coal water slurries prepared from different
coals. Fuel, 86:1439-1445.
[13] Zhou, Z. J,Li, X,Zhou, J.H,Liu, J. Z,Cen, K. F, 2012, Evaluation of surfactants used in biomass
coal water slurries. Journal of China coal Society 37:147-153.

455

MODELING FOR PASSIVE ALKALINE MEMBRANE

DIRECT METHANOL FUEL CELL
*

Hao Deng, Kui Jiao , Yan Yin, Qing Du

State Key Laboratory of Engines, Tianjin University, 92 Weijin Rd, Tianjin, China, 300072
*

Corresponding author: kjiao@tju.edu.cn; tel: +86-22-27404460; fax: +86-27383362

ABSTRACT
In this study, a two-dimensional two-phase steady-state numerical model is developed for
passive alkaline anion exchange membrane direct methanol fuel cell (AAEM-DMFC) based on
the appropriate simplifying assumptions, taking into account the major mass transport and
electrochemical phenomena. The numerical model is solved under galvanostatic conditions
(cell current density is fixed to obtain the corresponding cell voltage), and its prediction is
compared reasonably with experimental data in the literature. Two important parameters,
methanol feed concentration and operating temperature, are investigated. In the high current
density region, cell performance is improved with the increase of methanol feed concentration
and operating temperature due to the mass transfer processes and faster electrode kinetics.
However, greater methanol crossover also are reported, resulting in more significant cathode
polarization loss and lower open circuit voltage, and this effect is more significant in the low
current density region.
Keywords: passive alkaline anion exchange membrane direct methanol fuel cell,
two-dimensional two-phase steady-state numerical model, polarization loss, ohmic loss, mass
transport phenomena
1. INTRODUCTION
Because of the theoretically high energy density of methanol (6100 Wh/kg at 25

C ),

reasonable reaction kinetics and easy fuel handling, direct methanol fuel cell (DMFC) now
attracts significant attention as the promising power source candidate for mobile electronic
devices (Zago et al., 2012).

Fig. 1. Schematic diagram of a typical passive DMFC.

456

Recently, passive DMFC has been widely investigated due to its several outstanding
advantages, including much simpler structure compared to traditional active DMFC (with air
compressor and fuel pump), and increased energy efficiency brought by the minimized or
eliminated ancillary devices (Baglio et al., 2009). Fig. 1 shows the schematic diagram of a
typical passive DMFC, and it can be seen that methanol aqueous solution with KOH and air
are passively delivered without any moving element such as pumps and fans, thus, reducing
the parasitic power loss. However, that is also why passive DMFC suffers a relatively lower
performance than active DMFC, because the access of methanol to reactive sites relies on
diffusion only, and it cannot well handle the excess liquid water and may cause a severe
cathode flooding (Oliveira et al., 2011). Hence, significant attention should be given to the
transport phenomena analysis and water management of passive DMFC.
Many efforts were therefore directed for the research and development of passive proton
exchange membrane direct methanol fuel cell (PEM-DMFC), which is relatively widely used
among different kinds of fuel cells because it offers high energy efficiency, fast start-up and low
emission (Chen et al., 2008; Yang and Zhao, 2007; Wang et al., 2013). Chen et al. (2008)
presented a two-dimensional two-phase thermal model for passive PEM-DMFC, which
inherently coupled heat and mass transport, along with the electrochemical reactions
occurring in the cell. Their numerical results suggested that increasing methanol concentration
from 1.0 M to 4.0 M brings better cell performance, as the result of increased operating
temperature resulting from the exothermic reaction between the permeated methanol and
oxygen in the cathode and increased methanol transfer rate. Based on their work, a transient
two-phase mass transport model was developed by Yang and Zhao (2007). In their numerical
model, thee overshoot behaviors of cell voltage were observed corresponding to a sudden
change in the current density and methanol concentration. Wang et al. (2013) considered the
effect of natural convection in the fuel reservoir in their most recent study, and their numerical
results showed that when the passive PEM-DMFC is operated in the vertical direction, the cell
temperature exhibited a palpable gradient from the bottom of the cell to the top, caused by the
natural convection at the anode. Although significant improvements have been made on the
cell performance and cost, the commercialization of passive PEM-DMFC is still hindered by
several significant obstacles, such as the severe methanol crossover across the membrane,
sluggish reaction kinetics of methanol oxidation and inability to handle the passive mass
transport and water flooding in the cathode.
Recently, considerable attention has been devoted to passive alkaline anion exchange
membrane direct methanol fuel cell (AAEM-DMFC) as an alternative approach on the
replacement of PEM-DMFC. AAEM-DMFC has the great potential to address the challenges
faced by its acidic counterpart. First, alkaline electrolyte environment offers a more facile
electrode kinetic for both methanol oxidation and oxygen reduction reactions than in the acidic
media (Pan et al., 2011), and make possible to use non-noble metals as catalysts in the anode
and cathode, such as ruthenium and Au-Pd. Second, in an AAEM-DMFC, hydroxide ion
produced in oxygen reduction reaction moves from cathode to anode opposite to the direction
of PEM-DMFC, resulting in a reversed electro-osmotic drag for both methanol and liquid water,
thus, lowering the methanol crossover and cathode flooding and allowing the use of thinner

457

membrane to improve the cell performance (Yu and Scott, 2004).

However, different from passive PEM-DMFC, there are few modeling studies about passive
AAEM-DMFC, and dominating works now are concentrated on membranes and catalysts,
while the mass and heat transport processes are still not well understood. In the previous
works (Deng et al., 2013; Huo et al., 2012), the authors presented a three-dimensional
two-phase half-cell steady-state and transient model for AAEM hydrogen fuel cell, investigated
the gas and liquid water characteristics with different designs and under various working
conditions. And in the most recent study (Deng et al., 2014), a one-dimensional isothermal
analytical model was developed for active AAEM-DMFC by authors, taking into all the
necessary mass transport and electrochemical phenomena. Nevertheless, to the best of the
authors knowledge, the numerical study for passive AAEM-DMFC is still in a state of blank so
far. In this paper, a two-dimensional two-phase steady-state numerical model is therefore
developed for passive AAEM-DMFC to study the interior mass and heat transfer mechanism.
2. MODEL FORMULATION
2.1 Physical problem
The two-dimensional computational domain, as given in Fig. 2, is based on the typical
components of practical passive AAEM-DMFC, including the anode diffusion layer (ADL),
anode catalyst layer (ACL), A201 membrane (composed of the hydrocarbon polymer
backbone and the quaternary ammonium group, Tokuyama, Japan) (Duan et al., 2013),
cathode catalyst layer (CCL) and cathode diffusion layer (CDL). Aqueous methanol solution
and oxygen from air are passively supplied by fuel reservoir and ambient environment,
respectively. On the anode, methanol is electrochemically oxidized to carbon dioxide in the
ACL, which is transferred back to fuel reservoir and then emitted to ambient. On the cathode,
oxygen reacts with water to form hydroxide and oxidizes the methanol permeated through
membrane. The heat generated in the electrochemical reactions is lost from the ribs of anode
and cathode to ambient.

Fig. 2. Schematic diagram of computational domain and mesh

2.2 Assumptions
The numerical model is formulated under the appropriate assumptions and simplifications to
simplify the computations and transport processes. In this model, considering only carbon

458

dioxide in the gas phase, water vapor and methanol vapor are neglected on the anode.
Methanol permeated through membrane is assumed to be fully oxidized due to a relatively fast
reaction kinetic of methanol in the cathode. The liquid pressure in the anode and gas pressure
in the cathode are considered to be constant since their variation is relatively small.
2.3 Conservation equations
The two-phase model presented in this study can be concisely summarized by the following
conservation equations.
Electric potential in the solid electrode (solved in ADL, ACL, CCL and CDL):

seff s SVs 0

( 1)

Ionic potential in the membrane electrolyte (solved in ACL, CCL and membrane):

eff
m m SVm 0

(2)

Mass of methanol (solved in ADL and ACL):

D eff
me C me Sme 0

(3)

Mass of carbon dioxide (solved in ADL and ACL):

0.5
g Kk g

cos c J s S CO2 0
M g g

(4)

Mass of oxygen (solved in CDL and CCL):

Deff
o 2 C o 2 So 2 0

(5)

Mass of water vapor (solved in CDL and CCL):

D eff
wv C wv S wv 0

(6)

Mass of liquid water (solved in CDL and CCL):

0.5
lq Kk lq

cos c Js Slq 0
M lq lq

(7)

Energy (solved in ADL, ACL, membrane, CCL and CDL):

T ST 0

(8)

2.4 Boundary conditions

In the anode channel and cathode channel, methanol concentration, oxygen concentration
and water vapor concentration are specified based on the operating conditions, while the liquid
saturation is defined as 0.95 and 0.05 due to the supplied dilute aqueous methanol solution in
the anode and an easier water removal in the cathode channel.
For the boundary conditions of electronic and ionic potentials, electronic potential is fixed to be
zero at the cathode rib and the current density is imposed at the anode rib.

459

Non-slip and impermeable boundary conditions are applied at wall boundary conditions, and
internal interface boundary conditions are given based on the mass flux conservation of
reactants.
2.5 Performance prediction
The comparison of polarization curve between the above numerical model prediction and
experimental data in Ref. (Kim et al., 2009) (which also adopts A201 membrane) is presented
in Fig. 3, and it shows a reasonable agreement.

0.7
60

Cell voltage, V

0.5
40
0.4
30
0.3
20
0.2
Experimental data Kim et al., 2009)
Model prediction

0.1
0.0

10

50

100

150

200

250

300

Power density, W m

50

-2

0.6

0
350

-2

Current density, A m

Fig. 3. Comparison between model prediction and experimental data when the cell operates at
ambient temperature and a pressure of 1 atm for whole cell and supplied with 1 M aqueous
methanol solution containing 1 M KOH.
2.6 Numerical procedures
The two-dimensional two phase numerical model was implemented into Fluent, a commercial
computational fluid dynamics software. Utilizing its user-defined functions, the source terms,
transport parameters and boundary conditions can be implemented. The conservation
equations of electronic potential, ionic potential, methanol, carbon dioxide, liquid water, oxygen
and water vapor are executed by using user-defined scalars. A strict convergence criterion
with a residual of 10

-8

was applied to all governing equations. The mesh shown in Fig. 2

consists of 1000 grid cells and has carried out to be sufficient with a careful grid-independent
study.
3. RESULTS AND DISCUSSION
In this study, two operating parameters are considered to study the electrochemical

460

phenomena in the passive AAEM-DMFC, which are the methanol feed concentration and
operating temperature. In the base case, the cell operates at a temperature of 30 C and a
pressure of 1 atm, 3 M aqueous methanol solution containing 1 M KOH and oxygen from air
are passively supplied from fuel reservoir and ambient environment.
3.1 Methanol feed concentration
To examine the effects of methanol feed concentration on cell performance, 1 M, 2 M and 3 M
methanol aqueous solutions are passively supplied, as presented in Fig. 4.

0.7
1M
2M
3M

Cell voltage, V

0.6

0.5

0.4

0.3

400

800

1200

1600

-2

Current density, A m

(a)

0.8

Increasing methanol feed concentration

(1 M, 2 M, 3 M)

Ohmic loss
Anode polarization loss
Cathode polarization loss

0.6
0.4
0.2
0.0
0.8
0.6
0.4
0.2
0.0
0.8
0.6
0.4
0.2

200

400

600

800

1000

1200

1400

0.0

-2

Current density, A m

(b)
Fig. 4. Effects of methanol feed concentration (1 M, 2 M and 3 M) on cell performance (a) and

461

voltage losses (ohmic loss and polarization losses of anode and cathode) (b).
It can be observed from Fig. 4 (a) that different regions of polarization curve exhibit different
dependence on methanol feed concentration. Open circuit voltage, predicted by this model, is
much lower as the methanol feed concentration increases because of more severe methanol
crossover. As well as in the low current density region, the cell exhibits a lower performance for
higher methanol feed concentration, because the cathode polarization loss plays the
significant role in the typical voltage loss, while the difference in both the anode polarization
loss and ohmic loss can be neglected (Fig. 4 (b)).
However, at high current density, the cell yields better performance with increasing methanol
concentration from 1 M to 3 M, this result can be attributed to two factors. On the one hand,
improvement of methanol transport process with increasing methanol concentration can
reduce the anode polarization loss due to a faster reaction kinetic, as well as the ohmic loss
(Fig. 4 (b)). On the other hand, operating temperature increases for the reason that the certain
amount heat generates in the reaction between permeated methanol and oxygen, and the
increment becomes more significant as the methanol concentration increases.
3.2 Operating temperature
Fig. 5 shows the effects of operating temperature on cell performance from 30 C to
60 C .
Since mass transfer properties and electrode kinetics in both the anode and cathode strongly
depend on cell temperature, activation losses of anode and cathode are expected to decrease
with the increment of operating temperature. However, methanol crossover is also a thermally
activated behavior because the methanol diffusivity also gets enhanced, representing that
more

methanol

permeates

through

membrane

for

higher

operating

temperature,

corresponding to the fact that the cell performance decreases with the increase of operating
temperature in the low current density region, as well as the open circuit voltage. Therefore,
the variation of cathode polarization loss with operating temperature is decided by two
conflicting factors, and in this model, the results shown in Fig. 5 (b) indicate that methanol
crossover play a significant role and covers the other effects. Higher operating temperature
also boosts a progressive rise of A201 membrane conductivity, as reported by Duan et al.
(2013), explaining the reduced ohmic loss in Fig. 5 (b). Despite the greater methanol crossover,
cell performance is improved with the increase in operating temperature in general.

462

0.65

30 oC
o
45 C
o
60 C

0.60

Cell voltage, V

0.55
0.50
0.45
0.40
0.35
0.30

500

1000

1500

2000

-2

Current density, A m

(a)

0.8

Increasing operating temperature

(30 oC, 45 oC, 60 oC)

Ohmic loss
Anode polarization loss
Cathode polarization loss

0.6
0.4
0.2
0.0
0.8
0.6
0.4
0.2
0.0
0.8
0.6
0.4
0.2

400

800

1200

1600

2000

0.0

-2

Current density, A m

(b)
Fig. 5. Effects of operating temperature ( 30 C , 45 C and 60 C ) on cell performance (a)
voltage losses (ohmic loss and polarization losses of anode and cathode) (b).
4. CONCLUSIONS
In this study, a two-dimensional two-phase steady-state numerical model has been developed
for passive alkaline anion exchange membrane direct methanol fuel cell (AAEM-DMFC),
taking into account all the necessary mass transport and electrochemical phenomena. The

463

numerical model has been solved under galvanostatic conditions and its prediction is
compared with experimental data in the literature. Two operating parameters are considered to
study the cell performance under different working conditions, which are the methanol feed
concentration and operating temperature. The results show that the model prediction fits the
experimental data reasonably throughout the cell voltage-current density range investigated.
In the high current density region, the cell performance is improved with the increase of
methanol feed concentration and operating temperature due to the mass transfer processes
and faster electrode kinetics. However, greater methanol crossover also are reported, resulting
in more significant cathode polarization loss and lower open circuit voltage, and this effect is
more significant in the low current density region.
ACKNOWLEDGEMENT
This research is supported by the National Natural Science Foundation of China (Grant No.
51276121),

and

the

Natural

Science

Foundation

of

Tianjin

12JCYBJC30500).
NOMENCLATURE
C

molar concentration, mol m

mass diffusivity, m s

Leverett-J function

permeability, m

molecular weight, kg mol

liquid saturation

source term, mol m s

velocity, m s

-3

-1

-3

-1

-1

-1

Greek Letters
-1

-1

-1

-1

dynamic viscosity, kg m s

density, kg m

porosity

angle,

heat conductivity

dynamic viscosity, kg m s

density, kg m

conductivity, S m ; surface tension coefficient, N m

potential, V

-3

-3
-1

Subscripts
c

contact

CO2

carbon dioxide

CO2, bub CO2 bubble

g

gas

lq

liquid water

464

-1

(China)

(Grant

No.

membrane electrolyte

me

methanol

O2

oxygen

solid electrode

temperature

Vm

ionic potential in the membrane electrolyte

VS

electric potential in the solid electrode

Wv

water vapor

Superscripts
eff

effective

REFERENCES
Baglio V., Stassi A., Matera F.V., Antonucci V. and Arico A.S., 2009, Investigation of passive
DMFC mini-stacks at ambient temperature. Electrochimica Acta 54:2004-2009.
Chen R., Zhao T.S., Yang W.W. and Xu C., 2008, Two-dimensional two-phase thermal model
for passive direct methanol fuel cells. Journal of Power Sources 175:276-287.
Deng H., Huo S., Chang Y., Zhou Y. and Jiao K., 2013, Transient analysis of alkaline anion
exchange membrane fuel cell anode. International Journal of Hydrogen Energy 38:6509-6525.
Deng H., Jiao K., Chen J. and Huang X., 2014, An analytical model for alkaline membrane
direct methanol fuel cell. International Journal of Heat and Mass Transfer 74:376-390.
Duan Q., Ge S. and Wang C.Y., 2013, Water uptake, ionic conductivity and swelling properties
of anion-exchange membrane. Journal of Power Sources 243:773-778.
Huo S., Deng H., Chang Y. and Jiao K., 2012, Water management in alkaline anion exchange
membrane fuel cell anode. International Journal of Hydrogen Energy 37:18389-18402.
Kim J., Momma T. and Osaka T., 2009, Cell performance of Pd-Sn catalyst in passive direct
methanol alkaline fuel cell using anion exchange membrane. Journal of Power Sources
189:999-1002.
Oliveira V.B., Rangel C.M. and Pinto A.M.F.R., 2011, One-dimensional and non-isothermal
model for a passive DMFC. Journal of Power Sources 196:8973-8982.
Pan W.H., Lue S. Jessie, Chang C.M. and Liu Y.L., 2011, Alkali doped polyvinyl
alcohol/multi-walled carbon nano-tube electrolyte for direct methanol alkaline fuel cell. Journal
of Membrane Science 376:225-232.
Yang W.W. and Zhao T.S., 2007, Two-phase, mass-transport model for direct methanol fuel
cells with effect of non-equilibrium evaporation and condensation. Journal of Power Sources
174:136-147.
Wang L., Zhang Y., An Z., Huang S., Zhou Z. and Liu X., 2013, Non-isothermal modeling of a
small passive direct methanol fuel cell in vertical operation with anode natural convection
effect. Energy 58:283-295.
Yu E.H. and Scott K., 2004, Development of direct methanol alkaline fuel cells using anion
exchange membranes. Journal of Power Sources 137:248-256.
Zago M., Casalegno A., Santoro C. and Marchesi R., 2012, Water transport and flooding in
DMFC: Experimental and modeling analyses. Journal of Power Sources 217:381-391.

465

START-UP OF HT-PEMFC
*

Hao Huang, Kui Jiao , Yan Yin, Qing Du

State Key Laboratory of Engines, Tianjin University, 92 Weijin Rd, Tianjin, China, 300072
*

Corresponding author: kjiao@tju.edu.cn; tel: +86-22-27404460; fax: +86-27383362

ABSTRACT
In this study, a three-dimensional multi-phase unsteady-state numerical model is developed to
understand the start-up process of high temperature proton exchange membrane fuel cell
(HT-PEMFC). In the simulation, the HTPEMFC is started under constant voltage conditions,
and its predicted polarization curve and operating temperature is compared reasonably with
experimental data in the literature. In the start-up process, there is liquid water generated in
the cathode catalyst layer. With the start-up voltage increasing, cell start-up process becomes
more difficult. When the voltage is 0.5V, the cell temperature cannot reach 100. However,
with the lower start-up voltage, there is more liquid water generated in the cathode catalyst
layer, especially in the inlet zone.
Keywords: high temperature proton exchange membrane fuel cell, three-dimensional
multi-phase unsteady-state numerical model, start-up process, liquid water, fuel cell operating
temperature
INTRODUCTION
H2/air fuel cells based on proton exchange membranes have many attractive features,
including high power density, rapid start-up, high efficiency, which make them a promising
clean energy technology. Great advances have been made in proton exchange membrane fuel
cell (PEMFC) development (Zhang et al., 2006).
However, several technical obstacles hinder the commercialization of traditional PEMFC which
operating temperature is usually about 80. The water and heat management system of
PEMFC is inadequate and complicated which also make the cost of PEMFC increased. The
tolerance to fuel impuritiese.g. CO and sulphideof PEMFC is weak. The electrochemical
cathode kinetics is sluggish. Recent progress of PEMFC has focused on improving its
operating temperature.
High temperature proton exchange fuel cell (HT-PEMFC)

usually work at temperature above

100. Due to its excellent performance, it has allured worldwide attraction. There are several
compelling technological and commercial reasons, such as faster electrochemical kinetics,
higher power density, simpler water management and cooling, the easier useful waste heat
recovery, and higher tolerance to CO poisoning. However, with higher operating temperature,
there will be a longer start-up process. During the start-up process, the temperature of cell is
lower than 100. So there is liquid water generated in the cathode catalyst layer. After the
liquid water generated, it will transport to gas diffusion layer and cause the different
temperature distribution. If there is too much liquid water, the channel in gas diffusion layer will
be blocked and the performance of HT-PEMFC will be influenced. So the start-up strategy is
significant to HT-PEMFC.

466

So far, the research on HT-PEMFC has been concentrated on following aspects: 1. Improving
polymer electrolyte membranes proton exchange ability in high temperature to elevate
HT-PEMFC performance (Li et al., 2009); 2. simplifying the water and heat management
system of HT-PEMFC to reduce its cost and enhancing the CO tolerance ability of HT-PEMFC
to increase its working lifetime (Yuka et al., 2009). 3. understanding the working conditions
influence to HT-PEMFC by changing operating temperature, intake pressure, intake
stoichiometric and so on (Su et al., 2010). The research on the start-up process of HT-PEMFC
is inadequate. Andreason et al conducted an experiment to heat the HT-PEMFC and put up
with a one-dimensional model (Andreason et al., 2008). Singdeo et al gave a
three-dimensional model of HT-PEMFC and simulated its start-up process. But none of them
take the electrochemistry reaction of the HT-PEMFC into consideration. In this paper, a
three-dimensional multi-phase unsteady-state numerical model is developed for HT-PEMFC to
study its start-up process and the interior mass and heat transfer mechanism.
2. MODEL FORMULATION
2.1 Physical problem
The three-dimensional computational domain, as given in Fig. 1, is based on the typical
components of HT-PEMFC, including the anode bipolar plate, anode flow channel, anode gas
diffusion layer (AGDL), anode catalyst layer (ACL), proton exchange membrane (phosphoric
acid doped PBI membranes), cathode catalyst layer (CCL), cathode gas diffusion layer
(CGDL), cathode flow channel, cathode bipolar plate. Hydrogen and oxygen from air are
supplied by fuel reservoir and ambient environment for the fuel cell, respectively.

Fig. 1. Schematic diagram of computational domain and mesh

467

2.2 Assumptions
The numerical model is formulated under the appropriate assumptions and simplifications to
simplify the computations and transport processes. In this model, considering all H2O
generated by chemical reaction in the vapor phase and transferred into liquid water if its
pressure higher than saturated vapor pressure through phase transformation reactions.
Considering there is no electro-osmotic drag phenomenon in the proton exchange membrane
for the membrane is PBI membrane. The gas flow in the anode and cathode are considered to
be laminar flow since their Reynolds number is relatively small.
2.3 Conservation equations
The multi-phase model presented in this study can be concisely summarized by the following
conservation equations.
Mass (solved in flow channel, GDL, CL):

( (1 slq ) g ) ( g ug ) Sm
t

(1)

Momentum (solved in flow channel, GDL, CL):

uu
g ug

2 g
2

t (1 slq )
(1 slq )
(

uT
(1 slq )

))

u
(
)
- pg
g

(1
slq )

2
u
(
)) Su

g
3
(1 slq )

(2)
Gas species i: hydrogen, oxygen, water vapor (solved in flow channel, GDL, CL):

slq g Yi ( g ugYi ) ( g Dieff Y ) j ) Si

t

(3)

Liquid water (solved in GDL and CL):

slq lq
t

lq u g = lq Dlq slq +Slq

(4)

Electronic potential (solved in CL, GDL, BP):

eff
ele
ele Sele 0

(5)

Ionic potential (solved in Membrane, CL):

eff
ion
ion Sion 0

(6)

Energy (solved in All the domains):

eff
C p fleff, sl (Cp )eff
fl , sl ug T k fl , sl T ST
t

(7)

2.4 Boundary conditions

In the model, heat exchange only occurs in the surface of bipolar plate. The other surface is
adiabatic boundary conditions for they are assumed in the interior of cell. In the inlet of anode
channel and cathode channel, gas boundary conditions are set to mass flux.

468

For the boundary conditions of electronic and ionic potentials, electronic potential is fixed to be
zero at the cathode rib and the current density is solved according with voltage .
Non-slip and impermeable boundary conditions are applied at wall boundary conditions, and
internal interface boundary conditions are given based on the mass flux conservation of
reactants.
2.5 Performance prediction
The comparison of polarization curve between the above numerical model prediction and
experimental data in Ref. (Ahluwalia et al., 2003) is presented in Fig. 2, and it shows a
reasonable agreement.

Fig. 2. Comparison between model prediction and experimental data when the cell operates at
170 temperature.
2.6 Numerical procedures
The three-dimensional multi-phase unsteady model was implemented into Fluent, a
commercial computational fluid dynamics software. Utilizing its user-defined functions, the
source terms, transport parameters and boundary conditions can be implemented. The
conservation equations of electronic potential, ionic potential, hydrogen, oxygen, liquid water
and water vapor are executed by using user-defined scalars. A strict convergence criterion
with a residual of 10

-8

was applied to all governing equations. The mesh shown in Fig. 1

consists of 156800 grid cells and has carried out to be sufficient with a careful
grid-independent study.

469

3. RESULTS AND DISCUSSION

The distribution of temperature and liquid water is significant to the start-up process of
HT-PEMFC. So they are concentrated in the study. In the base case, the HT-PEMFC cell starts
under 0.3V constant voltage, at a temperature of 20 and a pressure of 1 atm. The
2

convective heat transfer coefficient is 10 W/(m ) . Hydrogen and oxygen from air are
passively supplied from fuel reservoir and ambient environment.
Start-up voltage
To examine the effects of start-up voltage on cell performance, 0.1V, 0.3V, 0.5V, 0.7V constant
voltage are set, as presented in Fig. 3.

(a)

(b)
Fig. 3. Effects of start-up voltage (0.1V, 0.3V, 0.5V, 0.7V) on cell average temperature (a) and
current density (b).
In the Fig. 3(a), it can be observed that with the increasing of start-up voltage, the average

470

temperature of HT-PEMFC is decreasing both the final steady temperature and the trend of it.
When the HT-PEMFC starts up at constant voltage 0.5V or 0.7V, it cannot reach to its normal
minimum operating temperature, 100, without other assistant start-up strategy. The reason
can be found in the Fig. 3(b). When the start-up voltage is a higher level, it will cause the
current density in a lower level. So the electrochemical reaction rate will be influenced and the
generated heat will be limited.

Fig. 4. Effects of start-up voltage (0.1V, 0.3V, 0.5V, 0.7V) on liquid water in cathode catalyst
layer
The start-up voltage also has effects on the amount of liquid water in cathode catalyst layered.
With higher of the start-up voltage, there are more liquid water generated for the
electrochemical reaction rate is relatively high. During the start-up process, the amount of
liquid water increases until getting its maximum then reduce. It is because the temperature of
HT-PEMFC is in a low level. The vapor generated in the electrochemical reaction condenses
into liquid water for its partial pressure higher than saturated vapor pressure. With time goes
on, there is more heat generated in HT-PEMFC and its temperature rise. When vapor partial
pressure lower than saturated vapor pressure. The condensed liquid water transfer into vapor
again.
0.3V constant start-up voltage
Fig. 5 shows the ratio of different heat source term: act (source of heat due to activation loss),
lat ((source of heat due to phase change), ohm (source of heat due to ohmic loss), rev (source
of heat due to reversible loss). Through the start-up process, the heat due to ohmic loss has
the most important influence, flowing by heat due to activation loss, heat due to reversible loss,
and heat due to phase change. Because the current density under 0.3V constant start-up
voltage is quite high and the cell ohmic resistance is relative large under low temperature. The
heat due to ohmic loss has the greatest ratio.

471

Fig. 5. Heat source term ration under 0.3 constant start-up voltage
It can be observed in Fig. 6 that the amount of liquid water in gas inlet part is largest because
of the higher the concentration of reactant gas and more vapor generated there. Whats more,
the lower temperature intake gas take a lot of heat from gas inlet part which can be shown in
Fig. 7. So the temperature of gas inlet part is relative lower, which will lead more vapor transfer
into liquid water. As time goes on , the temperature of HT-PEMFC increase, so liquid water
evaporate.

Fig. 6. Liquid water distribution in cathode catalyst layer under 0.3 constant start-up voltage

472

Fig. 7. Temperature distribution in cathode catalyst layer under 0.3 constant start-up voltage
4. CONCLUSIONS
In this study, to understand the start-up process of HT-PEMFC, a three-dimensional,
non-steady-state, non-isothermal, multiphase HT-PEMFC model is developed in this study.

The effects of the start-up voltage on the stat-up process of HT-PEMFC are simulated. It
is found that the higher the start-up voltage, the lower of the liquid water content and
the more difficult for the HT-PEMFC to start. During the start-up process, there will be a
great temperature distribution in the HT-PEMFC due to the low temperature intake gas,
which may has negative influence to its performance.
ACKNOWLEDGEMENT
This research is supported by the National Natural Science Foundation of China (Grant No.
51276121),

and

the

Natural

Science

Foundation

12JCYBJC30500).
NOMENCLATURE
C

molar concentration, mol m

mass diffusivity, m s

Leverett-J function

permeability, m

molecular weight, kg mol

-3

-1

liquid saturation

source term, mol m s

velocity, m s

-3

-1

-1

-1

Greek Letters
-1

dynamic viscosity, kg m s

density, kg m

-1

-3

473

of

Tianjin

(China)

(Grant

No.

porosity

angle,

heat conductivity

dynamic viscosity, kg m s

density, kg m

conductivity, S m ; surface tension coefficient, N m

potential, V

-1

-1

-3
-1

-1

Subscripts/ Superscripts
c

contact

gas

lq

liquid water

membrane electrolyte

H2

hydrogen

O2

oxygen

solid electrode

temperature

Vm

ionic potential in the membrane electrolyte

VS

electric potential in the solid electrode

REFERENCES

Li X G. Principles of fuel cells[M]. New York: Taylor & Francis, 2006.

Jiao K, Li X G. A three-dimensional non-isothermal model of high temperature proton
exchange membrane fuel cells with phosphoric acid doped polybenzimidazole
membranes[J]. Fuel Cells, 2010, 10: 351-362.
Jiao K, Alaefour I E, Li X G. Three-dimensional non-isothermal modeling of carbon
monoxide poisoning in high temperature proton exchange membrane fuel cells with
phosphoric acid doped polybenzimidazole membranes[J], Fuel, 2011, 90: 568-582.
Andrekus D J, Bloom I, Polzin E G, Fuel cell testing at argone national laboratory[J],.
IEE Vehicular Technology Laboratory Conference, 2002, 3: 6~9.
Li Q F, Jensen J O, Robert E et al, High temperature proton exchange membranes based
on polybenzimidazoles for fuel cells[J]. Progress in Polymer Science, 2009, 34:
1449-1477.
Yuka O, Takashi F, Atsuo S et al. Experimentally and numerically investigating cell
performance and localized characteristics for a hightemperature proton exchange
membrane fuel cell[J]. Applied Thermal Engineering, 2009, 29: 3409-3417.
Su A, Feng Y M. Shih J C. CFD investigating the effects of different operating conditions
on the performance and the characteristics of a high-temperature PEMFC[J]. Energy,
2010, 35:16-27.
Andreasen S J, Ker S k, Modeling and evaluation of heating strategies for high
temperature polymer electrolyte membrane fuel cell stacks[J], Journal of Hydrogen
Energy, 2008, 33:4655-4664.
Singdeo D, Dey T. Ghosh P. C. Modelling of start-up time for high temperature polymer
electrolyte fuel cells[J]. Energy, 2011, 36: 6081-6089.

474

STRUCTURE OPTIMIZATION OF
SEGMENTED THERMOELECTRIC GENERATOR
*

Guobin Zhang, Zhiqiang Niu, Kui Jiao , Yan Yin, Qing Du

State Key Laboratory of Engines, Tianjin University, 92 Weijin Rd, Tianjin, China, 300072
*

Corresponding author: kjiao@tju.edu.cn; tel: +86-22-27404460; fax: +86-27383362

ABSTRACT
Using different materials to form segmented thermoelectric generator (TEG) may be an effective way
to improve the performance. In this study, a theoretical correlation is derived to determine the length of
each material used in segmented TEGs. A segmented TEG is designed based on this correlation. The
segmented TEG is designed on the basis of the figure of merit (Z) of semiconductor materials. The
thermoelectric performance (including the output power and thermoelectric conversion efficiency) of the
segmented TEG is compared to other original TEGs (using the same semiconductor material).

Keywords: segmented thermoelectric generator; theoretical correlation; numerical model; conservation

equation; output power; thermal electric conversion efficiency.

1. INTRODUCTION
TEG is an environmentally friendly energy conversion device that converts thermal energy into electric
city directly. TEG is compact energy sources, it has many advantages, such as compact design and high
[1]

reliability . Recently, due to the increasing demand on energy saving, TEG received considerable
attention for the waste heat recovery in the major energy conversion devices, such as internal
combustion engines. In 1988, Birkholz et al.

[2]

installed a TEG on Porsche 944 automobile engines

exhaust pipe to explore the possibility of using FeSi 2 TEG.

However, the main problem of TEG is that the thermoelectric conversion efficiency is low. The
thermoelectric conversion efficiency depends on the value of Z, the geometry size of thermoelectric
element and the heat transfer conditions of the hot and cold sides. Larger the temperature difference
between the hot side and the cold side and the Z are, higher the thermoelectric conversion efficiency. But
almost all the semiconductor materials only have high Z within certain temperature range which severely
[3]

limits the application and development of the TEG .

People usually improve the thermoelectric conversion efficiency by getting high performance
thermoelectric materials. In 2002, Matsubara

[4]

did a lot of experiments on thermoelectric materials, he

found that the thermoelectric conversion efficiency can reach about 6%-8% when using Co-doped Bi2Te3
thermoelectric element. After that the concept of functionally gradient was proposed, people widely
believe that using functionally gradient materials is an effective way to enhance the thermoelectric
conversion efficiency: using segmented structure, i.e. link thermoelectric materials with different
thermoelectric performance one by one, forming a continuous hot road so that each thermoelectric
material can work at its suitable temperature range, to achieve the highest thermoelectric conversion
[1]

efficiency .

In 2004, the BSST company

[5]

designed a segmented thermoelectric element and proposed an

arrangement form of new interactive single thermoelectric element, which is expected to improve fuel

475

economy by 10%. Even today, many scholars still do research about segmented TEGs, such as Reddy et
al.

[6]

al.

[9]

[7]

and Hadjistassou et al. . In 2010, Chen et al.[8] developed a numerical model of TEGs. Freunek et
[10]

and Fraisse et al.

also developed multi-dimensional numerical models. These models can

effectively simulate various transport phenomena in the working process of TEGs, and have a strong
guiding significance to the design and optimization of TEGs.

However, so far, few scholars are able to supply a way to compute the best length ratio when the working
condition and the physical parameters of the materials are decided. Therefore, the authors try to derive a
theoretical guiding correlation of the best length ratio, and develop a three-dimensional numerical model
based on the result to simulate and amend the theoretical correlation. The research not only can help
deeply understand the various transport phenomena in the segmented thermoelectric generators, but
also has a high practical value to design and optimization.

2. DERIVATION OF CORRELATION

Figure 1. Schematic of the segmented TEG

The length ratio is important for a TEG. It is reasonable that we assume there is a suitable value of
temperature ( Ti ) at the interface of two semiconductor materials. One material establishes better
thermoelectric performance than the other as long as its working temperature is higher than Ti , while the
other lower than Ti . It is evident that the thermal conduction is the main factor affecting the temperature
gradient in the thermoelectric generators. So we ignore the effect of Joule heat, Peltier heat and
Thomson heat. As shown in Figure 1, we assume that
bigger than

Th T1 , Tc T2

(Because

cu

is much

p1 p 2 n1 n 2 ) . The heat flux from the heat source to heat sink can be defined as
q1 p1

dT
(0 x l1 )
dx

476

(1)

dT
(l1 x l1 l2 )
dx

(2)

q1 (W m-2) is the heat flux transferred in p1 type , and q2

(W m ) is the heat flux transferred

q2 p 2
where

in

-2

p2 type . In state heat conduction, there is

q1 q2

(3)

By integrating both sides of (1) and (2), we can achieve that

T1

q1

q2

Ti

p1dT
(4)

l1
Ti

T2

p 2 dT
(5)

l2

(4)/(5) , achieve that

l1
l2

T1

Ti
Ti

T2

p1dT
(6)

p 2 dT

Considering that assumptions

Th T1

(7)

Tc T2

(8)

Therefore,

l1
l2

Th

Ti
Ti

Tc

p1dT
(9)

p 2 dT

(9) is the final theoretical correlation based on which we can get the length of each semiconductor
material.

3. MODEL

DEVELOPMENT

A segmented thermoelectric generator element is composed of two

n type

p type semiconductors and two

semiconductors connected with a conductor (e.g. copper). The insulation of the TEGs is

achieved by placing the substrates (e.g. ceramic) on the top side and bottom side. Heat is conducted
through the substrates.

For this model, the steady-state conservation equation is written as

k p1, p 2,n1,n 2,copper Tp1, p 2,n1,n 2,copper ST 0

where

k p1, p 2,n1,n 2,copper

-1

(W m

-1

K ) is the thermal conductivity of

477

(10)

p1 type , p2 type , n1 type ,

n2 type

and copper units.

n1 type , n2 type

Tp1, p 2,n1,n 2,copper

and copper units.

ST

p1 type , p2 type ,

(K) is the temperature of

-3

(W m ) is the source term.

For the conservation equation of the Seebeck potential, the Seebeck potential

Vsbk

(V) is defined as

Vp1, p 2,n1,n 2 p1, p 2,n1,n 2 Tp1, p 2, n1, n2

where

and

Vp1, p 2,n1,n 2

n2 type

n1 type

and

(V) is the Seebeck voltage generated in the

units;

p1, p 2,n1,n 2

n2 type

p1 type , p2 type , n1 type

-1

(V K ) is the Seebeck coefficient of the

materials; and

hot side and the cold side of the

(11)

Tp1, p 2,n1,n 2

p1 type , p2 type ,

(K) is the temperature difference between the

p1 type , p2 type , n1 type

and

n2 type

units. Taking the

divergence of Vsbk , Equation 12 yields :

Vsbk Ssbk 0
where

S sbk

(12)

-2

(V m ) is the source term.

The conservation equation of the Ohmic potential in the

p1 type , p2 type , n1 type , n2 type

and copper units is written as

p1, p 2,n1,n 2,copper Vohm 0

where

Vohm

(V) is the Ohmic potential of

(13)

p1 type , p2 type , n1 type , n2 type and

copper

units.

For thermal boundary conditions, a constant temperature,

Th ( K )

or

Tc ( K )

is defined on the top

side and bottom side, for other walls, zero heat flux is defined.

The numerical model is implemented by using the FVM in the CFD software FLUENT. The default energy
conservation equation is solved, and the source term is defined by using the user-defined functions
(UDFs). The heat flux at the interfaces of different materials caused by the Peltier effect is considered as
the thickness of ceramic multiply a thermal source defined by UDFs. The conservation equations of the

478

Seebeck potential, Ohmic potential are all implemented by using the UDFs. The operating current density
or cell voltage can be defined at the boundaries to control the power output.

4. RESULTS AND DISCUSSION

For

p type

semiconductor materials, we chose BiSbTeC60 (with 0.5 vol.% content of C60)

(Li mol.% is 2.42%)

binder)

[13]

[12]

; for

, Zr0.5Hf0.5NiSn

[14]

n type

[11]

, LiNiO

semiconductor materials, we chose SbMg2SiNi(with 10wt.%Ni

650K , and Tc 450K .

. For thermal boundary conditions, Th

We choose the value of Z (shown in Figure 2) as the basis to determine the length ratio, and then
determine the length of each material.

-1

Z/K

-1

Z/K

T/K

T/K

a.
Figure 2 a. Z of the two

b.

p type semiconductor materials; b. Z of the two n type semiconductor

materials.

From Figure 2, we know

that the length of

Ti

for

p1 type

(Zr0.5Hf0.5NiSn) is 0.75mm, and

p type

is 571K,

(LiNiO) is 1.1mm,

n2 type

n type

is 548K. Based on Equation 9, we get

p2 type

(BiSbTeC60) is 0.7mm,

(SbMg2SiNi) is 1.05mm.

479

n1 type

Figure 3. Mesh of the segmented TEG

Figure 4Temperature distribution in the segmented TEG

Figure 3 shows the mesh. Figure 4 shows the temperature distribution, it can be seen that the
temperature in the interface of two

p type

materials and two

n type

materials is close to the

expected values.

In order to better illustrate the thermoelectric performance of the segmented TEG. We compare it with

480

other four thermoelectric generators. The results are shown in Figure 5.

/

Output power/W

PP1N1
PP2N1
PP1N2
PP2N2
P(segmented)

/
I/A
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
a.
6.00%

Thermoelectric conversion efficiency

EfficiencyP1N1
EfficiencyP2N1
EfficiencyP1N2
EfficiencyP2N2
Efficiency(segmented)

5.00%

4.00%

3.00%

2.00%

1.00%

0.00%
I/A
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
b.
Figure 5 a. the output power of the segmented TEG and others, b. the thermal electric conversion
efficiency of the segmented TEG and others.

It can be seen that the output power of the segmented TEG is larger than others when the current is
greater than 1.42A and lower than 3.35A , and for thermoelectric conversion efficiency, the value of
current is between 1.92A and 4.50A.

481

5. CONCLUSION
Using segmented TEG is an effective way to improve the output power and thermal energy conversion
efficiency of thermoelectric element. In this paper, a theoretical correlation to seek suitable length ratio of
different materials was found, and is tested numerically. It indicates that the length ratio mainly depends
on

Th , Tc

and the temperature of the interface of two semiconductor materials ( Ti ). On the basis of

this equation, A value that is directly relative to the output power or the thermoelectric conversion
efficiency of the thermoelectric element is vital. In this study, Z,which can reflect the thermoelectrical
performance of the semiconductor materials, is used. And a segmented TEG is designed according to
the length ratio computed by the theoretical correlation. The results indicate that the output power and
thermal electric efficiency of the segmented TEG can be improved. However, to our disappointment, the
segmented TEG does not work well in all the current range. It should be believed that a new value should
be defined to better reflect the relation between the material and the segmented TEG formed by these
semiconductor materials.

ACKNOWLEDGEMENT
This research is supported by the National Basic Research Program of China (973 Program, No.
2011CB707201) and the National Natural Science Foundation of China (Grant No. 51276121).
NOMENCLATURE

Th

The temperature of the hot side (K)

Tc

The temperature of the cold side (K)

T1

The temperature of the interface of the copper (hot side) and

T2

The temperature of the interface of the copper (cold side) and

Ti

The temperature of the interface of

l1

The length of

p1 type (mm)

l2

The length of

p2 type (mm)

S sbk

Source term of Seebeck potential (V m )

ST

Source term of energy conservation equation (W m )

Vohm

Ohmic potential of p-type, n-type and copper units (V)

Vsbk

Seebeck potential of p-type and n-type units (V)

J p1, p 2,n1,n 2,copper

Electrical current density through the

p1 type

and

p1 type (K)
p2 type (K)

p2 type (K)

-2

-3

482

p1 type

p2 type , n1 type

n2 type and copper units (A m-2)

Greek letters

p1, p 2,n1,n 2,cu (W m-1 K-1)

The thermal conductivity of

p1 type , p2 type , n1 type , n2 type

and copper

p1, p 2,n1,n 2

-1

(V K )

Seebeck coefficient of

p1 type , p2 type , n1 type and n2 type

material

p1, p 2,n1,n 2,copper

-1

(S m )

Electrical conductivity of

p1 type , p2 type , n1 type , n2 type

and copper units

Subscripts and superscripts

c

Cold side of TEG

Hot side of TEG

REFERENCES
[1]Ren B, Peng L, Zhang J.,2008, Study on simulation and design of PbTe/BiTe segmented
thermoelectric unicouple. Chinese Journal of Power Sources 9:025.
[2]Birkholz U, GroB E, Stohrer U, et al. Conversion of Waste Exhaust Heat in Automobiles Using
FeSi2-Thermoelements, Proc. 7th International Conference on Thermoelectric Energy Conversion, June
2-5, 2012. Harbin, China.
[3]Zhao Y, Zeng B, Li Y.,2010, Study on simulation of segmented thermoelectric unicouples performance.
Chinese Journal of Power Sources 5:025.
[4]Matsubara K. Development of a high efficient thermoelectric stack for a waste exhaust heat recovery
of vehicles, Twenty-First International Conference on. IEEE, August 25-29, 2002.
[5]LaGrandeur J, Crane D, Hung S, et al.,2006, Automotive waste heat conversion to electric power
using skutterudite, TAGS, PbTe and BiTe, 25th International Conference on. IEEE, August 6-10,2006.
Vienna.
[6]Reddy B V K, Barry M, Li J, et al.,2013, Mathematical modeling and numerical characterization of
composite thermoelectric devices.International Journal of Thermal Sciences 67:53-63.
[7]Hadjistassou C, Kyriakides E, Georgiou J.,2013, Designing high efficiency segmented thermoelectric
generators. Energy Conversion and Management 66:165-172.
[8]Chen M, Rosendahl L A.and Condra T.,2011, A three-dimensional numerical model of thermoelectric
generators in fluid power systems. International Journal of Heat and Mass Transfer 54(1):345-355.
[9]Freunek M, Mller M, Ungan T, et al.,2009, New physical model for thermoelectric generators. Journal
of electronic materials 38(7):1214-1220.
[10]Fraisse G, Ramousse J, Sgorlon D, et al.,2013, Comparison of different modeling approaches for
thermoelectric elements. Energy Conversion and Management 65:351-356.
[11]Kulbachinskii V A, Kytin V G, Popov M Y, et al.,2012, Composites of Bi2xSbxTe3 nanocrystals and
fullerene molecules for thermoelectricity. Journal of Solid State Chemistry 193:64-70.
[12]Shin W, Murayama N.,1999, Li-doped nickel oxide as a thermoelectric material Japanese. Journal of
applied physics 38(11B): L1336.

483

[13]Hayatsu Y, Iida T, Sakamoto T, et al.,2012, Fabrication of large sintered pellets of Sb-doped n-type
Mg2Si using a plasma activated sintering method. Journal of Solid State Chemistry 193: 161-165.
[14]Sakurada S, Shutoh N.,2005, Effect of Ti substitution on the thermoelectric properties of (Zr, Hf) NiSn
half-Heusler compounds. Applied Physics Letters 86(8):082105.

484

A MODEL PREDICTIVE CONTROL APPROACH FOR OPERATION EFFICIENCY

IN A VERTICAL SHAFT IMPACT CRUSHING PROCESS
B.P. Numbi, X. Xia
Department of Electrical, Electronic and Computer Engineering, University of Pretoria,
Pretoria 0002, South Africa
papy.numbi@up.ac.za (B.P. Numbi); xxia@up.ac.za (X. Xia)

ABSTRACT
This paper proposes a closed-loop model predictive control (MPC) for optimal efficiency control of
a vertical shaft impact (VSI) crushing process. Firstly, an open loop optimal control model that
takes into account the time-of-use electricity tariff and process constraints such as storage
capacity of the VSI crusher hopper, the capacity of the storage system that feeds the consumption
point (load), the cascade ratio limits, production requirement, etc. is developed and solved. The
control objective is to minimize the energy cost associated with the operation of the VSI crushing
process while meeting the aforesaid constraints. A closed-loop MPC strategy is therefore obtained
based on the open loop optimal control model. The simulation results demonstrate that the MPC
strategy is just as effective as the open-loop optimal control strategy in reducing the energy cost in
a VSI crushing process while meeting the operation and physical constraints. A cost saving of
about 34.43 % is obtained with the open-loop optimal control strategy, while the MPC strategy
achieves 33.50% with the advantage of the latter to be implementable for real-world applications.
Keywords: Vertical shaft impact crusher, optimal efficiency control, time-of-use tariff, model
predictive control.
INTRODUCTION
Vertical shaft impact (VSI) crushers are widely used in tertiary crushing stations of both aggregate
and mining industries. Some of the features of these processing are the ability to break hard rock
material or ores but also, the production yielded is of cubical shape and contains large amount of
fines (Bengtsson and Evertsson, 2008, Lindqvist, 2008). Crushed Product with cubical shape is
valuable in aggregate industries, while on the other hand, a product with large amount of fines is
valuable in mining industries. Moreover, When compared to other tertiary crushers such as cone
crushers, these machines are nowadays attractive due to their higher energy efficiency (Moray et
al., 2006, Lindqvist, 2008).
In general, the energy efficiency of most energy conversion systems can be improved at four
levels: technology level, equipment level, operation level and performance level (Xia and Zhang,
2010). The higher efficiency of a VSI crusher when compared to other tertiary crushers such as
cone crusher, as above discussed, is mainly due to its technology efficiency improvement. In
compressive crushers such as cone crushers, the technology is based on compressive action to
break the rock, whilst in VSI crushers this is based on impact breaking action using the rotor
kinetic energy. The cascade flow and bi-flow is another important feature which makes the VSI
crusher to be technologically efficient (Lindqvist, 2008). With this, a fraction of the feed material
bypasses the crusher rotor and is broken by collision action with the bed of rock material formed.
The cascade material does not therefore participate to the energy consumption of the VSI crusher,
which leads to some energy savings.
However, the energy efficiency of the VSI crusher can also be improved during their operation
through optimal coordination of its working time based on time-of-use (TOU) electricity tariff.
In the past, some research works have been undertaken in order to minimize the energy cost in
mining industries, while taking into account the TOU electricity tariff. However, most of them focus
on material handling equipment and water pumping systems. In (Middelberg et al., 2009, Zhang
and Xia, 2010, Zhang and Xia, 2011) for instance, the optimal control strategies of conveyor
systems for coal mining industries in order to achieve minimal energy cost are investigated. In
(Badenhorst et al., 2011), an optimal control strategy is studied for the optimal hoist scheduling of
a deep level mine twin rock winder system. Research works such as (van Staden et al., 2011,
Zhang et al., 2012, Xiangtao and Xiaohua, 2013, Zhuan and Xia, 2013) apply TOU tariff-based
DSM for minimization of the energy cost associated with the operation of water pumping stations.
In the above references, the open-loop optimal control strategy is used to solve the energy cost
problem in (Zhang and Xia, 2010, Zhang and Xia, 2011, Zhuan and Xia, 2013), while in

1
485

(Middelberg et al., 2009, Badenhorst et al., 2011, van Staden et al., 2011, Zhang et al., 2012,
Xiangtao and Xiaohua, 2013), a closed-loop model predictive control (MPC) strategy is considered.
In all the aforesaid research works, the potential of reducing the system energy cost based on
TOU tariff is proved. However, from the literature, the optimal energy management of crushing
processes is very rare to find.
The aim of this paper is to investigate the optimal operation efficiency model of VSI crushing
process where the energy cost associated with its operation is minimized by taking account of the
TOU electricity tariff and other system limitations such as the mass storage dynamics of the
upstream storage system (VSI crusher hopper), the mass storage dynamics of the downstream
storage system, cascade ratio limits, production requirement, etc. Three control variables are
optimally tuned in order to minimize the control objective. These are the belt conveyor feed flow
rate, the VSI crusher rotor feed rate and the bi-flow or cascade flow rate. Firstly an open-loop
optimal control is studied in order to assess the feasibility of the model. A closed-loop model
predictive control (MPC) approach is thereafter applied and compared to the open-loop optimal
control approach. A typical crushing process in a coal-fired power plant is taken as case study in
order to evaluate the performance achieved by the developed model.
OPTIMIZATION MODEL OF A VSI CRUSHING SYSTEM
The VSI crusher operating principle is explained in (Nikolov, 2002, Nikolov, 2004, Bengtsson and
Evertsson, 2008, Lindqvist, 2008). The ore or rock material falls vertically into the rotor through the
feed hopper and then accelerated to an edge speed of the high-speed rotor, before being
projected towards the surrounding rock bed formed during operation. However, during operation, a
fraction of material does not pass through the rotor, and this is crushed through collision action
with the projected rock particles from the rotor. This fraction is commonly referred to as cascade
flow or bi-flow. The rock breaking nature in VSI crusher is therefore achieved through rock-to-rock
impact; hence the name impact crusher. A typical VSI crushing station with closed circuit is shown
in Fig. 1.
In practice, the belt conveyor feed flow rate TF can be adjusted through the variable-speed drive
(VSD) system; the mass flow rate into the VSI crusher rotor TR is adjustable through a throttle
(Bengtsson and Evertsson, 2008), also called rotor feed throttle which is controlled by a hydraulic
motor, while the bi-flow mass rate TCSD is adjustable through a certain number of adjustable bi-flow
ports in the hexagonal hopper1.
Feed belt
conveyor

TF

TF +

Silo

+ TRC T2

T1

TCSD

VSI
crusher

VSI crusher
hopper

T2

M Hmax

Recirculated
material

Input/
Control
variables

MH

TR

VSI Crushing
process

M Hmin
Bi-flow
ports

Rotor feed
throttle

TR

TCSD

+
Input/
known
paramete
rs

T2

p(t) (TOU tariff)

Belt
conveyor

Belt
conveyor

Screen

Output/
Performance index :
ENERGY COST

Belt conveyor

T3

MS

Storage
system

TC

M Smax
M Smin
Consumption
point

Fig. 1: Schematic of a tertiary mining VSI crushing station (adapted from (Lindqvist, 2008))

Based on Fig.1, the open-loop optimal control model of the VSI crusher is given as follows:

Sandvik, Merlin-VSI:Setting the standard in VSI crushing, <http://www.miningandconstruction.sandvik.com>

2
486

2
R 2mcr

TRk

Pmcr ,0 pk ,
min J C t s

k 1 3.6

(1)

Subject to

TFmin TFk TFmax ,

1 k N ,
min
max
1 k N ,
TR TRk TR ,
max
T min T
1 k N ,
CSDk TCSD ,
CSD

min
max
T1 TFk TRk TCSDk T1 , 1 k N ,
min
max
1 k N ,
T2 TRk TCSDk T2 ,
min
max
T 1 T T
, 1 k N ,
Rk
CSDk T3
3
min
max
TRC
1 k N ,
TRk TCSDk TRC
,

t T 1T

(3)

k
min
M
M

M Hmax , 1 k N ,
H ,0
s
Fi
Ri TCSDi
H
i 1

k
min
max
, 1 k N ,
M
M
t

S
S ,0
s 1 TRi TCSDi TC i M S
1
i

N
N
1 TRk TCSDk ts TC k ts .
k 1
k 1
ref
TCSDk CSDTRk , 1 k N .

(2)

(4)

(5)

CURRENT CONTROL STRATEGY

Traditionally, most crushing processes are operated continuously, while the control objective is to
achieve the total plant throughput (production target) for a given operation period. The current
control strategy can therefore be formulated as an optimal control problem with the objective
function being the quadratic deviation between the total actual plant production and the total plant
target for a given control interval. Mathematically, this is written as:

min J PR

N
N

1 TRk TCSDk ts TCk ts ,

k 1
k 1

subject to constraints (2)-(5).

3
487

(6)

MODEL PREDICTIVE CONTROL MODEL

The open-loop optimal control problem is solved off-line over a unique control horizon [1, N] as
shown in Eq.(6). This means that the optimal solution over the control horizon is obtained once
and thereafter applied to predict the future states/outputs of the system. Consequently, if at some
instance, during the controller execution, the control system is subject to disturbances, or in some
cases, the prediction model of the process is uncertain due to model inaccuracy or its
simplification, the open-loop optimal control will not able to update its control actions in order to
respond to these changes. This is because the control actions are applied ahead of time to the
process, due to the off-line nature of the open-loop optimal control strategy. Based on the above,
the open-loop optimal control is shown to not be suitable for real-time control implementation. On
the other hand, with the closed-loop MPC strategy the open-loop optimal control problem is
repeatedly (on-line) solved over a finite control horizon by updating the process states at each
sampling interval (Mayne et al., 2000, Badenhorst et al., 2011, van Staden et al., 2011, Xia et al.,
2011, Zhang et al., 2012). This therefore makes it possible to compensate for effect of
unmeasured disturbances and or model inaccuracy. However, in this work, only the effect of model
inaccuracy is investigated. The minimization of the control objective previously by Eq.(20) is
therefore updated to:
2
R 2mcr

TRk

min J C t s
Pmcr ,0 pk ,

k 1 m 3.6

m N

(7)

Where m=0,,S is the sampling instant and hence, S denotes the last sampling instant. It is easy
to see that if S is infinite, then the control actions are executed infinitely. In (7), the finite control
horizon is [m, m+N] and its length depends on S. The closed-loop MPC algorithm for this problem
is described as follows:
1. Get the new mass storage states from both hopper and downstream storage system X (MH, MS).
For this problem, the state equation at each sampling interval [m, m+1], can be written as
follows:

X m 1 AX m BU m dm ,

(8)

whith

TR ,m
M H ,m1
M H ,m

1 0
,
X m1
, X m
, U m TCSD,m , A
0 1
M S ,m1
M S ,m
T

R ,m
0
1 1 1
.
, d m t s
Bm t s
T
1

0
,
C
m

From control view, Xm is the dynamic state vector, Um is the control input vector, A and B are,
respectively, the state and input matrices, and dm is defined as the measured disturbances,
assumed predictable or known for a given control horizon.
2. Solve the open-loop optimal control problem.
3. Apply only the first value from the control sequence and the rest are discarded. This means
that if u denotes the control sequence, the control sequence at each sampling instant m is
given as u=(um+1, um+2, um+3,, um+N); then the first control signal to be applied to update the
prediction model given by Eq. (22) is um+1 and um+2,um+3, um+N are discarded .
4. Update m=m+1 and go to 1.
The MPC algorithm above defined shows that at each sampling interval [m, m+1], the states X (MH,
MS) of the VSI crushing process are feedback to the controller in order to compute the next control
actions. With this, the effects of disturbances and inaccuracy of the model can be compensated by
the MPC approach. One should note that although the constraints on mass storage states of the
open-loop optimal control model are also taken into account into the MPC algorithm, their initial
values are updated after implementation of each control interval k.
In practice, the crushed material consumption rate TC considered as an input parameter to the
model is imposed by the consumption point. If TC is the coal consumption rate in a coal-fired power
plant, for instance, this is usually forecasted based on the load assignment. Therefore, for some
reasons, if the forecasted load assignment is not accurate, TC will also experience the same
inaccuracy, leading to the model inaccuracy of the VSI crushing process.

4
488

(9)

CASE STUDY: CRUSHING PROCESS IN A COAL-FIRED POWER PLANT

Optimal control strategies for energy minimization of coal belt conveying systems are studies in
(Zhang and Xia, 2010). However, in the aforesaid study, the coal crusher is not included in the
optimal energy control problem. Therefore, for simulation purpose, the same system used in
(Zhang and Xia, 2010) is considered in this work with a focus on the crushing energy cost
minimization. Furthermore, the crusher is assumed to be a VSI crusher.
Data presentation
Coal consumption and coal storage system
In view of the above, data such as power plant capacity, coal bin (storage system) capacity and
forecast coal consumption are obtained from reference (Zhang and Xia, 2010). The obtained
foretasted coal consumption rate TC is shown in Fig. 2. Based on the given coal-fired power plant
with two 600MW units, the estimated total bin capacity (TBC) is 5595.5 t.

Coal consumption [t/h]

475

470

465

460

455

450

10

15

20

25

Time [h]
Fig. 2: Forecasted coal consumption rate

In this work, the upper and lower limits of the material mass MS stored in the downstream storage
system (coal bin) are set, respectively, to 90% and 20% of TBC. The initial mass stored MS,0 in the
downstream storage system is assumed to be 50% of TBC.
VSI crusher
A 520kW (700 hp) Barmac B9100SE VSI crusher2 is used for simulation purpose in this work. Its
non-load power Pmcr,0 is taken as 12% of the rated power (Moray et al., 2006), that is to say, 62kW.
The linear speed of the crusher rotor Vcr is 45 m/s with a cascade ratio of 30% and maximum feed
rate of 765t/h. The maximum rotor feed rate is therefore obtained to be 588.5t/h. The overall drive
efficiency is set to 95%.
Time-of-use electricity tariff
The recent Eskom Megaflex Active Energy-TOU electricity tariff is used for simulation purpose. To
be more specific, the crushing station is supposed to operate under the non-local authority rate.
The control interval in this work is assumed to be within the high-demand season (from June to
August) weekday. This is given as3

po 0.3656 R / kWh if t 0, 6 22, 24,

pt ps 0.6733R / kWh if t 6, 7 10,18 20, 22,

p 2.2225R / kWh if t 7,10 18, 20,
p

where R is the South African currency Rand and t is the time of any weekday in hours (from 0 to
24).
Simulation results and discussion
The control horizon [t0, tf ] and sampling time ts of, respectively, 24h and 10 min are used for all
control strategies. For all simulations, the recirculated material is not considered (=0). The upper
2

Metso, Barmac VSI crushers, <http://www.metso.com>

Eskom, Tariffs \& Charges Booklet 2013/2014, <http://www.eskom.co.za>

5
489

(10)

limit on the flow rates of all belt conveyors is set to 765t/h which corresponds to the higher limit of
the throughput of the 520 kW Barmac B9100SE VSI crusher.
The fmincon function of MATLAB Optimization Toolboox is used to solve the current control
problem. As for the optimal control problem, the linprog function of MATLAB Optimization Toolbox
is used.
The aim of this section is to demonstrate that the closed-loop MPC strategy can achieve as much
energy cost saving as the open-loop optimal control for the case study in this work.
Firstly, the current control strategy taken as the baseline is applied to the VSI crushing process.
The result of this is shown in Fig 3. Secondly, the open-loop optimal control and closed-loop MPC
problems are solved, and the comparative simulation result is presented in Figs. 4-6. For all figures,
the dotted lines denote the upper and lower bounds of the variable (where applicable). Note that
the legend of Fig. 3 also applies to Figs. 4-5.
Fig. 3 and Fig. 4, respectively, prove the feasibility of the three control strategies in terms of
meeting both physical and operation constraints of the crushing plant. However, with the current
control strategy, the VSI crushing process runs most of the time, with evenly distributed flow rates
during the control horizon (0-24h) without shifting the load out of peak-time periods. This is due to
the fact the current control strategy does not have any information about the TOU tariff during the
process control. As result of this, a higher energy cost is incurred. The simulation results obtained
by the current control strategy in this work reflect the practical operation of most crushing
processes. In practice, most crushing processes run for long time with a continuous and even
feeding (material feed rate) for a given operation period while achieving the total production
requirement (total plant throughput) and meeting other constraints associated with the operation.
On the other hand, as can be seen from Fig. 4, both open-loop optimal control strategy and
closed-loop MPC strategy runs the VSI crushing process by optimally shifting the load (flow rate TR)
from peak-time periods to off-peak and standard-time periods in order to minimize the associated
energy cost. It can be seen from the first graph of Fig. 4 that during peak-time periods, the coal
flow rate through the crusher rotor, TR is zero so as to save the energy cost, whilst during off-peak
periods; this is maximized due to a cheaper energy cost. Fig. 5 further demonstrates that with both
open-loop optimal strategy and closed-loop MPC strategy, 100% of the morning peak-load (power
consumed between 7-10h) is shifted to the morning off-peak time (0-6h) while about 85% of the
evening peak-load (power consumed between 18-20h) is shifted to the morning off-peak time (2224h) and the remaining is shifted to the evening off-load time (0-6h). Since almost all the peakloads are shifted to off-peak time periods for energy cost saving purpose, it turns out that the
standard-loads achieved with the current control strategy is almost the same as after the optimal
energy control strategy is applied. Hence, for this case study, it is therefore worthy to mention that
the energy cost saving is achieved by shifting the peak-loads to off-peak time periods. Practically,
in some circumstances where all the peak-loads cannot be shifted to the off-peak time periods, a
portion of peak-loads can be shifted to standard-time periods in order to further save the energy
cost of the process.
The cumulative energy cost of the three control strategies are shown in Fig. 6, while Table 1
summarizes the performance of the open-loop optimal control strategy and closed-loop MPC
strategy. The analysis of Fig. 6 clearly shows that, at the end of the control horizon (24h), both the
optimal control and closed-loop MPC strategies dramatically reduce the energy cost with
comparison to the current control strategy taken as baseline.
The performance of the closed-loop MPC strategy is therefore proved in Fig. 4. The simulation results
in Fig. 4 show that the MPC strategy shifts the peak-loads from peak-time periods to off-peak time
periods as just the open-loop optimal control strategy does. From the same figure, it also easy to
notice that the shape of all the graphs obtained with the open-loop optimal controller is almost the
same as that obtained with MPC strategy. Moreover, Fig. 6 and Table 1 show that a slight much less
energy cost is achieved by the closed-loop MPC strategy as compared to the open-loop optimal
controller, which observation can be subject of a controversy. However, this is justified by the fact that
the MPC strategy yields lower amount of the daily production (total throughput) of 10119 tonnes
when compared to 11130 tonnes obtained by the open-loop optimal controller. This therefore
demonstrates the importance of using the unit energy cost (energy cost/production) as performance
index to calculate the energy cost saving as the case in this work. Hence, although the MPC strategy
seems to yield less energy cost, its unit energy cost (0.3604) is slightly higher as compared to the unit
energy cost of 0.3553 obtained by the open-loop optimal controller. Table 2 shows that energy cost
saving achieved by MPC controller is about 33.50% against 34.45 % achieved by the open-loop
optimal controller. The comparison results therefore prove the effectiveness of the closed-loop MPC

6
490

strategy as compared to the open-loop-optimal control strategy in saving the energy cost in a VSI
crushing process.
open-loop

peak

TR [t/h]

standard

500
0

10

15

20

25

TCSD [t/h]

200

TF=T1 [t/h]

10

15

20

25

500
0

10

15

20

MH [t]

20

25

10

15

20

25

10

15

20

25

10

15

20

25

10

15

20

25

500
0

10

15

20

25

10

15

20

25

5000

MS [t]

MS [t]

5000

Time [h]

Fig. 4. Open-loop optimal control strategy and MPC

strategy

Fig. 3. Current control strategy-baseline

7000

400

Cumulative energy cost [R]

current control strategy

open-loop optimal control
MPC
no-load power consumption

500

300

200

100

15

500

Time [h]

Power consumption [kW]

10

100

25

500

MH [t]

200

TF=T1 [t/h]

100

MPC

500

TCSD [t/h]

TR [t/h]

off-peak

current control strategy

open-loop optimal control
MPC

6000
5000
4000
3000
2000
1000
0

10

15

20

25

Time [h]

Fig. 5 Current control strategy, open-loop optimal

control strategy and closed-loop MPC strategy

7
491

10

15

20

25

Time [h]

Fig. 6 Current control strategy, open-loop optimal

control strategy and closed-loop MPC strategy

Table 1. Performances of Closed-loop MPC strategy and open-loop optimal control strategy
Strategy

Production (t)

Energy cost (R)

Current control
Open-loop optimal
control
Closed-loop MPC

11130
11130

6032.0
3955.1

Unit energy
(R/t)
0.5419
0.3553

10119

3646.8

0.3604

cost

Cost saving (%)

/
34.43
33.50

CONCLUSIONS
In this paper, a practical model to improve the operation efficiency of a VSI crushing process is
firstly developed. The performance index considered for this operation efficiency is the
minimization of the cost associated with the VSI energy consumption based TOU tariff. Secondly,
in order to evaluate the feasibility of the model, a case study on a crushing process in a fire-coal
power plant is solve based on both open-loop optimal control and closed-loop MPC strategies. The
simulation results performed through MATLAB Optimization Toolbox demonstrate the
effectiveness of the both optimal control strategies. Furthermore, it is shown that the MPC strategy
is just effective in achieving the energy cost saving as the open-loop optimal control strategy.
ACKNOWLEDGEMENT
The authors would like to thank the National Research Foundation (NRF) of South Africa for
financial support under grant unique number 88744. The support from the National Hub for Energy
Efficiency and Demand Side Management (EEDSM) is also acknowledged.
NOMENCLATURE
JC total energy cost, currency
Pel electrical power consumption of VSI crusher, W
t0 and tf initial and final time of the control horizon, h
p(t) time-of-use (TOU) electricity tariff, currency/Wh
E specific net energy of the VSI crusher, J/Kg
R rotor radius of VSI crusher, m
mcr mechanical rotational speed of VSI crusher, rad/s
Vcr linear speed of VSI crusher rotor, m/s
Pmc r mechanical crushing power, W
Pmcr,0 no-load mechanical crushing power, W
overall drive efficiency, %
ts sampling period, h
j jth sampling interval
Ns total number of sampling intervals
pj electricity price at jth sampling interval, currency
TR mass flow rate through the crusher rotor, t/h

TF belt conveyor feed flow rate into crusher, t/h

TCSD cascade flow rate, t/h
T1
mass flow rate into the crusher hopper, t/h
T2
mass flow rate from the crusher hopper, t/h
T3 mass flow rate from the screen, t/h
TRC recirculated material mass flow rate, t/h
min and max minimum and maximum

recirculated material flow ratio

CSD cascade or bi-flow ratio
MH material mass available in the crusher hopper, t
MH,0 initial value of MH, t
MS material mass available in downstream storage
system, t
MS,0 initial value of MS
po, ps, pp off-peak, standard and peak TOU prices,
currency

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BENGTSSON, M. & EVERTSSON, C. M. 2008. Modelling of output and power consumption in
vertical shaft impact crushers. International Journal of Mineral Processing, 88, 18-23.
LINDQVIST, M. 2008. Energy considerations in compressive and impact crushing of rock. Minerals
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MAYNE, D. Q., RAWLINGS, J. B., RAO, C. V. & SCOKAERT, P. O. M. 2000. Constrained model
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9
493

INVESTIGATION ON INTERMITTENT HEAT PUMP DRYING PROCESS OF GREEN

SOYBEAN
Zhao Yang*, Zongsheng Zhu, Fang Wang, Feng Zhao
School of Mechanical Engineering, Key Laboratory of Efficient Utilization of Low and Medium Grade
Energy, MOE, Tianjin University, Tianjin, China
Address: 92 Weijinnan Road, Nankai Distrist, Tianjin, 300072, China
E-mail address: zhaoyang@tju.edu.cn

Abstract: The aim of this paper was to investigated the benefits of intermittent drying with changed
intermittency ratio, compared with continuous drying and intermittent drying with stable
intermittency ratio. A new parallel conversion controller was promoted to achieve accurate
regulation of drying temperature at all the times. On the base of a heat pump drying system, the
drying kinetic of five intermittent drying methods were analyzed. The net energy and SMER allows
one to assess the effectiveness of intermittent drying. The highest SMER (specific moisture
extraction rates) appeared when the intermittent ratio was 1/3 during intermittent drying. The SMER
and amount of moisture removal of changed intermittency ratio were larger than that of stable
intermittency ration when the mean intermittency ration was same and equal to 0.5.
Key Words: intermittent drying; net energy; changed intermittency ratio; SMER

494

INTRODUCTION
The moisture content of seed can reached 25% to 45% when fresh harvested. The seed should be
processed using an appropriate dehydration method to lower the respiration intensity and to
prevent insect infestation and mold growth. Among all the dehydration techniques, drying is a one
of the oldest and widely used process to reduce food losses and increase shelf life ( Koyuncu et
al.,2007; Oliviero et al., 2013; Patel and Kar, 2012).
Due to the different properties of drying material, it is need to adopt appropriate drying equipment
and method. Seed contains life materials and needs a more gentle method to drying. Low
temperature dehydration is beneficial to seed vitality and the sowing quality. It is clear that the
drying conditions need vary with the seed kind. The equipment used to drying should be convenient
to adjust the drying temperature, air humidity and other parameters. What is more, the problem of
environment pollution and natural resources depletion has been expanded to the whole world. In
conclusion, an energy-saving and easy-control equipment and corresponding drying method gain
more interest for drying. Heat pumps assisting the hot air convective dryers which can recirculate
environmental and waste heat back into a drying process are proven to ensure the quality of
product especially food and agriculture products (Goh et al., 2011; Hawlader et al., 2006;
Prasertsan and Saen-saby, 1998). Compared with other drying equipment, the heat pump dryers
have potential to save up to 50% or more of the primary energy used. Drying method is as
important as drying equipment to improve product quality and save energy. Drying in steady-state
conditions is a widely used method but ineffective. The better process should be based on the
situation of the material being drying. When the material contains high moisture, there is little
damage and high drying rate can be maintained. With the decrease of moisture content, high drying
rate causes shrinkage and fissure and weakens the seed vitality. The negative effect should be
avoided by changing the drying parameters to slow down the drying rate.
Intermittent drying, as a modified drying process in which drying conditions are changed with time,
has been considered as one of the most energy efficient drying processes and offers some
advantages over traditional drying (Chua et al., 2003; Kowalski and Pawlowski, 2011). Due to its
taking material drying condition into account, intermittent has been widely adopted especially for
drying of heat-sensitive materials. Researchers have concentrated on the features of intermittent
drying and found the followed advantages: energy effective, shorter effective drying time, higher
moisture removal rates, lower product surface temperature and higher product quality. Yang et
al(2012) made a comparative simulation study on different heat pump drying of Chinese cabbage
seeds and found an obvious advantage of intermittent drying over continuous drying as regards
energy efficiency. Intermittent drying promoted the moisture diffusion uniformity and reduced the
probability of stress concentration and fissure, thus affecting rough rice moisture gradient and rice
fissuring (Dong et al., 2010). The fixed heat input throughout the drying process result in quality
degradation and heat damage to the surface (Zeki,2009). With the extension of time, the drying rate
decreases as the surface of the materials do not contain sufficient moisture to match the rate of
moisture that should be removed. So the surface becomes dry and the quality of material go
degradation. Intermittent drying should be based on the diffusion of moisture from inner to surface.
When the moisture diffusion rate from inner to surface is lower than that from material surface to air,
the energy input should be stopped. When opposite, the energy input should be resumed. This will
allow a tempering period for the material to redistribute the moisture, transferring the moisture from
the inside to the surface of the material. Various strategies of intermittency in energy input including

495

on-off, step-up and step-down, square, saw toothed and sinusoidal and cosine temperature
variation have been applied (Kumar et al., 2014). Thus, for optimal energy consumption and
improved quality, it is important to match the energy demand of the product with the external energy
input during drying using several possible modes of heat transfer simultaneously or sequentially.
Intermittent drying is an optimal method to save energy and the duration using to dry (Chou and
Chua, 2007; Chua, et al., 2003). Some researchers have investigated the energy savings by on/off
intermittency (Chin and Law, 2010). In order to describe the advantages of intermittent drying, a
new parameter which does not appear in continuous drying process has been promoted:
intermittency ratio. This parameter is defined as =on/(off+on), where off and on are the on and off
periods of heating, respectively. It is obvious that lower intermittency refers higher tempering period.
Increasing intermittency would increase the energy efficient but total drying time would be longer
too. Therefore, the value of intermittency should be selected based on the degradation properties of
materials. Many researchers have concentrated on merit of the constant intermittency during the
whole drying process, which does not according with the situation of the moisture in material. A
variation of intermittency should be considered to optimize the energy savings and product quality.
In this paper, a new temperature control method, namely parallel conversion control, was promoted
to achieve accurate regulation of drying temperature at all the times. On the base of a heat pump
drying system, the drying kinetic of five intermittent drying methods were analyzed. The net energy
calculated and SMER allows one to assess the effectiveness of intermittent drying. The results of
drying process were compared with each other which were carried out under stationary conditions
to found out the advantages of the intermittent drying. Whats more, the benefits of changed
intermittency ratio were also demonstrated.
MATERIALS AND METHODS
Sample Preparation
Samples of green soybean fresh-harvested were acquired from a agricultural market in Tianjin,
China. Initial moisture content of samples was about 20% (d.b.).
Heat Pump Drying System
The heat pump drying system (HPDS) used to dry green soybean was transformed from a
conventional system, by adding inverter for compressor, electric expansion valve (EEV) and
temperature and humidity sensors. Figure 1(Yang, et al., 2013) shows a schematic diagram of a
closed heat pump drying system. The system consisted of two main parts: a heat pump system and
a drying chamber. When the drying process converted between heating process and cooling
process, the parameters would generate fluctuations. In order to decrease the fluctuations and
improve the temperature precision, a new parallel conversion control method was used.
Because the drying process was divided into two aspects, its control strategy had a large difference
with the ordinary heat pump strategies and should be divided into heating fuzzy control and cooling
fuzzy control, as was shown in Fig. 2 (Yang, et al., 2013) for the heating and cooling control
schematic. The input signals to be fuzzified in this paper were selected as chamber temperature
error (e) and its deviation (ec), at the meantime, the output signal was compressor frequency (Hz).
We firstly measured the temperature of the dryer online and judge the process as heating or cooling.
Then, the fuzzy decision and output signal were made according to the error between the real-time
temperature and its given value. These outputs were transformed to real variables using triangular
fuzzy membership functions by the center-of-gravity method.

496

Compressor

Inverter

Heating
electromagnetic
valve

Cooling
electromagnetic
valve

Indoor condenser

Outdoor
condenser

Stop valve

Auxiliary fan

Main fan

Outdoor fan
Liquid storage
tank

Drying
chamber
EEV

Materials stent
Evaporator

Fig.1. A schematic illustration of a closed heat pump drying system

Temperture sensor
Tm

Ts-Th>Tm

Heating Fuzzy
Controller
Inventer

Set
Temperture
Ts

Ts-Th<Tm<Ts+Th

Drying
Temperture

No Change
Inventer

Ts+Th<Tm

HPDs Heating Process

HPDs Cooling Process

Cooling Fuzzy
Controller

Fig.2 Schematic of HPDS control strategy

Drying Procedure
In this paper, five drying methods were investigated and each of them have three drying circles.
Every circle is 1500s. The drying conditions is shown in Table 1.
Drying method 1: in an intermittent cycle, continuous access and 35 drying air 1000s,
then stop ventilation 500s, intermittency ratio =2/ 3
Drying method 2: in an intermittent cycle, continuous access and 35 drying air 750 s,
then stop ventilation 750s, intermittency ratio =1/ 2
Drying method 3: in an intermittent cycle, continuous access and 35 drying air 500s, then stop
ventilation 1000s; intermittency ratio =1/ 3
Drying method 5: continuous ventilation 40 drying air until time is over, =1.
Drying method 4: in the first intermittent cycle, continuous access and 35 drying air 1000s,
then stop ventilation 500s, intermittent ratio =2/ 3; in the second intermittent cycle, continuous
access and 35 drying air 750 s, then stop ventilation 750s, intermittent ratio =1/ 2; in the third
cycle, continuous access and 35 drying air 500s, then stop ventilation 1000s; intermittent ratio
=1/ 3.
In this paper, intermittency ratio =on/(off+on), where off and on are the on and off periods of

497

heating, respectively
Table 1 Operate conditions applied in the heat pump intermittent drying
1st circle

Drying

2nd circle

3rd circle

Drying

Methods

conditions
on(s)

off (s)

on(s)

off (s)

on(s)

off (s)

Tc=35

500

1000

1/3

500

1000

1/3

500

1000

1/3

V=1.2m/s

750

750

1/2

750

750

1/2

750

750

1/2

RH=40%

1000

500

2/3

1000

500

2/3

1000

500

2/3

X0=25%

1000

500

2/3

750

750

1/2

500

1000

1/3

1500

1500

1500

Drying Rate
The drying rates (DR) which enable the use of the obtained results to study the heat penetration and
deep bed drying (Silva et al., 2013), are calculated by approximation of derivatives to finite
differences (Hii et al., 2011) by using the following equations:

DR

M i 1 M i
ti 1 ti

(1)
Where Mi+1 is moisture content at time ti+1 (g water/g dry solid), Mi is moisture content at time ti (g
water/g dry solid), t is the drying time (h).
Specific Moisture Extraction Rates (SMER)
SMER is an important index to evaluate the dehumidification ability of the heat pump dryer. It is in
relation to the return air quantity, the air humidity at the outlet of the drying chamber and drying
temperature. SMER is calculated by the following equation:

SMER

Qd
W

(2)
Where Qd is the dehydration quantity during drying, and W is the electric energy using for operation.
Energy Analysis
The main aim of energy analysis of heat pump drying process is to find out more about the energy
aspects and behavior of drying air throughout the heat pump dryer. Intermittent drying process,
investigated in this study, contains two process: heat-input process no-heat-input process. When
analyzing the energy consumption of the whole drying process, it is convenient to divide the
process into the above two processes.
For heat-input process:
Having determined the temperature of the drying green soybean, T(t), and the drying curve at every
period, X(t), as a function of drying time, we can calculate the rate of heat used for heating the wet
green soybean and for moisture removal due to evaporation. The equation is shown as follow:

dQi (t )
d
mi (t ) ((cg cw X i (t ))(Ti (t ) Ti 0 ) ( X i 0 X i (t ))r )
dt
dt
(3)
We can write Eq.(3) in finite differences as follows:

Qi mi (cg cw X i )Ti mi (cwTi r )X i

498

(4)
Where:

Ti Ti Ti 1

and when i=1,

X i X i X i 1

Ti 1 T0

and when i=1,

X i 1 T0

cg cw X 1548.8 4190 x( J / kg K )
r=2394 (kJ/kg.), i is the number of drying circle and in this paper i=1,2,3.
For tempering period: There is no energy used for drying
Total energy used for heating of the dried body and the moisture removal in the whole process can
be written as follow:
3

Q Qi
i 1

(5)
RESULTS AND DISCUSSION
Among all the parameters affecting the rate of drying, the temperature of the drying air is
considered to be the most important factor to influence on the product drying kinetics and quality of
the products (Arroqui, et al., 2002 and Ramesh, et al., 2001). Fig.3 gives the comparison of the
experimental results among parallel conversion controller, PID controller and fixed-frequency
controller. The temperature becomes more stable with less undershoot and overshoot when the
parallel conversion control method was used, which indicates the optimized fuzzy controller gave
noticeable performance improvement compared to the others. Even though the PID controller gives
a better performance on overshoot than the fixed-frequency controller, it fails to lessen undershoot.
32

30

Temperature (C)

28

26
Parallel convension control
PID control
Fixed-fequency

24

22

20

18

100

200

300

400

500
Time (s)

600

700

800

900

1000

Fig.3 Variation of drying temperature using parallel conversion control method, PID control method,
fixed-frequency control method, respectively at 30C.
Velocity of the drying air is another important factor to affect the process when moisture diffuses
form the surface of the product to the drying air. In this experiment, the fan which drives the air
works or stops along with the heat input. The change of the air velocity is shown in fig.4. The mean
value of the air velocity is about 0.7m/s when the fan is working. It is obvious that the difference of

499

the drying rate investigated in this paper is affected by heat input and the air velocity. In the initial
stage of drying, a high air flow would enhance moisture removal from the surface of product ( Chin,
et al., 2009; Ong, et al., 2012)
About five kilogram green soybean was used to complete this research. The initial moisture content
of the samples is 20%. The intermittent drying conditions employed in the study were presented in
Table 1. In order to consider drying behavior, different drying curves of different intermittent drying
process should be plotted to investigated the relationship between moisture content with time. The
drying curve of the process carried out under the operation condition iss demonstrated in Fig.5.
Comparing all the curves, we could see that the continuous drying curve (=1) lost moisture most
quickly among the five drying methods and the Method 1 of intermittent drying (=1) gave the
smallest amount of removal moisture. It was obvious that the heat input and velocity were in direct
relation to the drying process. We should investigate a more effective method to realize the
moisture removal.
0.8

0.7

Wing velocity (m/s)

0.6
Method 1
Method 2
Method 3
Method 4
Method 5

0.5

0.4

0.3

0.2

0.1

500

1000

1500

2000
2500
Drying time (s)

3000

3500

4000

4500

Fig.4 Wind velocity vs. drying time

0.2
Method 1
Method 2
Method 3
Method 4
Method 5

Mean moisture content (g/g d.b.)

0.19

0.18

0.17

0.16

0.15

10

20

30

40
Drying time (mins)

50

60

70

80

Fig.5 Experimental moisture content vs. drying time

Drying rate, calculated by equation 1, is convenient to distinct different stage of drying. Fig.6
demonstrated the drying rate of the five intermittent drying process. The drying rate of continuous

500

drying decreased with drying time. And lower intermittency ratio leaded to a more fluctuation. From
the figure, it could be seen that lower intermittency ratio was not good when the moisture content of
the product was high. The intermittent drying with varied intermittency ratio took the moisture
content change into consideration and shown a much better drying curve. At the beginning of the
drying the moisture of the green soybean was high and it was need more heat to remove the water
at the surface. With the drying process going, the rate of moisture removing form the inner to
surface became slower and slower and the moisture distribution got non-uniform.

At this period,

longer tempering period allowed more uniform temperature and moisture distribution and hence
resulted in a positive influence in improve the effective of drying (Chua et al., 2003)
0.09

0.08

Model
Model
Model
Model
Model

Drying rate g/(g*min) d.b.

0.07

1
2
3
4
5

0.06

0.05

0.04

0.03

0.02

0.01

10

20

30

40
Drying time mins

50

60

70

80

Fig.6 Drying rate vs. drying time

Based on the experimental data, the energy used for heat green soybean and the removal of water
during every circle was calculated and was shown in Table 2. Compared the data shown in Table 2
and Fig.5, it can be found that the energy consumption was concerned with the amount of moisture
removal and temperature variation in tempering periods. The lowest final moisture content was
method 5 which drying method is continuous, for any intermittency ratio, intermittent drying gave a
higher moisture content than the continuous one when the drying time was same. Method 2 and
method 4 had the same effective drying time, but method 4 gave a lower moisture content. Hence, it
was effective to change the intermittency ratio based on the moisture content of the products during
drying process. Specific moisture extraction rate (SMER) was often used to measure the
performance of drying equipment and energy saving of drying process. The maximum SMER
appeared when method 1 was operated and with the increase of intermittency ratio, SMER
decreased. Higher SMER manifested that the same amount of removal moisture would consume
lower energy. Method 4 with changed intermittency ratio gave a optimal comprehensive parameters
with lower final moisture content and higher SMER.
Table 2 Effect of the intermittency on the performance of drying process
Drying
method

Final

Effective drying time

SMER

Energy consumption, kJ
2nd

3rd

circle

circle

circle

0.48

58.52

31.95

26.09

116.56

0.5

0.36

66.15

42.56

26.32

135.03

0.67

0.31

72.97

45.22

25.89

144.08

moisture

using for removing

content %

moisture (s/g)

11.634

0.33

11.192

10.952

g/kJ

501

st

Total

11.075

0.5

0.38

73.22

43.36

25.73

142.31

10.759

0.21

78.18

52.17

26.06

156.36

CONCLUSION
Five intermittent drying processes of green soybean utilizing a heat pump drying system were
investigated and following conclusions were drawn from this study:
(1) The temperature became more stable with less undershoot and overshoot when the parallel
conversion control method was used, which indicated the optimized fuzzy controller gave
noticeable performance improvement compared to the others
(2) The results of drying curves and SMER presented in this paper allows one to state that
intermittent drying had advantages on the drying of products. Among the five intermittent
drying process, the best intermittency ratio is 1/3 with highest SMER of 0.48g/kJ.
(3) Compared with the intermittent drying with stable intermittency ratio, the one with changed
intermittency ratio based on the moisture content of products had lower final moisture content
and higher SMER when the other parameters were equal.
ACKNOWLEDGE
Supported by the National Natural Science Foundation of China (Grant No. 51076112) and
National Natural Science Foundation of China (Grant No. 51276124) Science and Technology
Project of Tianjin City(Grant No. 12ZCDGGX49400).
REFERENCE
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quality evaluation of air-dried Ganoderma tsugae Murrill. Drying Technology 27(9): 975984.
Chin, S.K., Law, C.L., 2010. Product quality and drying characteristics of intermittent heat pump
drying of Ganoderma tsugae Murrill. Drying Technology 28 (12): 14571465.
Chou, S.K.; Chua, K.J., 2007. Heat pump drying systems. New York :Taylor & Francis Group.
Chua, K.J., Mujumdar, S.K., Chou, S.K., 2003. Intermittent drying of bioproducts - an overview.
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Dong, Renjie, Lu, Zhanhui, Liu, Zhuqing, ShojiKoide, Cao, Wei, 2010. Effect of drying and
tempering on rice ssuring analyzed by integrating intra-kernel moisture distribution. Journal of
Food Engineering 97:161167
Hawlader MNA; Perera CO; Tian M., 2006. Comparison of the retention of 6-gingerol in drying
under modified atmosphere heat pump drying and other drying methods. Drying Technology 24:
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Kowalski, S.J., Paw owski, A., 2011. Intermittent drying of initially saturated porous materials.
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Koyuncu, T., Tosun, I., Pinar, Y., 2007. Drying characteristics and heat energy requirement of
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Patel, K.K., Kar, A., 2012. Heat pump assisted drying of agricultural producean overview. Journal
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503

NUMERICAL AND EXPERIMENTAL RESEARCH ON MULTI-STAGE PUMP AS

TURBINE SYSTEM
1

HUANG Si , SU Xianghui , YANG Sunsheng

1. South China University of TechnologyGuangzhou 510640
2. Jiangsu UniversityZhenjiang 212013
huangsi@scut.edu.cn
ABSTRACT
Recently researches on pump as turbine (PAT) have been one of the hot issues in fluid machineries.
Of these hydraulic turbines, multi-stage PATs are widely used in industrial fields. However, research
and design havent caught up with the development. In this paper a three-stage PAT system with a
load pump was investigated. And computational fluid dynamics method (CFD) were adopted to study
the performance characteristics of PAT under the same feed flow conditions both single- and multistage, also operation rules of multi-stage PAT system were developed in a constant and various
speeds. In the next step, analyses of relationship between multi-stage PAT and its positive rotation
mode were performed. Then details of CFD were paid attentions including inner flow of PAT and
distribution of hydraulic loss. During CFD process, all fluid domains with the PAT control volume were
modeled and reticulated in meshing, then complete performance curves were gained. Test of PAT
confirmed validity of CFD at last, thus analyses in the paper was effective.
Keywords: pump as turbine, multi-PAT system, system efficiency, numerical investigation.
INTRODUCTION
Nowadays, energy storage and management has been of crucial importance to social and economic
development. And hydraulic power recovery turbine (HPRT) is a special device that can absorb
energy from high-pressure fluid and use them to generate or drive some rotating machinery in flexible
ways. In the mining and chemical industry, a large amount of fluid energy is dissipated in valves or
other throttling devices [1-4]. Therefore, HPRT can convert the hydraulic energy into rotating
mechanical energy to make energy re-used. Within HPRT, pump as turbine (PAT) has been widely
used for its convenience and availability [1]. Thus, many researchers has investigated single- PAT
performance characteristics and the relationships with its pump mode theoretically and experimentally
[5-7]. These researchers focus on turbine characteristics and pursue a higher efficiency and a
steadier shaft power output. Some uses CFD method to study PAT inner flow and influences on
performance from geometry parameters [6,8]. Relatively, rules of multi-PAT have been less clearly
understood than single-PAT. Shahram [6] experimentally researched a series of multi- PATs of various
specific speed and obtained some performance ratios of the two modes though it might not work for
lower specific speed ones. H.J. Van Antwerpen [4] developed relationship among PAT head,
efficiency and flow rate and concluded head and efficiency formulas based on test data and theory
analysis. Yet, there are a few papers investigate the multi-PAT system with load equipments [9-10].
Hence, its necessary to study PAT system including total energy conversion ratio and operation
characteristics.
EXPERIMENTAL SETUP
A test ring of multi-PAT was set up as shown in Fig.1, according to Yangs paper [11-12]. The feed
pump supplies high pressure fluid which drives the multi-PAT to rotate. Then the load pump works
with the rotation of PAT rotor. Of which, Valve 1 and 2 control flow rate of feed fluid, Valve 3 regulates
load pumps flow capacity. Flow rate of both PAT and load pump is measured by turbine flow meter,
and pipe pressure is measured by pressure gauge at inlet and outlet position of PAT or pump. Torque
meter is placed at the joint of their two. When the feed pump generates steady high pressure fluid
and all valves opening keeps unchanged, the system will operate at a constant rotation speed. When
flow rate into PAT increases or pump flow rate decreases the system will rotate faster, otherwise on
the contrary.

504

Fig.1. Test ring for multi-PAT system

PAT SYSTEM CONFIGURATION
The designed multi-PAT has three stages with each stage an impeller and a diffuser. The design point
is Q=353/h, H=100m. In order to research multi-PAT characteristic, a single-PAT with the same design
objectives is designed to compare. The geometry parameters of the two PATs are listed in Tab1. Their
axial projection draws are displayed in Fig2.
Table 1. Main geometry parameters of the designed PAT

Impeller

Multi-PAT
D1(mm)
D2(mm)
b2(mm)

Z
D3(mm)
b3(mm)
D4(mm)

53.2
121.1
11
21
33
7
250
17
60

Diffuser

Impeller

Volute

Single-PAT
D1(mm)
49.3
D2(mm)
204.5
b2(mm)
6
1
34
2
32
Z
8+8
D3(mm)
215
b3(mm)
14
Divergence 12
angle
Section
Trapezoid
shape

Fig.2. PAT axial projection draws

NUMERICAL STRATEGIES

505

The single- and multi-stage PAT are numerical investigated with finite-volume method to achieve
dimensional discretion. The same solution parameters are applied in CFD process. The volumetric
losses are taken into account by adding front and back chambers of multi-PAT rotor. Thus, flow
domains are combined by six components, suction and discharge chambers, impeller and diffuser
chambers, the front and back chambers. To reduce entrance and export effects, inlet and outlet
pipe are prolonged by three times. Fig 3 displays the flow domains.

(a) Multi-PAT
(b) Single-PAT
Fig.3. Computational domains
(1) Mesh generation
Girds generation is completed by ANSYS-ICEM software. Considering the complicated flow in the
rotation components, mesh in the core area of flow is special refined. Rotors, front and back
chamber, suction and discharge chambers are divided by hexahedral grids. The diffuser grids are
generated by tetrahedral meshes for its complex boundary. Grids independent test indicates that
when cell number achieves 1 million, the PAT efficiency will nearly remain unchanged. The total
mesh scale is 3.3 million and each component elements number is rotor 925873, diffuser
7557533, front chamber1002923, back chamber 859563, suction 154413 and discharge
42236. The single-PAT grids generating takes the similar meshing strategies.

Fig.4. Meshing of multi-PAT stage

(2) Solution parameters
The selected fluid in PAT system is clear water at 20 with physical parameters
=998.2kg / m3 , =1.003 10-3 kg / (m s) . Rotors domains are set in rotating coordinate system
and others in stationary system. Second order upwind scheme is adopted for convection term and
central difference scheme for diffusion term. Turbulence model is standard k model. The
boundary condition settings are mainly into two kinds:
A: When PAT rotates in a steady state (2900rpm), inlet boundary is set as mass flow rate and
outlet is static pressure (1atm). Inlet mass flow rate varies from 0.25Qd to 2.25Qd with interval of
0.25Qd, then PAT performance of constant speed is obtained.

506

B:When the feed fluid pressure is settled (150m H2O), inlet boundary is set as pressure-inlet with
value 10.3atm and outlet still static pressure of 1atm. Rotation speed changes from 500 to
3500rpm. Thus PAT rotation speed characteristic is gained.
SIMULATION RESULTS ANALYZE
1. Performance compare of multi-PAT and single-PAT
Though CFD calculation, PAT important operation parameters can be obtained by CFD-post,
including flow rate inlet and outlet total pressure and rotors torque. Hence, PAT head and effective
power and efficiency can be predicted. The following is performance characteristics compare of
single-PAT and multi-PAT.
From Fig 5, its known that multi-PAT has the similar trend with single-PAT. The single-PAT has a
higher head and shaft power with the same flow rate. The best efficiency point of multi-PAT occurs
at 30m3 with value of 0.7 that is slightly higher than single- best efficiency point about 40m3 with
efficiency of 0.67. However, multi-PAT performance is better in most operation interval ,for
outputting a nearly equivalent power the multi-PAT consumed a lower feed head and owns a
preferable energy conversion ratio. The specific speed of single- and multi-PAT are 33 and 75.8,
thus the latter behaves well especially in the high flow rate condition where efficiency of multi-PAT
is 2%~6% higher than single-.

Fig.5. Single- and multi-PAT performance at 2900rpm

Fig 6 shows that PAT head curve has a different variation trend with pump mode. Pump head
decreases and turbine head increases as flow rate increases. Shaft power curves of pump and
PAT are both rising, and PATs has a much bigger gradient. Efficiency curves vary in the similar
trend like a parabola going downwards. To be emphasized is that the best efficiency point almost
occurs at the same flow rate. Before the point pump efficiency is apparently larger than PATs. And
after the point, pump efficiency drop faster than PAT. Tab 2 indicts the performance ratios of the
two modes at HEP point are QT / QP 1.03 , H T / H P 1.22 , PT Shaft P / PP Shaft P 0.90 ,

T / P 0.99 .

507

Fig.6. Multi-PAT and its pump mode performance at 2900rpm

Table.2 Performance characteristics of multi-PAT and multi-pump at BEP point
Q/mh-1
H/m
Single-stage
P/kW

Head (m)
pump
35
83.38
27.8
7.69
0.71
PAT
36
101.41
33.8
6.94
0.70
In order to investigate PAT performance at different rotation speed, CFD compare are completed in
the same boundary condition B. Therefore, the head of PAT is about 150 m, other performance
data are presented in Fig. 7. The initial of rotation is the locked rotor state with stationary rotor, the
maximum of rotation 5000rpm is the runaway state with torque 0. Shaft power trend appears a
parabola going downward as rotation speed. The best efficiency point occurs near the rotation
3500rpm. The flow rate curve decreases as rotation speed. Both single- and multi- PAT has the
same performance trend. Of which, multi-PAT outputs more power and has a better efficiency
characteristic, though it consumes more high pressure fluid. Thus, the following section will focus
on multi-PAT and turbine system.

Fig.7. Multi-PAT performance characteristics at various speeds

2. Multi-PAT inner flow field analysis
The inner flow field of CFD reveals that the difference of velocity distribution in rotors is relatively
small. Therefore, velocity field in the second rotor is displayed in Fig.8 (a). It shows that flow
separation happens in the rotor channel. Fluid velocity near blade pressure side is relatively lower
than that in the suction side. And each rotor channel has a low velocity area distributed in the rotor
inlet toward blade pressure side. Fluid velocity near blade suction side changes a little along the
flow direction. Generally, velocity increases from inlet to outlet as shrinkage of rotor axial flow area.
Fig.8 (b) presents the pressure contour of the three rotors. As shown in picture, pressure drop
takes place from the first rotor to the end, and the active variation of pressure happens in the front
area of flow channel towards inlet. From the velocity and pressure distribution its known that the
designed blade with a relative large (0.85) and (125) can control the behavior of fluid
effectively.

508

(a). Rotor velocity distribution

(b). Rotor pressure distribution
Fig. 8 Mulit-PAT rotor inner flow field
Fig. 9 shows the velocity and pressure distribution in the guide vanes. From Fig. 9(a) its found that
streamlines distribute strongly unevenly along the flow direction, especially in the inlet passage.
There lie several small vortexes in the very inlet position. The velocity orientation changes greatly
in the first beginning of the guide vane. But flow in the discharge vane is much more smoothly. The
pressure distribution of diffusers in Fig.9 (b) indicts that its a pressure decreasing distribution from
the first stage to the end. And there is a tiny pressure drop along the flow direction in each diffuser
passage.

(a). Diffuser velocity distribution

(b). Diffuser pressure distribution
Fig. 9 Mulit-PAT diffuser inner flow field
MULTI-PAT SYSTEM OPERATION ANSLYSIS
1 Multi-PAT system with a load pump at constant rotate speed
In many applications PAT rotor is required to work in a constant rotation speed to output a steady
torque and power. In this case, the feed flow head is fixed in the pipe and flow rate can be
controlled. Its important to select a proper load pump. Thus the question that which opening of
turbine valves and which load pump for the best efficiency of the total system is worth studying. In
this multi-PAT system, the feasible and economic PAT feed flow rate is from 20m3/h to 80m3/h. To
ensure the best efficiency of the system, both the PAT and load pump should work in the BEP
area. Thus four flow rate points in the relative high efficiency area are selected for investigation. In
each PAT condition two pumps near designed point are chose. Tab 3 shows operation data of PAT
and pump at different feed flow rate obtained by test.
Table.3 Configuration and operation data of multi-PAT and load pump
Load Pump
Specifications
IS65-40-200a
IS80-65-125
IS80-50-200
IS100-80-160
IS80-50-250a
IS100-65-200a
IS125-100-210a
IS100-65-200

Multi-PAT
3

-1

Load Pump

P/kW

HT/m

30

4.57

87.4

0.646

40

8.70

117.2

0.685

50

14.22

159.9

0.648

60

20.71

214.9

0.599

Q/m h

Pe/kW

Q/m h

2.646

-1

System

HP

ns

23.4

40.0

0.59

53.7

0.382

3.267

50.0

20.0

0.70

132

0.452

5.970

50.0

50.0

0.61

66.3

0.418

6.098

100.0

32.0

0.71

131

0.486

8.938

45.0

64.8

0.63

51.8

0.408

10.644

95.0

45.1

0.72

98.8

0.466

15.778

148.7

40.0

0.76

135

0.455

15.353

100.0

50.0

0.77

93.8

0.461

Note: all the rotor works at rotation speed 2900rpm. Load pump shaft power equals to PAT output
power.

509

(a). Multi-PAT system Pe

(b). Multi-PAT system efficiency
Fig.10. Multi-PAT system Pe and efficiency at constant speed
In Fig 10 variables are feed low head and load pump specific speed, and functions are system
effective power and efficiency. From Fig. 10 (a), its easy to conclude that the bigger feed flow rate
is, the more power system outputs. And load pump specific speed still has effect when feed flow
head is the same. Relatively specific is bigger and output power is a little larger. Fig. 10 (b) shows
that system efficiency increases as increasing of pump specific speed generally. However,
relationship between system efficiency and pump ns is not very clear, the best efficiency point of
system occurs at the point that turbine feed flow rate is 40m3/h and load pump specific speed is
131.

Fig.11. Multi-PAT system performance characteristic

To draw a Summary Conclusion, the sample space of load pumps only contains the more excellent
pump of the two in the same feed flow condition in Tab.3. The new generated four load pumps with
multi-PAT create four combinations whose performances are displayed in Fig.11.
It shows that multi-PAT system efficiency actually doesnt change too much, though it really has
BEP at flow rate 40m3/h. When flow rate varies from 30m3/h to 70m3/h, efficiency fluctuation of
turbine itself is 9.66% and that of PAT system is only 3.4%. And PAT system actually expands the
big flow rate conditions, for turbine efficiency of 70m3/h is much lesser than other points and its
corresponding PAT system efficiency can nearly reach others level. A relatively important
conclusion is that the characteristic ratios of PAT and load pump at the best efficiency point are
QT / QP 0.4~0.6 , HT / H P 3.57~4.35 , separately.
2. Multi-PAT system with a load pump at a variable rotate speed
PAT system is not always work at a constant speed, for valve opening often needs to be changed.
In order to investigate multi-PAT performance at various speed, IS 120-100-210a centrifugal pump
is selected to match turbine whose feed flow pressure are settled to 150m. And system rotation
speed is regulated from 2500rpm to 3500rpm by controlling Valve 1 and 3. The load pump
performance data are presented in Fig 12. Its shown that system rotor runs faster as pump valve
turns up with increase of pump efficiency. Both pump head and shaft power have a slight variation
in the rotation accelerating process. By comparing pump performance at the two operation

510

conditions, its found that pump head is of great difference with that is fixed at 2900 rpm. By proper
changing of system rotation, pump can work in a more effective way. The whole system
performance data are shown in Fig 13. With increase of rotation, system output (effective power of
pump) and efficiency decrease. To be emphasized, system whole efficiency is 16%-49%. Of which,
maximum is nearly equivalent with that in constant rotation in section 6.1, but average is lower.

Fig.12. Performance characteristic of load pump at variable speed

Fig.13. Operation characteristic of multi-PAT system at variable speed

VALIDATION OF CFD RESLUTS
To validate accuracy of numerical calculation, experiments data are presented in Fig 14. For the
restriction of test condition, experimental data concentrate on the light and medium flow rate of
multi-PAT. However, in the investigated interval simulation conforms to test data very well. The
CFD average errors of H, P, are 4.3%, 4.6%, and 7.2% separately. The reason CFD results are
lightly higher than tests lies in the volume losses by pressure drop and mechanical losses by
bearings and sealing. Its reasonable to predict performance of multi-PAT using CFD.

511

Fig.14 Validation of multi-PAT performance characteristics

CONCLUSION
Experimental and numerical investigation on hydraulic energy storage and re-usage are carried out
on a multi-PAT system. CFD techniques are used to calculate PAT performance and inner flow
field at various rotation speeds. The multi-PAT is compared with single- by CFD. Then the
designed multi-PAT is used to drive a load pump to combine a PAT system. And rules of PAT
system are studied numerically and experimentally. Test data in constant rotation conforms to the
validation of CFD results and average errors of H, P, are 4.3%, 4.6%, and 7.2% separately.
Though analysis, the following conclusions are obtained:
(a). CFD method can be applied for prediction and investigation on multi-PAT with an acceptable
accuracy. By switching the boundary condition of two kinds, the performance characteristics can
be gained at constant and various speed.
(b). In many applications single-PAT can replace multi-. However, multi-PAT can perform better in
the case single-PAT specific speed is relatively low and shape of axial projection draws shrinks
serious, especially in the high flow rate points where efficiency of multi-PAT is 2%~6% higher than
single-.
(c). When PAT system runs in a constant rotation, head of feed flow is of a crucial importance to
system efficiency which increases with pressure of feed fluid. Load pump specific speed can
influence system efficiency limitedly. The studied multi-PAT system has a highest efficiency of
48.6% at the medium flow 40 m3/h.
(d). When PAT system runs at various speed, system efficiency is sensitive to flow rate of load
pump. The trend of total efficiency is going downward as flow rate. The highest efficiency of this
case is 49% which is nearly equivalent with that in the constant rotation, but the average of various
speeds is apparently lower.
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[1] .Chapallaz JM, Eichenberger P, Fischer G. Manual on pumps used as turbines, Vieweg,
Braunchweig; 1992
[2] Torbin RN. Alternate methods of energy recovery for the mining industry. IEEE Trans Ind Appl
1989;25(5):8118.
[3] Van Staden CO. Energy recovery in a deep mine with an asynchronous induction motor. M.Eng
Dissertation. Potchefstroom University for Christian Higher Education. Work in progress, 2002.
[4]. H.J.van Antwerpen, G.P.Greyvenstein. Use of turbine for simultaneous pressure regulation and
recovery in secondary cooling water systems in deep mines[J].Energy Conversion and
Management, 2005,46(4) :563-575
[5]. Shahram DerakhshanAhmad Nourbakhsh. Experimental study of characteristic curves of
centrifugal pumps working as turbines in different specific speeds[J].Experimental Thermal and
Fluid Science ,2008, 32(3):800-807
[6]. Shahram Derakhshan, Ahmad Nourbakhsh. Theoretical, numerical and experimental
investigation of centrifugal pumps in reverse operation[J].Experimental Thermal and Fluid Science,
2008 ,32(8):1620-1627

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[7]. G Ventrone, G Ardizzon, G Pavest. Direct and reverse flow conditions in radial flow hydraulic
turbomachines[A]. Proc Instn Mech Engrs,2000,214(A):635-644.
[8]. Sonia Rawal, J.T.Kshirsagar. Numerical simulation on a pump operating in a turbine
mode[A].Proceeding of the 23th International Pump Users Symposium, 2007,21-26
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spray chamber. J Min Ventilat Soc S Afr 1984;37(11):1216.
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Pump
engineering.
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turbocharger;
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513

INFLUENCE OF THE PROPORTION OF DIFFUSE RADIATION ON CPC

RECEPTION PERFORMANCE
*

Ming Yang, Gang Pei , Guiqiang Li , Jingyu Cao

Department of Thermal Science and Energy Engineering, University of Science and
Technology of China, Hefei 230027, P. R. China
Room 96, Jinzhai Road, Hefei City, Anhui Province, P. R. China
*

Corresponding author: peigang@ustc.edu.cn

ABSTRACT
The compound parabolic concentrator (CPC) is an ideal low-medium temperature solar
concentrator that receives a portion of the diffuse radiation without real-time tracking. China is
a vast territory; hence, portions of direct and diffuse radiation in the total annual radiation
between regions are extremely different. The effect of diffuse radiation on CPC reception
performance in series cities: Lhasa, Yinchuan, Beijing, Kunming, Hefei, and Guangzhou,
whose diffuse radiation accounts for 19.7%, 33.1%, 37.9%, 45.4%, and 51.1% of the total
annual radiation, respectively, was calculated and analyzed. According to the Energy Plus
weather data, the amount of radiation received by six kinds of CPC with concentration ratio
(CR) of 1.5, 2, 2.5, 3, 4, and 6 were calculated in a typical day and a year in these cities. The
result showed that diffuse radiation affects the CPC reception performance significantly. The
amount of radiation received by CPC with CR of 1.5 in Lhasa and Guangzhou decreased by
about 13 .7% and 43.1% compared with that of CPC with CR of 6. The amount of radiation that
CPC received was reduced significantly with increasing CR in a high proportion diffuse
radiation region than that in a low proportion diffuse radiation region. Finally, a suggestion of
selecting an appropriate CR of CPC to satisfy the requirement is given.
Keywords: CPC, concentrator, diffuse radiation, direct radiation
INTRODUCTION
Compound parabolic concentrator (CPC) is a non-imaging concentrator proposed by Rabl
(Ari Rabl, 1976), which concentrates on both direct radiation and diffuse radiation, and works
without tracking device. As a kind of low-medium temperature solar concentrator, CPC with
CR of 2 to 5 can achieve temperature of 80 C to 250 C, which can fulfill the general demands
for industry and human life. Kim et al. (Yong Sin Kim et al., 2013) elucidated that a CPC
collector reaching a temperature above 100 C can achieve a thermal efficiency of about 40%.
Perveen et al. (Gulnar Perveen et al., 2013) found that a CPC with a CR of 1.5 can collect more
Energy when the temperature is above 80 C compared with the flat and heat pipe vacuum
tube collector. A CPC concentrator can provide heat source for a low-temperature Organic
Rankine Cycle system to generate electrical energy (Gang Pei, 2011). CPC is also applied to
LiBr-H2O absorption chilling (Z.S. Lu, 2013) and silicone-water adsorption refrigeration (K.C.
Amanul Alam et al., 2013). Moreover, CPC has been utilized for air heating (Mohd.Yusof Hj.
Othman et al., 2005) and sewage purification (C. Navntoft et al., 2008).
These studies reported that CPC has an excellent performance for low-medium
temperature solar collecting and wide applications. Ronnelid et al. (M. RONNELID et al., 1997)
outlined a suitable method for summarizing the annual or seasonal solar irradiation data in

514

irradiation distribution diagrams including both direct and diffuse irradiation when estimating
the collect-able energy on solar devices with different angular acceptances. Suzuki et al.
(AKIO SUZUKI et al., 1995) optimized a two-dimensional CPC with a CR of 1.75 exhibited the
best performance for collecting irradiation. However, the aforementioned studies showed that
the influence of actual weather data including cloudiness and diffuse radiation has not been
considered. In this work, based on the actual weather data, collect-able energy received by
CPC with a of 6 CR, i.e., 1.5, 2, 2.5, 3, 4, and 6, were calculated and analyzed in regions
having different percentages of diffuse radiation, respectively. The relationship between the
performance of collect-able energy received by CPC and area diffuse radiation and CR is
discussed, and suggestions of choosing an appropriate CR in areas have been proposed.
RADIATION CHARACTERISTICS AND PRINCIPLE OF CPC
China has a vast area of 9.6 million square kilometers; hence, the climate in different
regions lead to an uneven distribution of radiation that differs in the total amount and in the
proportion of two components of direct radiation and diffuse radiation. More cloudy or rainy
days occur in the southeastern regions, but less in the northern and western regions. Thus, the
southeastern regions have high percentage of diffuse radiation in a year because cloudy days
lead to much diffuse radiation. By contrast, the north and west regions have a high percentage
of direct radiation, especially the Tibet province, with an annual direct radiation of 2010.2 kWh,
more than the global horizontal radiation. Table 1 shows the annual radiation data of six cities,
namely, Lhasa, Yinchuan, Beijing, Kunming, Hefei, and Guangzhou. The yearly amount of
global horizontal radiation varied from Guangzhou 1118.6 kWh to Lhasa 2004.2 kWh, and
diffuse radiation percentage is from 0.1970.648. This result clearly indicates that diffuse part
is more than the direct part in Guangzhou. Therefore, areas with richer global horizontal
radiation resource may have less diffuse radiation.
Table 1. Annual radiation in different cities.
Global
horizontal
City

Latitude

radiation
-2

Diffuse radiation
-2

( kwh m )

( kwh m )

Direct normal
radiation

Diffuse percentage

-2

( kwh m )

Lhasa

N 29.7

2004.3

395.2

2010.2

0.197

Yinchuan

N 38.5

1662.8

550.5

1360.8

0.331

Beijing

N 39.8

1381.1

523.8

1308.6

0.379

Kunming

N 25.0

1510.4

686.0

1096.1

0.454

Hefei

N 31.9

1137.4

582.1

802.2

0.511

Guangzhou

N 23.2

1118.6

725.3

568.2

0.648

A two-dimensional CPC is shown in Fig.1; AD and BC are the two parabolas symmetrical
about the center axis, with A and B as focus points, respectively. The geometric concentration
ratio of CPC is defined as the ratio of the opening area of the reception area, represented by C
and equal to the reciprocal of sin, where is the maximum half acceptable angle (HAA).
When the incidence angle is within the scope of CPC HAA, the absorber can receive the

515

sunlight directly or by reflecting through both sides of the parabolic. The sunlight reflected
several times out of the opening area cannot be received when the incidence angle is beyond
the scope of CPC HAA. Absorber types of compound parabolic concentrator are usually
divided into four categories, i.e., flat, vertical, triangles, and tube.

Fig. 1. Principle structure of CPC

The radiation collected by CPC contains two components: diffuse and direct. The direct
part on the aperture of the CPC for east and west (EW) orientation facing south is expressed
as Eq. (1), where is tilted angle and I n is direct normal radiation. Variables

and

s are

the solar elevation angle and sun azimuth angle calculated by Eq. (2) and Eq. (3).

I I n sin cos I n cos cos s sin

(1)

sin sin sin cos cos cos

(2)

sin s

cos sin
cos

(3)
Where

is the latitude,

is the declination angle, and

is the hour angle.

2 15
(T 12)
360
(4)

(5)
N is the number of days in a year.
Diffuse radiation on the tilted aperture is expressed as follows:

516

2 23.45
284 N
sin(2
)
360
365

I D I b cos 2

(6)
Where I b is the global diffuse radiation.
In Fig. 2, the angle between the south horizon and the projection of the solar radiation
vector on the north-south vertical plane, NS may be called as the projected solar altitude. The
absolute value of (90the projected anglethe tilt angle) is the projected incidence angle to the
aperture of a CPC for E-W orientation, the mathematical expression is represented as follows:

Fig. 2. Solar position diagram for the E-W orientation of a CPC

tan NS tan / cos s

(7)

90 NS
(8)
CPC receives solar radiation within the scope of HAA

I CPC I

1
* I D
C

(9)
Beyond HAA, CPC only receives part of the diffuse radiation

I CPC

1
* I D
C
(10)

RESULTS AND DISCUSSION

We selected a typical day where the proportion of diffuse radiation is approximately the

517

same as that of the annual global radiation. For example, the percentage of diffuse radiation in
Hefei is 52.25% on April 13th, close to the 51.1% for the whole year. The diffuse and direct
radiation on April 13th is shown in Fig.3; the tilted angle is settled as 23.4so that projected
incidence angle is zero at noon. The energy collected by six CPCs with CR from 1.5 to 6 is
shown in Fig. 4. The radiation collected by all kinds of CPC is very precise at sunny hours
because of a large proportion of the direct radiation. The amount of direct radiation received by
the CPC is equal within the range of HAA during the day, whereas the amount of the received
energy of a CR of 1.5 CPC is much higher than that of 6 during cloudy hours because of weak
direct radiation. For example, the received radiation difference between two kinds of CPC at
13:00 is 200 W. Meanwhile, the CPC with a CR of more than 4 presented a disadvantage on
the time for collecting direct radiation drops compared with CPC with a CR below 4 when the
projected incidence angle is out of the range of HAA. Fig. 5 shows the projected incidence
angle on a typical day in the six cities.
1000

D irect so lar rad iatio n

D iffu se so lar rad iatio n

S olar rad iation W /m

800

600

400

200

10

11

12

13

14

15

T im e

Fig. 3. Radiation on April 13th in Hefei

518

16

17

18

19

20

800

C R 1.5

700

CR 2
C R 2.5

C ellected so la r ra d ia tio n , W /m

600

CR 3
500

CR 4
CR 6

400

300

200

100

-1 0 0
6

10

11

12

13

14

15

16

17

18

19

20

T im e

Fig. 4. Radiation collected by the six kinds of CPC on April 13th in Hefei

160
140

L hasa M arch 9th

P rojiect in cid en ce an gle

120

Y inchuan M ay 24th
B eijing M arch 12th

100

K unm ing M arch 17th

H efei A pril 13th

80

G uangzhou M arch 5th

60
40
20
0
-2 0
6

10

12

14

16

18

20

T im e

Fig. 5. Projected incidence angle on a typical day

The solar radiation received by the CPCs with different CRS in the other five cities on a
typical day was also calculated, as shown in Table 2. A typical day should be near the equinox
day as possible, but the typical days in Yinchuan and Hefei are May 24th and April 13th,
respectively, because of the improper weather. On A typical day around the equinox day, the
CPC projected incidence angle changes little, and most direct radiation can be collected.
However, on a typical day calculation in Yinchuan and Hefei, the projected incidence angle
changes significantly in the morning and in the evening, and the time of receiving direct
radiation of CPC CR decreases with CR of more than 4. The aperture area radiation collected
by CPC with a CR 1.5 that is approximately the same as that with CR of 6 in Lhasa during the

519

day indicated that the difference in the above energy collected is only 2.42 MJ; whereas, the
difference that in Guangzhou is 5.63 MJ.
-2

Table 2. Collectable radiation on a typical day ( MJ m )

City

Typical day

CR 1.5

CR 2

CR 2.5

CR 3

CR 4

CR 6

Lhasa

Mar 9th

17.74

17.11

16.73

16.48

15.64

15.32

Yinchuan

May 24h

19.93

18.56

17.74

17.19

13.56

12.88

Beijing

Mar 12th

16.75

15.85

15.27

14.89

14.41

13.93

Kunming

Mar 17th

15.84

14.51

13.71

13.18

12.51

11.82

Hefei

Apr 13th

13.98

12.37

11.47

10.81

8.87

8.06

Guangzhou

Mar 5th

12.44

10.89

9.96

9.34

8.56

6.81

Sunlight is vertical to CPC aperture at noon for a typical daily calculation in the six cities.
However, the solar collector needs adjustments to guarantee that the projected incidence
angle is within the range of HAA to reduce losing direct radiation during the actual process
because the projected incidence angle varies with the Earths rotation. The adjustment of CPC
should be conducted when the CR is more than 2.5, and the CR of 2.5 to 3, 4, and 6 need to
be adjusted by 2, 4, and10 times in a year, respectively. Taking the adjusted tilt angle and
weather date into the model, the radiation energy collected by the six different CR CPCs in the

200
180

C R 1.5

CR 2

C R 2.5

CR 3

CR 4

CR 6

160
140
120
100
80
60
40
20
0
1

M o n th

10

11

12

2
Accumulative collected solar radiation , KWh/m (aperture)

A ccu m u lative collected solar rad iation , K W h /m

(ap ertu re)

six cities was calculated and shown in Fig. 6.

180

CR 1.5
CR 3

160

CR 2
CR 4

CR 2.5
CR 6

140
120
100
80
60
40
20
0
1

Month

Lhasa

Yinchuan

520

10

11

12

2
Accumulative collected solar radiation , KWh/m (aperture)

CR 1.5
CR 3

140

CR 2
CR 4

CR2.5
CR 6

120
100
80
60
40
20
0
2

10

11

12

Month

160

CR 1.5
CR 3

140

CR 2
CR 4

100
80
60
40
20
0
1

10

11

12

10

11

12

Hefei

180

CR 1.5
CR 3

Month

Beijing

160

CR 2.5
CR 6

120

2
Accumulative collected solar radiation , KWh/m (aperture)

2
Accumulative collected solar radiation , KWh/m (aperture)

2
Accumulative collected solar radiation , KWh/m (aperture)

160

CR 2
CR 4

CR 2.5
CR 6

140
120
100
80
60
40

140

CR 1.5
CR 3

120

CR 2
CR 4

CR 2.5
CR 6

100

80

60

40

20

0
1

Month

Guangzhou

20
0
1

10

11

12

Month

Kunming
Fig. 6. Radiation collected from the selected cities
Overall, the radiation collected by CPC was reduced with the increase in CR in all cities,
and the amount of reduction corresponds with the proportion of the diffuse radiation, because
the addition of the CR of CPC reduced the diffuse radiation collected. In addition, the time of
direct radiation receipted also deceased. In the cities where diffuse radiation has high
proportion, the reduction of energy is mainly attributed to the diffuse part. In the three cities
(Lhasa, Yinchuan, and Beijing) with lower proportion of diffuse radiation, the difference
between radiations received by CPC in a month varied irregularly. Diffuse radiation changes
with the adjusted tilted angel of CPC, and the time for direct part received may change.
However, after adjusting, CPC exhibited a better reception performance with longer time to
receive direct radiation, and the corresponding diffuse and direct radiation on the aperture
increases, so a CPC with higher CR receives more radiation in a month than that of a CPC
with lower CR. Figure 6 showed that the radiation collected by 2.5 CR CPC is higher than that

521

with 2 CR and 3 CR. Moreover, the energy collected by CPC with 6 CR is higher than that of 4
CR CPC in some months, and CR 4 is same with CR 3.
The amount of energy collected was reduced with the increase in CR. Given that the
annual total radiation is low in an area of high proportion of diffuse radiation, a higher CR CPC
will lose a large percentage of annual radiation energy. The annual radiation collected by CPC
with a CR of 6 was reduced by 43% than the CPC with CR of 1.5 in Guangzhou, but only
decreased by 13.7 % in Lhasa. This finding indicates that an area rich in direct radiation should
be applicable for higher CR CPC, even with the increase in the number of adjustments when
needing high temperature. In the areas of poor direct radiation, the application of CPC should
consider the loss of diffuse radiation energy CPC when choosing a higher CR.
-2

Table 3. Accumulative Collect-able radiation ( kwh m )

CONCLU
City

CR1.5

CR 2

CR2.5

CR 3

CR 4

CR 6

Lhasa

1730.8

1593.5

1653.1

1583.7

1570.8

1493.2

The

Yinchuan

1349.8

1191.4

1238.3

1192.3

1102.0

1162.8

difference

Beijing

1254.1

1096.3

1153.1

1072.9

995.6

958.8

on

Kunming

1226.2

1070.5

1045.7

974.3

929.9

856.7

Hefei

932.4

820.3

793.9

748.9

671.3

622.8

Guangzhou

878.0

736.9

681.6

623.5

564.0

498.6

SION

the

proportio
n

of
diffuse
radiation

between the regions in China is remarkable, and the amount of annual total radiation is
generally high in areas with low percentage of diffuse radiation. The proportion of diffuse
radiation has a significant effect on the reception performance of CPC in a typical day. The
radiation collected by CPC decreased rapidly with the increase in the concentration ratio in the
region with a large proportion of diffuse radiation, but slowly on the areas with low proportion of
diffuse radiation. The yearly amount of collect-able radiation by CPC decreased by 13.7% and
43.1% in Lhasa and Guangzhou, respectively, with the increase in from 1.5 to 6 CPC. With
higher CR in area as Guangzhou, CPC would loss much diffuse radiation in a year, but little in
the other areas, such as Lhasa. Therefore, a higher CR CPC should be used in regions rich
with direct radiation for a need of higher temperature, whereas a lower CR CPC is suitable in
regions week of direct radiation for using the diffuse part.

522

ACKNOWLEDGMENTS
The study was sponsored by the National Science Foundation of China (Grant
Nos.51178442) and the Fundamental Research Funds for the Central Universities.
NOMENCLATURE
C

Concentration ratio

Ib

Horizon diffuse radiation (W/m2)

I C PC

Radiation CPC received (W/m2)

I D

Diffuse on titled surface (W/m2)

In

Direct radiation (W/m2)

Day number in year

Local time

Greek Letters

Elevation angle

Tilted angle
Declination angle
Latitude

Azimuth angle

Half accept angle

NS

Projected angle

Hour angle

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524

Simulation and Analysis of Liquid-Vapor Separation Condenser in an Organic

Rankine Cycle
Ziwei Chen, Xianglong Luo*, Ying Chen, Songping Mo
School of Material and Energy, Guangdong University of Technology, Guangzhou, China
E-mail address:lxl-dte@gdut.edu.cn

ABSTRACT
Energy shortage and environmental deterioration are two serious issues that the human
beings facing. Develop clean renewable energy and improve energy utilization efficiency are
two possible ways to handle the energy and environmental problem. Organic Rankine cycle
(ORC) based power generation is a promising technology to recover waste energy and/or
effectively utilizing renewable energy of low enthalpy. Condenser is an important unit in ORC
and the optimum design of the condenser is significant for achieving high efficiency or low cost.
In this paper, a new type of air cooled fin-tube condenser with Liquid-vapor Separation (LSC)
is applied in the ORC system. Based on the mathematical model of LSC, some key geometric
parameters on the total heat transfer surface area and pressure drop of the condenser are
examined. An economic model is formulated for the evaluation of the LSC. The total cost of
investment and operation is selected as objective function to investigate the total performance
of heat transfer coefficient and presser drop under the constant heat transfer rate. The LSC
design geometry parameters are simulated using MATLAB. The LSC is also compared with
other condensers and the results show that the heat transfer area of LSC is lower than that of
serpentine condenser (SC) and parallel condenser (PFC). The internal pressure drop of LSC
is also lower than those of SC and PFC due to its more uniform flowing with higher quality. As
a result, the total cost is lower than that of SC and LSC.
Keywords: condenser; liquid-vapor separation; ORC; economic model
1 INTRODUCTION
Due to the rapid industrialization, energy shortage and environmental deterioration has
become two current serious issues. There is a great deal of waste heat being released into the
environment from industrial plant, which leads to serious energy loss and environmental
pollution. Organic Rankine cycle (ORC) based power generation is a promising technology to
recover waste energy and/or effectively utilizing renewable energy of low enthalpy [1-3].
However, the investment cost of ORC of low heat source and/or low design capacity is so high
[4] that it is lack of competitiveness compared with traditional power generation technologies.
Therefore, the research on the enhancement of the thermal efficiency and the reduction of
investment cost are significant for ORC.
The heat exchangers, such as evaporator and condenser, are the most important
components in ORC, as the effective heat transfer reflects on the overall energetic and
exergetic efficiency. The research showed that the exergy loss of condenser and evaporator
account for 70-90% of total exergy loss of ORC [5]. Similarly, the capital investment of heat
exchanger account for 40-90% of total ORC investment cost [6-9]. Among the heat
exchangers, the condenser possesses the largest proportion in investment cost in low heat
source driven ORC. Both the heat transfer coefficient and pressure drop have impacts on the
ORC. The high heat exchanger coefficient results in lower condenser area. The lower
pressure drop results in high pump power consumption or low turbine power generation. The
low temperature heat source driven ORC is more affected by the condenser pressure drop and
area than those of traditional power generation technology. Therefore, the design and
optimization of condenser is important for the thermal efficiency and cost. Many studies have
focused on the enhancement and optimization of the geometries of heat exchanger to
reducing the heat transfer area [10] or lowering the total cost of heat exchangers [11, 12].
However, the research showed that, in many cases, the enhancement of heat transfer usually
result in higher pressure drop [13,14]. Peng et al. [15] proposed the liquid-vapor separation
condenser (LSC) Similar with Parallel flow heat exchangers, the heat transfer tube of the LSC
is divided into several passes to reduce the mass flow rate and to gain the lower pressure drop.
A number of liquid-vapor separators are designed to remove the condensate between each
two adjacent passes so that the fluid with high vapor quality enters the next pass. Thus, the
LSC would possess both greater heat transfer coefficient and lower pressure drop. The
advantages of using LSC in refrigeration systems have been reported by Chen et al. [16,17],
the heat transfer area reduce 31% and the pressure drop is reduced at least 42.5% compare

525

with parallel flow condenser in the common refrigeration conditions.

In this paper, the LSC is applied in the ORC system. Based on the mathematical model of
LSC, some key geometric parameters on the total heat transfer surface area and pressure
drop of the condenser are examined. An economic model is formulated for the evaluation of
the LSC. The LSC design geometry parameters are achieved by solving the model using
MATLAB. The LSC is also compared with other condenser and the results show that the heat
transfer area of LSC is lower than that of serpentine condenser (SC) and parallel condenser
(PFC).
2 ORC SYSTEM DESCRIPTIONS
2.1 ORC system
The schematic diagram of an organic Rankine cycle for low grade waste heat recovery is
shown in Fig.1.The working fluid is compressed by a booster pump (point 1) is led to the
evaporator, where the working fluid evaporated and superheated by the waste heat (point 2).
The superheated vapor enters a turbine and expands (point 3) to a low pressure to generate
power output. Subsequently, the turbine exhaust condensed to liquid in the air cooled
condenser (point 4). The cooled liquid again goes to the pump (point) continuing the cycle. In
the ORC system, the condenser is an important component which can influence the overall
system thermodynamic performance, the heat transfer enhancement and presser drop
regarding the economic performance. In this study, simulation design of a fin-and-tube
exchanger as the condenser in an ORC is conducted under calculated conditions of heat
transfer rate and mass flow rate. Several types of condenser including liquid-vapor separation
condenser, parallel flow condenser and serpentine condenser were examined in same
simulation conditions of ORC.

Fig.1 Schematic diagram of an organic Rankine cycle

3 AIR COOLED CONDENSER WITH LIQUID-VAPOR SEPARATION
3.1 Structures of LSC
As shown in Fig.2a, the LSC consists of tube banks and a pair of headers at both ends.
Some aluminous baffles with varied round orifices with diameters of 0.5~2mm are set in the
headers, called liquid-vapor separators. They separate liquid from two-phase mixture working
fluid at the entrance of each tube pass except the first one in the inlet of the header. After the
working fluid enter the headers, a part of liquid drops down through the orifice due to the
gravity difference between liquid and vapor. If the orifice is designed appropriately, some liquid
would pass through the aluminous baffles along the headers while the rest left to form a liquid
film covering on the orifices. The film prevents the vapor through these orifices so it comes into
the next pass to be cooled continuously. The liquidvapor separators improves the average
working fluid quality of each tube passes.
In this paper, a single flow route serpentine condenser (SC) has the same tube geometric
construction inside and outside with those of the LSC. As shown in Fig. 2b, the SC is an
ordinary coiled pipe connected with the U-bends without liquid-vapor separation. Fig.2c
demonstrated a parallel flow condenser (PFC) also having the same tube geometric

526

construction except a liquid-vapor separation. The LSC is compared with the SC and PFC in
terms of heat transfer coefficient, pressure drop, and comprehensive performance under the
same operating conditions.

(a)

LSC

(b)

PFC

(c)SC
Fig. 2 Schematic diagram of the LSC, PFC and SC
3.2Heat transfer and pressure drop correlations for tube side
As is well known, heat transfer coefficient and pressure drop of condenser are heavily
sensible to the flow pattern. Cavallini et al [18] presented a two-phase heat transfer model in
microfin tube, as shown in Table 1. The total pressure drop during condensation are calculated
by Eq.(1), where Pf is the frictional pressure drop; Pb is the partial pressure drop; Pg is the
gravity pressure drop; Pa is the acceleration pressure drop. The gravity and acceleration
pressure drop are low compared to the others and therefore they are neglected. So the total
pressure drop in the tube side can be expressed by Eq.(2). The frictional pressure drop model
is given by Cavallini et al [19]. The partial pressure drop calculation given is by Collier and
Thome [20].These correlations are shown in Table 1.

Pi Pf Pb Pg Pa
(

Pi Pf Pb
(

3. Simulation procedure of inside tube

Following assumptions are proposed to simplify the theoretical models of LSC.
The heat load and mass flow rate of condenser work fluid in ORC is fixed.
The distribution of work fluid in each tube per pass is uniform. The mass flow rate of each
tube in the same tube pass is identical.
The tube wall temperature Tw through the whole condenser is constant.
The saturation temperature Tsat along entire working fluid route is identical.
The vapor qualities of inlet in for each pass are controlled by the liquid-vapor separator and
are given in advance.
Fouling effects are negligible.
The inlet and outlet temperatures of air side are known.
In the present study, the total number of tubes Nt are fixed.
In this paper, the tube length is variable and the numbers of tube per pass (NTP) are not
uniform. The NTP decreaes along the passes to meet the fluid velocity requirement due to the
reduction of mass flow rate after the liquid is separated. For example, NTP is
8-7-6-5-4-3-2-1means that the condenser has 8 passes and tube numbers in each pass are 8,
7, 6, 5, 4, 3, 2, 1. As a result, the heat transfer coefficient and pressure drop are not uniform
through the whole tube passes. Therefore, reasonable calculation procedure or algorithm of
heat transfer coefficient and pressure drop for LSC is necessary to be developed. Fig.3 shows
the flow chart of the simulation procedure for LSC. In the first tube pass, the given tube
parameters are the interior geometries of helical micro-fin tubes, the inside diameter, the
scheme of NTP, the condensing temperature, and the inlet mass flow rate. It is assumed that
all the condensate is drained away completely by the liquid-vapor separators and the entrance

527

degree of dryness of all passes are set to be 100%. The outlet degree of dryness is predicted
and verified via heat balance through a iteration procedure. The results of other passes can be
achieved in the same manner as that of the first pass except for the mass flow rate G. The
mass flow rate of the subsequent tube pass is revised by deducting the liquid of the previous
tube pass for the LSC. The total heat load Q is achieved by adding up the heat load of all
tubes of all passes as formulated by Eq. (3) while the total pressure drop is achieved by adding
up the pressure drop of the tube of all passes as formulated by Eq. (4). The calculating would
be ended when the convergence requirement is met. The properties of working fluid are
obtained using REFPROP 7.0 and the simulation procedure shown in Fig.3 is conducted in
MATLAB.
k n

i,tot

i ,k

Ai ,k

Ai

Pi , tot P i

4
)
It is worth mentioning that the proposed simulation procedure for LSC can be also applied to
SC and PFC. When it is applied to SC and PFC, the inlet quality of subsequent pass is directly
equal to the outlet quality of previous pass. A partial pressure drop correlation for bend pipe is
adopted to calculate the pressure drop of the SC.

Table1. Heat transfer and pressure drop models

Heat transfer correlation[18]:

2
(dp / dz) f (dp / dz) f.adiab LO
2 f LO G 2 /( d L )

Nu d c / L

i [ A3 D3 ]0.333

2
LO
E

A AS A C
AS

LO 1 1.128 0.817 L

0.3685

0.2363

1 G
L

2.144

PrL0.1

0.4
LO 0.023(L / d c )Re 0.8
LO Pr L
Re LO Gd c / L

Pr L L cpL / L

Fr G 2 /[gd c ( L G ) 2 ]

2h ng [1 - sin( /2)] 1
Rx
1
d c cos( / 2)
cos
tt [(1 x) / x]0.9 ( G / L ) 0.5 (L / G ) 0.1
C (nopt/ng )

f GO1 16/[Gdc / G ]

if( nopt/ng ) 0.8

laminar flow
(4 f LO2 ) 0.5 1.74 2 log 10[0.36(h/d c ) /(0.1 cos )]
(4 f GO2 ) 0.5 1.74 2 log 10[0.36(h/d c ) /(0.1 cos )]

d c d 2h

F /[exp(F ) 1]

D C[2.4 0.1206( Rx 1)1.466C10.6875 1] D,S

Gc M (dx / dz ) /(d c )

C (1 0.087 ) Rx LO
3L L ( L G )g hLG
0.725

0.3321
L d c T
1 0.741[(1 ) / ]

C1 1

if J G J G*

C1 ( J G / J G* )

if J G J G*

F x 0.78 (1 x)0.224
Fr G 2 /( gd m2 )
We G 2 dc /( m )

turbulent flow
f LO1 16/[Gdc / L ]

nopt 4064.4d c 23.257

D,S

E (1 x) 2 x 2 ( L f GO ) /( G f LO )

f GO1 0.079[Gdc / G ]0.25

if( nopt/ng ) 0.8

1.904

[3.23F ( L / G ) 0.91 ( G / L ) 0.19 (1 G / L ) 0.7 ]

(Fr 0.045We 0.035 )

f LO max( f LO1 , f LO2 )

f GO max( f GO1 , f GO2 )
f LO1 0.079[Gdc / L ]0.25

A 1 1.119Fr 0.3821( Rx 1) 0.3586

C 1

The friction pressure drop[19]:

F [Gc uG / 1 ]
1 (dp / dz) f.adiab d c / 4

uG Gx /( G )
( x L ) /{CO [ x L (1 x) G ] ( L G ugi ) / G}

0.25

ugi 1.18(1 x)[g( L - G ) / L2 ]1/ 4

CO 1 0.2(1 x)[gd C L2 / G 2 ]1/ 4

for 0.1

J G G /[gd c G ( L G )]0.5

CO 0

J G* 0.6{[7.5 /( 4.3 tt1.111 1)]3 2.53}0.3333

for 0

The partial pressure drop[20]:

528

Pcontraction G 2 1 Cc 1 1 1 c2 1 G L2 ( L G ) in 2 L
2

Pexpansion G c c 11 G ( L G ) out L
2

2
L

Cc 1 (1 c ) [2.081 c 0.5371]

Fig. 3 The simulation procedure of heat transfer coefficient and pressure drop for LSC
3.4 The air side model of condenser

529

Fig. 4 Geometry of fin-and-tube

Air is cooling medium of LSC, PFC and SC. The mass flow rate of air Mair is given by Eq. (5).
Q
M air
Cp a (Tin Tout )
(
5
)
As shown in Fig.4, the tubes are surrounded by circular fins. The fin geometry is partly fixed.
The configuration is shown in Fig.4. H, Y and S are, respectively, the geometry of fin height, fin
thickness, fin spacing, these values are referred from literature [21]. The Nusselt at the air side
is calculated by the correlation formulated by Eq.(6) [22]. The local heat transfer coefficients a
is calculated by Eq.(7). In Eq.(7), 0 is the overall surface efficiency and is computed by Eq.(8) ,
where, f is fin efficiency; Af and Atot are the outside finned area per unit length as formulated
by Eq.(9) and the total outside surface area per unit length as formulated by Eq.(10),
respectively.

Nu a

1
a0 d r
H
0.134 Re 0.68 Pr 3

a a 0o

(
o 1

Af
Atot

(
Af 2N f

0.2

Y

S

0.12

(1 f )

2
f

f
r

YN f

Atot d r 1 YN f A f

1
0
)
Wang [23] has done a lot of experiments research on fin-and-tube heat exchanger and
developed pressure drop correlations with high prediction accuracy. The friction factor is given
by Eq.(11). In Eq.(11), F1, F2, F3 are dimensional correlation parameters which are obtained
by Eq.(12)-(14) , where Rea is Reynolds number based on tube collar diameter and is
formulated by Eq.(15); Gmax is the maximum air mass velocity which is formulated by Eq.(16);
Amin refer to the minimum flow area in the tube bank which is given by Eq.(17).
F2

p S
f 0.0267 * Re aF 1 t
Pl d r

F3

1
Pt
S 0.00758
F1 0.764 0.739 * 0.177 *
Pl
dr
Nt
(
1
64.021
F 2 15.689
ln Re a
(

530

F 3 1.696

15.695
ln Re a

Re a

air

Gmax

Gmax d r

M
air
Amin

(
Amin N t l ( Pt Dr 2 N f HY )

Fig.5 shows the flow chart of the simulation program for air side for all the three types of
condenser. The mass flow rate of air is computed by heat load and temperature difference,
and the heat transfer coefficient a is determined by value of fins spacing. The heat load of air
side is matched to that of the working fluid side by adjusting the geometry of fin spacing.

Fig. 5 The calculation procedure of air side of condenser

4 ECONOMIC MODELS
In this paper, the economic cost is used as design criteria to evaluate the performance of the
condenser in ORC. The total cost Ctot is composed of the capital investment cost and total
operating cost as shown in Eq. (18).

Ctot Ci Cop
(

1
8
)
The investment cost is the function of condenser internal surface as shown in Eq. (19),
where, Cps is the cost of the condenser per square meter internal heat transfer area and is a
function of the material cost of copperas formulated by Eq.(20).

Ci C ps Ai 1000
(

14240 2
C ps
d d r2 YN f d t2 d r2
d

2
0
)
The total operating cost related to pumping power to overcome pressure loss of tube side
and air side is evaluated by using Eq.(21)-(23) [24], where Co and CE refer to the annual
operating cost and energy cost per year; i and Hyear refer to annual operating time; W condenser

531

refers to pumping power of the condenser.

ny

Co
k
k 1 (1 i )

Cop
(

Co Wcondenser CE H year
(

Wcondenser

m
1 mi
Pi ,tot a Pair
i
a

5 RESULTS AND DISCUSSION

The effectiveness of liquid-vapor separation approach in condenser of ORC system is
assessed and compared with PFC and SC by a demonstrate case. In this case, the ORC
design parameter shown in Table 2 is obtained from an ORC system that recovers low grade
waste heat from vehicle exhaust gas. A model of the ORC used R245fa is simulated by Excel
in combination with the REFPROP 7.0 for obtaining cycle conditions as shown in Table 3. The
condenser design conditions are steady with heat duty 19.1kW, and condensing temperature
is 308.15k. Table 4 lists some fixed geometric parameters of tube contained in all three types
of condenser. In this case the annual operating time is taken as 5000 hour/year. All values of
discounted operating costs are calculated with equipment life 10 years. The annual discount
rate is 0.02 and energy cost of power is 0.617/kWh.
For LSC, since annular flow shows good heat transfer characteristic, the tube number of the
first tube pass is fixed as 9 and the scheme of NTP of LSC is given by 9-8-7-6-5-4-3-2-2-1-1.
The scheme of NTP for PFC is the same as that of LSC. For SC, the total number of tubes is
48 with two parallel circuits. Table 5 lists the design results of LSC, PFC and SC by applying
the proposed simulation method.
Table 2. Waste heat conditions of a vehicle exhaust gas
Term

Value

Temperature of exhaust gas inlet

968.7 K

Mass flow rate of exhaust gas

0.00379 kg/s

Specific heat capacity

1.16 kJ/kgK

Mass fraction of exhaust gas

CO2

20.4%

H2O

7.8%

N2

71.8%

Table 3. Simulation of the organic Rankine cycle

Term

Value
Working fluid

R245fa

Mass flow rate

0.1037 kg/s

Environment temperature

293.15 K

Evaporator temperature

398.7 K

Condenser temperature

308.15 K

Turbine isentropic efficiency

80 %

Pump isentropic efficiency

70 %

Turbine power

3.426 kW

Absorption heat in evaporator

24.69 kW

Heat rejection in condenser

19.1 kW

532

Table 4. Fixed geometric parameters of condenser

Parameter

Description

Value

Inner diameter tube

0.015 m

dr

Finned tube root diameter

0.018 m

Fin height

0.014 m

Fin thickness

0.0003 m

Pt

Pitch

0.048 m

Tube length

0.8 m

The results show that LSC possess minimum total cost while the total cost of PFC and SC is
25.01% and 11.44% higher than that of LSC, respectively. The results show that SC does not
possess the best internal heat transfer capability, and the pressure drop inside tube of SC is
clearly higher than that of LSC and PFC. Specially, considering the similar tube constructions
owe to the same scheme of NTP, the internal heat transfer coefficient or pressure drop of each
passes of PFC and LSC are presented in Fig. 6. This figure obviously shows the effect of
liquid-vapor separator of each pass. The heat transfer coefficients are improved in each pass
and pressure drops are less than PFC after liquid fluid drained away by the separators.
Definitely, keeping the high fluid quality would enhance the condenser performance.
Table 5. Parameters for the ORC case using different condenser methods
LSC

PFC

SC

Ntot

48

48

48

l (m)

0.78

1.22

0.92

S (m)

0.00120

0.00150

0.00126

Nf

685

555

641

Gmax (kg/m2s)

2.84

1.75

2.39

i (W/m2K)

7368.7

4728.2

6117.5

a (W/m2K)

25.43

20.16

23.20

Pi (Pa)

8060.1

12788.0

35491.3

Pa (Pa)

7.79

6.10

7.11

Ai (m2)

1.76

2.76

2.14

Af (m2)

1.95

1.59

1.82

Aa (m2)

74.88

95.52

83.04

Amin (m2)

0.95

1.54

1.13

Wcondenser (W)

27.18

22.82

31.24

Ci ()

8471.1

10941

9410.5

Co ()

35.15

79.85

109.34

Cop ()

854.74

717.24

982.18

Ctot ()

9325.84

11658.24

10392.68

Thanks to the liquid-vapor separation, LSC shows the best average heat transfer coefficient
inside tube, therefore the tube length of LSC is shorter than that of others. The reduction of
tube length leads to the decrease of inside heat transfer area Ai. The total outside surface area
Aa is determined by fin spacing. Table 5 shows that although LSC has more number of fins per
unit length, the total outside surface area is less than that of PFC and SC. And therefore, the
capital investment cost of LSC reduces significant compared with that of others.
LSC reveals lowest total pressure drop inside tube than that of others. However, the

533

minimum flow area in the tube bank enabled to reduce maximum mass velocity leading to a
decline of pressure drop, so the pressure drop of PFC is little lower than that of others in air
side. The total pumping power of condenser is the summation of working fluid side power
consumption and air side power consumption to overcome the pressure drop. W condenser of PFC
is lowest and LSC takes the second place. Therefore, the annual condenser pumping cost of
PFC is slightly less than that of LSC. Since the tube length of the PFC is longest among the
three condensers, the investment cost of PFC is the most of them. As a result, the total cost of
LSC is the lowest among the three condensers.
Moreover, the working fluid pump power is influenced by different outlet enthalpy of
condenser due to the pressure loss in tube. The simulation results also show that the working
fluid pumping power of ORC using LSC is 0.54% lower than that of ORC using SC. This lower
pumping power directly reflects higher net power output in ORC.

(a)
(b)
Fig 6. (a) Heat transfer coefficient and (b) pressure drop in tube of each pass
6 CONCLUSIONS
In this paper, a LSC used in an ORC system is simulated and designed. The heat transfer
coefficient, pressure drop and total cost are achieved by the proposed simulation method and
compared with those of PFC and SC.
The LSC features lower pressure drop and higher heat transfer coefficient than those of
PFC and SC under the condition of the assumed same tube numbers for the three types of
condensers. Although the LSC features largest fin area per unit length, the LSC is superior to
PFC and SC on economic cost due to the comprehensive effect of heat transfer enhancement
and pressure drop reduction in working fluid side. The simulation and design results show that
the LSC is a better candidate for ORC condenser and the proposed simulation algorithm is
effective. The research on the optimization based on the proposed algorithm for ORC using
LSC is our future pursuing work.
ACKNOWLEDGEMENT
The authors gratefully acknowledge the nancial support from the Guangzhou Pearl River
Technology Star Project (Grant No. 2013J2200096).
NOMENCLATURE
A

area, m

cp

specific

Ci

capital

heat,

J/(kgK)
Amin

minimum flow area in the tube bank, m

investment,
Atot

total outside surface area per unit length, m

Af

outside finned area per unit length, m

cost,

534

CE

energy cost,

Co

annual operating

Cop

total discounted operating cost,

Inside

fin collar outside diameter, m

df

fin

Roughness, m

friction factor

Froude number

mass

gravitational

Fin height, m

JG

the

tube

diameter, m
dr

outside

diameter, m
e
Fr

flux,

kg/(m s))
Gmax

maximum mass velocity, kg/(sm )

acceleration, m/s

enthalpy, J/kg or helicoidal fin height, m

HLG

specific enthalpy of evaporation, J/kg

dimensionless gas velocity

k

Number of flow pass

tube length ,m

working fluid mass flow rate, kg/s

Mair

air mass flow rate,

total tube numbers

ng

number

of

nf

number of fins per unit length, 1/m

Nu

Nusselt

number

NTP

number of tube per pass

Pr

Prandtl number

pl

longitudinal tube pitch, m

pt

transverse

heat transfer rate, W

Re

Reynolds number

Rx

geometry enhancement factor

fin spacing, m

Tw

wall temperature, K

Tsat

saturation

Tout

air

kg/s
Nt
grooves

tube

pitch, m
2

temperature, K
Tin

air inlet temperature, K

outlet

temperature, K
W condenser

condenser power consumption, W

We

Weber number

W pump

Working pump consumption, W

Xtt

Martinelli

Y
fin thickness, m
Greek Letters

heat transfer coefficient, W/(m2K)

apex angle, rad

helix angle, rad

Density, kg/m3

pressure drop, Pa

void fraction

dynamic viscosity, kg/(ms)

surface

section area ratio of tube and header

shear stress, Pa

two-phase multiplier

mass quality

thickness , m

pump efficiency

thermal conductivity, W/mK

finned

parameter

tension,

N/m

efficiency

correction factor for frictional pressure

gradient caused by condensation occurring

535

total

at the vapor-liquid interface

a

acceleration or air

adiab

adiabation

ave

average value

partial

T-independent flow regime

con

condenser

T-dependent flow regime

fin

eva

evaporator

gas phase

GO

gas phase with total flow

gravity

In

inlet

inside

LO

liquid phase with total flow

liquid phase

LG

between liquid and vapor

max

maximum value

out

outlet

tot

total

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537

A NEW APPROACH TO MODEL CONCENTRATING SOLAR CELLS UNDER

NON-UNIFORM ILLUMINATION
Hang Zhou, Yuehong Su, Saffa Riffat
Institute of Sustainable Energy Technology, Department of Architecture and Built
Environment, University of Nottingham, University Park, NG7 2RD, UK
Corresponding email: hang.zhou@nottingham.ac.uk , yuehong.su@nottingham.ac.uk

ABSTRACT

Concentrator solar cells often designed optimally depending on the concentrating

photovoltaic (CPV) system, application and operating conditions to ensure the best
system performance. The irradiation incident on the PV cell while being concentrated
experiences several losses caused by the different physical phenomenas occurring in the
system. A particular issue for CPV technology is the non-uniformity of the incident flux on
the solar cell, which tends to cause power dissipation and reduce the overall efficiency of
the system. Considering those issues, understanding of the effects and designing the
cells could improve the overall performance of the system. This study focuses on
modeling a concentrating solar cell, and analyzing the effects of the non-uniform
illumination on the overall output of the system.
This paper presents a new approach for modelling concentrating solar cell under
non-uniform illumination condition, in which a solar cell is represent by an equivalent array
of cell splits. The main advantage is in the possibility to express each cell splits voltage as
an explicit function of the current by using the Lambert-W function. The output
characteristics are simulated and analyzed using proposed simulation model built in
MATLAB/Simulink. Through the analysis of the results, a comprehensive expression of
the concentrating solar cell under non-uniform illumination could be present.
KEYWORD:CPC, CPV, Cell splits, Array, Non-uniform illumination, MATLAB/Simulink,
Lambert-W function.

Nomenclature
2

Solar radiation W/m

Solar cell/module Current A

Solar cell/module Voltage V

Electronic charge: 1.602176e-19 C

Boltzmann constant: 1.38065e-23 J/K

1

538

Diode ideal factor

Iph

Photocurrent A

Io

Reverse saturation current A

Rs

Series resistance Ohm

Rsh

Shunt resistance Ohm

Rsho

Slop of I-V at V=o

Rso

Slop of I-V at I=o

Eg

Band-gap energy eV

Temperature coefficient %A/C

Material constant

Impp

Maximum power point current A

Vmpp

Maximum power point voltage V

FF

Fill factor

1. INTRODUCTION

Solar cell is the key element in all of photovoltaic design. Concentrator Photovoltaic (CPV)
offers the best use of the silicon material for the manufacturing of solar cells and has
potential to increase the electrical output by several times while using the same amount of
silicon solar cells.
A particular issue for CPV technology is the non-uniformity of illumination, which tends to
cause power dissipations and reduce the overall efficiency of the system. The use of
concentrators modifies the incident light on the solar cells, while enlarge it to several times
and could generate non-uniform illumination patterns. Non-uniformity could happen on a
single surface of solar or to a series of cells connected together and each being
illuminated. In the case of non-uniform illumination, there is excessive illumination on
some regions of the solar cell and some are less illuminated. The regions illuminate
excessively generate huge currents and get heated. This reduces the electrical output of
the solar cell and the generation of cross current causes physical damage to the cell.
Non-uniform illumination leads a decrease in solar cell performance since higher light
intensities occur near the cell center in compare with edges. This increases the power
losses in the cell front grid and front surface diffused regions of conventional planar cells.
Vishnoi, [2], described the combination effect of non-uniform illumination and surface
resistance on the performance of solar cell.
The concentrator geometry and optics play an important role in determine the flux incident
on solar cells. Fig.1 gives an example of flux distribution from a mirror Compound
Parabolic Concentrator (CPC) [1 and 3]. The CPC is design to collect solar radiation for an
extended period and the incident angle is changing through the day, which gives a
non-uniform illumination profile. The optical analyze could be able to tracking each flux
2

539

and its distribution. How to analyze the concentrating solar cell electrical performance
under non-uniform illumination in more details become challenging.
This paper proposed a method which to consider the concentrating solar cell to be
equivalent to an array of cell splits connected in parallel. Each split has different
illumination profile in order to modelling the non-uniform illumination condition. The
electrical performance for each splits and parallel group will be simulate by designed
program. Different illumination distributions have been simulated which gives a
comprehensive analyze of the concentrating solar cell behaviors under non-uniform
illumination.

Fig.1. Flux distribution on the base of a mirror CPC

2. EXPERIMENT VALIDATION OF USING PRALLEL CONNECTED SOLAR CELL SPLITS

TO RESTORE ORIGINAL SOLAR CELL PERFORMANCE

In order to analyze the concentrated solar cell performance under non-uniform illumination,
it could divide the solar cell into several splits to fit the illumination profile, where each
splits could has separate irradiance and cell temperature. It is propose the concentrated
solar cell could seem to be form by those splits connected in parallel.
However, the electrical characteristics of solar cell are influence by the size changing. It is
important to understand the relationship between cell size and its electrical characteristics.
Additionally, it also significant that the cell spits could maintain the same output as the
original cell.
Single piece silicon solar cell is common material used in solar module design, the
manufacturers normally provide basic electrical characteristics such as short-circuit
current, open-circuit voltage and maximum power. One objective of this experiment is to
use the given electrical characteristics of original solar cell to deduce the performance of
cut solar cell.
The short-circuit current is the current though the solar cell when the voltage across the
cell is zero.
3

540

The short-circuit current is due to the generation and collection of light-generated carriers
and it is directly depends on the light intensity. It is more common to list it as short-circuit
current density in unit such as A/m2. Hence, the short-circuit current is proportional to the
cell surface area.
The voltage characteristics depend on the material properties of solar cell. Open-circuit
voltage is then a measure of the amount of recombination in the device. Depending on the
material, solar cells of different types have typical value for the open-circuit voltage and
have no obvious changing with cell surface area.
In the parallel connection circuit, the same voltage is applicable to all circuit components
and the total current is the sum of the currents through the individual components, in
accordance with Kirchhoffs current law.
An indoor experiment has been set up in University of Nottingham in order to verify the
proposed theory. In the experiment, a single piece mono-crystalline silicon solar cell has
been cut by diamond knife into 4 equally splits and connected in parallel. Fig.2. Fig.3. The
general electrical characteristics and dimension for the original single solar cell are list in
Table 1.

Fig.2 Legend of solar cell

Fig.3. Parallely connected splits

Table1. Data sheet for testing cell

Test solar cell

Mono-crystalline silicon solar cell

Dimension

15.5CMX15.5CM

Short-circuit current

3.6A

Open-circuit voltage

0.55V (STC: 1000W/m 25C AM1.5)

Average power

1.8W

(STC: 1000W/m 25C AM1.5)

2

(STC: 1000W/m 25C AM1.5)

The incident light is provided by a Hernia light (HID). The electrical outputs are measure
and recorded by RS solar analyzer (ISM-490). The solar cell temperature is measure by
thermocouple and displayed by multi-meter.
The I-V curves for 4 splits are shown in Fig.4. The splits were test under same irradiance
level at 640W/m2, where they provide roughly same output power as the results. The
difference is mainly due to temperature varying. The cell temperature increase rapidly
when exposed to the light. The cell temperature for splits is around 45C at the beginning
to the test. Like other semiconductor devices, solar cell is very sensitive to temperature.
4

541

The increased temperature reduces the band gap of solar cells which leads to an increase
in short-circuit current and decrease in open-circuit voltage. The error from manually cut
also has some effect on the testing results.

Fig.4 I-V for 4 cell splits

Fig.5. Gives the I-V curves for both original single cell and parallely connected cell splits.
The illumination level is stay at 640W/m2. From the results, it is confirm that parallel splits
group could restore same power output as original single cell.

Fig.6 I-V for original single cell and parallely connected splits under non-uniform illumination

3. MODELLING OF SOLAR CELL

The simulation begins with the modelling of solar cell. The most common methods to carry
out the electrical simulation is to divide the cell into smaller sub-circuits representing
different parts of the solar cell and model every sub-circuit by an electrical circuit as one
diode with distributed diode effect , two diode model. The lateral resistance in the solar
cell leads to a voltage drop across the cell, which produces different current densities. By
taking consider of this phenomena, the current from each row of unit cell flow to the
contact grid bar, where adds to the current contribution of other rows. The voltage drops
due to series resistance along the row of unit cell are additive, and the voltage drop along
the contact bar are additive. A simplified representation of the electrical circuit model for a
single solar cell is represent in Fig. 7.

542

Fig.7 Equivalent circuit for a single solar cell

This consists of a photocurrent source, a diode, a shunt resistor expressing a leakage

current and series resistor describing an internal resistance to the current flow. In link with
the equivalent circuit, the PV cell output current is represent by following equation.
I I ph I o [exp(

q
V IRs
(V IRs )) 1]
kTn
Rsh

(1)

By using this equation the solar cell could be modelled. However, different approaches
have been adopted by different research to analyse the effects of non-uniformity.
Francisco M [15] proposed a model, which ignore the parallel resistor and simplify the
equation into three parameters current equation. The calculation in that method is simple,
but has low accuracy. Huan-Liang Tsai [11] suggest using differential equation at both
short-circuit point and open-circuit point to form a closure equations group related to five
parameters. However, the I-V equation is non-linear equation, which requires using
iteration to get the solution. In the iteration process, the results could loss accuracy due to
parameters changing to large extent. Soto [16] proposed a model by using manufactory
data to predict the PV module performance, but it require special calculation software to
implement and assuming the series resistance does change with temperature. In fact, the
PV module operating temperature strongly influences the series resistance. This study
proposed a method which is similar as Huan-Liang Tsias [11] method, but using some
mathematics technique to change the current non-linear equation to algebraic equation.
Theoretically, the output characteristic of PV is solving by calculating five parameters and
substitute into I-V equation. The five parameters including diode ideal factor n, reverse
saturation current Io, photo-current Iph, series resistance Rs, parallel resistance Rsh.
However, the current equation is a non-linear equation which cannot be solved directly. In
order to obtain the required five parameters, it is necessary to propose the relevant
closure equations. By using some mathematical techniques, it is possible to change the
current non-leaner equation to algebraic equation and get following closure equation
groups.

543

V ( R Rso )[Vm Rsho ( I sc I m )] Rso (Vm Rsho I m )(Voc Rsho I sc )

Rs m sho

I m ( Rsho Rso )[Vm Rsho ( I sc I m )] (Vm Rsho I m )(Voc Rsho I sc )

Rsh Rsho Rs

Rs

I ph I sc (1
)

Rsh

( R Rsho )(Voc Rsho I sc )

n s

Vth ( Rsho Rso )

V
I ph oc

Rsh

Io

V
exp( oc ) 1

nVth

Accounting to one cells Isc, Voc, Vm, Im, dV |v 0 Rsho , dV |v 0 Rso , the cells five
dI

dI

parameters including Rs, Rsh, Iph, Io and n could be solved. It is now possible to produce
single solar cell output characteristic by substitute five parameters into I-V equation.

4. PARAMETER CALCULATION FOR DIFFERENT IRRADIANCE AND TEMPERATURE

The output power of PV module is depending on the incident irradiance, cell operation
temperature and load. The manufacturer normally only provide I-V curve tested under
Standard Testing Condition. By considering the non-uniformity of environment conditions,
a prediction of module performance under different conditions could be necessary. The
output characteristic of PV is a non-linear equation related with environment factors and
self-parameters. Through the past research, the relationship between module parameters
and environment factors are listed as follow.
Photo-current
Townsend [17], described the photo-current Iph using following equation:
I ph =

S
(I ph,ref +1sc (T-Tref ))
Sref

(3)

Reverse saturation current

Messenger and Ventre [18] using to the diode equation and describe the reverse
saturation current as follow:
Io
I o,ref

T
=
T
ref

Eg
Eg ,Tref

1 Eg ,Tref Eg ,T
exp (
k Tref
T

(4)

=1-0.0002677(T-Tref )

Series resistance
The series resistance could be described as a function related with cell temperature. The
resistance value is increasing with the temperature rises.
Rs
T
S
=
(1- ln
)
Rs ,ref Tref
Sref

(5)

= 0.217 for silicon solar cell

7

544

Shunt resistance
Schroder [19] proposed the parallel resistance is inversely proportional to the short-circuit
current at very low irradiation level.
(6)

I sc ,ref
Rsh
=
Rsh ,ref
I sc

I sc =I sc ,ref

S
[1+1sc (T-Tref )]
Sref

5. MODELLING OF PARALLELLY CONNECTED SOLAR CELL SPLITS

Above discussion proves the possibility to use parallel connection cell splits to restore the
concentrating solar cell performance. The general current model of PV is an implicit
function transcendental equation about V; it is not easy to decouple I and V together. The
introducing of Lambert W function is the solution to solve the decoupling problem of I and
V. By using Lambert W function, it could transform the current equation in to the following
equation.
I

Rsh ( I ph I o ) - V nVth
W (X )
Rs Rsh
Rs

R ( R I Rs I o V )
Rs Rsh I o
exp( sh s ph
)
nVth ( Rs Rsh )
nVth ( Rs Rsh )

(7)

The main advantage is the possibility to express each cell splits voltage as an explicit
function of the current by using the Lambert-W function. This makes it possible to predict
the output characteristic of cell groups under any environment condition.
Assuming N splits parallely connected together, the new voltage output V is form by
voltage from each split. The total output current is sum of the current from each split. The
parallel group output current could be given as:
N

( I ph1 I o1 ) Rsh1 V

i =1

Rs1 Rsh1

I Ii =

nV
N 1 th W {
Rs1

I o1 Rsh1 Rs1 exp[

Rsh1 ( I ph1Rs1 I o1Rs1 V )

n1Vth ( Rs1 Rsh1 )

n1Vth ( Rs1 Rsh1 )

]
}

(8)

Because each split has different parameters according to the cell condition, it is difficult to
give out the new parameters after they connected together. However, each parameter
could be deduce from different working points.
At short circuit point, substituting V=0 into Eq.(8), gives
I SC [

Rsh1 ( I ph1 I o1 )
Rs1 Rsh1

n1Vth
W ( X sc1 )]
Rsh

(9)

At open circuit point, substituting I=0 into Eq.(8), gives

0 [

Rsh1 ( I ph1 I o1 ) - VOC

Rs1 Rsh1

n1Vth
W ( X OC1 )]
Rs1

(10)
At maximum power point
8

545

I M [

( I ph1 _ I o1 ) Rsh1 - VM
Rs1 Rsh1

n1Vth
W (YM 1 )]
Rsh

(11)
Differential current equation Eq.(8)
Rsh1
dI1
1

dV1
Rs1 Rs1 ( Rs Rsh1 )(1 W ( X 1 ))

(12)
N
N
dI
dI
dI
1 1
dV i 1 dV i 1 dV1
At short circuit point
dI
dV

I =I SC

dI1
i =1 dV1

N
1

Rsh1
=

Rs1 Rs1 ( Rs Rsh1 )(1 W ( X SC1 ))

i =1
I =I SC

(13)
At open circuit point
dI
dV

V -VOC

=
i =1

N
dI1
=
dV1 V =V i =1
OC

Rsh1

R
R
(
R

R
)(1

W
(
X
))
s1
s
sh1
OC1
s1

(14)
dV
dI

=
I =I SC

1
dI
dV

dV
dI

=
V -VOC

I =I SC

1
dI
dV

V -VOC

The parameters required for parallely connected cell splits could be calculate by following
above steps. The simulation program is basing on this theory and general solving
progress is present in Fig.8.

Fig.8 Logic flow chart of simulation program

6.

MODELLING

OF

CONCENTRATING

SOLAR

CELL

UNDER

NON-UNIFORM

ILLUMINATION

An example concentrating solar cell in a CPC design is choose to verify the simulation
model. This concentrating solar cell has dimension of 1CM*20CM, Fig.9. Some of the
basic electrical characteristics for the cell are list in Table 2.

Fig.9 .Concentrating solar cell

546

Table2: Reference data for single concentrating solar cell

Parameter
Short-circuit current Isc

0.437A

Open-circuit voltage Voc

0.429V

Maximum power point current Impp

0.397A

Maximum power point voltage V mpp

0.337V

Rsho

15.113

Rso

0.144

In the simulation, the concentrating cell is consider to form by an array of 10 cell splits
connected in parallel. According to theory and experiment validation in the previous
section, the current characteristics of small splits will be 1/10 of the original solar cell value
and given in Table 3.
Table3. Reference data for single cell split
Parameter
Short-circuit current Isc

0.0437A

Open-circuit voltage Voc

0.429V

Maximum power point current Impp

0.0397A

Maximum power point voltage Vmpp

0.337V

Rsho

151.13

Rso

1.44

By using those data as reference, the five parameters for the original single cell and splits
are calculated. The results are list in Table 4 and Table 5.
Table4. Five Parameters for single concentrating solar cell
Parameter
Photo-current Iph

0.4402A

Reverse saturation current Io

3.7112e-14A

Series resistance Rs

0.1094 ohm

Shunt resistance Rsh

15.0036 ohm

Ideal factor

0.5559

Table5. Five Parameters for single cell split

Parameter
Photo-current Iph

0.044A

Reverse saturation current Io

3.71112e-15A

Series resistance Rs

1.0938 ohm

Shunt resistance Rsh

15.0036 ohm

Ideal factor

0.5559

In the simulation study, the non-uniform illumination is achieved different irradiance on

each splits. Table 6 is presents 6 different distributions illumination profile, where they all
10

547

have an average illumination at 1000W/m2. From distribution 1 to 6, the degree of

non-uniformity has been increase systematically. In order to gives more accurate analysis
on the concentrating cell behavior under non-uniform illumination. It is assume the cell
operating temperature for each splits and original cell are stay constant at 25C. The
single cell has only one single input or irradiance and temperature.
Table6. Illumination distribution profile
1

10

Average S
W/m2

1000

1000

1000

1000

1000

1000

1000

1000

1000

1000

1000

Distribution 1

800

800

800

800

1800

1800

800

800

800

800

1000

Distribution 2

600

600

600

600

2600

2600

600

600

600

600

1000

Distribution 3

400

400

400

400

3400

3400

400

400

400

400

1000

Distribution 4

200

200

200

200

4200

4200

200

200

200

200

1000

Distribution 5

4996

4996

1000

Distribution 6

Table 7 gives simulation results for cell parameters at different distributions. Since the
average illumination and temperature stay the same, some parameters like short-circuit
current Isc, photocurrent Iph and open-circuit voltage Voc have no obvious changes.
However, there is a significant difference in fill factor (FF) for different distributions. The fill
factor determines the maximum power from a solar cell and it is define as the ratio of
maximum power from the solar cell to the product of Voc and Isc. The fill factor is calculate
by using formula:
FF

Vm I m
Voc I sc

(15)
Table7. Simulation results for different illumination distributions
Isc (A)

Iph (A)

Voc (V)

Pm (W)

Vm (V)

Im (A)

Rs (ohm)

Rsh (ohm)

FF

Sing cell

0.437

0.440

0.429

0.135

0.341

0.397

0.109

15.004

0.72

Distribution 1

0.437

0.440

0.429

0.135

0.341

0.396

0.109

15.004

0.72

Distribution 2

0.437

0.440

0.429

0.133

0.338

0.394

0.110

15.017

0.71

Distribution 3

0.436

0.439

0.428

0.128

0.329

0.388

0.115

15.054

0.68

Distribution 4

0.434

0.437

0.427

0.120

0.315

0.383

0.120

15.102

0.65

Distribution 5

0.432

0.436

0.425

0.113

0.298

0.380

0.120

15.154

0.62

Distribution 6

0.430

0.435

0.427

0.107

0.283

0.377

0.183

15.176

0.58

11

548

Fig.10 I-V for different illumination distribution

Fig.11. provides more details about the relationship between irradiance and series
resistance. The data is obtain based on Distribution 5. The photocurrent is directly
proportional to the irradiance. It founds the splits on the sides have much less irradiance
than center part and have higher series resistance values, refer to Eq.5. This confirms the
dropping of fill-factor is mainly from series resistance rising in the less illuminated splits.

Fig.11. Parameter numerical distribution for distribution 5

7. CONCLUSIONS
This paper proposed a method to consider the concentrating solar cell as a parallel
connection group by several cell splits and analyze its electrical performance under
non-uniform illumination. The experiment in the first section provides the evidence of the
reliability of proposed method. The simulation takes concern of several illumination
profiles and models the concentrating solar cell behaviors according to the different
degree of non-uniformity. The simulation model is able to analyze the concentrating solar
cell in more details and provide an accurate prediction of its performance under
non-uniform illumination. As the degree of non-uniformity increase, the concentrating cell
efficiency could decrease by 14%. Under the constant temperature condition, the main
factor to reduce the efficiency is the rising of series resistance. The concentrating solar
cell is normally very small and common light source is hard to modelling the non-uniform
condition. However, it is encourages to verify the presented study through experiment with
suitable equipment.

12

549

REFERENCE
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Nacional Experimental Politcnica, Carretera Nacional Maracay-Mariara,
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[18]Messenger, R.A., Ventre, J., 2004. Photovoltaic Systems Engineering, second ed. CRC Press LLC,
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Sons Inc., New York

14

551

SOLAR THERMAL DISSOCIATION OF CO2: TOWARDS HIGHER EFFICIENCIES

Yong Hao
Institute of Engineering Thermophysics, Chinese Academy of Sciences
11 Beisihuanxi Rd., Haidian District, Beijing, 100190, China
Email: haoyong@iet.cn

ABSTRACT
Isothermal solar thermochemistry is a novel approach for deriving solar fuels from concentrated solar heat
with potential advantages in reactor design and heat recovery. Previous work has demonstrated the
feasibility of isothermal water splitting with ceria but efficiencies and operating temperature range are
relatively undesirable. In this study, thermodynamic analyses are performed on isothermal solar
thermochemical splitting of CO2, and the cycling reactions are found to exhibit considerably higher
efficiencies than that of H2O (e.g. 12% for CO2 and 3% for H2O at 1500C, no heat recovery). Equivalently,
same efficiencies as that of isothermal H2O splitting can be achieved at 100-200C lower. Thermodynamic
reasons for the enhancement in efficiency are identified to be the favorable Gibbs free energy change of CO2
splitting reaction at elevated temperatures and the lower thermal energy requirement for gas heating due to
the lack of phase change of CO2. Through the comparison with conventional two-temperature cycling
strategy, the advantages and disadvantages of both methodologies, as well as indications on system and
reactor design are discussed.
Keywords: solar fuel, isothermal, thermochemical cycling, carbon dioxide, syngas

INTRODUCTION
Among a wide spectrum of solar energy harvesting technologies, one promising means is the direct
synthesis of chemical fuels via dissociating water or CO2, through which solar energy may be transformed
into a form that is both storable and transportable, and which can be used in existing equipment (Kodama,
2003). Compared with indirect approaches such as photovoltaics or concentrating solar power followed by
batteries or electrolysis, direct conversion of solar energy into chemical energy of fuels may offer better
compactness, cost-effectiveness, versatility and potentially higher efficiencies. Although a wide selection of
routes are capable of direct fuel synthesis, efficiency appears to be one of the major barriers towards
practicality for many of them, such as photosynthesis, photocatalysis and photoelectrochemistry, partially
due to their preferences towards specific ranges of the solar spectrum. In comparison, chemical reactions
driven by solar thermal energy (via concentration) are potentially more efficient and more practical owing
not only to the utilization of the entire spectrum, but also to a reasonable combination of thermodynamics
and kinetics. Such processes involve a sequence of reduction and oxidation (redox) reactions, proceed
cyclically and produce oxygen and fuel (e.g. hydrogen) in separate steps. Compared with the direct thermal
dissociation of water or CO2 (i.e. thermolysis), thermochemical cycles involve as few as only two steps, but
significantly decrease reaction temperature (e.g. 1500C in contrast to 4000C for water). In recent years,
there has been a revival in the research and development of thermochemical cycles, enabled by the everincreasing awareness and concerns over energy and environmental issues, with the goal of producing
hydrogen as a greenhouse-gas-free energy carrier (Roeb et al., 2012). In particular, special significance is
carried by solar thermochemical dissociation of CO2, for it provides a beneficial approach of converting a
major greenhouse gas to useful fuels driven by a major renewable energy source. Besides cost advantages
of using CO2 as a feedstock, the value of this approach is also underscored by its complementary nature
with carbon sequestration and storage where the latter is unsuitable (Centi et al., 2009). Furthermore, when
CO2 is co-split with water, the synthesis gas thus produced can be transformed into liquid, transportable
fuels with well-established industrial routes. Such reactions are analogous to photosynthesis in the sense of
storing solar energy and fixing carbon, but are much more efficient (Graves et al., 2011).
Efficient solar thermochemical cycles rely critically on materials and cycling strategies. Recently, cerium oxide
(i.e. ceria) has attracted considerable attention and is regarded as one of the most promising materials for twostep water-splitting cycles (Roeb et al., 2012; Graves et al., 2011; Miller et al., 2014). The underlying reason is
that ceria has a favorable fluorite crystal structure that can stand significant losses of oxygen without phase
change and simultaneously allows rapid transport of oxygen ions, in addition to its well-known advantages of
being an ideal catalyst for redox reactions and being a refractory material. Pioneering studies on water splitting
with ceria were carried out by Otsuka and Abanades, respectively, but the temperature required for a complete
reduction of ceria was too high and phase change occurred (i.e. ceria was converted to Ce2O3) (Otsuka et al.,
1985; Abanades et al., 2006). Later studies took advantage of partial reduction of ceria at lower temperatures
and its capability of retaining the cubic fluorite crystal structure. Rapid dissociation of both water and CO2 was
reported by several research groups with pure or doped ceria (Chueh et al., 2010; Furler et al., 2012; Abanades
et al., 2012) with conventional temperature swing cycling strategy. Such strategy thermally reduces the material
552

at a high temperature (e.g. 1500C) to release oxygen, and oxidizes it with water or CO2 at a lower temperature
(e.g. 800C) to generate fuel. However, such a two-temperature (i.e. two-T) mode inevitably incurs a high
energy penalty because the greatest portion of the total thermal energy input of the entire cycle is usually
dumped to the environment by the (solid) material during cooling. Although attempts on high-efficacy heat
recovery from solids were made by a few research groups and encouraging progress was achieved (Diver et
al., 2008; Lapp et al., 2012; Roeb et al., 2012), such processes are inherently limited by challenges from
material to system levels, and their practicality esp. for scale-up is unclear. Lately, an isothermal
thermochemical cycling strategy was proposed by two groups (Muhich et al., 2013; Hao et al., 2013), in which
the temperature difference as in the two-T cycling mode is eliminated, and reaction steps proceed by merely
swinging oxygen partial pressure. In particular, the same author of this work discovered ceria-based isothermal
thermochemistry and performed detailed thermodynamic analysis to reveal the underlying mechanisms for this
unconventional approach: by combining oxygen-starving, pre-reduced ceria with partial thermolysis of water in
the oxidation step, oxygen is partially removed from water by ceria and a net production of hydrogen follows.
Highlights of this novel approach lie mainly in its potentials for simpler reactor design (since no heat needs to be
exchanged through walls) and that for better heat recovery (since unused thermal energy is completely carried
away by gases).
For solar thermal applications, CO2 has some advantages over water as it does not involve the heat of
evaporation of water and it can be handled more easily (Kodama, 2003). In addition, it is well known that CO2 is
thermodynamically less stable than water at elevated temperatures, so that the thermolysis effect of CO2 is
more pronounced. Such factors, when combined, may result in higher efficiencies for CO2 splitting than that for
water. Theoretical analyses on both isothermal and two-T solar thermochemical cycling for CO2 splitting with
ceria are presented in this work.
THEORETICAL
A ceria-based thermochemical cycle for CO2 splitting (e.g. for two-T) can be expressed as:
Oxidation (at TOx): 1CeO2 i CO2 1CeO2 f CO

(1)

Reduction (at TRe): 1CeO2-f 1CeO2- i + 0.5 O2

(2)

Combined: CO2 CO 0.5 O2

(3)

where stands for the oxygen nonstoichiometry (i.e. deviation from the stoichiometry of 2 for oxygen) of ceria,
and a fluorite structure can be maintained up to = 0.35 (Roeb et al., 2012); i and f stand for values at
the beginning and end of the oxidation step, respectively ( i > f ), while i f is the net change in
oxygen nonstoichiometry, and is also a numerical equivalent of the amount of fuel produced per mole of ceria
per cycle; TOx and TRe are the temperatures at which oxidation and reduction reactions occur, respectively. For
two-T cycling, TOx < TRe, for isothermal cycling, TOx = TRe.
Thermodynamic efficiency of CO2 solar thermochemical splitting cycles, both two-T and isothermal, is analyzed
and compared. The significance of efficiency analysis mainly resides in its capability of screening out material
systems or reactions that are incapable of producing fuels beyond a certain performance threshold, but may fall
short on predicting those that would excel in reality. But given that solar thermochemical technology is in the
early stage of development, discussions on efficiency still offers a meaningful theoretical basis for comparison
(Siegel et al., 2013). For efficiency analysis on two-T cycling, the formalism of Chueh et al. is adopted (Chueh et
al., 2010); for efficiency analysis on isothermal cycling, the formalism of the previous work of the same author
(Hao et al. 2013) is adopted. The first-law efficiency of the thermochemical cycling is derived based on a
closed-system assumption, in which ceria is assumed to be readily reduced by Eq. (2) and is in contact with a
specified amount of CO2, during which the nonstoichiometry of ceria starts at i and ends at f . The efficiency
is defined as the heating value of the fuel derived to the minimum solar thermal energy required for the ceriaCO2 system to complete the cycle, taking solar re-radiation losses into account. The efficiency of the two cycling
strategies can be unified as:

abs HHVCO
Qredu QCO2 Qceria

(4)

553

where

abs 1

T 4

(5)

I C

is the solar absorption efficiency of an ideal blackbody reactor in which the cycling reactions are assumed to
take place (Fletcher et al., 1977), is Boltzmanns constant, T is the temperature of the reactor, I is solar
irradiation, and C is concentration ratio; HHVCO is the heating value of CO defined at 25C; Qredu , QCO2 and

Qceria stand for the thermal energy required to reduce ceria, heat CO2 and heat ceria, respectively. In specific,
the thermal energy for extracting 1 mole of O atoms from ceria (i.e. to produce 1 mole of CO) is evaluated by
i

Qredu 1 Hceria d

(6)

where Hceria is the molar enthalpy change of ceria oxidation reaction. The nonstoichiometry terms i and
f are solved from the thermodynamic equilibrium of oxygen between the gas phase and ceria (Eq. (2)):

G ,T H ceria T Sceria RT ln pO2

(7)

where Sceria is the entropy change of ceria oxidation reaction (Panlener et al., 1975), and pO2 is the
oxygen partial pressure in the gas phase during thermal reduction. The other two heating terms are:

QCO2 1 fg nCO2

TOx

25C

Qceria 1 fs 1

TRe

TOx

Cp,CO2 dT

(8)

Cp,ceriadT

(9)

where fg and fs are the fraction of heat recovery from gas and solid phases, respectively; nCO2 is the
amount of CO2 used to actually produce 1 mole of CO; Cp,CO2 and Cp,ceria are the specific heat of CO2 and
ceria under 1 atm, respectively. To avoid redundancy, only key equations, Eq. (4) to Eq. (9), are outlined
above for completeness. More details can be found from the two references mentioned above.
RESULTS AND DISCUSSION
To start with, this work focuses on evaluating the thermodynamic efficiency of isothermal solar thermochemical
splitting of CO2. Conditions common to all cases are given in Table 1. Other conditions are case-specific.
Thermodynamic calculations are performed by HSC software (HSC 5.11, Finland) and an in-house python
code.
Table 1. Common conditions for all calculation cases.
I
C
pO2,Re
1000 W/m2
5000
1.0 Pa
pO2,Re is the oxygen partial pressure for thermal reduction, Eq. (2).

Key factors affecting the efficiency of isothermal thermochemical splitting of CO2 are first analyzed. As
shown in Fig. 1 (a), the Gibbs free energy change of CO2 splitting reaction CO2 CO 0.5O2 is smaller
than that of water splitting reaction H2O H2 0.5O2 above 817C, resulting in a significantly higher partial
pressure of oxygen in the case of CO2 (partial) thermolysis. Since a thermodynamic equilibrium is first
reached between lattice oxygen in ceria and oxygen in the gas phase (pO2,Re) in the reduction step (Eq. (2)),
the driving force for the oxidation step (Eq. (1)), i.e. the difference in chemical potentials of oxygen between
the gas phase and solid phase, is higher for CO2 than that for H2O. Consequently, higher fuel productivity
and higher efficiency can be expected. Another important factor is the thermal energy required to heat the
reactant (CO2 or H2O) to the operation temperature of the isothermal reactions. As shown in Fig. 1 (b),

554

although the specific heat of CO2 is higher than that of H2O for the majority part of the temperature range,
the latent heat of H2O due to phase change at 100C dramatically boosts the energy cost, so that heating
CO2 is more energy-efficient. For example, heating 1 mole of CO2 to 1500C costs 26% less energy than
H2O does.
500

1000

250

2000
2.8

(a)

225

G (kJ/mol)

1500

2.4

H2O

H2O

CO2

CO2)

2.0

200

1.6

175
1.2

150

0.8

125

0.4

100
75

817

500

1000

1500

0.0
2000

140

500

120
100

1000

H2O

H 2O
(b)

CO2

CO2

1500

2000
100
80

80

60

60

40

40
20

20
0

Cp (J/mol/K)

O2 Partial Pressure (x103 Pa)

Energy for Heating Gas to TH (kJ/mol)

275

500

1000

1500

0
2000

TH (C)

Temperature (C)

Figure 1. Key factors affecting the efficiency of isothermal thermochemical splitting of CO2; (a) Gibbs free energy change and pO2 due to thermolysis at
thermodynamic equilibrium of CO2 and H2O; (b) specific heat and thermal energy required to heat CO2 or H2O to a given temperature TH.

The thermodynamic efficiency (Eq. (4), also called HHV efficiency in the context) is then calculated. For the
convenience of discussion, the ratio of CO2 to available oxygen vacancies upon reduction, is defined as:
rCO2

nCO2

(10)

i nceria

Fig. 2 (a) shows the efficiency at various operating temperatures from 1300 to 1900C. The overall trend is
very similar to that of isothermal water splitting (Hao et al., 2013): 1) maximum efficiency is achieved in the
limit of rCO2 0; 2) efficiency increases with increasing temperature; 3) the plateau region in which the
efficiency virtually keeps constant is rCO2 ~ 1. However, closer inspections reveal quantitative difference the
efficiency of CO2 splitting is much higher. For example, at 1500C, the efficiency reaches 12%, while the
value is only 3% for isothermal splitting of water.
40

(a)

1900C

25

1600C

20
15

1500C

10
5

1400C

10-3

10-2

10-1

100

101

102

103

C
1800

H2O

C
1900

40
30
20
10

C
1600

00
17

C
00
15

1500C

104

0
190

C
1700

1400C
1300C
0 1200C

1300C

0
10-4

(b)

CO2

50

30 1700C

HHV Efficiency (%)

HHV Efficiency (%)

35 1800C

60
0% heat recovery

0C
130

20

40

60

80

100

Heat Recovery (%)

rCO2
Figure 2. Thermodynamic efficiency of isothermal solar thermochemical splitting of CO2; (a) without heat recovery; (b) maximum efficiency at different
heat recovery percentages, in comparison with H2O.

As mentioned earlier, one of the major advantages for isothermal thermochemical cycling is the convenience
of heat recovery from gas phases. The maximum efficiencies for isothermal splitting of CO2 and H2O as
functions of heat recovery percentage from gas phase are overlain in Fig. 2 (b) for comparison. Indeed, CO2
outperforms H2O for all temperatures shown, and same efficiencies can be achieved with CO2 at 100-200C

555

lower than H2O, a significant and beneficial decrease for operations in such a high temperature range. In
particular, both panels of Fig. 2 show that the best sensitivity of efficiency versus temperature is achieved
between 1500 and 1700C. The underlying reason comes in two folds: when temperature is relatively low,
the exponential increase of pO2 due to thermolysis dominates; when temperature is high, the decrease in
solar absorption efficiency (Eq. (5)) excels. Even without any heat recovery, the maximum efficiencies for
temperatures of 1500 to 1700C, namely 12%, 22% and 31%, respectively, are already attractive. A not
unreasonable heat recovery rate of 80% would bring up the efficiencies to 33%, 45% and 51%, respectively.
Under circumstances with significant heat recovery, the most sensitive temperature region is shifted down to
1300 to 1600C. Considering tradeoffs between efficiency and requirement on materials at high
temperatures, the optimum temperature window for isothermal CO2 splitting is perhaps around 15001600C. Also, due to the absence of phase change of CO2 in the temperature range of operation, heat
exchanger for achieving the desired recovery rate is expected to be much simpler.

8
7

1300

1400

1500

1600

1700

30

7.12
CO2

25

6
20

15

4 92%
3
2
1
0

10

2.45
H2O

1.68
90%

1300

89%

0.56

0.98

0.46
0.25
85% 0.24
83%
78% 0.13 68%0.09 0
71%
55%
40%

1400

1500

1600

Conversion rate to fuel (%)

Thermal Energy (x104 kJ/mol-fuel)

It would then be instructive to obtain quantitative understanding on major causes of the much higher efficiency
of CO2 splitting. Corresponding to the possible causes shown in Fig. 1, the conversion rate (of reactant to fuel)
and thermal energy costs for producing 1 mole of fuel are plotted in Fig. 3 in the temperature range of 13001700C for isothermal splitting without any heat recovery. Analysis shows that the fundamental reason for the
higher efficiency of CO2 splitting is ascribed to its thermodynamic nature, i.e. a higher conversion rate due to a
higher pO2 by thermolysis, which in turn is due to the more favorable Gibbs free energy change at elevated
temperatures (Fig. 1 (a)). Take 1500C for example, the G for CO2 and H2O splitting reactions is 129 and 149
kJ/mol, respectively, and pO2 resulting from thermolysis is 181 and 75 Pa, respectively. Based on the analysis
mentioned above, the conversion rate of CO2 turns out to be 3.67 times that of H2O. Higher conversion means
more fuel production per cycle, and so it follows that the total thermal energy cost for producing 1 mole of fuel is
much less, which is only 2.4103 kJ for CO2 (compared with 9.8103 kJ for H2O). Lower thermal energy cost for
heating reactant gas proves to be the secondary reason for the higher efficiency of CO2. Still taking 1500C for
example, due to the lack of phase transition, the percentage of heating among the total thermal energy cost for
CO2 splitting is 71%, significantly lower than 85% for H2O splitting. Overall, the conversion rate of reactants
increases exponentially with temperature. The total thermal energy cost per mole of fuel and the percentage of
heating both exhibit exponential decays accordingly.

1700

Temperature ( C)
Figure 3. Thermal energy for producing 1 mole of fuel (columns) and the conversion rate of reactant gas to fuel (lines) for isothermal solar thermochemical
splitting at selected temperatures without heat recovery. For columns, black/gray represents water splitting, orange/yellow presents CO2 splitting. For
each column, the number on top is the total thermal energy cost for producing one mole of fuel (H2 for H2O; CO for CO2), and the percentage underneath
is the fraction of thermal energy required for heating the reactant gas to the isothermal reaction temperature.

The temperature range for isothermal splitting is relatively high, so that re-radiation from the reactor back to the
environment is often non-negligible. In the expression of solar absorption efficiency defined by Eq. (5), besides
operating temperature, concentration ratio is another factor that affects efficiency. As reflected by Fig. 4, higher

556

concentration ratio generally leads to higher efficiencies, but the efficiency curves level off versus concentration
ratio at different rates, depending on operating temperature. Efficiency at higher temperatures has a stronger
dependence on the concentration ratio. Physically, this is because solar reactors would need an increasingly
smaller throat (i.e. inlet for solar irradiation) area to reduce the re-radiation loss to environment. In the optimum
temperature range of 1500-1600C for isothermal CO2 splitting, a concentration ratio of 3000 or above appears
to be sufficient for achieving high enough efficiencies. For example, at 1500C and 1600C, the efficiency
achieved at C=3000 is 86% and 83% of that achieved at C=10000, respectively; at C=5000, the percentage
enhances to 92% for both cases. In the literature, even lower concentration ratios (e.g. 1500) were used
(Chueh et al., 2010) for the same temperature range (for two-T cycling). In Fig. 4, this corresponds to a much
reduced efficiency, only at 67% and 58% of the extreme efficiencies for 1500C and 1600C, respectively.
Although the concentration ratio of 1500 and beyond is within the reach of dish concentrators (Tian et al., 2013),
the determination of optimum concentration ratio is oftentimes an issue that has to be resolved taking into
account the reactor operation conditions (e.g. temperature, efficiency) and economic factors.
1900C

HHV Efficiency (%)

40

1800C
1700C

30
1600C

20
1500C

10

1400C

1300C
1200C

2000

4000

6000

8000

10000

Concentration Level
Figure 4. Efficiency of isothermal solar thermochemical CO2 splitting at various concentration ratios and operating temperatures.

Considering the importance of cycling strategy to practical efficiencies and reactor design, isothermal and two-T
cycling modes are compared next in terms of efficiencies without heat recovery (Fig. 5). In consistency with
previous work (Hao et al., 2013), temperature of the oxidation step (Eq. (1)) of two-T cycling is assumed to be
700C lower than that for reduction (700C is an approximately optimum temperature difference for two-T
efficiency). With two-T strategy, the efficiency for CO2 splitting is slightly higher than that of H2O, and the primary
reason is the lower energy cost for heating CO2 than heating H2O. Fuel productivity per cycle (i.e. ) is almost
identical between the two cases for reduction temperatures of 1600C and lower, because the oxidation
reaction of ceria (Eq. (1)) at 900C and below is dominated by the thermodynamics of ceria (Chueh et al.,
2010). At even higher temperatures, CO2 exhibits a higher fuel productivity, since the oxidation temperature
(>1000C) starts to play an increasingly important role in promoting thermolysis, which is more pronounced for
CO2 than for H2O, thereby resulting in a smaller f and thus larger for the former.
On the other hand, the efficiency of isothermal water splitting with ceria, under the circumstance of zero heat
recovery, is much lower than that of two-T, primarily due to the unfavorable thermodynamics of H2O. As
discussed previously, a heat recovery percentage of 50-90% is necessary to achieve comparable or higher
efficiencies than two-T splitting (Hao et al., 2013). But the situation is much different for isothermal CO2 splitting:
the efficiency is roughly half of the value of its two-T splitting for a reduction temperature of 1400C, and starts
to exceed the latter at 1580C, while the temperature range of 1500-1600C is well within the reach of current
solar thermochemical reactors (Chueh et al., 2010). Also, the ratio of efficiency between CO2 splitting and H2O
splitting (Fig. 5, inset) shows that for isothermal cycling, CO2 splitting is much more efficient than H2O splitting,
while the situation is completely different for two-T cycling for reasons stated above. At 1400C where the peak
ratio for isothermal cycling occurs, even though the efficiency is only half that of two-T, savings in cycling time
(for reactor heating/cooling is avoided) could compensate, rendering the two strategies comparable in reality.

557

The influence of high temperatures on efficiency is also different between the two cycling strategies. For two-T
cycling, efficiency for temperatures beyond 1600C levels off and then slight decreases due to the decrease of
solar absorption efficiency, abs ; in the case of isothermal cycling, the adverse effect of decreasing abs is
partially cancelled out by the exponential increase of pO2 with temperature due to thermolysis, thereby deferring
the plateau region to 1800C. Given effective gas-phase heat recovery, isothermal solar thermochemical CO2
splitting could be more advantageous than two-T strategy in general. The quantitative effect of heat recovery on
efficiency enhancement is not discussed further, since there is no key difference between CO2 and H2O cases.

1200 1300 1400 1500 1600 1700 1800 1900

40
0.20

25
20

isothermal

isothermal CO2 splitting

3
2
1
0
1200

two-T CO2 splitting

two-T

0.15

TRe (oC)
1400

1600

1800

0.10
two-T H2O splitting

15
10

isothermal H2O splitting

= i - f

30

CO2 / H2O

HHV Efficiency, (%)

35

0.05

5
0
0.00
1200 1300 1400 1500 1600 1700 1800 1900

TRe (C)
Figure 5. Comparison of efficiencies of two-temperature (i.e. two-T) and isothermal solar thermochemical splitting of CO2 and H2O at given reduction
temperature TRe and pO2,Re=1.0 Pa, without heat recovery; for two-T cycling, oxidation temperature TOx is 700C lower than TRe individually, and fuel
productivity is also plotted. Inset: comparison of efficiency ratio of CO2-splitting to H2O-splitting for isothermal and two-T cycling strategies.

O2 Partial Pressure (x103 Pa)

3.0
2.5
2.0
1.5

H 2O
H2O:CO2=2:1
H2O:CO2=1:1
H2O:CO2=1:2
CO2

1.0
0.5
0.0
1200

1400

1600

1800

2000

Temperature ( C)
Figure 6. Oxygen partial pressure due to thermolysis of pure H2O, pure CO2 and their mixtures at selected mixing ratios.

As noted by several authors in the literature, an important objective for CO2 chemical recycling is turning it into
liquid fuels (Centi et al., 2009; Graves et al., 2011), for which the derivation of syngas is a key intermediate step.
The feasibility of syngas production with ceria was demonstrated by Steinfeld et al. experimentally (Furler et al.,
2012) by way of co-splitting H2O and CO2 with two-T thermochemical cycling. By its working principle,
isothermal cycling shall also be able to split H2O-CO2 mixtures and produce syngas. Although neither

558

theoretical nor experimental study has been reported in this respect, the efficiency of isothermal splitting of H2OCO2 mixtures can be roughly inferred from thermolysis-derived pO2. A preliminary analysis (Fig. 6) indicates
that when such a mixture is subject to high temperatures, the pO2 in the gas phase stays within the range
demarcated by those from the thermolysis of pure H2O (lower limit) and pure CO2 (higher limit), and shows a
monotonic increase with decreasing H2O:CO2 ratio. By the thermodynamic analysis process demonstrated in
this study, it can be qualitatively predicted that the energy conversion efficiency for isothermal splitting of H2OCO2 mixtures shall be higher than that for pure H2O but lower than that for pure CO2, with higher percentages of
CO2 being more favorable. Alternatively, the high-temperature exhaust of isothermal cycling can be utilized to
drive reactions that produce hydrogen from CO, probably a better approach for heat recovery and further
efficiency enhancement. Quantitative studies on efficiencies and fuel composition of the co-splitting of H2O and
CO2 is beyond the scope of this work, and will be discussed in future studies.
CONCLUSIONS
Analysis is performed on isothermal solar thermochemical splitting of CO2 at elevated temperatures, and its
efficiency is found to be considerably higher than that of isothermal splitting of H2O. The fundamental reason is
primarily the favorable thermodynamic nature of CO2, which leads to higher oxygen partial pressures due to
thermolysis and thus higher driving forces for the oxidation step of the splitting cycle. Consequently, conversion
rate of CO2 and fuel produced per cycle are significantly higher than those of H2O, resulting in much enhanced
efficiencies. The lack of phase change and thus of latent heat while heating CO2 is a secondary contributor to its
efficiency enhancement. Isothermal CO2 splitting appears to be a more practical rof solar fuel production
compared with isothermal water splitting, for requirements on the concentration ratio of solar concentrators and
operating temperature range of the reactors could be readily satisfied with the state-of-the-art technologies in
the area. Even when compared with conventional two-temperature splitting of CO2, the isothermal strategy is
able to achieve comparable or higher efficiencies within the temperature range of 1500-1600C without heat
recovery. For both cycling strategies, competitiveness would in a large part originate from practically achievable
efficiency, which has a strong correlation with the theoretical efficiency but is also affected by many other
factors. Given the infancy of solid-phase heat recovery and nonexistence of fluid-based, ultra-high temperature
(e.g. 1500C) heat exchanger, conclusions on which strategy shall excel in the real world may sound
premature. But the high theoretical efficiency of isothermal CO2 splitting and its potential advantages for reactor
design and heat recovery certainly provide a strong basis for it to be considered as a great candidate approach
for efficient solar fuel production.
ACKNOWLEDGMENTS
The author would like to thank the Recruitment Program of Global Experts of China for funding support, and
thank the Institute of Engineering Thermophysics, Chinese Academy of Science for early career startup
funding support. The author would also like to thank Professor Sossina M. Haile at the California Institute of
Technology, U.S.A. for inspirational discussions.
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560

CHIMNEY EFFECT OF SOLAR HYBRID-DOUBLE WALL WITH PCM OF

Na2CO310H2O
Liu Bin, Li Peng, Dang Chao, Li Cheng
(Tianjin Key Lab of Refrigeration Technology, Tianjin University of Commerce, Tianjin 300134, China)

ABSTRACT
The experiment of the chimney effect of the solar hybrid-double wall with a thickness of 1cm of
Na2CO310H2O was carried out by the simulated solar energy resulted from the adaptable voltage
heater. The effect of the light density on the temperature distribution of the both side of PCM, the air
gap and on the velocity distribution of the air gap were discussed and analyzed. The nature
ventilation air volume induced by the chimney effect and the heat gained by the air were also
discussed. The results show that the average temperature of PCM increases continually, while the
difference between the sides of PCM decreases. And both of the average and difference
temperature increase with the increasing of the voltage, which is opposite to the change of the
conductivity of Na2CO310H2O. The value of the air temperature, the air velocity and the mass
volume in the air gap will be kept constantly after the one hour, which increases with the increasing
of the voltage. As for the heat gained by the air in the gap, it will increase quickly to reach the
maximum value before the first hour and then decreases to zero. The maximum heat gained by the
air will also increase with the increasing of the light voltage. The application of PCM
(Na2CO310H2O) will reduce the temperature of the outlet air resulting in a lower heat gained by the
air, which is important for energy saving in nature ventilation. And the heat stored by PCM can be
used to produce the chimney effect at night where there is no solar energy.
Keywords: hybrid-double wall; heat storage layer; chimney effect

INTRODUCTION
The solar chimney is a kind of energy-saving technologies utilizing solar radiation energy to
strengthen the natural ventilation, which improves the utilization of the natural solar energy and
reduces the consumption of the non-renewable energy. Up to now, numerous researches have
been carried out at home and abroad. And certain achievements have been achieved in terms of
theory, experiment and numerical simulation. Atit Koonsrisuk simulated the simple theoretical
model of the solar chimney, in which he took the power efficiency and output of chimney effect as
an index and optimized the theoretical model in terms of the model size and radioactive intensity [1];
Frederick N. OnyangoX.Q. Zhai etc. studied deeply on the application of the solar chimney in
thermoelectric conversion device[2] and natural cooling system[3]; Professor Rakesh Khanal used
CFD technology to study the affections of geometric factors on the performance of ventilation and
vibration of the solar chimney[4]; H.F. Nouangu optimized the aspect ratiowidth ratio and heat
flux ratio of

the chimney air channel with the conjugate numerical calculation method of the finite

difference control volume[5]; Hoy-Yen Chan and Mirunalini Thirugnanasambandam discussed and
then gave their evaluations on the work mechanism of passive solar energy technology including
advantages, limitations, and challenging as well as the design [6] and research of solar energy heat
utilization technology[7]. They additionally gave out their suggestions on the future research in this

561

field; Ramadan Bassiouny, Nadia Saifi and other scholars studied on the effect of chimney angle on
the natural ventilation rate with CFD software used to carry on the numerical simulation. And then
verified the simulation results through the experiments

[8-9]

; With experiments and calculations on

the induced mass flow rate, Nusselt and Rayleigh of the solar chimney, B. Zamora got a deviation
of about 6% of the non-dimensional mass flow rate[10] and at the same time got the best aspect ratio
through numerical stimulations on the chimney geometry[11]; Through observing and calculating the
related parameters of the solar chimney at the different time during a day, J. Arce obtained the
effect of outside temperature on the chimney performance[12]; D. Ryan has carried on an
experimental study about the asymmetric heating channel and the results showed that the thermal
efficiency is a function of heat input and stack height, which has nothing to do with the chimney
channel depth[13]; Lu Zuo is committed in the research and development of solar chimney
integration system so as to meet the demand of multi-objective production such as power supply
and fresh water[14].
However, none of those studies above considered the chimney effects attached with HSL(heat
storage layer), therefore, this experiment research mainly focused on whether the light intensity and
ventilation channels width have an effect on the unsteady change process of chimney effect of
solar hybrid-double wall with HSL.

And it also analyzed the impact of the light intensity, ventilation

channels width and regenerative heating effect on both sides of the HSLs temperature fields as
well as the chimney internal spaces temperature field, velocity field, mass air flow and heat gain,
therefore, established the qualitative and quantitative relationship between the two influence factors
and the ventilation effect, which provided the necessary basis on improving the indoor natural
ventilation effect and reducing the building energy consumption.

1 EXPERIMENTAL SETUP
Experimental apparatus include chimney models and warm light equipment, which were shown
in figure 1. Devices of the chimney model is made up of mixing wall, transparent glass and model
architecture, in which the hybrid wall system is superimposed by 9.5 mm gypsum board, 10 mm
Na2CO310H2O HSL (the transformation temperature is 34 ), and 100 mm polyurethane heat
preservation material. The ventilation channels width in this model can be adjusted from 10 to 60
cm and the effective illumination area is 1 m * 1 m (high * width).
To make the experiment devices produce certain chimney effect, the chimney models air inlet
must be put at 500 mm high from the ground. At the same time warm light equipment should be put
at 900 mm distance from the chimney model; In addition, 100 mm polyurethane heat preservation
material of the hybrid wall of the lateral can reduce the convective heat transfer between the wall
and outside air. Whats more, the temperature should control within 25 + / - 1 through the whole
experiment process.
The conclusion of literature [15] shows: when the voltage is between 60 ~ 160 v, the
wavelength of the warm lights emitted by the device is roughly between 0.34 ~ 1.03 microns,
which concentrates in the visible portion of sunlight.

562

Fig.1 Experimental setup

1-100mm Polyurethane insulation 3-9.5mm Drywall
2-10mm HSL(Na2CO310H2O)

4- Frame of measure points5- translucent glass

6-

Framework of the model

7- Warm light equipment
1.1 Experimental description
During the experimentthe power supply of the warm light equipment which is used to simulate
the heat of solar radiation should be turned on so as to heat evenly. Through using the 1560
multichannel anemometer to measure the gas velocity of the import, export and middle part of
chimney air channel, MR-4 bolometer to measure the radiation projected onto the outer surface of
the glass, and at the same time 34970A Temperature Inspecting Instrument to show and record the
thermocouple values, lastly the temperature values of the HSL, the chimney internal space and the
wall can be got. The width of the chimney ventilation is set at 300mm, through adjusting the voltage
of lamp heating equipment to 100, 120 and 140v by the voltage regulator to simulate different light
intensity so as to conduct three experiments to measure the distribution of ventilation rate, internal
temperature field and velocity field of solar chimney under different light intensity.
In addition, the Hot Disk TPS2500 are used to test the thermal conductivity of the phase
change material Na2CO310H2O at the different temperatures.
1.2 Measurement of the temperature field
This experiment selected the spatial region, 125 mm away from the chimneys entry and exit,
consisted of the both-section of HSL and the chimney walls as the temperature measuring objects.
Distribution of the internal chimney temperature measuring points (including the glass and the inner
surface of the wall) and the two-section of the HSL: First, dividing the chimney internal space into
several horizontal and vertical measurement sections, constituting a cross grid and making every
intersection as a measuring point. In order to improve the measuring precision of this experiment,
the measuring points horizontal spacing is set at 100 mm (taking channel width of 300 mm as an
example) and 250 mm, and the longitudinal spacing 250 mm, and utilizing the same arrangement to
the glass and the layout 10 mm away from the inner surface of the wall, then 96 measure points can
be got. Second, projecting the measuring points within the internal space along the thickness
direction of the air channel onto both surfaces of the HSL will get the locations of temperature
measuring points, a total of 32 measuring points. The final size partition of the horizontal and
vertical section measuring points layout drawing is shown below in figure 2. All of measuring points
are arranged the copper constantan thermocouple in a measurement accuracy at 0.2 . First of all,
it is necessary to cut grooves in the inner wall surface, and then buried thermocouple into those
grooves. However, the thermocouple can be directly pasted on the inner surface of the glass and

563

the thermocouple in the internal space of chimney can be arranged in a thin wire built frame.

Fig.2 The layout of the measuring points

1-HSL

2- Drywall layer

3- Insulating layer

4-Measure points of the wind speed

5- Measure points of the temperature

6- Air passage

1.3 Measurement of the velocity field

The 1560 multichannel anemometer with a measuring range and precision respectively at 0 ~
9.99 m/s and 0.01 m/s is used in this experiment. Because of the distribution of the gas velocity
which is uneven at the chimney entrance and the obvious backflow at the outlet, the velocity
distributions there are not representative. While it is evener near the central area of the chimney as
less affection from the import and export influence and the flow direction nearly keeps in parallel
with the channel [16]. Therefore, this experiment takes the two-section 250 mm away from the inlet
and outlet of the chimney model and the center of the horizontal section of which models are
perpendicular to height direction as the measuring surface. Each measuring plane is arranged 3
points, a total of 9 points, as shown in figure 2. During the experiment, each probe is vertically put
from the exit and fixed by chimney architecture and temperature measurement frame, in order to
allow the air to flow vertically and ensure that the instrument probe is in a state of stable
measurement.

2 EXPERIMENTAL RESULTS AND ANALYSIS

2.1 Analysis of the thermal storage effect
According to figure 3, the thermal conductivity of Na2CO310H2O declined sharply, when the
temperature is between 23 and 26 , but it would rebound sharply and then keep In a constant
state of steady increase, when the temperature is between 26 and 29 , which suggests that the
phase change temperature of Na2CO310H2O is 26 .
As shown in figure 4, Change in temperature difference across the both sides of HSL has
almost the same tendency along with the change of its average temperature. Namely, sharply
increase first and then decrease, at last kept a stable declining state, which was just opposite to that
of the thermal conductivity of Na2CO310H2O since

the phase-change thermal storage effect

of thermal storage material. Taking the voltage of 140V curve as an analysis subject, the light
intensity of the warm light equipment is constant as the voltage is unchanging, thus the heat flux
density passing through the entire model keeps the same. According to the Fourier's law (

dt
dx

),

decreasing the temperature difference will lead to a decline in the temperature gradient, when the

564

thickness of the HSL is in constant. In the case of constant density heat, thermal conductivity of the
HSL should continue to increase, and vice versa, should continue to decrease, which is consistent
with the result shown in Figure 3. In addition, it can be also found out from the figure that, when the
voltage rise, not only the temperature difference on both sides of the HSL will increase but also the
average temperature has increasing trend shifting to the left, which means as the heat flux density,
the temperature gradient and the coefficient of thermal conductivity of HSL also increasing with the
rising of the voltage. Similarly, by the Fourier's law, the increases of the temperature gradient and
the coefficient of thermal conductivity of HSL are less than the increase of heat flux density through
the entire model.
The Figure 5 takes the variation of temperature throughout the model with time under 140v
voltage as an example to give a clearer evidence that a stable temperature value can be achieved
in a very short time and then do not change obviously any more for the transparent glasses and the
air in the channel that have scarcely abilities of thermal storage, when they receive the radiant
energy. For the gypsum board wall that has some ability of heat storage, its temperature can rise to
a certain value in a short time, but instead of keeping stable it will have a slight rise with time going;
Whilst, for the HSL with obvious effect of the heat storage, the temperature will keep rising with time.
Therefore, when the temperature of other parts is relatively stable, most of the radiation heat will be
absorbed by the HSL, and at the same time, the wall will absorb a few calories as well.

The thermal conductivity( W / m2.K)

0.22

0.20

0.18

0.16

0.14

0.12

0.10
20

25

30

35

40

45

50

55

Temperature(oC)
2.2

100V
120V
140V

Temperature difference
oC

2.0
1.8
1.6
1.4
1.2
1.0
0.8
25

26

27

28

29

30

31

32

33

Average temperature
oC

Fig.3

The relationship between temperature

and thermal coefficient of Na2CO310H2O Fig.

Fig.4 The heat storage layer temperature on

both sides changes with its average
temperature among different voltage

565

Glass surface
Channel air
Heat storage layer near the wall
Heat storage layer far the wall

55

Wall surface

Temperature( oC)

50
45
40
35
30
25
20

-1

Time (h)

Fig.5 The variation of temperature with time around the same voltage (140V)
2.2 Analysis of the temperature field
2.2.1 Distribution of temperature along the width direction in the model
The figure 6-a is a 3D strip chart obtained by decomposing the temperature distribution along
the width direction under different time points and voltage. According to it, the temperature of glass,
wall surface, air in the channel and temperature of the HSL on both sides is rising along with the
increase of the voltage of the warm light devices; And under the same voltages, the temperature of
air in the channel will firstly rise to a value within a short time, then tends to be stable, and its
temperature distribution in the width direction is almost consistent.
The figure 6b shows the temperature variation condition throughout the model along the width
direction of the air channel with time under 120v voltage. It can be further confirmed through this
figure, when the voltage is constant, the temperature distribution along the width direction of the air
channel is almost the same. With the time going, the temperature will not change clearly when the
air is heated to a value, the same as the glass surface; but the temperature of the both sides of HSL
and the wall surface (the gypsum board wall also has some ability to storage heat) is rising as the
time goes on. The limited heat storage effect of glasses is the main cause for this phenomenon.
And directly receiving radiation heat helps it reach a peak temperature in a short time. However, as
the existence of heat storage effect, the temperature increase of the HSL and the wall was
obviously slower in time. Therefore, when the surface temperature of glass reaches peak, the
temperature of the HSL and the wall has a certain degree of lag. At this time, most of the radiation
heat continues to be absorbed by HSL and the wall, whilst the air in the channel gets very few
calories, that is why the air temperature almost does no change.
The figure 6-c takes the time t=5.5h as an example, illustrating the effects generated by
different voltages on the temperature distribution in the width direction of the channel. It can be
seen more clearly through this graph, at the same time point, when the voltage rises, the
temperature in all parts of the model also rises; and it can also be found that the larger the voltage
value is, the greater increase of the temperature will happen. This is mainly due to the warm light
equipment power is the square of its voltage, so the radiant heat approximately rise in the square of
the voltage increase rate, but the increase of the thermal conductivity of the HSL and the wall rise
less than 1 after the temperature reaching 31, and it can be found by the previous conclusions
that the temperature of the air and the glass surface is in a stable state, so the thermal conductivity

566

is almost in the same. Then, according to the Fourier's law, the temperature in all parts of the model
will increase along with the increase of voltage at a certain temperature range. In addition, the
conclusion got in 2.1 shows the temperature slope on both sides of the HSL decreases with time in
figure 6 - b; but it shows the temperature slope on both sides of HSL increases with the increase of
voltage in figure 6 - c.
t=0
t=1.5
t=3.5
t=5.5
t=7.5

st

350
300
250
al 200
on
g 150100
t

an

ce

he

wi

dt

Temperature (oC)

Di

54
52
50
48
46
44
42
40
38
36
34
32
30
28
26
140V24

120V
K

100V

50
0
-50

h(
mm
)

50
48
46

t=0
t=1.5
t=3.5
t=5.5
t=7.5

44

Temperature (oC)

42
40
38
36
34
32
30
28
26
24
22
-50

50

100

150

200

250

300

350

Distance along the width ( mm)

Fig.6-a The distribution of temperature among

Fig.6-b The distribution of temperature with

different voltage and time

time around the same voltage (120V)

54
52
50

100V
120V
140V

Temperature (oC)

48
46
44
42
40
38
36
34
32
30
28
-50

50

100

150

200

250

300

350

Distance along the width (mm)

Fig.6-c The distribution of temperature with voltage at the same time (5.5h)
Fig.6 The distribution of temperature along the width direction in the model

567

2.2.2 Distribution of temperature along the height direction in the model

In figure 7-a and 7-b, the temperature distribution of the walls, the surface of glass and the
both sides of HSL has roughly the same trend along the height direction, namely the temperature is
low around the inlet and outlet of the channel, but is relatively higher in the central area. In addition,
with the increase of the height, the temperature of the air continues to rise, but the rising speed
decreases. When the voltage increases, it is possible that the temperature drops near the outlet, as
shown in figure 7-b. Through the analysis of above phenomenon, the air kept receiving the radiant
heat of the light heat warming equipment from the inlet to outlet, which means it has been in a
heated state all the time, so the temperature will rise. However, as the cold air around the outlet
outside the channel will be driven back into the channel, and mixes with the rising hot air inside the
channel, so the rising speed of temperature will drop down. According to the 2.3, the greater the
voltage is, the greater the flow rate of the hot air in the channel will be, which causes more cold air
backflow, as the phenomenon shown in figure 7-b. Similarly, this kind of backflow makes the
temperature of the wall and the surface of the glass decline, and as for the heat conduction effect,
the temperature of the HSL will correspondingly decline near the outlet. In addition, the air around
the channel inlet is in a turbulent state, which to some extent aggravates the heat exchange of the
nearby wall and the glass surface with the surrounding, lowering the temperature, and finally
produces the similar phenomenon like the backflow of the cold air.
Glass surface
Channel air
Heat storage layer near the wall
Heat storage layer far the wall

50
48

Wall surface

46

Temperature (oC)

44
42
40
38
36
34
32
30
28

100

200

300

400

500

600

700

800

900

Distance along the height (mm)

surface
Channel
Fig.7-a The distributionGlass
of temperature
55
around the same

air
Heat storage layer near the wall
Heat storage
layer far the wall
voltage
(120V)

Wall surface

Temperature (oC)

50

45

40

35

30

100

200

300

400

500

600

700

800

900

Distance along the height (mm)

Fig.7-b The distribution of temperature

around the same voltage (140V)

568

Fig.7 The distribution of temperature along the height direction in the model at the same time(5.5h)
2.3 Analysis of the velocity field
The figure 8 shows the relations between the air velocity and the time at the different height
when the voltage is at 120v. It can be found that the air velocity of the heights will reach a peak in a
short time and no longer has obvious changes. Additionally, the air velocity is a little higher in the
entrance than the central area and has a relatively lower value near the outlet. The reason for this
phenomenon is the influence of the air turbulent flow in the inlet and the backflow in the outlet.
Whilst, the measuring points of the air velocity taken from the highest point and the lowest point at
the experiment are not very close to the inlet and outlet, so the velocity differences between those
three parts are very small and can be approximately regarded as equal. The figure 9 shows that
when the voltage rises, the average air velocity of the channel also rise due to the fact that the
increasing voltage will increase the radiant heat generated by the warm light equipment, thereby
deepening the chimney effect of this model. Therefore, it can make the air velocity increase in all
parts of the channel.
0.20
0.18

Wind speed (m/s)

0.16
0.14
0.12
0.10
0.08

L=250mm
L=500mm
L=750mm

0.06
0.04
0.02
-1

Time (h)

Average wind speed(m/s)

0.24
0.22

Fig.8 The wind speed at different heights

0.20

within the channel changes over time

0.18
0.16
0.14
0.12
0.10

100V
120V
140V

0.08
0.06
0.04
0.02
-1

Time (h)

Fig.9 The average wind speed of the

channel changes over time around
different voltage
2.4 Analysis of the natural ventilation and the heat gained by the air
It can be found from figure 10 that the air mass velocity is very similar with the average

569

velocity in terms of changing with time, which also increase to a certain value and no longer has
obvious changes and its value will rise with the increasing of the voltage. The main reason for this
phenomenon is that the width of channel is constant, and according to the analysis of 2.2.1, the
temperature of the air will tend to a stable value over time in the channel, the change of which has
little influence on its density (when the temperature increased from 20 to 40 , the density
reduced from 1.205 kg/m3 to 1.128 kg/m3), so the mass flow of the air approximately has a
proportionality relationship with the air velocity.
0.080
0.075

Air mass flow ?kg / s

0.070
0.065
0.060
0.055
0.050
0.045
0.040
0.035

100V
120V
140V

0.030
0.025
0.020
0.015
0.010
0.005

-1

Time (h)
340

Fig.10 Air mass flow 320

in relation to time around
300

The heat of air (J)

280 voltage
different
260
240
220
200
180
160
140
120
100
80
60
40
20
0
-20

100V
120V
140V

-1

Time (h)

Fig.11 The heat of air in relation to time

around different voltage

As it was shown in the figure 11, under different voltage values, the heat gained by the air will
surly increase quickly (in about 1 hour) and then decreases sharply to around zero. Besides, the
higher the voltage, the larger peak heat gained over time, the more intense degree of the initial
rising stage and the later falling stage. According the previous conclusions, the temperature and the
mass velocity of the air will increase quickly at the beginning of the heating time and eventually
stably reach a certain value. Therefore, the temperature difference of the air will increase quickly to
reach the maximum value at the beginning and then decreases to zero. With the formula of the heat
gained by the air ( Q qmc p T ), the heat is very similar with the product of the temperature and the
mass velocity in terms of change. In addition, the increase of the voltage will make the mass
velocity of the air increase, which is same to the temperature variation of the air during the initial
stage. Therefore, the phenomenon appears as shown in figure 11.

570

3 Conclusion
Through the experiment on the solar hybrid wall with the HSL under the different voltages,
discussing and analyzing about the impacts of the heat storage effect, the voltage and the time on
the temperature, velocity and chimney effect, the following conclusions was captured.
1. Under the different voltages, the changes of the temperature variation on both sides of the
HSL along with the average temperature are opposite of the changes of the thermal conductivity of
Na2CO310H2O along with the temperature.
2. When the voltage increases, the increases on the thermal conductivity and the temperature
gradient of the HSL are less than the increase on the heat flux which crosses the entire model, and
the temperature increases throughout the model becomes large.
3. After heating, the air temperature, the mass velocity and the average air velocity increase
quickly to the maximum value (in about 1 hour) and then tend to be stable, which value has a
positive correlation with the voltage value, whilst the temperature of HSL and the wall surface has
been rising over time.
4. The temperature slope on both sides of the HSL decreases with the time going, while
increases with the increase of voltage.
5. The air backflow in the outlet and turbulent flow in the inlet will drop down the surrounding
temperature, and impact the air velocity of both the import and export. The phenomenon will be
seen more obviously with the increase of the voltage.
6. As for the heat gained by the air in the channel, it will increase quickly to a maximum value
(in about 1 hour) and then decreases to around zero. Besides, the heat peak will increase with the
increasing of the voltage.
Comparing the situation with or without the HSL, using HSL or not has little influence on the air
velocity and Natural chimney ventilation. But the application of PCM (Na 2CO310H2O) will reduce
the temperature of the outlet air resulting in a lower heat gained by the air, which is useful for
energy saving in natural ventilation. And the heat stored by PCM can be used as the power of
chimney effect when there is no solar energy.

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Frederick N. Onyango, Reccab M. Ochieng. The potential of solar chimney for application in
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X.Q. Zhai, Z.P. Song, R.Z. Wang. A review for the applications of solar chimneys in buildings[J].
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Rakesh Khanal , Chengwang Lei. Solar chimneyA passive strategy for natural ventilation[J].
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H.F. Nouangu, E. Bilgen, Heat transfer by convection, conduction and radiation in solar
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572

Effective Thermal Conductivity of MOF-5 Powder under a Hydrogen

Atmosphere
a

a,*

H .Wang , Z.G. Qu , W. Zhang , L. Zhou , Q. N. Yu

a

MOE Key Laboratory of Thermo-Fluid Science and Engineering, School of Energy and Power
Engineering, Xi'an Jiaotong University, Xi'an, Shaanxi 710049, China
b

School of Science, Xi'an Jiaotong University, Xi'an, Shaanxi 710049, China

National Key Laboratory of Human Factors Engineering, China Astronaut Research and Training
Center, Beijing, 100094, China
* Corresponding author. Tel/Fax: +86-029-82668543; E-mail address: zgqu@mail.xjtu.edu.cn

ABSTRACT:
The effective thermal conductivity is one of the important thermophysical properties in the
design of MOF-5-based hydrogen storage tanks, and it is related to the sorbent uptake,
temperature and pressure. A modified thermal conductivity model was built by coupling theoretical
model with grand canonical Monte Carlo simulation (GCMC) to predict the effect of H 2 adsorption
situation on the effective thermal conductivity of MOF-5 powder bed at pressure range (0.01-50MPa)
and temperature range (273.15K-368.15K). The results showed that the mean pore diameter in
MOF-5 crystals decreased with pressure enhanced, increased with temperature elevated as the H2
adsorption occurred. The density profiles of the adsorption gave insight into this phenomenon at
molecule level. The thermal conductivity of MOF-5 crystals was significantly enhanced by
adsorption H2 at high pressure and low temperature. The effective thermal conductivity of MOF-5
powder bed increased with pressure enhanced but remained nearly unchanged with temperature
increased. The thermal conductivity of adsorbed H2 increased with amount of H2 adsorption grown.
The conductivity of MOF-5 powder bed increased linearly with decrease of porosity and increase of
thermal conductivity of the skeleton of MOF-5 crystals.
Key words: GCMC, effective thermal conductivity, H2 adsorption, MOF-5 powder bed
1. INTRODUCTION
MOF-5 is a promising hydrogen storage material for its high-surface area and permanent
porosity, which can absorb up to 7.1 wt% H2 at 77 K and 40 bar [1]. It is comprised of
1,4-benzenedicarboxylate (BDC) organic linkers and Zn4O tetrahedral clusters as secondary
building units[2]. The amount of H2 adsorption decreases rapidly with increase of temperature. In
order to get higher amount of H2 adsorption, the temperature should kept lower for the fuel storage
tank during hydrogenation. It is an exothermic reaction with a heat of H2 adsorption ranging from 2
to 5 kJ/mol [3]. Therefore, the released heat should be removed in time to keep high H2 adsorption
capacity. The effective thermal conductivity is an important criterion to judge how fast the heat of
adsorption is dissipated.
Huang et al.[4], [5] found the thermal conductivity of MOF-5 crystal is 0.32 W/m K at a
temperature of 300 K under vacuum, and it has very weak relation with the temperature using ab
into calculation and experimental results when the temperature was above 100K, which means the
thermal conductivity of MOF-5 crystal is constant at atmospheric temperature. In fact, MOF-5
powder in the tank is very loose which consists of small crystallites. The thermal conductivity of
MOF-5 powders is less than the single-crystal value because of their large pore sizes and high
free volumes. Purewal et al.[6], [7] adopted two experimental ways to increase the effective
thermal conductivity of MOF-5 powder in the storage tank. One is powder densification; the other
is adding natural graphite (ENG) to form MOF-5-based composites. They found the density is
1

573

0.5g/cm3 for the optimal hydrogen storage properties. Yielding a 350% increase in volumetric H2
density with only a modest 15% reduction in gravimetric H2 excess comparing with the powder, but
mechanical compaction leaded the pore of MOF-5 crystals to collapse, because the compressing
has a low surface area[8]. However, the powder as adsorbent put in fuel storage tank directly
could avoid the phenomena which depended on the compressing by storage pressure at a higher
pressure. The addition of ENG to MOF-5 does not significantly lower the capacity of adsorption,
but improves the effect thermal conductivity of MOF-5 powder. The optimal property is realized by
adding 5-10wt% ENG.
In fact, the effective thermal conductivity is related to the sorbent uptake, temperature and
pressure [8]. The related properties can be predicted by grand canonical Monte Carlo, which only
needs the macroscopic variables such as the temperature and pressure. Walton et al. [10] used
GCMC to simulate the CO2 adsorption in MOF-5, and found step phenomenon during the
adsorption process because of the electrostatic interactions between CO2 molecules. Zhang et al.
[11] simulated H2 adsorption in MOF-5 at 77 K at different pressure range (0-1.0 bar) which fits
well with experimental data, and then they obtained computer tomography for MOF-5 at
adsorption process which shows the adsorption process at molecular level. Yang et al. [12]
combined grand canonical Monte Carlo simulation and density functional theory calculation
together on predicting the adsorption of hydrogen in MOF-505, and found the metal oxygen
clusters are preferential adsorption sites for hydrogen, the unsaturated open metal sites have a
strongest adsorption of hydrogen.
However, the aforementioned studies focused only on improving the effective thermal
conductivity of MOF-5, measuring the thermal conductivity of crystal of MOF-5 and simulating the
adsorption properties at the atmospheric environment, and they did not consider the effective
thermal conductivity of MOF-5 powder in adsorption bed under H2 atmosphere and the effect of
adsorbed phase. Meanwhile, there was not a model predicting the effective thermal conductivity of
H2 adsorption bed. In this work, the thermal conductivity model coupled with GCMC was used to
predict the effective thermal conductivity of MOF-5 crystal and powder bed at different pressure and
temperature under H2 atmosphere and thermal conductivity mechanism were given at molecule
level. Then the key factors of thermal conductivity were also studied.
2. THEORETICAL MODELING
2.1 The effective thermal conductivity
The cubic crystal structure of MOF-5 in powder bed is shown in Fig.1(a) . The free volumes of
MOF-5 powder bed decreased with pressure enhanced as shown in Fig.1(b).

(a) The structure of MOF-5 and its topology. (ZnO4 tetrahedral: blue polyhedra; benzene
dicarboxylate linkers: O, red and C, black; pore: yellow sphere)

574

(b)

The varied free volumes at different pressure

Fig.1 The structure of MOF-5 crystal and varied free volumes at different pressure
In this work, it was assumed that at the study pressure (0.01-50MPa) the pore in the crystal did not
collapse and the relation between the density and pressure was linear, which was expressed as:

0. 1 3 0. 0 0P6
(1a)

0.13 0.006 P
0.605

(1b)
where is the density and is the porosity of adsorption bed.
The two components were assumed a completely random distribution. The Effective Medium
Theory (EMT) model was adopted [13]:

kseff keff
kseff 2keff

k g keff
k g 2keff

(2a) which can be solved as:

keff

kseff
2

kg
4

3 k g
4

3 kseff
4

k 2g 1 8 k2 g kseff 92 k 2seff 6k 2 g 1k8g kseff 1k 22seff k 2g 4k g kseff 4k 2 seff

(2b) where is the porosity of adsorption bed, k g is the thermal conductivity of gaseous and

seff is the effective thermal conductivity of MOF-5 crystals. As the MOF-5 crystals comprise of
skeleton of MOF-5 and gaseous phase in pore whose diameter is 1.12nm [2], so the effect thermal
conductivity is expressed as [14]

seff

c 3 1
wvo

1 2l Kn

w 3 q 1

z
w

(3)
Among which

l 2kl 2 / kl 1
(4)
where kl is the ratio of the heat capacities of the gases, is the effectiveness of energy transfer
between the gas molecule and the skeleton of MOF-5, is the porosity of crystal, q is amount of
adsorption which can be got from GCMC simulation. Kn is the Knudsen number defined as

Kn / d
(5a)
where d is the mean pore diameter of the adsorbed MOF-5 structure, which can be got as follows
[15].

q z 1

d d e 1 3

(5b)
where w is the density of the adsorbed phase, which is assumed to be equal to the density at the
3

575

1
2

boiling point at 1bar, d e is the mean pore diameter of the MOF-5 structure. is the mean free path
of molecule

p0 T
p T0

(5c)
where p0 and T0 is the refers at 0.1MPa and 298.15 K, respectively, 0 is the mean free path of gas
under this reference condition. The values of the main parameters are shown in Table 1.
Table1. Constant parameters
Parameter
Value
Unit
Reference
3
N
729
kg/m
2

kg/m3

67

skMOF 5
LN

2030

Kg/m

[6]

0.02475

W/m/K

LH

0.1314

W/m/K

0.17064

W/m/K

0.0646

W/m/K

wv 0 H 2

1.27810-7

[16]

wv 0 N2

6.2810-8

0.702

[6]

rN2

1.92

rH 2

1.95

1.57
1.4

MOF 5

0.75

wv 0 H
wv 0 N

de

1.1210

W/m/K

[2]

-9

2.2 The GCMC models

The adsorption characteristics were calculated using GCMC simulation in which the chemical
potential ( ), the volume of the simulation box ( V ) and temperature ( T ) were constant. The
given temperature and pressure were input parameters. The size of simulation box was 5.1788 nm
5.1788 nm 5.1788 nm which had 222 unit cells. MOF-5was treated as the adsorbent which
was put into the simulation box with periodic boundary condition and hydrogen was treated as
adsorbate. The structures for MOF-5, nitrogen and hydrogen were both built and optimized in
Materials Studio packages [17]. The simulation box, adsorbent and adsorbate are shown in Fig.2.

Fig.2 The computed physical model

4

576

The number of adsorbate ( N m ) was assumed in the simulation box treated as an initial
configuration ( m ). One of three processes among random move, as well as insertion and deletion
adsorbate molecule was chosen at the same probability in the simulation box. The most stable
adsorption structure was obtained by random move producing potential energy difference. An
adsorbed molecule was added or decreased by the processes of insertion or deletion, as could
adjust the number of adsorbate molecules in the simulation box to get the number of adsorbed
molecules at equilibrium state. The detailed solution process can be found in Ref. [18].
The acceptance probability, which means the probability of the new configuration ( n ) is
accepted. The acceptance probabilities for move (

p*mn ), insertion ( p*mn ), and deletion ( p*mn )

can be expressed as

p*mn min 1,exp U n U m

(6a)

p *

mn

fV

min 1,
exp U n U m
Nn

p* min 1, m exp U n U m
fV

(6b)

mn

(6c)
Move processes were accepted when attempted move probabilities
over 50%. p
parameter
pressure

mn

mn

reached more

p * held when insertion, and deletion acceptance probabilities occurred. The

mn

is the Boltzmann constant and

is the fugacity which can be translated into

P through the Peng-Robinson equation. The coefficient

The chemical potential

is defined as:

1
kT

(7a)
is given by

V
kT l n e x p U n U m kT
3
N m 1

kT l n

Nm

(7b)
where is the thermal de Broglie wavelength,

is the ensemble average.

The potential energy in the simulation box would be changed in all three conditions to get the
most stable configuration at the adsorption equilibrium state. U n and U m are the energy of the
configurations

and

m , which are considered with the Lennard-Jones (LJ) given by

ij
ij
U ij 4 ij ( )12 ( )6
rij

rij

(8)
where i and j are interacting atoms, rij is the distance between atoms i and j, ij and ij are the
LJ depth and diameter, qi and q j are the partial charges of the interacting atoms, and 0 is the
dielectric constant. The cutoff radius was set to 1.3 nm for the LJ interactions. All LJ
cross-interaction parameters were determined using Lorentz-Berthelot mixing rules. The number of
adsorbate molecule was obtained in the process of insertion expressed in Eq.(9a)

Nn Nm 1

(9a) while the number of adsorbate molecule in deletion was

Nn Nm 1

(9b)
For every state point of pressure or temperature, 1107 steps were used to guarantee the
5

577

number of adsorption molecule and desorption molecules to be equal, as meant that the chemical
potential in the adsorbed phase and bulk phase was the same. Thus, the Eq.(10) was satisfied.

Nn p*mn Nm p*nm
(10)
7

Another 110 steps was used to attain the desired thermodynamics properties. The total number of
adsorbed molecule ( N n ) was calculated by Eq. (9).
Absolute amount should be converted to excess quantity (

N ex

) for comparison with

experimental data.

N M

Nex 1000 n a bV free N A

Na

MsMa

(11)
where M s is the amount of substance of single crystal cell and V free is the free volume of single
crystal cell which all can be obtained from Materials Studio packages [17],
molecule mass,

N a is

M a is

the adsorbate

the number of the structure cell. N A is the avogadro's constant,

b is the

bulk density that can be obtained from the Peng-Robinson equation

In the process of N2 and H2 adsorption, N2 and H2 were treated as spherical molecule which
just considered the LJ potential. The LJ potential parameters of N2 and H2 were taken from Ref.
[19-21]. The LJ parameters for N2 and H2 atoms are summarized in Table 2.
Table2. LJ parameters and partial atomic charges for N2 atoms and H2 atom

kB K

Ref

2.598

36.7

[19]

3.73

148

[20],[21]

species

Atom

( )

N2

H2

MOF-5 was treated as rigid, with atoms fixed at their crystallographic positions during
simulation. The boxes had 222 unit cells. The all-atom OPLS (OPLS-AA) force field [22] was
used to calculate the interactions between guest molecule and MOF-5 framework. The partial
potential parameters of MOF-5 were also taken from the work of Yang et al. [23]. They are shown in
Fig.3 and Table 3.

Zn
O C1 C2 H

Fig.3 Model clusters for different atoms

Table3. New LJ parameters for MOF-5 atoms

kB K

Atom type

C1

3.75a

52.84a

C2

3.55a

35.23a

2.96a

73.98b

2.42a

15.10a

Zn

2.46c

62.40c

578

Taken from the OPLS-AA force field of Jorgensen et al. [22]

Taken from Yang et al.[23]

Taken from the all-atom UFF force field(missing in the OPLS-AA force field)[24]

3. RESULTS AND DISCUSSES

3.1 Validation
Fig.4(a) shows the simulated adsorption isotherm of H2 adsorption in MOF-5 at 298 K
compared with the experimental data[25]. It can be seen that the simulated adsorption isotherm
fits well with the experimental data at different pressure, whose standard deviation is less than
6.57%. Therefore, the rescaled LJ parameters in present work are precise enough to learn further
on H2 adsorption behavior on MOF-5.
Fig.4 (b) shows the simulated effective thermal conductivity of MOF-5 powder under the N2
atmosphere compared with experimental data by Purewal et al.[6]. The theoretical calculated
porosity was 0.43, but under this condition, the standard deviation was 86.8%. The main reason
was that mechanical compaction in Ref. [6] leading the pore in crystal to collapse slightly, so in fact
the free volumes in the powder bed was higher than that by theoretical calculation. While the
porosity was set to 0.63, the standard deviation was only 7.8%. The model in this work can be
further used to study H2 adsorption bed in a way.
1.6

Experiemental data by Panella et al.[25]

simulation data by GCMC

1.4
Nex(mol/kg)

1.2
1.0
0.8
0.6
0.4
0.2
1

Thermal coductivity (W m-1K-1)

0.30
0.25

4
5
P(MPa)

(a) Comparison of simulated and experimental

(b) Comparison of simulated and experimental

adsorption isotherm of H2 in MOF-5 at 298 K

thermal conductivity at different temperature

Experimental data by Purewal et al.[6]

Simulation with
Simulation with

0.20
0.15
0.10
0.05
20

30

40

50

60

70

T(C)

Fig.4 Comparison of simulated result and experimental data

3.2 The effect of amount of adsorption on micropore width
Fig.5 plots the mean pore diameter of adsorbed MOF-5 crystal against hydrogen pressure
(0.01-50 MPa). The plots indicated that the mean pore mean pore diameter depended on
hydrogen pressure as shown in Fig. 5(a). With increase of pressure, the amount of H 2 adsorption
increased, which occupied the free volume, so that the mean pore of adsorbed MOF-5 decreased.
7

579

It was also indicated by the density profile of adsorption at different pressure as shown in Fig. 5(b).
The density of H2 near the Zn2+ was the highest, which meant hydrogen molecule was first
adsorbed near the Zn2+, then near the framework.
3.5

1.2

3.0

0.8
0.6

2.5
2.0

Pore width
Amount of adsorption

1.5
1.0

0.4

0.5

0.2
0.0
0.01

Nex(mol/kg)

d(nm)

1.0

0.0
0.1

1
P(MPa)

10

-0.5

(a) The varied pore with and amount of H2 adsorption at different pressure and 298.15K

0.1MPa

1MPa

20 MPa

(b) The density profile of H2 adsorption in MOF-5 at different pressure and 298.15K
Fig.5 The varied mean pore diameter at different pressure and 298.15K
Fig.6 shows the varied mean pore diameter at temperature range (273.15K-368.15K). The
mean pore diameter decreased with increase of temperature, because of amount of H2 adsorption
enhaced as shown in Fig. 6(a). The amount of adsorption decreased linearly with increased
temperature which leaded the mean pore diameter to decrease linearly. Fig .6 (b) also shows the
density profile of H2 adsorption at different temperature. It indicated that desorption occurred from
the periphery of pore at first, then near the pore with increase of temperature.

580

3.5

0.96

3.0
Pore width
Amount of adsorption

0.88

2.5

d(nm)

1.5

0.72

1.0

0.64

0.5

0.56

0.0

270

285

300

315
330
T(K)

345

360

Nex(mol/kg)

2.0

0.80

-0.5

(c) The varied pore with and amount of H2 adsorption at different temperature and 10MPa

273.15K

338.15K

368.15K

(d) The density profile of H2 adsorption in MOF-5 at different temperature and 10MPa
Fig.6 The varied mean pore diameter at different temperature and 10MPa
3.3 The effect of pressure
Fig.7 shows the effective thermal conductivity of adsorbed MOF-5 crystal and adsorption bed
at different pressure range (0.01-50MPa) and 298.15K. The effective thermal conductivity of MOF-5
powder bed kept in constant at first (pressure range from 0.01-2MPa), then increased faster at high
pressure range (2-50MPa). The effective thermal conductivity of MOF-5 crystals at H2 atmosphere
increased in S shape, which was similar to the experiments of H2 atmosphere in zeolite K [9]. The
effective thermal conductivity of MOF-5 crystals and powder bed considering the adsorbed phase
was higher than that without considering. The difference was bigger with increase of pressure, due
to the thermal conductivity of adsorbed phase. The thermal conductivity of adsorbed phase
increased for the amount of H2 adsorption increased with increase of pressure. As the porosity in
the powder tank was high at low pressure (range I and II), which leaded the gaseous thermal
conductivity to play an important role. While with increase of pressure, the free volumes of MOF-5
powder bed was compressed fast so that the porosity was low at III region; the thermal conductivity
of crystal gradually played a leading role in the ratio of increased effective thermal conductivity of
MOF-5 bed. For the MOF-5 crystals, the change of thermal conductivity was decided by the
adsorbed phase and gas phase in the crystals. At I region (0.01-0.1MPa), the amount of H2
adsorption was little so the thermal conductivity of adsorbed phase was low which could be ignored.
The change mainly came from the mean free path of molecule which decreased with increase of
pressure causing the thermal conductivity of gas phase increasing slowing. At II region (0.1-2MPa),
the change was mainly decided by adsorbed phase and gas phase. At this region, the amount of
adsorption increased leaded the thermal conductivity of adsorbed phase increasing. The ratio of
increased amount of adsorption was fast, which resulted in the mean pore diameter of crystal
9

581

decreased rapidly. However, mean free path of molecule decreased to slow down the increase of
the Knudsen number, which meant slowing down the decrease of thermal conductivity of gas phase.
It could be noted that the varied of mean pore diameter of crystal affected the effective thermal
conductivity a lot. In this region, the increased thermal conductivity of MOF-5 crystal came from the
adsorbed phase and gas phase. At III region (2-50MPa), the change was mainly caused by the
adsorbed phase. The ratio of increased amount of adsorption was slow, so the mean pore diameter
changed a little, and the mean free path of molecule decreased slowly, leading the Knudsen
number to vary slowly. As amount of adsorption was much, the thermal conductivity of adsorbed
phase was high, which was the main reason leading the difference between two models at high
pressure. From above all, it could be noted that varied thermal conductivity of MOF-5 crystal was
caused not only the Knudsen number as Shim et al.[6] explained, but also the amount of adsorption,
while for MOF-5 powder bed, the varied thermal conductivity came from the variation of crystal and
porosity among the powder.

-1

-1

Thermal conductivity (Wm K )

0.8

ad
seff without considering the adsorbate

0.7

seff considering the adsorbate

0.6

eff without considering the adsorbate

eff considering the adsorbate

0.5
0.4
0.3
0.2

0.0

II

0.1
0.01

0.1

1
P(MPa)

III

10

Fig.7 The varied thermal conductivity at different pressure and 298.15K

3.4 The effect of temperature
Fig.8 shows the effective thermal conductivity of adsorbed MOF-5 crystal and bed at different
temperature range (273.15K-368.15K) and at 10 MPa. The effective thermal conductivity of
MOF-5 crystal and bed was a little higher for considering the adsorbed phase than that without
considering the adsorbed phase, because the adsorbed phase had thermal conductivity itself and
the adsorbed H2 molecule could reduce the mean pore diameter of crystal, which made
contribution to change the thermal conductivity of gas phase in MOF-5 crystal.

The difference

between two models was smaller with increase of temperature, as the amount of H 2 adsorption
decreased with temperature increased. The effective thermal conductivity of MOF-5 powder bed
remained nearly unchanged with increased temperature, while the MOF-5 powder crystal
decreased slowly. The reasons for MOF-5 bed was that the porosity of bed at this condition was
0.686, so the gaseous phase in powder bed played a dominate role in the conductivity of MOF-5,
whose conductivity property was unchanged at low temperature. While for MOF-5 crystal without
considering the adsorbed phase, the thermal conductivity of gas phase decreased with increase of
temperature, because of Knudsen number increased with increase of temperature. For MOF-5
crystal considering the adsorbed phase, the ratio of decreased effective thermal conductivity is
faster than that without considering, due to the decreased amount of adsorption although the
mean pore diameter increased helping improve the thermal conductivity of gas phase, which
played a small part in the whole thermal conductivity.

10

582

Thermal coductivity (W m-1K-1)

0.9

ad

0.8

eff without considering the adsorbate

0.7

eff considering the adsorbate

seff without considering the adsorbate
seff considering the adsorbate

0.6
0.5
0.4
0.3
0.2
0.1
0.0
270

285

300

315
330
T(C)

345

360

Fig.8 The varied thermal conductivity at different temperature and 10MPa

3.5 The effect of main parameter on effective thermal conductivity
Fig.9 shows the varied effective thermal conductivity of MOF-5 bed and porosity at different
slope of function between density and pressure range (0-0.009) at 298.15K and 10MPa.
Increased the speed of compression apparently enhanced the effective thermal conductivity of
MOF-5 bed by decreasing the amount of interstitial voids between the crystal in the bed. Fig.10
shows the effect of varied thermal conductivity of MOF-5 solid on the thermal conductivity of the
crystal and bed. It could be noted that they were just linear relationship.
0.80
Thermal conductivity of MOF-5 powder bed
porosity

0.27

0.78
0.76

0.26

0.74

0.25

0.72

0.24

0.70

0.23

0.68

0.22

0.66

0.21

0.64

0.20

0.000

0.002

0.004
K

0.006

0.008

0.62
0.010

Fig. 9 The varied porosity and thermal

-1

-1

Thermal conductivity Wm
(
K )

0.8

conductivity at different slope

Fig. 10 The varied porosity and thermal

conductivity at different solid thermal

MOF-5 crystal
MOF-5 powder bed

0.7

Thermal coductivity (W m-1K-1)

0.28

conductivity

0.6
0.5
0.4
0.3
0.2
0.2

0.4

0.6

0.8

1.0

1.2

1.4
-1

-1

The thermal conductivity of MOF-5 skeleton(Wm

K )

4. CONCLUSION
A modified thermal conductivity model was built by coupling theoretical model with grand
canonical Monte Carlo simulation (GCMC) to predict the effect of H2 adsorption situation on the
effective thermal conductivity of MOF-5 powder bed at pressure range (0.01-100MPa) and
11

583

temperature range (273.15K-368.15K). The results showed that the mean pore diameter in MOF-5
powder crystal decreased with pressure enhanced and increased with temperature elevated as
the H2 adsorption occurred. The density profiles of the adsorption gave insight into this
phenomenon at molecule level. The effective thermal conductivity of MOF-5 powder bed
increased with pressure increased; the reasons mainly because that the free volumes of
adsorption bed decreased with increase of pressure as the MOF-5 powder compacted and the
thermal conductivity of adsorbed phase increased with amount of H2 adsorption increased. While
the temperature rose, the effective thermal conductivity of MOF-5 powder bed remained nearly
unchanged due to the high porosity. The thermal conductivity of MOF-5 powder bed increased
linearly with decrease of porosity and increase of thermal conductivity of the skeleton of MOF-5
crystals.
ACKNOWLEDGEMENT
This work was financially sponsored by the National Natural Science Foundation of China (No.
51322604), the National Key Projects of Fundamental R/D of China (973 Project: 2011CB610306),
the Fundamental Research Funds for the Central Universities (No.08143053) and the Open

Funding Project of National Key Laboratory of Human Factors Engineering, Grant No.J20131108.
NOMENCLATURE

d
f
h
k
kl
Kn
q
Nm , Nn
NA
N ex

P
p*
R
r
U ij , U ff , U fs
V
V free

ij

Mean pore diameter, m

Fugacity, kPa
Planck constant
Boltzmann constant, J/K
The ratio of the heat capacities of the gases
Knudsen number
Molecular mass, mol/kg
Number of adsorbed molecules
Avogadro's constant
Excess amount, mol/kg
Pressure, MPa
Acceptance probability
Gas constant, J/mol/ K
Effectiveness of energy transfer
Interaction energy, kJ
The volume of simulation box,cm3
Free volume, cm3
The factor
Chemical potential, kJ/mol
Thermal conductivity, W/m/K
Porosity of crystal
Porosity of adsorption bed
LJ depth, K

Mean free path molecule, m

<>

LJ diameter,
Ensemble average

ij

SUPERSCRIPT
+,SUBSCRIPT

Bulk density, kg/m3

Insertion and deletion
12

584

ad

m, n
ex
ff
fs
i, j

adsorbate
Configuration m, n
Excess
Adsorbate-adsorbate
Adsorbate-adsorbent
Atom i, j
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14

586

SUSTAINABLE DESIGN OF A SMART GRID PHOTOVOLTAICS SYSTEM

FOR SUBARTIC REGIONS
Steve Hsueh Ming Wang, Lei Yao, Shi Jing*, Benjamin Koo**
University of Alaska Anchorage, North Dakoda State University*, Tsinghua University**
th
3211 Providence Dr., Anchorage, AK 99508, USA, 1410 14 Avenue N., Fargo, ND 58108, USA*
hswang@alaska.edu, Jing.Shi@ndsu.edu*, benkoo@tsinghua.edu.cn**

ABSTRACT
This research develops a smart grid photovoltaics (PV) system by using the current technologies to
demonstrate whether the system is feasible for off-grid rural communities in the subarctic region. In
order to define the objective, the PV conversion model, the PV system generation algorithm, and the
smart grid PV system business model are built. A pilot hybrid LED-solar-wind system performance is
analyzed to provide the technical feasibility for the PVs application in the subarctic region. By using
PV F-Chart software, a solar energy conversion model forecasts the unit area PV electricity output.
Based on that and a flat-plate non-tracking PV system, a 70 tilt angle in winter, and a 34 tilt angle in
summer can be recommended as best angles for electricity output. Based on the PV electricity
output, 37.7 cents/kWh was calculated as the system electricity cost for the proposed system. If this
system is put into usage, it can mitigate 1055 ton Carbon Dioxide emission per year. Under the
current median electricity price of 46.8 cents/kWh in the rural subarctic region, it shows the system
provider should at least charge 26 percent of the electricity transaction that it can make a profit. The
smart grid PV system can achieve an electricity cost than less the median unsubsidized electricity
cost in off-grid rural communities in Alaska. Moreover, it can let the system provider make profits just
in 26 percent of the electricity transaction. As such, the system is feasible during the contract period.
Under further incentives and governmental subsidies, smart grid PV systems application may have
more competitive advantage.
Keywords: Smart grid, Photovoltaics, Subarctic region, Off-grid, Sustainable design.
INTRODUCTION
Subarctic regions, as shown in the Figure 1, fall between 50N and 70N latitude. Energy
independence is a critical issue for these areas. These areas have long usually very cold winters and
short cool to mild summers.

Figure 1. Distribution of subarctic climate regions (Peel, 2007)

The statistical data shows over 180 rural Alaskan communities that are served by electrical microgrids isolated from larger population centers (Crimp, 2009). The smart grid that is shown greater for
rural grid systems than urban systems is interoperability, efficiency, stability, and security (Saint,
2009). Interoperability describes the capacity of different programs to exchange data via a common
set of exchange formats, to read and write the same file formats, and to use the same protocols
(Gunther, 2009). The high energy cost may cause these communities to replace systems by using
renewable energy such as the PV generation system. Colt stated that 88% energy used for electricity,
heating, and transportation came from diesel in the off-grid rural communities in Alaska. Inland
transportation costs can take account for more than 32% of diesel price, which leads to electricity
price in rural communities five times higher than Anchorage (Colt, 2002). At the same time, diesel
generators usage also causes environmental pollution.
Considering the availability of renewable energy sources in Alaska, a PV system is convenient to
obtain solar energy in the summer and operate with low maintenance costs. The PV system may
especially suit for off-grid rural Alaskan communities because the unique geographical location of
Alaska. During the summer, solar radiation is usually longer than 18 hours per day. However, the PV

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source is intermittent in nature, depending on the solar radiation to generate electricity. Thus, any
power infrastructure integrating intermittent renewable energy resources must have a way to
effectively reduce electric demand by load shedding. With the trend of rising energy consumption and
higher energy costs, utilities also should be able to anticipate changing patterns to manage power
supply and demand. A smart grid system can be a good choice because the system can be
intelligently operated and has more than two-way power sources in which at least one power source
is municipal grid. The main objective of this research is to demonstrate whether a smart grid PV
system is feasible in the subarctic region in Alaska. This research presents the feasibility study of a
smart grid PV system, which is proposed in the subarctic region in Alaska. As for the smart grid PV
systems application in the subarctic region, the system may suffer the following issues:
Low temperature is a big challenge to the life cycle and operation of batteries in the system.
The cost for replacement of a battery is relatively high to compare with the other energy systems.
The operation and maintenance cost may be high in these areas.
In order to efficiently collect data and to consider that the smart grid technology and renewable
energy may be the future trend in energy utilization field, the ADM building at University of Alaska
Anchorage, as shown in Figure 2, is an ideal place to be a demonstration place for this kind of pilot
project. Figure 3 shows the monthly average electricity consumption trend based on the data from
the academic year 2000 to 2009. The electricity consumption remained relatively stable in the period,
and the electricity consumption fluctuated between 67,000 and 86,000 kWh per month. During the
day, the peak hour of the ADM building is from 9 AM to 5 PM, and it occupies two-thirds of the daily
electricity demand of the whole building.

Figure 2. The location for the smart grid PV system at UAA (Google maps, 2010)

Figure 3. Monthly average electric consumption of ADM building at UAA (UAA Office of Sustainability, 2010)

DEVELOPMENT OF THE SMART GRID PV SYSTEM

The smart grid PV system for the ADM building at UAA is defined as an area smart grid system
incorporating a PV generation system and the municipal grid sources. The municipal electricity is
directly from the municipal grid, which is operated by the Anchorage Municipal Light & Power Inc. The
PV generation system adopts the non-tracking flat-plate PV arrays as the electricity generators. This
is because 1-axis and 2-axis tracking systems cannot contribute more electricity output compared
with non-tracking systems in high latitude areas, such as Anchorage. The smart grid is an advanced
electricity transmission and distribution network that utilizes digital information and control technology
to improve electricity reliability, security, and efficiency (Energy & Natural Resources, 2009). A typical
smart grid incorporates power sources, transmission systems, distribution systems, distribution
system Supervisory Control And Data Acquisition (SCADA) facilities, substations, Advanced Metering
Infrastructure (AMI), communications systems, smart meters, and the control center (Cisco Smart
Grid, 2009). Each system does include several subsystems. The whole breakdown structure of a
typical smart grid is shown in Figure 4. In Figure 4, the smart grid PV system excludes subsystems of

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distribution, substation, and SCADA, which are not needed for an area-wide in the case study site.
The PV generation system and municipal electric source are included in the power sources
subsystem because PV electricity is intermittent energy, which highly depends on local weather
conditions. The municipal electric source can serve as a compensative source but also a competitive
source to the PV generation system. The municipal power source can be an alternative supply when
PV electricity does not work well in unstable conditions, like rainy, snowy, cloudy, and foggy weather.
Meanwhile, it also needs to provide electricity to the ADM building during the off-peak hour periods
and at night.

Figure 4. A typical smart grid system breakdown structure (Cisco Smart Grid, 2009)

Control of the Smart Grid PV System

As for the control flow of the whole system, it can be mainly regarded as three parts, which are smart
grid PV system, municipal grid power, and customers. When the whole system works, smart meters
can get the real-time electricity price information and transmit data to AMI gatekeepers. Then, AMI
gatekeepers transit data through communications networks to AMI. AMI can translate the information
sent from a various AMI gatekeepers into a format that the central computer can understand. Then
the central computer in the control center can make decisions based on the information from smart
meters and give commends to these smart meters following specific routines. The detailed
communication and power flows of the whole system can be seen in Figure 5.

Figure 5. Smart grid PV system power and communication flows

Methodology
The analysis of the system includes the solar energy conversion model (PV electricity analysis
software PV F-Chart), the smart grid PV system scale methodology, the system scale algorithm,
and the system business model. The procedures are described as follows:
1. The solar energy conversion model can predict the average monthly unit area PV electricity output
at the case study site under the best tilt angles.
2. The system scale methodology describes determination of the system scale according to the ADM
buildings electric demand and the relationship of different system components.
3. The system scale algorithm (O. R. model) is used for determining the scale of the system.
4. Based on the results from the above three models and algorithms, the smart grid PV system
business model is built to make the feasibility analysis.
Solar Energy Conversion Model
A lot of PV software is available to estimate PV output. The National Renewable Energy Laboratory
(NREL) has developed software named PV Watts. PV performance is first calculated for the nearest
TMY2 location and then translated to the desired Version II 40 km grid cell location. Because the

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translation process uses monthly values, hourly values of PV performance are not available for
Version II (NREL, 2010). PV F-Chart is a comprehensive photovoltaic system analysis and design
program. The program provides monthly average performance estimates for each hour of the day.
The calculations are based upon methods developed by the University of Wisconsin, which use solar
radiation utilization to account for statistical variation of radiation and the load. Some simple PV
output calculators can also be found online, like Watsun solar trackers (Watsun, 2010). However,
Watsuns calculator uses simple formulas and does not take into account the density of the
atmosphere. Compared to these PV output estimating software programs, PV F-Chart is a more
accurate and comprehensive PV system analysis program for our research usage. We use the
photovoltaic analysis software (PV F-Chart, 2008) to determine the unit PV electricity output on the
case study site location.
Meteorological influence is one of the main factors of the PV electricity output, which includes solar
radiation, temperature, humidity, and reflection coefficient. The strength of solar radiation is the
primary consideration in selecting the location for the PV system installation. The electricity output of
a PV array is directly proportional to the solar radiation input. Local climatic and environmental factors
will constrain the output of the PV array. However, these are all secondary effects when compared
with solar radiation intensity. All of the data in Table 1 come from the National Renewable Energy
Laboratory (NREL) TMY 3 data base, and will be used in the PV F-Chart software.
Table 1. Meteorological data of Anchorage (NREL, 2010)
Solar radiation
Temperature
kWh/m2
C
Jan
0.23
-2.0
Feb
0.90
-5.8
Mar
1.92
-1.9
Apr
3.01
2.6
May
3.68
9.1
Jun
5.49
15.3
Jul
4.61
14.3
Aug
3.65
16.1
Sep
2.48
7.2
Oct
1.03
1.7
Nov
0.37
1.3
Dec
0.14
-4.7
Average
2.29
4.4

Humidity
Abs(kg/kg)
0.0026
0.0020
0.0025
0.0031
0.0039
0.0057
0.0073
0.0079
0.0045
0.0036
0.0035
0.0024
0.0041

Reflection
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2

Under the same climatic condition, both tilt angle and azimuth are two main parameters which can
affect the amount of solar radiation that PV arrays receive. Tilt is the angle between the horizontal
ground and the PV array, which is marked in Figure 6. In this research, the tilt angle is assumed to
be set in two different angles during the entire year, one angle for the summer from April to
September and another angle for the winter from October to March. It is divided according to the
length of daytime and the weather in the subarctic region.
According to Buresch (1983), the optimal tilt angle for a south-facing (zero azimuth) surface equals
the sites latitude. This surface would receive the optimal amount of direct-beam solar radiation over
the entire year. If the maximum solar energy is expected to be received during the winter months, the
surface tilt angle should approximately equal the latitude angle plus 11. Consequently, the best tilt
angle during the summer months is the sites latitude angle minus 11. However, according to Kreith
and Goswami (2007), the optimal tilt angle can be approximately equal to the sites latitude angle plus
15 during the winter months. Therefore, the optimal tilt angle during the summer month is the sites
latitude angle minus 15.
Considering that the latitude of Anchorage is 6113 N, the monthly average unit PV electricity output
will be calculated at different tilt angles from latitude angle minus 37 (24) through latitude angle plus
29 (90) (here L represents the latitude of Anchorage) within a 2 increase as an interval. Based on
the maximum output in winter and summer, the optimal tilt angles can be found.

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Figure 6. Tilt angle of PV panels (Power from the Sun, 2010)

Scale of the Smart Grid PV System

PV generation system
In order to maximize the utilization of the renewable energy but also consider the renewable energy
utilization condition in Alaska, the PV generation system is assumed to satisfy the total electricity
demand of the ADM building in the summer (April to September) in this research. In the winter, from
October to March, the PV generation system may support partial power of the ADM buildings
demand. Referring to Figure 3, the highest electricity demand month of ADM building in the summer
is August according to the past ten years data.
The PV array size
The PV generation capacity, W p, (kWh) can be determined by the PV array
size, A, (m2) and the unit area PV electricity output, W up, (kWh/m2), which can be expressed in Eq.
(1). After getting the PV generation capacity, the number of PV arrays (Np) can be calculated from the
PV generation capacity and average output of a PV module, W pp, (kWh/set) through Eq. (2).
(1)
(2)
The AC/DC inverter size
The continuous input rating power of the AC/DC inverters (KW)
should be set 25% higher than the PV array generation capacity (SECO, 2010). Therefore, the
AC/DC inverters rating power (W i, kWh) can be determined by the highest electric demand month in
the summer of the ADM building by using Eq. (3). The number of AC/DC inverters (Ni) can be
calculated by the AC/DC inverters rating power and each inverters capacity (W pi, kWh/set) as Eq. (4)
(3)
(4)
The AC/DC inverter in the current market is available in the range of 4, 5, and 6 kW. In this research,
the AC/DC inverter with 5 kW capacity is considered for the system.
The storage battery bank size
The storage battery bank serves as the energy storage in the
smart grid PV system. It can be used in the time when PV arrays do not work during the bad weather
conditions or at night. At the same time, it serves as the backup for the ADM building when it suffers a
blackout. In this research, storage battery banks are designed to be charged when PV arrays
generate more than the demand from ADM building. Thus the storage battery bank size (Ahb, Ah) can
be determined by the surplus electricity (W s, kWh) and the battery bank voltage (Vb, V) as Eq. (5)
while the number of batteries (Nb) can be expressed Eq. (6), respectively.

(5)
(6)
where Ahbb (Ah/set) is the power capacity for each battery.
Referring to the Rock Island Lodge project on Kalgin Island in Alaska, gel battery with 24V and 700
Ah is considered to use in the case study site (John, 2010).

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The charge controller electric capacity The charge controller capacity (Ac, A) can be determined
based on the PV generation capacity and battery bank voltage as follows in Eq. (7)

(7)
The smart meter size
Estimating the number of smart meters (Ns) depends on the population
being served. For the residential area, each individual house needs one smart meter (PG&E, 2010). If
we assume that every house has four residents, a village with a population of 200 needs 50 smart
meters for residential houses. Combining the public facilities and buildings, the amount of smart
meters can be assumed to fluctuate based on population being served (P) as Eq. (8).

(8)
The AMI gatekeeper
AMI gatekeeper deployments involve all customer sites across the
distribution grid and are extremely cost sensitive (Hart, 2008). Estimating the number of AMI
gatekeeper is dependent on the population being served. For the residential area, each individual
house needs one AMI gatekeeper (PG&E, 2010). Combining the public facilities and buildings, the
scale of AMI gatekeeper (NA) can be assumed as Eq. (9).
(9)
The Smart Grid PV System Design
The algorithm of the smart grid PV system satisfies the following conditions:
1) The PV electricity is proposed to satisfy the to the ADM buildings electric demand in the
summer (April to September), which has the highest electric demand during a year.
2) At the time, if the PV generates more than the ADM buildings electric demand, the surplus
electricity will be charged into storage battery banks.
3) The AC/DC inverter capacity should be 25% higher than the highest electricity demand
month in the summer (August).
4) Considering the sites land limitation, the number of PV panels is assumed to no more than
550.
5) The initial capital cost of PV generation system should be limited within $620,000, which is
similar with the relative size diesel generator system.
C the present worth of the cost of the smart grid PV system during the contract period

(10)
k = 1, 2, ~, 30
j = 5, 10, ~, 30
l = 10, 20, 30
Obj.
(11)

Min

where Cp is the cost of PV arrays, Cad represents the cost of AC/DC inverter, Cb stands for the cost of
battery bank, Cme means the capital cost of smart meter, Cami stands for the capital cost of the AMI
gatekeeper, Ccon represents for the capital cost of control center, Cint is the installation cost, CO&M
represents for the annual O&M cost, Citc is the investment tax credit of this project, Ce stands for the
environmental cost, and i represents for the interest rate.
Substitute the unit price of all the components of the PV generation system, the Eq. (11) becomes to
Eq. (12). The unit price of the all the components of the PV generation system are listed in the Table
2. Costs in Table 2 are obtained from product manufacturers and vendors.
Table 2. Parameters for cost analysis
Name
Life (yr)
PV array
30
AC/DC inverter
30

Cost
$741/m2
$662/kW

Source
GE solar
SMA

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Battery
AMI gatekeeper
Smart meter
Control center
O&M

5
10
10
5
annual

$550/set
$2280/set
$350/set
$250,000
$150,000

Surrette
Product manufacturers
Product manufacturers
Assumption
Annual assumption

(12)
Subject to:
A:
(13)
Np 550;
Np, Nad, Nb I
I: Integer
B: The PV generation system can meet the summer electric demand from April to September

(14)
(15)
(16)
where k April, May, June, July, August, September, ad is the efficiency of the AC/DC inverters, E
stands for the monthly electric demand, and Es is the surplus electricity.
The algorithm of the smart grid PV system is built and run under the software Solver 7.0 by
evolutionary algorithm.
The Smart Grid PV Electric Business Model
The electric service is categorized into the utility service. The electric utility model is based on
metering usage and constitutes a pay as you go approach (Rappa, 2004). Simply, it means your
payment or bill is just determined by the metering usage.
In this research, the smart grid PV electric business model should be built based on the concept of
the total solution. That means the system provider will provide the whole system to the utilities. Then,
the system provider will sign a contract with the utilities to charge a certain percentage from the
electric revenue of the electric consumption by end users.
The assumption of the smart grid PV system business model refers to the cell phone total business
solution (SONY, 2010). They are illustrated as follows:
1. The system provider takes responsibility for providing the whole smart grid PV system, installing it,
and test running the system. The system is then transferred to the utilities.
2. The utilities take responsibility for operating the smart grid PV system and affording operations
and maintenance.
3. During the contract period, the system provider can provide the necessary components for
maintenance demand, but the cost of these equipments should be afforded by the utilities.
4. During the contract period, the system provider will charge a certain percentage from electric
revenue of the electric usage from the end users.
5. The electricity price will be considered to increase with the annual inflation rate. The population of
users and the electric demand are assumed to be stable throughout the contract period. The
contract period is as long as the system life cycle period that is 30 years.
Scenario analysis
According to the smart grid PV system business model, the net present
worth (NPW) of the system should be calculated in order to determine the system breakeven point of
the system provider. NPW of the smart grid PV system is equal to present worth of the electricity
revenue (PW R) minus present worth of the system life cycle cost (PW C). It can be expressed as Eq.
(17). While the PW C of system life cycle cost is determined by the present value of the system capital
cost, installation cost, maintenance cost, environmental cost, and the federal ITC that is expressed in
Eq. (18). In the business model, the maintenance cost is assumed as a yearly constant value.

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(17)
(18)
(19)
j = 1, 2, ~ , 30
where (%) stands for the percentage of the electric charge shared by the system provider, A
represents for the area of PV arrays, Pe is the unit electricity price, Titax means the income tax rate.
As for the PW c, it is constructed by the smart grid PV system capital cost, O&M cost, environmental
cost, and the federal investment tax credit. PW c in the right part of Eq. (18) will be elaborated in the
following paragraphs.
The system capital cost consists of the capital cost of PV generation components including PV
arrays, storage battery banks, and AC/DC inverters. The capital cost of the smart grid contains
communications system (Ccon, $), AMI gatekeeper (Cami, $), and smart meters (Cme, $). The present
value of the system capital cost can be formulated as the following Eq. (20).

(20)
l = 10, 20, 30
j = 5, 10, ~, 30
Investment tax credit concerns According to the federal ITC, the renewable energy project can
receive 30% of the project capital cost as credit. The ITC in this research can be expressed as Eq.
(21)

(21)
Environmental cost
The environmental cost is related to the emission of CO2 as compared to
the same amount of electricity generated by a traditional power plant. In Alaska, the natural gas
power plant is taken as the reference. The PV generation system does not emit any greenhouse
gases such as CO2, NOx and O3, and other health damaging gases during the operation period.
Considering the severe global warming issue, a carbon trading policy has been adopted to resolve
the problem. Because of this issue of global warming, the carbon emission cost savings should also
be calculated into the system cost. If power plants such as natural gas power plants generate the
same amount of electricity as the PV system, the cost charged for CO2 emission should be paid by
the natural gas power plant. The environmental cost is equal to the total PV system electricity output
multiplied by the amount of CO2 unit electricity emission by natural gas power plants. Referring to the
Chicago Climate Exchanges data of the CO2 trading contract price during the last six years, the
average trading price can be obtained at $2.3124/ton (Chicago Climate Exchange), which is shown in
Figure 7.

Figure 7. Carbon trading price from 2004 to 2010 (Chicago Climate Exchange)

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The national average of CO2 emission by electricity generation is 1.34 lbs/kWh (U.S. DOE, 2004),
which can be converted into 0.608 ton/1000 kWh. The environmental cost can be formulated as
shown in Eq. (22).

(22)
By substituting Eqs. (20), (21), and (22) for Eq. (18), the systems present worth of the life cycle cost
can be obtained. Then by combining Eqs. (18) and (19) with Eq. (17), the systems net present worth
can be obtained.
RESULTS
The PV Electricity Conversion Model
Entering the climatic data presented in Table 3 into the photovoltaic analysis software, the unit PV
electricity output at different tilt angles can be calculated. The range of tilt angle is chosen from
angles 24 to 90 with 2 as an interval. The tilt angle of this research case is assumed to be set at
two different angles during the year; one is the predictable optimal tilt angle in the winter, and the
other is that in the summer.
Table 3. PV electricity outputs (kWh) at different tilt angles
Winter
64
66
68
70
October
63.3
63.4
63.4
63.4
November
35.1
35.3
35.5
35.7
December
22.1
22.3
22.5
22.7
January
26.9
27.1
27.3
27.5
February
61.8
62.0
62.2
62.3
March
90.8
90.4
90.0
89.5
Total
300
300.5
300.9
301.1
Summer
April
May
June
July
August
September
Total

46
107.2
114.7
160.8
142.3
127.2
104.4
756.6

44
107.4
115.6
162.3
143.5
127.7
104.1
760.6

42
107.5
116.4
163.8
144.6
128.1
103.6
764.0

40
107.6
117.1
165.2
145.7
128.4
103.1
767.1

72
63.3
35.8
22.9
27.6
62.3
89.0
300.9

74
63.1
35.9
23.0
27.7
62.3
88.3
300.3

76
62.9
36.0
23.1
27.8
62.2
87.5
299.5

78
62.6
36.0
23.2
27.9
62.1
86.7
298.5

80
62.2
36.0
23.2
27.9
61.8
85.8
296.9

38
107.5
117.8
166.5
146.7
128.6
102.4
769.5

36
107.4
118.5
167.6
147.6
128.7
101.7
771.5

34
107.1
119.0
168.6
148.4
128.6
110.9
782.6

32
106.8
119.5
169.5
149.0
128.5
100.0
773.3

30
106.4
119.9
170.2
149.5
128.3
99.0
773.3

The monthly PV outputs are plotted in Figure 8 and Figure 9. Comparing the unit PV electricity
outputs under different tilt angles, Figure 8 shows that the PVs can achieve the highest output in
June, which is 170 kWh/m2. Figure 9 shows that December is the lowest month of the PV output,
which can just reach around 22 kWh/m2 no matter what the tilt angles are. From the photovoltaic
analysis software results, Table 7 shows that at a 34 tilt angle in the summer (the sites latitude
minus 29), the PV arrays produce the highest accumulative electricity. On the other hand, Table 7
illustrates that when the tilt angle is at 70 in the winter (the sites latitude plus 9), the PV arrays
produce the highest accumulative electricity. According to the data in Table 5 and simple calculation,
the PV outputs during the winter just contribute 28% of the annual outputs during the year. The rest of
the energy is contributed in the summer. However, in the whole year, June is ranked as number one
for PV electricity output with an average of 168.6 kWh/m2. Consequently, July and August are ranked
as number two and three, which have outputs of 148.4 and 128.6 kWh/m2, respectively. The lowest
month of PV electricity output is December, which just produces an average of 22.7 kWh/m2. January
and November are ranked as second and third for the lowest monthly electricity outputs with 27.5 and
35.7 kWh/m2, respectively.

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Figure 8. PV electricity output at different tilt angles in summer

Figure 9. PV electricity output at different tilt angles in winter

From the results, the software recommends that the PV arrays tilt angle should be set at 34 in the
summer and 70 in the winter in order to get the highest unit area electricity output. After obtaining the
two tilt angles in the year, the monthly unit electricity output in summer and winter can be combined
together into a whole year as shown in Figure 24. After determining the optimal tilt angles in summer
and winter, they will be taken as constants into the system scale algorithm to determine the optimal
scale of the smart grid PV system.

Figure 10. Monthly PV electricity output

The PV Generation System Scale

Based on that, 500 sets of PV panels, 44 sets of AC/DC inverters, and 88 sets of storage battery
banks are needed for the system. Table 4 gives parameters for the PV generation system scale
calculation. The inflation rate is used to calculate the annual escalation of the electric price increase.
The detailed system scale is described in Table 5.
Table 4. Parameters for cost analysis
Rate
Percentage
IRR
8%
Inflation rate
3.7%
ITC
30%

Sourece
Assumption
U.S. bureau of labor statistics
The American Recovery and Reinvestment Act of 2009

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Table 5. Scale of the PV generation system

Components
Results
Specifications
PV array
496 sets
One module contains 60 cells with each cell size 256mm 256 mm
AC/DC inverter
44 sets
5 KW capacity
Battery
88 sets
24V, 700Ah Gel battery

After calculating the scale of PV arrays, we can also obtain the system electricity cost and the total
PV electricity outputs based on the scale of PV arrays. The system electricity cost is 34.2 cents under
this condition. In order to provide sufficient PV electricity to satisfy electric demand of the ADM
building during the summer, the PV generation system can produce 750,516 kWh per year, while
95,550 kWh is surplus, which can be charged into the storage battery banks. Table 6 illustrates that
PV electricity can support more than 80 percent (83.0%) of the ADM buildings annual electricity
demand, while the rest of the electricity can be supplied from the municipal electric grid. Within the
integration of the PV generation system, it can mitigate 1,055 tons of CO2 emission.
Table 6. Electrical production and demand of the smart grid PV system
Electricity fraction
Energy amount (yearly)
PV system
750,516 kWh
Municipal grid
157,494 kWh
ADM building consumption
908,010 kWh
Surplus electricity from PV
95,550 kWh

Percentage
83.0%
17.0%
100.0%
10.5%

Scenario Analysis of the Smart Grid PV System

According to the smart grid PV business model, the system provider will charge the transaction cost
as their return on investment. However, how much percentage of the electric revenue should be
charged in order to achieve the projects financial balance for the system provider? Also, how many
residents using the system can make the system provider become profitable during the contract
period? It is assumed that the system users (residents) will vary from 100 to 200. As it was mentioned
in the previous chapter, the medium unsubsidized electricity price is 46.8 cents/kWh in off-grid rural
Alaskan communities. It is assumed that 46.8 cents/kWh will be charged to residents in this research.
Under the assumed unit electricity price, the percentage of electric revenue charge is assumed to
vary from 25% to 60% within 5% as an interval.
In Figure 11, we assume all the residents will use the system. Based on that, a series of IRRs are
calculated according to a different percentage of electric revenue charge. Figure 11 and Table 7
illustrate that this system may be economically feasible to the system provider when it can charge
more than 26% from the electricity price so that the IRR can be above 8% which can at least meet the
interest rate.

Figure 11. System IRR under different percentage of electricity charge

Table 7. Results of system IRR in different percentage of share
Percentage of charge %
25
30
35
System IRR %
7.58
9.61
11.50

40
13.29

45
15.01

50
16.68

55
18.32

60
19.93

Based on the results above, we select 25, 35, 45, and 55 percent as the electricity percentage of
charge for the payback period research, which is shown in Figure 12. With the electricity charge at 25
percent, the system provider cannot make any profit during the project life cycle time. However, when
compared to a 35 percent electricity charge, the system is more attractive. The project payback period
is in the 17th year. With 45 and 55 percent of the electricity charge, the payback period increases in
the twelfth and eighth year, respectively.

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Figure 12. Project payback period under different percentage of share

However, in the real situation, residents in the off-grid rural Alaskan communities may not all accept
using the smart grid system. Also, the employment of smart meters and AMI gatekeepers varies in a
certain range. In this situation it is assumed that residents who accept using the smart grid system
vary from 100 to 200 with 20 people as an interval. The employment of smart meters and AMI
gatekeepers varies from 25 percent to 50 percent of the population being served. At the same time,
the percentage of electricity charge also varies from 25 to 60 percent within 5 percent as an interval.
The detailed results are shown in Figure 13 and Table 8.
The results show that the system IRR increases when the percentage of electricity charge, the
population being served, and the employment of smart meters and AMI gatekeepers increase. At an
electricity charge of 25 percent, the IRRs are all under eight percent, no matter what population is
being served and if the employment of smart meters and AMI gatekeepers changes. The system can
begin to become feasible to the system provider when 160 residents use the smart grid, 30 percent of
electricity is charged, and 40 percent of the meters and gatekeepers are employed. However, when
the percentage of electricity charged is 45 percent and even higher, it can be economically feasible to
the system provider even if the other two parameters change.

Figure 13. System IRRs under different electricity charge, serving population, and employment of smart meters & AMI gatekeepers
Table 8. Data for system IRRs under
gatekeepers
Charge (%)
25
Population
100
2.30
120
3.90
140
5.10
160
6.10
180
6.90
200
7.60

different electricity charge, serving population, and employment of smart meters & AMI
30

35

40

45

50

55

60

4.00
5.70
7.00
8.00
8.90
9.60

5.60
7.30
8.70
9.80
10.70
11.50

7.00
8.80
10.20
11.40
12.50
13.30

8.30
10.20
11.70
13.00
14.10
15.00

9.50
11.50
13.20
14.60
15.70
16.70

10.70
12.80
14.60
16.00
17.30
18.30

11.90
14.10
15.90
17.50
18.80
19.90

Smart meters
employment
0.25
0.3
0.35
0.4
0.45
0.5

Based on the system cost analysis, a sensitivity analysis was done in order to figure out which are the
most and least sensitive parameters affecting the system EAC. In the sensitivity analysis, the
sensitive parameters include the system components capital cost, ITC, IRR, and system life cycle.

598

The cost range of this analysis is from 5 percent to 130 percent. As in Figure 14, it is evident that the
communications system is the most positive sensitive parameter, while the most negative parameter
is the system life cycle.

Figure 14. System sensitivity analysis

CONCLUSIONS
The purpose of research is to access the feasibility of a smart grid PV system application in off-grid
rural communities from technical and economic perspectives. Results of the PV electricity conversion
model show that the best PV array tilt angle in the case study site is 70 in the winter and 34 in the
summer, where the azimuth angle is zero. It means the PV arrays face to the south, and they are a
flat-plate non-tracking system. The tilt angles will vary based on different latitudes in the subarctic
region.
Based on the PV generation system scale algorithm, the studied number of PV modules is 496. Each
module includes 60 cells, which are 256mm 256mm in size. Fifty-four sets of AC/DC inverters
should be used, with each inverter having a 5 kW capacity. Eighty-eight sets of gel batteries (24V,
700Ah) are studied to be included in the PV generation system.
The smart grid PV system business model helps make a series of analyses.
According to the median electricity price, 46.8 cents/kWh, in the off-grid rural Alaskan
communities. The percentage share of the electricity charge should be higher than 26 percent
for the system provider. This kind of project can be attractive based on the fact that such a low
percentage can let the system provider make a profit. As for how much profits the system
provider and the utilities can make, it really depends on their contract negotiation of the
percentage of electric revenue charge.
With a 25 percent electricity charge, the IRRs all remain under eight percent no matter what
population is being served and what changes may be made in the employment of smart meters
and AMI gatekeepers. The system can begin to become feasible to the system provider when
160 residents use the smart grid, 30 percent of electricity is charged, and 40 percent of meters
and gatekeepers are in employment. However, when the percentage of electricity is charged at
45 percent and even higher, the system can be economically feasible to the system provider
even if the other two parameters change.
Under the current investment tax credit, the system electricity cost (37.7 cents/kWh) from the
proposed smart grid PV system is lower than the unsubsidized electricity price (46.8 cents/ kWh) in
the off-grid rural communities. From this result, it is evident that the smart grid PV system can be
economically feasible in the off-grid rural Alaskan communities. With the cost of system components
decreasing and the system life cycle increasing, the smart grid PV system can become a more
attractive option for the subarctic regions such as those in the State of Alaska.
This research contributes a new possible approach to help people reduce the extremely high
electricity cost in the off-grid Alaskan communities. The analysis is done from technical and economic
perspectives, which show that the smart grid PV system can be feasible when applied in off-grid rural
communities in the subarctic regions. However, the system may also encounter some problems.
These problems may be finished in the further research.
PV arrays can work in most Alaskan regions during the summer. However, it is not wise to use
PVs in the west coastal Alaska and Aleutian Islands, because of the good wind and rainy
summer.

599

The logistic issue of batteries is recommended to be studied in the future work.

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Buresch, M, 1983, Photovoltaic Energy Systems: Design & Installation. New York, McGraw-Hill
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Crimp, P.M., Colt, S., Foster, M.A., 2009, Renewable Power in Rural Alaska: Improved
Opportunities for Economic Deployment, 1-1.
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EnerNex Corporation.
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Supply Chains, 2002 Rural Alaska Energy Conference, Anchorage, AK.
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Supply Chains, University of Alaska Anchorage.
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Solution for the Next-Generation Energy Network.
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National Energy Technology Laboratory.
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Power from the Sun.
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Office, Austin, Texas, Estimating PV system size and cost, Fact Sheet No. 24: 1-4.
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Alaska Solar Tour.
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August 13, 2010, Smart Meter Installation Progress.
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energy Supply Chains, 2002 Rural Alaska Energy Conference, Anchorage, AK.
Website: www.nrel.gov/gis/solar.html, Accessed on February 22, 2010, U.S. Department of Energy:
National Renewable Energy Laboratory. (2004), Dynamic Maps, GIS Data, & Analysis Tools.

600

Heat Dissipation Performance Analysis of High Heat Flux Radiator

123

Zhu kai

Yang yang Wang yabo Wei jie Cui zhuo

(1.Key Laboratory of Refrigeration Technology of Tianjin University of Commerce,300134)

2.Environment Engineering College of Tianjin University,300072
3. Key Laboratory of Efficient Utilization of Low and Medium Grade Energy(Tianjin University),Ministry
of Education,300072

Abstract: At present, large computer servers usually have dozens or even hundreds of pieces of
CPU. The servers are asked to run uninterruptedly for 24 hours a day for the special nature of work.
The chips of the server with better performance are always in the high load condition accompanied
with higher heat budget. The heat dissipation problem of high heat flux components, i.e. CPU is
focused by industry experts all the time. How to ensure the dissipation of higher heat flux of the
component and how to keep lower energy consumption of heat dissipation have become urgent
problem to be solved for multiple industries. A kind of heat dissipation device, in which the heat pipes
are embedded in the fins in a specific way and are integrated with the bottom plate of the radiator, is
proposed in this paper. The core role of the heat pipes is to transfer the heat which is generated in the
high heat flux component to the constant temperature plate and the fins of the radiator quickly, and
then the heat is taken away by air convection. The focus of the study is not to explore the mechanism
of heat piper but to mainly discuss the energy saving and energy conservation with using basic
research in high heat flux devices. The performance of the radiator is researched by experimental
comparison and analyzed by numerical simulation. The results indicate that to improve the
performance of radiator depend not only the measures of heat transfer enhancement but also the
degree of synergy between the flow and temperature fields. Based on the experimental research,
the flow and temperature fields around the radiator are experimentally measured by PIV, and then the
heat transfer process are analyzed by field synergy principle. Finally, the conclusions with reference
values are obtained.
Key words: high heat flux component, radiator, PIV, field synergy analysis
Introduction
High-performance computer servers which are accompanied with a sharp increase of heat flux
during their work process have high-speed and large-scale data computing capabilities. As is well
known, CPU of the large computer is the most typical component of high heat flux. With
microelectronic technology and manufacturing process becoming more and more sophisticated, the
number of components integrated on one chip is also increasing. At present, the number of VLSI
(Very Large Scale Integrated Circuits) components has reached up to about 105 [1]. As peoples
demand of high-performance of large and very large computers is increasing, CPU heat dissipation
becomes a bottleneck which restricts the development and application of computer because the
performance of the CPU is the key to evaluate the performance of the computer [2-3]. As is well
known, the failure rate of electronic component increases exponentially with the increase of working
temperature. When the component temperature is above 70-80, the reliability will decrease by 5%
at every 1 increasing. The higher temperature will endanger the semiconductor junctions, damage
the connected interface of the electrical circuit and increase the conductor resistance and mechanical

601

stress damage, and hence influence the stability, mechanical strength and service life of the chip,
eventually resulting in a heat-induced failure. Studies have shown that more than 55% failure of the
electronic equipments is caused by high temperature [4]. So how to dissipate the higher heat in a
highly effective way and keep the temperature of the high heat flux device at a low level has become
an urgent problem.
In recent years, heat pipe technology is widely used in the heat dissipation region of PC and
many related papers are published [5-8]. In particular, the heat pipe and radiator are combined as a
whole for cooling electronic equipment and that achieves remarkable effects. Wei [9] studied in detail
the design method of flat heat pipe (FHP) in rectangular flow channel and the heat transfer
performance of chips. Mochizuki [10] experimentally studied the FHP cooling performance and
indicated that flat heat pipe radiator is an effective way to solve the cooling problems of chip. Grubb
[11] conducted CFD simulations on an aluminum radiator whose base are flat plate heat pipe. Sauciuc
[12] experimentally compared the heat transfer performance between flat heat pipe radiator and
solid-metal-base radiator. Y. Avenas et.al [13] investigated flat heat pipe which is used for electronics
cooling and analyzed the thermal resistance of flat heat pipe.
Based on years of research, we propose a radiator in which heat pipes are embedded in the
base plate and the condenser section of the heat pipe and fins are integrated as a whole. The effect of
the heat pipes is to deliver heat of CPU to the base plate of the radiator, and then the heat is removed
by forced convection of the fins which is embedded in the base plate. To check up the thermal
performance of the radiator, numerical simulations and experiments were conducted, and the results
were compared with FHP radiator in order to quantificationally describe the cooling performance of
the radiator. In the study, we found that not only heat transfer enhancement methods but also the
synergy degree between fluid velocity field and temperature field could affect the thermal performance
of the radiator. Guo Zeng Yuan proposed the field synergy theory in the process of studying
convective heat transfer and indicated that convective heat transfer performance depends primarily
on four parameters, namely, the velocity of the fluid, the physical properties of the fluid, the
temperature difference between the fluid and the wall and the synergy angle. The field synergy theory
can be also expressed as that the degree of synergy between velocity field and temperature field
directly affect the thermal performance of convection [14]. The theory of factors influencing the heat
convection has been studied by large numbers of scholars and has been theoretically and
experimentally validated [15-19].
Based on the physical model of the radiator which is generated by PRO-E software, the velocity
and temperature fields around the radiator in the test duct are obtained by fluid-solid coupled
numerical simulation. At the same flow and heat transfer conditions, the field synergy theory is used to
analyze the angle between the velocity vector and temperature gradient vector, and the relationship
between the heat transfer intensity and the field synergy are researched. Meanwhile, in this paper the
digital particle image velocimetry technology (PIV) are used to obtain the flow field around the
radiator, and the relationship between the radiator with high heat flux components and the operating
parameters are researched.
2. Simulation of radiator structure and the temperature field
Figure 1 shows the radiator structure in which the condensing section of heat pipe is
strengthened. The bottom plate of the radiator is divided into three sections and a total of five heat
pipes are embedded in the bottom plate. The middle section of the three cylindrical heat pipes are

602

embedded in the bottom plate and the ends are embedded in the fins. The other two cylindrical heat
pipes are bent into U-shaped. One-third of these two bent heat pipes are embedded in the bottom
plate and the remaining two-thirds are embedded in the fins. The bent sections of the heat pipe are
located outside of fins. As can be seen from the illustrated structure, the condensing section of all the
5 heat pipes are embedded in fins. The diameter of heat pipe is 6mm. The material of the bottom plate
is copper, and the fin thickness is 0.5mm. It should be noted that the area of this radiator bottom plate
is half of that of the flat heat pipe radiator.

hot-wire anemometer

T out

Tin
Fan

P
Air

Radiator
Thermal diffusion plate
Adiabatic apparatus

T1
T2

Simulation of
CPU heat source

T3

DC
voltage regulator

Heating element

Fig.1 The equipment figure of experimentation

The radiator is placed in the duct shown in Figure 2. The numerical simulations are conducted
under the following assumptions: (1) the fluid satisfies the Boussinesq assumptions; (2) physical
parameters of fluid and solid are constant; (3) the fluid is incompressible; (4) the flow is steady; (5) the
fluid on the wall is no wall-slip; (6) the heat pipes are in good contact with fins and bottom plate of the
radiator, and the contact thermal resistance is negligible; (7) the effects of natural convection and the
radiation heat transfer can be neglected.
The mean air velocity of inlet in experimental channel is 3m/s and the heat flux is 44.3W/cm2. The
numerical results of temperature distributions are shown in Fig. 3 and Fig. 4. Fig. 3 shows
temperature distribution of the five heat pipes in the radiator. Figure 4 is the temperature distribution
on the top of the fin.

Fig.2 The radiator with heat pipe for CPU

Fig.3 3 m/s PIV three-dimensional

velocity contour map

603

Fig.4 The velocity vector diagram of 3 m/s

Fig. 5 the velocity streamline of 3 m/s

under experiments section wind tunnel

under experiments section wind tunnel

Fig. 3 shows that the highest temperature of the middle three heat pipes (evaporating section)
can reach up to 41.53. The highest temperatures on both sides of the heat pipes are gradually
reduced, and the minimum temperature of the heat pipe is 40.06. The temperature difference is
1.57. On the whole, the temperature decreasing rate is relatively uniform.
Fig. 4 shows that the highest temperature of the fins is 41.06, the lowest temperature is
40.01 and the temperature difference is 1.05. By comparing the temperature distributions of fins
with that of heat pipes, we find that the temperature gradient decreases, which makes the heat
spreading as soon as possible and efficiently.
In order to illustrate the performance of this new type of radiator, we make a comparison between
the new radiator and flat heat pipe radiator which has a good effect on chip cooling. Table 1 gives the
temperature comparison of the two kinds of radiator under different heat flux (24.3 W/cm2 and 68.6
W/cm2 respectively) with the same mean air velocity of inlet.
Table 1 Heat pipe body temperature distribution of two kinds of heat pipe radiators
Heat flux density
T

24.3 W/cm2

68.6 W/cm2

min

max

mean

min

max

mean

FHP radiator

42.82

28.23

25.525

25.89

44.56

34.615

Enhanced radiator

20.47

21.99

21.23

23.76

25.37

24.565

2.35

6.24

4.295

2.13

19.19

10.05

The bottom plate area of the new radiator (condensing section getting enhanced) is half of that of
the flat heat pipe radiator when the physical dimensions of the two kinds of the radiators are the same.
It means that thermal performance of the new radiator can be significantly improved by strengthening
heat transfer in condensing section of heat pipes. Meanwhile, the bottom plate has better temperature
uniformity because of its smaller area and that is good for heat dissipation of the chip hot spots [20].
As previously mentioned, the radiator performance is related to the heat transfer enhancement
methods and the synergy degree between flow field and temperature field around it. Heat conduction
plays a key role in the heat transfer process from inside to the outside of radiator. However, the major
way of heat transfer between the radiator and the air around the radiator is heat convection. So the
temperature difference between the fluid and wall and the synergy angle between the velocity field
and the temperature field can directly reflect the heat convection performance.
3. PIV and numerical simulation
PIVparticle image velocimetry) is a non-contact measure technology of flow field. The overall

604

structure of the flow field in the plane and transient images are obtained by testing the flow field [21].
The flow field is analyzed and studied by the images characteristics of the flow. The PIV is used to get
the flow field in this experiment. The experimental conditions are as follow: (1) heat flux density is
constant, (2) the air velocity changes between 3~6m/s. When the radiator in the duct reaches steady
condition, the smoke is used as tracer particles to get the air flow field around the radiator. Comparing
the data and images got from experiment with the results of simulation, the simulation results agree
well with these of experiments.
Fluid-solid coupled mechanics is an important multidiscipline of fluid mechanics and solid
mechanics, and fluid-solid coupling is generally divided into two categories: one-way flow-solid
coupling and two-way flow-solid coupling. This paper uses the one-way flow-solid coupling, and the
boundary changes of flow field can be ignored since solid boundary changes very small when the fluid
flows through the solid surface. The heat of the radiator is dissipated by forced convection in the
channel. The air flow has no effect on the deformation of the radiator and also has slight effect on the
structure of the flow field, so the numerical simulation employs one-way flow-solid coupling for
analysis and calculation.
Taking velocity of inlet 3m/s in the experimental channel as an example, Fig. 3 shows the
three-dimensional velocity contour at constant value of the experimental section obtained by PIV. Fig.
4 and Fig. 5 show the velocity vector and the streamline obtained by simulation respectively.
4. Flied synergy analysis of radiator
4.1 Introduction of field synergy analysis

According to the radiator's working condition, the flow is assumed to be two-dimensional, steady
and laminar. The energy equation for incompressible fluid is expressed as follows:
T

cp [u x + v y ] = y [ x ]

3-1

where is the density of the fluid, Cp is the specific heat at constant pressure, is the heat
conduction coefficient, u is the velocity of X-direction, v is the velocity of Y-direction. The energy
equation is integrated in both sides in the thermal boundary layer.

t ,x

c p U T dy

T
y

qw x 3-2

T
y
The dimensionless variables U
are added to Equation 3-1:
1

Re x Pr U T d y Nux
0

3-3

Where u is the fluid velocity vector, T is the fluid temperature gradient and is the angle between
the velocity gradient vector and the temperature gradient vector. As mentioned above, the heat
convection performance depends not only on the velocity, temperature difference and fluid properties
but also on the matching degree between velocity field and the temperature field (the angle between
the velocity gradient vector and the temperature gradient vector). When the other conditions are
constant, the more synergy we applied to the velocity gradient vector and the temperature gradient
vector, the more benefits of heat transfer we could get. According to the basic principles of synergy,
the middle section of the radiator is selected. The temperature contour and velocity contour of this
section are obtained by simulation, and then the velocity gradient vector, the temperature gradient
vector and synergy angle are obtained. These results are studied to get the optimal operation
condition of heat transfer enhancement.

605

4.2 Filed synergy analysis under the same velocity of inlet and different heat flux

Fig. 6 and Fig. 7 show the comparison between temperature contour and the velocity gradient
vector of the bottom plate of the radiator under the condition that the velocity is 4.5m/s and heat flux is
24.3W/cm2. The angle between the temperature gradient vector and the velocity gradient vector is
43under the above condition. The angles between the temperature gradient vector and the velocity
gradient vector are calculated under the condition that the velocity is 4.5m/s and heat flux is
44.3W/cm2 and 68.6W/cm2 respectively, and the results are 32and 40respectively. The direction of
flow is indicated as arrow shown in Fig. 6. Table 2 shows the maximum value, the minimum value and
the average value of the velocity gradient and the temperature gradient in the direction mentioned
above with the same synergy angle.

Fig. 6 temperature distribution

Fig. 7 the velocity vector diagram

2

under the heat flux density is 24.3 W/ cm2

under the heat flux density is 24.3 W/cm

Tab2 Temperature and velocity differences under different heat flux density
Heat flux density

24.3 W/cm
Max

T
U m/s

44.3 W/cm

68.6 W/cm

Min

Ave

Max

Min

Ave

0.12

0.06

0.09

0.26

0.23

0.245

7.433

2.478

4.955

7.435

2.483

4.959

Max

Min

Ave

0.11

0.18

2.483

4.959

0.25
7.435

U T U T cos U T cos 43 2.478 0.06 0.731 0.1087

U T U T cos U T cos 43 7.433 0.12 0.731 0.652
U T U T cos U T cos 32 2.483 0.23 0.848 0.4843
U T U T cos U T cos 32 7.435 0.26 0.848 1.6393
U T U T cos U T cos 40 2.483 0.11 0.766 0.2092
U T U T cos U T cos 40 7.435 0.25 0.766 1.424

Under the three conditions mentioned above, the synergy angle is 43, 32, 40respectively. The
uneven distribution of the velocity is because of the increase of viscosity and decrease of density of
the air which is heated by the radiator. The changes of the air physical parameters lead to the sharp
variation of air velocity in the channel.
When the heat flux density is increasing and the velocity difference is constant, the temperature
gradient will increase. When heat flux density increases to 68.6 W/cm2, the temperature gradient

606

decreases. From the data shown in Table 2, it can be found that when the velocity of inlet is constant
and the heat flux density of chip increases gradually, the integrated function of the second operating
condition (velocity 4.5m/s, heat flux density 44.3W/cm2) has the largest value that is obtained by
synergy analysis of the results. Therefore it has the best heat transfer performance because the
synergy degree is the best.
4.3 Field synergy analysis under the same heat flux density and different mean velocity of inlet

Figure 8 to Figure 11 show the comparison between temperature contour and the velocity vector
under the condition that the heat flux density of the radiator is constant at 44.5 W/cm2 and the velocity
of inlet is 4.5m/s and 6m/s respectively. The angle between the temperature gradient vector and the
velocity gradient vector is 33and 45.
Keeping the heat flux constant at 44.5 W/cm2, the angle between the temperature gradient
vector and the velocity gradient vector is 45with velocity of inlet 3m/s. The minimum and maximum
values of velocity and temperature gradients are provided in the direction of flow shown in Figure 8
and Figure 10 with constant synergy angle. Table 3 shows the maximum value, the minimum value
and the average value of the velocity and the temperature differences under different velocity.

Fig. 8 temperature distribution

Fig. 9 the velocity image

under the speed of 4.5m/s

under the speed of 4.5 m/s

Fig. 10 temperature distribution

Fig. 11 the velocity image

under the speed of 6m/s

under the speed of 6m/s

Tab.3 the minimum, maximum and average values of velocity and the temperature differences with different velocity
3m/s

Velocity

4.5m/s

6m/s

Max

Min

Ave

Max

Min

Ave

Max

Min

Ave

0.22

0.12

0.17

0.27

0.23

0.25

0.26

0.11

0.18

U m/s

6.964

3.309

5.136

7.435

4.959

6.197

9.901

6.601

8.251

U T U T cos U T cos 45 3.309 0.06 0.707 0.14037

U T U T cos U T cos 45 6.964 0.22 0.707 1.0832
U T U T cos U T cos 32 4.959 0.23 0.848 0.9672

607

U T U T cos U T cos 32 7.435 0.27 0.848 1.70232

U T U T cos U T cos 45 6.601 0.11 0.707 0.51336
U T U T cos U T cos 45 9.901 0.26 0.707 1.82

Under the three conditions mentioned above, the synergy angle is 4532, 45 respectively.
From the calculations above and the data in Table 3 it can be found that, when the heat flux density is
constant and the mean velocity of inlet increases, the temperature difference will increase gradually.
Although operating condition 3 has a larger synergy angle than operating condition 2, the product of
the three parts is higher than that of operating condition 2 when the velocity and temperature gradient
values are largest. However, the product of velocity gradient, the average value of temperature
gradient and the cosine value of the synergy angle is lower than that of operating condition 2 when the
synergy angle is constant. Considering the average values of field synergy, heat transfer performance
of operating condition 2 is better than that of operating condition 3. Meanwhile it proves that using filed
synergy theory to analyze the heat transfer enhancement of radiator is feasible.
In order to check up the accuracy of our work between the experiment and simulation, Table 4
shows the comparison between those two sets of results. Considering the three-dimensional velocity
contour obtained by PIV and the velocity vector and the streamline got from simulation, we can find
that the main velocity has a relatively high value, meanwhile air velocity in the boundary layer and
vortex region has a relatively low value when the heat flux density is constant. The simulation results
agree well with the experimental results.
Tab.4 Comparison between experimental and simulation results with different velocity
Velocity

3m/s
Max

4.5m/s

6m/s

Min

Ave

Max

Min

Ave

Max

Min

Ave

experiment

5.391

1.347

3.369

7.700

1.925

4.812

10.587

2.646

6.617

simulation

5.421

1.415

3.537

7.897

1.979

4.943

10.633

2.685

6.685

0.029

0.067

0.167

0.197

0.054

0.1307

0.045

0.0382

0.068

In order to compare the air velocity obtained by experiment and simulation across the radiator,
the velocity of mainstream is only analyzed because that the velocity in the boundary layer zone is
lower compared with the mainstream velocity and trailing vortex generates in the boundary layer zone.
From the details of Fig. 3, it can be seen that the velocity boundary layer is thinner that indicates a
good heat transfer performance. From the data of table 4 above, we can see that the experiment
values are smaller than simulation values with the same heat flux density and different velocity. The
reason is that the condition of experimental duct is more complicated than that of simulation.
Meanwhile the uneven smoke distribution leads to the unsteady air velocity. However, the differences
between experiment and the simulation values are slight, so the simulation results are accuracy and
reasonable.
5. Conclusions
The heat transfer enhancement of high heat flux components is investigated in this paper. A new

608

type of radiator whose heat pipe condensing section applied heat transfer enhancement structures is
numerically simulated. The heat transfer performance of this new radiator is compared with that of
FHP radiator with the same working conditions. The PIV is used to test the flow field around the
radiator. The field synergy theory is applied to analyze the heat transfer performance of the radiator.
The conclusions are expressed as follow:
1Radiator with structure of heat transfer enhancement has a better heat transfer performance
than that of FHP radiator by embedding condensing section of heat pipes into fins which reduces the
area of bottom plate of the radiator by 50%. Furthermore, the smaller area of bottom plate is in favor
of improving the temperature uniformity and heat transfer efficiency of the fins.
2By simulating the synergy degree between the velocity filed and the temperature gradient
field around the radiator, the working performance of the radiator can be evaluated from the point of
heat convection. Using PIV to obtain the velocity field of the radiator and keeping other experiment
conditions unchanged, the heat convection performance is evaluated by calculating the synergy angle
between velocity vector field and temperature gradient field. When the synergy degree between the
velocity vector and temperature gradient vector is better, the heat transfer performance is better.
Using the field synergy theory to evaluate the heat transfer performance of the radiator can guide the
selection of working conditions.
3From the experimental results and field synergy theory analysis it can be noted that when
the heat flux density is 44.3 W/cm2 or the velocity of inlet is 4.5m/s and other conditions are
unchanged at the same time, velocity and temperature gradient are in good synergy, and the radiator
can reach optimal performance. By combining PIV experiment and field synergy theory analysis to
investigate the radiator performance, it provide theoretical basis to solve the heat dissipation problem
of high heat flux components and design the radiator optimally and improve the experiments.
Acknowledgements
This work is supported by Project (No.51376137) of Chinese National Science Foundation and
Project (No.13JCZDJC27300) of Chinese Tianjin City Science Foundation.
NOMENCLATURE
A

area, m2

cp

specific heat, J/kgC

temperature, C

velocity, m/s

thermal conductivity, W/mk

609

References
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performance of vapor chamber under hot spot heating conditions, Proceedings of IPACK 2005
ASME Inter PACK '05, 2005,San Francisco, California, USA.
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InterPACK05, 2005, San Francisco, USA.
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Cooling. Proceedings of InterPACK01, 2001, Hawaii, USA, p.1-10.
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[6] Vasiliev, L, Lossouarn, D., Romestant, C., et al., 2008, Loop heat pipe for cooling of high-power
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[7] Tian Jinying, Zhu Kai, Liu Jianlin, Wei Jie, 2007, Experiments Investigation on Thermal
Conductivity of Flat Heat Pipes Used to Cool Electric Die. Journal of Refrigeration 28(6):18-22.
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with heat pipesCryo. & Supercond 41(2):56-61.
[9] Wei J, Cha A, Copeland D, 2003, Measurement of Vapor Chamber Performance. IEEE
SEMI-THERM Symposium: 191-194.
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[12] Sauciuc I., Chrysler G., Mahajan R., and Prasher R, 2002, Spreading in the Heat Sink Base:
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[17] Guo Z Y, Li D Y, Wang B X,1998, A novel concept for convective heat transfer enhancement
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611

EXPERIMENTAL INVESTIGATION OF SUPERCOOLING REDUCTION AND

FREEZING POINT DEPRESSION OF ETHYLENE GLYCOL SOLUTION
BASED NANOFLUID
*

Songping Mo , Ying Chen, Xianglong Luo, Jun Li

School of Materials and Energy, Guangdong University of Technology
No. 100 Waihuanxi Road, Guangzhou Higher Education Mega Center, Guangzhou 510006, China
*
mosp@ustc.edu

ABSTRACT
Nanoparticles have been proved to be able to reduce the supercooling degree of water and waterbased nanofluids. This study aims to evaluate the potential of ethylene glycol (EG) solution based
nanofluids as a new phase change material for the low-temperature thermal energy storage of
cooling systems. Different mass fractions of TiO2 nanofluids were prepared by adding TiO2
nanoparticles and sodium dodecyl benzene sulfonate (SDBS) into EGH2O solution. The
supercooling degree and freezing point of the nanofluids were investigated in solidification tests. The
experimental results showed that, the TiO2EGH2O nanofluids showed vitrification character during
solidification process; the supercooling degree of the nanofluids was obviously reduced with
increasing mass fraction of TiO2 nanoparticles; the freezing point of the aqueous ethylene glycol
solution was only slightly reduced by adding TiO2 nanoparticles.
Keywords: Nanofluid, Supercooling degree, Freezing point, Ethylene glycol, Ice storage.
INTRODUCTION
Ice storage techniques have been employed to solve the problem of imbalance of supply and
consumption of electrical power. The energy efficiency of ice storage system decreases as the
evaporation temperature decreases. The supercooling of water during solidification process reduces
the energy efficiency of the ice storage system since the evaporation temperature should be lower to
freeze water.
Nanofluids, a suspension of nanoparticles in base liquid, have been considered as a new-type of
phase change material because of their enhanced thermal conductivities (Murshed et al. 2008,
Godson et al. 2010, Ahmeda et al. 2012) and potentials to enhance energy storage efficiency (Liu et
al., 2009; Wu et al., 2009; Kumaresan et al., 2013). Since water is the usually used phase change
material in cooling systems, the previous researchers on nanofluids energy storage primarily focused
on water-based nanofluids. Wu et al. (Wu et al., 2009) found that the supercooling degree of 0.2 wt%
Al2O3H2O nanofluid is reduced by 70.9%, the beginning time of freezing is ahead by 32.9% and the
phase change temperature of nanofluids is about 1 higher than that of the deionized water.
Kumaresan et al. found that the presence of multi wall carbon nanotubes also caused appreciable
reduction in the subcooling (Kumaresan et al., 2013).
Meanwhile, the freezing point (equilibrium phase change temperature from liquid to solid) is another
important parameter for judging the potential application of a phase change material. The phase
change temperatures of water and water-based nanofluids are around 0 . But in some situations
such as brewhouse and chemical plant, the refrigerant temperature should be controlled below 0
and water-based nanofluids would no longer be applicable. Up till now, few investigations on
nanofluid for phase changer materials in low temperature cool storage has been reported. He et al.
developed TiO2BaCl2H2O nanofluid (He et al., 2012) with the phase change temperatures of about
-8.6 and found that, the supercooling degree is reduced by 84.92% with 1.130% volume fraction of
TiO2 nanoparticles.
Ethylene glycol solution is commonly used as the cooling medium if the temperature of the process is
below the freezing temperature of water, for instance, it can be used as a secondary refrigerant in
indirect cooling systems. The changeable phase change temperature of EG solution by conveniently
changing its concentration makes it an alternative phase change material for use below 0 . Another
benefit comes from its ice-adhesion-suppression property. In an ice storage system, ice adhesion to
the cooling wall directly hinders system performance due to the increase of flow and thermal
resistance. A study has shown that ice adhesion was suppressed when the EG solution had relative
high initial mass concentration (4 % and 7 %) of EG (Hong et al., 2004).
The effect of addition of nanoparticles on the supercooling of EGH2O solution has not been studied
to the best of our knowledge. But it has been reported that carbon nanotubes and metal oxide
nanoparticles (Al2O3, MgO) could efficiently lower the freezing point of 50% water/50% ethylene
glycol (EG) solution (Hong et al., 2007).

612

In this study, aqueous ethylene glycol solution was used as a low-temperature phase change
material, and TiO2 nanoparticles were added into the solution to prepare nanofluids. The aim is to
analyze the effect of the suspended nanoparticles on supercooling degree and freezing point of EG
H2O solution.
MATERIALS AND METHOD
Two groups of TiO2EGH2O nanofluids were prepared for measurement by dispersing anatase TiO2
nanoparticles (Shanghai Huzheng nanotechnology Co., Ltd, China) in EGH2O solutions with 10 %
and 18% volume fraction of EG, respectively. Two-step method was adopted to prepare the
nanofluids. In order to enhance the dispersion of the nanoparticles, the anionic surfactant sodium
dodecyl benzene sulfonate (SDBS, analytical reagent, provided by Tianjin Damao Chemical reagent
Co., Ltd, China) was used. The TiO2 nanoparticles and SDBS were added into the EGH2O solutions.
The mass of surfactants was the same as that of the TiO2 nanoparticles in each sample. The
suspension was whisked by a magnetic stirring apparatus (Type 95-1, Shanghai Sile Appliance Co.,
Ltd, China) for 10 min and ultrasonicated by an ultrasonic cleaner (KQ3200DE, Kunshan of Jiangsu
Equipment Company, China) for 40 min. The nanoparticle mass fraction of the samples in each group
was 0.1 wt. %, 0.2 wt. %, 0.3 wt. % and 0.4 wt. %, respectively.
Fig. 1 shows the photographs of the two groups of TiO2EGH2O nanofluids 12 h later after they were
prepared. It indicates that the nanoparticles were well dispersed in the EG solutions. In our
experimental, the nanofluids were tested immediately after preparation to minimize the influence of
the settlement of nanoparticles.

Fig.1. Photographs of TiO2EGH2O nanofluids with (a) 10 vol.% EG and (b) 18 vol.% EG containing (from left to right) 0.1 wt.%,
0.2 wt.%, 0.3 wt.% and 0.4 wt.% TiO2.

The measurement of the particle size and zeta potential of nanofluids was performed and the results
for the TiO2EGH2O nanofluids with 10 vol. % EG are shown in Fig. 2. The absolute values of zeta
potential and the values of particle size indicated that the TiO2EGH2O nanofluids have acceptable
stability. The stability of the TiO2EGH2O nanofluids with 18 vol. % EG was also verified by similar
results.

380
-28

Zeta potential
Particle size

360
340

-32

320

-34

300

-36

280

Particle size (nm)

Zeta potential (mV)

-30

260

-38

240
-40
0.10

0.15

0.20

0.25

0.30

0.35

0.40

Mass fraction of TiO2 (%)

Fig.2. Particle size and zeta potential versus mass fraction for TiO2EGH2O nanofluids with 10 vol. % EG.

613

The experimental setup for the solidification test is shown in Fig. 3. Solidification experiments were
performed for the TiO2EGH2O nanofluids and EGH2O solution. Each sample (10ml) was
transferred into a test tube. The temperatures inside the test tubes were measured by 0.2 mm
sheathed T-type thermocouples with precision of 0.2 . These tubes were immersed into the
thermostatic bath (DLSB-5/40, Zhengzhou Greatwall science instrument and trading Co., Ltd, China).
The bath temperature was kept at -25 during the cooling process. The temperature values of the
samples were recorded by a data logger (Agilent 34970A, Agilent Technologies Co., Ltd, America)
and the time interval of data acquisition was 1 s. Each experiment was repeated seven times to
calculate the mean value of the experimental data.

1- thermostatic bath, 2-nanofluids, 3- thermocouple, 4- tube

Fig.3. Schematic diagram of supercooling degree measuring system.

RESULTS AND DISCUSSION

The typical cooling curves of the TiO2EGH2O nanofluids with 10 vol. % and 18 vol. % EG and
different nanoparticle mass fraction are shown in Figs. 4 and 5. For each sample, the temperature
first decreased to the lowest value Ts and suddenly increased to the highest value Tf then slowly
decreased again. For instance, the position of Ts and Tf of the 10 vol. % EG solution are indicated in
Fig. 4. At the point of Ts the supercooling break down and the sample begins to freeze. The slowly
decreased temperature after the point of Tf indicated that the antifreeze capability of ethylene glycol
made the solidification process show some vitrification character. The temperature of Ts is regarded
as the phase change temperature, i.e., the freezing point. The supercooling degree can be calculated
as

T Tf Ts
(1)

0.0% TiO2
0.1% TiO2
0.2% TiO2
0.3% TiO2
0.4% TiO2

20

Temperature ( C)

10
0

Tf

-10
Ts
-20
0

200

400

600

Time (s)

Fig.4. Cooling curves of TiO2EGH2O with 10 vol.% EG and different nanoparticle mass fraction.

614

30
0% TiO2
0.1% TiO2
0.2% TiO2
0.3% TiO2
0.4% TiO2

Temperature ( C)

20
10
0
-10
-20
0

200

400

600

Time (s)

Fig.5. Cooling curves of TiO2EGH2O with 18 vol.% EG and different nanoparticle mass fraction.

In this way the phase change temperatures can be read from the cooling curves and the supercooling
degree of the EGH2O solutions TEG and the TiO2EGH2O nanofluids Tnf can be calculated. The
specific values are listed in Tables 1 and 2. The results show that the nanoparticles had obvious
influence on the supercooling degree and the beginning freezing time. The efficiency of supercooling
degree reduction can be evaluated by

T (TEG Tnf ) / TEG

(2)
Table 1. Supercooling degree of TiO2-EG-H2O with 10 vol. % EG.
0.0
0.1
TiO2 Mass fraction (%)
-3.99(-3.7)
-4.22
Tf
-12.61
-12.70
Ts
8.62
8.48
T
/
-0.23
Tfnf -TfEG
/
1.62
(TEG -Tnf)/TEG (%)

0.2
-4.56
-10.40
5.84
-0.57
32.25

0.3
-4.22
-8.96
4.74
-0.23
45.01

0.4
-4.21
-6.83
2.62
-0.22
69.61

Table 2. Supercooling degree of TiO2-EG-H2O with 18 vol. % EG.

0.0
0.1
TiO2 Mass fraction (%)
-8.08(-7.85)
-8.01
Tf
-16.43
-15.77
Ts
8.35
7.76
T
/
0.07
Tfnf -TfEG
/
7.07
(TEG -Tnf)/TEG (%)

0.2
-8.31
-12.95
4.64
-0.23
44.43

0.3
-8.28
-11.83
3.55
-0.27
57.49

0.4
-8.15
-11.47
3.32
-0.07
60.24

The supercooling reduction efficiencies of the TiO2EGH2O nanofluids are shown in Fig.6. The
supercooling degree of EG solution based nanofluids was reduced with increasing mass fraction of
TiO2 nanoparticles. As the nanoparticle mass fraction increased to 0.4 wt%, the supercooling degree
was reduced by 69.61% and 60.24% for the TiO2EGH2O nanofluids with 10 vol. % and 18 vol. %
EG, respectively. Similar results were reported for water-based nanofluids with alumina nanoparticles
(Wu et al., 2009) and multi wall carbon nanotubes (Kumaresan et al., 2013), and BaCl2-H2O solution
based nanofluids (He et al., 2012) with TiO2 nanoparticles.

615

80

Supercooling reduction (%)

70
60
50
40
30
20
10 vol.% EG
18 vol.% EG

10
0
0.10

0.15

0.20

0.25

0.30

0.35

0.40

Mass fraction of TiO2 (%)

Fig.6. Supercooling reduction efficiency of TiO2EGH2O with different nanoparticle mass fraction.

Moreover, the beginning freezing time of the TiO2EGH2O nanofluids were ahead of that of the EG
H2O solution, as seen from Figs. 4 and 5. It is due to the supercooling reduction. Since the
supercooling degree of the TiO2EGH2O nanofluids were smaller compared to the EGH2O solution,
corresponding to higher temperature Ts at which the supercooling breaks down, then the cooling time
from the same initial temperature to Ts should be less and resulted in shorter beginning freezing time.
The effect of nanoparticles on the freezing point of EGH2O solution can also be analyzed from the
experimental results. The differences between the freezing point of the TiO2EGH2O nanofluids and
that of the EGH2O solution are also listed in Tables 1 and 2. The freezing point of the 10 vol. % and
18 vol. % EGH2O solution was slightly decreased by adding TiO2 nanoparticles. More remarkable
freezing point depression was reported by Hong et al. (2009). Their results indicated that, 0.1 wt% of
carbon nanotubes, Al2O3 and MgO nanoparticles decrease the freezing point of 50% water/50%
ethylene glycol solution by 5.0, 3.7 and 2.4 , respectively. In contrast to their results, the freezing
point depression of the 10 vol. % and 18 vol. % EGH2O solutions was less than 0.6 in this study.
This may be due to the less fraction of EG, because adding nanoparticles to water did not show
obvious freezing point depression phenomenon (Liu et al., 2009; Kumaresan et al., 2013) or even
increase the freezing point (Wu et al., 2009).
CONCLUSIONS
In this study, aqueous ethylene glycol solution was used as low-temperature phase change material,
and TiO2 nanoparticles were added into the solution to prepare nanofluids. The supercooling degree,
beginning freezing time and freezing point of the nanofluids were investigated to study of the effect of
nanoparticles. The experimental results showed that,
(1). The supercooling degree and the beginning freezing time were reduced with increasing addition
of nanoparticles; as the nanoparticle mass fraction was increased to 0.4%, the supercooling
degree was reduced by 69.61% and 60.24% for the TiO2EGH2O nanofluids with 10 vol.% and
18 vol.% ethylene glycol, respectively.
(2). The freezing point of aqueous ethylene glycol solution was only slightly reduced by
nanoparticles.
The nanofluids showed vitrification character during solidification process; it is recommended that
TiO2EGH2O nanofluid can be an alternative phase change material for cryopreservation of
biological tissues and organs.
ACKNOWLEDGEMENT
The authors gratefully acknowledge the financial support provided by the Natural Science Foundation
of China (Grant No. 51106031).
NOMENCLATURE
T
temperature, C
T
supercooling degree, C
Greek Letters

efficiency of supercooling degree reduction

Subscripts
EG
ethylene glycol
f
freezing
s
supercooling
nf
nanofluid

616

REFERENCES
Ahmeda H. E., H. A. Mohammed and M. Z. Yusoff, 2012, An overview on heat transfer augmentation
using vortex generators and nanofluids: Approaches and applications. Renewable and Sustainable
Energy Reviews 16: 59515993.
He Q. B., Wang S. F., Tong M. W. and Liu Y. D., 2012, Experimental study on thermophysical
properties of nanouids as phase-change material (PCM) in low temperature cool storage. Energy
Conversion and Management 64: 199205.
Hiki Hong, Jong Hyeon Peck and Chaedong Kang, 2004, Ice adhesion of an aqueous solution
including a surfactant with stirring on cooling wall: ethylene glycola silane coupling agent
aqueous solution. International Journal of Refrigeration 27: 985992.
Haiping Hong, Yingsong Zheng and Walter Roy, 2007, Nanomaterials for Efficiently Lowering the
Freezing Point of Anti-Freeze Coolants. Journal of Nanoscience and Nanotechnology 7: 31803184.
Kumaresan V., P. Chandrasekaran, Maitreyee Nanda, A. K. Maini and R. Velraj, 2013, Role of PCM
based nanofluids for energy efficient cool thermal storage system. International Journal of
Refrigeration 36: 16411647.
Lazarus Godson, B. Raja, D. Mohan Lal and S. Wongwises, 2010, Enhancement of heat transfer
using nanofluidsAn overview. Renewable and Sustainable Energy Reviews 14: 629641.
Murshed S. M. S., Leong K. C. and Yang C., 2008, Thermophysical and electrokinetic properties of
nanofluids A critical review. Applied Thermal Engineering 28: 21092125.
Wu S., Zhu D., Li X., Li H. and Lei J., 2009, Thermal energy storage behavior of Al2O3H2O
nanofluids. Thermochim Acta 483:7377.

617

Numerical Investigation on Molten Salt Mixed Convection in Bottom-heated

Horizontal Square Tube
Chao Wang, Yu-Ting Wu, Cong Chen, Bin Liu, Chong-Fang Ma
Affiliation: Key Laboratory of Enhanced Heat Transfer and Energy Conservation, Ministry of Education,
College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124,
China
Address: No 100,Ping Leyuan, Chao Yang district, Beijing
E-mail: wc19900409@126.com

Abstract:
A numerical simulation is presented on the mixed convective heat transfer of molten salts in
bottom-heated horizontal square tube, analyzing the flow and heat transfer characteristics of molten
salt. Temperature, velocity profiles and streamline diagram of each cross-section along flowing
direction are acquired. The results show that under non-uniform heated condition with high heating
flux, shape of main core area changed with the increase of flow distance due to buoyancy effects;
Symmetrical secondary vortex form in channel cross-section area; Increasing Re leads to the
increase of local Nux under the same heating flux; Under the same Re, Nux increases with the
increase of Ri; Good agreement between simulated data and turbulent mixed convective correlation
was reached and deviation is within 15%.
Key words: Mixed convection; Molten salt; Horizontal square tube; Numerical simulation
1. Introduction
In some practical heat transfer process, a large temperature differences is found between solid
surface and fluid. Under the effect of gravity, the buoyancy effects caused by the temperature
difference of density gradient in working fluid cannot be ignored. Mixed convection forms when
buoyancy effect superimposes to mainstream flowing direction. Mixed convection heat transfer
exists due to non-uniform heating conditions in many industrial applications, such as solar receiver,
nuclear reactor emergency closure devices and so on. Numerical simulation and experiments on
mixed convective heat transfer in horizontal channels have been carried out by many researchers.
Studies on the laminar flow, transitional flow and turbulent flow mixed convective heat transfer
of air[1-6], water[7-11], nano-fluids[12-13] and non-newtonian[16] fluid in pipe, tube inserts[17-18] and
eccentric ring pipe horizontal channels[19] can be found in open literature, acquiring the mechanism
that buoyancy effect strengthened convective heat transfer in mixed convection. However, the
research aiming at molten salt mixed convection heat transfer cannot be found in open literatures. It
is quite necessary to study the mechanism of molten salt mixed convection heat transfer for its wide
existence in solar receiver, nuclear reactor emergency closure devices, etc.
2. Flow and Heat Transfer Model in square tube
2.1 Geometric Model and Control Equation
For the flow and heat transfer of molten salt in horizontal square tube, the simulation is done at
the assumption of the liquid is incompressible, the distribution of velocity and temperature is
uniform at the inlet cross-section of square tube and cross-sectional area of square tube is much
smaller than the length of tube. The square tube is 19mm in width, 1000mm in length. Geometric
model of square tube in the simulation is shown in Fig.1.

618

Fig. 1 Geometric model of square tube in the simulation

The flow of the liquid follows the basic conservation law, such as mass conservation,
momentum conservation, energy conservation and so on. Control equations are mathematical
description of these basic conservation laws.
1) Continuity equation: for incompressible flow, the equation is as follows:
( u ) ( v) ( w)

0
x
y
z

(1)

2) Momentum equation: Liquid micro-unit mass quality only stands the gravity from Z axis in
negative direction, the equation is as follows:
uu
x

uv
y

uw
z

2u 2u 2u
p

2
x
y 2
z 2
x

vu vv vw
2v 2v 2v
p

2
x
y
z
y
y 2 z 2
x

wu wv ww
2w 2w 2w
p

2
x
y
z
z
y 2
z 2
x

(2)

3) Energy equation: Ignore the heat source term caused by viscous dissipation, the equation is
as follows:
uT vT wT 2T 2T 2T

2
c

x
y
z
y 2
z 2
p x

In the equation:

(3)

stands for thermal conductivity of fluid, cp stands for heat capacity at

constant pressure, T stands for temperature.

If the fluid is in the state of turbulent flow, the turbulence model equation also need to be taken
into consideration. In this simulation, K- two equation models are utilized, the equation of turbulent
kinetic energy k and dissipation rate are as follows:

k
dk

[( t )
] G k Gb YM
dt xi
k xi

[( t )
] Cl (Gk C3 Gb ) C2
dt
xi
xi
k
k

(4)

In this equation: Gk stands for the production of turbulent kinetic energy caused by mean
velocity gradient, Gb is the production of turbulent kinetic energy caused by buoyancy effect; YM is
the effect of compressible turbulence fluctuating dilatation on the dissipation rate, turbulent viscosity

619

2
is C k
t

Fluent is regarded as default constant, Cl 1.44 C2 1.92 C3 0.99 . The model

constants of turbulent Kinetic energy k and dissipation rate are

k 1.0 , 1.3 .

The definition of dimensionless Re, Pr, Gr, average Nu and local Nux are shown as follows:

Re

vd

; Pr

; Gr

g td 3

; Nu

hd

; Nux

hx d

; Ri

Gr
Re2

(5)

In the equation is kinematic viscositya is thermal diffusivity is expansion coefficient

the relationship is

1
T

The tube wall heat conduction of solid follows the law of conservation of energy and Fourier law,
the heat conduction differential equation can be acquired as follows:
2t
2t
2t

0
2
2
x
y
z 2

(6)

2.2 Boundary Conditions and Verification of Grid Independence

Boundary conditions is set as follows: the velocity inlet boundary is set as entrance boundary to
calculate the fluid speed and inlet temperature; pressure outlet boundary is regarded as outlet; no
slipping happens on tube wall; the heating wall is set as constant heat flux boundary; non-heated
wall is set as adiabatic wall; k- and RNG are applied in this turbulent model; full buoyancy effects.
When solving the equations, convergence is acquired within 4000 steps, the residual of
convergence is between 10-6 and 10-8.
For the verification of mesh independence, the mesh is divided into 5 forms, they
are24x20x100029x28x100038x36x100044x40x100054x48x1000 respectively with heat flux
of 200kW/m2 , inlet velocity at 0.3m/s.With consideration of pressure differences between inlet and
outlet, fluid temperature, accuracy of calculation and time, grid of 44x40x1000 was utilized in this
article.

Fig. 2 Grid independent validation of pressure difference and stream temperature under the condition

620

with heating flux of 200kW/m and velocity at 0.3m/s

2.3 Physical Parameter of the Mixed Molten Salts

In this article, mixed nitrate Hitec salt (NaNO3-NaNO2-KNO3, 7-40-53wt %) is utilized as
working fluid to carry out simulation.
1) Density: the calculation formula of density Hitec is:

2287.7993 0.7484T

(7)

2) Heat capacity at constant pressure: the specific heat at constant pressure in liquid interval is:

c p 1507 0.1T

(8)

3) Thermal conductivity: the calculation formula is:

0.8099 7.827 104 T 1.043 107 T 2

(9)

4) Dynamic viscosity: the calculation formula is:

0.06284 2.253 104 T 2.7903 107 T 2 1.1738 1010 T 3

In the equation: stands for dynamic viscosityPa.s ;

(10)

TtemperatureK

3. Analysis of Numerical Simulation Results

3.1

The

Characte
ristics of
Flow and
Heat
transfer
Fig 3
Cross-sec
tional
velocity
and
streamlin
e profiles
at the
2

condition with heating flux of 200kW/m and velocity at 0.3m/s-y=100,300 and 500

3.1.1 The Characteristics of Flow

As shown in Fig 3, the velocity distribution gradually reduces from mainstream area to layer
area, and velocity of mainstream area is much higher than that of layer area. The main core area
changes with increase of flow distance, its shape transfer from circular to ellipse gradually, due to
molten salt density difference caused by temperature differences between main core area and
heated wall, with influence of gravity, the buoyancy effect leads to this phenomenon. Then the
natural convection caused by buoyancy effect superimposes with forced convection to form mixed
convection. After fluid fully-develops, turbulent region forms in forced convection, the shape of the
main core area is circular; its shape is fixed in spite of the increase of flow distance. This
morphological difference between mixed convection and forced convection in horizontal tube is
clearly proved by this typical shape distinction. At y=100mm, only weak vortexes form at lateral wall,
its flowing direction is from bottom center to lateral wall and then flows back to mainstream area
again. The vortex in two sides occupies a very little part of the whole flowing cross-section, so it
does not cause much influence on mainstream area and fluid in tube wall converges to center. With

621

increase of flowing distance, secondary vortexes form. At y=300mm, complete and symmetrical
secondary vortexes has already formed. This is because mixed convection forms when secondary
vortex superimposes to mainstream direction and its heat exchange capacity is better than that of
forced convection. At y=500mm, velocity of mainstream core area is already stable and complete
vortex forms.
3.1.2 Heat Transfer Characteristics
Shown in Fig 4, temperature of each cross-section increased gradually. A large temperature gap
can be found between mainstream core area and layer area.The temperature of two lateral walls is
much higher than that of mainstream core area in the same level, the reason for this profile is
heated fluid in bottom center moves upward under influence of secondary vortex. Reason for
abnormal temperature of bottom border and lateral wall is that weaker vortex leads to the
stagnation of fluid. In stagnation area, heat exchange rely on molten salt heat conduction is limited,
so a high temperature distribution appears due to stack of heat.

Fig 4 Cross-sectional temperature profiles at the condition with bottom heating flux of 200kW/m and
velocity at 0.3m/s with y=100,300,500,700

3.2 The Trend of Nux Varied with y/d

As shown in the figure 5, with the increase of y/d, the Nux decreases quickly and reaches
minimum at 15d, and then Nux increases slowly with the further increase of y/d. This is because
decrease of heat transfer capacity between surface and fluid caused by thickening of the boundary
layer , the temperature difference between surface and fluid reaches its maximum under heat
accumulation then leads to the minimum Nux; For the fully-developed region, the Nux increases
slowly. A conclusion can be drawn that the changing trend of Nux in mixed convection is different
from that of pure forced convection due to the existence of secondary vortex through analysis of
flowing characteristic.
As shown in fig 6, the trend of local Nux number varied with y/d is almost the same to that in Fig
5, Nux increases with the increase of Re under condition of same heating flux.

622

3.3The
Relationshi
p

between

Nu and Ri,
Re
As
shown in the
figure 7, Ri
decreases
Fig5 The trend of Nux varied with y/d under

Fig6 The trend of Nux varied with y/d

condition of same Re number and different

under same heating flux and different Re

Ri number

number

with
increase

of

Re under the
condition of

same bottom heating flux; a big change of physical parameters of molten salt caused by increase of
inlet temperature results in a big change of Re under the condition of same inlet axial flow velocity.
So under condition of same heating flux, a large difference of Re between solid and hollow
numerical point can be found, but the change relationship between Ri and Re is consistent.
Fig.8 shows the relationship between Nu number and Ri number. As shown in the figure, Nu
increases with increase of Ri under the same Re; as a whole, the Nu also increased with increase
of Re.
3.4
Compariso
n

between
Simulated

Data

and

Accepted
Correlation
As
widely-believ
Fig 7 Relationship between Re and Ri

Fig 8 Relationship between Nu and Ri

ed
Gr/Re

when
2

10

the impact of forced convection compared with natural convection can be ignored. These impact of
these two convections should both be taken into consideration when 0.1

Gr/Re2 10[ 1 9].

Mentioned in theHeat Transferby J. P. Holman, for the decision of flow state of fluid in horizontal
tube, a decision diagram put forward by Metais and Eckert[20] can be utilized. Natural convection
area or mixed convection area can be decided by the relationship between dimensionless number
Re and GrPrD/L. By summary of these simulated data, its scope is as follows: 0.078<Ri<0.211,
1500<Re<3730, 1.086x105<GrPrD/L<3.931x105, 0.279<Pr(D/L)<0.369. As shown in Fig 14, the
fluid is located in the region of mixed convective turbulence flow in the horizontal tube.

623

Fig.9 Range of simulated data in the flow regime map

As mentioned above, the classical correlation of Metais which is suitable for mixed convective
turbulent flow was as follow:
Nu=4.69 Re0.27 Pr0.21 Gr0.07 (D/L)0.36

(10)

As shown in the figure 10, as a whole, the Nu increases with increase of Re and deviation
between simulated data and mixed convective correlation is within 15% which shows a good
agreement.

Fig.10 Comparison between the simulated data and correlation of mixed turbulent flow

4. Conclusion
The flow and heat characteristic of molten salt mixed convection and the relationship between
Nux and dimensionless distance y/d were analyzed. The results show that:
1Under non-uniform heating conditions, the shape of main core area will change with the
increase of flow distance. Symmetrical vortexes form in channel cross-section and these vortexes
can strengthen heat transfer capacity.
2) Under the same heating flux, the Nux will increase with increase of Re. Under the same Re, Nu
will increase with increase of Ri when the tube is heated in three different heating positions.
3) With the criteria of mixed convection judgement, the numerical simulation data locates at
mixed convective turbulent flow region can be known. Good agreement between simulated data
and mixed convective correlation is reached and deviation between simulated data and correlation
is within 15%.
Reference
[1]
[2]
[3]

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Channel[J]. International Communications in Heat and Mass Transfer, 2009, 36: 841-849.
CHONG Daotong, LIU Jiping, ZHANG Qingfu, et al. Numerical Simulations of 3D-flow for Laminar Mixed Convection
in Horizontal Rectangular Tubes[J]. Journal of Engineering Thermophysics, 2009. 30(1): 141-143.
ZHANG Yingli, CHONG Daotong, Liu Jiping, et al. Numerical Investigation of the Conjugate Heat Transfer of

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[14]
[15]
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Horizontal Rectangular Channel[J]. International Jouranl of Heat and Mass Transfer, 2010, 53: 2149-2158.
WANG Mengchun, WU Shengmin, ZHANG Xiuting, et al. Experimental Research on Heat Transfer Characteristics of
Mixed Convection in the Square Duct with Single Wall Heated[J]. Journal of Engineering Thermophysics, 2012, 33(1):
105-108.
YANG C S, JENG D Z, LIU C W, et al. Fluid Flow and Heat Transfer in a Horizontal Channel with Divergent Top Wall
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OSBORNE D G, INCROPERA F P. Laminar Mixed Convection Heat Transfer for Flow Between Horizontal Parallel
Plates with Asymmetric Heating[J]. International Journal of Heat and Mass Transfer, 1985, 28: 207-217.
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Supercritical Water in Horizontal Tubes in the Large Specific Heat Region[J]. Computers&Fluids, 2012, 64: 127-140.
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Effect[J]. Thermal Science, 2012, 16(1): 56-67.
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Horizontal Thermal Gradient[J]. Heat and Mass Transfer, 2011, 47: 1251-1260.
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Plain Square Duct[J]. Heat Mass Transfer, 2012, 48: 2013-2021.
ZHANG Xuexue, ZHANG Chao, LIU Jing. Laminar Mixed Heat Convection under Circumferentially Nonhomogeneous
Boundary Heating[J]. Tsinghua Science and Technology, 1997, 37(2): 73-76.
GAU C, JENG Y C, LIU C G. An Experimental Study on Mixed Convection in a Horizontal Rectangular Channel Heated
From a Side[J]. Journal of Heat Transfer, 2000, 122: 701-707.
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Thermal Engineering, 2006, 26: 1677-1683.
ALLAHYARI S, BEHZADMEHR A, HOSSEINI SARVARI S M. Conjugate Heat Transfer of Laminar Mixed Convection
of a Nanofluid Through a Horizontal Tube with Circumferentially Non-Uniform Heating[J]. International Journal of
Thermal Sciences, 2011, 50: 1963-1972.
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Horizontal Circular Tube[D]. Zhejiang: Masteral Dissertation of Zhejiang University, 2011: 45-58.
AIT MESSAOUDENE N, HORIMEK A, NOUAR C, et al. Laminar Mixed Convection in an Eccentric Annular
Horizontal Duct for a Thermodependent Non-Newtonian Fluid[J]. International Journal of Heat and Mass Transfer, 2011,
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International Journal of Heat and Mass Transfer, 2012, 55: 1113-1125.
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295-296.

Nomenclature
C

constant

cp

specific heat, kJ/(kgK)

equivalent diameter, m

heat transfer coefficient, W/(m 2 K)

turbulent kinetic energy, J

Gr

Grashof number, g

turbulent kinetic energy, J

Nu

Nusselt number

Nux

local Nusselt number

Pr

Prandtl number

Re

Reynolds number

Ri

Richardson number,

temperature, K

velocity, m/s

y/d

dimensionless length

YM

the effect of compressible turbulence fluctuating dilatation on the dissipation rate

Greek Symbols

thermal diffusivity, m2/s

expansion coefficient1/K

thermal conductivity, W/(m K)

625

dynamic viscosity, Pa s

kinematic viscosity, m2/s

density, kg/m3

model constants

dissipation rate, W/m3

Subscripts
b

buoyancy effect

mean velocity gradient

turbulence

626

THERMODYNAMIC PERFORMANCE OF PARALLEL FLOW MICROCHANNEL

CONDENSER WITH LIQUID-VAPOR SEPARATION
Ying Chen, Tianming Zhong, Wenpu Le, Wenxian Zheng, Xianglong LuoNan Hua
Faculty of materials and energy, Guangdong University of technology, Guangzhou, China
Tel./fax: +86 20 39322581. E-mail address: chenying@gdut.edu.cn (Ying Chen)

ABSTRACT
In order to keep a high refrigerant quality condensation, an orifice baffle called liquid-vapor
separator was applied to parallel flow microchannel condenser (PFMC) whose hydraulic diameters
were 0.5 to 1.5mm. Another PFMC without vapor-liquid separation was chosen as a baseline which
had an identical fin and tube geometry structure. The in-tube average heat transfer coefficients
(AHTC) and pressure drops of the two condensers were measured under the mass flux from 450
kg/(m2s) to 770 kg/(m2s) and the vapor quality ranging from 0.28 to 0.72.
It was found that the AHTC of the LSMC was lower than the PFMC at a relative small-scale mass
flux and low vapor quality, but when the mass flux increased consistently, the AHTC of the LSMC
exceeded the PFMC, especially, at mass flux 770 kg/(m2s) and average vapor quality 0.70, the
AHTC of the LSMC was 8.6% and 7.4% higher than the PFMC, when the condensing temperature
was 45 oC and 50 oC, respectively. On the other hand, the total pressure drops of the LSMC were
much lower than those of the PFMC. The maximum reduction pressure drop exceeded 65% of that
in the PFMC.
In this paper, the penalty factor (PF) and the minimum entropy generation number (Ns) were
employed to evaluate the thermodynamic performances of the two condensers. The observation
suggested that the liquid-vapor separation has an important influence on the thermodynamic
performance of the LSMC, which has great enhancement on the thermodynamic performance of
the PFMC.
Keywords: Liquid-vapor separation microchannel condenser, Condensation heat transfer, Penalty
factor, Minimum entropy generation number
1 INTRODUCTION
Condenser is an important device in air conditioning and efficiency and energy conservation air
conditioning systems are being the aims at present. So a condenser which has advantaged
thermodynamic performance is important on air conditioning systems. Because of the Efficiency
and compactness, parallel flow microchannel condenser is applied more and more widely.
Some researchers had investigated the thermodynamic performance of microchannel tubes and
parallel flow microchannel condensers. Yang and Webb[1], Vardhan and Dunn[2], Yan and Lin[3]
had investigated the condensation heat transfer coefficient of refrigerants inside microchannels or
small diameter tubes. In recent years, Bandhauer[4] measured the thermodynamic property during
condensation in the channels with 1.5mm > dh > 0.5 mm with water as the coolant. They declared at
hydraulic diameter of 0.76 mm, the refrigerant side thermal resistance is much higher than the
coolant side thermal resistance. For the whole experimental mass fluxes, the resistance ratios of
both sides were between 5 and 29. Matkovic [5] used the R134a and R32 to investigate the heat
transfer coefficient in a circular 0.96 mm diameter minichannel experimentally. It showed when the
mass flux was beyond 600 kg/(m2s), the heat transfer coefficient in the minichannel increased close
to an exponential function with the increasing vapor quality. Akhil[6] studied the heat transfer
coefficients of R134a in six non-circular horizontal microchannels (0.424 < Dh < 0.839 mm) by a
series of experiments and models. At mass flux of 150 kg/(m2s) to 750 kg/(m2s), the heat transfer
coefficients all had no significant difference at low vapor quality (0.2), but at high vapor

627

qualities(0.6-0.8), the heat transfer coefficients at 750 kg/(m2s) were 2 to 4 times of which at 750
kg/(m2s). A mist-flow-based model was found to the better for the prediction of the heat transfer.
It is a pity that though microchannels bring high heat transfer efficiency, in return, significant
pressure drop follows. Kawahara[7] employed de-ionized water and nitrogen gas to investigate the
two-phase flow pressure drop in a 100m diameter circular tube experimentally. They found when
the liquid superficial velocity was 1.3 m/s to 1.5 m/s, and the gas superficial velocity was ranging
from 0.1m/s to 65m/s, the total pressure drops changed from over 240 kPa to 560 kPa. Moreover,
the contribution of friction pressure drop was over 90%. Shin[8] developed a new experimental
technique to measure the in-tube heat transfer coefficient and pressure drop during condensation of
R134a in a horizontal single round tube with an inner diameter of 0.691 mm. The data showed, at
mass flux of 200 kg/(m2s) to 600 kg/(m2s), with high heat transfer coefficients during condensation,
the pressure drops were increasing sharply. Particularly, under the same vapor quality, the pressure
drops at mass flux of 600 kg/(m2s) were over 5 times of those at 200 kg/(m2s). Qi[9] presented a
novel subcooling parallel flow condenser, and studied in a mobile air conditioning system. The
condenser was more compact, and was 15.1% volume weight reduction of the original parallel flow
condenser. The authors found that though the novel condenser can increase by about 5% of
cooling capacity, the pressure drop of refrigerant was over 50% higher than the original one.
The liquid-vapor separation condenser (LSC) presented in recent years is a novel efficient
condenser. The condenser employed outer diameters of 7 mm and 9.52 mm had been investigated
by Chen[10] and Hua[11]. This paper presented a liquid-vapor separation microchannel condenser
(LSMC) according to the principle of liquid-vapor separation and discussed the thermodynamic
performance of the LSMC. The in-tube condensation heat transfer coefficient and pressure drop of
the LSMC and the PFMC were tested under fixed condensation temperatures and heat fluxes.
Authoritative evaluation criteria the penalty factor (PF) and the minimum entropy generation
number (Ns) were applied to rank both condensers.
2 THE TEST SECTIONS AND EXPERIMENTAL APPARATUS
2.1 The test sections

(a)

(b)
Fig. 1(a),(b) The test sections

As shown in Figure 1(a), the LSMC consists of a microchannel tube bank and two headers at
both ends. An aluminous baffle with varied round holes having diameters of 0.5 mm to 1.5 mm is

628

equipped in the header before the second tube pass. It is called liquid-vapor separator that divides
the refrigerant route into several passes. It separates liquid from the two-phase mixture refrigerant
at the entrance of the second tube pass (in order to investigate the effect of a liquid-vapor separator
on the condenser, only the second tube pass is installed). As a two-phase refrigerant enters the
header, the liquid takes the lead to drop down by the gravity difference between the liquid and
vapor. Controlled by the holes structure, some liquids can pass through the aluminous baffles
along the headers, and the others are left to form a film thickness covering on the holes. The film
prevents the vapor from passing through these holes, so it comes into the next pass to be cooled
continuously. The liquid-vapor separator can help to keep a high average refrigerant quality in the
next tube pass. Figure 1(b) demonstrates a common parallel flow microchannel condenser (PFMC)
owned the same structure parameters with the condenser, except the baffles with holes in headers.
In this paper, it was chosen as a baseline. All the parameters of both condensers are listed in table
1.
Table 1 Parameters of the microchannel condensers
Items

size

Items

size

Length of the microchannel tube (mm)

650

I.D. of the header (LSMC and PFMC)/mm

18.0

Width of the microchannel tube (mm)

16

Header length (LSMC and PFMC)/mm

480

Height of the microchannel tube (mm)

1.8

Pitch of the fins (mm)

1.0

Hydraulic diameter microchannel (mm)

1.05

Thickness of the fins (mm)

0.12

Pitch of the microchannel tube (mm)

10

Width of the fins (mm)

16

Channel number of a tube

12

Height of the fins (mm)

Thickness of the tube wall (mm)

0.30

Angle of the louver fins ()

20

Thickness of the channel baffles (mm)

0.20

Slit length of the louver fins (mm)

6.50

I.D. of the header (LSMC and PFMC)/mm

18.0

Slit pitch of the louver fins (mm)

1.30

Diameter/ Number of holes on the second

1 mm/3 and 1.5

baffle

mm/5

2.2 Test apparatus

1. Inerter compressor 2.Oil separator 3.Precooler 4.Water chilling unit 5.water tank 6.Flow meter
7.Centrifugal pump 8. Filter 9.Auxiliary condenser 10.Test section 11.Temperature sample 12.Subcooler
13.Flow meter 14. Accumulator 15. Filter/Drier 16.Mass flow meter 17.Sight glass 18.Electronic

629

expansion valve 19.Manual throttle valve 20.Evaporator 21.Liquid-vapor separator

Fig. 2 Schematic diagram of the experimental setup

Figure 2 shows the air-cooled condenser test system consists of three loops, namely, refrigerant
circulation, water circulation, and air measurement and handling. After leaving the compressor, the
refrigerant vapor goes through an oil separator and a pre-cooler, and then comes into the tested
condenser. Subsequently, the vapor passes through a sub-cooler, a liquid trap, a dryer, an
electronic flow meter, a sight glass, an evaporator, and finally, returns to the compressor. The
pre-cooler, sub-cooler, and evaporator are all spiral-channel double pipe counter flow heat
exchangers. The refrigerant quality at the inlet of the test section can be regulated through heat
exchange between the refrigerant and the cold water in the pre-cooler.
The tested section is equipped in an air tunnel at a constant temperature chamber. The air
handling apparatus in the chamber can regulate the temperature of the air blowing to the tested
condenser. Pressure transducers measure the pressures of the inlet and outlet air, while a platinum
resistance thermometer PT-100 records the temperatures of the inlet and outlet air in the air sample
collector. A nozzle flow meter measures the mass flow of the inlet air. Platinum resistance
thermometer PT-100 and pressure transducers test the refrigerant temperature and pressure at the
inlet and outlet of these condensers. Ninety-six copper-constant thermocouples (T type) are
attached to the surface at the end of each tube to monitor the diabatic tube wall temperature. Each
test point is settled at two thermocouples at the top and bottom of the tube wall. A Coriolis effect
mass flow meter measured the refrigerant mass flow rate within a range of 0.3 to 18 kg/min. Water
flow rates through the pre-cooler, sub-cooler, and the evaporator are gauged by using magnetic
flow meters with a nominal flow range of 0 to 6.361 m3/h. Test data are collected by using a hybrid
recorder, and were analyzed in real time with a PC running the visual basic data reduction program.
Table 2 lists the accuracies of the measuring apparatus.
Table 2 Measuring apparatus and uncertainty
Items

Type

Range

Accuracy

Pt-100

TR/02010

-50 C to 200 C

0.15 K

Thermocouple

Type-T

-200 C to 350 C

0.5 K

Pressure transducer

Strain-gage

0 MPa to 1.6 MPa

0.5%

Air flow meters

Differential pressure gage

0 Pa to 800 Pa

1.0%

Mass flow meter

Coriolis effect

0 kg/s to 0.2 kg/s

Volumetric flow meter

Magnetic

0 m /h to 6.361 m /h

0.15%
3

0.17%

2.3 Test method and test conditions

Table 3 presents the test conditions. At the experiments, the temperature and relative humidity of
the air are controlled to keep a fixed value (dry/wet bulb temperatures are 35 C and 24 C). The
output of the compressor and the auxiliary condenser regulated the refrigerant condensation
pressure. The quality of the refrigerant that enters the condenser is regulated according to a series
of values by changing the volume flow and temperature of the water in the precooler. The air
volume flow entering the condensers maintained the heat fluxes of 1.5 and 2.5 kW/m2.
The hybrid recorder read and stored data every 10 s when the system entered a steady state
(energy balance between the refrigerant and air corresponded within 5%). The PC collected and
recorded the average value of the test data every 5 min. The results were obtained according to the
average value of the available data collected for over 45 min after the system keeps stabilized.
Table 3 Test conditions

630

Items

Range

Refrigerant

R134a

Condensing temperature (C)

45 and 50

Heat flux (kW/m )

1.5 and 2.5

-2 -1

Mass flux (kgm s )

450 to 770

Average quality range

0.28 to 0.72

2.4 Experimental uncertainty analysis

The uncertainty of the measurement results can be analyzed using Type-A and Type-B
uncertainty evaluations. Type-A evaluation is used to determine the standard uncertainty of certain
structure sizes, that is, inner tube diameter and tube length. The average values of the measured
data for 26 times are used as results. The obtained relative standard uncertainties of inner tube
diameter and tube length are 1.37% and 0.66%, respectively. Type -B is used to evaluate the
accuracy data of all the transducers. In the paper, uniform distribution is assumed for each
uncertainty component with coverage factor

. The uncertainty of each calculated parameter

is evaluated using the corresponding calibrated accuracy of transducers used for measurement,
including the thermocouple, resistance thermometer, and mass flow meter, as seen in Table 2.
2.4.1 Uncertainty of inner tube surface area
The inner tube surface area is calculated as follows:
(1

Ai di LN

Thus, the uncertainty of heat transfer area based on the inner tube is given by
2

A
A
U Ai i U d2i i U L2
L
di

(2
)

The relative standard uncertainty of Ai is evaluated as 1.49%.

2.4.2 Temperature uncertainty
The uncertainty of the average diabatic tube wall temperature (the algebraic average of 96 test
points) is determined using
2

1
UTw ,m UT2w 96
96

(3)

The uncertainty of the average refrigerant temperature (the algebraic average of the temperature
at the inlet and outlet of the condenser) is described by:
(4

UTr , m 0.5UT2r

The obtained relative standard uncertainties of the temperature of the tube wall and the
refrigerant are 0.23% and 0.61%, respectively.
2.4.3 Uncertainty of heat load
In the experiments, conducted in this study, cooling capacity is calculated using

Q C p m a Ta,outTa,in
(5)

631

The uncertainty of Q is a function of the relative standard uncertainty of each input measurement,
and can be expressed as
2

Q 2
Q 2 Q 2
UQ
UTa ,out
UTa ,in
U ma T
ma
a ,out
Ta ,in

(6)

The relative standard uncertainty of heat load Q is 1.37 %.

2.4.4 Uncertainty of in-tube heat transfer coefficient
Considering a tube wall thickness of 0.3 mm together with the high conductivity of copper
material, the inner wall surface temperature is assumed to be the same as the external wall surface
temperature. The in-tube heat transfer coefficient can be simply calculated by
i

(7

Q
Ai Tr Tw

Thus, the uncertainty of the in-tube heat transfer coefficient can be expressed as
2

U i i U Q2 i U A2i i UT2r i UT2w
Q
Tr
Ai
Tw

(8)

The obtained maximum relative expanded uncertainty of the in-tube heat transfer coefficient is
9.4%.
2.4. 5 Uncertainty of in-tube pressure drop
The in-tube pressure drop is calculated using:

P Pin Pout
(9)
So the uncertainty of pressure drop is

U p (

P 2
P 2
) U P2in (
) U P2out
Pin
Pout

(10)
The obtained maximum uncertainty of the in-tube pressure drop is 2.15 kPa.
3 DATA REDUCTION
3.1 Average tube wall temperature
The average tube wall temperatures of the inlet and outlet for the k tube pass were calculated
using the following equations:

Tm,in,k T1,in T2 ,in ...Tn,in n

(11)

Tm,out ,k T1,out T2 ,out ...Tn,out n

(12)
where k stands for the tube pass number, and n stands for the tube number per pass.
The average tube wall temperature of the flow route length with four tube passes is calculated
using

632

Tm,w

1 4 Tm,in,k Tm,out ,k

4 k 1
2

(13)
3.2 Average refrigerant temperature
The average refrigerant temperature was calculated using

Tm,r Tr ,in Tr ,out 2

(14)
3.3 Average vapor quality
The inlet vapor quality was calculated using

mr hpre, in Q mr hl, sat mr hv, sat mr hl, sat

in

pre

(15)
The outlet vapor quality was calculated using

mr hsub, out +Qsub mr hl, sat mr hv, sat mr hl, sat

out

(16)
Thus, the average vapor quality can be calculated from:

in out 2
m

(17)
3.4 Heat load
The heat transfer rates of the air side and refrigerant side were calculated using

Q aVa Cp, inTa, in Cp, outTa, out

(18 Q mr (hr, in hr, out )
(19)
The properties of the refrigerant were obtained using REFPROP 7.0.
3.5 Average condensation heat transfer coefficient

i Q Ai tr ,m tw,m
(20)
where Ai is the in-tube heat transfer area counted by the dimeter of the inner tube.
3.6 Penalty factor
According to Cavallini et al[12], the PF of the condensation process is expressed as

PF =DTsr DTdr

G di Tsat 1 1 d P

4 i l v d z

(22)
The PF consists of the condensing temperature drop DTsr, which is caused by pressure drop, and
the differential temperature between saturation refrigerant and the in-tube wall DTdr, which is
related with heat transfer efficiency and pressure drop. This method considers both flow resistance
and heat transfer efficiency, and is fit to evaluate the phase change heat transfer process. For the

633

whole condenser, the total pressure drop (dP/dz) mainly includes the friction pressure drop and
partial pressure drop.
3.7

Minimum entropy generation number

According to the correlation proposed by Saechan[13], the total entropy generation rate of the
system is the sum of the entropy generation rates of the refrigerant and the air. Thus, minimum
entropy generation can be expressed as:

Ns (Sgen,a Sgen,r ) (C p m)a

(23)
where Sgen,a is the entropy generation rate on the air side, and Sgen,r is the entropy generation rate
on the refrigerant side, which can be calculated using

Sgen,a (mCp )aln(Ta,o Ta,i ) (mR)aln( Pa,o Pa,i )

(24)

S gen,r Sr,out Sr,in

(25)
4 RESULTS AND DISCUSSION
Figure 3 shows the in-tube AHTCs of both condensers at an average vapor quality 0.7, and at
condensing temperatures of 45 C and 50 C. All the AHTCs increased significantly when the mass
flux ranged from 450 kg/(m2s) to 770 kg/(m2s) at both condensing temperatures, and the curves of
the LSMC were the steepest. When the condensing temperature were raised from 45 C to 50 C,
the AHTCs of the LSMC and the PFMC decreased by 4.1% to 10.3% and 4.5% to 8.9%,
respectively. This is because at a higher condensation temperature, the specific volume of vapor
was lower and the velocity of the vapor decreased, which reduced the shear stress at the interface
of the vapor and liquid. In addition, higher condensation temperature lowered the thermal
conductivity of refrigerant R134a and reduced the average heat transfer coefficient. The liquid
vapor separation effect on the AHTC was hardly affected by the condensing temperature.
At condensing temperature either 45 oC or 50 oC, the AHTCs of the LSMC were less than the
PFMC, when the inlet mass fluxes were relative small-scale (450 kg/(m2s) to 618 kg/(m2s) for 45 oC,
450 kg/(m2s) to 690 kg/(m2s) for 50 oC), however, when the inlet mass fluxes increased continually,
the AHTCs of the LSMC exceeded the PFMC. Spectacularly, under mass flux of 770 kg/(m2s), the
AHTCs of the LSMC were 8.6% and 7.4% higher than the PFMC, when the condensing
temperature were 45 oC and 50 oC separately. This is because when the mass flux is relative
small-scale, the velocity conducted by mass flux is the main effect on the AHTC, but with the larger
and larger mass flux, the effect of velocity on the AHTC reduce, and the vapor quality plays a more
important role on the AHTC, so that the AHTCs of the LSMC exceeded the PFMC.

634

Fig. 3 The effect of condensing temperature on the in-tube AHTCs

Figure 4 shows the in-tube AHTCs of both condensers at heat flux of 1.5 kW/m2 and 2.5 kW/m2,
when the average vapor qualities were ranged from 0.28 to 0.72. With the increasing average vapor
quality, the AHTCs of the LSMC and the PFMC raised a lot. Under the same average vapor quality,
the AHTCs at heat flux of 2.5 kW/m2 were 3.3% to 10.0% higher than which at heat flux of 1.5
kW/m2 for the LSMC. The analogous phenomenon can be seen for the PFMC. This is because the
increase of the vapor shear for the condensate improves the average heat transfer coefficients
when the heat flux increased.
The AHTC of the LSMC increased more rapidly than the PFMC at the whole vapor quality
(0.280.72), implying that the high average quality had the greatest effect on the in-tube heat
transfer. At low average vapor quality (0.28 to 0.48 for heat flux 2.5 kW/m2), the AHTCs of the
LSMC was the lower ones for both condensing temperatures, however, when the average vapor
quality increased consistently (about 0.66 to 0.72 for heat flux 1.5 kW/m2), the AHTCs of the LSMC
surpassed the PFMC confirmedly. The reason maybe the low average vapor quality refrigerant
owns a small specific volume and the velocity of the refrigerant is quite slow, in this case, a
reduction mass flux caused by the liquid-vapor separator in the LSMC combines the
incomplete-drain out condensation decrease the AHTC. When the average vapor quality increases
consistently, the velocity of the refrigerant is quite large and the condensation can be drained out
completely, as a result, the AHTC of the LSMC is higher than the PFMC at high vapor quality.

Fig. 4 The effect of heat flux on the in-tube AHTCs

Figure 5 shows the total pressure drop of both condensers at an average vapor quality 0.7, and
at condensing temperatures of 45 C and 50 C. We can see that the pressure drop of both
condensers at condensing temperatures of 45 C was larger than that at condensing temperatures
of 50 C. For the LSMC, when the condensing temperature from 50 C drop to 45 C, the total
pressure drop only increased 13.2% to 40.4%, however, for the PFMC, it was 34.4% to 109.5%
instead. This phenomenon indicated the condensing temperature has a quite limited effect on the
pressure drop of the LSMC. Whats more, at the whole experimental mass flux, the pressure drop of
the LSMC only increased gently, but the pressure drop of the PFMC showed a sharp increase,
when the mass flux was raised up.
As shown, the LSMC showed a much better flow performance than the PFMC. At mass flux
ranging from 450 kg/(m2s) to 770 kg/(m2s) the pressure drops of the LSMC were only 30.7% to 69.5%
and 47.1% to 76.8% of the PFMC, when the condensing temperature was 45oC and 50oC
respectively. Because the liquid-vapor separation in the LSMC thinners the liquid film, which not
only reduced the mass flux in the tube pass, but also weaken the interface shear force between
vapor and liquid phase.

635

Fig. 5 The effect of condensing temperature on the pressure drop

Figure 6 shows the total pressure drop of both condensers at average vapor qualities of 0.28 to
0.72, and heat flux of 1.5 kW/m2 and 2.5 kW/m2. As shown, the total pressure drop of both
condensers showed a steady raise with the increasing vapor quality. For both condensers, the
pressure drop at heat flux of 1.5kW/m2 was larger than that at heat flux of 2.5 kW/m2 obviously. The
reason maybe though the average vapor quality at both heat fluxes are identical, the interface
shear force between vapor and liquid phase decreased harder with the refrigerant flow route at heat
flux of 2.5 kW/m2. In addition, the total pressure drop distribution at different vapor quality also leads
the lower pressure drop.
For both heat fluxes, the total pressure drop in the LSMC was far lower than the PFMC,
especially at higher vapor quality. At the whole experimental vapor quality, the pressure drops in the
LSMC were 9.1% to 43.6% and 15.1% to 44.4% lower than the PFMC by the heat flux of 1.5 kW/m2
and 2.5 kW/m2 respectively. The main reason also is the reduction mass flux leads to the low
pressure drop.

Fig. 6 The effect of heat flux on the pressure drop

Figure 7 shows the effect of condensing temperatures on the PF at mass fluxes from 450 kg/(m2s)
to 770 kg/(m2s). The PF value of the LSC was relatively insensitive to the condensing temperature,
which at condensing temperature 45 oC were 7.9% to 26.6% when the condensing temperature
reached 50 C. However, the PF values of the PFC reduced from 24.5% to 52.0% at 50 C
condensing temperature. In addition, the PF sharply rose, when a larger mass flux ran through the
PFMC, which means the thermodynamic performance of the PFMC deteriorated rapidly. Because
the large mass flux leads to an enormous pressure drop. When the mass flux increased, the PF of
the LSMC only rose gently and this dramatic phenomenon indicated that the LSMC can suit to a
larger mass flux range.
After all, the PFs of the LSMC were far less than those of the PFMC at the experimental
condensing temperatures. Thus, based on the heat conversation, the LSMC had the best in-tube
comprehensive performance.

636

Fig. 7 The effect of condensing temperature on the PF

Figure 8 shows the effect of heat flux on the PF at vapor quality from 0.28 to 0.72. The PF curve
of the LSMC was the lowest between both condensers at any heat flux. As shown, the PFs of the
LSMC were 8.6% to 44.4% and 6.9% to 37.8% lower than those of the PFMC at heat flux of
1.5 kWm-2 and 2.5 kWm-2, respectively. Apparently, the LSMC had the best thermodynamic
performance between both condensers. This result can be attributed to the lesser pressure drop
and smaller temperature difference between the saturation refrigerant and the inner wall in the
LSMC during condensation. The LSMC had a good comprehensive performance even at a higher
average quality unlike the PFs of the PFMC which increased consistently as the quality improved.
Moreover, the PFs of both condensers decreased at higher heat flux, and the smallest increase of
the PF occurred in the LSMC when at the equivalent heat flux. These findings prove that LSMC has
excellent thermodynamic performance given a wide variety of working conditions

Fig. 8 The effect of heat flux on the PF

Figure 9 shows the Ns of both condensers at an average vapor quality 0.7, and condensing
temperatures of 45 C and 50 C. We can see that the Ns increased consistently with the
increasing vapor quality. The Ns at condensing temperatures of 50 C was much larger than that at
45 C for both condensers. The main reason is the increase of the condensing temperature
increases the heat transfer temperature difference, which is the most important factor to lead to
irreversibility. Though the increasing in the condensing temperature can reduce the irreversibility by
friction resistance, it is just a secondary factor. Nevertheless, when the mass flux increased, the Ns
raise became larger for the PFMC, because the friction resistance mainly caused by mass flux
increased sharper.
At condensing temperature 45 C, the Ns of the LSMC were 16.9% to 33.6% less than the PFMC.
When the condensing temperature increased to 50 C, the Ns variation of both condensers with the
mass flux was similar to that at 45 C.

637

Fig. 9 The effect of condensing temperature on the Ns

Figure 10 shows the Ns of both condensers at heat flux of 1.5 kW/m2 and 2.5 kW/m2 when the
average vapor qualities were ranged from 0.28 to 0.72. The Ns of the LSMC and the PFMC
increased confirmedly with the average vapor quality increased. However, for the LSMC, the Ns
only improved relative slightly as the average quality increased. With the assistance of the
liquid-vapor separators in the LSMC, the condensation heat transfer processes in the front two tube
passes were controlled as nearly similar. Therefore, the quality variation at the inlet and outlet of the
condensers had less effect on its condensation heat transfer process. The Ns of the LSMC were
about 18.3% to 26.0% lower than those of the PFMC, at a heat flux of 1.5 kWm-2. All the Ns of both
condensers increased when the heat flux was increased to 2.5 kWm-2, this is because according to
the similar heat transfer temperature difference, the heat flux of 2.5 kWm-2 almost twice to
1.5 kWm-2, the irreversibility caused by heat transfer temperature difference exceeds by friction
resistance. At both condensing temperature, the raised ranges for the LSMC and PFMC were even
close to each other at an equivalent quality, which were ranged from about 35.6% to 80.2%. At
either heat fluxes, the Ns of the LSMC were the lowest.

Fig. 10 The effect of heat flux on the Ns

5 CONCLUSION
1. At the experimental conditions, the AHTC of the LSMC exceeds the PFMC only if a higher
average vapor quality combines a large enough mass flux in the condenser.
2. At the experimental conditions, the total pressure drop of the LSMC is much lower than the
PFMC, moreover, the condensing temperature has quite limit effect on the pressure drop of the
LSMC, but a dramatic effect on that of the PFMC.
3. The thermodynamic performance of the LSMC has great advantage over the PFMC, in
addition, the LSMC owns a greater advantage at the condition of low condensing temperature and
large heat flux.

ACKNOWLEDGEMENTS

638

We gratefully acknowledge the financial support provided by Natural Science Foundation of

China (NSFC) and Guangdong Provincial Department of Science and Technology (GPDST)
through contract No. U0934006.
NOMENCLATURE
Abbreviation
LSMC

Liquid-vapor separation microchannel condenser

PF

Penalty factor

PFMC

Parallel-flow microchannel condenser

AHTC

Average heat transfer coefficient

Vapor quality

Heat load, (W)

Symbols
x

-2

Heat flux, (Wm )

DTs

Condensing temperature drop

Specific enthalpy, (Jkg-1)

DTd

Driving temperature difference

cp

Specific heat capacity, (Jkg K )

mass flux, (kgm-2s-1)

Thermodynamic temperature, (K)

Diameter of tube (mm)

Pressure drop, (kPa)

Pressure difference, (kPa)

Coordinate of flow direction, (m)

Entropy, (W/K)

V
m
i

-1

-1

-3

Density, (kgm )
3

-1

Volume flow rate, (m s )

-1

Mass flow rate, (kgs )

-2

-1

In-tube heat transfer coefficient, (Wm K )

2

Ai

In-tube heat transfer area, (m )

Tube length in a tube pass

Total tube number

Tube number in one tube pass

Ns

Minimum entropy generation number

Subscripts
m

Average

Refrigerant

pre

Pre-cooler

Tube side

sub

Sub-cooler

sat

Saturate

v;l

Vapor ; Liquid

Air

Tube pass number

in ; out

Inlet ; outlet

gen

generation

Tube wall

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[1] C.Y. Yang and R.L. Webb, 1996, Condensation of R-12 in small hydraulic diameter extruded
aluminum tubes with and without micro-fins, Int. J. Heat Mass Transfer 39: 791800.
[2] A. Vardhan and E.E. Dunn, 1997, Heat Transfer and Pressure Drop Characteristics of R-22,
R-134a and R-407C in Microchannel Tubes. Air Conditioning and Refrigeration Center TR-133,
November 1997, University of Illinois at Urbana-Champaign.
[3] Y.Y. Yan and T.F. Lin, 1999, Condensation heat transfer and pressure drop of refrigerant R134a
in a small pipe, International Journal of Heat Mass Transfer 42: 697708.
[4] T.M. Bandhauer, A. Agarwal and S. Garimella, 2006, Measurement and modeling of
condensation heat transfer coefficients in circular microchannels. Journal of Heat Transfer
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Mass Transfer 52:23112323.
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heat transfer in non-circular microchannels. international journal of refrigeration 33: 11691179.
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639

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28:14111435.
[8] J. S. Shin and M.H. Kim, 2004, An experimental study of condensation heat transfer inside a
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[9] Z. Qi, Y. Zhao and J. Chen, 2010, Performance enhancement study of mobile air conditioning
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[10] E. Chen, Y. Chen and X. Chen, .2012, The theory design of tube-pass and thermodynamic
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[11] N. Hua, Y. Chen, E. Chen and L. Deng, 2013, Prediction and verification of the thermodynamic
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[13] P. Saechan and S Wongwises, 2008, Optimal conguration of cross ow plate nned tube
condenser based on the second law of thermodynamics. International Journal of Thermal Sciences
47: 14731481.

640

Investigation on the capacitive performance of the polyaniline/modified

graphite composite electrodes
Xinzhuang Fana*, Lian Zhongb, Haibo Xub, Jianguo Liua, Chuanwei Yana
Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
b College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao 266100, China
xzfan@imr.ac.cn
a

ABSTRACT
The polyaniline/modified graphite composite electrode (PANi/MGE) was prepared through the
electrochemical deposition. The surface morphology and electrochemical property of the
composite electrode were examined by scanning electron microscopy (SEM), cyclic voltammetry
(CV), galvanostatic charge-discharge and electrochemical impedance spectroscopy (EIS). The
SEM images show that little thready PANi was observed after the electrochemical deposition on
modified graphite electrode (MGE), the plentiful pore structures and surface oxides may changed
the existence form of PANi. The electrochemical tests demonstrate that the PANi/MGE possesses
an excellent pseudo-capacitive performance and ratio characteristics, with an apparent specific
capacitance reached up to 2.65 F cm-2, which might attributed to the synergistic effect between
PANi and MGE.
Keywords: polyaniline, composite electrode, ratio characteristics, pseudo-capacitive, synergistic
effect.
INTRODUCTION
Supercapacitors, which possess high power density, excellent reversibility, and have longer cycle-life
as compared to batteries, have been gaining momentum for the last decade. 1 Because of the preferable
pseudo-capacitive characteristic, the noble metal oxides and electrically conducting polymers greatly
pushed the development of supercapacitors in recent years.2-3
As a common conductive polymer, the polyaniline (PANi) attracts more attentions because of its
inexpensive raw material, simple preparation method, high electrical conductivity, excellent chemical
stability and electrochemical reversibility.3 Along with the fast transformation between the doped and
dedoped polyaniline in the polymer film, a highly reversible redox reaction occured during the
charge/discharge process. Therefore, a large pseudo-capacitance is generated due to the high density
charge in the interface even the entire volume of the polymer, which makes PANi as a research focus of
electrode material for supercapacitors.
With the advantages of low cost, high chemical stability, good conductivity and large surface area,
Carbon materials such as activate carbon, carbon aerogel, carbon fiber, carbon nanotubes and
graphene are often used as electrode materials for double layer capacitor.4 In consideration of the large
double layer capacitance of carbon material with a high surface area, in addition to the good pseudocapacitance of PANi, the specific capacitance may be vastly improved through the preparation of a
composite material of both carbon material and PANi included. The benefits of introducing carbon
materials into conducting polymers through chemical in-situ polymerisation have been intensively
studied, with many interesting properties and behaviors of the composites having been discovered. Jang
et al obtained the polyaniline/carbon nanofibers composite materials by vapor deposition polymerization,
the results showed that the thickness of deposit for the polymer film was about 20 nm and the specific
capacitance was high up to 264 F g-1, which mainly ascribed to the faraday pseudo-capacitance of
PANi.5
PEDOT/CNTs
was
prepared
through
direct
chemical
oxidation
and
electrochemical polymerization by Frackowiak et al, the capacitive characteristic of the composite
material was examined both in aqueous solution and organic electrolyte, with a specific capacitance
from 60 to 160 F g-1.6 Bguin et al synthesized the PANI/CNTs and PPy/CNTs by direct chemical
oxidation method, it was found that not only the potential range and system conditions, but also the
assembly method had significant effects on the specific capacitance of the composite materials. 7 Hu et
al deposited PANi on graphite electrode (GE) by cyclic voltammetry (CV), the specific capacitance is
greatly improved.8
In the previous work,9-10 in spite of a fairly low surface area (6 m2 g-1), the modified graphite
electrode (MGE) prepared by recurrent galvanic pulses presented an excellent pseudo-capacitive
performance, which mainly due to the plenty of the active groups such as the hydroxyl, carbonyl and
carboxyl groups, suggesting a promising electrode material for pseudo-capacitor. On this basis, the
PANi is in-situ deposited on the MGE by electrochemical deposition in this communication, the
electrochemical performance of the PANi/MGE composite material is evaluated by CV, galvanostatic
charge-discharge and electrochemical impedance spectroscopy (EIS).

641

EXPERIMENTAL
The PANi/MGE composite electrode was prepared by electrochemical deposition. The MGE, obtained
in the previous work,10 was assembled as the working electrode (1 cm 2 surface area) in Flat Cell K0235
(AMETEK Princeton Applied Research, USA), which was a three-electrode cell configuration immersed
in the mixed solution with 2.0 M H2SO4 and 0.5 M aniline. A 10 cm2 platinum sheet and a saturated
calomel electrode (SCE) were used as the counter electrode and reference electrode, respectively. All
potentials reported here were referred to SCE. No attempt was made to eliminate O 2 from the
electrolyte.
The aniline was in situ polymerized on MGE by CV test, cycling 6 times from -0.2 to 0.8 V, with a scan
-1
rate of 50 mV s .
then the PANi/MGE was obtained. The micro-domain morphology of PANi/MGE was observed by
scanning electron microscopy (SEM; KYKY-2800B). In order to evaluate the pseudo-capacitive
performance, the CV tests were performed on PANi/MGE within a range of 0.351.0 V at different scan
rates. Here, a pre-polarization was conducted at 0.2 V for 200 s before each CV test. Galvanostatic
charge-discharge tests with different current density were also carried out to investigate the ratio
characteristics of the composite material. The EIS were measured with different polarization potential,
with 5 mV potential amplitude and a frequency range of 10 kHz10 mHz. All electrochemical
measurements were carried out using an EG&G PAR Model 2263 Potentiostat/Galvanostat at ambient
temperature.

RESULTS AND DISCUSSION

Generally, the PANi could prepared by chemical oxidation or electrochemical method. 3 As a result of the
unique advantage that the proton acids doping and electrosynthesis occur in one step, in addition to the
high purity of the synthetic product, it is preferred to synthesize PANi by electrochemical method.
Chronopotentiometry, chronoamperometry and CV are often used in the polymerization process of PANi
on the porous carbon materials. In this work, CV test was employed and Fig. 1 is the CV curves of
electrochemical polymerization for PANi at the surface of MGE with different circles. As shown in Fig. 1,
the current response constantly reinforces with the increase of cycle number, suggesting the amount of
PANi deposited on MGE is ever-increasing. The current density reaches an relative steady state at 5-6
circles, meaning the accomplishment of the polymerization of PANi on MGE, and the
electropolymerization PANi might cover the entire surface of MGE. Two pairs characteristic redox peak
of PANi are also observed, one correspond to the redox process from non-conducting fully reduced
PANi to conductive intermediate oxidized PANi, the other peak is the redox process from the further
oxidation PANi to fully oxidized PANi.11

0.4

Current density / A cm

-2

1 circle
2 circle
3 circle
4 circle
5 circle
6 circle

0.2

0.0

-0.2
-0.2

0.0

0.2

0.4

0.6

0.8

Potential / Vvs.SCE

Fig. 1 CV curves of electrochemical polymerization for PANi at the surface of MGE with different circles.
Different with the smooth and compact graphite, MGE presents an obviously porous and rough threedimensional active layers with microcrystalline flake structure. 9 Fig. 2 is the SEM images of PANi/GE
(A) and PANi/MGE (B) composite electrodes. Although the same electrochemical polymerization was
used, the morphologies of PANi/GE and PANi/MGE are entirely different. Unlike the Cross-linked
reticular fiber structure of PANi/GE as shown in Fig. 2A, the obvious fibers PANi is not observed for
PANi/MGE in Fig. 2B (little fibers could be seen in the solid line circle). Compared with the SEM image
of MGE,9 it is found that the sheeting structure at the edge side is apparently thickened which mean the
PANi film is deposited on the surface of MGE. In addition, some spherical agglomeration exists in local
region, the results illustrated that the special physical structure and chemical compositions of MGE have
an important effect on the polymerization process and the morphology of product. Therefore, it was

642

thought that the abundant surface oxide and/or the porosity effect changed the way PANi grow, and
made the in situ coating deposition on the surface of the graphite oxide occurred, instead of the fiber
structure. Almost the same phenomenon has been reported in the literature,8 and the author explained it
with a similar viewpoint.
CV tests were performed to evaluated the electrochemical performance of PANi/MGE. As a result of
the three-dimensional active layers and abundant oxygen-containing functional groups, a couple of
redox peaks appear at 0.4 V in the CV curve of MGE, which mainly attributed to the continuous
reversible redox reactions among the hydroxyl(reduced states), carbonyl (half-oxidized states) and
carboxyl (fully oxidized states) groups.9 As shown in Fig. 3, CV curves of PANi/MGE in 2.0 M H2SO4
solution present a more wide redox peaks at 0.5 V, compared with that of MGE at the same scan rate.
The large peak area and substantially symmetric redox peaks indicate a favorable pseudo-capacitive
character. The main redox peaks of PANi at 0.5 V is so strong that the redox peaks among the surface
oxide of MGE are almost covered, in spite of a small oxidation peak at 0.4 V. In addition, the potential
difference between the redox peaks at 0.5 V increased with the increase of the scan rate, the probable
reason for that is the redox reaction of PANi involve the transformation of proton and the diffusion of
anion, which make the diffusion step as the rate controlling step at higher scan rate, consequently the
active particles in bulk solution have not enough time to diffuse to the surface of the electrode and the
polarized voltage is enlarged.

Fig. 2 SEM images of PANi/GE (A) and PANi/MGE (B) composite electrodes

643

0.4

Current density / A cm

-2

2mv/s
5mv/s
10mv/s
25mv/s
50mv/s

0.2

0.0

-0.2

-0.4
-0.4

0.0

0.4

0.8

1.2

Potential / Vvs.SCE

Fig. 3 CV curves of PANi/MGE at different scan rate in 2.0 M H2SO4 solution.

Galvanostatic chargedischarge curves at different currents in 2.0 M H2SO4 were constructed to
further investigate the capacitive behavior of PANi/MGE. Good symmetry of charge and discharge
curves in Fig. 4 also suggests a favorable capacitive character of PANi/MGE, and the slope of the
charge/discharge curve changes obviously, meaning a predominant pseudo-capacitance, which is
consistent with the CV results. Moreover, the charge/discharge curves still present symmetric even the
current density up to 50 mA cm-2, indicating an excellent capacitive property of PANi/MGE and a
promising application in the high power field.
The specific capacitance of MGE can be calculated from the charge by the galvanostatic charge
discharge curves according to eqn (1):12
C (i dt) dE
(1)
where C, i, dt and dE are the specific capacitance, the discharge current, discharge time, and the
potential range of discharge process, respectively. Here C represents the specific capacitance with an
apparent area of 1 cm2. The apparent specific capacitance at different current density was calculated
using eqn (1) and its relationships of discharge current density with capacitance (--) and capacitance
holding ratio (--) in 2.0 M H2SO4 shown as Fig. 5. Along with the current density increasing from 2 to
50 mA cm-2, the apparent specific capacitance changed from 2.65 to 2.34 F cm-2, eighty eight percent of
the capacitance remained means a favorable ratio characteristic. In addition, the apparent specific
capacitance of PANi/MGE (2.51 F cm-2 at 10 mA cm-2 ) is greatly improved compared with MGE (1.63 F
cm-2 at 10 mA cm-2),9 revealing a significant enhancement on the capacitive performance maybe
ascribed to the synergistic effect between PANi and MGE.

1.2

10 mA

1.0

50 mA

Potential / Vvs.SCE

25 mA

0.9
0.5

5 mA
0.6

0.0
0

200

400

0.3
2 mA

0.0

1000

2000

3000

4000

Times / s

Fig. 4 Galvanostatic charge/discharge curves at different currents in 2.0 M H2SO4 (including an enlarged graph).

644

100

Capacitance holding ratio / %

Capacitance / F cm-2

2.6
80

2.4
2.2

60

2.0

40

1.8

20

1.6
0
0

10

20

30

40

50

Current density / A cm-2

Fig. 5 Relationships of discharge current density with capacitance (--) and capacitance holding ratio (--) in 2.0 M H2SO4.
The synthesis condition, polarization potential, film thickness and coverage of PANi have an
importance effect on the resistance response, consequently the ac impedance spectroscopy of
PANi/MGE is quite complicated.13 Nyquist diagram of PANi/MGE measured at different potential in 2.0
M H2SO4 solution. It is noticed that a vertical line is observed at low frequency and an approximately
straight line with a 45 slope is visible at high frequency (see enlarged graph in Fig. 6). The
approximately vertical increase in the imaginary part at low frequency demonstrated the typical
capacitive characteristic, which was mainly governed by a faradaic process of the electroactive material.
In the meanwhile, the high frequency straight line with a 45slope was attributed to the diffusion process,
in according with the transmission line model.14 In addition, the resistance response at high frequency
almost unchanged with the increase of polarization potential, indicating the excellent conductivity of
MGE make up for the lack of PANi on the electronic conductivity. However, the resistance response at
low frequency have a maximum at 0.4 V with the increase of polarization potential, it can be seen that
the capacitance of PANi/MGE is variational with the potential and the maximum corresponding to the
coupling potential of redox peaks for PANi and MGE at 0.4-0.5 V. Therefore, the composite material
possess a markedly pseudo-capacitive character, and the EIS results are also agree with CV tests.
Furthermore, the nyquist plot did not present a vertical line at low frequency when the dc potential is 1.0
V, suggesting an irreversible electrochemical process or an limited diffusion process occurred. So the
preferable potential range of PANi/MGE in 2.0 M H2SO4 is -0.2-0.8 V, and the composite electrode
presents an excellent pseudo-capacitive performance within the potential range.

25
-Zim /ohm cm

0.8

-Zim /ohm cm

20
15

0.6
0.4
0.2
0.0
0.4

0.6

0.8

1.0

1.2

Zre / ohm cm2

1.0V
0.8V
0.6V
0.4V
0.2V
0V
-0.2V

10
5
0
0

12

16

20

Zre / ohm cm2

Fig. 6 Nyquist diagram of PANi/MGE measured at different potential in 2.0 M H2SO4 solution.

CONCLUSIONS
The electrochemical performance of PANi/MGE 2.0 M H2SO4 is preliminarily examined by different
electrochemical measurements. After the deposion of PANi on MGE, the apparent specific capacitance

645

is greatly improved (2.51 to 1.63 F cm-2), about 1.6 times compared with that of MGE. The excellent
pseudo-capacitive performance and ratio characteristics might attributed to the synergistic effect
between PANi and MGE.
In addition, deeper problems such as how did the PANi and MGE combine, the mechanism of
synergistic effect between PANi and MGE are still in research, and should be further studied.

ACKNOWLEDGEMENT
The project was assisted by the National Basic Research Program of China (2010CB227203) and the
Natural Science
Foundation of Liaoning Province (O4F0A111A7).

REFERENCE
1 Conway B. E., 1999, Electrochemical supercapacitorsscientific fundamentals and technological
applications. New York: Kluwer Academic/Plenum Publishers, 1999. 200-225.
2 Zheng J. P., P. J. Cygan, T. R. Jow, 1995, Hydrous ruthenium oxide as an electrode material for
electrochemical capacitors. Journal of the Electrochemical Society, 142: 2699-2703.
3 Marina M., A. Catia, and S. Francesca, 2002, Conducting polymers as electrode materials in
supercapacitors. Solid State Ionics, 148: 493-498.
4 Pandolfo A. G., A. F. Hollenkamp, 2006, Carbon properties and their role in supercapacitors. Journal
of Power Sources, 157:11-27.
5 Frackowiak E., V. Khomenko, K.,Jurewicz, et al, 2006, Supercapacitors based on conducting
polymers/nanotubes composites. Journal of Power Sources, 153: 413-418.
6 Bguin F., K. Szostak, M. Lillo-Rodenas, et al, 2004, Carbon nanotubes as backbones for composite
electrodes of supercapacitors. AIP Conference Proceedings, 723: 460-464.
7 Li J. L., J. Liang, J. M. Xu, et al, 2001, Research on the organic electrolyte of the Electric double layer
capacitor. Chinese Journal of Power Sources, 25: 229-234.
8 Hu C. C., C. H. Chu, 2001, Electrochemical impedance characterization of polyaniline-coated graphite
electrodes for dectrochemical capacitors-effects of film coverage/thickness and anions. Journal of
Electroanalytical Chemistry, 503: 105-116.
9 Fan X. Z., Y. H. Lu, H. B. Xu, et al, 2011, Reversible redox reaction on the oxygen-containing
functional groups of an electrochemically modified graphite electrode for the pseudo-capacitance.
Journal of Materials Chemistry, 21: 18753-18760.
10 Xu H. B., X. Z. Fan, Y. H. Lu et al, 2010, Preparation of an electrochemically modified graphite
electrode and its electrochemical performance for pseudo-capacitors in a sulfuric acid electrolyte.
Carbon, 48: 3300-3303.
11 Shilpa T., D. Mukesh, J. V. Yakhmi, 2002, Redox behavior of polyaniline as influenced by aromatic
sulphonate anions: cycle voltammetry and molecular modeling. Synthetic Metals, 125:401-413.
12 Ye J. S., X. Liu, H. F. Cui, et al, 2005, Electrochemicaloxidation of multi-walled carbon nanotubes
and its application to electrochemical double layer capacitors. Electrochemical Communication. 7:
249-255.
13 Chen W. C., T. C. Wen, 2003, Electrochemical and capacitive properties of polyaniline-implanted
porous carbon electrode for supercapacitors. Journal of Power Sources, 117: 273-282
14 Wu Q., Y. X. Xu, Z. Y. Yao, et al, 2010, Supercapacitors based on flexible graphene/polyaniline
nanofiber composite films. ACS Nano, 4: 1963-1970.

646

Preparation and Properties of Novel Side-chain Type Sulfonated Poly (ether

sulfone ) Membranes for Fuel Cell Applications
Zufeng Yuan, Ying Ling, Shouwen Chen, Zhaoxia Hu
School of Environmental & Biological Engineering, Nanjing University of Science &
Technology
Nanjing 210094, China
anfanyhu@hotmail.com

ABSTRACT
A series of novel side-chain-type sulfonated poly(ether sulfone)s (SPES-NDS) copolymers were
successfully synthesized by two steps. The polymer containing active fluorine was synthesized from
4,4-sulfonyldiphenol, decafluorobiphenyl, and then reacted with 2-naphthol-6,8-disulfonic acid
di-potassium salt (NDS-K) to get the sulfonated copolymers.

13

C NMR spectrum was performed to

characterize the copolymers chemical structure, ductile membranes were prepared by solution casting.
Fundamental properties of the obtained membranes such as ion exchange capacity, water uptake,
dimensional swelling, mechanical strength, proton conductivity as well as hydrolytic stability were
investigated. The as-prepared membranes with ion exchange capacity (IEC) of 1.22-2.07 mmol/g
showed low water uptakes, good dimensional stability, high proton conductivity. The membranes with
IEC<1.68 mmol/g exhibited excellent hydrolytic stability.
Keywords: sulfonated poly(ether sulfones), side-chain-type copolymer, proton conductivity

1 INTRODUCTION
Aromatic polymer electrolyte membranes (PEMFCs) are one of the promising PEM
alternative because of their availability, diversity of structural composition and anticipated
thermal, mechanical and chemical stability (Bae et al., 2002; Hickner et al., 2004; Miyatae et
al., 2007). In recent years, domestic and foreign scientists have especially focused on the
applications of sulfonated derivatives of poly(arylene ether ketone)s (SPAEK), poly(arylene
ether sulfone)s (SPAES), and polyimides for PEM applications (Chen et al., 2005; Fang et al.,
2007; Wang et al., 2011; Xu et al., 2008; Zhou et al., 2012), due to their rigid, aromatic
backbones could provide high thermal stability, good mechanical strength, and reasonable
chemical stability (Chang et al., 2011; Zhang et al., 2011).
But there is one common shortcoming associated with these materials, that is, the strong
dependence of proton conductivity on ion exchange capacity (IEC) and their balance with
membrane swelling. Usually, PEMs with high IEC often show high proton conductivity, water
uptakes but large membrane swelling. Therefore, it is necessary to solve this problem to gain
high performance PEM materials. Studies have confirmed that the graft structure, or
attaching sulfonic acid groups to the side-chain of the hydrocarbon polymers could improve
the proton conductivity and physical properties of the membranes at the same time (Li et al.,
2011; Zhang et al., 2011). Ueda introduced decafluorobiphenyl and hexafluorobenzene

647

moieties into the polymer structure, and successfully prepared a series of sulfonated
poly(ether sulfone) with perfluorosulfonic acid side-chain. The obtained membranes exhibited
good stability and high proton conductivity (Nakabayashi et al., 2011). Manthiram also
synthesized a novel side-chain type PEMs based on chloromethylated poly(ether sulfone)s
which bearing 4-hydroxyl acid potassium or 2-naphthol-6, 8- disulfonic acid di-potassium salt
side-chains. The results showed that the naphthols side-chain was more stable than the
conventional aliphatic side-chain, and suppressed the membrane swelling much better (Zhu
et al., 2011).
In this paper, we used fluorinated poly(ether sulfone) (PES) as the polymer precursors,
and introduced a naphthalenyl side-chain bearing sulfonic acid groups by nucleophilic
substitution reaction with the active fluorine on the PES backbone. By varying the
composition of the sulfonated side-chains in the resulting polymers, a series of side-chain
type sulfonated PES-based membranes were prepared. Fundamental properties including
water uptake, membrane swelling, mechanical strength, proton conductivity and hydrolytic
stability were investigated to evaluate their potentials for PEM applications.
2 EXPERIMENTAL
2.1 Materials
Reagents used all were analytical grade, including 4,4-sulfonyldiphenol (SDP),
decafluorobiphenyl (DFBP), 2-naphthol-6,8-disulfonic acid di-potassium salt (NDS-K), N,
N-dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), anhydrous potassium carbonate,
toluene, and sodium chloride. SDP was purified by recrystallization from toluene, DMAc and
DMSO were firstly dehydrated with calcium hydride, then purified by distillation under
reduced pressure. Other reagents were use as received.
2.2 Characterization and measurements
1

H NMR spectra of the copolymers were recorded at 300 MHz on an Avance 300

spectrometer in CDCl3. Mechanical tensile measurements were performed with a universal

o

testing instrument (SHIMAZU-AGS-100NX) at 30 C and 50% RH. IEC was measured by a

titration method. Water uptakes, size changes were measured by a reported method (Zhang
et al., 2011). Hydroxide ion conductivity () was determined by an EIS technique over the
frequency of 0.01-100 KHz (Hioki 3532-50).
2.3 Synthesis of the fluorinated poly(ether sulfone) copolymers (PES)
The fluorinated PES copolymers were synthesized according to the reported method and
depicted as follows (Chen et al., 2011): To a 100-mL 3-neck flask equipped with a magnetic
stirrer, a nitrogen inlet/outlet, were successively added 1.282 g (5.12 mmol) of SDP, 1.718 g
(5.14 mmol) of DFBP, 1.982 g (14.34 mmol) of K2CO3 and 25.6 mL of DMAc. The solution was
o

slowly heated to 80 C for 14 hrs, then cooled to room temperature and poured into around
200 mL de-ionized water. The precipitated white fibers were washed thoroughly with
o

de-ionized water, filtered and dried under vacuum at 60 C for 24 hrs to get the PES
copolymers, Yield: 91%.
2.4 Synthesis of the side-chain-type sulfonated poly(ether sulfone)s (SPES-NDS)
copolymers

648

The synthesized side-chain-type sulfonated poly(ether sulfone) copolymers were named

as SPES-NDSx, where x refers to the feed molar ratio of NDS to PES. As an example, the
synthesis of SPES-NDS60 was depicted as follows: To a 100-mL 3-neck flask equipped with a
magnetic stirrer, a nitrogen inlet/outlet, were successively added 1.734 g (3.19 mmol) of PES,
0.727 g (1.91 mmol) of NDS-K (dissolved in 6.6 mL DMSO in advance), 0.302 g of (2.19 mmol)
o

K2CO3 and 19.3 mL of DMSO. The solution was slowly heated to 80 C for 15 hrs, then cooled
to room temperature and poured into around 200 mL de-ionized water. The precipitated fibers
o

were washed thoroughly with de-ionized water, filtered and dried under vacuum at 60 C for 24
hrs to get the SPES-NDS60 copolymers, Yield: 82%.

2.5 Membrane preparation

Membranes were prepared by casting 5wt % (in DMSO) SPES-NDSx solutions onto a
o

glass plate at 80 C and 120 C each for 12h. The peeled-off membranes were then washed
with de-ionized water for 24 h, immersed in 2 M HCl for 72 hrs for proton exchange, rinsed with
o

de-ionized water adequately, and dried at 120 C under vacuum for 2 hrs, successively, to get
proton-type SPES-NDSx membranes. Thickness of the as-cast membranes was about 50 m.

3 RESULTS AND DISCUSSION

3.1 Copolymer synthesis and characterization
The synthesis of SPES-NDS copolymers was carried out through two steps as illustrated
in Fig. 1: (1) PES copolymers sysnthesized by direct aromatic substitution copolymerization of
SDP and DFBP, wherein 0.4% excess molar equivalent of DFBP was added in order to avoid
the occurrence of gel during the reaction (Schonberger et al., 2010); (2) sulfonated side groups
NDS-K introduced by nucleophilic substitution reaction.

Fig.1. The synthetic route of SPES-NDS copolymers.

Their chemical structures were confirmed by

13

C NMR spectra as shown in Fig. 2 and 3

Peaks belonging to each carbon atom were clearly observed for the PES copolymer in Fig. 2.
For instance, the peaks for C5-C8 located in 134.17,144.58,141.58 and 103.61 ppm,
respectively. After the introduction of NDS-K side groups, new peaks belonging to the carbon
atoms of naphthalene rings (C15-C24) appeared in Fig. 3 Chemical shifts were also observed

649

for C6, C8 and C9 due to the introduction of the side groups, indicating the successful
attachment of NDS-K to the PES backbone. It also indicated that the NDS-K reacted with the
fluorine atom neighouring to the ether linkage preferably.
3.2 IEC, water uptake, dimensional change and mechanical property
Table 1 summerizes the basic properties of obtained SPES-NDS membranes. Reduced
viscosities of the synthesized SPES-NDS copolymers were about 1.07-1.88 dL/g, suggesting
the rather high molecular weight of the copolymers. This could guarantee the good mechanical
toughness of the final solution-casting membranes.
The IEC values estimated according to the materials feed ratio were in the range of
1.22-2.07 mmol/g. However, the actual IEC values determined by the acidbase titration
method were in the range of 1.101.67 mmol/g, 10-20% lower than the theoretical ones. This
might be caused by the imcomplete reaction between NDS-K and PES. Water uptake,
membrane swelling in the in-plane (l) and through-plane (t) directions are closely related to
the IEC level and have a profound influence on membrane dimensional stability and proton
conductivity.

2 3
O

O
S

F 6 7 F F 11 F
10
5
12
8 9

n
F

F F

10,11

160
ppm (t1)

150

12
7

140

8,9

130

120

Fig.2. 13C NMR spectrum of PES in CDCl3

650

110

2 3
O

F 6 7 F F
10
8
5
9
13 14
F F
16 15 O
KO3S 17
24
18
19
22 23
20
21
KO 3S
O
S
O

11 F
12

2
n

3,13

6,11

17,23

10

15

23 21,22

16
19 24 9

18,20

14

160
ppm (t1)

12

150

140

130

120

110

Fig.3. 13C NMR spectrum of SPES-NDS40 in DMSO-d6.

o

Fig. 4 shows the water uptakes of the obtained SPES-NDS membranes at 30-90 C. As
expected, all membranes showed increasing water uptakes both with increase in IEC and
temperature. For example, the water uptake increased by 19.7% from 30-90

C for

SPES-NDS80, but only by 5.6% for SPES-NDS40. In addition, SPES-NDS40-60 showed

o

lower water uptake than Nafion 112 from 30-90 C, while their IEC are higher than Nafion 112.
Fig. 5 and 6 show the membrane swelling in the in-plane (l) and through-plane (t)
o

directions of the SPES-NDS in water at 30-90 C. Comparing the two figures, it was noted that
all the SPES-NDS membranes exhibited nearly isotropic expansion properties, silimar to those
main-chain type ones (Zhang et al., 2011). They also showed the same ascending tendency to
water uptakes in respective of IEC and temperature. For example, at 60 oC, the l and t
values of SPES-NDS60 (1.68 mmol/g) were 12% and 10%, respectively, while 14% and 12%
for SPES-NDS70 (1.88 mmol/g), respectively.
Table1 Basic properties of sulfonated polyether sulfone membranes.

IEC (mmol/g)

(dL/g)

Cal.

SPES-NDS40

1.88

1.22

SPES-NDS50

1.41

SPES-NDS60

Code

Titr.

Hydrolytic stability

Mechanical property

Thoughness

Weight loss%

MS(MPa)

Eb(%)

YM(GPa)

1.10

39.8

9.6

1.75

1.46

1.22

48.0

12.1

1.39

1.37

1.68

1.31

6.74

41.9

10.2

1.28

SPES-NDS70

1.07

1.88

1.54

-e

42.1

9.8

1.23

SPES-NDS80

1.69

2.07

1.67

-e

38.3

12.7

1.13

Nafion112

-f

0.91

0.89

-f

-f

40

377

0.24

theoretical value;

titration value; c immersed in water at 140 oC for 24 hrs;

and returned back without fracture;

samples could be folded

samples dissolved in water that can not be measured;

measured.

651

not

80

SPES-NDS40
SPES-NDS50

70
Water Uptake (%)

SPES-NDS60
SPES-NDS70

60

SPES-NDS80
50

40
30
20
20

30

40

50

60
T oC

70

80

90

100

Fig.4. Temperature dependence of the water uptake of the SPES-NDS membranes.

Due to their low water uptake, the series of SPES-NDS except SPES-NDS80 exhibited
lower dimensional swelling than that of Nafion 112 at 80 C. The present side-chain-type
sulfonated SPES-NDS also showed generally lower swelling than many main-chain-type
sulfonated poly(arylene ether)s with similar IEC values (Xing et al., 2004; Qiang et al., 2011),
this might be attributed to the better hydrophilichydrophobic separation between the polymer
main chain and the sulfonate groups in SPES-NDS membranes. Because of the incorporation
of highly ionic groups, the absorption of water can be restricted to a specific hydrophilic
domain in the membrane that is molecularly separated from the hydrophobic domain, and the
latter domain may retain its cohesion and restrict the swelling (Norsten et al., 2006),
Meanwhile, the fluorinated polymer backbone has high hydrophobicity, as well the conjugation
action between - naphthalene ring, force naphthalene ring to stacke together and the
membrane maintains a relatively low water absorption ,the final result is that the membrane
exhibits a good dimensional stability (Lafitte et al., 2007).
20
SPES-NDS40
18

SPES-NDS50

16

SPES-NDS60
SPES-NDS70

l%

14

SPES-NDS80
12

10
8

6
4
30

40

50

60

70

80

90

o
Fig.5. The in-plain dimensional change (l ) of T
theCSPES-NDS membrane in water.

652

22

SPES-NDS40

20

SPES-NDS50
SPES-NDS60

18

SPES-NDS70

t %

16

SPES-NDS80

14
12
10

8
6
30

40

50

60

70

80

90

T oC

Fig.6. The through-plain dimensional change (t) of the SPES-NDS membrane in water.

As listed in Table 1, the obtained SPES-NDS membranes all displayed quite good
mechanical properties. The Young's modula (YM) were in the range of 1.13-1.75 GPa,
maximum stress (MS) and the maximum elongation at break (Eb) were 38.3-48.0 MPa and
9.6-12.7%, respectively. A slightly decrease in Youngs modulus was found with the increase of
the IEC, this may be because the water molecules serve as a small role in the hydration state
of the plasticizer in the film, thereby weakening the mechanical properties and the interaction
between the polymer chains of the membrane (Zhang et al., 2011).
3.3 Proton conductivity and hydrolytic stability
Proton conductivities of all the fully-hydrated membranes were measured in the
temperature range of 30-90 oC and are plotted as a function of temperature in Fig. 7. As can be
seen from the figure, the conductivity increases with increasing temperature and IEC.

Proton conductivity (mS/cm)

300

SPES-NDS40
SPES-NDS50
SPES-NDS60
SPES-NDS70

SPES-NDS80
30
2.7

2.8

2.9

3
1000/T(K-1)

3.1

3.2

3.3

3.4

Fig.7. Temperature dependence of the proton conductivity of the SPES-NDS membranes.

Despite a lower water uptake, the SPES-NDS exhibit relatively high proton conductivity.

653

For example, the SPES-NDS70 and 80s proton conductivity in water at 80 oC are 235 mS / cm
and 277 mS / cm, respectively, both are much more higher than Nafion 112 (185 mS / cm).
With increasing IEC values for SPES-NDS from 1.10 to 1.67 g/mol, proton conductivities
increased from 32 to 119 mS/cm at 30 C and from 118 to 322 mS/cm at 90 C. Compared to
many other main-chain-type sulfonated poly(arylene ether)s with similar IEC (Wang et al.,
2002) the SPES-NDS also showed higher conductivities.
Table 1 also shows the accelerating-aging hydrolytic stability test results of the
SPES-NDS membranes, where the membranes were immersed in water at 140 oC for 24 hrs.
The obtained membranes showed quite different hydrolytic stability. In particular, no losses in
weight and mechanical toughness were observed for the membranes of SPES-NDS40 and
SPES-NBS50 after the test, indicating their excellent hydrolytic stability. The membrane of
SPES-NDS60 lost 6.74% of its original weight but still kept high mechanical toughness. On the
other hand, other two membranes with IECs>1.88 mmol/g lost their mechanical toughness
drastically, they even dissolved completely in the water. IEC seems to play an important role.
To enhance the hydrolytic stability of this kind of membrane with higher IECs, further
modifications such as structural design and crosslinking is necessary.

4 CONCLUSIONS
A series of novel side-chain type proton exchange membranes derived from poly(ether
sulfone) copolymers bearing sulfonated naphthalenyl groups (SPES-NDS) were successfully
prepared, and their chemical were confirmed by

13

C NMR. The as-prepared membranes with

IEC of 1.22-2.07 mmol/g showed good dimensional stability of very low water uptake (27-58%)
and dimensional swelling. SPES-NDS60 (1.68 mmol/g) displayed water uptake of 40% and the
o

proton conductivity reached 124 mS/cm in water at 60 C. The membranes with IEC<1.68
mmol/g exhibited excellent hydrolytic stability, suggesting its good potentials for fuel cell
applications.

ACKNOWLEDGEMENT
This work was financial supported by, or in part by, the National Natural Science
Foundation of China (21006052, 21276128), Basic Research Program of JiangSu Province of
China (BK2011713), the Scientific Research Foundation for the Returned Overseas Chinese
Scholars, the Fundamental Research Funds for the Central Universities (30920130121014).
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(SPEEK)/Nafion for direct methanol fuel cells (DMFCs). Hydrogen Energy 11025-11033.
Zhang X., Z. X. Hu and L. J. Wang, 2011, Preparation and Properties of Crosslinked Multiblock
Sulfonated Poly(arylene ether sulfone) Membrane for Fuel Cell Applications. Journal of
Applied Polymer Science 121: 1707-1716.
Zhang Z. H., L. Wu and T. W. Xu, 2011, Synthesis and properties of side-chain-type sulfonated
poly(phenylene oxide) for proton exchange membranes. Journal of Membrane Science
373: 16
Zhou S., D. Kim, 2012, Cross-linked arly-sulfonated poly(arylene ether ketone) proton
exchange membranes for full cell. Electrochimica Acta 63: 238.
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sulfonated side chains for direct methanol fuel cells. Journal of Power Sources 196:
7481-7487.

655

THE EFFECTS OF HUMIDIFICATION TEMPERATURE ON THE PERFORMANCE

OF A SINGLE PEM FUEL CELL WITHOUT AN EXTERNAL COOLING
CONTROLLER
a

He Qi , Shixue Wang *
a: School of Mechanical Engineering, Tianjin University, 92 Weijin Road, Nankai, Tianjin, China
b: State Key Laboratory of Engines, Tianjin University, 92 Weijin Road, Nankai, Tianjin, China
* E-mail address: wangshixue_64@tju.edu.cn

ABSTRACT
Water management in PEM fuel cells is a basic but significant issue, which has been widely studied.
The cell voltage increased slowly to the top, then decreased to zero when a PEM fuel cell was tested
under a constant current mode of 0.8A/cm2. The temperature of the fuel cell and the decrease in
pressure between the inlet and outlet of the flow fields were monitored during the tests. It was
observed that the temperature of the fuel cell increased rapidly throughout the duration of the test,
the relatively high temperature resulted in the dehydration of membrane and that experimental results
indicated that the dehydration was the cause of monotonous voltage decay. A different humidification
temperature of hydrogen and air suggested that the main factor which affected the dehydration of
membrane was associated with the cathode, and that air humidification played an important role in
improving the dehydration of membrane and ensuring the fuel cell operating in a stable state.
Keywords: Dehydration; Water management; Thermal management; PEM fuel cells;
humidification temperature.
INTRODUCTION
Proton Exchange Membrane Fuel Cells (PEMFC) are capable of converting the chemical energy of
hydrogen and oxygen into electrical energy directly with additional benefits which include: nonpollution, high efficiency, simplicity in design and reliability. As a result, PEMFCs are considered to be
more effective for use in automotive applications, portable electrical devices and stationary cogeneration units. Over the past twenty years, as environmental concerns grow, a significant amount
of work has focused on improving their performance and reducing their costs.
During the operation of a PEMFC, water and large amounts of heat are produced, in addition to
electricity. The performance of fuel cell is related to the proton conductivity of the polymer electrolyte
membrane, while the proton conductivity is highly dependent on the water content of the membrane,
improper water management lead to drying or flooding (Yousfi-Steiner et al., 2008). Generally,
thermal management is required to remove the excessive heat in order to ensure the fuel cell
operating at a suitable temperature range, as the excessive temperature may cause the dehydration
of the membrane and may even damage it. On the other hand, a relatively lower temperature will
prevent the cell from achieving a satisfactory power output. So maintaining a satisfactory hydration
balance for the membrane is not only dependent on proper water management but also proper
thermal management or more specifically, a proper cooperation between water management and
thermal management (Rowe A. et al., 2001).
Operating parameters are key factors impacting the performance and stability of fuel cells, and also
the main research contents of water and thermal management. In recent years, several papers
focusing on these parameters, such as operating temperatures, operating pressures and
humidification temperatures, have been published. Wang L et al. (Wang L et al., 2003) carried out
experiments with different fuel cell operating temperatures, different cathode and anode
humidification temperatures, different operating pressures, and various combinations of these
parameters to discuss the possible mechanisms of the parameter effects and their interrelationships.
Jeon D.H. et al. (Jeon D.H. et al., 2011) carried out experiments to study the effect of relative
humidity of the cathode on PEM fuel cells focusing on automotive operation. Wong K.H. et al. (Wong
K.H. et al., 2011) used a two-dimensional, two-phase PEM fuel cell model to discuss the influences of
individual roles of inlet anode and cathode humidification on PEM fuel cells performance. They both
concluded that the humidity of the cathode played a key role on the cells performance and its
uniformity.
At present, several steady state simulation models have been developed for studying the effects of
operation parameters on PEM fuel cell performances. Few studies however exist for single PEM fuel
cells on the dynamic period from start up to steady state without an external cooling controller.
Therefore, in this paper, we will focus on the experimental study of the functioning of a PEM fuel cell
during the dynamic period and observations on its temperature and the pressure at the inlet of the
channel fields. The objective of this article is to discuss the interaction of the operational parameters
which impact the performance of a fuel cell especially the humidification temperature of gases, and

656

also the effect of reaction heat on water management, to provide a better understanding of the
functioning of fuel cells work during the dynamic period, especially the effects of parameters on fuel
cell performance from start up to steady state. The results obtained in this study would be useful for
PEM fuel cells that require frequent startups and shutdowns or experience changes in their operating
temperature.
EXPERIMENT
1. Design of PEM fuel cell

The single PEM fuel cell used for this experiment consisted of the membrane electrode assembly
(MEA), two graphite plates (90mm90mm20mm) and two end plates. The active surface area of
the MEA was 50mm50mm, and consisted of Nafion 212 membrane with platinum loadings of
0.4mg/cm2, TGP-H-060 carbon paper was used as the gas diffusion layer (GDL).
Fig.1 shows the graphite flow field plate. Single serpentine flow fields were used in both the anode
and cathode. The width and depth of serpentine channel were both 1mm. The width of rib was also
1mm.
The temperature of this fuel cell was not controlled, as we were interested in the effects of changes in
cell temperature. The cell temperature was observed through a thermocouple embedded in the well
as showed in Fig.1. Because the maximum temperature difference inside the cell was very small and
the temperature distribution was even (Hashimasa Y. et al., 2006), only one temperature was used
to represent the cells average temperature. In the fuel cell test system ,this temperature was
expressed as theend-plate temperature.

Fig.1 Graphite flow field plate

2. Experimental set-up

The fuel cell test system as showed in Fig.2 was manufactured by Ningbo Bate Technologies. It is
capable of controlling the gas flow rate, humidification temperatures and back pressures of both the
anode and cathode through a computer. Reactant gases are humidified by passing through internal
water tanks, and the temperature of water in the tank can be changed to control the humidification
temperature of the gases. When the gases are released from the water tank, they are prevented from
cooling and condensing on the way to the fuel cell by the regulation of the dew point and inlet
temperatures. The gas connection between the fuel cell test system and the fuel cell inlets are well
insulated. We can also record the temperature of fuel cell, inlet pressure of both the anode and
cathode through the test system. Since the back pressure of fuel cell remains basically unchanged,
the inlet pressure is used to represent the pressure drop of the channel field. The electric load used
in the system is 100 W.

657

Fig.2 Schematic diagram of experimental setup

3. Experimental conditions

The single PEM fuel cell was operated under a constant current discharge mode of 0.8A/cm2. The
hydrogen flow rate was 240sccm (stoichiometic: 1.5) and air flow rate was 760sccm (stoichiometic:
2.0). Both the back pressure of the anode and cathode were 0. In the absence of an external cooling
controller, the cooling of the cell by means of natural convection and radiation from the surrounding
environment. To prevent the humidified gases from cooling and condensing on the way to the fuel
cell, the dew point temperature was maintained at 1 higher than the humidification temperature,
and the inlet temperature at 1 higher than the dew point temperature. For example, the dew point
temperature would be set to 41 for a humidification temperature of air at 40, and the inlet
temperature to 42.
4. Experimental procedures

(1) The anode and cathode were purged with nitrogen.

(2) The experimental parameters: flow rate, humidification temperature, dew point temperature,
inlet temperature and back pressure, were set.
(3) The electric load was set once the relevant temperatures had reached the required levels.
(4) The computer program for recording the voltage and the temperature of the fuel cell and the
inlet pressure of cathode and anode was started.
A delay of 1s was selected between every two data points to make sure every point of voltage
was accounted for when the fuel cell functioned in a constant current discharge mode.
RESULTS AND DISCUSSION
In Fig.3, air and hydrogen is not humidified and the cell voltage increases slowly, before decreasing
rapidly. The value of the cell voltage is less than 50mV when fuel cell has operated for 37 minutes.
The dehydration of membrane is responsible for the monotonous voltage decay (Barbir F. et al.,
2005). There are no external cooling measures between the fuel cell and its surroundings, and any
cooling is due to natural convection and radiation. As a result, the end-plate temperature (cell
temperature) of the fuel cell increases from 25 to 55 in Fig.3, due to the heat produced. The inlet
pressure of the cathode decreases during the full operating time while the fluctuation of the cathode
inlet pressure line reduces gradually. We know that water is generated at the cathode of the PEM fuel
cell and the liquid water in the cathode channel is the main factor which influences the drop in
pressure (Liu X. et al., 2007). Both the decrease in fluctuation and decay of the pressure line indicate
a reduction of the liquid water in the cathode flow channels. The decrease of the cathode inlet
pressure also indicates a lower air velocity, which causes a decrease in the rate at which heat is
eliminated from the cathode through the flow of air. We know that water will be caused to flow from
the anode to the cathode by protons moving through the electrolyte, and also from the cathode to
anode through back-diffusion. In Fig.3, the anode inlet pressure initially increases, before stabilizing,
as the hydrogen is not humidified, hence the attribution of the increase in the anode inlet pressure to
back-diffusion.

658

Fig.3 Cell voltage, end-plate temperature, anode inlet pressure and cathode inlet pressure vs.
operating time. (Hydrogen humidification temperature: dry hydrogen at room temperature, Air
humidification temperature: dry air at room temperature. Hydrogen flow rate: 240sccm, Air flow rate:
760sccm. Current density: 0.8A/cm2.)
In Fig.4, the humidification temperature of the hydrogen and air is 40. Compared to Fig.3, the
maximum value of the cell voltage in Fig.4 is higher and the operation time is longer. However in
spite of this, the cell voltage still falls below 50mV. The temperature gradually increases, and the
cathode inlet pressure decreases gradually, preventing the fuel cell from functioning efficiently at a
humidification temperature of 40 and resulting in the dehydration of the membrane. In Fig.4, from
70 minutes to 80 minutes, there is a jump of the voltage line corresponding to the jump of cathode
inlet pressure line and anode inlet pressure line, indicating they are positively related. We know that
the increase in channel pressure contributes to an increase in cell performance. On the other hand,
liquid water results in an increase in pressure and contributes to an improvement in performance
when the MEA is about to become completely dry. Hence liquid water can be considered beneficial.
Its source however is uncertain and may be the condensed water vapor in the inlet pipe or the
uneven distribution of liquid water in the flow fields. The anode inlet pressure decreases initially, and
then increase to a steady state due to fact that the PEM fuel cell was started at a temperature of
25, while the humidification temperature of hydrogen was 40. As a result, the water vapor in the
hydrogen flow will condense on entering the fuel cell and the liquid water will enter the GDL and
humidify the membrane. This may be considered as the humidification stage of the membrane during
start-up. When this stage is completed, the anode inlet pressure will increase gradually due to of the
accumulation of liquid water.

Fig.4 Cell voltage, end-plate temperature, anode inlet pressure and cathode inlet pressure vs.
operating time. (Hydrogen humidification temperature: 40, Air humidification temperature:40.
Hydrogen flow rate: 240sccm, Air flow rate: 760sccm. Current density: 0.8A/cm2.)
In Fig.5, the humidification temperature of air and hydrogen is 60 and the cell voltage does not
decrease as it did in Fig.3 and Fig.4, but remains stable while the fuel cell temperature increases as it
did previously before finally becoming stable. The oscillations in the pressure line are caused by
liquid water being flushed out and reaccumulated in the channel (He W. et al., 2003). However the
oscillations do not cause corresponding oscillations in the voltage line. Hence, it is possible that MEA
may operate under suitable conditions and that the change of liquid water and the pressure in
channel had a minute impact on performance in this occasion. The gas flow in the channel of the
PEM fuel cell used in this experiment was influential in eliminating the heat produced by the reaction.
The presence of liquid water in channel was also influential in alleviating the dehydration of

659

membrane while also causing an increase in pressure, which was instrumental in eliminating the heat
generated in the catalyst layer.

Fig.5 Cell voltage, end-plate temperature, anode inlet pressure and cathode inlet pressure vs.
operating time. (Hydrogen humidification temperature: 60, Air humidification temperature: 60.
Hydrogen flow rate: 240sccm, Air flow rate: 760sccm. Current density: 0.8A/cm2.)
The humidification temperature of hydrogen and air was set to different values to observe their
impact on cell performance. In Fig.6, the hydrogen humidification temperature is 60 while the air
humidification temperature is 40. During this experiment, the fuel cell was observed for 150
minutes and the cell voltage did not fall below 50mV, although the voltage line was rather erratic,
similar to the results of Cai Y et al. (Cai Y et al., 2006). It can be concluded that the increase in the
hydrogens temperature from 40 to 60 could improve the dehydration of membrane to some
extent, but is incapable of functioning suitably. In Fig.6, the erratic voltage line has been divided into
two regions: A and B. In region A, cell voltage is relatively higher while the temperature does not
change due to the higher pressure in the cathode channel, which could eliminate more heat. In
region B, the cell voltage falls, while the cathode inlet pressure decreases gradually, resulting in an
increase in the reaction heat retained within the fuel cell causing an increase in the temperature of
the fuel cell once again. This phenomenon can also be observed in Fig.4.

Fig.6 Cell voltage, end-plate temperature, anode inlet pressure and cathode inlet pressure vs.
operating time. (Hydrogen humidification temperature: 60, Air humidification temperature: 40.
Hydrogen flow rate: 240sccm, Air flow rate: 760sccm. Current density: 0.8A/cm2.)
In Fig.7, the hydrogen humidification temperature is set at 40 and the air humidification
temperature at 60. We can see that the performance improves due to the increase in the
humidification temperature of the air and that the voltage line also remains stable. Compared to
hydrogen humidification, air humidification is more important for improving the dehydration of the
membrane. This is similar to the modeling results of the alkaline anion exchange membrane fuel cell
by Jiao K et al. (Jiao K et al., 2014). The reasons for this may be due to the fact that the air flow rate
is significantly higher than the hydrogen flow rate resulting in an increase in the water vapor provided
by the air; secondly, the pressure in cathode channel is higher than in the anode channel and the
purging ability of air is increased making it easier to dry the cathode; thirdly, the differential pressure
between the cathode and anode results in an increase in the water transported from the cathode to
the anode through back-diffusion. As a result of the three reasons which have been stated, we can
conclude that although water is generated in the cathode, the main factor affecting the dehydration of
membrane can also be found in the cathode. The humidification of air is more important than the
humidification of hydrogen for improving the dehydration of the membrane. However, the maximum

660

value of the cell voltage in Fig.6 is higher than in Fig.7 and can be attributed to the porous GDL
material: if more water is brought by the air into the cathode channel the GDL would be blocked
resulting in mass transport loss.

Fig.7 Cell voltage, end-plate temperature, anode inlet pressure and cathode inlet pressure vs.
operating time. (Hydrogen humidification temperature: 40, Air humidification temperature: 60.
Hydrogen flow rate: 240sccm, Air flow rate: 760sccm. Current density: 0.8A/cm2.)

CONCLUSION
A single PEM fuel cell with a serpentine flow field was tested under a constant current discharge
mode of 0.8A/cm2 in this paper. Due to a lack of external cooling measures, the heat of the
reaction caused the cell temperature to increase. During the test, we found the reaction heat
greatly influences the performance of the cell and effectively combining operational parameters
(cell temperature, channel pressure and humidification temperature) enables the fuel cell to
operate efficiently.
At gas humidification temperatures below 40, the dehydration of the membrane occurs resulting
in monotonous voltage decay or erratic cell voltage.
By varying the humidification temperature of hydrogen and air, we found that the main factor
affecting the dehydration of membrane could be found in the cathode side, the humidification of air
as opposed to the humidification of hydrogen, is more important for improving the dehydration of
the membrane, and also essential for maintaining a stable working state possibly due to the higher
air flow rate and cathode channel pressure. However, a relatively higher humidification
temperature of air means more water will be brought into cathode, resulting in an inevitable loss of
mass transport.
NOMENCLATURE
sccm standard-state cubic centimeter per minute
REFERENCES
Barbir F., Gorgun H., and Wang X.. 2005. Relationship between pressure drop and cell resistance as
a diagnostic tool for PEM fuel cells. Journal of Power Sources 141(1): 96-101.
Cai Y., Hu J., Ma H., Yi B., and Zhang H.. 2006. Effect of water transport properties on a PEM fuel
cell operating with dry hydrogen. Electrochimica Acta 51(28): 6361-6366.
Hashimasa Y., Numata T., Moriya K., and Watanabe S.. 2006. Study of fuel cell structure and
heating method: Development of JARI's standard single cell. Journal of Power Sources 155(2): 182189.
He W., Lin G., and Van Nguyen T.. 2003. Diagnostic tool to detect electrode flooding in proton
exchange membrane fuel cells. AIChE Journal 49(12): 3221-3228.
Jeon D. H., Kim K. N., Baek S. M. and Nam, J. H.. 2011. The effect of relative humidity of the
cathode on the performance and the uniformity of PEM fuel cells. International Journal of Hydrogen
Energy 36(19): 12499-12511.

661

Jiao K., He P., Du Q., and Yin Y.. 2014. Three-dimensional multiphase modeling of alkaline
anion exchange membrane fuel cell. International Journal of Hydrogen Energy,
http://dx.doi.org/10.1016/j.ijhydene.2014.01.180
Liu X., Guo H., Ye F., and Ma C. F.. 2007. Water flooding and pressure drop characteristics in flow
channels of proton exchange membrane fuel cells. Electrochimica Acta 52(11): 3607-3614.
Rowe A., and Li X.. 2001. Mathematical modeling of proton exchange membrane fuel cells. Journal
of Power Sources 102(1): 82-96.
Wang L., Husar A., Zhou T., and Liu H.. 2003. A parametric study of PEM fuel cell performances.
International Journal of Hydrogen Energy 28(11): 1263-1272.
Wong K. H., Loo K. H., Lai Y. M., Tan S. C., and Tse C. K.. 2011. A theoretical study of inlet relative
humidity control in PEM fuel cell. International Journal of Hydrogen Energy 36(18): 11871-11885.
Yousfi-Steiner N., Mootguy P., Candusso D., Hissel D., Hernandez A., and Aslanides A.. 2008. A
review on PEM voltage degradation associated with water management: Impacts, influent factors
and characterization. Journal of Power Sources 183(1): 260-274.

662

Lean Methane Premixed Combustion over Catalytically Stabilized Zirconia

Foam Burner
Xiangbo Feng, Zhiguo Qu*
MOE Key Laboratory of Thermo-Fluid Science and Engineering, Energy and Power Engineering School,
Xian Jiaotong University, Xian 710049Shaanxi, China
*Corresponding author: zgqu@mail.xjtu.edu.cn

Abstract
This study experimentally investigated a lean methane/air premixed catalytic combustion in
catalytic zironia foam burner. The burner was packed with 3 mm alumina pileup-pellets at the
preheating zone and catalytic zirconia foam at the combustion zone. The catalytic zironia foam
prepared by a modified perovskite catalyst (LaMn0.4Co0.6O3), in which the transition metal ion Co
was partially substituted by Mn, was supported on the zironia foam. Results indicated that the flame
stability limits of catalytic and inert zironia expanded with increase of equivalence ratio. The
stabilization region of catalytic zironia was larger than that of inert zironia, and notably, the
heterogeneous catalytic combustion effect decreased the lower flame stability limit (LFL) and
increased the upper flame stability limit (UFL). The central temperature of flame front for catalytic
zironia was higher than the equivalent inert zironia. The pressure drop for catalytic zironia was
almost equal to that of inert zironia in cold flow, whereas was significantly higher than that of inert
zironia in reaction flow. The thermal radiation efficiency of the catalytic zironia varied between 0.24
and 0.39 and it was favorably superior to that of inert zironia ranging from 0.11 to 0.20. Compared to
the inert zironia, only a small amounts of carbon monoxide, nitric oxide and hydrocarbon emissions
were detected in catalytic zironia.
Keywords: methane combustion; catalytical zironia; equivalence ratio; flame stability limit; pollution
emission.
1. Introduction
In recent decades, pre-mixed combustion in porous media has received extensive
experimental [1,2] and theoretical attention [3,4] especially for its potential superiorities in
enhancing the efficiency of heat transfer and reducing the environmental impact due to decrease of
pollutant emissions( monoxide (CO), nitrogen oxide (NOx), and hydrocarbon (HC) ). In this
technology, the fuel/ air mixture is fed into a porous media, where combustion is ignited by sparking
and, depending on the operating conditions (volumetric flow rate, equivalence ratio, structure of the
combustion burner), the flame front is stabilized close to the downstream surface of porous foam or
partly inside of it. As opposed to free flame technology, porous media combustion allows a stronger
heat exchange by radiation and conduction from solid foam to boiler surface, this tentails both an
increase of the thermal radiation efficiency and a reduction of flame temperature, thereby enabling
a lower formation of thermal NOx. Despite various advantages on

porous media combustion, the

relative level of HC emission is inevitable, particularly, in lean methane combustion because

homogeneous inert porous media combustion has no definable benefit for HC emission reductions
at such lean methane conditions as indicated in [5].
Catalytic combustion is a promising technology for complete lean methane/air premixed
combustion, which has been shown to be an alternative to free flame combustion or inert porous
media combustion as indicated in [6]. Catalytic combustion is an environmental driven combustion
technology to achieve ultra low emissions. Catalysts allow starting combustion well below the
typical lower flame stability limit level, resulting in a lower flame temperature. This lower gas phase
flame temperature eliminates the large formation of thermal NOx and, the activity and stability over
1

663

the catalyst facilitates the fuel complete combustion. Besides, catalytic combustion also helps to
reduce the emission of CO and other partially oxidized compounds.
So far, the catalysts mostly employed for complete methane catalytic combustion are
supported noble metals catalysts, which, however, besides being expensive, can generate harmful
compounds and may sinter or inactivate rather easily [7]. Therefore, Perovskite-type catalyst has
attracted great attention for methane complete combustion as alternative to the noble metal catalyst
[8]. Development of the perovskite-based catalysts appears to be a very promising strategy to cope
with all of those applications of methane catalytic combustion, which not only develops relatively
high activity at high temperature , and but also can benefit from a more heat-resistant and durable
catalyst [9]. Perovskite-type catalysts are also excellent methane combustion catalysts for their
thermal stability and catalytic activity can be enhanced by transition metal A/or B-site metal
substitutions as reported in [10, 11]. Considering that transition metal ion Mn had several relative
advantages on specific surface area and thermal stability compared with ion Co. The modified
perovskite catalyst (LaMn0.4Co0.6O3) in which the transition metal ion Co was partially substituted by
Mn was designed in experimental preparation.
Despite a considerable number of papers dealing with perovskite in the oxidation reactions,
few papers have focused on the preparation of perovskite-based zironia foam catalyst which
directly depositing the perovskite catalyst on the zironia foam. In addition, a few studies have
compared the combustion performance of perovskite catalyst-supported zironia foam with their inert
zironia foam counterpart. This paper mainly compared the results of combustion performance of
zironia foam supported modified perovskite catalyst and inert zironia foam. The flame stability limits,
central temperature of flame front foam, radiation efficiency, exhaust gas temperature, pressure
drop, and pollution emissions of modified perovskite-supported zironia foam and inert zironia were
evaluated.
2. Experimental section
2.1. Preparation and characterization of catalytic foam
The modified perovskite LaMn0.4Co0.6O3 powder was prepared with via a modified version of
the

so-called

citrateswetness

impregnation

method.

Solid

mixtures

La(NO3)3.6H2O,

Mn(NO3)2.6H2O, and Co(NO3)2.6H2O were mixed with a 40 wt.% amount of citric acid and 50%
water. The obtained solution was slowly heated up to120until a slight gas emission (NOx, CO,
and water vapour) started. The very viscous liquid generated was then rapidly poured in a stainless
vessel, kept in oven at 250, thereby causing immediate and massive gas formation, which led to
the formation of a solid scum, quite friable and porous. The scum was then finely ground in an
agate mortar and kept in oven for 2 h in calm air at 900. In order to obtain the relative stable
thermal stability, the catalyst was calcined at 1100 for 4 h. The final perovskite powder was
produced. Then, the perovskite catalyst will deposite on the support, which used the zironia foam
as the support. The support required pretreatment before loading catalyst. zironia foam was first
rinsed with distilled water and then with acetone, followed by drying at 110 C for 2 h and
calcinations at 900 C for 4 h. The following preparation procedure was conducted to achieve a
LaMn0.4Co0.6O3 concentration of 5wt.%. The pretreated zironia foam was impregnated in the slurry
of perovskite catalyst for approximately 2 h to coat the catalyst on the zironia foam and then dried
and weighed. The impregnating processes were repeated four times to obtain preliminary catalytic
foam. The contents of the perovskite active phase accounting for support foam were 5wt.%. The
surface morphology of catalytic zironia and inert zironia counterpart was observed by a scanning
2

664

electron microscopy (HITACHI S-4700, Japan). The obtained micrographs were shown in Figure 1.

(a)

(b)

Fig.1 SEM micrographs: (a) inert zironia support foam; (b) catalytic zironia foam.
Specific surface area is one of the most important factors influencing the catalytic combustion
performance. The specific surface areas of powder perovskite catalyst, catalytic zironia, and inert
zironia foam support before and after combustion were evaluated with an automatic gas sorption
analyzer (Quantachrone-Autosorb-IQ, USA). The testing results were shown inTable 1.
Table1. Specific surface areas of perovskite catalyst powder, catalytic zironia foam and inert
zironia foam
specific surface area (m2/g)

specific surface area (m2/g)

(before combustion)

(after combustion)

LaMn0.4Co0.6O3 (powder)

33.5

11.0

inert zironia (support)

0.8

0.1

catalytic zironia (foam)

6.1

4.0

Material

The effective thermal conductivities of catalytic zironia and inert zironia were measured using a
Hot Disk thermal analyzer (Hot Disk AB, Uppsala, Sweden), which were summarized in Table 2.
Table 2. Properties parameters of foams (catalytic and inert)
Material
Catalytic
zironia
inert zironia

Pore

Pore

Effective thermal

density(ppi)

diameter(mm)

conductivity(W/(mK))

0.78

10

3.92

0.44

0.80

10

3.97

0.41

Porosity

2.2. Experimental setup

Fig.2 shows the schematic diagram of the experimental apparatus, which consists of four parts:
fuel/air supply system, mixing chamber, catalytic porous foam burner, and measuring and data
processing equipment.

665

Fig.2. Schematic of the experimental setup.

The CH4 was stored in high-pressure bottle to flow with through the pressure-reducing. The
volumetric flow rate was regulated by a mass flow controller (methane-C10 Smart-Trak, Sierra
Instruments, USA) to satisfy the required equivalence ratio before entering the mixing chamber. The
air was supplied by an air compressor connected to an air storage tank for pressure stabilization,
passed through a filter and was controlled by another mass flow controller(methane-C100
Smart-Trak, Sierra Instruments, USA). The fuel and air were fed into a mixing chamber to ensure
that the fuel-air mixture was spatially uniform and to maintain a constant equivalence ratio during
the experimental course. Then, the mixed gas was entered into the porous foam burner. Fig. 3
shows the configuration of the catalytic porous foam burner, which was insulated around the
circumference by a Kaowool high-temperature insulation material layer with thickness of 20 mm.

Fig.3. Schematic of the catalytic porous foam burner.

The catalytic porous foam burner was a corundum tube with diameter of 50 mm, and thickness
of 5 mm. A 30 mm thickness alumina foam plate with pore density of 60 ppi was located at the
chamber inlet preheating zone

to ensure

homogeneous mixture, preheat mixed gas, and prevent flashback. In combustion zone, a 120 mm
long catalytic zironia foam with the pore density of 10 ppi was arranged. Alternatively, the
combustion zone can be arranged the inert zironia foam with the pore density of 10 ppi as the
comparison. The burner had nine B-type thermocouples (TC1 to TC9) located along the length at
1.25 cm intervals that monitored central temperature distributions of catalytic or inert zironia foam.
4

666

The pressure drop p across the porous foam was measured using a pressure transducer
(Rosemount 3051, Rosemount, USA). All signals for thermocouples and pressure transducer were
recorded using an Agilent data acquisition system. Exhaust gas was collected using a stainless
steel probe placed at the top of the burner, both the exhaust gas temperature (Tex) and the
concentrations of HC, CO, and NOx in the exhaust gas were measured using a portable flue gas
analyzer (Testo 350 Pro, Testo Inc., Germany). Uncertainty analyses were conducted for
temperature measurement, flow velocity, and equivalence ratio using root-sum-squares method by
Moffat [12]. The uncertainties of the central temperature measurement, flow velocity, and
equivalence ratio were 8.59, 1.08%, and 2.1%, respectively. The pressure drop had an uncertainty
of 1.5 Pa, and the CO, NOx, and HC emission measurements had uncertainties of 1, 2, and 10 ppm
according to the manufacturer. The detailed uncertainty analysis can be consulted in the study of
Gao et al.[13].
2.3. Parameter definations
The following parameter definitions can be consulted based on Gao et al. [14]. The
equivalence ratio and mean flow velocity of mixed gas S are shown in Eqs. (1) and (2),
respectively.

m
m

fu

fu

/ mair

actu

/ mair

9.52

stoic

VCH 4

(1)

Vair

V VCH 4 Vair

A
A

(2)

In Eqs. (1) and (2), m fu and mair are the mass flow rates of fuel and air, respectively. VCH 4 and

Vair are the respective volumetric flow rates of CH 4 and air under standard conditions, which
obtained from the mass flow
controllers. V and A are the total volumetric flow rates of methane/air and inner cross-section of
combustion burner, respectively. In the present study, the equivalence ratio ranged from 0.55 to
0.70.
The thermal radiation efficiency rad is shown in Eqs. (3), which can be obtained based on the
previous experimental study by Dupont et al. [15].

rad Qrad / Qinput FA eff (Tcex4 Ta4 ) / (VCH LHVCH

4

(3)

4 , net

In Eq. (3), Qrad , Qinput , F , eff , , Tcex , Ta , and LHVCH4 , net are the thermal radiation

output, heat input of CH4, view factor, blackness of material, StephanBoltzmann constant, central
temperature of foam exit(TC9), ambient temperature, and low heating value of CH4 under standard
conditions, respectively. During the calculation of thermal radiation efficiency, the ambient
temperature Ta , view factor F and blackness of material eff were defined as 25, 0.8, and 0.8,
respectively.
3. Results and discussion
Flame stability limits are important factors that determine the general catalytic combustion
performance of a catalytic porous foam burner. The flame stability limits is defined as the maximum
and minimum flow velocity that the flame can sustained in the catalytic foam region at the given
equivalence ratio. The lower flame stability limits (LSL) was designed as the flow velocity at which
the flame front reached the position of thermocouple TC2 (seen in Fig 3); below this velocity,
flash-back or flameout occurred. The upper flame stability limits (USL) was defined as the velocity
at which the flame front floated on the catalytic foam exit of thermocouple TC9 (seen in Fig 3). The
5

667

stabilization region was defined as the flow velocity is higher than the flow velocity of LSL and lower
than the flow velocity of USL. The flame stability limits of catalytic zironia burner and inert zironia
burner for equivalence ratio ranging from 0.55 to 0.70 are shown in Fig. 4. The stabilization regions
for both catalytic zironia and inert zironia increased and shifted to larger values with increase of
equivalence ratio because of higher heat input. The results from the present experimental study
and results from previous studies [16, 17] showed similar tendencies. However, the stabilization
region of catalytic zironia for different equivalence ratios were significantly expanded compared of
inert zironia, and notably, the lower flame stability limit (LFL) of catalytic zironia was lower than that
of inert zironia and, the upper flame stability limit (UFL) was higher than that of inert zironia. The
results can be mainly attributed to following two reasons. In one hand, the intense gassolid
heterogeneous catalytic combustion reduced the heat input and combustion temperature required
for stable combustion and, increased the diffusion rate of mixed gases, in another hand, the
improved heat transfer in catalytic burner for higher effective thermal conductivity also contributed
to the expansion of the stabilization region.
180
catalytic ZrO2

150

inert ZrO2
LSL
LSL
Stabilization region Stabilization region
USL
USL

S (cm/s)

120
90
60
30
0

0.55

0.60
0.65
Equivalence ratio,

0.70

Fig.4. Flame stability limits of catalytic zironia and inert zironia with different equivalence ratio.
Fig. 5 shows the central temperature of flame front as a function of flow velocity for catalytic
zironia and inert zironia with different equivalence ratio. Both the central temperature of flame front
for catalytic zironia and the inert zironia increased with increase of flow velocity, and significantly
increased with an increase of equivalence ratio owing to higher fuel and heat input. However, the
increase for the central temperature of flame front became mild with increase of flow velocity,
particularly, the central temperature of flame front for catalytic zironia almost decreased when the
flow velocity was higher than 70cm/s. The reason was that the flame front gradually moved to the
foam exit with the increase of flow velocity, resulting that more significant heat loss. Compared with
the central temperature of flame front for inert zironia foam at given equivalence ratio and flow
velocity, the central temperature of flame front was significantly improved by catalytic zironia
because gassolid heterogeneous catalytic combustion was more prominent than homogeneous
gas phase combustion in catalytic combustion, and the local heat mass transfer on catalytic foam
was also significantly enhanced for higher effective thermal conductivity and enhancive diffusion
rate between the mixed gas and the catalytic zironia.

668

1500
1400

TC ()

1300
1200
1100

inert ZrO2

catalyticZrO2

1000
900
0

20

40

60
S (cm/s)

80

100

120

Fig.5. Central temperature of flame front as a function of flow velocity for catalytic zironia and
inert zironia with different equivalence ratio.
The maximum central temperature of flame front for catalytic zironia and inert zironia for
equivalence ratio ranging from 0.55 to 0.70 is shown in Fig. 6. The maximum central temperature of
flame front was identified as the maximum central temperature of flame front foam at fixed
equivalence ratio with different flow velocities. The maximum central temperature of flame front
increased significantly with an increase in equivalence ratio owing to the high power input per unit
volume. However, the maximum central temperature of flame front for catalytic zironia was
extremely higher than that of inert zironia at fixed equivalence ratio because more heat was
released on the catalytic zironia by gassolid heterogeneous catalytic combustion, increased
diffusion rate between the mixed gas and catalytic zironia, and more optimal preheating
performance for more heat feedback from the combustion zone to the preheating zone because of
higher effective thermal conductivity.
1600
inert ZrO2 foam
catalytic ZrO2 foam

1500

Tcff-max ()

1400
1300
1200
1100
1000

0.55

0.60

0.65

0.70

Fig.6. Maximum central temperature of flame front for catalytic zironia and inert zironia with different
equivalence ratio.
The exhaust gas temperature for catalytic zironia and inert zironia as a function of flow velocity
with different equivalence ratio is shown in Fig.7. The exhaust gas temperature is identified as the
test result at which is measured by portable flue gas analyzer. The exhaust gas temperature for
both catalytic zironia and inert zironia increased with increased flow velocity and slowly increased
with increase in equivalence ratio because more heat released from the burner. However, the
exhaust gas temperature of catalytic zironia was found to be lower than that of inert zironia at given
equivalence ratio and flow velocity. This finding can be explained by the catalysis effect, on one
hand, the gassolid heterogeneous catalytic combustion suppressed the gas phase homogeneous
combustion, which significantly reduced the gas phase combustion rate, resulting in decreasing the
7

669

exhaust gas temperature, on the other hand, the gassolid catalytic combustion contributed to a
more complete and fast burning for fuel, which also favored to the decrease of exhaust gas
temperature.
1100
1000
900

Tg (C)

800
700
600
inert

500

0.55
0.60
0.65
0.70

400
300
200

20

40

60
80
S (cm/s)

catalytic
0.55
0.60
0.65
0.70
100

120

Fig.7. Exhaust gas temperature of catalytic zironia and inert zironia with different equivalence ratio.
The pressure drops for catalytic zironia and inert zironia as a function of flow velocity in
reaction and cold flow for equivalence ratio ranging from 0.55 to 0.70 are shown in Fig. 8(a) and Fig.
8(b), respectively. The pressure drops for both the reaction and cold flows increased with increase
in flow velocity and equivalence ratio. The pressure drops of reaction flow for both catalytic zironia
and inert zironia were higher than that of the corresponding cold flow because of the significant gas
density discrepancy in the reaction flow. The pressure drop of catalytic zironia in cold flow was
almost equal to that of inert zironia with increase of flow velocity. However, the pressure drop of
reaction flow was significantly higher than that of inert zironia. This finding can be explained by the
enhancive temperature uniformity of higher effective thermal conductivity for catalytic zironia and
lower gas density in combustion zone for higher central temperature of flame front in catalytic
zironia.
1200
cold flow
reaction flow

800
600
400
200
0

20

40

60
S (cm/s)

80

100

120

800
cold flow
reaction flow

700

600

Pressure drop (Pa)

Pressure drop (Pa)

1000

500
400
300
200
100
0

20

40

60
S (cm/s)

80

670

100

120

(a)

(b)

Fig.8. Pressure drop as a function of flow velocity for catalytic zironia (a) and inert zironia (b) with
different equivalence ratio.
Fig. 9 shows the HC emissions for catalytic zironia and inert zironia as a function of flow
velocity with different equivalence ratio. The HC emissions decreased with increased flow velocity
for both catalytic zironia and inert zironia. The maximum HC emission for catalytic zironia was less
than750 ppm (S<50cm/s) and nearly approached zero (S>50cm/s), particularly, the HC emissions
almost kept unchanged with increase of the equivalence ratio. Comparetively, the HC emission of
inert zironia ranged from 500 to 3750 ppm and tremendously increased with increase in
equivalence ratio, which was significantly higher than that of catalytic zironia. The phenomenona
can be attributed to the following facts, the fuel supply increased with increase of equivalence ratio
in inert zironia, resulting in a more incomplete burnring of fuel for a relative reduced excess air
coefficient, however, intense heterogeneous surface catalytic combustion in catalytic zironia greatly
improved the methane combustion rate and restricted the negative effect of increased equivalence
ratio for favorable active oxygen mobility ability and tremendously reduction in activation energy,
which greatly decreased the emission level of HC.
3750

inert

3000
HC (ppm)

catalytic

2250
1500
750
0
0

20

40

60
S (cm/s)

80

100

120

Fig.9. HC emissions of catalytic zironia and inert zironia with different equivalence ratio.
Fig 10 shows the CO emissions for catalytic zironia and inert zironia as a function of flow
velocity with different equivalence ratio. CO emission was controlled by catalysis effect, central
temperature of flame front, and residence time. The CO emission of catalytic zironia decreased with
increase of flow velocity (S<30cm/s) and finally approached zero when the flow velocity was above
the turning point velocity (S=30cm/s). Comparatively, the CO emission of inert zironia also
decreased with increase of flow velocity and ranged from 100 ppm to 1600 ppm with increase of
equivalence ratio, which was significantly higher than that of catalytic zironia, particularly, when the
flow velocity was less than 40cm/s. These results generally implied that heterogeneous catalytic
combustion effect and higher centre temperature were the two prevailing factors that determining
the CO emission. The CO emission of inert zironia increased with increased equivalence ratio,
owing to the incomplete combustion of CH4, lower central temperature, relatively lower excess air
coefficient, and lower diffusion rate of mixed gas .

671

1600
inert

1200
CO (ppm)

catalytic

800

400

0
0

20

40

60
S (cm/s)

80

100

120

Fig.10. Exhaust CO emissions of catalytic zironia and inert zironia with different equivalence
ratio.
Fig. 11 shows the NOx emissions for catalytic zironia and inert zironia as a function of flow
velocity with different equivalence ratio. The NOx emission for both inert zironia and catalytic zironia
increased with increase of equivalence ratio. This phenomenon was mainly due to that the central
temperature of flame front increased with increased equivalence ratio, resulting in increased
thermal NOx formation. The NOx emission of inert zironia increased with increase in equivalence
ratio ranging from 4 to 15 ppm, which was extremely higher than that of catalytic zironia burner that
ranging from 0 to 5 ppm. The NOx emission of inert zironia was governed by combination of
residence time of mixed gas and central temperature of flame front. An increased flow velocity can
result in decrease of residence time and increase of central temperature. The former played a
negative role in NOx formation, and the latter favored NOx formation. Hence, the NOx generally
increased initially and then slightly decreased with increased flow velocity. However, the NOx
emission of catalytic zironia was controlled by catalysis effect, residence time of mixed gas, and
central temperature of flame front. It was obviously discovered from the Fig. 11 that the catalysis
effect dominated the NOx emission for catalytic zironia. The NOx was formed by two mechanisms
of the thermal (Zeldovich) and prompt (Fenimore) pathway in methane combustion. The NOx
emission of lean methane catalytic combustion was mainly ascribed to the mechanism of Zeldovich.
Severe gassolid heterogeneous surface catalytic combustion that restricted homogeneous gas
phase combustion and the catalytic effect that selectively reduced NOx into N2, as previously
reported in [18, 19]. The heterogeneous catalytic combustion mainly occurred on the surface of
catalyst and controlled the combustion process, which produced little thermal NOx because the
thermal NOx mainly generated on the gas phase.
24
inert
0.55
0.60
0.65
0.70

20

NOx (ppm)

16

catalytic
0.55
0.60
0.65
0.70

12
8
4
0
0

20

40

60
S (cm/s)

80

100

120

Fig.11. Exhaust NOx emissions of catalytic zironia and inert zironia with different equivalence ratio.
10

672

Fig. 12 shows the thermal radiation efficiencies for catalytic zironia and inert zironia as a
function of flow velocity for equivalence ratio ranging from 0.55 to 0.70. The thermal radiation
efficiencies for both catalytic zironia and inert zironia increased with decrease of equivalence ratio
or decreased with increase of flow velocity. The findings can be attributed to the two facts, firstly,
relative higher fuel heat loss increased with increased equivalence ratio because of higher HC
emission as indicated in Fig.9, resulting that the thermal radiation decreased with increased
equivalence because relative less fuel heat radiated on the foam exit(TC9), secondly, heat transfer
between the mixed gas and the foam exit was weakened because the residence time of mixed gas
decreased with increase of flow velocity. The thermal radiation efficiency of catalytic zironia burner
ranged from 0.24 to 0.39 with the increase of equivalence ratio, which was significantly higher than
that of inert zironia burner ranged from 0.11 to 0.20. This result was attributed to that the enhanced
heat and mass transfer rates from combustion zone to foam exit induced by intensified gassolid
heterogeneous catalytic combustion and improved specific surface area as indicated in Table 1.
0.42
inert
0.55
0.60
0.65
0.70

0.36

rad(%)

0.30

catalytic
0.55
0.60
0.65
0.70

0.24
0.18
0.12
0

20

40

60
80
S (cm/s)

100

120

Fig.12. Thermal radiation efficiencies of catalytic zironia and inert zironia with different equivalence
ratio.
4. Conclusions
The lower flame stability limits and the upper flame stability limits for catalytic zironia and inert
zironia can be expanded with increase of equivalence ratio. The stabilization region of catalytic
zironia was extremely larger than that of inert zironia. The central temperature of flame front for
both catalytic zironia and inert zironia significantly increased with increase in equivalence ratio. The
central temperature of flame front for catalytic zironia was higher than that of inert zironia. The
exhaust gas temperature of catalytic zironia was found to be lower than that of inert zironia. The
pressure drop for catalytic zironia was nearly equal to that inert zironia in cold flow, whereas
significantly higher than that of inert zironia in reaction flow. The HC emissions of inert zironia
ranged from 500 ppm to 3750 ppm and increased with increase in equivalence ratio. The maximum
HC emission of catalytic zironia was less than 750 ppm and significantly lower than that of inert
zironia. The CO emission of catalytic zironia was significantly lower than that of inert zironia when
the flow velocity was less than the turning velocity (40cm/s), whereas both two burners kept a
relative low level when the flow velocity was higher than the turning velocity. The NOx emission of
catalytic zironia was less than 5 ppm and significantly lower than that of inert zironia burner. The
thermal radiation efficiency of catalytic zironia ranged from 0.24 to 0.39 , which was significantly
higher that of inert zironia that ranging from 0.11 to 0.20.
Acknowledgment
This work was supported by the National Key Projects of Fundamental R/D of China (973 Project:
11

673

No. 2011CB610306) and the National Natural Science Foundation of China (No. 51322604).
NOMENCLATURE

mair

inner cross-sectional area of burner, m 2

mass flow rate of air, kg / s

m fu

mass flow rate of fuel, kg / s

m
m

fu

/ mair

fu

/ mair

actual mass fuelair ratio

actu

stoichiometric mass fuelair ratio

stoic

LHVCH4 , net

low heating value of CH 4 , J / m3

S
Qrad
Qinput
TC
Tc ff

mean flow velocity, cm / s

radiation output heat, J / s

Tc ff max

maximum central temperature of flame front, C

Tcex
Tg

central temperature of foam exit, C

pressure drop, Pa

Ta
F
V
Vair

ambient temperature, C
view factor
total volumetric flow rate of methaneair, m3 / s

VCH 4

volumetric flow rate of CH4, m3 / s

heat input of CH 4 , J / s
centerline temperature, C
central temperature of flame front, C

exhaust gas temperature, C

volumetric flow rate of air, m3 / s

GREEK LETTERS

eff

rad

[1]

surface blackness of material

equivalence ratio
radiation efficiency, %
StefanBoltzmann constant, W / m2 K 4
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13

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Biofuels, Biomass and Bioenergy

676

The Application of Sulfonated Poly(arylene ether sulfones) Membranes

in the Dual-Chamber Microbial Fuel Cells
Dongqin Ran, Tong Xue, Zufeng Yuan, Jiangtao Li, Zhaoxia Hu, Shouwen Chen
School of Environmental & Biological Engineering, Nanjing University of Science &
Technology,
Xiaolingwei 200, Nanjing, China
shouwenchen@hotmail.com

ABSTRACT
A series of sulfonated poly(arylene ether sulfone) (SPAES) membranes were prepared for the
microbial fuel cell (MFC) application. The membrane properties such as proton conductivity, water
stability and mechanical properties were investigated. The performance of the MFCs equipped by
SPAES membranes was researched in details. The results showed that the membrane structure
had significant influence on the MFC performance. The MFC equipped with SPAES (4-6) (1.66
mmol/g) had the best performance compared with other membranes with a maximum power
density of 14.4 W/m3 at current density of 40.1 A/m3, and the open circuit voltage reached 0.68 V.
The influence of inoculum amount and load on the MFC performance was also investigated.

Keywords: proton exchange membrane, sulfonated poly (arylene ether sulfones), microbial fuel
cell
1 INTRODUCTION
Energy shortage and environmental pollution have restricted the development of society and
economy. Microbial fuel cells (MFCs) meet the need exactly. MFCs are devices which select
inorganic or organic substrates to produce energy by bacteria (Logan & Elimelech, 2012). MFCs
commonly consisted of anode and cathode chambers, which are separated by membranes. The
substrates are oxidized by bacteria in the anode, producing electrons, protons and carbon dioxide
gas. Electrons transfer to the electrode, then migrate to the cathode through the external circuit in
order to complete the circuit and generate the electricity. Protons migrate to the cathode through the
membrane. Then they combine with the protons and electron acceptor to produce water by
reduction reaction. Therefore MFCs have great potentials in generating electricity while
simultaneously treating pollutants. Future suitable applications of MFCs include wastewater
treatment (Ha et al., 2012; Liu et al., 2013; Savizi et al., 2012; Zhai et al., 2013), hydrogen
production (Rozendal et al., 2008), generation of electricity (Tyagi & Lo, 2013; Zhou et al., 2013)
and biosensors (Donovan et al., 2008; Shantaram et al., 2005).
There are many factors that influence the performance of MFCs including bacteria, electrode
materials, operation parameters (such as pH, temperature, and energy sources), and the
separators in the dual-chamber reactor. The electrode materials and their structure will affect
bacterial attachment and growth, as well as the electron transfer. Therefore, it is of great
importance to select and develop suitable electrode materials to optimize and promote the
performance of MFCs. Materials applied in MFCs should be highly conductive, nontoxic, high
porosity and low cost. The use of carbon-based electrodes (e.g. carbon paper, carbon cloth) is

677

common. Many graphite-based materials and polymers have been investigated in the study of
MFCs. To improve the performance of MFCs, various attempts on anode modication have been
made to change the physical and chemical properties. Some authors have attempted to change the
wettability (Guo et al., 2013; Santoro et al., 2014) and surface area. Other authors have discovered
that it worked well when some groups or molecules were introduced onto the anode surface (Jin et
al., 2013). Recently, some researchers have prepared high-performance and low cost activated
carbon (Xia et al., 2013) or carbon nanotubes (Mink et al., 2012) .
Some researchers discovered the relationship between pH, redox potential and biofilm growth.
Microbial communities were affected by different operational conditions (the potential of anode,
external resistance) and can be optimized for accelerated wastewater treatment rates. Liu et al. (Liu
et al., 2012)studied the effect of temperature on the performance of MFCs. And they suggested the
strategy to promote the development of anodic biolms at low temperatures that are capable of
yielding electricity at constant voltage. Carmen et al. (Fuentes-Albarrn et al., 2012) discovered that
the addition of some inorganic matters could increase the performance of MFCs. Song et al. (Song
et al., 2014) found that addition of biomass greatly improved the output power of MFC. Suitable
buffer types and conductivity could decrease the internal resistance and thus increase the power
production (Nam et al., 2010).
Membranes strongly affect the performance of dual-chamber MFCs. The membranes used in
MFCs should have high proton conductivity, stability in water, good mechanical performance, and
low cost. Naon is the most popularly used as PEM in MFCs because of a highly selective
permeability of proton. However, Naon is quite expensive and also has high oxygen permeability.
ULTREX CMI-7000S membranes have high mechanical properties, but the internal resistance is
high. In the past few years, membranes that yield effective performance at low expense have been
discovered. Cation exchange membranes were used as the membranes of choice in previous
works (Degrenne et al., 2013; Lim et al., 2012; Winfield et al., 2013). In 2013, Ghasemi et al.
(Ghasemi et al., 2013) compared the performance and cost of MFC with Nafion 117 and SPEEK
membrane as separators. They concluded that the MFC with SPEEK membrane can produce high
CE. Some authors prepared and applied the PES/SPEEK composite membranes in MFC, which
produced a maximum power density of 170 mW/m2 at the maximum current density of 340 mA /m2.
Other membranes can be used in MFC, such as reverse osmosis membranes (Zhao et al., 2013),
anion exchange membranes, ultrafiltration membranes (Kim et al., 2007) and other novel porous
materials.
SPAES membranes have been considered promising candidates because of their excellent
thermal and oxidative stability, good mechanical properties, and process ability, and their properties
and performances for PEM applications. In order to comprehensively evaluate the suitability of
SPAES membranes, we prepared and applied SPAES membranes in MFCs. And studied the
performance and effect on MFC with SPAES membranes on three levels: 1) the structure of
membranes; 2) the load; 3) the amount of inoculum effect on MFCs.
2.

MATERIALS AND METHODS

2.1. Synthesis and characterization of sulfonated poly (arylene ether sulfone) (SPAES)
The synthesis of the SPAES copolymers and the preparation of the analogue membranes were
carried out according to the reported methods (Zhang et al., 2011). Their chemical structure is
illustrated in Fig. 1. The thickness of the SPAES membranes were controlled about 100 m.

678

Fig. 1. Chemical structure of the SPAES copolymers

2.2. Two-chamber MFC construction and operation

The cylindrical MFCs were constructed by two chambers (230 mL capacity). Each chamber had
provision for a sample port, wire point inputs (top), and inlet and outlet ports. SPAES membranes
used in these reactors had a projected area of

. The anode and cathode used were both made of

graphite felt. Electrodes were soaked in ethanol and deionized water before being used. Titanium
wires were connected with the anode and cathode to connect the circuit, and all exposed metal
surfaces were sealed with conductive material.
The anode chamber was filled with medium containing (1 L): 50 mM phosphate buffer solution
(PBS, pH 7.0): NaH2PO42H2O, 5620 mg; Na2HPO412H2O, 6930 mg; NH4Cl, 310 mg; KCl,130 mg;
CaCl2, 10 mg; MgCl2 6H2O, 20 mg; NaCl, 500 mg (Logan et al., 2007); vitamin and mineral
solution,2.5 ml. 20 mM acetate was used as the energy resource. The medium was then sterilized
at 121 C for 15 min. Culture collected from the effluent to the pre-acclimated microbial community
from previous MFCs was used as an inoculum in the anode. The distance between the nearest face
of anode and cathode electrode was approximately 4 cm and kept constant. In this experiment,
potassium ferricyanide (50 mM) was used as the electron acceptor. Once the voltage decreased,
the anode was replaced with medium. The initial pH value of each feed was adjusted to 7, and all
MFCs were operated at a constant temperature of 30 oC.
2.3. Analysis of bioelectrochemistry
The voltage (V) across an external resistor circuit (1000 , unless stated otherwise) was
monitored at 1 min intervals using a data acquisition software connected to a personal computer.
An Ag/AgCl reference electrode (+0.197 V corrected to the normal hydrogen electrode; NHE) was
placed into the anode compartments to determine individual electrode potentials. For cyclic
voltammetry measures, the anode used as a working electrode, a platinum disk was used as a
counter electrode, and, as stated, the Ag/AgCl electrode was used as the reference electrode. The
scan rate of the potentiostat was 50 mV/s.
The cell power output (P) was calculated from the voltage and the resistance of the load, and the
power and the current density were calculated based on the anode working volume. The average
time required for obtaining stable data was about 20 min.
3. RESULTS AND DISCUSSION
3.1. Properties of the SPAES membranes
The SPAES polymers were synthesized according to the literature, and the IEC values of the
SPAES membranes were controlled in 0.48-2.08 mmol/g by changing the feed ratio of SDFDPS to
DFDPS. As shown in Table 1, the obtained polymers owned the reduced viscosity of 0.6 to 1.0 dL/g,
and indicated the high molecular weight. The IEC values determined by titration method were close
to the theoretical ones, indicating that the proton exchange was almost fully performed. SPAES (5-5)
membranes had the highest conductivity (131 mS) and were in the order of SPAES (5-5) > SPAES
(4-6) > SPAES (3-7) > SPAES (1-9). This was reasonable considering their respective IEC and
water uptake.

679

Good physical and chemical properties was important to MFCs. Table 1 also lists the mechanical
properties of SPAES membranes ,which were characterized by Youngs modulus (M),maximum
stress (S),and elongation at break( E). The values of maximum stress increased from 46.1 MPa to
53.6 MPa as the sulfonic degree decreased. Youngs modulus and elongation at break reached
maximum 200% and 1.22 GPa, respectively.
Table 1. Physicochemical properties of SPAES membranes
SDFDPS

Code

/DFDPS a

(dL/g)

SPAES(5-5)

5/5

SPAES(4-6)
SPAES(3-7)
SPAES(1-9)
a)

dc
(

IEC

104

(mmol/g)

Stress-Strain

WU c

(mS/cm)

(%)

(MPa)

(%)

(GPa)

um)

Cal.

Titr.

0.8

104

2.08

1.99

131

37.0

46.1

200

1.22

4/6

1.0

102

1.72

1.66

85

38.0

46.3

154

1.09

3/7

0.6

101

1.34

1.31

38

17.9

50.2

53.3

0.94

1/9

-e

94

0.48

0.46

<1.0

7.1

53.6

17.0

0.07

molar ratio; In 0.5wt.% DMSO (containing 1% LiCl) at 35

b)

oC; c) At

30 oC; d)

In water at

30 oC; e)

Not measured.

3.2. Start-up of MFCs

Initially, anaerobic anodic chambers of MFCs were fed with inoculation (containing 50% v/v
inoculum). At first, an anodic half-cell potential of about -0.22-0.15 V was observed. Hardly any
current was recorded because the anode didnt react with bacteria. After a period of time, the
potential of all the anodes gradually reached a plateau of about -0.44 V (Vs Ag/AgCl). As far as we
knew, the biofilm of anode was gradually developing and getting mature. Take MFC with SPAES
(5-5) for an example, Fig. 2 shows CV curves of its anode at cycle 2. We couldnt find any peak in
the curve at 0 h, due to the lack of biotic reaction in anode chamber. We could observe the oxidation
peak gradually growing, evidently from 35.5 h to 83.5 h, suggesting the biofilm attached to the
anode was mature. The corresponding shapes of all the 35.5 h, 60 h and 83.5 h CVs suggested
that the electrochemical active bacteria were very similar.
0.03

0.02

0h
35.5h
60h
83.5h

SPAES(5-5)

Current (A)

0.01

0.00

-0.01

-0.02

-1.5

-1.0

-0.5

0.0

0.5

1.0

Potential (V)

Fig.2. Development of biofilm in anode

3.3. Performances of MFCs equipped with SPAES membranes

Fig. 3 shows the power density of MFCs quipped with the different membranes of SPAES (5-5),

680

SPAES (4-6), SPAES (3-7) and SPAES (1-9) at 12th day, 14th day, 16th day and 18th day after
inoculation, respectively. The MFC with SPAES (5-5) membrane reached stability first after 12 days,
followed by the MFCs with SPAES (4-6), SPAES (3-7), and finally SPAES (1-9). The reason maybe
was that it took a much longer time for the anode with the lower sulfonic group to reach mature
biofilm stage. Therefore, the most sluggish start-up time was the MFC with SPAES (1-9)
membrane.
Most interestingly, except for MFC with SPAES (1-9) membrane, the open circuit voltage, and
maximum power density corresponding to the current density at day 18 (Table 2) are very similar. It
is suggested that the structure of the membrane (the number of sulfonic groups) affected initial
bacteria adhesion, which resulted in the biofilm development. The performance of MFC equipped
with SPAES (1-9) was lower than the others, because the conductivity of SPAES (1-9) membrane
was very low, which resulted in a higher transfer resistance of membranes, and in addition the pH of
the anode decreased at a high rate. The change of pH may have had a bad effect on the bacteria.

12

12

SPAES(5-5)

12d
14d
16d
18d

Power Density (W/m )

12d
14d
16d
18d

10

Power Density (W/m )

10

SPAES(4-6)

0
0

10

15

20

25

30

10

25

30

25

30

12

12d
14d
16d
18d

SPAES(3-7)

12d
14d
16d
18d

10

10

Power Density (W/m )

20

Current Density (A/m )

12

Power Density (W/m )

15

Current Density (A/m )

SPAES(1-9)

0
0

10

15

20

25

30

10

15

20
3

Current Density (A/m )

Current Density (A/m )

Fig.3. Power curves for MFCs using different membranes: SPAES(5-5), SPAES(4-6), SPAES(3-7), SPAES(1-9) at different
days after inoculation.
Table 2. Performance of MFCs with different membranes at 18d

Code

OCV (mV)

Pmax (W/m3)

I (A/cm3)

681

Rext ()

Rint ()

SPAES(5-5)

689

10.36

22.3

68

68

SPAES(4-6)

680

9.64

23.6

75

75

SPAES(3-7)

660

9.76

25.0

68

68

SPAES(1-9)

680

2.20

6.90

200

200

3.4. Effect of load on power density

In order to investigate the effect of load on power density, voltage generation was monitored
when SPAES membrane based MFCs were operated individually under different external
resistances (5,100,1000, open circuit) throughout the batch operation. Comparing the power
density of different loads (Fig. 4), the trend is similar for all MFCs. It was observed that the
maximum power density of the MFC with a load of 1000 was higher than the other conditions in
descending order of P(1000) > P(open circuit) > P(5) > P(100). Worthy of note was MFC with
SPAES (1-9). Its power density curves were relatively shallow and short in comparison and had no
great variation that we could observe. The power density is low for the same reason as discussed in
3.3.

16

5 ohm
100 ohm
1000 ohm
open circuit

14

5 ohm
100 ohm
1000 ohm
open circuit

14

SPAES(4-6)

12
3

Power Density (W/m )

Power Density (W/m )

12

16

SPAES(5-5)

10
8
6
4

10
8
6
4

10

15

20

25

30

35

40

45

50

10

15

5 ohm
100 ohm
1000 ohm
open circuit

16
14

25

30

35

40

45

50

35

40

45

50

16

SPAES(3-7)

5 ohm
100 ohm
1000 ohm
open circuit

14

12

SPAES(1-9)

Power Density (W/m )

12
3

Power Density (W/m )

20

Current Density (A/m )

Current Density (A/m )

10
8
6
4
2

10
8
6
4
2

0
0

10

15

20

25

30

35

40

45

50

10

15

20

25

30
3

Current Density (A/m )

Current Density (A/m )

Fig.4. Effect of load (5,100, 1000, open circuit) on power density of MFCs

3.5. Effect of inoculum amount on MFCs performance

682

We changed the volume ratio of inoculum in medium (20% and 50%) to test whether inoculum
amount would have an effect on MFCs performance, leaving all other conditions the same. As Fig.
5 shows, the power density curves of MFCs inoculated with 50% inoculum were higher than MFCs
with 20%. This result suggested that the bacterial was active and the amount of bacteria in the
anode benefited the power production.
16

5-5,20%
4-6,20%
3-7,20%
1-9,20%

Power Density (W/m )

12

5-5,50%
4-6,50%
3-7,50%
1-9,50%

0
10

100

1000

External Resistance ()

Fig.5. Power density of MFCs with 20% and 50% inoculum

4. CONCLUSIONS
A series of sulfonated poly (arylene ether sulfone) (SPAES) membranes was prepared for the
microbial fuel cell (MFC) application. The membranes showed high conductivity and
physicochemical properties, demonstrating they could be used as PEMs in MFCs. The growth of
biofilm was confirmed by the potential and CV curves of the anode. The average potential of a
mature anode was -0.44 V Vs Ag/AgCl. The load and the amount of inoculum could have effect on
the power density of MFCs. High concentration of inoculum and the load of 1000 contributed to
the development of high power density in the MFCs.
MFCs with more sulfonic group membranes, SPAES (5-5) reached the maximum power density
first, but the performance of MFCs equipped with different SPAES membranes reached a similar
status after a period of time. It appeared that the membrane structures influenced the star-up of
MFCs, accelerating initial cell attachment and biofilm development. After a month of continuous
operation, the MFC equipped with SPAES (4-6) (IEC=1.66 meq/g) had the best performance with a
maximum power density of 14.4 W/m3 at the maximum current density of 40.1 A/m3 compared with
other membranes, and the open circuit voltage reached 0.68 V. Furthermore, the price of SPAES
membranes is cheap. These results demonstrated SPAES membranes can be expected to be used
in MFCs as an alternative to PEMs.
ACKNOWLEDGMENT
This work was financial supported by, or in part by, the National Natural Science Foundation of
China (21006052, 21276128), Basic Research Program of Jiang Su Province of China
(BK2011713), the Scientific Research Foundation for the Returned Overseas Chinese Scholars, the
Fundamental Research Funds for the Central Universities (30920130121014).
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685

DISTRIBUTION AND CHARACTERIZATION OF LIQUID PRODUCTS FROM

SOYBEAN OIL HYDROCRACKING WITH COMMERICAL PETROLUEM
CATALYST
1,a

1,b

1,c

2,d

1,e*

Ziyuan Zhou , Weian Zhang , Rui Li , Dafeng Sun , Jianxin Jiang

Department of Chemistry and Chemical Engineering, Beijing Forestry University, Beijing 100083, China
2
Nanjing Academy of Wild Plant, Nanjing 210042, China
c
*Address correspondence to Jianxin Jiang, Department of Chemistry and Chemical Engineering,
Beijing Forestry University, Beijing 100083, China
a
b
c
d
ziyuanbeijing@163.com, 610395554@qq.com, boxlr@126.com, Sdafeng@163.com,
e*
jiangjx@bjfu.edu.cn (*corresponding author)

ABSTRACT
This paper deals with the hydrocracking of soybean oil representing a potential way of the
development of new bio-based energy. Fossil fuels are limited resources concentrated in certain
regions of the world and decreasing rapidly. Biodiesel fuels have attracted much more attention
worldwide as direct substitutes or blending components for diesel fuel. Traditional methods to
produce biodiesel have many drawbacks, such as waste of liquids, excess glycerol without full
application. Hydrocracking is a prominent way to produce biodiesel whose composition is close to
diesel and generates less waste. This biodiesel has better properties than the biodiesel from
traditional transesterifiaction. Hydrocracking of soybean oil was conducted at various temperatures
(240-300oC) for 2-4h under a pressure of 10MPa in a laboratory autoclave. A commercial petroleum
hydrocracking catalyst was used and characterized by XPS, N2-BET, SEM and XRD. Reaction
products were analyzed by GC and GC-MS. At a low reaction temperature about 240oC, soybean oil
nearly did not react and the liquid product still contains triglycerides. At reaction temperature of higher
than 240oC, alkanes, aromatics and olefins were detected in liquid products, and the main
components of the liquid products were substances with 8 to 17 carbons/molecule. Influences of
reaction temperature and time on the composition and distribution of reaction products were
discussed. The optimal reaction temperature is ranged of 260-280oC and the optimal residence time
is of 2.5-3h.
Keywords: Soybean oil, Biodiesel, Hydrocracking, Commercial Petroleum Catalyst.
INTRODUCTION
In recent years, rising prices of petroleum, dwindling petroleum deposits, and a strong desire for
energy dependence, are driving more exploration to renewable biofuel. Biofuel (Liu et al. 2012) is
one of potential alternative energy sources which has attracted increasing attention because it is
renewable and available throughout the world (Demirbas 2009).Whats more, it gives out
significantly less greenhouse gas emission than that of fossil fuels and can be greenhouse neutral
if efficient methods for production are developed (Huber and Corma 2007).
Biodiesel is a group of widely used biofuels all over the world, which is produced by transesterification of triglycerides with short chain alcohol, like methanol. However, biodiesel still suffers
from some drawbacks when compared to traditional petroleum-based fuel. The main by-product
from biodiesel production process is glycerin, which is economic but also is an environmental
consideration (Bezergianni et al., 2009). Furthermore, biodiesel is sensitive to hydrolysis and
oxidation. The most significant consideration of biodiesel is its poor low-temperature properties. It
tends to form sludge and deposits at low temperature or after long-term storage, no matter whether
pure biodiesel or biodiesel and diesel fuel mixture. Consequently, it causes the plugging of fuel
system. All of these deficiencies inhibit biodiesels large utilization. Besides conventional biodiesel
production, there are many other methods to produce renewable biofuel to take place of fossil fuel.
A prominent approach to produce biofuel which is an important conversion technology in pertrochemical refining, is the hydrocracking of vegetable oil (Huber and Corma, 2007; Stumborg et.al,
1996). This technology can employ the existing infrastructure of petroleum refineries to transform
fatty acid triglycerides of vegetable oils, animal fats and other tall oil to hydrocarbons (mainly
straight chain alkanes) without developing new equipment. After isomerization, these hydrocarbons
are very similar to present fossil fuel. Furthermore, this method produces few by-products, like
glycerol and reduces waste of liquids. Compared with the traditional biodiesel produced by transesterification, the biodiesel produced from hydrocracking of vegetable oils has better properties, such
as oxidation stability and high cetane numbers. Bezergianni et al. (2009) compared the product yields
and quality of catalytic hydrocracking of fresh and used cooking oil at three typical hydrocracking
temperatures. Cracking, heteroatom removal and saturation reaction mechanisms are studied as

686

well. They found that both feedstocks were suitable for high diesel production. Hydrocracking of used
cooking oil was proved to be a potential process to produce biofuels (Bezergianni et.al, 2009).
Gusmo et al. studied hydrocracking of vegetable oils in a batch reactor at temperatures from 623
673 K under high hydrogen partial pressure (10200 bars), catalyzed by either sulphided Ni-Mo/Al2O3 or reduced Ni/SiO2 catalysts. The corresponding product was a mixture of hydrocarbons
(mainly normal alkanes in the diesel fraction).
In this study, the results of hydrocracking of soybean oil under five different reaction temperatures
and residence time using a commercial petroleum hydrocracking catalyst are presented. The aim of
our experiments is to describe in detail the effects of reaction temperature and residence time on the
composition of reaction products as well as the distribution.
EXPERIMENTAL
Material
The soybean oil was purchased from China Oil& Foodstuffs Corporation. A commercial petroleum
catalyst for hydrocracking (supplied by the China Petroleum Institute of Science and Technology) was
used. CS2 used in liquid analysis was chromatographic grade.
Catalyst characterization
The specific Brunauer-Emmett-Teller (BET) surface area and pore size distribution were determined
by N2-adsorption-desorption using TriStar II 3020 V1.03.01 instrument from Micromeritics. Electron
microcopy (SEM) images of the catalyst were taken with Hitachi 3400 N scanning electron
microscope. Quantitative compositional analysis was carried out with X-ray energy-dispersive (EDX)
microanalyzer attached to the electron microscope. Surface analysis of catalyst was performed by Xray photoelectron spectroscopy (XPS) using a Quantera SXM scanning X-ray microprobe. Binding
energies (BE) were reference to the BE of C1s considered to be 284.6 eV.
Hydrocracking of soybean oil
The hydrocracking experiments were performed in a 1000mL laboratory autoclave equipped with
electrically heating system. The soybean oil was stirred using a motorized agitator. For each run,
catalyst (10 g) and soybean oil (200g) were loaded. After displacing air, the autoclave was
pressurized with H2 to 10MPa. The reactor was heated to desired temperatures (ranged from 240 to
300oC) for residence time of 2-4 h, with 0.5h intervals. The liquid products were collected after
cooling the reactor and releasing the pressure.
Analysis of liquid product
Quantitative analysis of liquid products were performed by gas chromatography (GC) (Agilent GC7890F with a flame ionization detector (FID) and a HP-5MS column, 30 m0.250 mm0.25 m, He
as carrier gas with 99.9999% purity). The liquid products, dissolved in CS2, were injected in a split
mode. The injector temperature was 280C.The oven temperature program ranged from 50C (1min)
to 290C at the rate of 6oC min1.
The hydrocracking reaction liquid yield% (YLiquid) and product selectivity were calculated based on the
formulas:
Y
(%)
Liquid

m(Liquidproduct )

100% (1)

m(Feed )

Where m(Liquid products) and m(Feed) represent the weights of the liquid product and feed,
respectively.
Y(C 8 C17 )( % ) = C(C 8 C17) Y
100% (2)
Liquid

Where Y(C8-C17) is the yield of the components with retention times between the C8-C17 (%) in the
liquid product C(C8-C17) is the concentration of C8-C17 which was determined by GC analysis, and
YLiquid is the yield of liquid product (%) calculated by Eq.(1)
RESULTS AND DISCUSSION
Characterization of catalyst
N2 isotherm at 77K of fresh catalyst was presented in Fig. 1. The catalyst used in the study
presents isotherm with superposition of typical micro-, meso- and macroporous effects. The
specific surface area, pore volumes, average pore size of the fresh commercial catalyst used in

687

the study were 257.3591m2/g, 0.324434cm3/g and 5.04252nm, respectively. The average pore size
of this kind catalyst was located in the typical mesopore range. From the pore size distribution of
catalyst (Fig. 2), the most probable pore size was about 6.63nm.
Ad
De

240
220

Quantity Adsorbed(cm3/g STP)

200
180
160
140
120
100
80
60
40
20
0
0.0

0.2

0.4

0.6

0.8

1.0

P/P0

Fig.1. N2 isotherm of fresh catalyst

0.040

0.030
0.025

Pore Volume(cm /(gnm))

0.035

0.020
0.015
0.010
0.005
0.000
-0.005
0

20

40

60

80

100

120

140

160

Width(nm)

Fig.2. Pore distribution of fresh catalyst.

SEM photograph was obtained to examine the fresh catalyst morphology. As was shown in Fig. 3,
the catalyst had a rough surface and some cracks. EDX measurements were carried out to
determine the chemical composition of the catalyst. Quantitative analysis of different elements
showed that Ni and W content were 5.36wt% and 19.87wt%, respectively. EDX mapping (Fig. 3)
indicated that most of the Ni and W were homogeneously dispersed in the support.

688

Ni
Fig.3. SEM-EDX images of fresh catalyst

Figure 4 showed Ni 2p XPS spectra of catalyst. The Ni 2p core level spectra showed a Ni 2p3/2 and
Ni 2p1/2 spectrum doublet, at about 854.9 eV and 873 eV, with the corresponding shake-up satellite
at 861.3 eV. BE of Ni 2p3/2 were in the region of 855 eV-861 eV, corresponding to Ni2+ ions (Jin et
al., 2010), which indicated that the Ni species on the catalyst are presented as Ni 2+.

Ni 2p

840

845

850

855

860

865

870

875

880

885

890

Bindiing Energy (eV)

Fig.4. Ni XPS spectrum of the fresh catalyst

Effect of reaction temperature on the composition of liquid products

689

In general, the hydrocracking temperature is the most dominant parameter for conversion of
soybean oil. Thus, in the study, the effect of reaction temperature on the composition and yield of
liquid product in the hydrocracking of soybean oil was investigated.
The GC charts of liquid products obtained from hydrocracking of soybean oil at the reaction
temperatures (240oC, 250oC, 300oC) were presented in Fig. 5. It could be found that the main
components in liquid product are straight chain alkanes ranging from C8 to C17. Pentadecane and
Heptadecane were the two most abundant liquid alkanes. The products remained solid at room
temperature with the low reaction temperature about 240oC. According to the GC/GC-MS
chromatogram, it could be clearly seen that no hydrocarbons were formed at the low temperature.
As the temperature increased, the content of small molecules increased at the expense of large
molecules (Toba et al., 2011; Jing et al., 2012). It meant that hydrocracking of soybean oil was
favored at the higher temperature.
240oC

Intensity

250oC

300oC

Time/min
Fig.5. Gas chromatograms of the hydrocracking soybean oil products obtained at various reaction temperatures with residence
time of 3h.

690

The comparison of the product yields (liquid product, <C8 fraction, C8-C17 fraction, >C17 fraction)
resulting from hydrocracking of soybean oil was given in Fig. 6. Reaction temperature has a
relatively strong effect on the yield of liquid product. Soybean oil did not transform to hydrocarbons
when temperature was around 240oC. With the temperature increasing, the liquid product
decreased in accordance to the literature reported on hydrotreating of pomace oil (Pinto et al.,
2014). At the same time, much light gaseous compounds were released. The maximum yield
61.6% of the C8-C17 fraction was observed at 250oC. There was no notable effect on the yield of
C8-C17 with the reaction temperature ranged from 250 to 280oC. When the temperature increased
to 300oC, the yield of C8-C17 decreased greatly (52.02%). The yield of heavy fraction kept stable
at low level. While yield of light fraction showed a downtrend. From yields of product oil, the
optional reaction temperature is ranged of 260-280oC.
YLiquid%
Light Fraction
C8-C17 Fraction
Heavy Fraction

80
70
60

Yield%

50
40
30
20
10
0
250

260

270

280

290

300

Reaction temperature/ C

Fig.6. Yields of product oil obtained from soybean oil hydrocracking at reaction temperature ranged from 240oC to 300oC for 3h

Effect of residence time on composition of liquid products

A series of experiments were conducted to investigate the effects of time on product composition
and distribution of product oil. According to GC-MS/GC, the result of product composition at
different residence time was listed in Table 1. The main components of liquid products were C8C17 of straight chain alkanes. Residence time did not affect the main components of liquid
products. However, residence time had a significant influence on the content of these main
components. It was apparent that as the residence time extended, the content of alkanes with odd
carbon number increased at the expense of alkanes with even carbon number. From the
composition of liquid products, it could be deduced that the hydrocracking of soybean oil took
place via two routes. One was hydro-deoxygenation yielding alkanes with even carbon number;
the other was hydro-decarboxylation yielding alkanes with odd carbon number (imek et al.,
2009). In soybean oil hydrocracking, hydro-carboxylation was more prominent than hydrodeoxygenation.

691

Table 1. The main components of liquid products at different residence time (reaction temperature 280oC)
Content( wt. %)
Components

2h

2.5h

3h

3.5h

4h

Octane

3.08

2.65

2.62

4.24

3.28

Nonane

2.76

3.21

3.17

3.80

3.33

Decane

2.67

3.36

3.43

3.50

3.25

Undecane

2.49

3.28

3.50

3.14

3.12

Dodecane

2.47

3.31

3.69

3.06

3.01

Tridecane

2.33

3.06

3.33

2.87

2.70

Tetradecane

2.54

1.90

2.02

2.18

1.71

Pentadecane

5.91

7.73

6.93

6.44

6.39

Hexadecane

1.1 4

1.26

0.97

1.11

0.88

Heptadecane

3.67

4.51

3.41

3.93

3.72

The comparison of the product yields (light fraction, C8-C17fraction, heavy fraction) was shown in
Fig. 7. The yield of liquid products was the highest (about 75.76%) among the five residence time
when it was 2h. As residence time expanded, yield of liquid products decreased. The liquid
products yield dropped down to approximately 66.25% when residence time was 4h. This trend
agreed with those of Chen et al. Bezergianni et al. also studied that decreasing residence time
caused less cracking and therefore a smaller production of the light products. Whats more, it could
be clearly seen that hydrocracking of soybean oil tended to produce C8-C17 fraction. The
residence time did not have significant effect on yields of light and heavy fraction. Compared to
heavy fraction, the light fraction had a high yield. It was suspected that with the rise of residence
time, some products and intermediates also reacted to small molecules. In terms of product
collection, the optimal residence time is 2.5-3h.
YLiquid%
Light Fraction
C8-C17 Fraction
Heavy Fraction

80
70
60

Yield%

50
40
30
20
10
0
2.0

2.5

3.0

3.5

4.0

Residence time/h

Fig. 7.Yields of product oil obtained from soybean oil hydrocracking at residence time ranged from 2 to 4h at 280oC.

CONCLUSIONS
Hydrocracking of soybean oil by a commercial petroleum catalyst is an alternative method to produce
biodiesel, which composition is much close to fossil fuel compared with the biodiesel produced from
traditional trans-esterification. Two main hydrocracking operating parameters of reaction temperature
and residence time have been studied on the conversion of soybean oil, composition and distribution
of reaction products. The main components of the liquid products were substances with 8 to 17
carbons/molecule. The effect of temperature was more dominant than that of residence time in the

692

hydrocracking process. At low temperature, triglycerides transformed to saturated triglycerides rather

than hydrocarbons. High temperature promotes cracking reactions to produce more gases. The rise
of both temperature and residence time decreased yield of liquid products with producing more
gases, probably because cracking reactions of soybean oil were favored. In conclusion, the optimal
reaction temperature is ranged from 260 to 280oC and the optimal residence time is of 2.5-3h.
ACKNOWLEDGEMENT
The authors are grateful for the financial support of this research from State Forestry Administration
(2012-03) and China Ministry of Science and Technology (2012BAD36B01).
REFERENCES
Liu, J., Fan, K., Tian, W., Liu, C., and L. Rong, 2012, Hydroprocessing of Jatropha oil over
NiMoCe/Al2O3 catalyst. International journal of hydrogen energy 37:17731-17737.
Demirbas, A., 2009, Energy Conversion And Management. Biofuels securing the planets future
energy needs.
Huber, G. W., A. Corma, 2007, Synergies between Bio- and Oil Refineries for the Production of
Fuels from Biomass. Angewandte Chemie International Edition 46:7184-7201.
Bezergianni, S., Voutetakis, S., and A. Kalogianni, 2009, Catalytic hydrocracking of fresh and used
cooking oil. Industrial & Engineering Chemistry Research 48:8402-8406.
Stumborg, M., Wong, A., and E. Hogan, 1996, Hydroprocessed vegetable oils for diesel fuel
improvement. Bioresource Technology 56:13-18.
Gusmo, J., Brodzki, D., Djga-Mariadassou, G., and R. Frety, 1989, Utilization of vegetable oils
as an alternative source for diesel-type fuel: hydrocracking on reduced Ni/SiO2and sulphided NiMo/-Al2O3. Catalysis Today 5:533-544.
Jin, H., Yi, X., Sun, X., Qiu, B., Fang, W., Weng, W., and H. Wan, 2010, Influence of H4SiW 12O40
loading on hydrocracking activity of non-sulfide Ni-H4SiW 12O40/SiO2 catalysts. Fuel 89:1953-1960.
Toba, M., Abe, Y., Kuramochi, H., Osako, M., T. Mochizuki, and Yoshimura, Y., 2011,
Hydrodeoxygenation of waste vegetable oil over sulfide catalysts. Catalysis today 164: 533-537.
Pinto, F., Varela, F. T., Gonalves, M., Neto Andr, R., Costa, P., and B. Mendes, 2014, Production
of bio-hydrocarbons by hydrotreating of pomace oil. Fuel 116:84-93.
imek, P., Kubika, D., ebor, G., and M. Pospil, 2009, Hydroprocessed rapeseed oil as a
source of hydrocarbon-based biodiesel. Fuel 88:456-460.
Chen, Y., Yang, F., Wu, L., Wang, C., and Z. Yang, 2011, Co-deoxy-liquefaction of biomass and
vegetable oil to hydrocarbon oil: Influence of temperature, residence time, and catalyst.
Bioresource technology 102:1933-1941.
Bezergianni, S., Dimitriadis, A., Kalogianni, A., and K. G. Knudsen, 2011, Toward hydrotreating of
waste cooking oil for biodiesel production. Effect of pressure, H2/oil ratio, and liquid hourly space
velocity. Industrial & Engineering Chemistry Research 50: 3874-3879.

693

USING BANANA PSEUDOSTEM SAP AS AN ELECTROLYTE IN BATTERIES

Sy-Ruen Huanga, Chih-Hung Chungb,*, Hoang-Jyh Leuc, Chow-Yen-Desmond Sima, Chiu-Yue Lind
a

b,

Department of Electrical Engineering, FengChia University, Taichung, Taiwan 40724, ROC

*Ph.D. Program of Electrical and Communications Engineering, FengChia University, Taichung,

Taiwan 40724, ROC

Department of Fiber and Composite Materials, FengChia University, Taichung, Taiwan 40724, ROC
d

Department of Water Resources Engineering and Conservations, FengChia University, Taichung,

Taiwan 40724, ROC
address: No.100, Wenhua Rd., Xitun Dist., Taichung City 407, Taiwan (R.O.C.)
e-mails: srhuang@fcu.edu.tw, bigh@ms39.hinet.net, hjleu@fcu.edu.tw, cysim@fcu.edu.tw,
cylin@fcu.edu.tw

ABSTRACT
Each year, more bananas are produced globally than any other fruit. The banana is also the
primary fruit of Taiwan. Banana harvesting produces approximately 1.5 million t in fresh
weight of residual stems in Taiwan every year. In addition to becoming agricultural waste
and increasing farmers processing costs, these stems often lead to pests and become
hotbeds of infection. Therefore, to further the development of agriculture and integrate it
with bioenergy, we extracted the sap from the agricultural waste of banana pseudostems as
a raw material to serve as an electrolyte in zinc-copper batteries, which improved the low
electrical output of fruit batteries. Our experiments confirmed that zinc-copper batteries
with banana electrolytes could act as power supplies for smartphone charging and
illumination with light-emitting diodes. Subsequent research can apply these zinc-copper
batteries as power sources for lighting, communications, and monitoring on farms. They
can be further applied in parallel power grids to become sources of renewable energy.
Keywords: Banana, Sap, Electrolyte, Battery, Renewable energy.

1. INTRODUCTION
1.1 BACKGROUND
In the global fruit economy, bananas are the fourth most important fruit, behind only
apples, oranges, and grapes. In recent years, the annual cultivation area of bananas in the
world has been approximately 10 million ha, with approximately 120 million t produced each
year. Bananas are grown in Asia, the Americas, Africa, Oceania, and even Europe. The
climate range of the banana is from tropical to subtropical climates. Testing has indicated that
bananas can be efficiently grown at temperatures as low as 8 C to 10 C. India, Brazil, and
China are currently the three largest producers of bananas. Because Taiwan is located in the
subtropics, bananas can be grown throughout the year in every part of the country. Between
2008 and 2012, the economic cultivation area for bananas in Taiwan was an average of
approximately 13,000 ha. An average of approximately 25,000 t of bananas were produced
each year, resulting in approximately 1.5 million t in fresh weight of residual banana stems.
Estimating based on acreage, approximately 1.15 billion t in fresh weight of residual banana
stems are produced globally each year. Residual stems result in substantial agricultural waste.
Farmers typically cut the residual stems after banana harvests and pile them in their banana
plantations to decay naturally.
Climate change has led to the promotion of green energy. Solar and wind power are the
most highly developed types of green energy. However, sunshine intensity severely affects
solar power, limiting power generation. Wind power requires wind farms, which are influenced
by regional restrictions. Traditional methods of power generation, such as nuclear energy,
thermal power, and hydropower, generate high costs and large amounts of pollution. In
contrast, biomass energy using agricultural waste is environmentally friendly, low cost, and

694

ubiquitous. It has an excellent development foundation and results in generation costs lower
than those of solar power and is able to generate electricity 24 hours a day. Banana
pseudostems contain more than 80% sap and substantial amounts of electrolytes. Thus,
bananas can become a rich source of electrolytes for zinc-copper batteries.
1.2 CELL REACTIONS
The first true battery was invented in 1800. This battery was a voltaic cell in which zinc
and copper discs are piled, separated by cloth soaked in sulfuric acid. Fruit batteries use
lemons or other fruits. Two metals with different ionization tendencies are inserted in fruits to
function as cathodes and anodes. This automatically triggers electrochemical reactions that
develop into battery systems. Zinc-copper batteries use zinc as an anode (battery negative)
and copper as a cathode (battery positive) for electrochemical reactions. Types of cells
include galvanic cells, voltaic piles, Daniell cells (Boulabiar et al. 2004), and lemon batteries
(Ensman, Hacker, and Wentworth 1988; Letcher and Sonemann 1992; Swartling and Morgan
1998; Goodisman 2001; Harris 2005; Muske, Nigh, and Weinstein 2007). Voltaic piles use
brine as an electrolyte, whereas Daniell cells use ZnSO4 and CuSO4. By contrast, lemon
batteries use lemon juice as an electrolyte, which results in a potential difference of
approximately 0.9 V (Mano, Mao, and Heller 2003). The chemical formula is shown as follows:
The oxidation half-reaction of anode (zinc electrode):
Zn Zn

2+

(aq)

0
1/2

+2e

-0.89

(1)

The reduction half-reaction of cathode (copper electrode):

+

2 H + 2 e H2

(g)

0
1/2

(H is from citric acid)

0V

(2)

The overall battery reaction:

+

Zn + 2 H H2 (g) + Zn

2+

(aq)

+2e

0.9

(3)

The potential difference in lemon batteries can be calculated using the Nernst equation
(Feiner and McEvoy 1994). The potential difference depends on the concentrations of zinc
ions, citric acid, and H+. The potential difference produced by lemon batteries can change if
other anode electrode materials are used. The range is from 1.5 V (magnesium/copper) to 0.3
V (lead/copper) (Fortman and Battino 1993). The battery life of lemon batteries is short, which
is primarily because the chemical reactions between the two electrodes rapidly decrease the
electrolytes within lemons (Ensman et al. 1988; Letcher and Sonemann 1992), electrolytes
that cannot be replenished. In contrast, residual banana stems contain approximately 80%
sap and substantial amounts of electrolytes. Thus, this sap can continuously provide the
electrolytes that the zinc-copper batteries require and supply power for long periods.
2. MATERIALS AND METHODS
We sought a plant electrolyte capable of resolving the electrolyte replenishment
problems in lemons (Wetzel, Mills, and Safron 1986; Fortman and Battino 1993). This plant
would have to be available in mass quantities, rich in electrolytes, unrestricted by the seasons,
and not a human food (to avoid reducing the human food supply or increasing prices). The
banana meets all of these conditions (which is as a perennial herbaceous plant; Thomas and
Turner 2001; Oliveira et al. 2006; Oliveira et al. 2008). First, it is a plant that grows quickly and
in mass quantities in tropical and subtropical regions. It can be harvested in approximately 1

695

year. Second, the banana does not have a fixed harvesting time. Bananas are produced at all
times. Thus, sources of residual banana stems are rich and immediately available. In contrast,
lemons, other citrus fruits, and potato tubers lack these advantages. To make batteries with
banana sap as electrolytes, the sap from the banana pseudostems or suckers is extracted
and stored in containers. Zinc and copper plates are immersed in parallel in the banana sap to
generate potential difference approximately 1 V.
2.1 ELECTROLYTES
Banana pseudostems are rich in moisture and organic matter (Aguirre et al. 2006), and
processing sap is extremely easy. The banana sap electrolytes are obtained during the
banana fertility period. Suckers between 50 cm and 100 cm are excised and the residual
stems of the banana harvest are collected. The suckers and stems are cut into sections and
placed in juicers for residue separation to obtain the banana sap. Additionally, because they
are convenient to transport and store, banana pseudostems can be retained for approximately
4 weeks in a cool environment of approximately 25 C after cutting. Minimal rotting occurs at
the incision during this period, but this does not affect sap extraction.
2.2. INSULATION BETWEEN THE ELECTRODES AND THE BATTERY BOX
The copper electrodes are copper plates with a thickness of 0.1 mm, width of 150 mm,
and length of 200 mm. Purity is 99.99%. A single cell has 8 plates and 6 cells have a total of
48 plates. The zinc electrodes are electrogalvanized steel plates. The amount of zinc is 70
g/m2. The thickness is 1.0 mm, width is 150 mm, and length is 200 mm. A single cell has 8
plates and 6 cells have a total of 48 plates. The insulating material is black nylon mesh with a
mesh size of 4.0 mm 4.0 mm and a wire diameter of 1.0 mm. The battery box is the pack of
a 100 Ah lead-acid battery. The material is polypropylene resin. The length is 407 mm, width
is 173 mm, and slot height is 211 mm. The tank body contains 6 cells. A single cell has
approximately 1 L of electrolytes (Fig. 1).
2.3. BATTERY ASSEMBLY METHOD
The electrode configuration assembly is based on the lead-acid battery model. To
avoid electrode contact between the anodes and cathodes, the electrodes and the
insulation are placed in the following continuous arrangement: copper plate insulation
zinc plate insulation copper plate insulation zinc plate. Next, the electrodes are
placed in the slot of a single cell within the battery box. Each of the copper and zinc plates
within a single cell is placed in parallel to increase the active area of the cell reactions,
increasing current output. Finally, a multimeter is used to measure the resistance between
the anodes and cathodes. Acceptable resistance values are above 1 M(Fig. 1).
After completing the 6-cell electrode assembly, each cell is connected in series to
increase the output voltage of the battery. After completing these connections, the resistance
between the positive and negative electrodes is measured again. Correct resistance values
should be above 1 M.
3. OPERATION MECHANISM
The organic nutrient components (e.g., corosolic acid, pantothenic acid, and folate) within
the banana plant (Aguirre et al. 2006) can be used to develop a using banana pseudostem sap
as an electrolyte battery. If operating in coordination with zinc and copper electrodes, the
battery reactions are assumed as follows:
The oxidation half-reaction of the zinc electrode:
2+

m Zn m Zn

(aq)

E1/2 -0.9 V

+ 2m e

(4)
The reduction half-reaction of the copper electrode:
+

n H + n e 1/2n H2(g)

E1/2 0.0 V

(5)
The overall battery reaction: (if 2m = n)

696

2+

m Zn + n H + n e m Zn

+ 2m e + 1/2n H2(g)

E 0.9 V

(6)
where n is the number of dissociable hydrogen ions within the organic compounds.
Moreover, m is the coefficients of half-reactions for involved molecules. From this redox
battery reaction, high purity of hydrogen (>99%) was produced in copper electrode (cathode)
side with no other gas co-production. The study was achieved and analyzed by gas
chromatogram (data not shown).
4. ELECTRICITY AND PERFORMANCE
Banana sap is poured into the slots of each cell. The voltage of each cell is measured
after pouring. The voltages will be between 0.9 V and 0.95 V. After pouring the banana
electrolytes into 6 cells, the voltage of the complete battery should be between 5.4 V and 5.7
V. Our actual measurement was 5.129 V. Two factors may have led to lower voltage: (1) the
resistance of the connecting wires between the cells; and (2) unfiltered fibers in the banana
sap. If the jumpers between the zinc and copper electrodes caused the direct current to flow
through the fibers, this would have reduced battery current and voltage output values. This is
similar to the phenomenon of self-discharge inside batteries. We continuously recorded a
battery output end connected with 100 resistance for 7 days (Table 1). Current output was
between 3.2 mA and 7.4 mA. Current output was extremely stable and sustained, and output
power was between 6.2 mW and 32.7 mW. This is sufficient for a variety of low-power
devices, such as light-emitting diodes and mobile phones. Moreover, we estimated the
2
generating capacity of a unit electrode and obtained power density between 6.4 mW/m and
2
34 mW/m . Simply increasing electrode area can increase generating capacity.
5. CONCLUSION
(1) The battery operated with banana electrolytes is based on battery equipment. With a
sufficient supply of banana sap, batteries with banana electrolytes can provide long-term and
stable operation, facilitating long-term use. (2) The sap from banana pseudostems can
replace fruit electrolytes for long-term power supply, thus preventing the shortcomings of other
fruits with limited organic electrolytes. (3) We used banana sap to generate electricity without
increasing the total amount of carbon dioxide on the planet. This innovative method of power
generation is a crucial development that satisfies contemporary requirements for carbon
reduction. (4) Batteries with banana electrolytes can provide long-term power supply. Thus,
they can be applied to centers of banana production. Specific applications can include
supplying electricity for illumination and mobile communications in areas lacking electricity and
for climate and environmental sensors. By increasing power generation to between 1 kW and
15 kW, these batteries could have economic value in large-scale use (with stable time in
power generation superior to that of solar or wind power).
REFERENCES
Aguirre, M.C., C. Delporte, N. Backhouse, M.E. Letelier, B.K. Cassels, X. Silva, S. Alegra,
and R. Negrete. 2006. Topical anti-inflammatory activity of 2-hydroxy pentacyclic triterpene
acids from the leaves of Ugni molinae. Bioorganic & Medicinal Chemistry 14:5673-7.
Boulabiar, A., K. Bouraoui, M. Chastrette, and M. Abderrabba. 2004. A historical analysis of
the daniell cell and electrochemistry teaching in French and Tunisian textbooks. Journal of
Chemical Education 81(5):754.
Ensman, R., T.R. Hacker, and R.A.D. Wentworth. 1988. Vegetable voltage and fruit juice: An
electrochemical demonstration. Journal of Chemical Education 65:727.
Feiner, A.S., and A.J. McEvoy. 1994. The nernst equation. Journal of Chemical Education
71:493-4.
Fortman, J.J., and R. Battino. 1993. Determining the metal activity series using a potato
porcupine. Journal of Chemical Education 70:939-40.
Goodisman, J. 2001. Observations on lemon cells. Journal of Chemical Education 78:516-8.

697

Harris, D. 2005. Exploring Chemical Analysis, third edition. New York: Freeman.
Letcher, T.M., and A.W. Sonemann. 1992. A lemon-powered clock. Journal of Chemical
Education 69:157-8.
Mano, N., F. Mao, and A. Heller. 2003. Characteristics of a miniature compartment-less
glucose-O2 biofuel cell and its operation in a living plant. Journal of the American Chemical
Society 125:6588-94.
Muske, K.R., C.W. Nigh, and R.D. Weinstein. 2007. A lemon cell battery for high-power
applications. Journal of Chemical Education 84:635-8.
Oliveira, L., C.S.R. Freire, A.J.D. Silvestre, and N. Cordeiro. 2008. Lipophilic extracts from
banana fruit residues: a source of valuable phytosterols. Journal of Agricultural and Food
Chemistry 56:9520-4.
Oliveira, L., D.V. Evtuguin, N. Cordeiro, A.J.D. Silvestre, A.M.S. Silva, and I.C. Torres. 2006.
Structural characterization of lignin from leaf sheaths of Dwarf Cavendish banana plant.
Journal of Agricultural and Food Chemistry 54:2598-605.
Swartling, D.J., and C. Morgan. 1998. Lemon cells revisited the lemon-powered calculator.
Journal of Chemical Education 75:181-2.
Thomas, D.S., and D.W. Turner. 2001. Banana (Musa sp.) leaf gas exchange and chlorophyll
fluorescence in response to soil drought, shading and lamina folding. Scientia Horticulturae
90:93-108.
Wetzel, T.L., T.E. Mills, and S.A. Safron. 1986. Chemical potentials and activities. Journal of
Chemical Education 63:492-5.

Fig.1. The battery box is assembled, including the electrodes and the insulators.

698

Fig.2. Open circuit (O/C) voltage measurement of 6 cells is connected in series in a battery. An O/C voltage of approximately
5.129V is measured.

699

Table 1. Battery output experimental data.

40

35

30

Output(mA/mW)

25
current(mA)
watts(mW)/m2
battery watts(mW)

20

15

10

0
1

7 13 19 25 31 37 43 49 55 61 67 73 79 85 91 97 103 109 115 121 127 133 139 145 151 157 163
Time(hours)

700

PROSPECTIVE USE OF ANTIOXIDANTS IN 2ND GENERATION BIODIESEL FOR

DIESEL ENGINES IN AUSTRALIA
M. A. Hazrat*, M. G. Rasul, M. M. K. Khan
School of Engineering & Technology, Central Queensland University, North Rockhampton, Qld 4702,
Australia
*Corresponding Author Email: h.ali@cqu.edu.au

ABSTRACT
Biodiesel is well accepted in Australian vehicles. As per the recommendation of the Prime
Ministers taskforce of Australia, there is no requirement of labelling the biodiesel-diesel
blends up to 5% (B5) biodiesel in the commercial outlets. However, the CSIRO
(Commonwealth Scientific and Industrial Research Organisation) noted that extensive
research should be carried out to resolve the issues of using higher biodiesel content (up to
26%, B26) that meet the petroleum standard but engendered some inconsistencies in engine
performance, emission contents and durability. In this article, the non-edible feedstock,
Beauty Leaf (Calophyllum Inophyllum) has been studied in terms of its sustainability and
nd
stability as a 2 generation biodiesel fuel in internal combustion engine. It has been found
that the amount of polyunsaturated fatty acid esters tend to peroxidized due to its high
polymerization contents resulting into gumming in the engine. But the extent of more
monounsaturated fatty acid esters increases the viability of the biodiesel as a transport engine
fuel. Since the polyunsaturated contents of a biodiesel affect the engine performance in
addition to oxidation stability and cetane number of the fuel, the effect of adding antioxidants
to inhibit the peroxidation of the fuel is focused in this study. Various groups of antioxidants
(natural/synthetic, phenolic/amine type) could be used in the biodiesel as per their inherent
properties. The study showed that the phenolic type antioxidants could be a better choice in
stabilizing the non edible biodiesel.
nd

KEYWORDS: 2 Generation Biodiesel, Calophyllum Inophyllum, Antioxidant, Oxidation

Stability, Engine Performance.
INTRODUCTION
Biodiesels are accepted as a clean combustion transport fuel due to its effective contribution
in reducing emission(Masjuki et al. 2013) of carbon di oxide (CO2), carbon monoxide (CO),
particulate matter (PM), total hydrocarbon (THC), etc. Reportedly, the biodiesel fuel
combustion increases the emission of NOx in all loads (An et al. 2013; Palash et al. 2013) of
engine operation.These fuels are mostly derived from the renewable feedstocks and
inherently biodegradable, less toxic as well as contains negligible amount of sulfur which are
favourable emission performance factors to be considered as transport fuel (Ashraful et al.
2014). The oil content of non-edible biodiesel feedstock Calophyllum Inophyllum which is
known as beauty leaf in Australia is 46.51%4.49% (Ashwath 2010). It usually grows
abundantly in coastal areas of Queensland and the Northern Territories in Australia, and also
available in South-East Asian countries like India, Sri Lanka, Thailand, Malaysia, Indonesia,
etc. but known in various regional names distinctly. Fuel obtained from the non-edible oil
feedstocks generally reduces the Food-vs-Fuel contradiction and these are mostly produced
in unproductive or fallow lands(Ashraful et al. 2014; Gui et al. 2008) facilitating work
opportunity for people. The Calophyllum Inophyllum trees can survive until 50 years and it is
also used in pharmaceuticals or to conserve the coaster areas from natural calamities (Rao et
al. 2013). Researchers have been conducting the combustion performance and emission
characteristic analysis with the Calophyllum Inophyllum methyl ester (CIME) blends with
diesel or with the neat biodiesel for decades (Atabani et al. 2013b; Atabani et al. 2013a;
Atabani et al. 2012). Ong et al.(2014) mentioned that the 10% blend of CIME (i.e. CIME10)
demonstrates the better combustion characteristics with higher brake thermal efficiency (BTE)
and reduces the CO and smoke opacity with slight increase of NOx in comparison to diesel
fuel. They also found that, the brake specific fuel consumption (BSFC) of CIME10 (302.9
g/kW.h) was lower than that of diesel (313.8 g/kW.h) with the same CI engine used. Due to
higher cetane number of CIME blends than the diesel fuel, it also reduces the knocking and
unburnt hydrocarbon emission through less incomplete combustion of the fuel in combustion

701

chamber (Pinzi et al. 2013; Knothe 2014; Knothe et al. 2003; Sanjay 2013; Ong et al.
2014).The unsaturated fatty acid content also increases with the maturity of the beauty leaf
(Calophyllum Inophyllum) seeds(Hathurusingha 2012). Fatty acid composition of Beauty Leaf
derived biodiesel is provided in Table 1. There are about 78% unsaturated fatty acid contents
in the Calophyllum Inophyllum methyl esters (Hathurusingha 2012).The cooler environment
helps forming the unsaturated fatty acids in the oil seeds and due to experiencing the cooler
temperature in the mature stages of the Calophyllum Inophyllum, its unsaturated fatty acid
content increases with its maturity (Hathurusingha et al. 2011; Harris et al. 1978). Sokoto et
al.( 2011) stated that the amount and types of unsaturated fatty acid in the biodiesel governs
both the oxidation stability as well as the cetane number, whereas, the quality of Methyl Fatty
Acids Esters determine the viability of being treated as a fuel in the internal combustion
engine (Knothe 2009).Moreover, the amount of polyunsaturated fatty acid esters tend to
peroxidized due to its higher polymerization contents resulting into gumming in the engine
(Sokoto et al. 2011; Mohibbe Azam et al. 2005). But the extent of more monounsaturated fatty
acid esters increases the viability of the biodiesel as a transport engine fuel.
Table 1. Fatty acid Profile of Beauty Leaf derived biodiesel
Fatty
acid
(Sanjay 2013)

Ong et
al.
(2014)
0.1

Hathurusingh
a (2012)

Sahoo et
al.(2007)

Crane et
al. (2005)

Lauric acid

Structure
(Sanjay
2013)
C12:0

Adeyey
e
(1991)
-

Myristic acid

C14:0

0.1

<0.1

Palmitic acid

C16:0

14.2

13.6

12.01

13.70

14.60

Sapienic
acid/Palmitoic
Acid
Stearic acid

C16:1

0.3

2.39

0.2

C18:0

15.9

13.2

12.95

14.30

16.50

Oleic acid

C18:1

39.8

35.2

34.09

39.11.4

39.80

Linoleic acid

C18:2

28.1

36.3

38.26

31.11.4

27.60

-Linolenic
acid
Arachidic
acid/Eicosanic
Acid
Behenic Acid

C18:3

0.2

0.5

0.30

0.30.1

0.38

C20:0

0.8

0.7

0.60.3

C22:0

0.5

Saturated
acids
(Approx.)
Unsaturated
acids
(Approx.)

31.1

28

24.96

29.10

31.10

68.5

72

75.04

70.80

67.78

0.20

Like the diesel fuels, the biodiesels are not stable in long time storage. Primarily they oxidized
by the atmospheric oxygen and forms peroxides. After that the ester contents of the biodiesel
react completely and then the secondary oxidation occurs generating various organic acids
(low molecular weight), volatile organic acids (VOC), gum and sludge etc. (Rizwanul Fattah et
al. 2014). These products are severely harmful for injector of the engine and deteriorate the
combustion performance. Serrano et al. (2014) mentioned that the amount of double bonds in
the fatty acids along with their double bond number, condition of storing the biodiesel or the
crude oil before transesterification, etc. regulate the oxidation stability of the fuel. The
Australian origin beauty leaf contains higher amount of linoleic acid (30.3-36.5%) in
comparison to the other origins like Sri Lanka and India (Hathurusingha 2012). But the bisallylic carbons found in linoleic (C 18:2) as well as linolenic (C 18:3) acids are more
susceptible to the oxidation initiators for the free radical reactions (Serrano et al. 2014).
Hence, vegetable oils rich in linoleic and linolenic acids tend to impart poor oxidation stability
to fuels (Knothe et al. 1998), i.e. the higher amount of polyunsaturated fatty acid in the
biodiesel feedstocks lead to more instable biodiesel (Hathurusingha et al. 2011). Therefore,

702

the beauty leaf derived biodiesel in Australia must be treated to increase its oxidation stability.
Generally, various anti-oxidants are used to improve the oxidation stability of the biodiesel.
This article has reviewed the available non-edible biodiesel fuel production systems with
optimal conversion efficiency, combustion and emission characteristics and presented the
effect of various antioxidants which improved the stability of the fuel. Thus referring the
prospective use of second generation biodiesel obtained from beauty leaf in Australia.
Production of Calophyllum Inophyllum biodiesel
Calophyllum oil contains 19.58wt% free fatty acids (FFA) where the maximum allowable
amount of FFA in oil is 2 wt%(Ong et al. 2014). Therefore, a two stage production process (i.e.
Esterification and Transesterification processes subsequently) is applied to produce biodiesel
from this oil (Marchetti and Errazu 2008; Chavan et al. 2013). The process flow chart of
Calophyllum Inophyllum Methyl Ester (CIME) biodiesel production is presented in Fig.1(Ong
et al. 2014). Also, the physical and chemical properties are presented in the Table
2.Generally, the phosphates, protein, carbohydrates, residues in water contents, and resins
form gum in the oil extracted from the seed and it can deteriorate the oxidation stability of the
fuel. Therefore, the degumming process (Fig. 2) is done to gain better oxidation stability in the
biodiesel. The neutralization process (Fig. 4) is carried out following the acid esterification (Fig.
3) as the esterified oil also could not reach up to the allowable FFA content for better
biodiesel production. Then the Transesterification process (Fig. 5), Purification and Drying
(acidic neutralization and water washing, centrifugal removal of water and methanol solution,
drying of wet extracted biodiesel) are performed subsequently to obtain the Calophyllum
Inophyllum Methyl Ester (CIME) Biodiesel as a final product. The byproduct of the
Transesterification is a mixture of glycerine, water and methanol which is sent to further
purification processes to separate the methanol (methanol recovery distillation) and water
(water recovery distillation) respectively. Thus, the usable crude glycerine, methanol and
water are obtained to use then in the industries, Transesterification process and crude
biodiesel washing process respectively. Effective neutralizing, washing and drying processes
yield a better biodiesel as a final product. The optimized process reaction parameters
O
(methanol to oil ratio= 9:1, 50 C, 1 wt.% of NaOH, 2 h, agitation speed 1150 rpm,
atmospheric pressure) yields 98.92% CIME (Ong et al. 2014).Venkanna et al. (2009) also
adopted these production methodologies, but they mentioned it as a three stage methodology
(i.e. acid esterification, alkali transesterification and post treatment) of biodiesel production.
The yield of biodiesel reduces if the transesterification reaction temperature goes beyond
O
601 C causing saponification of the triglycerides prior to the end of the process reaction
completely(Venkanna and Venkataramana Reddy 2009; Meher et al. 2006). On the other
hand, Samniang et al. (Samniang et al. 2014) mentioned that higher temperature system can
increase the rate of fatty acid methyl ester and the methanol to oil molar ratio of 40:1 (at 16
O
MPa, 260 C, 5 min) provides optimal CIME (~90.3%) conversion rate in the non-catalytic
transesterification process. This process took less time due to utilization of supercritical
methanol(Olivares-Carrillo and Quesada-Medina 2011)but the fatty acid ester methyl ester
conversion ratio is lower than the catalytic transesterification(Chavan et al. 2013; Ong et al.
2014; Sahoo et al. 2007).Besides, the oil extraction process also influence the quality of
biodiesel production and the chemical extraction process was effective in producing higher
yield of oil(Jahirul et al. 2013). Though this process was expensive due to higher price of
solvents, solvent recycling can reduce the process cost for regular production. Maturity of the
Calophyllum Inophyllum Oil seed and effective purification in addition to the washing and
drying in every process govern the quality of the biodiesel fuel obtained (Ong et al. 2014;
Sahoo et al. 2007; Mohibbe Azam et al. 2005; Hathurusingha 2012). Therefore, the
production of biodiesel from the beauty leaf seed could be economical and effective following
the convenient approach.

703

Calophyllum
Inophyllum Seed

Collection, Peeling,
and Drying

Esterification

Neutralization

Oil Extraction (Crude

Calophyllum
Inophyllum)

Transesterification

Degumming

Purification and Drying

Calophyllum Inophyllum Methyl

Ester (CIME) Biodiesel
Fig.1. Biodiesel Production Processes from Calophyllum Inophyllum (Ong et al. 2014; Sahoo
et al. 2007)

Crude
Calophyllum
Inophyllum

Preheat
(60 OC) &
Stirr (1000
rpm)

Removal of
Phosphate
Compounds and
other gums

Add 0.5% (v/v) of phosphoric

acid (20% H3PO4) solution at
60 OC, 1000 rpm, 30 min

Washing
(Distilled water,
40 OC)

Water Evaporation (with

vacuum pump, 30 min)
to avoid oil oxidation

Density separation
process (with
separating funnel, 4 h)

Degummed
Calophyllum
Inophyllum Oil

Fig.2. Degumming Process of Calophyllum Inophyllum Oil (Ong et al. 2014; Sahoo et al. 2007)

Degummed
Calophyllum
Inophyllum Oil

Feed the mixture into

reactor (stirr with
overhead stirrer, 1150
rpm, 3 h, 60 OC)

Washing of Esterified oil

(distilled water, 40 OC)

Reactor (preheat,
60 OC)

Mix 1% (v/v) H2SO4 (acid

catalyist) and Methanol (9:1
methanol to Oil) and stirr.

Obtain Layers in the reactor

of Esterified Oil (upper layer)
and water-methanol mixture
(lower layer)

Evaporation to remove excess

methanol and water (Rotary
evaporator, 30min, 65 OC)

Remove water and extra

methanol (Separation
funnel, 4h)

Pure Esterified
Oil

Fig.3. Acidic Esterification Process of Calophyllum Inophyllum Oil (Ong et al. 2014; Sahoo et
al. 2007)

704

Esterified Calophyllum
Inophyllum Oil

Double Jacketed
Reactor (with stirrer,
reflux condenser and
thermometer)

Putting the solution into

reactor (stirring, 50 OC,
30 min)

Transfer the exterified oil

mixture into Separation
Funnel (30 min)

Collecting pure Esterified Oil with

allowable FFA content

Mixing 50ml methanol

with 0.23 wt% NaHCO3

Removing excess methanol,

gum and particles from bottom
layer

Proceed to
Transesterification

Fig.4. Neutralization Process of Esterified Oil Containing Higher FFA and Impurities(Ong et al.
2014; Sahoo et al. 2007)

Dissolving 1 wt.%. alkali catalyst (NaOH) into

methanol (amount of methanol is 9:1,
methanol to oil) in a separate reactor

Preheat, 50 OC

Esterified C. Inophyllum oil

Mix the NaOH and Methanol

solution into preheated Oil

Stirr the mixture (1150 rpm,

2h, 50 OC)

Gravity/ Centrifuge Separation

(Glycerine removed from lower
layer)

Proceed to acidic neutralization,

washing, purification and drying

Crude Biodiesel

Fig.5. Transesterification Process to Produce Crude Biodiesel from Calophyllum Inophyllum

Oil (Energy 2012; Ong et al. 2014; Sahoo et al. 2007)
Table 2: Physical and Chemical Properties of CIME in Comparison to its Crude Oil (Atabani et
al. 2013a; Ong et al. 2014)

1
2
3
4
5
6
7

Properties

CIME

ASTM D6751 Test Code (Limits)

5.5377

C.
Inophyllum
Oil
55.478

Kinematic Viscosity at 40
O
2
C (mm /s)
O
Dynamic Viscosity at 40 C
(mpa.s)
Kinematic Viscosity at 100
O
2
C (mm /s)
Viscosity index (VI)
O
3
Density at 40 C (kg/m )
Oxidation stability (h at 110
O
C)
Cold filter plugging point,
O
CFPP ( C)

4.8599

51.311

Not Specified (N/S)

1.998

9.5608

D 445 (1.9-6 mm /s)

183.2
877.6
6.12

165.4
0.9249
0.23

(N/S)
D 1298 (N/S)
D 675 (3 h minimum)

11

D 445 (1.9-6 mm /s)

D 6371 (N/S)
26

705

8
9
10
11
12
13
14

Cloud Point ( C)
O
Pour Point ( C)
O
Flash Point ( C)
Copper Strip Corrosion (3h
O
at 50 C)
High caloric value (MJ/kg)
CCR (m/m %)
Total Sulfur (mg/kg)

12
13
162.5
1a
39.513
0.4069
4.11

236.5
1a
38.511

15

D 2500
D 97
130 (minimum)
D 130 (No.3 max)
(N/S)
D 4530 (0.050% m max)
D 5453 (15 Max for S15 and 500
Max S500)
N/S

Absorbance (abs) at WL 0.057

0.46
656.1
16
Transmission (%) at WL 87.7
34.7
N/S
656.1
17
Refractive index (RI) at 25 1.4574 1.4784
N/S
O
C
18
Cetane Number (CN)
57.3
19
Iodine number(gI2/100g)
97-100
20
Carbon residue (% mass)
0.1-0.2
ASTM D4530 (max. 0.05)
21
Water
and
sediment 410(mg/kg)
450
23
Acid value (mg KOH/g)
0.34
59.30
ASTMD664 (0.5 max)
PERFORMANCE AND EMISSION CHARACTERISTICS OF CIME (CALOPHYLLUM
INOPHYLLUM METHYL ESTER) BIODIESEL
Sahoo et al. (2007) noted that the brake specific fuel consumption (BSFC, kg/kWh) could not
be an acceptable parameter to compare the biodiesels due to different calorific value and
density from based on their feedstocks. Rather, the authors reported that the brake specific
energy consumption (BSEC, kJ/kWh) could be reliable parameter for the fuel performance
comparison. They found that the 100% neat biodiesel of CIME (i.e. CIME100)demonstrated
higher BSEC in all loads but with improved brake thermal efficiency (BTE). They concluded
that the better combustion and the inherent lubricity of the biodiesel might have influenced
this performance to consider CIME100 as acceptable biodiesel for vehicle engines. Moreover,
though contradictory with other experimental results of various types of biodiesel fuels, they
found that the CIME100 emits about 4% lesser NOx than the diesel fuel.
Hegde and Rao (2012) conducted an investigation on a 4S CI Engine [1 Cylinder, DI, Water
O
Cooled, 1500 rpm, Nozzle (3x 0.3mmx 120 Spray Angle), Eddy current dynamometer] with
CIME biodiesel blends and SC5D additive (mainly a diesel fuel additive, 1:2000-1:2500 for
SC5D to diesel). They concluded that the CIME40 mixed with this additive reduces the BSFC,
HC, CO in all brake loading but NOx emission increases marginally within that region.
Besides, the brake thermal efficiency (BTE) increased effectively which is also similar to the
pure diesel mixed with the same additive. Moreover, they mentioned that the exhaust gas
temperature increased the percentage increase of CIME blends for all loads.

Oxidation Stability of Biodiesel

The instability of biodiesel through oxidation rancidity may cause the plugging in the fuel filters,
clogging and fouling in the injectors, and deteriorate the performance of the engine operation.
Literature reviews (Madarasz and Kumar 2011; Rizwanul Fattah et al. 2014; Sengupta and
Mazumder 1976)showed that the relative susceptibility ratio the unsaturated fatty acid methyl
esters like oleic (18:1), linoleic (18:2), and linolenic (18:3) acids is 1:12:25. Biodiesels which
can resist the auto-oxidation with more saturated fatty acid contents are more stable than the
biodiesels which contains more unsaturated fatty acids (mostly the polyunsaturated esters).
These unsaturated fatty acid esters form various by-products like acids, aldehydes, ketones,
lactones, etc. through auto-oxidation. Sarin et al.(2007)also described that, from their
O
O
O
experimental investigation (at 100 C, 110 C and 120 C, EN 14112 (6h minimum at 110
O
C)) between Palm biodiesel and Jatropha biodiesel,due to more saturated fatty acid the
Palm biodiesel (43.4%)shows more oxidation stability than the non-edible Jatropha biodiesel
(21.1%).Also the oxidation process was rushed due to temperature increase. The induction
O
periods were 6h, 4.5h, 1.4h for Jatropha and18h, 13.4h, 6.8h for Palm biodiesel at 100 C,
O
O
110 C and 120 C respectively. Atabani et al. (2013a) found that the oxidation stability of
O
O
CIME is 6.12 h at 110 C (ASTM D675, minimum 3h at 110 C) indicating the consistency

706

with the ASTM D6751standard for biodiesel specification. Whereas, the crude Calophyllum
O
Inophyllum oil had the oxidation stability of 0.23 h (ASTM D675, minimum 3h at 110 C).
Hence it is imperative to use anti-oxidant to meet the standard specification and to increase
the performance as fuel (Atabani et al. 2013b; Sarin et al. 2010a; Sarin et al. 2010b; Atabani
et al. 2013a; Rizwanul Fattah et al. 2014).
Slight amounts of higher unsaturated fatty acid ester compounds comprising bis-allylic
carbons can have a strong influence on the oxidative stability of biodiesel (Knothe and Dunn
2003). Generally, oxidative stability is expresses in terms of oxidative stability index (OSI) by
determining the induction period (IP) at a standard temperature based on ASTM D6751
O
O
(minimum 3h at 110 C) or EN 14112 (6h minimum at 110 C). Moreover, there are other
parameters like peroxide value (PV), Iodine value (IV) and Acid value, etc. or various
established methods could be used to determine the oxidative stability of the biodiesel
(Knothe and Dunn 2003; Rizwanul Fattah et al. 2014).But both the PV(Knothe and Dunn
2003)(as the higher unsaturated fatty acids breaks down to generate hydropersoxides at a
lower amount being decomposed promptly in presence of metallic or contaminating catalysts)
and the IV(Knothe 2002)could not meet the suitability of measuring the biodiesel fuels
oxidative stability index. Rather, the researchers (Knothe and Dunn 2003) proposed an
alternative of Iodine value to bebis-allylic position equivalents (BAPE) which can suitably
assess the oxidative stability due to relatively higher oxidation of the bis-allylic CH2
positions in the unsaturated fatty acid compounds. The regression equation of determining
2
the OSI could be expressed as in eq. 1 with R =0.983.
OSI = 3.91 0.045 BAPE
----- (eq. 1)
Moreover, Sarin et al. (2010a) proposed to blend different biodiesels possessing higher
induction period (e.g. Palm Biodiesel, PBD) along with a lower oxidative stable biodiesel (e.g.
Jatropha Biodiesel, JBD) to improve the combined effect. They found the correlation between
oxidation stability (OS) and palmitic acid methyl ester (PAME) content (wt%) of the blend (eq.
2
2, with R =0.994 and est = 0.149)as the PAME is significant component among the saturated
fatty acid methyl esters (FAME) in biodiesel blend. But they could not determine the similar
correlation between OS and individual unsaturated FAMEs (e.g. oleic acid, and linoleic acid,
etc.). Nevertheless, a higher degree and reliable correlation have been proposed by the
2
authors with the effect of total unsaturated FAME to OS of the blend(eq.3, with R =0.998 and
est = 0.091, X = wt% of total unsaturated FAME). The authors (Sarin et al. 2010a) found that,
minimum 40 wt% of PBD need to be blended with JBD to meet the EN-14112 specification[i.e.
O
min. 6h at 110 C].
OS = 0.214(PAME) + 0.671 ;(0<PAME<45)
-----(eq. 2)
OS = 0.234(X) + 22.318 ;(0<X84)
-----(eq. 3)
The FAME composition of JBD and PBD can be shown as in Table 3(Sarin et al. 2009a) and
the correlations from eq.2 and eq.3 are presented in fig. 6 (Sarin et al. 2010a).
Table 3. Fatty acid methyl ester (FAME) composition of JBD and PBD blends
Biodiesel Blending Palmitic
Stearic acid Palmitolic acid Oleic acid Linoleic acid
Ratio
(wt%) acid methyl methyl
methyl ester methyl
methyl ester
Palm:Jatropha
ester (wt%) ester (wt%) (wt%)
ester (wt%) (wt%)
100:00
40.3
4.1

43.4
12.2
80:20
35.1
4.7
0.3
43.3
16.6
60:40
29.8
5.2
0.6
43.3
21.1
40:60
24.6
5.8
0.8
43.2
25.6
20:80
19.5
6.3
1.1
43.2
29.9
00:100
14.2
6.9
1.4
43.1
34.4
Nevertheless, the extensive application of biodiesel like the diesel fuel is restrained due to
poor thermo-oxidative stability of the biodiesels, especially, the non-edible feedstock
resourced. This oxidative instability is also influenced by the CFPP, cloud point (CP), pour
point (PP), etc. (Sarin et al. 2009b; Atabani et al. 2013a; Sarin et al. 2009a). Therefore,

707

synthesis of surrogated -branched fatty acidmethyl ester(Sarin et al. 2009b) blend could
increase the oxidation stability (24h) of the fuel as required and lower thetemperatures of the
O
O
O
governing parameters (CP<-36 C, PP<-42 C, CFPP<-21 C).The synthesized esters dont
contain any double bond in the alkyl ester chain, all the synthesized methyl, ethyl esters
exhibits more than 24h induction period and due to absence of any double bond they dont
have any iodine value (IV).

Fig.6. Oxidation Stability (OS) correlation to PAME (wt%) and Total Unsaturated FAME (wt%)
of Blended Biodiesels
Liang et al. (Liang et al. 2006) mentioned that the crude palm oil methyl ester (crude biodiesel
after the transesterification process) has better oxidation stability (induction period >25h),
whereas, the distilled (purified and dried) palm oil methyl ester (palm biodiesel, PBD)
possesses only about 3.5h of induction period that only meets the criteria of ASTM D6751
standard. The researchers mentioned that the presence of natural antioxidant (vitamin E,
~600ppm and -carotene, ~711 ppm) in the crude palm oil stabilizes the oil, but the distilled
PBD only contains a meagre amount of vitamin E (<50 ppm) resulting the poor oxidation
rancidity. Therefore, utilization of antioxidants in the biodiesel fuel can facilitate the oxidation
stability as per biodiesel fuel standards of ASTM D6751 and EN14214.
OXIDATION AND ANTIOXIDANT EFFECTS ON BIODIESEL OXIDATION STABILITY
Antioxidants could be divided into several groups(Shahidi et al. 1992), namely, free radical
terminators, oxygen scavengers reacting with the excess oxygen in a closed system or metal
contaminants acting as a catalyst for lipid oxidation(Knothe and Dunn 2003). The efficacy of
the antioxidant is termed as Stabilization factor, expressed as, F = IP x/IPo, whre the IPx is
the induction period with antioxidants and the IP o is the induction period without the
antioxidants(Loh et al. 2006).
Mostly, the free radical terminator type antioxidants are used and the Phenolic antioxidants
(AH) are of that type.Detail mechanisms of oxidation and anti-oxidation chemistry can be
obtained from authors earlier publication (Rizwanul Fattah et al. 2014). Generally, hydrogens
are donated by Phenolic antioxidants. The mono-phenolic antioxidants, Butylated
hydroxytoluene (BHT) and Butylated hydroxyanisole (BHA) can be found commercially and
they are completely soluble into the fats being insoluble into water yielding radical
intermediates alongwith adequate delocalized resonances. Moreover, the Tert-butyl
hydroxyquinone (TBHQ) is a diphenolic antioxidant which is sufficiently soluble into fats.
Diphenolic antioxidants can form various dimers and dismutates reacting with each other and
can regenerate the semiquuinone. Amine type antioxidants (e.g. Octylatedbutylateddiphenyl
amine (OBPA))are also regarded as free radical terminators. The reactive hydrogens in the
phenolic antioxidants governs their anti-oxidative capacity as BHA BHT< DTBHQ TBHQ <
PG PY. Where,PY is Pyrogalllol, PG is Propyl gallate and DTBHQ is 2,5-di-tert-butyl-1,4dihydroxybenzene.Besides, the Gallic acid (GA), -Tocopheroland the Caffeic acid (CA) are

708

phenolic type and N,N'-diphenyl-p-phenylenediamine (DPD) is amine type antioxidants often

used for increasing the oxidation stability of the biodiesels.
Liang et al. (Liang et al. 2006) studied the effect of three antioxidants, namely the-tocopherol
(-T, natural), the butylatedhydroxytoluene (BHT, synthetic) as well as thetert-butyl
hydroquinone (TBHQ, synthetic), on distilled palm biodiesel (DPBD) with a range of dosage
rates. They found that both the BHT and TBHQ improve the induction period up to 6.42h and
8.85h respective meeting the European standard with a dose of 50 ppm each; but the dose of
natural antioxidant was about 1000 ppm to obtain the minimal oxidation stability (6.17h) of the
distilled biodiesel. The researchers also reported that the use of TBHQ at a dose of 500 ppm
and 1000 ppm can increase the induction period up to 30.2h and >48h respectively.
Therefore, this study shows the effectiveness of using synthetic antioxidants to improve the
induction period.The effectiveness rank of the antioxidants was TBHQ>BHT>-tocopherol.
As a non-edible fuel, the Jatropha biodiesel blends of 5 , 10 , 15 , 20 (i.e. JB5, JB10,
JB15, JB20) mixed with the 0.15
(m) of , -diphenyl-1,4-phenylenediamine (DPPD)
antioxidant additive demonstrates significant reduction of NOx emission at full throttle and all
speed ranges (Palash et al. 2014). The amount of NOx reduction was 8.03%, 3.503%,
13.65% and 16.54% respectively in comparison to the same biodiesel blends without the
antioxidant additive. Moreover, the exhaust gas temperature also reduces with the addition of
the DPPD antioxidant in to the biodiesel.All the other emissions were almost similar to the
neat biodiesel emissions.
Moreover, Varatharajan et al. (Varatharajan and Cheralathan 2013) found from the quantumchemical study that the DPPD antioxidant can retain its antioxidant capacity at the increasing
temperature throughout the combustion phase. They used it with edible feedstock derived
biodiesel, Soybean methyl ester (SME), and observed a reduction of NO of about 28.36% for
SME100 and for SME20 it was reduced by 9.35%. But they observed increase of CO (9.09%
and 14.28% ) and HC (10.52% and 16.92%) at 75% loading condition for SME20 and
SME100 biodiesel blends respectively. Addition of antioxidant also reduces the BTE by 0.8%.
Thus it may be inferred that the addition of amine base antioxidants in the edible feedstock
derived biodiesel was not much favourable though it reduces the NOx emission.
Focke et al. (2012) studied the oxidation stability of Sunflower, Soybean and Canola Oils with
the di-tert-butylhydroquinone (DTBHQ) and poly(1,2-dihydro-2,2,4-trimethylquinoline) (Orox
PK) at a dosage rate of 0.5 wt%. They found that the oxidation stability of both Canola and
Sunflower based biodiesel increases the induction period and thus meet the EN14214
specification. But the addition of tris-(nonylphenyl) phosphite (Naugard P) just ceased the
stability of the already stable canola biodiesel (7.1h). Soybean biodiesel responded well with
the DTBHQ additive to improve and meet the oxidation stability as per European standard.
Sarin et al. (2010b) conducted the oxidation stability test ofJatropha biodiesel (Induction
Period 3.95h) with antioxidants -tocopherol (-T), tert-butylatedhydroxytoluene (BHT), tertbutylated phenol derivative (TBP), octylatedbutylateddiphenyl amine (OBPA), and tertbutylhydroxquinone (TBHQ). They found that, the oxidation stability gradually increases with
the gradual increase of additives in the fuel blend. There was a requirement of 600 ppm -T,
300 ppm of TBPand OBPA, 200 ppm of BHT and 150 ppm of TBHQ were needed to stabilize
the Jatropha biodiesel in this experiment. Therefore, the rank of activity of the antioxidants
were found as TBHQ > BHT > TBP > OBPA > -T with the leading side by the synthetic
antioxidants.
Similarly, Agarwal and Khurana(2013)also confirmed that the synthetic phenolic type
antioxidants effectively improves the oxidation stability of the non-edible resourced biodiesels.
They observe d the storage stability of Karanja oil methyl ester (KOME) for long duration
experiments with the antioxidants 2,6-di-tert butyl-4-methyl phenol (BHT), 2-tert butyl4methoxy phenol (BHA), 2-tert butyl hydroquinone (TBHQ), 1,2,3 tri-hydroxy benzene (PY) and
3,4,5-tri hydroxyl benzoic acid (PG).The researchers mentioned that the addition of
antioxidants should be performed as soon as the biodiesel is produced to avoid any peroxide
reactions and to maintain the quality of the fuel at a competitive range. They found that both
the PY and PG antioxidants could maintain a stability of the biodiesel fuel up to 4 months of
storage period. The higher concentration of these two antioxidants could reduce the rate of
rancidity of the oxidation of KOME after 4 months. But the other antioxidants could not meet
the criteria after 4 months. They also observed that the exposing to the sunlight and air
adversely deteriorate the oxidation stability of the fuel and the PY antioxidant provided good
prospect of using with the KOME storing at a darker place.

709

Thus the phenolic synthetic type antioxidants effectively increase the oxidation stability of the
non-edible oil biodiesels with lesser dosage rates than that of the natural antioxidants.
CONCLUSION AND RECOMMENDATIONS
From this review we have found that there are not enough investigations performed on the
beauty leaf oxidation stability for long term storage cases in Australia. Though there were
some research outputs on its Indian origin to improve the oxidation stability, those were not
based on long term storing. Hence, it is essential to derive the better antioxidant to stabilize
the beauty leaf biodiesel for long time to use them in the engines. The other prospective
issues of considering this as a transport fuel area) CIME10 and higher blends can be used as feasible diesel fuel replacement in the
internal combustion engines.
b) CIME blends reduce the emissions and if the additive can be used it may reduce the
NOx emission like the Jatropha blends performed with phenolic synthetic antioxidants.
c) To obtain better fatty acid methyl ester contents, the processes described should be
followed carefully and efficiently.
d) The more mature seed will give better fuel output with effective purification,
neutralization and drying process.
e) Only PY antioxidant showed effectiveness for long term oxidation stability
maintenance of non-edible biodiesel Karanja. Therefore, it can be tested with the
beauty leaf biodiesel to observe the stability for long term storage cases.
f) It has been observed that the gradual increase of antioxidants increases the oxidation
stability (i.e. the induction period).
g) The synthetic antioxidants are less required than the natural antioxidants for better
oxidation inhibition of the biodiesels.
h) Biodiesels converted into surrogated -branched fatty acid methyl ester also showed
prospect as the outputs (i.e. higher oxidation stability, higher cetane number, less
viscosity and lower thermal properties) are favourable for engine combustion
performances.
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713

EFFECT OF COPPER OXIDE, ZINC OXIDE AND CALCIUM OXIDE ON THE

CONVERSION OF BIO-ETHANOL TO HYDROCARBONS OVER HZSM-5
CATALYST
T. A. Abdullah and H.A. Zaidi

University School of Chemical Technology Guru Gobind Singh Indraprastha University Sector 16-C
Dwarka New Delhi, India-110078

ABSTRACT
Bio-ethanol transformation into hydrocarbons was studied on HZSM-5, 1wt% CaO/HZSM-5,
1wt%ZnO/HZSM-5 and 1wt% CuO/HZSM-5.All experimental runs were conducted at 400C,
pressure =1atm and WHSV=2.5 h-1.It was found that 1wt% CaO/HZSM-5 significantly reduces the
amount of coke and rate of deactivation during the reaction. It was observed 1wt% CuO/HZSM-5
and 1wt%ZnO/HZSM-5 loose activity faster as compared to 1wt%CaO/HZSM-5. Addition of CaO in
HZSM-5 catalyst further causes a decrease in aromatic hydrocarbons yield thus the catalyst
deactivation mainly occurs due to coke deposition. This coke deposition is mainly due to
production of aromatic content during ethanol to hydrocarbon reaction. Experimental results
demonstrated that CaO modified HZSM-5 offered the outstanding catalytic performance and
enhanced the anti coking ability.
Keywords: HZSM-5, carbon deposition, bio-ethanol conversion
*Correspondence concerning this article should be addressed to Dr.H.A.Zaidi University School of
Chemical Technology Guru Gobind Singh Indraprastha University Sector 16-C Dwarka New Delhi,
India-110078 (Email address: hasan.azaidi@gmail.com)

INTRODUCTION
Nowadays, there has been a continuing rise in the global demand for fuel which is derived from
non renewable sources such as petroleum. As there is the depletion of worldwide crude oil
deposits due to massive usage of non renewable resources. Search for future energy sources
which can serve as an alternative to crude oil has become one of the most important topic in
researches relating to the renewable source of energy. One of the best alternatives is biomass
because it is abundant in nature such as agricultural crop and waste, forestry residues, aquatic
plant and animal and municipal waste and can be thermo chemically or biochemically converted to
combustible liquid such as ethanol. The transformation of ethanol from renewable sources like
biomass into hydrocarbons is potentially of great importance to countries like India. By its
property, ethanol can naturally be added to gasoline pool but incorporation at high levels requires
the modification of motorization system. It has been reported HZSM-5 catalyst is widely used for
the conversion of ethanol to olefins (Gayubo et al., 2010; Gayubo et al., 2011; Zhan et al., 2010;
Song et al., 2010; Ramesh et al., 2010; Takahashi et al., 2012; Ramesh et al., 2009; Lu and Liu,
2011) and hydrocarbons. (Ni et al., 2010; Machado et al., 2005; Machado et al., 2006; Gayubo et
al., 2012; Chang et al., 1990; Tertyakov et al 2010; Madeira et al., 2009; Saha, and Sivasanker,
1992; Viswanadham et al., 2012). Ramesh et al., (2009) has reported that H3PO4 modified HZSM5 catalyst gives very high activity and stability during ethanol conversion to ethylene at 673 K. PHZSM-5 modified were used for ethanol conversion to lower olefins, and it was found that 3wt%
loading over HZSM-5 catalyst was the optimum phosphorus content Bi et al., (2011) investigated
the conversion of bioethanol into olefins using Ce modified HZSM-5 catalyst at 400C and it was
found that the strong acidic site of HZSM-5 zeolite decreases due to the Ce loading over HZSM-5
catalyst and it was also observed that there is a decrease in the rate of coke formation. Lu et al.,
(2011) found that HZSM-5 catalyst has been modified with different wt% of Fe which were
prepared by impregnation method and due to the Fe modification over HZSM-5 Catalyst there is a
decrease in the strong acidic sites at 300 C to 500 C.
Catalytic conversion of ethanol to olefins using ZSM-5 catalysts has been studied due to increase
in worldwide demand of ethylene and propylene in the market (Ouyang et al., 2009; Bi et al., 2011;
Lu et al., 2011; Goto et al., 2010; Tertyakov et al., 2010; Xia et al., 2010; Sheng et al., 2013; Bi et
al., 2010; Furumoto et al., 2012; Meng et al., 2012; Zhang, and Yu, 2013; Takahashi et al., 2013).
Recently extensive study has been conducted to modify HZSM-5 catalyst using various metals
such as Mg, Cr, Fe, Co, Ni, Cu, Ru, Ag, Ir, Pt and Au (Inaba et al., 2006) . Effect of acidity over

714

HZSM-5 catalyst due to the doping Al, Ga and Fe has been studied for the conversion of ethanol to
propylene by Furumoto et al., (2011). ZSM-5 catalyst had been used in the conversion of cheap
and easily available compound such as biomass, sugar, starch etc. along with solid waste of the
wood industry (Tertyakov et al., 2010; Makarfi et al., 2009; Talukdar et al., 1997; Madeira et al.,
2012; Inaba et al., 2006; Zaidi and Pant 2004; Zaidi and Pant 2014). Recently, due to formation of
new polices for environmental protection and increase in the oil price (because of depletion of
crude oil reserves in the world), ethanol has become a viable and realistic alternative source of
fuel in the world (Bi et al., 2010; Furumoto et al., 2011; Zhang, and Yu, 2013).
Present research work is focussed on catalyst development for the conversion of ethanol to
hydrocarbons products and modification of HZSM-5 with 1 wt% of CuO/ HZSM-5,
1wt%ZnO/HZSM-5 and 1wt%CaO/HZSM-5. Catalysts were prepared, characterized and
experimental runs were conducted to study the catalytic conversion and hydrocarbon yield.
EXPERMENTAL
HZSM-5 (Si/Al=80) is the catalyst used for ethanol to hydrocarbon conversion was supplied by Sd
Chemie (Germany). The starting HZSM-5 was used as a support for calcium oxide, copper oxide
and zinc oxide respectively. Other starting material such as copper nitrate salt, zinc nitrate salt and
calcium nitrate salt was procured from Merck (Germany). Catalyst was prepared by doping
separately 1wt% ZnO, 1wt % CuO and CaO onto HZSM-5 prepared by impregnation techniques.
The final solution was stirred for 12 h at 303 K. The final catalyst slurry was transferred to a rotary
evaporator to remove excess water under vacuum at 353 K followed by drying in an oven at 393 K
for 12 h. The dried pellets were calcined in a furnace at 823 K for 5 h to decompose calcium, zinc
and copper complex to CaO, ZnO and CuO.
The prepared catalysts were characterized by X-ray diffraction (XRD), Surface area and pore size
analyzer, Metal trace analyzer and Scanning electron microscopy (SEM). The surface areas and
pore volumes of the catalysts were determined by using ASAP 2010 (Micromeritics, USA) by
adsorption with nitrogen (99.99 % purity) at 77 K, employing the static volumetric technique. Prior
to the analysis the catalysts samples were degassed for 6 h at 383 K under vacuum. The samples
were placed in the evacuated sample tube, cooled to cryogenic temperature and then exposed to
the analysis gas at precisely controlled pressures. With each incremental pressure, the number of
gas molecules adsorbed on the surface increases. The pressure at which adsorption equilibrium
occurs was measured and quantity of gas adsorbed was determined. Adsorption/desorption sets of
data were used to describe the isotherms. Analysis of the isotherm gave information about the
surface characteristics of the material and was done by microcomputer processing software
(ASAP 2010).
X-ray diffraction patterns (XRD) of all the catalysts were taken in order to characterize the phases
present and also the crystallinity of the catalyst. The diffraction patterns were measured by X ray
diffraction method using Bruker D-8 advance X-ray diffractometer with monochromatic CuK-
radiation and scanning 2 from 00 to 400. The wavelength of adsorption was kept 1.54 A0.
Catalysts samples were crushed and ground to fine powder for the analysis. The distance between
crystal planes were calculated using Braggs law: n=2d sin where =1.54 A0 and 2 were taken
at particular peak height.To determine the actual amount of CaO,CuO and ZnO doped over
HZSM-5, and the Si/Al ratio, the catalyst samples were digested with nitric acid at 353 K for 2 h
under reflux. The final metal content on the catalyst was determined by a metal trace analyzer
(Metrohm 757 VA Computrace, Switzerland). A standard solution of Copper nitrite, zinc nitrite and
calcium nitrates were used for calibration for this purpose.To obtain surface textural details of the
support, scanning electron microscopy (SEM) of fresh and used samples were done. The
morphology and structure of the catalysts were studied using Hitachi S-3700N scanning electron
microscope (SEM).
ETH reaction was conducted at 400 C in fixed bed reactor using 1.5 g of the catalyst. All the
catalysts were compared for their performance for ethanol conversion by conducting experiments
under identical conditions. The reaction temperature was measured by K type thermocouple
inserted in the reactor through thermocouple well. Prior to reaction, the sample of 1.5g were
pretreated in nitrogen at 400C for 2 h. Liquid ethanol was evaporated by preheater at 200C.
Ethanol was fed to reactor by a dosing pump and vaporized ethanol was made to enter in reactor
at WHSV=2.5h-1.The reactor effluent was analyzed by two gas chromatographs equipped with
flame ionization detector and thermal conductivity detector. In flame ionization detector the
capillary column was used to determine the C1-C12 hydrocarbons.

715

RESULTS AND DISCUSSION

To investigate the morphology of sample, SEM micrographs have been obtained. SEM images
show that crystal grows into spherical polycrystalline aggregates and particle of undefined shape
was also present as shown in Fig. 1.
Fig. 2 shows the XRD patterns of 1wt% each of CaO, CuO, and ZnO doped HZSM-5 and parent
HZSM-5 catalyst. There is similarity of XRD patterns between unmodified HZSM-5 and modified
HZSM-5 catalyst. It was found the original structure of HZSM-5 has not been destroyed during
impregnation process. It was observed from Fig. 2 that no CuO, ZnO and CaO species could be
identified and significant changes were not observed in XRD patterns as compared with parent
HZSM-5 catalyst.

Figure 1
catalyst

SEM micro graphs of the sample (a) HZSM-5 and (b) 1wt%-CaO/HZSM-5

Fig. 2 shows that crystalline phase is present in HZ(CaO), HZ(CuO), HZ(ZnO) and HZ(0) catalyst.
In crystalline phase no new species were observed by XRD in the HZSM-5 (CuO), HZ (ZnO) and
HZ (CaO) catalyst. The intensity of metal oxide doped catalyst had slightly decreased. It was
observed that the over all structure of catalysts remained same.

716

Figure 2

XRD patterns of HZ (CuO), HZ (ZnO), HZ(CaO) and HZ(0) catalysts

The surface area and pore volume of the catalyst were determined by BET surface area technique.
The BET surface area analysis results are shown in Table 1. The surface area of catalyst
decreases on increasing metal oxide loading. Volume of N2 adsorbed decreased with 1wt% of
calcium oxide, 1wt% zinc oxide and 1 wt% copper oxide. Due to partial coverage of the surface
with calcium oxide, zinc oxide and copper oxide it was observed that some calcium oxide, zinc
oxide and copper oxide may enter into the channels, due to this there is decrease in pore radius of
the CaO, CuO and ZnO doped HZSM-5 as compared to parent HZSM-5. This showed that calcium
oxide, zinc oxide and copper oxide were present in the pores of HZSM-5 catalyst. During
experimental run it was found that coke further filled the pores of the catalyst because of which
there is decrease in the pore volume and surface area (as shown in Table 1).
100
90
80

Conversion(%)

70
60

HZ(0)
HZ(ZnO)
HZ(CaO)
HZ(CuO)

50
40
30
20
10
0
0

12

15

18

21

24

Time, h

Figure 3

Conversion of ethanol versus Time in a Fixed Bed Reactor

[T=400C, P=1 atm and WHSV=2.5h-1]

Effect of ZnO,CaO and CuO addition over HZSM-5 catalyst on conversion and products yield as
function of time on stream has been shown in Fig. 3 and Fig. 4 Incorporation of CaO onto HZSM-5
catalyst shows resistance to deactivation as compared to HZ (CuO) and HZ(ZnO) catalyst.
Compared to HZSM-5 catalysts there was an increase in conversion and hydrocarbon yield was

717

observed with ZnO/HZSM-5, CuO/HZSM-5 and CaO/HZSM-5. The detailed products distribution
with all the catalysts is compared in Table 2. The major products of the reaction were methane,
ethylene, propylene, ethylmethyl ether, toluene, ethyl benzene, xylene, isopropyl benzene, ethyl
toluene, and trimethyl benzene and tetra methylbenzene.

60

HZ(0)
HZ(ZnO)

Hydrocarbons Yeild (wt%)

50

HZ(CaO)
HZ(CuO)

40

30

20

10

0
0

12

15

18

21

24

Time,h

Figure 4

Yield of Hydrocarbon versus Time in a Fixed Bed Reactor

[T=400C, P=1 atm and WHSV=2.5h-1]

Fig. 3 and Fig. 4 show that conversion and hydrocarbon yield are higher initially in CuO doped
HZSM-5 catalyst. In this the rate of deactivation of ethanol conversion and hydrocarbon yield are
higher as compare to HZ(CaO) catalyst. Table 2 shows the hydrocarbons distribution with different
metal oxide doped catalyst and compared product distribution under isothermal conditions. Table 2
shows that more aromatic yield is produced during the experimental run while using HZ(CuO) as
compared to other modified catalyst. HZ(CuO) and HZ(CaO) resulted in 18.2wt% and 17.08 wt% of
aromatic yeild respectively, which indicates that addition of CaO slightly reduced the conversion
and aromatics yield due to suppression of active sites. The main aim of adding CaO on HZ(0)
catalyst is to reduce the deactivation of catalyst.

Table 1

BET Surface Area and Pore Volume of Fresh and Aged Catalyst.
*(Run Time: 24 h)

The effect of run time on conversion and hydrocarbons yield was investigated over HZ (CuO),
HZ(ZnO) and HZ(CaO). Fig. 3 also shows a comparison of effect of run time on conversion with
HZ (CuO) and HZ(ZnO) and HZ (CaO) catalysts. As can be seen from this Figure, conversion of
ethanol decreases with increase in time on stream. However the decrease in conversion of HZ
(CuO) was higher as compared to HZ (CaO). Initial conversion of HZ (CuO) and HZ (CaO) were
97.1% and 94.06% respectively and after 24 h run ethanol conversion decreased to 71.6% and
79.7% respectively.

718

Table 2 Effect of copper oxide, zinc oxide and calcium loading over HZSM-5
catalyst on the product distribution [T=400 C, WHSV=2.5 h-1, P=1 atm]

Fig. 4 shows the yield of hydrocarbons with respect to time. The increase in time of stream also
results the decrease in the yield of hydrocarbons. In Fig. 4, HZ (CaO) shows the relatively lower
decrease in the yield of hydrocarbon with run time compared to HZ (CuO) catalyst. These results
indicate that incorporation of CaO to the HZSM-5 catalyst significantly reduces the deactivation
rate. Addition of CaO most probably reduces the acidic sites on HZSM-5 but on the other side it
also generates more active sites, which are highly selective to gasoline range of hydrocarbons but
also helps in reducing the deactivation rate.
CONCLUSIONS
1wt% CaO modified HZSM-5 catalyst showed very high reactivity and stability as compared with
HZ(CuO), HZ(ZnO) and HZ(0) catalyst in ethanol conversion to hydrocarbons. HZ (CaO) catalyst
shows better stability and resistance to coke formation as compared with HZ (CuO), HZ (ZnO) and
HZ (0) catalysts, this is possibly due to higher decrease in acidity after doping CaO over HZSM-5
catalyst as compared to the modified catalysts. Addition of CaO over HZSM-5 catalyst showed
more resistance to deactivation and further causes a decrease in aromatic hydrocarbons yield,
thus the catalyst deactivation mainly occurs due to coke deposition. This coke deposition is mainly
due to production of aromatic content during ethanol to hydrocarbon reaction. It was also observed
that HZ (CaO) catalyst convert higher amount of ethanol to hydrocarbons before catalyst was
completely deactivated.

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722

DRY REFORMING OF METHANE OVER OIL PALM SHELL ACTIVATED CARBON

AND ZSM-5 SUPPORTED COBALT CATALYST
1,2

1*

Izirwan Izhab , Nor Aishah Saidina Amin , and Mohd Asmadi

Chemical Reaction Engineering Group(CREG), Energy Research Alliance, Faculty of Chemical
Engineering, Universiti Teknologi Malaysia, 81310 Johor Bahru, Johor, Malaysia.
2
Faculty of Chemical Engineering and Natural Resources, Universiti Malaysia Pahang, Lebuhraya Tun
Razak, 26300 Gambang Kuantan, Pahang, Malaysia.
1

*E-mail address: noraishah@cheme.utm.my

ABSTRACT
In this study, cobalt supported oil palm shell activated carbon (Co/OPS-AC) and ZSM-5 zeolite
(Co/ZSM-5) catalysts have been prepared for dry reforming of methane. Cobalt ratios of 0.0, 6.0
and 14.0 wt% were deposited via wet impregnation method to the OPS-AC and ZSM-5,
respectively and characterized by XRD, N2 adsorption-desorption isotherms, BET surface area,
SEM and FESEM-EDX. The dry reforming of methane was performed using a micro reactor
system under the condition of 10,000 ml/h.g-cat, 3 atm, CH4/CO2 ratio of 1.2:1 and temperature
range from 923K to 1023K. The gaseous products were analyzed by gas chromatography (GC)
with thermal conductivity detector (TCD) and further quantified to determine the conversion of CH 4
and CO2, and the yield of CO and H2. The results showed that both catalysts exhibited the
reduction in conversion of CO2 and CH4 with the increase in temperature from 923K to 1023K. The
reduction on the conversion of CO2 and CH4 may be due to the formation of carboneous substance
on the catalyst known as coking activity which is favorable at higher temperatures. The formation
of coke on the catalyst results in less catalytic activity of the catalysts. However, comparatively
Co/OPS-AC gave higher conversions of CO2 and CH4 as well as higher yields of H2 and CO as this
catalyst had higher surface area than Co/ZSM-5 which subsequently showed a higher activity for
the reforming of methane. Based on these results, cobalt supported OPS activated carbon catalyst
was suggested to be more effective for CO2 and CH4 conversion and the formation of H2 and CO.
Keywords: Methane dry reforming, oil palm shell, activated carbon support, ZSM-5 support, cobalt
catalyst
INTRODUCTION
The dry reforming of methane is mainly conducted at atmospheric pressure but fewer studies were
done at elevated pressure (Corthals, et al., 2011). However, the reaction of dry reforming of
methane was required to be investigated under pressure due to the consecutive reaction, such as
methanol synthesis in the gas to liquid (GTL) process and dimethyl ether (DME) is operated at
high pressure (Omata, et al., 2004). Hence, the catalytic effectiveness for dry reforming of
methane at high pressure is also obliged to be identified. Furthermore, methane is typically
preserved at high pressure in natural gas field but the major drawback for the reaction at high
pressure is due to inclination of coke formation that deactivated the catalysts (Nagaoka, Takanabe,
and Aika, 2004).
The undesired greenhouse gases (CO2 and CH4) are important to be utilized for the beneficial
processes such as production of syngas in carbon dioxide reforming of methane. However, the
commercialization of carbon dioxide reforming of methane is a great challenge due to the severe
deactivation of the active sites of the catalysts. In addition, the majorly employed catalysts such as
Ni based catalysts in the carbon dioxide reforming of methane suffer from a severe catalysts
deactivation such as coke formation, sintering effect due to high reaction temperature and metal
oxidation. Therefore, cobalt based catalysts and noble metal catalysts are highly selected for
catalytic reactions due to their high activity, less side reactions such as low water-gas shift activity
and high selectivity of desired products. Even though noble transition metals such as Ru, Pd, Pt
are better in their reaction performances, extremely expensive in price hinder their utilization in
large scale. Hence, cobalt catalysts are comparatively inexpensive than the transition metals with
good reaction performances
In Malaysia, palm shell plantations offer a large amount of biomass feedstock such as oil palm
fronds, empty fruit bunches (EFB), oil palm kernel shells (PKS) and mesocarp fibres (MCF). The
generated wastes from oil palm were widely employed for the application in adsorption (Hasnain
Isa, et al., 2007; Ho and Ofomaja, 2006; Sajab, et al., 2013; Tan, Hameed, and Ahmad, 2007) but
less in the application as support of catalysts (Sumathi, et al., 2010) (Baroutian, et al., 2011) or

723

catalysts in chemical reactions (Abbas and Daud, 2009, 2010). The characterization of oil palm
shell activated carbon (OPS-AC) suggests a good selection as a catalysts support with the
additional attributes of having high surface area, high volume, rich in micropores and high carbon
content. The cobalt precursor is dispersed onto the surface of porous materials to enhance the
active metal sites on the catalytic surface. In addition, the porous supports of OPS-AC and ZSM-5
zeolite were selected to provide the catalysts surface area, pore diameter, pore volume and metalsupport interaction that have a great effect on the size, dispersion and catalytic performance of
cobalt catalysts. The objective of this study is to prepare, characterize and conduct the activity
testing of impregnated cobalt based catalysts onto the different porous supports of ZSM-5 zeolite
and OPS activated carbon. Moreover, the micropore of OPS activated carbon and mesopore of
ZSM-5 zeolite is expected to affect the catalysts reaction performance.
MATERIALS AND METHOD
Materials
Cobalt metal was used as the catalyst and supported on the two selected porous materials of oil
palm shell activated carbon (OPS-AC) and zeolite ZSM-5. The OPS-AC was purchased from Multi
Filter Sdn Bhd (Malaysia). The OPS-AC was washed with distilled water to remove impurities and
dried in oven at 110 C overnight. Zeolite ammonium ZSM-5 powder (CBV8014, Si/Al=40) was
supplied by Zeolysts International and used without further modification. The cobalt metal
precursor was cobalt (II) nitrate hexahydrate, Co(NO3)2.6H2O supplied by Friendemann Schmidt.
Catalysis synthesis
The cobalt catalysts precursor were dissolved in distilled water and loaded onto the supports via wet
impregnation method by varying the ratio of 0.0, 6.0, 14.0 wt%. The mixtures were stirred on a
magnetic stirrer plate at room temperature overnight. After the impregnation, the catalysts were dried
in oven at 110 C for 3 days to remove the moisture. Only cobalt supported ZSM-5 catalysts were
calcined at 823K for 5 hours at a heating rate of 10 C/min (Izirwan et al., 2013). The prepared
cobalt catalysts of OPS-AC and ZSM-5 supports were denoted as OPS-AC(0), OPS-AC(6), OPSAC(14), ZSM-5(0), ZSM-5(6) and ZSM-5(14) respectively.
Characterization
The X-Ray Diffraction (XRD) analysis was conducted by using a benchtop X-Ray Diffractometer
Rigaku Miniflex II with CuK radiation (a = 0.1541 nm). The setting parameters were at the step
size of 0.02 and scan speed of 0.3 s/ step. The operating conditions of X-ray tube were at 10 kV
and 50pA. The N2 adsorption-desorption experiments were conducted at 77 K using a Micromeretics
ASAP 2020 V4.00 surface area and porosity analyzer. Prior to the experiment, the samples were
degassed at 473 K for 5 h. The Brunauer-Emmett-Teller (BET) surface areas were obtained for the
adsorption data from 0.05 to 0.30 in relative pressure. The obtained Y-interceipt was a positive value
to validate the BET model with a good co-efficient correlation of more than 0.99. The pore size
distributions and the pore volume of all the samples were calculated by Barret-Joyner-Halenda (BJH)
method from the desorption values of the isotherms. The surface morphology of the catalysts was
observed with a Scanning Electron Microscope (SEM, Zeiss EV050). The images were captured in
SEM mode at 10,000 times magnification. Energy dispersive X-ray (EDX) spectroscopy coupled with
field emission scanning electron microscopy (FESEM) of Hitachi SU8020 was used to analyze the
elemental composition of the OPS-AC.
Catalyst activity testing
A process flow diagram of the micro reactor system is illustrated in Fig. 1.

724

Fig. 1. Process flow diagram of a micro reactor system

A micro reactor system consists of a fixed bed reactor (length 300 mm x 10 mm ID) with a
pressured condition, a piping system for the downstream and upstream of the reactor, a control
panel and a computer system. The catalyst of 1 g was placed at the centre of reactor by holding
with quarts wool. The system was purged with N2 for 0.5 h to remove the air content in the system
and heated up to 923 K for another 30 min. The temperature of the system was slowly reduced to
the room temperature. Afterwards, the feedstock gases of CH4 and CO2 with the ratio of 1.2:1 was
fed into the system until reaching a constant flow. The whole system was heated again to the
desired operating temperature. The condition of reactor was set at 3 bar, 923 - 1023 K and 10,000
ml/h.g-cat
RESULTS AND DISCUSSION
The XRD pattern of OPS-AC shows two broadening peaks observed at 23 and 43 degree which are
assigned to activated carbon. In Fig.2, the magnitudes of the two broadening peaks were reduced
significantly after the impregnation of cobalt catalyst onto the OPS-AC. However, the peaks of cobalt
metal were not detected due to overlapping with broadening of the peaks. The XRD patterns for
Co/ZSM-5 showed the similarity in reduction of peaks after the impregnation as shown in Fig.2.
Furthermore, the reductions of peaks for both supports were apparent with the increase of cobalt
loadings. The typical spinel phase of cobalt oxide (Co3O4) was found at 30.2, 37.0, 45.2, 58.3 and
65.4 degree.
10

Intensity

20

40

60

80

2-theta (deg)

10

Intensity

20

40

60

80

2-theta(deg)

Fig. 2. XRD patterns of 0.0, 6.0 and 14.0 wt% of Co/OPS-AC and Co/ZSM-5 respectively.

The N2 adsorption-desorption isotherms of OPS-AC(0)/(6) were a Type I of the International Union

of Pure and Applied Chemistry (IUPAC) classification showing a marked microporous behavior
(Fig.3). The steep initial region of the isotherm represented the higher adsorption energy and filling
of micropores. The latter region of the isotherms showed the limiting value of the plateau was due

725

Adsorption
Desorption

250
AC (0)
200
150
AC (6)
100
50
0.0

0.2

0.4

0.6

0.8

Quantity Adsorbed (cm3/g STP)

Quantity Adsorbed (cm /g STP)

to the filled pores and essentially zeros external areas. However, ZSM-5(0)/(6) exhibited a Type IV
isotherm with the small hysteresis indicating the capillary
Adsorption
Desorption

250
200

ZSM-5(0)
150
ZSM-5(6)

100
50
0
0.0

1.0

0.2

0.4

0.6

0.8

1.0

Relative Pressure(p/p )

Relative Pressure (p/p )

Fig. 3. Adsorption-desorption isotherms of N2 at -196 oC on : (a) 0.0 and 6.0 wt% of Co/OPS-AC (b) 0.0 and 6.0 wt% of
Co/ZSM-5.

condensation in mesopores. The low slope region in the middle of isotherms indicated the first few
multilayers on external surface including meso and macropores without reaching a saturation limit
due to an indefinite multilayers formation.
The pore size distributions of both supports of OPS-AC and ZSM-5 were shown in Fig. 4. The
highest pore size distribution for OPS-AC (0)/(6) was at the pore width 12 and 8 Ao respectively. In
general, the pore size distributions of both OPS-AC(0)/(6) were comparatively in narrowed range
showing from 8 to 12 Ao. On the contrary, the pore size distributions of ZSM-5(0)/(6) showed a
broader range up to 500 Ao. In addition, the highest distribution for ZSM-5(0)/(6) was at 6 and 22
Ao respectively. The pore width of ZSM-5 was bigger than of OPS-AC due to the mesoporous type
of ZSM-5 and microporous type of OPS-AC.
1.0

Differential Pore Volume (cm /g)

ZSM-5(0)

OPS-AC(0)

Differential Pore Volume (cm /g)

OPS-AC(6)

1.0

0.8

ZSM-5(6)

0.8
0.6

0.6

0.4
0.2

0.4

0.0
0

10

20

30

40

50

0.2

0.0

0
0

10

20

30

40

200

400

Pore width (A )
Fig. 4. Pore size distribution of : (a) 0.0 and 6.0 wt% of Co/OPS-AC (b 0.0 and 6.0 wt% of Co/ZSM-5.

600

800

1000 1200 1400

o

Pore width (A )

In general, the total pore volume of ZSM-5 was slightly higher than of OPS-AC as shown in Tab.1.
However, even the total pore volume of OPS-AC was comparatively lower but the micropore
volume of OPS-AC was found higher than ZSM-5. This is in parallel with the previous explanation
in Fig. 3 that OPS-AC showed a typical Type I consisting of the mass micropores. In contrast,
ZSM-5 exhibited richer in mesopore volume which was represented by the middle portion of
isotherm showing the unreached saturation limit. The BET surface area of OPS-AC showed a
greater value than of ZSM-5 with the representative value of micropore surface area. However,
ZSM-5 exhibited an almost equal value of micropore and external surface areas. In comparison,
the pore size of ZSM-5 was almost two times bigger than of OPS-AC. However, both supports
indicated less volume and surface area due to the impregnation of cobalt catalysts.

726

Table 1. BET analysis of 0.0 and 6.0 wt% of Co/OPS-AC and 0.0 and 6.0 wt% of Co/ZSM-5
Support(catalyst wt%)
ZSM-5 (0)
ZSM-5(6)
OPS-AC(0) OPS-AC(6)
Total pore volume (cm3/g)
0.37
0.29
0.31
0.25
Micropore volume (cm3/g)
0.10
0.09
0.25
0.20
Mesopore volume (cm3/g)
0.27
0.20
0.06
0.05
BET surface area (m2/g)
435
397
731
567
Micropore surface area (m2/g)
233
220
622
484
External surface area (m2/g)
202
178
108
84
Pore size (Ao)
34.8
30.0
17.1
17.6

The SEM images of OPS-AC(0) and OPS-AC(6) are presented in Fig. 5. As shown in Fig. 5 (a),
the pores are obviously discovered on the surface of OPS activated carbon in variant sizes.
However, the pores on the surface of OPS-AC were not presented due to the impregnation and the
available pores were fully covered with cobalt particles as shown in Fig. 5 (b). Furthermore, the
cobalt particles of the catalysts were found to be scattered on the surface and showed non-uniform
distributions. Besides the availability of cobalt particles found on the surface of OPS-AC(6), the
reductions in intensity of XRD of OPS-AC as previously mentioned have further supported the
success impregnation of cobalt catalysts. Fig. 6 exhibits the SEM images of ZSM-5(0) and ZSM5(10). The surface of ZSM-5 was observed with the aggregation of zeolite particles as shown in
Fig.6 (a). After the impregnation with the cobalt precursor, the cobalt catalyst particles were hardly
differentiated from the zeolite particles. However, the reduction in intensity of XRD peaks of ZSM-5
suggested the success impregnation of cobalt catalysts.

Mag = 10.00 K X EHT = 10.00

1 m
Mag = 10.00 K X EHT = 10.00
1 m
kV

kV

m
Fig. 5. SEM images
of
OPS-AC
at
10,000x
magnification:
(a)
0.0
wt%
of
Co/OPS-AC
and
(b)
6.0 wt% of Co/OPS-AC.
m

Mag = 10.00 K X EHT = 10.00

1 m
Mag = 10.00 K X EHT = 10.00
1 m
kV

kV

m
m
Fig. 6. SEM images of Zeolite ZSM-5 at 10,000x magnification: (a) 0.0 wt% of Co/ZSM-5 and (b) 6.0 wt% of Co/ZSM-5.

727

Fig. 7. FESEM images of 0.0 wt% of Co/OPS-AC at (a) 1500 and (b) 7000 magnification.

The FESEM image showed the available pores on the surface of OPS-AC as shown in Fig.7. The
pores were detected in different sizes and shapes but micropores were found in major as
supported by the micropore surface area (Tab. 1). The elements of OPS-AC were analyzed by
FESEM-EDX and tabulated as in Tab.2. The major element was carbon at almost 94 wt% and the
remaining content was oxygen. Hence, the content in OPS-AC was greatly richer in carbon with
the minimal impurities which represented a good selection of activated carbon.
Table 2. EDX elements analyzed, magnification 607 x, accelerating voltage 10 kV, processing time 5 for 0.0 wt% of Co/OPSAC.
Element (wt%)

Spectrum 1

93.46

6.54

Spectrum 2

93.88

6.12

Spectrum 3

93.70

6.30

Mean

93.68

6.32

Std. deviation

0.21

0.21

As shown in Fig.8, both of 14wt% Co/OPS-AC and 14wt% Co/ZSM-5 exhibited the reduction in
conversion of CO2 and CH4 when the temperature increased from 923 to 1023K. The reduction on
the conversion of CO2 and CH4 may be due to the formation of carboneous substance on the
catalyst known as coking activity. The formation of carbonaceous material on the catalyst is
favorable at higher temperature resulting in less catalytic activity of the catalysts. Comparing the
conversion of both catalysts, cobalt supported OPS-AC catalyst demonstrated a higher conversion
of CO2 and CH4 for both operating temperature 923 and 1023K. However, cobalt based ZSM-5
zeolite catalyst showed almost an equal conversion of CO2 and CH4. Two identified products of
syngas were derived from dry reforming of CH4 namely H2 and CO. Although the conversion of
CO2 and CH4 were found to be reduced at higher temperature for both catalysts, syngas products
(H2 and CO) were in favor in their yields. This may be due to the endothermicity nature of the
reaction that prefers to higher temperature. The yield of H2 for cobalt supported OPS activated
carbon was higher than of ZSM-5 zeolite. On the contrary, the conversions of 6wt% Co/OPS-AC
and 6wt% Co/ZSM-5 were lower due to the lower ratio of metal in the catalysts. Moreover, the
yields of both supports 6wt% Co/OPS-AC and 6wt% Co/ZSM-5 were difficult to obtain. The yield
of CO was highly detected for 6wt% Co/OPS-AC after increasing the temperature from 923 to
1023K due to carbon element in OPS-AC. No yield was found for 6wt% Co/ZSM-5 even after the
increase of temperature from 923 to 1023K. Based on the previous catalyst characterizations,
Co/OPS-AC was higher in surface area than of Co/ZSM-5. Therefore, higher surface area in OPSAC has immensely favored the reaction of carbon dioxide reforming of methane. In addition, the
higher surface area of OPS-AC has also contained the larger volume of micropores. However, the
total pore volume of Co/OPS-AC and Co/ZSM-5 was almost similar and has a lesser affect on the
conversion and yield.

728

14wt% Co/OPS-AC

6wt% Co/OPS-AC

14wt% Co/ZSM-5

6wt% Co/ZSM-5

30

Conversion (%)

CH4
CO2
20

10

0
H2
CO

Yield (%)

60

40

20

0
923

1023

923

1023

923

1023

923

Reaction Temperature (K)

Fig. 8. Catalyst activity testing.

CONCLUSIONS
The cobalt based OPS-AC support has showed a promised in the catalytic conversion of dry
reforming of methane
than by using of ZSM-5 support. Nevertheless, the lower yield of H2 for ZSM-5 zeolite was
contained with the minimal amount of CO which possibly be suppressed for higher purity in the
production of H2.
ACKNOWLEDGEMENT
The authors are thankful to Zainab Salleh from the faculty of Chemical Engineering, Universiti
Teknologi Malaysia for the catalyst analyses. The authors gratefully acknowledge the given
schorlarship and financial support from the Malaysia Ministry of Higher Education under
Fundamental Research Grant Scheme (Vot. No. 4F160).
REFERENCES
Abbas, H. F., and Daud, W. M. A. W. 2009. Deactivation of palm shell-based activated carbon
catalyst used for hydrogen production by thermocatalytic decomposition of methane. International
Journal of Hydrogen Energy, 34(15), 6231-6241.
Abbas, H. F., and Daud, W. M. A. W. 2010. An experimental investigation into the CO2 gasification
of deactivated activated-carbon catalyst used for methane decomposition to produce hydrogen.
International Journal of Hydrogen Energy, 35(1), 141-150.
Baroutian, S., Aroua, M. K., Raman, A. A. A., et al. 2011. A packed bed membrane reactor for
production of biodiesel using activated carbon supported catalyst. Bioresource Technology,
102(2), 1095-1102.
Corthals, S., Witvrouwen, T., Jacobs, P., et al. 2011. Development of dry reforming catalysts at
elevated pressure: D-optimal vs. full factorial design. Catalysis Today, 159(1), 12-24.
Hasnain Isa, M., Siew Lang, L., Asaari, F. A. H., et al. 2007. Low cost removal of disperse dyes
from aqueous solution using palm ash. Dyes and Pigments, 74(2), 446-453.
Ho, Y.-S., and Ofomaja, A. E. 2006. Kinetic studies of copper ion adsorption on palm kernel fibre.
Journal of Hazardous Materials, 137(3), 1796-1802.

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1023

Izirwan, I., Mohd A and Saidina Amin N.A., 2013. Characterization of Oil Palm Shell Activated
Carbon and ZSM-5 Supported Cobalt Catalysts, Research Journal of Chemistry and Environment,.
17(10): p.64-68.
Nagaoka, K., Takanabe, K., and Aika, K. (2004). Co/TiO2 catalyst for high pressure dry reforming
of methane and its modification by other metals. In B. Xinhe & X. Yide (Eds.), Studies in Surface
Science and Catalysis (Vol. Volume 147, pp. 187-192): Elsevier.
Omata, K., Nukui, N., Hottai, T., et al. 2004. Cobaltmagnesia catalyst by oxalate co-precipitation
method for dry reforming of methane under pressure. Catalysis Communications, 5(12), 771-775.
Sajab, M. S., Chia, C. H., Zakaria, S., et al. 2013. Cationic and anionic modifications of oil palm
empty fruit bunch fibers for the removal of dyes from aqueous solutions. Bioresource Technology,
128(0), 571-577.
Sumathi, S., Bhatia, S., Lee, K. T., et al. 2010. Cerium impregnated palm shell activated carbon
(Ce/PSAC) sorbent for simultaneous removal of SO2 and NOProcess study. Chemical
Engineering Journal, 162(1), 51-57.
Tan, I. A. W., Hameed, B. H., and Ahmad, A. L. 2007. Equilibrium and kinetic studies on basic dye
adsorption by oil palm fibre activated carbon. Chemical Engineering Journal, 127(13), 111-119.

730

COMPARISON OF CEIBA PENTANDRA, NIGELLA SATIVA AND THEIR BLENDS

AS PROSPECTIVE BIODIESEL FUELS FOR IC ENGINES
a

a1*

a2*

T.M. Yunus khan , A.E. Atabani , Irfan Anjum Badruddin , Ahmed Badrudin
Department of Mechanical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala
Lumpur, Malaysia
1. A.E. Atabani. E-mail address: a_atabani2@msn.com. Tel.: +60 122314659.
2. Irfan Anjum Badruddin. E-mail address: irfan_magami@rediffmail.com. Tel.: +60 0379674463;
Fax: +60 0379675317.

ABSTRACT
Globally, there are more than 350 oil-bearing crops identified as potential sources for
biodiesel production. The wide range of available feedstocks for biodiesel production
represents one of the most significant factors of producing biodiesel. In this research paper
work is carried out on the fuel properties of biodiesel prepared from Ceiba pentandra,
Nigella sativa and their mixture. Nigella sativa is believed to be investigated for the first
time as a biodiesel fuel while Ceiba pentandra has been reported recently in some studies.
Owing to the higher acid values, acid-esterification and alkali-transesterification processes
have been applied for biodiesel production. The fuel properties of Ceiba pentandra methyl
esters (CPME), Nigella sativa methyl esters (NSME) and their feedstock mixture
(NSME/CPME) were determined and evaluated.
It has been found that the produced biodiesel matches the properties set by ASTM 6751
biodiesel standards. The fuel properties of Ceiba pentandra biodiesel possess better
calorific value, viscosity and flash point than Nigella sativa. However, Nigella sativa
biodiesel possesses more excellent cold flow properties than Ceiba pentandra.
Key words: Biodiesel feedstocks, Ceiba pentandra, Nigella sativa, Physico-chemical
properties. Blending.

NOMENCLATURE
CCPO
CCPO+CNSO
CNSO
CPME
NSME
NSME+CPME

Crude Ceiba pentandra oil

Mixture of crude oils of Ceiba pentandra and Nigella sativa
Crude Nigella sativa oil
Ceiba pentandra methyl ester
Nigella sativa methyl ester
Methyl esters from mixture of crude oils of Ceiba pentandra and
Nigella sativa

1.0 INTRODUCTION
The fast depletion and rising prices of crude petroleum products beside their harmful emissions
are the main concerns for many countries. In fact many researchers have been giving the attention

1
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for the aforesaid problems. However, the consumption of these products is increasing rapidly
leading to serious issues such as environmental pollution and global warming. According to Shahid
and Jamal (Shahid and Jamal, 2011) the whole world would require 50% more energy than todays
requirement. Globally, transportation sector is the second largest oil consuming sector after
industrial sector (Perez-Lombard et al., 2008) and one cannot imagine the world without internal
combustion engines. The transportation sector is the fundamental requirement for any society for
its overall development and improvements (He et al., 2005). Therefor it is the vital to look forward
for alternative oil resources for the future needs. Biodiesel is emerging as an alternative fuel
because of its renewability and environmental friendly nature (Murugesan et al., 2009). Apart from
these advantages biodiesel could be used in the existing compression ignition internal combustion
engines without any further modifications (Gerpen 2005, Canakci 2007).
Biodiesel (methyl esters of fatty acids FAME) which is a potential diesel alternative can be
produced by the transesterification reaction of triglycerides of vegetable oils or animal fats with
short chain alcohols, mainly methanol (Boz et al., 2013). Biodiesel has many advantages
compared to diesel such as non-poisonous, non-flammable, portable, easily available,
biodegradable, environment friendly and free from sulfur and aromatic contents (Balat, 2011). The
feedstocks for biodiesel can be broadly divided into three categories i.e. vegetable oils (edible and
non-edible), animal fats and waste cooking oils (Karmakar eta al., 2010). However due to the
problems of the food and fuel crisis (Chen and Khanna 2013, Atabani et al., 2013) starvation faced
by many developing countries, land availability problem (Atabani et al., 2013) attention is focused
mainly towards biodiesel from non-edible feedstocks. Moreover, production of biodiesel from nonedible oils reduces the cost of biodiesel significantly (Atabani et al., 2013). Some of the important
non-edible feedstocks are; Jatropha curcas, Mahua (Madhuca indica), Karanja (Pongamia pinnata),
Neem (Azadirachta indica), Moringa (Moringa oleifera), castor, soapnut etc. (Atabani et al., 2012).
(Ong et al., 2013) determined the fuel properties of Jatropha curcas methyl ester (JCME), Sterculia
foetida methyl ester (SFME) and Ceiba pentandra methyl ester (CPME). They found all the
properties within the standards. The dual step transesterification was proved to be effective to
obtain the quality biodiesel from karanja oil (Malaya, 2008). Similarly neem (Azadirachta indica) oil,
Moringa oleifera have been proved the potential resources for the biodiesel production (Md. Hasan
Ali et al., 2013).
In this paper an attempt has been made to investigate and analyze Physico-chemical properties
and suitability of Ceiba pentandra and Nigella sativa as biodiesel feedstocks. Nigella sativa as

2
732

biodiesel feedstock is investigated for the first time. While Ceiba pentandra has been reported
recently in some studies. Moreover, Ceiba pentandra biodiesel and its blends with diesel, Nigella
sativa biodiesel and its blends with diesel and the feedstock mixture of both the oils and their
blends with diesel have been given full consideration in the current study and investigated and
compared for the properties.

2.0

MATERIALS AND METHODS

2.1 Materials and chemicals

The crude oils of Ceiba pentandra and Nigella sativa are obtained from Indonesia and Bangladesh
respectively. Chemicals required for biodiesel production such as methanol, sulfuric acid,
hydrochloric acid, potassium hydroxide and sodium sulphate were purchased from the local
market of Kuala Lumpur, Malaysia.

2.2 Biodiesel production method

The process of producing biodiesel from any feedstock is known as transesterification. The
transesterification is regarded as best method compared to others due to its simplicity and lower
cost (Atabani et al., 2012). However, the direct employment of the transesterification reaction
depends on the acid value of the crude oil. In this study both the crude oils of Ceiba pentandra;
Nigella sativa and their blend have a high acid value, determined by titration of crude oils with the
standardized base solution. Hence, two steps of esterification and transesterification catalyzed
reactions were employed. The biodiesel from the above two crude oils, were produced in the
laboratory using a 1L batch reactor.
In esterification process the crude oils were mixed with methanol in the ratio of 1:1 by volume. In
this study 1% of sulphuric acid (v/v oil) was used with Ceiba pentandra, while 1% of hydrochloric
acid (v/v oil) was used with Nigella sativa and also the mixture of Ceiba pentandra and Nigella
sativa. The crude oil, methanol and the respective catalysts were reacted in the reactor at 60 C for
3 h under the stirrer speed of 600 rpm approximately.
After 3 h, the reaction was stopped. The mixture obtained had two layers, the upper layer of
methanol and sulphuric acid, the lower layer that of esterified oil. The esterified oil was separated
from the methanol and other impurities with the help of separating funnel. The esterified oil was
further put into the rotary evaporator to remove the traces of moisture content and excess alcohol.

3
733

The rotary evaporator filled with distilled water was maintained at a temperature of 50-60 C. The
pure esterified oil was then collected and made ready for the transesterification process.
In the alkaline transesterification process the esterified oil was mixed with the mixture of methanol
(25% v/v oil) and potassium hydroxide (1% w/w oil). The reaction was maintained at 60 C
temperature and stirring speed of 600 rpm for 2 h.
After 2 h of the reaction the reaction was stopped and all products were deposited in the
separation funnel overnight. The upper layer of the biodiesel was then separated from the lower
layer of methanol and other impurities. This was followed by the post treatment processes. In
which the transesterified oil was washed several times by warm distilled water (55-60 C). The
washed biodiesel was then put into the rotary evaporator and the same procedure was applied to
evaporate the moisture and excess methanol from the biodiesel, as did for the esterified oil. Finally
the biodiesel was further dried using sodium sulphate and filtered with a filter paper to get the final
high quality biodiesel which is free from impurities.

2.3 Analysis of properties

In this study the Physico-chemical properties of crude oils of Ceiba pentandra, Nigella sativa,
mixture of the two crude oils and their respective methyl esters and their blends were studied in
accordance with the ASTM 6751 standards.

2.4 Biodiesel-diesel blending

The fuels to be tested are blended with diesel with different ratios (0-100% v/v) using a
homogenizer device at a speed of 2000 rpm. Homogenizer was fixed on a clamp on a vertical
stand, which allows changing of the homogenizers height. The two fuels i.e. biodiesel and diesel
were mixed in proper ratios by turning on the plug of the homogenizer. In this study, 10%, 20%,
40%, 60% and 80% by volume biodiesel was blended with respective quantity of diesel. Hence the
10% biodiesel and 90% diesel by volume was assigned as B10. Similarly others were labeled as
B20, B40, B60 and B80 respectively.

3.0 RESULTS AND DISCUSSION

3.1 Characterization of crude oils and their methyl esters
The different properties of the crude oils along with their respective methyl esters have been
tabulated in Table 1. The main findings indicate that Nigella sativa has a comparatively lower

4
734

calorific value (39,251 kJ/kg) than Ceiba pentandra (39,498 kJ/kg) and the feedstock mixture
(39,372 kJ/kg). However, a marginal difference in calorific values in terms of their respective
methyl esters was observed. Kinematic viscosity of Ceiba pentandra methyl ester (4.4180 mm2/s)
is better compared to other methyl esters though the crude oil has highest viscosity than other two.
The cold flow properties of Nigella sativa methyl ester seem to be better than other two methyl
esters. After observing the different properties of the methyl ester of Ceiba pentandra and Nigella
sativa, one has got some advantages and some limitations one over the other. However, the
methyl ester from the feedstock mixture possesses excellent properties including the calorific value,
kinematic viscosity, cold flow properties and oxidation stability etc.
Table 1 The properties of crude oils and their respective methyl esters (biodiesel)
Property
CCPO CPME
CNSO
NSME
CCPO+CNSO
NSME+CPME
Calorific value (kJ/kg)
39,498
40,064
39,251
39,967
39,372
39,945
Kinematic viscosity (mm2/s) at 40 C 34.592
4.4180
32.3680 4.5026
33.375
4.4421
Flash point (C)
282.5
202.5
150.5
172.5
184.5
186.5
Density (kg/m3) at 15 C
0.9216
0.8844
0.9247
0.8861
0.9230
0.8848
Acid value (mg KOH/g oil)
22.73
N/D
40.706
N/D
25.690
N/D
Cloud point (C)
-7
3
7
-1
-4
0
Pour point (C)
-3
5
-7
-1
-2
-1
CFPP (C)
44
4
29
-4
32
-1
N/D= Not determined
3.2 Fatty acid composition of biodiesel
The free fatty acid composition of the biodiesel is shown in Table 2. It can be seen that the main
constituents are palmitic acid, oleic acid and linoleic acid. Biodiesel from Nigella sativa possesses
the highest contents of linoleic and oleic acids (43.1% and 25.8%) followed by the mixture of
feedstock (41.0% and 23.2%) and Ceiba pentandra (38.1% and 20.1%), while Ceiba pentandra
biodiesel possesses the highest contents of palmitic acid (20.8%) followed by the mixture of
feedstock (15.3%) and Nigella sativa (10.2%).
Table 2 The fatty acid composition of different biodiesel
Fatty acid Name
Structure
NSME
CPME
CPME+NSME
Caprylic
C8:0
< 0.1
< 0.1
< 0.1
Capric
C10:0
< 0.1
< 0.1
< 0.1
Lauric
C12:0
< 0.1
< 0.1
< 0.1
Myristic
C14:0
0.1
0.1
0.1
Palmitic
C16:0
10.2
20.8
15.3
Palmitoleic
C16:1
0.2
0.3
0.3
Margaric
C17:0
0.1
0.1
0.1
Stearic
C18:0
3.7
2.7
3.1
Oleic
C18:1
25.8
20.1
23.2
Linoleic
C18:2
43.1
41.6
42.2
Linolenic
C18:3
1.4
1.7
1.6
Arachidic
C20:0
2.1
1.6
1.4
Gondoic
C20:1
1.4
0.1
0.8
Behenic
C22:0
0.6
0.4
0.5
Erucic
C22:1
9.0
0.1
4.5
Lignoceric
C24:0
0.3
0.1
0.3

5
735

3.3 Physical and chemical properties of biodiesel with their respective blends
Biodiesel is seen as the most acceptable alternative fuel for diesel engines with little or no
modifications of the engines apart from their technical and environmental benefits. In addition to
this, they are completely soluble in petroleum diesel. However, differences in the chemical
structure of biodiesel and diesel fuel makes the differences in their basic properties such as
kinematic viscosity, calorific value, flash point, cloud and pour point etc. which affect the engine
performance and emissions (Benjumea et al., 2008). The fuel properties of biodiesel, either
physical or chemical are strongly influenced by the properties of their respective fatty ester in
biodiesel ( Knothe, 2005). Hence it is important to know the basic properties of the biodiesel before
using it into engines as a fuel. Tables (3-5) present the findings of physical and chemical
properties of CPME, NSME and CPE/NSME respectively.

Table 3 The properties of Ceiba pentandra methyl ester and its blends
Property
B0
B10
B20
B40
Calorific value (kJ/kg)
45,369
44,900
44,155
43,245
Kinematic viscosity (mm2/s) at 40 C
3.6056
3.6572
3.7089
3.8594
Flash point (C)
81.5
87.5
91.5
89.5
Density (kg/m3) at 15 C
0.8518
0.8553
0.8579
0.8645
Cloud point (C)
7
7
5
7
Pour point (C)
2
2
3
3
CFPP (C)
0
5
4
3
Table 4 The properties of Nigella sativa methyl ester and its blends
Property
B0
B10
B20
B40
Calorific value (kJ/kg)
45,369
44,887
44,131
43,197
Kinematic viscosity (mm2/s) at 40 C 3.6056
3.645
3.7016
3.8897
Flash point (C)
81.5
85.5
88.5
95.5
Density (kg/m3) at 15 C
0.8518
0.8554
0.8592
0.8651
Cloud point (C)
7
7
6
6
Pour point (C)
2
3
3
-2
CFPP (C)
0
7
7
6

B60
42,007
4.0245
108.5
0.8712
4
0
3

B60
41,814
4.0603
106.5
0.8725
5
0
2

B80
40,952
4.2251
128.5
0.8780
2
3
0

B80
41,027
4.2418
122.5
0.8804
1
0
-3

Table 5 The properties of methyl ester from the feedstock mixture (NSME/CPME) and its blends
Property
B0
B10
B20
B40
B60
B80
Calorific value (kJ/kg)
45,369
44,921
44,283
43,046
42,041
40,923
Kinematic viscosity (mm2/s) at 40 C 3.6056
3.7038
3.753
3.8615
4.0256
4.2441
Flash point (C)
81.5
87.5
90.5
97.5
106.5
124.5
Cloud point (C)
7
7
7
5
4
1
Pour point (C)
2
2
2
5
2
-1
CFPP (C)
0
5
5
3
2
-2

3.3.1

Calorific value

The calorific value is generally termed as the energy content or the energy per unit mass of the
fuel. The calorific value of biodiesel is lower compared to diesel due to the presence of high energy

6
736

contents (Atabani et al., 2013). Fig.1 shows the variation of the calorific value with the variation in
the blends. The observation on the biodiesel shows that there is a marginal difference in the
calorific value of Ceiba pentandra and Nigella sativa.
Calorific value kJ/kg v/s blends
46,000
45,000
44,000
43,000
CPME

42,000

NSME

41,000

CPME+NSME

40,000
39,000
38,000
37,000
B10

B20

B40

B60

B80

B100

Fig.1 Calorific value of different biodiesel with different blends

3.3.2

Kinematic viscosity

Kinematic viscosity is an important property of any fuel because high viscosity could cause
excessive fuel injection pressures during engine warm-up (Tat et al., 1999). Though the viscosity
of biodiesel is higher than the petro diesel

(Knothe et al., 2007) nonetheless still it can be

observed that all the methyl esters and their blends have acceptable viscosities according to the
limit specified by ASTM D6751of (1.9-6 mm2/s). From Fig. 2, it is evident that the viscosity
increases with the quantity of biodiesel in the blend.

7
737

Kinematic viscosity mm2/s v/s blends

5
4.5
4
3.5
3
CPME
2.5

NSME

CPME+NSME

1.5
1
0.5
0
B10

B20

B40

B60

B80

B100

Fig.2 Kinematic viscosity of different biodiesel with different blends

3.3.3

Flash point

The flash point of any fuel is the lowest temperature at which it possesses enough vapors to ignite
in the presence of a source of ignition. It is the important parameter as far storage and handling
issues are concerned ( Elliott, 2013). The flash point of Ceiba pentandra (202.5 C) is the highest
among all blends than the Nigella sativa (172.5 C) and the feed stock mixture methyl ester
(186.5 C). It is interesting to note that all the biodiesel are within the limit set by ASTM D6751 of
minimum of 130 C. Fig. 3 shows the flash point of different biodiesel with different blends.

Flash point C v/s blends

250

200

150

CPME
NSME

100

CPME+NSME

50

0
B10

B20

B40

B60

B80

B100

Fig.3 Flash point of different biodiesel with different blends

Conclusion

8
738

The fuel properties of biodiesel and their blends especially B10, B20 and B40 are comparable with
that of diesel. The fuel properties of the Ceiba pentandra biodiesel are superior to the Nigella
sativa biodiesel as far as calorific value, viscosity and flash point are concerned. However, Nigella
sativa biodiesel possesses excellent cold flow properties such as CFPP, cloud point and pour point.
It is interesting to conclude that both the Ciba pentandra and Nigella sativa biodiesel possess
some advantages and disadvantages one over the other. However, the biodiesel prepared from
their feedstock mixture gives the average and better fuel properties than their individual biodiesel.
All the fuel properties fit well with the ASTM D6751 standards. Further attention needs to be given
on research and development on internal combustion engine before the wider utilization of these
biodiesel fuels in diesel engines without modifications on them.
References
Atabani, A.E., T. M. I. Mahlia, Irfan Anjum. Badruddin, H. H. Masjuki, W. T. Chong, Lee and Keat
Teong, 2013, Investigation of physical and chemical properties of potential edible and
non-edible feedstocks for biodiesel production, a comparative analysis. Renewable and
Sustainable Energy Reviews 21(0):749-755.
Atabani, A. E., A.S. Silitonga, H.C. Ong, T.M.I. Mahlia, H.H. Masjuki, Irfan Anjum. Badruddin, and
H. Fayaz, 2013, Non-edible vegetable oils: A critical evaluation of oil extraction, fatty acid
compositions, biodiesel production, characteristics, engine performance and emissions
production. Renewable and Sustainable Energy Reviews 18:211-245.
Atabani, A.E., T. M. I. Mahlia, H. H. Masjuki, Irfan Anjum. Badruddin, Yussof, Hafizuddin, Wan, W.
T. Chong, and K.T. Lee, 2013, A comparative evaluation of physical and chemical
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Boz, N., N. Degirmenbasi, and D.M. Kalyon, 2013,Transesterification of canola oil to biodiesel
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11
741

ENERGY AND EXERGY ANALYSIS OF A LARGE SCALE BIOMASS

GASIFICATION PROCESS
*1

Sharmina Begum , M. G. Rasul and Delwar Akbar

1,2

School of Engineering and Technology, School of Business and Law,

Central Queensland University, Australia.
1*

Email: s.begum@cqu.edu.au; m.rasul@cqu.edu.au; d.akbar@cqu.edu.au

*

Corresponding authors contact email

ABSTRACT
The economic value of energy processing depends on both quality and quantity of energy. In
case of all thermodynamic energy conversion processes (such as gasification and pyrolysis),
the conservation of energy (first law of thermodynamics) and the quality of energy (second
law of thermodynamics) are significant. This paper presents energy and exergy analysis of a
large scale biomass gasification process based on chemical equilibrium considerations. The
gasification model was developed on the basis of Gibbs free energy minimisation approach,
controlled by mass and energy balances for the system using Aspen Plus. Wood was used as
solid waste biomass for this study. Energy and exergy (available energy) losses were
analysed by using the composition of dry biomass. The analysis was carried out in an
adiabatic system at atmospheric pressure, with input of biomass and air at ambient conditions
and steam at atmospheric pressure and temperature of 25C. The study found that the
exergy efficiency of wood waste is 23% and corresponding energy efficiency is 78%.

Keywords: Energy, Exergy, Gasification, Cold-gas efficiency.

INTRODUCTION
According to Albert Einstein energy cannot be created or destroyed; it can only be changed
from one form to another form, it is therefore fair to say that energy conversion processes do
not have energy losses, except for the losses from the process system to the environment.
The second law of thermodynamics deals with the quality of energy production, which is also
known as exergy. Both energy and exergy analyses of biomass gasification are essential for
efficient utilization of energy resources. The goal of all thermo chemical conversion
technologies such as, gasification, pyrolysis and incineration is to maximise the production of
products. The development of efficient thermo chemical technologies for biomass gasification
is governed by the tools deployed to achieve the maximum energy available from the process.
For a given set of operating conditions, syngas production from biomass gasification can be
improved through optimization of operating parameters; and this can be done by a
combination of energy and exergy analyses.
A number of researches have been performed on energy and exergy analyses. Most recently,
Heyne at el [1] performed a study on exergy-based comparison of indirect and direct biomass
gasification technologies within a framework of bio-SNG production. In their study, an exergybased comparison of two gasification technologies was performed using a simplified
gasification reactor model. The resulting cold-gas efficiencies of the processes were in the
range of 66% 84% on a lower heating value basis. Exergy efficiencies for the ideal systems
are in the range of 70% to 79% for the systems including losses. Another study was
performed by Wongsiriamnuay et al [2] on effect of operating conditions on catalytic
gasification of bamboo in a fluidized bed gasifier. They found the carbon conversion efficiency
of 98.5% at gasifier temperature of 400C with air/steam gasification. Eftekhari et al (2012) [3]
studied on exergy analysis of underground coal gasification with simultaneous storage of
carbon dioxide. They found underground gasification of deep coal could optimally be

742

extracted 52.68% of the coal chemical exergy but zero-emission extraction gave a negative
recovery indicating that it was not practical with current state of the art CO2 capture and
sequestration technology (CCS). Kasembe at el (2012) [4] performed a research on exergy
analysis of high temperature biomass gasification at a temperature range of 527C-1127C.
In their study, the maximum efficiency obtained based on chemical energy and physical
exergy analysis was lower than the efficiency based on chemical exergy (84.64% vs. 76.94%)
because of sensible or physical heat is less beneficial for efficiency based total exergy.
Karamarkovic at el (2010) [5] also performed similar study on energy and exergy analysis of
biomass gasification at different temperature (range 627C1100C). They identified that the
gasification process at a given gasification temperature can be improved by the use of dry
biomass and by the carbon-boundary temperature approaching the required temperature with
the change of gasification pressure or with the addition of heat in the process. Pellegrini et al
(2007) [6] conducted their study on exergy analysis of sugarcane bagasse gasification via
presenting a simplified model for the gasification process based on chemical equilibrium
considerations. Based on the parametric study, they performed an exergy analysis in order to
evaluate irreversibility associated to the process, and the influence of temperature, moisture,
charcoal production, and thermal losses on them. Prins and Ptasinski (2005) [7] conducted a
research on energy and exergy analyses of the oxidation and gasification of carbon. The
outcome of their research was, at optimum gasification temperatures in the ranges of 827C
927C (for atmospheric pressure) and 9271000C (for 10 bar pressure), up to 75% of the
chemical exergy contained in solid carbon can be preserved in the chemical exergy of carbon
monoxide and hydrogen.
This paper presents energy and exergy analysis of a large scale gasification plant using solid
waste biomass. A numerical model energy and exergy is developed and validated with
experimental and published data [8]. Wood was used as a solid waste biomass. Effects of
gasifier operating conditions (such as, gasifier temperature, air-fuel ratio and steam-fuel ratio)
on gasifier performance via energetic and exegetic analysis are performed in order to provide
information regarding the operating conditions that most influence the process.

ENERGY AND EXERGY ANALYSIS: THEORITICAL CONSIDERATIONS

The fluidised bed gasification process considered in this study is schematically shown in
Figure 1. Solid waste enters the gasifier at ambient temperature and pressure at 25C and 1
atmosphere respectively. The gaseous products (syngas and unconverted carbon) leave the
gasifier at the reactor temperature. Gasification involves partial oxidation of the feedstock, so
chemical energy of solid waste is converted into chemical and thermal energy of synthesis
gas.

Solid waste

Air
Steam

Unconverted
Carbon

Syngas

Figure 1: Schematic diagram of the gasifier

2
743

A number of equilibrium reactions are relevant for carbon conversion into gaseous
components [9,10]:

(R1)

(R2)

(R3)

(R4)

(R5)
The exothermic methane formation (R1) is coupled with the endothermic water-gas (R2) and
Boudouard (R3) reactions. The water-gas shift reaction (R4) is coupled with the
homogeneous methane formation reaction (R5).

Energy Analysis
The energy distribution of the biomass conversion process can be obtained from the energy
balance, equations given below:

(1)

Where
and
are the enthalpy flow rate of all entering and leaving material
streams, respectively. In order to moderate the system, the energy balance was imposed to
the process:

(2)

(3)

(4)

(5)
where Q and f is the heat transfer and coefficient of thermal losses respectively.
The performance of a gasifier can be expressed in terms of its cold gas and hot gas efficiency.
Generally, the hot gas efficiency is used for thermal applications where the gas is not cooled
before combustion and the sensible heat of the gas is useful. On the other hand, the cold gas
efficiency is useful for the gas used for running an internal combustion engine in which the
gas is cooled down to the ambient temperature. The cold gas efficiency ( ), is defined as [10]:

(6)
3
744

where, Vg is the Gas generation rate (m /sec), qg is the heating value of the gas (kJ/m ), Mb is
3
the fuel consumption rate (kg/sec) and Cb is the heating value of fuel (kJ/m ).
Exergy Analysis
Exergy analysis, which is considered as a basic tool for evaluating processes and systems, is
a combination of the first and second laws of thermodynamics and accounts for irreversibility
(I). Exergy can be defined as the potential to do work [11]. More particularly, exergy is the
maximum amount of work that can be achieved as a state of matter comes into equilibrium
with its environment. Exergy is generally divided into two parts, the thermo mechanical
contribution or physical exergy and the chemical contribution or chemical exergy
Physical exergy is equal to the maximum amount of work obtained when the stream of
substance is brought from its initial state to the environment state defined by Po and To by
physical processes involving only thermal interaction with the environment [10]. The physical
exergy of a pure compound of a mixture can be calculated using enthalpy and entropy data
for a given system:

(7)
where h and s are enthalpy and entropy of a system at given temperature and pressure, and
h0 and s0 are the values of these functions at the environmental temperature and pressure.
On the other hand, chemical exergy is equal to the maximum amount of work obtainable
when the substance under consideration is bought from the environmental state to the dead
state by process involving heat transfer and exchange of substances only with the
environment [10].
The exergy balance of the biomass conversion process can be represented in equation (8);

(8)

Where
and
are the exergy flow of all entering and leaving material streams,
respectively. The difference between all entering exergy streams and that of leaving streams
is called irreversibility (I). The difference between exergy and energy balance is that exergy is
not conserved but subjected to dissipation. It means that the exergy leaving any process step
will always be less than the exergy in.
Szargut et al. [12, 13] introduced a concept and method of standard chemical exergy analysis
that could be compiled and used for multiple exergy analyses. A number of researchers used
the method of Szargut [12, 13] to perform the exergy analysis of biomass gasification [4, 9, 14,
15, 16]. In this study, exergy analysis was performed for a large scale biomass gasification
process using the similar method of Szargut et al [12, 13]. Chemical exergy of the biomass
(
) can be calculated from the correlations of fuels using the lower heating value
(LHV). As for the biomass fuel, thermodynamic properties are not available, therefore,
efficiency was determined using the statistical correlation ( ) of Szargut and Styrylska [13], as
given below:

(9)
where LHVbiomass is the lower heating value, i.e. net enthalpy of combustion of the biomass.

4
745

valid for
(10)
Where zO2, zC, zH2 and zN are weight fraction of oxygen, carbon, hydrogen and nitrogen
respectively in the biomass.
LHV was calculated using the equation from Heyne et al. [1]
(

(11)
The chemical exergy of a product gas (syngas) of multiple components can be computed by
summation of their partial chemical exergies. The chemical exergy (
) of the product gas
was computed by [10, 12]:

(12)

Where R0 is the universal gas constant (8.314 kJ/kmol K), T0 is the standard temperature
(25C), x and
are the mole fraction and chemical exergy of individual gas component
respectively. The standard exergy values (
) and higher heating value (HHV) of syngas
component (H2, CO, CO2, CH4 and N2) are obtained from Kotas [10] and Basu [16]
respectively, shown in Table 1 and Table 2.

Table 1: Standard Exergy values of syngas component [10]

Component
CO
CO2
CH4

Exergy (kJ/mol)
275.1
19.87
831.65

Component
H2
N2

Exergy (kJ/mol)
236.1
0.72

Table 2: Higher heating value of gas [16]

Gas
CO
H2
CH4

HHV(MJ/kg mol)
282.99
285.84
890.36

Efficiency can be defined as the ratio of desired output over input. If only gas is regarded as a
desired product, the efficiency could be defined as the sum of exergy of desired products
divided by the total process inputs. The exergy of air is considered zero because it is a
reference component at reference conditions (1 atmosphere and 25C). Exergy efficiency
( ) can be expressed by;

(13)

SIMULATION MODEL DEVELOPMENT

A simulation model was developed using Advanced System for Process ENgineering (Aspen)
Plus, which is a proven and acceptable process modelling software used for biomass
5
746

gasification. Aspen Plus is a powerful process modelling tool that offers to include customise
user models to embed with built in Aspen reactor blocks. The fluidised bed gasification model
Table 3: Proximate and ultimate analyses of biomass
Moisture content (MC) (%)
Proximate analysis (mass %) (Dry
basis)
Ultimate Analysis (mass %)

25
Volatile matter (VM)

82.6

Fixed carbon (FC)

16.3

Ash

1.1

Carbon (C)

49.8

is comprised with a number of Aspen reactor blocks. In order to show the overall gasification
process, different phases were considered in the simulation and these were drying, pyrolysis
(decomposition), volatile reactions, char gasification and gas-solid separation. The main
processes were simulated by three reactors in Aspen Plus: RYield, RGibbs and RCSTR.
Additionally, a MIXER and a number of SEPERATOR blocks were incorporated in the
simulation model to complete the entire process. The whole gasification consists of four
processes, namely drying, decomposition, volatile reaction and char gasification and
combustion. A schematic diagram of the gasification process and Aspen Plus simulation flow
sheet of biomass gasification are shown in Figures 2 and 3 respectively.
Feed (biomass), dry-feed and ash are specified as a non-conventional component in Aspen
Plus and defined in the simulation model by using the ultimate and proximate analysis. The
proximate and ultimate analyses of biomass (wood) used in this study are shown in Table 3.
An Aspen Plus block, RYield (block ID: DRYER in Figure 3) was used to simulate the drying
process of biomass. Another RYield (block ID: DCOMP in Figure 3), was used to decompose
the feed in the simulation. RYield was used when reaction stoichiometry and reaction kinetics
were unknown but the component yield distribution was known. In this step, biomass was
converted into its constituent components H2, O2, C, sulphur (S), N2 and ash by specifying the
yield distribution according to the feeds ultimate analysis. An Aspen Plus reactor, RGibbs
(block ID: GASIFY in Figure 3), uses Gibbs free energy minimization with phase splitting to
calculate equilibrium. This reactor does not require specifying the reaction stoichiometry, but
reactor temperature and pressure was known from the experiment. The reactor, RCSTR
(block ID: BED and FREEBRD in Figure 3) was used to perform char gasification using
reaction kinetics as discussed previously. The reaction kinetics was integrated by written
FORTRAN and Excel code via the CALCULATOR block. A splitter block, CYCLONE, was
used in this model to separate C solid from the gas mixture provided by the split fraction of
MIXED and NCPSD.

6
747

H2

6.1

Oxygen (O2)

33.9

N2

0.2

Sulphur (S)

0.1

Gross specific energy (MJ/kg)

18.6

Figure 2. A schematic diagram of biomass gasification process

Figure 3. Aspen Plus simulation flowsheet

7
748

RESULTS AND DISCUSSIONS

Model Validation
The developed Aspen Plus model is validated with experimental data which is compared in
Figure 4. It is observed from Figure 4 that the model results are in good agreement with the
experimental results. It shows less that 10% variation between them.
Experimental and Simulation results of SW gasification
M
e
a
s
u
r
e
m
n
e
t

30
25
20
15
10
5

(
%
)

0
H2

CO

CO2

Experimental

CH4

Simulation

Figure 4: Experimental and simulation results of syngas composition

Energy and Exergy Efficiency

Using the validated model, energy and exergy efficiency were analysed. The cold gas
efficiency was found to be 78% for the gasification process. The biomass considered has a
higher heating value of 18.6 MJ/kg and calculated lower heating value of 17.29 MJ/kg. The
chemical exergy of fuel biomass and product gas were calculated as 19.49 MJ/kg and 4.35
MJ/kg respectively. The exergy efficiency was determined as 23%. It was found from the
study that the exergy efficiency of wood waste is 23% and corresponding energetic efficiency
is 78%.

Effect of operating parameters

Gasifier performance can be represented by gasifier energetic and exergetic analysis. Effect
of gasifier operating conditions plays a significant role on gasifier performance. Therefore,
effects of gasifier operating conditions, such as, gasifier temperature, effect of air-fuel ratio
and effect of steam-fuel ratio have been performed to identify the optimum operating
conditions of gasifier.

Effect of air-fuel ratio

The effects of air-fuel ratio on energy and exergy efficiencies are shown in Figure 5. The airfuel ratio was considered in the range of 0.5 to 1.0 at gasifier temperature of 1000 and
steam-fuel ratio of 6. It can be observed from Figure 5, the energy efficiencies decreases with
increase in amount of air-fuel ratio in the range of 91% to 78%. On the other hand, exergy
efficiency increases with a small range of 22% to 23% with increase in air-fuel ratio.

8
749

Air-fuel ratio vs. energy and exergy eficiency

100

Efficiency (%)

80

60

40

20

0
0.5

0.6

0.7

0.8

0.9

Air-fuel ratio
Exergy efficiency

Energy Efficiency

Figure 5: Effect of air-fuel ratio on energy and exergy efficiency

Effect of steam-fuel ratio

The primarily role of steam in gasification process is to enhance the yield of syngas and also
controls the selectivity of H2 and CO. The effects of steam-fuel ratio on energy and exergy
efficiencies are shown in Figure 6. The effect of steam to fuel ratio on gasification process
3
was assessed for the range of 4 to 10 at a fixed air flow rate of 10 m /hr and fuel flow rate of
3
10 m /hr. Figure 6 exhibits that with increasing steam-fuel ratio, exergy efficiencies increases
proportionately in the range of 13 % to 45% with steam-fuel ratio of 4 to 10. Energy efficiency
increases within a small range from 72% to 84% for similar steam-fuel ratio.

9
750

Steam-fuel ratio vs. energy and exergy efficiency

100

Efficiency (%)

80

60

40

20

0
4

10

Steam-fuel ratio
Energy efficiency

Exergy efficiency

Figure 6: Effect of steam-fuel ratio on energy and exergy efficiency

Effect of gasifier temperature

The effects of gasifier temperature on energy and exergy efficiencies are shown in Figure 7.
The gasifier temperature considered varies from 600 C to 1000 C for air-fuel ratio of 1 and
steam-fuel ratio of 6. With increasing gasifier temperature, calculated efficiency values are
found in the range of 67 % to 79% and 22% to 27% for energy and exergy respectively. At
low temperature (600) energy efficiency is observed about 67% whereas at higher
temperature (>= 850C) that is about 79%. Exergy efficiency reduces in a small range from
higher temperature to lower temperature.
Gasifier temperature vs. energy and exergy efficiency
100

Efficiency (%)

80

60

40

20

0
600

700

800

850

900

950

1000

Gasifier Temperature(C)
Energy efficiency

Exergy efficiency

10
751

Figure 7: Effect of gasifier temperature on energy and exergy efficiency

CONCLUSIONS
This paper presents energy and exergy analysis for a large scale biomass gasification
process. A simulation model was developed and validated with experimental data. Energy
and exergy analysis were performed based on syngas composition. Energy efficiency was
found to be 78% and corresponding exergy efficiency was found to be 23%. Finally, the
effects of gasifier operating conditions, such as, gasifier temperature, air-fuel ratio and steamfuel ratio were analysed to optimise energy and exergy efficiency of gasification process.

REFERENCES

1.

Stefan Heyne, Henrik Thunman, & Harvey, Simon. (2013). Exergy-based

comparison of indirect and direct biomass gasification technologies within the
framework of bio-SNG production. Biomass Conversion and Biorefinery 3, 337352

2.

Wongsiriamnuay, Thanasit , Kannang, Nattakarn , & Tippayawong, Nakorn

(2013). Effect of Operating Conditions on Catalytic Gasification of Bamboo in a
Fluidized Bed. International Journal of Chemical Engineering, 2013.

3.

Ali, Akbar Eftekhari, Hedzer, Van Der Kooi, & Hans, Bruining. (2012). Exergy
analysis of underground coal gasification with simultaneous storage of carbon
dioxide. Energy, 45, 729-745.

4.

Kasembe, Ethel D., John, Geoffrey R., & Mhilu, Cuthbert F. (2012). Exergy
analysis of high temperature biomass gasification. OIDA International Journal of
Sustainable Development.

5.

Karamarkovic, Rade, & Karamarkovic, Vladan. (2010). Energy and exergy

analysis of biomass gasification at different temperatures. Energy, 35(2), 537-549.

6.

Pellegrini, Luiz Felipe, & Oliveira Jr., Silvio de (2007). Exergy analysis of
sugarcane bagasse gasification. Energy, 32(4), 314-327.

7.

Prins, MJ, & Ptasinski, KJ. (2005). Energy and exergy analyses of the oxidation
and gasification of carbon. Energy, 30(7), 982-1002.

8.

Begum, S., Rasul, M. G., Akbar, D., Ramzan, N., (2014), An Experimental and
Numerical Investigation of Fluidised Bed Gasification of Solid Waste, Energies
2014, 7(1), 43-61.

9.

J Prins, M, J Ptasinski, K, & JJG Janssen, F. (2003). Thermodynamics of gaschar reactions: first and second law analysis. Chemical Engineering Science,
58(3), 1003-1011.

10.

Kotas, T. J. (1995). The Exergy Method of Tharmal Plant Analysis. Florida:

Krieger Publishing Compant.

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752

11.

Moran, M.J. (1989). Availability Analysis (Corrected Ed.). New York: ASME Press.

12.

Szargut J, Morris DR, Steward FR. Exergy analysis of thermal, chemical and
metallurgical processes. Berlin: Springer; 1988.

13.

Szargut, J., & Styrylska, T. (1964). Approximate evaluation of the exergy of fuels.
Brennstoff Warme Kraft, 16(12), 589596 (in German).

14.

Pellegrini, Luiz Felipe, & Oliveira Jr., Silvio de (2007). Exergy analysis of
sugarcane bagasse gasification. Energy, 32(4), 314-327.

15.

Karamarkovic, Rade, & Karamarkovic, Vladan. (2010). Energy and exergy

analysis of biomass gasification at different temperatures. Energy, 35(2), 537-549.

16.

Basu, Prabir (2006). Combustion and Gasification in Fluidized Beds: CRC Press.

12
753

SEPARATION OF SOLID PHASE PRODUCTS FROM HYDROTHERMAL

LIQUEFACTION OF RICE STRAW
a

Tingting Zhang , Changjun Li , Xiao Yang , Zhongchao Tan , Shicheng Zhang* , Jianmin Chen
a

Shanghai Key Laboratory of Atmospheric Particle Pollution and Prevention (LAP ), Department of
Environmental Science and Engineering, Fudan University, Shanghai 200433, China

Department of Mechanical & Mechatronics Engineering, University of Waterloo, Waterloo, Ontario,

Canada N2L 3G1
* Corresponding author e-mail address: zhangsc@fudan.edu.cn

ABSTRACT
A novel method has been developed to separate the solid phase products derived from
hydrothermal liquefaction of rice straw into four chemical groups, i.e. phenols, furans, fatty acids
and cyclopentenone ketones. The solid phase products were performed the basification and
subsequently the acidification. The organic solvents with different polarities were used to extract the
different fractions of the solid phase products. Results showed that, after basification using NaOH
or KOH and sequential acidification using HCl solution (added dropwise, with pH 1.5), phenol
precipitates had increased tremendously. The yields of different fractions of the oil products were
studied. Component analysis of each product was detected by GC-MS, FTIR, and TG-DTA. The
maximum yields of phenols, furans, fatty acids and cyclopentenone ketones were 19.20%, 52.50%,
12.54% and 13.74%, respectively. The new method will have the potential application in the
separation of high-value-added chemicals from the hydrothermal liquefaction products of rice straw.
Keywords: Biomass and biofuels; Basification-acidification; Hydrothermal liquefaction; Rice straw.
INTRODUCTION
Hydrothermal liquefaction (HTL) is a promising thermochemical conversion process which could be
used to convert wet biomass into biofuels. HTL based bio-oil is a complex mixture of hundreds
chemicals. HTL bio-oil is a promising source of high value-added chemicals. Separation of the
chemicals from the bio-oil is the key to the success of the new research direction. Solvent extraction
is a common and effective way to separate different chemicals from bio-oil. In general polar organic
solvents were used to extract phenols from water phase and acetone and n-hexane can extract
heavy oil and light oil. A review of separation methods and technologies related to bio-refining
including pre-extraction of hemicellulose and other value-added chemicals is presented by Huang
et al. (2008).
Few studies have been conducted on the separation of different compounds from the HTL solid
products, especially those from rice straw performed by the basification and subsequently the
acidification. In the basification process, some compounds of bio-oil, e.g., phenols, cyclopentene
ketones and esters, can form organic salts which are easily to be transferred into water. In the
subsequent acidification of the water layer, such salts are protonized again and form compounds
with lower solubility in water and tend to precipitate. Followed with basification and acidification, the
organic solvents with different polarities were used to extract the different fractions of the solid
phase products and different solvents have different extraction effects on different chemical family.
This paper aims at evaluating the feasibility of this approach.

754

MATERIALS AND METNODS

Materials
The HTL solid product samples were obtained from the Shanghai Fuhuan Bioenergy Co. Ltd. Rice
straws obtained from Songjiang District, Shanghai, Southern China, were used as the raw material
feedstock. HTL was operated at 553.15 K for 30 min. The samples average moisture content was
62.13 %. The sample was first washed with tetrahydrofuran (THF) followed by filtration. Then THF
solution was evaporated at 65 using a rotary evaporator, and the solid phase was defined as
heavy oil (HO) in this paper. The THF insoluble fraction was dried at 60 for 24 hr to obtain the
reaction residue, which is referred to as solid residue (SR) herein. The corresponding yiled fractions
of HO and SR were the mass ratio of HO or SR over the original sample weight. The samples were
separated following the procedure in Figure 1. Four separation methods were used by using
different aqueous alkali and organic solvents according to the properties and the four methods were
present in Table 1.

Sample
5 % base solution extration
(NaOH and KOH)
solid

solution

Extraction by B

10 % HCl solution acidification pH=1.5

Filtration

Filtration
HCl solution

HCl insoluble
Extraction by A

Extraction by A
Aqueous
phase

A-2

B solution

A
insolute

A
solution

Extraction by THF

B insolute

Evaporation

Extraction by THF

THF-1

Solid Residue 1
SR-1

B-1

Evaporation

Solid Residue 2
SR-2

THF-2

A-1

Figure 1. Solid residue separation

Table 1 The solvents used in four methods
Method

Weak Polar Solvent

Strong Polar Solvent

Acidification

Basification

Solvent A

Solvent B

Method1

HCl

NaOH

Methylene chloride

Ethyl acetate

Tetrahydrofuran

Method2

HCl

KOH

Methylene chloride

Ethyl acetate

Tetrahydrofuran

Method3

HCl

NaOH

Ethyl ether

Ethyl ether

Tetrahydrofuran

Method4

HCl

NaOH

Ethyl acetate

n-Hexane

Tetrahydrofuran

The sample was first mixed with 5wt.% aqueous alkali (NaOH and KOH) followed by extraction and

755

filtration. The post-filtration aqueous phase with 10wt.% HCl solution had changed pH value to be
acidic. In order to explore the optimum conditions for the precipitant generation, the aqueous phase
was adjusted to different pH values in the acidification process. A brown solid material was not
achieved in the basification process until the pH value of aqueous phase reached 3.2 in the
acidification process. When the pH value was 1.5, the amount of the precipitant would not increase
with the decrease of pH values. Therefore, the most economical conditions for precipitation were
considered at pH 1.5. Under acidic environment, phenols, cyclopentene ketones and esters tended
to precipitate. The precipitant was very sticky, and it was filtered to get solid phase and aqueous
phase. The solid phase was extracted by weak polarity solvent A, and the A solution was
evaporated using the rotary evaporator to measure the weight of the solute which was defined as oil
A-1. The residue was extracted by strong polarity solvent tetrahydrofuran (THF). After extraction,
the THF solution was evaporated using the rotary evaporator and the oil was designated as THF-2.
The insoluble fractions were dried at 65 for 24 h to obtain the reaction residue which was defined
as Solid Residue 2 (SR-2). The aqueous phase is extracted with solvent A, and the A solution was
evaporated using the rotary evaporator while its oil was designated as A-2.
The solid phase was dissolved in weak polarity solvent B, and after filtration, the B solution was
evaporated using the rotary evaporator, and its oil was defined as B-1. The extraction capacity of
solvent B was limited. The residue was extracted by strong polarity solvent tetrahydrofuran (THF)
and after extraction, the THF solution was evaporated by the rotary evaporator and the oil was
designated as THF-1. The insoluble fractions were dried at 65 for 24 h to obtain the reaction
residue, and the residue was defined as Solid Residue 1 (SR-1).
Two independent runs were conducted under nominally identical conditions to determine the
uncertainties in the experimental results. Results reported hereon represent the mean values for the
independent trails. The yields of liquefaction products including A-1, A-2, B-1, THF-1, THF-2, SR-1
and SR-2 are calculated by diving their respective mass over the total weight as follows:
Product Analysis
GC-MS analysis of HO, method-1 (A-1, A-2, B-1, THF-1 and THF-2), method-2 (A-1, A-2, B-1,
THF-1 and THF-2), method-3 (THF-1 and THF-2) and method 4 (A-1, A-2, B-1, THF-1 and THF-2)
were performed on a Thermo FOCUS DSQ with an HP-5 MS column (5% phenyl and 95%
dimethylpolysiloxane, 30mm 0.25 mm 0.25m). The carrier gas was helium with a flow rate at 1
mL min-1. A total of 1 L of sample was injected into the column. The GC oven temperature program
was as follows: hold at 60 for 2 min, raise to 300 with a heating rate of 20 min-1, and hold
for 5 min. GC-MS analysis of method-3 (A-1, A-2B-1) were carried out using a Finnigan Voyager
with a HP-INNOWax column (100% polyethylene glycol, 30mm 0.25 mm 0.25m). The carrier
gas was also helium with a flow rate of 1 mL min-1. A total of 1 L of sample was injected into the
column. The GC oven temperature program was as follows: hold at 60 for 2 min, raise to 250
with a heating rate of 15 min-1, and hold for 10 min. Identification of compounds was performed
by analyzing the MS data using the HP Chem Station software. The matching degrees of all the
identified compounds with known MS spectra were above 80%. And it should be noted that only a
fraction of the oil products obtained in this research can be identified by GC-MS due to the
temperature limit of the instrument (maximum boiling point detected ~ 300).

756

The elemental compositions (C, H and N) of HO, SR and A-1 (method-1, method-3, method-4) were
analyzed by CHNS Elemental Analyzer Vario EL III. The content of O was estimated by the
difference, assuming a negligible content of sulfur (S) in products. The higher heating value (HHV)
was calculated by the Dulong formula: HHV (MJkg-1) = 0.3383 C+1.422 (H- O/8).
Fourier transform infrared (FTIR) spectroscopic analysis of HO was performed by Thermo Nicolet
Nexus 470 over a range of 400-4000 cm-1. All measurements were carried out by means of KBr
plates. The TG of HO and A-1(method-1, method-3 and method-4) were analyzed by analyzer 7
(Perkin Elmer, USA) from room temperature to 900.
RESULTS AND DISCUSSIONS
Product Analysis of Bio-oil Sample
The properties of the solid product samples were list in Table 2. The GC-MS analysis results
showed that HO was a very complex mixture composed of alcohols, aldehydes and ketones
aromatic ring compounds, fatty acids, esters, furans and phenols. By comparing the peak areas of
GC-MS spectra, it was found the ketones, phenols, fatty acids and furans compounds were the
main compounds of HO. For the sample produced at 553.15 K, phenols, alcohols, furans and fatty
acids were found. The formation of phenols and ketones demonstrated the decomposition of lignin
part in rice straw (Anastasakis and Ross, 2011; Kumar and Gupta, 2009; Zou et al., 2011). The fatty
acids, alcohols and furans could be produced due to the dehydration of saccharides produced from
the hydrolysis of hemicellulose and cellulose (Zou et al., 2011). The N-containing ring compounds
like pyrroles detected were mainly formed from the liquefaction of protein fraction in rice straw
(Biller and Ross, 2011).
Table 2 The elemental analysis of HO and SR obtained from sample (wt. %)
Entry

Value

HHV of HO (MJ/kg)

29.18

HHV of SR (MJ/kg)

10.20

Water content (wt.%)

62.13

Elemental composition of HO (wt.%)

C

68.27

7.22

0.96

23.55

The analysis of functional groups in HO was determined by FTIR to demonstrate the compounds in
HO. The FTIR spectra of HO are shown in Figure 2. Table 3 presents the analysis results of the
functional group in HO. The absorbance peak at 3380 cm-1 was the OH stretching vibration
(Sugano et al., 2008), while the absorbance peaks at 2850 2960 cm-1 were ascribed to C-H
stretching vibration of CH3 and CH2 groups (Zou et al., 2010). The C=O vibration at 1700 cm-1
indicated the presence of ketone, aldehydes, fatty acid or esters (Fan et al., 2011). The bands at
1000 1270 cm-1 and 750800 cm-1 may be attributed to C-O bending vibration and C-H bending
vibration, which suggested the presence of aromatic compounds such as phenols (Fan et al., 2011).

757

The probable compounds existed in HO determined by FTIR were well consistent with the analysis
results of GC-MS.

100

Transmittance%

bio-oil

80

60

4000

3500

3000

2500

2000

1500

1000

500

-1

Wavenumber(cm )
Figure 2. The FTIR spectra of HO
Table 3 Analysis of functional groups in HO by FTIR
/cm-1

Functional

Probable Compounds

/cm-1

Group

Functional

Probable Compounds

Group

3380

O-H

Hydroxyl Compound

1512

-NO2

-R-NO2

2956,2924, 2852

C-H

Methyl/Methylene Compound

1450,1377

C-H

Methyl

1700

C=O

Ketone, Aldehydes, Acid, Ester

1269,1113, 1047

C-O

Phenol, Ester, Alcohol

1610

C=C

Alkenes

803,750

C-H

Aromatic Compound

TGA of HO in nitrogen can be regarded as a miniature distillation process. Although some thermal
degradation is likely, TGA provides an estimate of the boiling range of HO. Figure 6 shows the
thermogravimetry (TG)/differential thermal analysis (DTA) curves of HO obtained from sample in
nitrogen atmosphere at a flow rate of 20 mL min-1. HO was heated from room temperature to 900
under an inert atmosphere, resulting in a mass loss of about 90 wt %. As seen in Figure 3, the
weight loss of HO in TG curve is observed to transform from a high rate to a low rate at the point
around 400. The DTG curve for HO show that the maximum weight loss rate of HO appears at
around 190 and 410. The weight loss below 300 is 25.89 wt %. Overall, the TG/DTA
characterization of HO indicates a direct understanding about Thermal properties of HO.
The properties of HO are studied by means of GC-MS, FTIR, and TG/DTA, and it is beneficial for
sequent separation research. The results show HO obtained from sample was a very complex
mixture composed of hundreds of oxygenated organic matters and hydrocarbons (Sipil et al.,
1998). Hence, it is necessary to separate, classify, and identify HO into bio-based chemicals to
increase the added value of the hydrothermal liquefaction products.

758

110

TG
DTG

TG

90

Weight % (%)

-1
80

DTG

70

-2

60
-3

50
40

-4

Weight loss rate (% /)

100

30
20

-5
0

100

200

300

400

500

600

700

800

900

Temperature ()

Figure 3. TGA and DTGA results

Effects of separation method on product yield

As it can be seen from Figure 4, contrast to the HO yield of 58.93%, the total bio-oil product yields in
four methods are 46.87%, 49.01%, 39.96%, 51.29%, respectively. After separation processes, the
total bio-oil product yields in three methods declined slightly. The reasons for the decrease in
product yields by using four methods have been found to be multiple extraction residues in the
reagent bottle, experimental errors and system errors. Method 3 had been responsible for the
greatest damage of about 18.97%. The main reason is the use of diethyl ether as solvent with
34.6 boiling point. Furthermore, diethyl ether was highly volatile at room temperature, and during
the separation, the bio-oil component may volatilize with it.

100

SR
HO

110
100
90

80
70

70

Percentage %

Percentage %

80

60
50
40

60
50
40

30

30

20

20

10

10

SR2
SR1
THF-2
THF-1
B-1
A-2
A-1

90

Method-1

Method-2

Method-3

Method-4

Full product

method-1

method-2

method-3

method-4

Fig. 4. Effect of separation method on SO and HO mass percentage

The different polarity of the solvents leads to different product yields among four methods. The
overall trend is that SR-1 had the highest product yield in three methods, which is 52.21%, 49.97%,
59.13% and 48.64%, respectively. The second-highest yield is THF-2 occupied a second proportion
of 24.60%, 29.77%, 19.67% and 22.32% in four methods. THF-1 and A-1 constituted the third major
product of the sample, and the yields of them are 9.00% and 5.84%, 7.00% and 3.83%, 8.91% and
6.67%, 14.46% and 11.90%, respectively. The product yield of B-1, A-2 and SR-2 are particularly
low, only covering about 2%.
The method concerned the organic solvents with different polarities extracted the different fractions
of the solid phase products performed by the basification and subsequently the acidification, and

759

the products include A-1, A-2, B-1, THF-1 and THF-2. Sequentially, by contrast of the classified
product yields, the product component in different methods by GC-MS analysis, FTIR results
analysis, TGA analysis and element analysis, the separation process can be optimized.
GC-MS analysis also showed that tThe separation mechanism depended on the acidity value of the
products and their solubilities in different solutions. The rough acidities of the lignin products are as
follows: low-molecular-weight organic acid > H2CO3 > phenolics > alcohol, ester, weak-polar
organics. In the basification process, phenols, cyclopentene ketones and esters, can form organic
salts which are easily to be transferred into water. And in the subsequent acidification of the water
layer, such salts are reacted again and form compounds with lower solubility in water and tend to
precipitate. Most organic acids are water-soluble, can occur acid-base neutralization reaction with
NaOH, and can be recovered from organic acid salt the by acidification. Also, different polarities of
solvents have different extraction effects on different chemical family. The organic solvents include
n-hexane, ethyl ether, ethyl acetate, methylene chloride and tetrahydrofuran. Among these solvents
n-hexane has the weakest polarity and tetrahydrofuran owns the strongest polarity.
In the component analysis of A-1, the main compounds are phenols, and after the basification and
acidification pretreatment, phenols mainly tend to concentrate in A-1.Run 1 can detect 12 different
compounds, and the effective content is 100%, where the phenolic area is 79.72%. Method 2 can
detect 12 different compounds, and 90.16% is the effective content of the total area, where the
phenolic area is 70.15%. Method 4 can detect 11 different compounds, and the effective content is
90.27% of the total area, where the phenolic area is 69.33%. In the three runs, phenol
4-ethyl-2-methoxy- has high area and it accounts for 45.86%, 32.17%, 37.58%, respectively.
However, in method 2, ether having lower boiling temperature, it has no ability extract all the
compounds in bio-oil completely compared with method 1 and 4. In addition, it is beneficial to
separate benzenediols and monophenolics, because the two phenolic categories also have
different physical and chemical properties and applications.
A-2 mainly includes two chemical groups, that is phenolic derivatives and cyclopentenone
compounds. Method 1 could detect 16 different compounds, and the effective content is 100%;
method 2 could detect 16 different chemicals, and the effective content is 94.78%; method 4 could
detect 13 different compounds, and the effective content is 100%. In the three methods, The yields
of A-2 are considerably low. In method 1, 2-hydrocy-3-propyl-2-cyclopenten-1-one and
phenol,4-ethyl-2-methoxy- takes up 33.03% and 14.66% of the total area, respectively; In method 2,
2-hydrocy-3-propyl-2-cyclopenten-1-one and Phenol,2-methoxy- is 23.36% and 23.05% of the total
area, respectively; In method 4, ethanone,1-(4-hydroxy-3,5 -dimethoxyphenyl)- and
2-hydrocy-3-propyl-2-cyclopenten-1-one accounts for 35.03% and 13.86% of the total area.
Concerned with the GCMS analysis of B-1, 11 different compounds can be detected in method 1,
and the effective content is 82.65%. The number of chemicals detected from method 2 and method
4 is also 11, and the effective content is 72.84% and 70.56% respectively. Among the three
methods, cyclopentenone compounds occupy a large area compared with other chemical groups.
2-pentadecanone, 6, 10, 14-trimethyl- has a high content in all methods, which is 7.65%, 15.88%
and 19.72%, respectively. As an important intermediate for the synthesis of vitamin E acetate, it has

760

wide applications in medicine. To analyze B-1 obtained from extraction, the effective content
become lower because of the polarity change of the solvent. The polarity order of different solvents
is as follows: Ethyl acetate> ether> n-hexane. Especially in method 4, n-hexanes extraction ability
is limited. Thus it cannot extract fatty acids out.
In the component analysis of THF-1, 11 different compounds can be detected by method 1 and the
effective content is 98.38%, where the fatty acids content accounts for 77.95%. The method 3 can
detect the same number of compounds as method 1, but the effective area increases to 99.99%,
where the fatty acids content is 55.73%. The number of compounds detected by method 4 rises to
13, with 96.98% effective content and 39.49% fatty acids content. In method 1, the highest content
is fatty acids, including some long-chain fatty acids such as n-hexadecanoic acid and oleic acid. In
contrast to other two methods, the THF-1 of method 4 contains more furans compounds,
accounting for 42.35%.Moreover, organic acids are also valuable and widely applied chemicals.
Organic acids and their anions can be used as catalysts, corrosion inhibitors, and reducing agents.
The THF-2 in three runs mainly contains furans compound, and the effective content is 100%.
Among the four compounds detected from the THF-2 in three methods, the contents of
2-furanmethanol, tetrahydro- and tetrahydrofuran,2-propyl- are higher than the others. The content
of 2-furanmethanol,tetrahydro- is 59.26%, 33.38% and 51.58% respectively while
tetrahydrofuran,2-propyl- is 19.07%, 53.73% and 11.66% respectively.
Overall, the GC-MS results show the approach of organic solvents with different polarities extracted
the different fractions of the solid phase products performed by the basification and subsequently
the acidification, can effectively separate hydrothermal liquefaction products into four chemical
groups, i.e. phenols, furans, fatty acids and cyclopentenone ketones.
Elemental analysis of A-1 and SR-1 Obtained from Different Methods
As shown in Table 4, the carbon content, the ratios of carbon/hydrogen, the higher heating values
(HHVs) in A-1 were 66.58% to 70.08%, 1.13% to 1.17%, 26.81 MJkg-1 to 29.45 MJkg-1,
respectively. The carbon content, the ratios of carbon/hydrogen, and the higher heating values
(HHVs) in SR-1 were 37.20% to 39.00%, 1.45% to 1.58%, 8.78 MJkg-1 to 10.77 MJkg-1,
respectively. A-1 contained more carbon and hydrogen but less oxygen and nitrogen than SR-1.
The higher heating value (HHV) is determined by bringing all the products of combustion back to
the original pre-combustion temperature, and in particular condensing any vapor produced. The
basic trends were that HHVs of A-1 were much higher than that of SR-1. Contrasting to the higher
heating value (HHV) of HO of 29.18 MJ/kg-1, the higher heating values (HHVs) of A-1 in different
methods were a litter higher than that of HO. The HHV of HO is equivalent to the heating value of
medium-rank and high-rank coals, according to the Chinese National Standard (GB/T
15224.3-2010, China. CN-GB, 2010). Furthermore, comparing with the higher heating value (HHV)
of SR of 10.20MJ/kg-1, the higher heating values (HHVs) of SR-1 in different methods were a litter
lower than that of SR.
Table 4 The elemental analysis of A-1 obtained from different methods (wt. %)a
Method

C%

H%

N%

761

O%b

HHV(MJkg-1) c

H/C

A-1

SR-1
a

Method 1

70.08

6.81

0.93

22.18

29.45

1.17

Method 3

69.51

6.9

0.49

23.09

29.24

1.19

Method 4

66.58

6.28

1.04

26.1

26.81

1.13

Method 1

39

5.15

1.01

54.84

10.77

1.58

Method 3

38.59

4.87

1.2

55.34

10.14

1.51

Method 4

37.2

4.48

1.1

57.22

8.78

1.45

All measured on a dry basis except the moisture; By difference; By Dulong Formula: HHV (MJ/kg) = 0.3383 C +1.422 (H b

O/8).

TG/DTA analysis of A-1 Obtained from Different Methods

Table 5 lists the boiling point distribution of HO and A-1 obtained from three different methods. It
can be seen that the A-1 have a large fraction at distillation temperatures lower than 300,
accounting for 25.56 wt % to 33.34 wt %, respectively, higher than that of HO obtained from the
sample(25.89 wt%). Furthermore, the results indicate that HO still contains a certain amount of
high-boiling-point compounds that could not be analyzed by GC MS. For A-1 (obtained from
different methods), the light fraction with a boiling point < 400 takes up 57.34 wt%, 57.06 wt%
and 40.53 wt % of the total, respectively. Although the light fraction of A-1 with a boiling point <
400(method 1 and method 3 ) is much higher than HO with a boiling point < 400(47.98wt%). It
indicates that A-1 are favorable for further separation and refining to produce chemicals.
Table 5 Boiling point distribution of HO and A-1 obtained from different methods
Boiling Point of A-1( C)

Percent of the Total Weight (wt %)

Method-1

Method-3

Method-4

HO

20300

33.24

36.85

25.56

25.89

300350

14.52

12.93

6.54

9.81

350400

9.61

7.28

8.43

12.28

400450

5.05

4.87

5.27

6.66

450500

2.5

2.69

3.62

3.28

500550

1.55

2.34

3.16

2.21

550900

5.21

8.6

12.95

9.88

CONCLUSIONS
This research work shows that the separation products depend on the method of separation. By
comparing different methods we conclude that solid phase products can be effectively separated
into four chemical groups, i.e. phenols, furans, fatty acids and cyclopentenone ketones. The solid
phase products were treated by basification and followed by acidification. After basification using
NaOH or KOH and sequential acidification using HCl solution (added dropwise, with pH 1.5),
phenol precipitates had increased tremendously. The yields of different fractions of the oil products
were studied. Component analysis of each product was detected by GC-MS, FTIR, and TG-DTA.
The maximum yields of phenols, furans, fatty acids and cyclopentenone ketones were 19.20%,
52.50%, 12.54% and 13.74%, respectively. This new method will have the potential application in
the separation of high-value-added chemicals from the hydrothermal liquefaction products of rice
straw.

762

ACKNOWLEDGEMENT
The authors are thankful for financial support from the Helongjiang Beidahuang Agriculture Co. Ltd.
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Sipila, K., E. Kuoppala, L. Fagerns, and A. Oasmaa, 1998, Characterization of biomass based flash
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Sugano, M., H. Takagi, K. Hirano and K. Mashimo, 2008, Hydrothermal liquefaction of plantation biomass
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Zou, S.P., Y.L. Wu, M.D. Yang, I. Kaleem, C. Li, and J. M. Tong, 2010, Production and characterization of
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763

EFFECT OF TORREFACTION PRETREATMENT ON GASIFICATION OF BIOMASS

1

Manoj K. Raut , Prabir Basu , Bishnu Acharya

1. Mechanical Engineering Department, Dalhousie University, P. O. Box 15000, Halifax, NS B3H 4R2, Canada
2. Greenfield Research Incorporated, P. O. Box 25018, Halifax, NS, B3M 4H4, Canada
manoj.raut@dal.ca: prabir.basu@dal.ca: bishnu.acharya@greenfieldresearch.ca

ABSTRACT

Raw biomass as a feedstock for gasification has enormous potential, but its inherent characteristics limit its
wide scale use. Properties such as high moisture content, low bulk density, heterogeneous nature, and lower
grindability make its handling and gasification difficult. Furthermore, higher tar formation during gasification
of raw biomass increases the downstream cost of gas separation. Pre-treatment of biomass through
torrefaction could remove these limitations, making biomass more suitable for gasification. This paper
examine what effect torrefaction bring on the gasification of biomass. Both batch and continuous mode of
steam-gasification show that torrefaction pre-treatment decreases the tar production and slightly increases
the quality of product gas, but it reduces the gas yield when compared to raw biomass. Also, the reactivity for
gasification of char from torrefied biomass is found to be lower than that from raw biomass. The detail
experimental findings are discussed in the paper.

Keywords: Torrefaction, Gasification, Kinetics of Gasification, Tar Yield

INTRODUCTION
Biomass resources are seen as an alternative renewable fuel for heat, power and liquid fuel production
(Svoboda et al., 2009). However, the inherent properties of biomass like high moisture content, low bulk
density and heating value, fibrous nature, hydroscopic nature, bio-degradability, difficulty in grinding, etc.
makes it use very limited. Biomass is consumed mostly in developing countries in large for cooking and such
application faces the challenges of in-door air pollution and inefficiency. Attempt is being made to modify the
stove design. For power generation, biomass is mostly used for co-firing in the form of bio-pellets. Biopellets, even though is denser but still carries other characteristics of raw biomass. Hence, its share in cofiring in existing coal-fired power plant is limited up to 5-10%. Gasification is another thermochemical route
for utilization of raw biomass for producing heat and power as well as liquid fuels. However, the tar produced
during gasification is another challenge that is hindering its progress (Devi et al., 2003). The attempt made to
reduce the tar content either by burning like in downdraft gasifier or by using catalyst either lowers the quality
of the gas or adds additional complexity to the system. So to overcome such negative aspect of biomass, it
needs to be pre-treated.
Torrefaction is seen as such pre-treatment process. It is a mild pyrolysis process within the temperature
o
range of 200-300 C in an inert environment (Basu, 2013). It makes the biomass more brittle, increases the
bulk density and heating value, makes biomass hydrophobic, more stable and homogenous (Bergman et al.,
2004). Further, it helps to reduce the H/C and O/C ratio of biomass to the values similar to the coal. This
reduction in H/C and O/C ratio further helps to improve the quality of the gas produced during gasification
(Prins et al., 2006). Not only that, the major advantage of such pre-treatment is reduction in tar produced
during gasification process. Because of all these benefits, there has been lots of interest in torrefaction and
several studies has been done to understand the process, effect of operating parameters on quality of
torrefied product, characteristics for combustion and co-firing. However, the gasification application of
torrefied biomass is less studied. Fisher et al. (2012) and Couhert et al. (2009) has done some study to
understand the kinetics of torrefied biomass char and effect on the physical structure of biomass when
torrefied. Seeing the potential of torrefied biomass for its use in gasification, the authors had carried out the
detail study on this. This paper discusses about the kinetic of steam gasification reaction for raw and
torrefied biomass. Steam gasification studies of torrefied biomass in a bubbling fluidized bed gasifier is also

1
764

discussed which presents the result on difference in gas composition and yield between raw and torrefied
biomass. The effect of torrefaction temperature on tar yield during gasification is also included in the paper.
METHODOLOGY
A poplar wood is used for the experiments. The proximate and ultimate analysis of the wood is shown in
Table 1.
Table 1: Proximate and ultimate analysis of raw and torrefied poplar wood
Proximate Analysis (%)
MC
Raw
Biomass

4.64

VM
85.25

Ultimate Analysis (%)

Dry Basis
Ash
FC
5.52

9.23

47.47

7.18

0.55

44.79

0.009

Heating
Value
HHV
(MJ/kg)
18.34

For comparing gasification of two feedstock (raw biomass and torrefied biomass) on the uniform base, both
o
feedstock were devolatilized at a fixed temperature of 800 C, and then subjected to steam gasification in
batch (QWM) as well as continuous (BFB) reactor.
Kinetics Studies
The kinetic study of gasification of raw and torrefied
biomass in presence of steam is done in Quartz Wool
Matrix (QWM) reactor (Figure 1). It consists of a stainless
steel reactor 50 mm in diameter that encircles an electric
heater. A temperature controller controls temperature
inside the reactor, which is continuously monitored with a
K type thermocouple. A precision balance sits on the top
of the reactor to facilitate the continuous measurement of
mass of the substance being examined. A wire basket,
whose one end is connected to the balance, holds the
sample being studied inside the reactor. Flow rate of
gases is continuously measured with an electronic flow
meter. But for steam, it is first calibrated to measure the
flow with valve opening and then fed into the reactor.
Figure 1: Schematic of QWM reactor
For kinetics studies one sample of raw biomass and 2
o
samples of torrefied biomass (torrefied at 250 C and
o
o
300 C for 1 hour) are considered and each of these samples is gasified at five different temperatures: 750 C,
o
o
o
o
800 C, 850 C, 900 C, and 950 C. To produce the torrefied biomass a raw poplar of size 25 mm diameter
and 75 mm long is considered. For this, at first the reactor is heated to the desired torrefaction temperature
and then the raw biomass is placed in the bucket and dropped inside the reactor. The biomass starts to get
heated. Both the temperature of the biomass and the mass loss is continuously measured. The biomass is
placed for 1 hour and is taken out.
For gasification, the raw and torrefied biomass is devolatilized to produce char. For devolatilization, reactor is
o
heated to 800 C and then the biomass sample i.e. raw and torrefied biomass is dropped into the reactor. N2
is supplied as a gaseous medium to drive off the volatiles and also provide inert environment to supress the
chances of occurrence of any other reaction. The mass loss is continuously measured and as the mass loss
becomes constant, sample is taken out and cooled in a desiccator. The cooled sample is then ground to
small size. For gasification, the char particles of size in the range of 300-450 microns are considered. For
gasification also, the reactor is first heated to desired gasification temperature and then the char of raw
biomass and that obtained from torrefied biomass are placed in the bucket and kept inside the reactor for 1
hour. Steam is supplied from the bottom of the reactor. The mass of the char is continuously measured
which is later used to calculate the char conversion rate for determining the kinetics. The Arrhenius equation

2
765

(Eq. 1) is considered for comparing the kinetics of gasification between raw and torrefied biomass (Slopiecka
et al., 2012).

k(T ) = Ae

" EA %
$
'
# RT &

(1)

Where, Activation energy, EA (kJ/mol) is the minimum energy needed for the reaction to occur, A (1/min) is
frequency factor, T is the absolute temperature (K) and Universal gas constant, R = 8.3144 J/mol/K.
For collecting the char, gas and tar, the reactor is closed from the top. The char sample is kept in the basket
and the gas formed is taken to the condenser and then collected in a gasbag. The condensed liquid is then
evaporated to remove the moisture and the mass is measured for gravimetric tar.

Gasification studies in bubbling fluidized bed gasifier

The poplar wood used for the experiment is cut into cylindrical pieces of size 38mm 10mm. The small
o
o
cylindrical piece is then torrefied at 250 C and 275 C for 1 hour. The torrefied biomass as well as the raw
biomass is later chipped into small size. The average particles size used for the experiment is 10mm
10mm 4mm.

Figure 2: Photographs of biomass for gasifying (A) raw biomass (B) torrefied biomass at 250 C (C)
raw biomass grinded for gasification (D) torrefied biomass grounded for gasification
Figure 3 shows the schematic diagram of bubbling bed gasifier used for this studies. The gasifier is circular
in cross-section with an inside diameter of 152.4 mm and height 1525 mm. The bottom part of the gasifier
encircles an electric heater to heat the gasifier to desired gasification temperature. The silica sand of
average diameter 250-300 micron is placed inside the gasifier as a bed material. The bed height to diameter
ratio is maintained at 1. Saturated steam is generated in a steam generator and is superheated with the wrap
o
heater to 250 C, before feeding it to the gasifier. Steam here plays a dual role of fluidizing agent and
gasifying medium. The raw and the torrefied biomass are fed through the screw feeder into the gasifier
reactor. The gas produced during reaction leaves from the top of the reactor and passes through the
cyclone. The dust particles are separated in the cyclone and then the gas enters into condenser. In the
condenser, excess moisture and tar component are separated. Finally the sample of clean gas is collected in
one litre tedlar gasbag from the gas sampling point located at the exit of the condenser. The gas sample is
collected at 5 minutes time interval for 30 minutes. The dry and clean gas is analysed on a SRI 8610C Gas
Chromatograph with helium as carrier gas. Rest of the gases are burnt and passed through a bag house to
the atmosphere. A number of thermocouples along the height of the reactor continuously measure the
temperature inside the reactor.
o

Gasification study is carried out at four different temperatures: 700 C, 750 C, 800 C, and 850 C. The fuel
feed rate is maintained at 3 kg/h and the steam feed rate at 1.8 kg/h to maintain the S/B ratio of 0.6. This
steam flow rate gives the fluidization velocity of 0.18 m/s in the bed and maintains the bed in a bubbling
condition.
3
766

Figure 3: Schematic diagram of lab scale bubbling fluidized bed gasifier

1: bag house, 2: gas sampling point, 3: cyclone, 4: thermocouple, 5: ash collector, 6: fluidized bed, 7:
heater, 8: tape heater, 9: steam generator, 10: drain, 11: distributor plate, 12: freeboard, 13: screw
feeder, 14: biomass hopper, 15: motor, 16: view point, 17: cooling tank.
RESULT AND DISCUSSION
Product Yield
Table 2 shows the mass yield of char, volatiles and tar obtained during torrefaction, devolatilization and
gasification in terms of per unit of raw biomass weight. From the table, it is very distinct that char yield during
devolatilization is in average 43% higher for torrefied biomass than the raw biomass where as tar yield is
lower for torrefied biomass. During gasification, gas yield for raw biomass char is higher. Average value of
gasification yield for char conversion is 82.07% for raw biomass compared to 47.21% for torrefied biomass.
The average value of Tar yield of gasification of raw biomass char is 79% lower than that for torrefied
biomass.
Table 2: Char, volatile and tar yield during torrefaction, devolatilization and gasification
Initial
Mass
Sample

Torrefaction
o
(250 C/1hr, N2)
Biomass Volatiles
Tar
(g/g)
(g/g)
(g/g)

Devolatilization
o
(800 C/1hr, N2)
Char
Volatiles
Tar
(g/g)
(g/g)
(g/g)

Gasification
o
(800 C/15min, Steam)
Char
Gas
Tar
(g/g)
(g/g)
(g/g)

Raw1

5.7203

0.0813

0.9086

0.0101

0.0103

0.0695

0.0015

Raw 2

5.6949

0.1024

0.8885

0.0091

0.0203

0.0805

0.0016

Raw 3

5.7218

0.1073

0.8815

0.0112

0.0229

0.0831

0.0013

Torrefied 1

5.72

0.7596

0.2391

0.0013

0.1301

0.6248

0.0047

0.0673

0.0626

0.0002

Torrefied 2

5.7046

0.7321

0.2667

0.0012

0.1553

0.5731

0.0038

0.0784

0.0763

0.0005

Torrefied 3

5.7152

0.7499

0.2488

0.0013

0.1314

0.6138

0.0047

0.0738

0.0575

0.0002

4
767

Kinetics Study
The Arrhenius plot for the gasification reaction of char produced from raw and torrefied biomass in presence
of steam is shown in Figure 4: It shows that the kinetic rate of gasification of torrefied biomass is lower than
that of raw biomass. The difference in reactivity could be because of the changes happened during
torrefaction, as the other processes are similar for both raw and torrefied biomass. During torrefaction, which
is characterized by slow heating rate, the volatiles find sufficient time to undergo condensation on pore walls
of char forming secondary char. This is more prominent in larger size biomass similar to that considered in
this study (Dhungana, 2011). For this reason the char yield from torrefied biomass after devolatilization is
around 43% higher than that from the raw biomass, which confirms the formation of secondary char. Fisher
et al. (2012) found secondary char formed during torrefaction has lower reactivity. So, gasification of torrefied
mass involves gasification of less reactive secondary char and generally reactive primary char. Therefore,
the overall reactivity of torrefied biomass during gasification is lower than the raw biomass.

1/T (K-1)
0.0008
-6.00
-6.50

0.00085
TB_250 C 1 hr

0.0009
TB_300 C 1hr

0.00095

0.001

Raw

ln (k) (min-1)

-7.00
-7.50
-8.00
-8.50
-9.00
-9.50
Figure 4: Arrhenius plot for gasification reaction of char obtained from raw and torrefied biomass
Tar Yield
o

Figure 5 shows the total tar yields of gasification of raw and torrefied biomass (produced at 250 C and 1
o
hour residence time) at 800 C in presence of steam. From Fig. 5, it is evident that the tar yield for torrefied
biomass is lower than that of raw biomass. Sweeney (2012) also found 66% reduction in tar yield of
gasification for dark roasted torrefied biomass as compared to raw biomass when gasified in a bubbling
fluidized bed gasifier.
This reduction can be explained as below. The lignin and the hemicellulose components in a lignocellulose
biomass make major contribution to the tar formation (Kiel et al., 2004). During torrefaction, most of the
hemicellulose is devolatilized and lignin is partially devolatilized. Thus when the torrefied product is gasified
less tar remains to be produced.
Studies done on the pyrolysis of lignin showed that major decomposition of lignin occurs within the
o
temperature range of 200-400 C (Beis et al., 2010). During this decomposition, aromatic hydrocarbons,
phenolic, hydroxyphenolics and guaiacyl/syringyl-type compounds, which mostly have phenolic-OH groups,
are formed. These constitute the bulk of the tar (Brebu and Vasile, 2009). During torrefaction, which occurs
o
between 200-300 C, some of these tar components are released thereby reducing the tar produced during
subsequent devoltilization of the torrefied biomass. Also as the heating rate is relatively low during
torrefaction, the rate of volatilization of lignin fragments is not sufficiently high to avoid formation of
5
768

secondary char (Brebu and Vasile, 2009). The secondary char is therefore formed, and since it is more
stable during devolatilization, the tar yield during devolatilization is less for torrefied biomass compared to
that for raw biomass.

Gasification

Devolatilization

torrefaction

Tar Yield (mg/g of raw biomass)

14
12
10
8
6
4
2
0
Raw biomass

Torrefied Biomass

Figure 5: Total tar yield during gasification of raw and torrefied biomass
Measured tar yield from gasification of char obtained from raw and torrefied biomass are 1.2 mg/g of raw
biomass and 0.1 mg/g of raw biomass respectively. This could be because of the lower reactivity of the
secondary char formed during torrefaction. Experimental results showed that the gas yield during gasification
is 0.775 g/g of raw biomass char as compared to 0.48 g/g of torrefied biomass char. The primary char,
formed during devolatilization of raw biomass reacts more quickly with steam producing gas and giving off
the phenolic group, main constituents of lignin, as tar. While torrefied biomass char being less reactive is
relatively more stable during gasification conditions and gives less gas as well as tar.
Gasification in bubbling bed
This section analyses results of continuous gasification of char in the bubbling fluidized bed. The gas sample
collected during experiments in bubbling bed is analysed for gas components hydrogen (H2), carbon
monoxide (CO), carbon dioxide (CO2), and methane (CH4). The effect of temperature on the gas yield,
composition and heating value of product gas is also discussed here.
Effect of gasification temperature on gas composition
Figure 6 shows the effect of gasification temperature on the concentration of hydrogen and carbon monoxide
in product gas. As seen in Figure 6, percentage of hydrogen and carbon monoxide increases with increase
in gasification temperature. As the temperature increases, it enhances the steam char reaction (C + H2O =
CO + H2) forming higher hydrogen and carbon monoxide (Gao et al., 2008; Rapagna and Latif, 1997). When
compared to raw biomass, torrefied biomass gasification shows higher concentration of hydrogen and lower
carbon monoxide in product gas. Sweeney (2012) also found a similar trend for the raw and torrefied
biomass. During torrefaction, non-condensable volatiles are mainly CO and CO2. So when torrefied biomass
is gasified, it gives lower CO and CO2 as compared to raw biomass. For this reason, CO concentration is
lower for torrefied biomass. This also results in higher H2/CO ratio in product gas for torrefied biomass
compared to raw biomass (Fig. 7). Also Fig. 7 shows that initially when the temperature is increased from
o
700 to 750 C, there is an increase in H2/CO ratio and it becomes more or less constant at higher
o
temperature. This is because the temperature range of 700-750 C still favours the water gas shift reaction
(CO + H2O = CO2 + H2) by which some CO is converted into hydrogen. Thus the H2/CO ratio increases in
6
769

this temperature range. But at higher temperature, the water gas shift reaction ceases resulting in more
constant H2/CO ratio.

H2 & CO in product gas (%)

70

H2_Raw
CO_Raw

60

H2_TB_250
CO_TB_250

H2_TB_275
CO_TB_275

50
40
30
20
10
0
650

700

750
800
850
Gasification Temperature (oC)

900

Figure 6: Effect of gasification temperature on H2 and CO concentration

H2 / CO ratio in product gas

2.20
Raw

TB_250

TB_275

2.00
1.80
1.60
1.40
1.20
650

700

750
800
Gasification Temperature (oC)

850

900

Figure 7: Effect of gasification temperature on H2/CO ratio

Figure 8 shows the effect of gasification temperature and torrefaction temperature on CO2 and CH4 content
of the product gas. Both CO2 and CH4 decrease with increase in temperature. The higher steam gasification
temperature favours reformation of the volatiles, resulting in lower CH4 in the product gas. During
torrefaction, as some of the volatile and CO2 are released, the concentrations of CO2 and CH4 are lower in
the product gas for torrefied biomass as compared to those for raw biomass.

7
770

CO2 & CH4 in product gas (%)

40

30

CO2_Raw

CO2_TB_250

CO2_TB_275

CH4_Raw

CH4_TB_250

CH4_TB_275

20

10

0
650

700

750
800
Gasification Temperature (oC)

850

900

Figure 8: Effect of gasification temperature on CO2 and CH4 concentration

Effect of gasification temperature on gas yield

Figure 9 shows the gas yield obtained from gasification of raw and torrefied biomass at different
temperature. It shows that with increase in gasification temperature, gas yield increases. Higher temperature
favours the steam char reaction resulting in higher gas yield. Also, tar formed during gasification is reformed
at higher temperature in presence of steam, therefore increasing the overall gas yield. Fig. 9 shows that the
gas yield for torrefied biomass is less than that for the raw biomass. During torrefaction, some of the gas is
released. So when it is gasified, the gas yield is lower. Additionally, the low char reactivity of torrefied
biomass resulted in a lower gas yield during gasification.

3.00
Raw

TB_250

TB_275

Gas Yield (Nm3/kg)

2.50
2.00
1.50
1.00
0.50
0.00
650

700

750

800

Gasification Temperature

850

900

(oC)

Figure 9: Effect of gasification temperature on gas yield

8
771

Effect of gasification temperature on gas heating value

Figure 10 compares the heating value of product gas obtained from raw biomass and torrefied biomass
gasification at different gasification temperature. The heating value of product gas from raw biomass
gasification is higher than that for the torrefied biomass. This is due to the fact that LHV of hydrogen, CO,
3
3
3
and methane are 10.78 MJ/Nm , 12.63 MJ/Nm and 35.88 MJ/Nm respectively. Lower hydrogen, higher CO
and higher CH4 in raw biomass product gas is responsible for the higher heating value. This difference is
even significant at higher gasification temperature. The energy loss during torrefaction process resulted in
lower heating value of the product gas obtained from gasification of torrefied biomass. Also as discussed in
tar section, more tar is released from raw biomass char gasification as compared to torrefied biomass. Some
of this tar component undergoes reformation adding more energy value to the product gas. As the tar
reformation is significant at higher temperature, so the heating value of product gas is higher for raw biomass
at higher temperature compared to torrefied biomass.

Heating Value of Product Gas(MJ/Nm3)

14.00
Raw

13.50

TB_250

TB_275

13.00

12.50

12.00

11.50
650

700

750
800
Gasification Temperature (oC)

850

900

Figure 10: Effect of gasification temperature on heating value

CONCLUSION
The study on gasification of torrefied biomass showed both positive and negative aspects of the process.
The positive side is the lower tar production during gasification. This can reduce the cost and effort for
downstream gas cleaning. Higher H2/CO ratio for torrefied biomass is another positive aspect of torrefied
biomass gasification. Higher H2/CO ratio product gas with small tar content makes it very suitable for
application such as biofuel production. On the other side, the lower char conversion, which leads to lower
gasification efficiency, could be a limiting factor for torrefied biomass. Kinetic studies showed that torrefied
biomass has reduced gasification reactivity due to the formation of secondary char during the process.
However, superior handling properties, hygroscopic and non-biodegradable nature, and an enhanced energy
density could well compensate some of its limitation, and make it more suitable fuel for gasification. Also,
study done here is for conventional dry woody biomass, but the difference in gasification output could be
minimal if fuels such as bio-waste, MSW, agricultural wastes are to be used for gasification. Handling,
heterogeneous nature and high moisture content is limiting the use of such opportunity fuel, which can be
eliminated by torrefaction and can make it more favourable for gasification.

9
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REFERENCES
Basu, P., 2013. Biomass gasification, pyrolysis and torrefaction: Practical design and theory, Second edition.
Academic press, an imprint of Elsevier, London NW1 7BY, UK.
Bergman, P.C.A., Boersma, A. R., Kiel, J. H. A., Prins, M. J., Ptasinski, K. J., and Janssen, F. J. J. G. 2004.
Torrefaction for entrained flow gasification of biomass. The 2nd World Conference and Technology
Exhibition on Biomass for Energy, Industry and Climate Protection, Rome, Italy.
Beis, H. S., Mukkamala, S., Hill, N., Joseph, J., Baker, C., Jensen, B. and Stemmler, E. A., 2010. Fast
pyrolysis of lignins. Bio Resources 5, 1408-1424.
Brebu, M. and Vasile, C., 2010. Thermal degradation of lignin a review. Cellulose chem. Technol., 44 (9),
353-363.
Couhert, C., Salvador, S., and Commangre, J-M., 2009. Impact of torrefaction on syngas production from
wood. Fuel, 88, 22862290.
Devi, L., Ptasinski, K. J., and Janssen, F. J. J. G., 2003. A review of the primary measures for tar elimination
in biomass gasification processes. Biomass and Bioenergy, 24, 125 140.
Dhungana, A. 2011. Torrefaction of biomass. M. A. Sc. Thesis, Dalhousie University, Halifax, Nova Scotia.
Fisher, E. M., Dupont, C., Darvell, L. I., Commandr, J.-M., Saddawi, A., Jones, J. M., Grateau, M.,
Nocquet, T. and Salvador, S. 2012. Combustion and gasification characteristics of chars from raw and
torrefied biomass. Bioresource Technology, 119, 157165.
Gao, N., Li, A., Quan, C., and Gao, F. 2008. Hydrogen-rich gas production from biomass steam gasification
in an updraft fixed-bed gasifier combined with a porous ceramic reformer. International Journal of Hydrogen
Energy, 33, 5430-5438.
Kiel, J.H.A., van Paasen, S.V.B., Neeft, J.P.A., Devi, L., Ptasinski, K.J., Janssen, F.J.J.G., Meijer, R.,
Berends, R.H., Temmink, H.M.G., Brem, G., Padban, N. and Bramer, E.A. 2004. Primary Measures to
Reduce Tar Formation in Fluidized-Bed Biomass Gasifiers. ECN-C-04014. The Netherlands, Energy
Research Center of the Netherlands (ECN).
Rapagna, S. and Latif, A. 1997. Steam gasification of almond shells in a fluidised bed reactor: the influence
of temperature and particle size on product yield and distribution. Biomass and Bioenergy 12, 281-288.
Sweeney, D. J. 2012. Performance of a pilot scale, steam blown, pressurized fluidized bed biomass gasifier.
Ph.D. Thesis, Department Of Mechanical Engineering, The University Of Utah, USA.
Prins, M. J., Ptasinski, K. J., and Janssen, F. J. J. G. 2006. More efficient biomass gasification via
torrefaction. Energy, 31, 3458-3470.
Svoboda, K., Pohorel, M., Hartman, M., and Martinec, J. 2009. Pretreatment and feeding of biomass for
pressurized entrained flow gasification. Fuel Processing Technology, 90, 629635.
Slopiecka, K., Bartocci, P., and Fantozzi, F. 2012. Thermogravimetric analysis and kinetic study of poplar
wood pyrolysis. Applied Energy, 97, 491-497.

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NOMENCLATURE
A
C
CO
CO2
CH4
EA
H2
H 2O
LHV
MSW
N
R
T

-1

Frequency factor [min ]

Carbon
Carbon monoxide
Carbon dioxide
Methane
Activation Energy [kJ/mol]
Hydrogen
Steam/moisture
Low heating value
Municipal solid waste
Normal atmospheric condition
Universal gas constant [J/mol/K]
Temperature [Kelvin]

11
774

THE NOVEL TECHNOLOGY FOR BIO-DIESEL PRODUCTION FROM COOKING

AND WASTE COOKING OIL BY HETEROGENEOUS CATALYSTS AND
MICROWAVE IRRADIATIONT
Teng-Chien Chen a, Ricky priambodo b, Yao-Hui Huang b, Aharon Gedanken c , Jiunn-Der Liao a*
a Department of Materials Science and Engineering, National Cheng Kung University, Tainan 701,
Taiwan
b Department of Chemical Engineering, National Cheng Kung University, Tainan 701,Taiwan
c Department of Chemistry, Kanbar Laboratory for Nanomaterials, Institute of Nanotechnology and
Advanced Materials, Bar-Ilan University, Ramat-Gan, Israel 52900
* jdliao@mail.ncku.edu.tw

ABSTRACT
In the transitional process, acid or base catalysts are common technology to produce bio-diesel
from waste cooking oil; however, the catalysts only can be use one time. Highly reaction time is
requirement for the transitional technology. For improvement these concern issues, this study applied
a novel technology to create bio-diesel product from cooking oil and waste cooking oil by microwave
irritation. The microwave irradiation can provide strong power and reach reaction temperature in a
short time. The SrO catalyst is a heterogeneous catalyst which is not dissolution into any liquid
solution therefore, it can be recycling and reusing again.
In this research, the optimum conditions were using commercial SrO, 40 to 180 seconds reaction
time, around 80oC reaction temperature, 6 methanol to oil ratio, and 1000W microwave power output.
99% and 93 % biodiesel conversion efficiency for cooking oil and waste cooking oil were reached
within in these conditions. The determined specifications of obtained biodiesel according to ASTM
D6751 and EN14214 standards were in accordance with the required limits. As a conclusion, the
present study indicates that derived fuel promises being an alternative for diesel, and could be used
in engines without a major modification due to its qualifications.
Keywords: Waste cooking oil; SrO catalyst; Microwave irradiation; Bio-diesel .
INTRODUCTION
One hundred years ago, Rudolf Diesel tested vegetable oil as fuel for his engine (shay.1993). With
the advent of cheap petroleum, appropriate crude oil fractions were refined to serve as fuel and diesel
fuels and diesel engines evolved together. In the 1930s and 1940s vegetable oils were used as diesel
fuels from time to time, but usually only in emergency situations. In the past three decades, the
increasing world population and rapid industrial developments have drastically increased the
consumption of fossil fuel derived oils. The current use of fossil fuels in various sectors for heat and
power generation continues to threaten global stability and sustainability (Dov` et al., 2009;Battaglini
et al., 2009). Thus, countries around the world have devoted their resources to solving the shortage of
fossil fuel energy and lowering energy costs. The oil price trendy was shown in Fig .1.
In general, the predominant energy policies have been divided into two categories: (1) the
development of renewable energy resources and (2) the recycling and reuse of waste energy.
As an important aspect of the interaction between nature and society, energy is a major concern for
economic development. In the last two decades, the consumption of fossil fuels has markedly
increased as a result of the increasing world population and rapid technological development.
Unfortunately, the current use of fossil fuels in various sectors for heat and power generation
threatens global stability and the global economys sustainability. To eliminate toxic exhaust and to
develop sustainable fossil fuel energy, countries around the world have devoted much effort to
lowering their energy costs. Recycling and reusing waste energy is essential to achieving this
objective (Tsai and Chou, 2004; Tsai, 2010).

775

Fig.1. The trendy for Oil Price from 2008 to 2011.

As a result, there is increasing interest in developing alternative energy resources, which include
hydrogen cells (Penner, 2006), solar energy (Kruse et al., 2005), and wind power (Blackler and Iqbal,
2006). However, these technologies are still at the developing stage and the cost of applying them is
high. Biomass is the only renewable energy resource that can lead to competitive prices for liquid
fuels in transport. The main benefits of using this renewable resources are the increased
environmental protection, lower emissions, new jobs opportunities, lower level of oil imports (67% of
oil is for transportation fuels), increased safety of fuel supply (Demirbas, 2009).
The conversion of renewable biomass in biofuels are more and more attractive, and obtaining /
using unconventional fuels, such as biodiesel, as alternatives to fossil fuels is an important scientific
and technological goal, in a world where pollution has reached more and more alarming levels and oil
reserves are becoming more and more limited.Bio-diesel, which is made from renewable biological
sources,has gained importance as an alternative energy source. When consideringthe pollution
caused by the combustion of conventional petroleum-based diesel (McKendry, 2002; Reijnders,
2006), a shift to non-conventional sources such as bio-diesel is inevitable. Biodiesel, which consists
of fatty acid methyl esters (FAME), has lower CO, CO2 and hydrocarbon emissions; in addition, it is
non-toxic and biodegradable (Barnard et al., 2007).
Bio-diesel, which consists of fatty acid methyl esters (FAME), has lower CO and hydrocarbon
emissions; in addition, it is nontoxic and biod egradable.The lifecycle of energy balance for biodiesel
is about 3.2:1 (biodiesel yields 3 units of fuel energy for every one unit of fossil energy consumed in
its lifecycle) Today, the global biofuels market consists of approximately 85% bio-ethanol and 15%
biodiesel.
Biodiesel is the result of a simple trans-esterification reaction using vegetable oil and methanol as
substrates (Fig. 2). The most commonly used catalysts in trans-esterification reactions are NaOH,
KOH and H2SO4. The starting oil and methanol are generally heated and stirred with the catalyst or
else, in the case of the basic catalysts, the base is first dissolved in the methanol prior to addition.
Trans-esterification is not the only route to production of fatty acid methyl esters. An alternative
approach is to hydrolyze all tri-glycerides to free fatty acids, and then directly esterify these fatty acids
with methanol. However, trans-esterification is the process of choice in the majority, if not all, of the
commercial biodiesel production facilities that have come on line. The Preparation of biodiesel by
trans-esterification was shown in the Fig.2.

Fig 2. Preparation of biodiesel by trans-esterification

The increasing production of cooked oils from household and industrial sources is a growing
problem in Taiwan and all around the world. This residue is regularly poured down the drain, resulting
in problems for wastewater treatment plants and energy loss, or is integrated into the food chain
through animal feeding, thus becoming a potential cause of human health problems (Costa Neto et
al., 2000). The cooked oil will become the major material to make bio-diesel.

776

There are many different types of catalyst to create the bio-diesel, including, acid-catalyzed,
base-catalyzed, heterogeneous catalysts, and enzymatic.The most common way to produce biodiesel is to transesterify triglycerides in vegetable oil with alcohol in the presence of an alkali or acid
catalyst (Vicente et al.,2005; Serio et al., 2005; Peiro et al., 2008). Catalytic reactions can use alkali
catalysts, acid catalysts, or enzymatic transesterification, of which the first achieves the best results.
Biodiesel can be produced at a lower temperature and shorter reaction time with an alkali catalyst
compared to those required for an acid catalyst (Fukuda et al., 2001.,Dmytryshyn et al.,2004.,
Saifuddin et al.,2004.,Vicene et al., 2004)
Sodium and potassium hydroxide are commonly used as base catalysts, but there are many
obstacles to their utilization (Yang et al., 2008; Sun et al., 2008; Rashid and Anwar, 2008).Acidic
catalysts are also being used for the transesterification reaction. However, despite the increase in the
yield of the bio-diesel, the acid catalyzed reaction is much slower than the alkali catalyzed reaction,
and it also requires higher temperatures and pressures (Serio et al., 2007; Talukder et al., 2009).
Heterogeneous (solid) catalysts is the general advantage of easy separation from the reaction
medium and reusability. Heterogeneous catalysis is thus considered to be a green process. The
process requires neither catalyst recovery nor aqueous treatment steps: the purification steps of
products are then much more simplified and very high yields of methyl esters, close to the theoretical
value, are obtained. Glycerin is directly produced with high purity levels (at least 98%) and is exempt
from any salt contaminants (Bournay et al., 2005).
Many types of alkaline earth metal oxide catalysts can catalyz transesterification reactions. The
order of activity between alkaline earth metal oxide catalysts is BaO > SrO > CaO > MgO (Seki et al.,
2001; Cantrell et al., 2005).MgO and CaO have a low activity in the transesterification of vegetable
oils to bio-diesel and provide a slow reaction rate. BaO is noxious and can be dissolved by methanol.
Therefore, BaO is not suitable for bio-diesel production (Buyevskaya and Baerns, 1998).
SrO is insoluble in vegetable oil, methanol, and fatty acid methylester. Despite the lower surface
area of SrO as reported elsewhere (Patil and Deng, 2009) there are other factors that cause the high
activity of SrO. Besides the specific surface area, alkalinities, and acid/base sites of alkaline earth
metal oxides affect also the activity of the catalyst (Patil and Deng, 2009).
Disadvantages and advantages for different types of catalyst are summarized in the table 1:
Table 1: summarize disadvantages and advantages for different types of catalyst
Catalyst
Advantage
Disadvantage
Base-catalyzed Base-catalyzed
It is sensitive to FFA content
transesterification is the most
of the feedstock oils. A high
commonly used technique as it is
FFA content (> 1 % w/w) will
the most economical process
lead to soap formation
since it requires only low
Reduces catalyst efficiency,
temperatures and pressures;
causes an increase in
produces over 98 % conversion
viscosity,
yield(provided the starting oil is
leads to gel formation and
low in moisture and FFA)and
makes the separation of
Direct conversion to biodiesel
glycerol difficult
with no intermediate compounds;
also, no special materials of
construction are needed (Singh et
al, 2006)
Acid-catalyzed
They can directly produce
High alcohol to oil molar ratio,
biodiesel from low-cost lipid
high catalyst concentration
feedstock generally associated
and high temperature.
with high FFA concentrations,
The reaction is relatively slow
including waste frying oils (Lotero
and the catalyst ends up in the
et al., 2005)
byproducts causing serious
separation problems.
All these factors in addition
to the serious environmental
and corrosion-related
problems limit their use.
Heterogeneous The general advantage of easy
Heterogeneously catalyzed
catalysts
separation from the reaction
transesterification generally
medium and reusability.
requires more severe operating
conditions(relatively elevated
Heterogeneous catalysis is thus
considered to be a green process. temperatures and pressures)
The performance of
heterogeneous catalysts is

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Enzymatic

There is a current interest in

using enzymatic catalysis to
commercially convert vegetable
oils and fats to FAME as biodiesel
fuel, since it is more efficient,
highly selective, involves less
energy consumption (reactions can
be carried out in mild conditions)
and produces less side products or
waste (environmentally favorable)
(Akoh et al., 2007)

generally lower than that of the

commonly used homogeneous
catalysts.
One of the main problems
with heterogeneous catalysts is
their deactivation with time
owing to many possible
phenomena, such as
poisoning, coking, sintering
and leaching (Sivasamy et al.,
2009).
The drawbacks of enzymatic
catalysts are significantly
higher production cost (Meher
et al., 2006) as well as difficulty
during manufacturing due to
the need for a careful control of
reaction parameters (Cerver
et al., 2008).
For the use of enzymes, there
are some critical factors: There
is a minimum water content
needed by the lipase, below
which it does not work;
alcohol has an effect on the
reaction, being methanol the
most commonly employed; the
effect of temperature effect is
significant because instead of
increasing the reaction rate by
increasing temperature,
enzymes can become
denatured at high
temperatures;
Obviously the raw material
is important, because not all
oils have the same amount or
type of fatty acids and lipase
specificity can become more
attractive in some oils than in
others (Cerver et al., 2008).

An issue with using a trans-esterification approach to biodiesel manufacture is that the

reaction can be slow to reach completion and also because it is an equilibrium an excess of methanol
is often used to drive the reaction towards formation of products. Trans esterification is usually
conducted by conventional heating for introducing energy into reactions. Recently, the microwave
dielectric heating effect was used as an alternative heating source to conventional heating for driving
the trans esterification reaction (Barnard et al., 2007; Smith et al., 2009). Indeed, one approach that
has been taken to accelerate the reaction is the use of microwave heating as a tool.
In this research, leveraging the rapid reaction times, it is possible using microwave heating and
the inherent advantages of using a heterogeneous catalyst, it will be possible to develop a very rapid,
easy method to high-throughput biodiesel production form fresh cooking oil and waste cooking oil.
Materials and Methods
Materials:
The fresh cooking oil was mustard oil which was purchased in supermarket. Waste cooking oil
were collected from restaurants in Taiwan and then filtered to remove any inorganic residues and
suspended matters. All the chemicals used in experiments were purchased from Merck chemicals.
The certified reference standards for Gas Chromatography (GC) were purchased from Sigma-Aldrich.
The microwave oven was Panasonic NN-SF550, and also was modified Taiwan. The maximum
input power was 1000W. The Fig 3 was the modified microwave.

778

Fig. 3.The microwave reactor system for bio-diesel making

Methods:
All the experiments were carried out at least three times in order to determine the variability of the
results and to assess the experimental errors. In this way, the arithmetical averages were calculated
for all the results which had an experimental error of less than 0.5%. Experiments was repeated at
various conditions such as, catalyst concentration (1.4 3.25 wt.% of Oil), reaction time (1-4 min),
methanol/oil molar ratio (4:1-10:1) were studied.
Analysis Methods:
The fuel characteristics of the final biodiesel product were determined according to the ASTM D
6751, EN 14214 standard test methods. Methyl ester content is defined as below:

A -A

EI

C=

AEI

CEI
X 100%
m

where C: Total fatty acid methyl ester content (mg mg-1); A: sum of peak area of fatty acid methyl
ester from C14 to C24:1 ; AEI : peak area of internal standard, heptadecanoic acid acid methyl ester;
CEI : concentration of heptadecanoic acid methyl ester (mg ml-1); VEI : Volume of heptadecanoic acid
acid methyl ester (ml-1); and m: mass of input biodiesel (mg). Then, biodiesel yield was calculated
relative to the initial amount of waste cooking oil by weight. Similar calculations were used by others
(Zhang et al., 2010; Azcan et al., 2008; Suppalakpanya et al., 2010a.b).
Result and Discussion:
Effects of catalyst concentration on biodiesel yield:
The catalyst concentration is an important parameter in the bio-diesel making. In this part, the
reaction temperature of 80oC, reaction time of 40 sec, and methanol/oil molar ratio of 6:1, and
agitation intensity of 600 rpm were maintained as constant with heterogeneous catalyst (SrO)
concentrations (1.42wt%-3.25wt% of oil) for the production of bio-diesel. The results are given in
Fig.4.
As shown, the maximum biodiesel yield was obtained as 99.1% with 1.85 wt. % SrO, and the
bio-diesel conversion efficiency was decrease dramatically as addition more than 1.85 wt. % SrO.
This can be explained as addition of excess amount of catalyst caused more triglycerides
participating in the saponification reaction and caused the formation of soap in presence of high
catalyst concentration and a slight decrease in biodiesel yields.

779

Fig.4. : Effects of catalyst concentration on biodiesel

Effects of reaction time on biodiesel yield:

In this part, to measure the effect of reaction time on formation of methyl esters, various
experimental reaction times were carried out from 40 to 160 sec at catalyst concentration of 1.85
wt. SrO, reaction temperature around 80o C, molar ratio of methanol to oil 6:1, and the speed of
magnetic stirring in 600 rpm. The experimental results are shown in Fig. 5.

Fig.5. Effects of reaction time on the biodiesel making

As seen, biodiesel yield increased with reaction time at the beginning, reached at a yield of
99.3% in the first 40 sec and was also the best conversion efficiency, and then decreased
dramatically with increasing reaction time. Due to longer reaction times led the hydrolysis of esters
and caused more fatty acids to produce soap (Leung et al., 2006). According to experiment results,
reaction time had a significant effect on the conversion of the triglycerides up to 40 sec, but
increasing further the reaction time had decreased the biodiesel yield. Due to reaching the
maximum biodiesel yield as 99.3 %, 40 sec was selected as the optimal reaction time for cooking
oil transesterification in the present conditions.
Effect of methanol-to-oil molar ratio
In order to investigate the effect of molar ratio on biodiesel yields, experiments were conducted
with various molar ratios ranging from 3:1 to 12:1 with a constant catalyst concentration of 1.85
wt.% SrO, reaction time of 40 sec, reaction temperature of 80o C, and the speed of magnetic
stirring in 600 rpm. The stoichiometric molar ratio of methanol to oil is 3:1. In bio-diesel making
processes with heterogeneous catalysis, mass transfer and the adsorption of reactants onto the
catalyst play an important role. Moreover, the transesterification reaction consists of a sequence of

780

three consecutive reversible reactions. Thus, the methanol-to-oil molar ratio should be larger than
that of stoichiometric molar ratio in order to shift the equilibrium conversion of the reaction. The
effect of methanol-to-oil molar ratio on the bio-diesel conversion efficiency was shown in Fig. 6. As
seen, the stoichiometric ratio (3:1) was the lowest biodiesel conversion efficiency as
48.34%.During the experimental study, the best biodiesel conversion efficiency was 6:1methanol:
oil molar ratio. This result was similar with previous studies (Ma et al.,1999; Meher et al., 2006).
Nevertheless, increasing the molar ratio more than 6:1 reduced the biodiesel conversion efficiency.
Due to excess methanol increased the solubility of glycerol; this caused the interference of a little
amount of glycerol with the ester phase. The diluted glycerol in ester phase leaded more foam
formation with the lower product (Predojevic et al., 2008).

Fig.6. methanol-to-oil molar ratio on the biodiesel making

The bio-diesel conversion for soybean oil and waste cooking oil
In this research, the optimal condition for the fresh cooking oil was 99.3% in the condition of
1.85 wt. % SrO, 6:1 methanol: oil molar ratio, and 40 second microwave irrational time. In the
section, the bio-diesel conversion efficiency for waste cooking oil was also evaluated in this study.
According to Freedman et al. (1984) studied the influence of the free fatty acids (FFA) and
water content in the production process of biodiesel. They found that the oil acid value should be
less than 1 mg KOH/g and that all raw materials should be anhydrous (water content <0.3%). If
these requirements are not met it is still possible to produce biodiesel, but the reaction is reduced
due to the deactivation of the catalyst and the formation of soaps. Due to waste cooking oil was
degradation by hydrolytic and oxidative reactions, both processes being responsible for changes in
the chemical and physical properties, as compared to the fresh oil (Costa Neto et al., 2000). In this
research, the acid value for waste cooking oil was upto 2.02mg KOH/g, and the water content was
around 1%. This waste cooking condition will affect the worse bio-diesel efficiency than fresh
cooking oil. Figure 7 showed the best bio-diesel conversion efficiency form waste cooking oil was
around 93% in the conditions of 1.85 wt.% SrO, 6:1 methanol: oil molar ratio, and 3 minutes
microwave irrational time. This situation was similar with Costa Neto et al. experimental result.

781

Fig. 7. methanol-to-oil molar ratio on the biodiesel making

Conclusion:
The study of transesterification reaction of fresh cooking oil and waste cooking oil showed that
the main factors affecting the process are the molar ratio methanol / oil, the catalyst amount, and
the reaction time. From the obtained results, using the conventional technique, the best bio-diesel
99% and 93% for the production of biodiesel from fresh cooking oil and waste cooking oil were
obtained using a methanol/oil molar ratio of 6:1, SrO as catalyst (1.85%), and a reaction time 40
seconds and 3 minutes.
The results showed that application of radio frequency microwave energy offers a fast, easy
route to this valuable biofuel with advantages of enhancing the reaction rate and improving the
separation process. The reaction time was reduced to 40 seconds for fresh cooking oil and 3
minutes for waste cooking oil instead of 150 minutes in previous experiment, because, by using
the microwave technique, no pretreatment is required. The methodology also allows for the use of
high free fatty acid content feedstock, including waste cooking oil. Although, the bio-diesel
conversion efficiency for waste cooking oil was less than fresh cooking oil, it was still useful for
bio-diesel production. The heterogeneous catalysts and microwave irradiation provide new and
efficiency method to create energy sources via bio-diesel recovery and utilization technologies
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785

Production of Bioelectricity in MFC by Pseudomonas fragi DRR-2 (Psychrophilic)

isolated from goat rumen fluid
1a

1b

Deepika Jothinathan , Richard Thilagaraj Wilson*

Department of Biotechnology, School of Bioengineering, SRM University, Kattankulathur, 603 203,

India
a
b
Email address: deep.friend3@gmail.com , richard.thilagaraj@gmail.com

ABSTRACT:
Microbial Fuel Cell (MFC) is a promising technology for the production of sustainable energy.
Almost all wastewater and waste have been tried out as the raw material for the energy
production under mesophilic conditions. However, there are very few reports pertaining to the
study of MFC operating at low temperatures. The present study focuses on bioelectricity
production by Pseudomonas fragi DRR-2, psychrophilic gram-negative bacteria isolated from
goat rumen fluid. The experiments were conducted at four different temperatures namely 4C,
10C, 20C and room temperature (around 30C) at neutral pH. The maximum voltage of
510mV was obtained on the tenth day at 20C, 320mV at 10C and 250mV at 4C
respectively. The growth curve and total protein of P.fragi were estimated and the results
were correlated with the voltage graph. The SEM analysis confirmed that the bacteria
produced biofilm which act as an electron carrier at the anode. The redox potential was
calculated using cyclic voltammograms which confirms that the bacterium is electrochemically
active. Based on the experimental results, it was observed that P. fragi produced more
electricity at 20C. This is the first hand information of power production by P.fragi at low
temperatures.

1. INTRODUCTION
In the rumen ecosystem, wide range of bacterial community habitats with different
temperature gradients shows complex metabolic function, such as physical, physiological and
environmental factors. Ruminants feed on various cellulosic materials with different
composition which leads to acquire different microbial consortia. Some of the cold adapted
microorganisms (Psychrophilic) would have entered through frozen cellulosic sources. These
microorganisms tend to adapt in the rumen system with different temperature gradients
thereby showing shift from cold to warm and warm to cold conditions. The physiology of these
cold adapted microorganisms (psychrophilic) and its metabolic activity at different
temperatures are not well studied.

The production of bioelectricity using psychrophilic bacteria at low temperature has recently
gained attention. The power production by microbial fuel cells (MFCs) will require optimum
conditions such as temperature, pH, substrate concentration and microbial consortium. The
substrate depletion and temperature adaptation of microorganisms varies species to species
during MFC experiments. According to Pomeroy & Wiebe (2001), the effect of temperature on
*Corresponding author: Richard Thilagaraj, Wilson., Department of Biotechnology, School of Bioengineering, SRM
University, Kattankulathur, 603 203, India
786

bacterial growth is resource dependent which leads to growth pattern with respect to low
temperature with high resources as well, high-temperature with low-resources.

Over the period of time, MFC has been examined at ambient temperature with different
microbes. There are many bacteria isolated from different places other than rumen such as
Rhodoferax ferrireducens (Chaudhuri and Lovely, 2003), Shewanella putrefaciens (Kim et al,
2002), Geobacter sulfurreducens (Bond and Lovely, 2003) and Desulfobulbus propionicus
(Holmes et al, 2004) has been reported for power production in MFC. A recent study has
focused on bioelectricity production from Geopsychrobacter electrodiphilus gen. nov., sp. nov.,
a psychrotolerant bacteria which can grow between 4C and 30C with an optimum
temperature of 22C (Dawn E. Holmes et al, 2004). Rhodoferax ferrireducens is capable of
transferring electrons to electrodes at 4C in a mediatorless Microbial Fuel cell (Chaudhuri
and Lovely, 2003). Previous studies shows that mesophilic bacteria shows higher growth rate,
higher electron transfer, shorter lag phase and lower respiration which is not found in low
temperature adapted microbes (Edward K. Hall et al, 2010).

There are many cold adapted microorganisms (psychrophilic) present in our environment
which need to be explored for MFC research. The purpose of this study was to investigate
bioelectricity generation by Pseudomonas fragi, psychrophilic bacterium under low
temperature. Based on the experimental results, it can be concluded that the bacteria showed
higher growth rate, higher electron transfer and shorter lag phase. This is the first report on
Pseudomonas fragi for the production of bioelectricity at low temperature which is discussed
in this paper in detail.
2. MATERIALS AND METHODS
2.1. Isolation of Bacteria from the Anodic Biofilm
Bacteria were isolated from the anodic biofilm of a double-chambered pre-run MFC with
rumen fluid as anodic substance. They were isolated by serial dilution method and colonies
-6

-8

were taken from dilution 10 to 10 based on the colony morphology. The bacteria were then
sub cultured many times to obtain pure culture which was maintained in nutrient agar slants for
further use.
2.2. Identification of Bacteria by Biochemical Tests and 16S rRNA Sequencing
The bacterial isolate which was taken for the study in Microbial fuel cell was tested in various
biochemical tests and 16S rRNA sequencing was done to identify the genus and species of the
bacteria using the primers: Forward-8F (5-GAGTTTGATCATGGCTCAG-3) Reverse-1495r(5CTACGGCTACCTTGTTACG-3). The partial sequence was submitted to NCBI and the accession
number has been given.
2.3. Growth curve and protein content by Pseudomonas fragi DRR-2 at different
temperatures

787

Pseudomonas fragi overnight culture is inoculated in 5ml nutrient broth and incubated at four
temperatures namely 4C, 10C, 20C and Room temperature (around 30C) and has been
checked for the growth every 24 hours for 15 days and the absorbance was measured at
600nm. In parallel, the total protein content of the culture in all the temperatures was
estimated by Lowrys method (Oliver H. Lowry, 1951).
2.4. Construction of MFC
A two chambered MFC made up of plastic with the dimension of 15 cm height X 7 cm
diameter has been designed for the experiments. Carbon electrodes of diameter 1.5 and 13
cm long served as both anode and cathode. The electrodes were initially treated with 0.1N
HCl overnight before using for the experiment and cleaned with 0.1N NaOH after the
completion of experiment. They were suspended in the liquid from the top in both the
chambers. The anode compartment was filled with 500 mL of nutrient broth and 1%
preinoculum of Pseudomonas fragi DRR-2 was inoculated in four different MFCs respectively.
The cathode compartment was filled with distilled water which acted as air cathode. Both the
compartments were connected with a 0.5 cm diameter and 14 cm long tube which was filled
up with salt bridge made of sodium chloride and agar in the ratio of 1:2.
A rectangular shaped MFC made of acrylic with reactor volume of 300ml each was used
for the pure culture study in different temperatures. Pre-treated carbon paper and Nafion 117
membrane replacing the salt bridge was employed in this model. The membrane of diameter
6cm was treated with acids to remove the chemicals before placing them in the membrane
holder. The anode compartment was filled with 300ml nutrient broth with 1% preinoculum of
Pseudomonas fragi DRR-2 and cathode with 300ml distilled water and the entire MFC has
been incubated at different temperatures.
2.5. Pure Culture MFC
Microbial fuel cell with both salt bridge and Nafion membrane 117 as proton exchanger were
performed and after the addition of the preinoculum, the reactors were incubated at four
different temperature respectively.The potential and current readings were measured using a
digital multimeter every 24 h for 15 days.
2.6. Electrochemical Activity of the Bacterial Biofilm
To confirm the presence of electrochemical activity of the anodic bacteria, the electrodes
were taken after 15 days and the cyclic voltammograms were recorded in 100 mM phosphate
buffer pH-7.0 (61.5 mL of 1M Dipotassium hydrogen phosphate and 38.5 mL of 1M
Potassium dihydrogen phosphate were taken and made up to 1 litre with distilled water).The
redox potential was measured in the presence of phosphate buffer pH-7.0 in the absence of
microorganisms by cyclic voltammetry using a SP300 (Biologic Instrument) (Park et al.,
2001; Cuong et al., 2003). Measurements were made at different sweep rates of 2mV/s,
5mV/s and 10mV/s in a three-chambered electrochemical cell consisting of working electrode

788

(Anode of surface area 61.28 cm ), a counter electrode (platinum electrode) and an Ag/AgCl
reference electrode.

2.7. Scanning Electron Microscopy analysis

The samples were carefully removed from the MFC setup and the biofilm coated on the
carbon sheet (Anode) were analysed using FEI Quanta FEG 200- High resolution Scanning
Electron Microscope after 15 days growth of Pseudomonas fragi DRR-2 in anode.

3. RESULTS AND DISCUSSION

3.1 Isolation and Identification of the bacterial strain

The bacteria which was isolated from the anodic biofilm of pre-run rumen fluid MFC was
identified by various biochemical tests and 16S rRNA sequencing. By the BLAST search, the
bacteria was identified as Pseudomonas fragi, pschrophilic bacteria. The accession number
of the bacterial strain was obtained from NCBI and the number is KJ000741.The phylogenetic
and molecular evolutionary analysis was done using MEGA software 6.0 (Koichiro Tamura et
al, 2013) and the tree has been represented in Figure 1. From the phylogenetic tree, the
Pseudomonas fragi shows 99% sequence similarity with Pseudomonas psychrophila.

Figure 1: Phylogenetic position of Pseudomonas fragi DRR-3 with the related genus.
The phylogenetic tree was constructed using MEGA 6.0 software with the available
sequences in database.

789

3.2 Growth Curve and protein content of Pseudomonas fragi DRR-2 at different
temperatures
The bacterial growth was measured every 24 hrs for a period of 15 days at different
th

temperatures.The maximum growth was observed on the 6 day at 20C. The protein content
th

was maximum on 6 day at 10C whereas for other temperature grown bacteria shows less
content. This confirms that the optimum temperature for growth is 20C and the bacteria has
the ability to grow in low temperatures (>4C). At all the temperatures the total protein was
th

th

observed to be highest between the 6 day and 10 day. Figure 2 a) and 2 b) shows the
growth curve and total protein of Pseudomonas fragi DRR-2 at low temperatures.

Figure 2 a): Growth curve of Pseudomonas fragi DRR-2at different temperatures

Figure 2 b): Total Protein of Pseudomonas fragi DRR-2 at different temperatures

790

Under high nutrient conditions, bacteria tend to alter their membrane lipid composition to
adapt to the changing temperatures (van de Vossenberg et al. 1999), by the method known
as homeoviscous adaptation (Sinensky 1974). According to Edward et al, 2010 report, the
membrane fluidity plays a main role in the proton motive force. At low temperatures,
membranes can be highly firm and prevent the efficient function of transmembrane proteins,
important for resource utilisation. However, in bacteria the cellular membrane is also used to
create an electro-chemical gradient, which makes the synthesis of ATP as protons move
down the proton gradient into the cell. As membrane lipids plays a main role in the maintain
the membrane fluidity

it has been observed that the organisms dominated in cold

environments are rich in MUFA or branched chain fatty acids while organisms in warmer
environments have Saturated fatty acids (SAFA) (Kaneda, 1991). Mesophilic bacteria shows
higher growth rate, higher electron transfer, shorter lag phase and lower respiration which is
not found in low temperature adapted microbes (Edward et al, 2010). Our experimental
results confirms that Pseudomonas fragi (Psychrophilic) shows higher activity at low
temperature (10C) where the protein concentration was found to be maximum.

3.3 Microbial Fuel Cell performance of Pseudomonas fragi DRR-2 using salt bridge as
proton exchanger:
th

The bacterium produced a maximum voltage of 540mV on the 10 day at 20C indicating that
the favourable temperature for the growth gave the maximum electricity production. The
maximum current was only 20mA since salt bridge was used as the proton exchanger due to
higher internal resistance. Compared to the room temperature, the bacteria produced more
voltage in low temperatures.

791

Figure 3 a): Potential of Pseudomonas fragi DRR-2 at low temperatures using salt
bridge

Figure 3 b): Current of Pseudomonas fragi DRR-2 at low temperatures using salt bridge
3.4 Microbial Fuel Cell performance of Pseudomonas fragi DRR-2 using Nafion 117
membrane as proton exchanger:
th

A maximum voltage of 380mV on the 10 day at 20C and a maximum current of 70mA on
th

the 7 day at 4C confirms that the bacteria is active at low temperatures between 4C to
20C. When compared to the salt bridge, Nafion 117 membrane gave a maximum current,
indicating that the internal resistance of the fuel cell is decreased thereby improving the cell
performance. Geopsychrobacter electrodiphilus produced a maximum current of 3.73 mA/cm

when acetate was provided as the electron donor (Dawn E. Holmes et al, 2004). Rumen
microbes when they grow in low temperatures tend to produce less methane comparatively to
the mesophilic conditions (Graham et al, 1959 & Kennedy and Milligan, 1978). Based on the
above information, we prove that the isolated strain might have produced less methane and
more hydrogen for the electron and proton transfer. This may be the reason for the increased
bioelectricity production of P. fragi at low temperatures.

792

Figure 4 a) Potential of Pseudomonas fragi DRR-2 at low temperatures using Nafion

117

Figure 4 b) Current of Pseudomonas fragi DRR-2 at low temperatures using Nafion 117

3.5 Electrochemical nature of the biofilm in low temperatures

The Cyclic voltammograms of the anodic biofilm clearly gives a anodic potential and cathodic
potential. This confirms that the bacteria grown in low temperatures exhibit a sigmoidal curve
indicating that they are electrochemically active in nature. Figure 5 A) B) and C) shows the
voltammogram of the anodic biofilm. From the voltammograms, it has been observed that at
4C, a sharp oxidation peak at 0.04V was found indicating the maximum substrate utilisation
of the microbe has taken place at low temperature. At the same time, a reduction peak at 0.2V reveals that there the electron transfer has taken place. However, the electron transfer
was found to be maximum at 20C and the corresponding voltammogram confirms it with
three reduction peaks in the reverse scan at -0.14V, -0.8V and -0.6V.

793

5 (A)

5 (B)

794

5 (C)
Figure 5 (A), (B) and (C) Cyclic voltammograms of the bacterium at low temperature
(4C, 10C and 20C)

3.6 SEM analysis of the anodic biofilm

The anode subjected to scanning electron microscope analysis shows the biofilm formation
attached on the surface of the electrode. From this image, it was found that biofilm was
spreaded on the carbon sheet which facilitates bioelectricity production. Figure 6 a) shows the
plain carbon sheet (Control) and figure 6 b) shows bacteria adhering to the surface of the
carbon sheet. A thick biofilm of Aeromonas hydrophila PA3 on the anode surface with uniform
cells was observed through SEM. It has been reported that the the biofilm has contributed for
the maximum current (Cuong Anh Pham et al, 2003).

795

Figure 6 a) Scanning electron

micrograph of the carbon sheet (Control) b) Pseudomonas fragi growth on carbon
sheet.

4. CONCLUSION
Pseudomonas fragi, a known psychrophilic bacteria was subjected to different low
temperatures namely 4C to 20C in MFC operation. The effect of temperature plays a main
role in this study which was proven by the experiments done for MFC. The cold adapted
microbes maintain the membrane rigidity by different lipid composition. At low temperature,
the bioelectricity production is higher when compared to the room temperature (around 30C).
This indicates that the power production is directly proportional to the bacterial growth which
solely depends on the optimum temperature. For the effective performance of MFC, microbial
adaptation plays a vital role. This study has contributed a MFC with a psychrophilic bacteria
which can be used in remote places with low temperature.

5. ACKNOWLEDGEMENTS

796

We are very much thankful to the Head of the Department, Chemistry, SRM University for
providing us the Instrumentaton facility for the cyclic voltammogram experiments. We wish to
convey our special thanks to Nanotechnology Research Centre, SRM University for helping in
the Scanning Electron Microscope images.

6. REFERENCES

Bond, D. R.; Lovley, D. R., 2003, Electricity Production by Geobacter sulfurreducens Attached
to Electrodes Applied and Environmental Microbiology, 69:1548-1555.
Chaudhuri, S. K., and D. R. Lovley. 2003. Electricity generation by direct oxidation of glucose
in mediatorless microbial fuel cells. Nature Biotechnology. 21:12291232.
Cuong Anh Pham., Sung Je Jung., Nguyet Thu Phung., Jiyoung Lee., In Seop Chang., Byung
Hong Kim., Hana Yi., Jongsik Chun., 2003. A novel electrochemically active and Fe(III)reducing bacterium phylogenetically related to Aeromonas hydrophila, isolated from a
microbial fuel cell. FEMS Microbiology Letters 223: 129-34.
Dawn E. Holmes, Julie S. Nicoll, Daniel R. Bond and Derek R. Lovley., 2004. Potential Role
of a Novel Psychrotolerant Member of the Family Geobacteraceae, Geopsychrobacter
electrodiphilus gen. nov., sp. nov., in Electricity Production by a Marine Sediment Fuel Cell.
Applied and Environmental Microbiology, 70(10): 60236030.
Edward K. Hall, Gabriel A. Singer, Martin J. Kainz and Jay T. Lennon, 2010. Evidence for a
temperature acclimation mechanism in bacteria: an empirical test of a membrane-mediated
trade-off. Functional Ecology, 24 (4): 898908.
Gilichinsky, D.; Rivkina, E.; Bakermans, C.; Shcherbakova, V.; Petrovskaya, L.; Ozerskaya,
S.;Graham, N. M., Wainman, F. W., Blaxter, K. L. and Armstrong, D. G.,1959, Environmental
temperature, energy metabolism and heat regulation in sheep. I. Energy metabolism in
closely clipped sheep. Journal of Agricultural Science, 52: 13-17.
Holmes, D. E.; Bond, D. R.; Lovley, D. R., 2004, Electron Transfer by Desulfobulbus
propionicus to Fe(III) and Graphite Electrodes. Applied and Environmental Microbiology.
70:1234-1237.
Ivanushkina, N.; Kochkina, G.; Laurinavichuis, K.; Pecheritsina, S., 2005, Biodiversity of
cryopegs in permafrost. FEMS Microbiology Ecology., 53: 117128.
Kaneda, T.,1991, Iso- and anteiso-fatty acids in bacteria biosynthesis, function, and
taxonomic significance. Microbiological Reviews, 55, 288302.
Kennedy, P. M' and Milligan, L. P.,1978, Effects of cold exposure on digestion, microbial
synthesis and nitrogen transformations in sheep. British Journal of Nutrition 39: 105-117.
Kim, H. J.; Park, H. S.; Hyun, M. S.; Chang, I. S.; Kim, M.; Kim, B. H, 2002. A mediator-less
microbial fuel cell using a metal reducing bacterium, Shewanella putrefaciens. Enzyme and
Microbial Technology. 30: 145-152.
Koichiro Tamura, Glen Stecher, Daniel Peterson, Alan Filipski, and Sudhir Kumar 2013,
MEGA6: Molecular Evolutionary Genetics Analysis version 6.0. Molecular Biology and
Evolution. 30: 2725-2729.
Lowry, O. H., Rosebrough, N. J., Farr, A. L., and Randall, R. J. 1951, Protein Measurement
with the Folin Phenol Reagent Journal of Biological Chemistry.193: 265275.

797

Pomeroy, L.R. & Wiebe,W.J.,2001, Temperature and substrates as interactive limiting factors
for marine heterotrophic bacteria. Aquatic Microbial Ecology, 23: 187204.
Rivkin, R.B., Anderson, M.R. & Lajzerowicz, C. 1996, Microbial processes in cold oceans. I.
Relationship between temperature and bacterial growth rate. Aquatic Microbial Ecology, 10:
243254.
Sinensky, M.,1974, Homeoviscous adaptation a homeostatic process that regulates the
viscosity of membrane lipids in Escherichia coli. Proceedings of the National Academy of
Sciences of the United States of America, 71, 522525.
van de Vossenberg, J.L.C.M., Driessen, A.J.M., da Costa, M.S. & Konings, W.N., 1999.
Homeostasis of the membrane proton permeability in Bacillus subtilis grown at different
temperatures. Biochimica et Biophysica Acta, 1419, 97104.

798

STUDY ON THE EFFECT OF pH ON BIOGAS PRODUCTION FROM FOOD

WASTE
BY ANAEROBIC DIGESTION
1

S. Jayaraj , B. Deepanraj , V. Sivasubramanian

Department of Mechanical Engineering, National Institute of Technology, Calicut-673601, India
2
Department of Chemical Engineering, National Institute of Technology, Calicut-673601, India
sjayaraj@nitc.ac.in, babudeepan@gmail.com, siva@nitc.ac.in

ABSTRACT
Irrepressible urbanization has resulted in release of excessive and erratic food waste, which contains
abundant organic matter and can suitably be harnessed to produce biogas by controlled
decomposition with microorganisms. The yield of biogas apparently depends on parameters like solid
content, pH, temperature, C/N ratio, mixing/agitation, retention time, etc. In the present study, the
effect of pH on the biogas yield is experimentally analyzed in five laboratory-scale batch reactors
maintained at pH 5, 6, 7, 8 and 9. The reactors were operated at mesophilic temperature condition
with a hydraulic retention time of 30 days. The food wastes used in this experiment were subjected to
characterization studies before and after digestion. The daily biogas production, cumulative biogas
production, methane and carbon-di-oxide composition were measured. The results show that, biogas
yield and degradation efficiency were substantially higher for the substrate of pH 7 compared to other
pH values. The methane and carbon-di-oxide composition in the biogas produced with pH 7 was
determined as 60.8% (v/v) and 36.3% (v/v), respectively. For the same pH, the cumulative biogas
production for a retention period of 30 days was measured as 5655ml from a 2 liter batch reactor. The
TS, VS and COD removal efficiency of pH 7 were found to be 49.44, 50.91 and 38.93% respectively.
The lowest biogas yield and degradation efficiency was obtained with the substrate of pH 5. The
experimental cumulative biogas produced was compared with theoretical cumulative biogas predicted
from first order rate of decay equation.
Keywords: Anaerobic digestion, food waste, biogas, pH effect.
INTRODUCTION
The increasing demand for energy, hikes in oil prices, depletion of fossil fuel resources and the
increasing concern for environmental issues are confronted the researchers at present to look for
new technological processes to obtain clean and sustainable energy from alternate energy sources
(Chynoweth et al., 2000; Gurung et al., 2012). Rapid population growth and urbanization have led to
an enormous increase of solid waste generation. Under-developed and developing countries have
great challenges concerning appropriate solid waste management to minimize the risk to human
health and pollution problems. These problems of energy and environment could be simultaneously
handled by biogas production from waste. Biogas can be generated from a wide range of solid or
liquid wastes (Zamalloa et al., 2012; Weiland., 2010).
In anaerobic digestion process, microorganisms uses the organic matter available in the waste to
produce a mixture of gases known as biogas (predominantly containing CH4 and CO2), which will
result in the reduction of environmental pollution. The process is brought about by a consortium of
interdependent and symbiotic populations of heterotrophic microorganisms which are capable of
utilizing elements and compounds from a diverse spectrum of substrates for the synthesis of new
cellular materials (Murphy and Keogh., 2004; Ghaly et al., 2000). Anaerobic digestion process can be
described by a four-stage scheme namely hydrolysis, acidogenesis, acetogenesis and
methanogensis (Demirbasa Balat., 2009). First stage is hydrolysis, in which the complex organic
structure of the substrate is broken down into simpler structure. In acidogenesis, the simple organic
compounds formed at the end of first stage are converted into volatile organic acids (acetate,
propionate, butyrate and valeric acid), carbon dioxide and hydrogen. Subsequently, acetate, hydrogen
and carbon dioxide are synthesized from the organic acids during the acetogenesis. In
methanogensis, the products of third stage are converted into biogas which mainly consists of
methane and carbon dioxide as its major composition (Yebo et al., 2011; Chandra et al., 2012;
Geraradi., 2003).
The gas yield in anaerobic digestion process depends on number of operating parameters such as
solid concentration, temperature, pH, C/N ratio, retention time, etc. Many researchers investigated

799

the effects of operating parameters on biogas production and reported their findings. Budiyono (2010)
studied the effect of substrate concentration (2.6, 4.6, 6.2, 7.4, 9.2, 12.3, and 18.4% of total solids) on
biogas production from cattle manure with rumen fluid as inoculum and reported that the substrate
concentration of 9.2% of total solids yielded more biogas (186.28ml/g of VS) followed by 7.4%
(184.09 ml/g of VS). Kim et al. (2006) investigated the influence of temperature and hydraulic
retention time on anaerobic digestion using food waste as feed. They reported that the performance
of anaerobic digestion and food waste digestion efficiency increased at 50C with 12 days hydraulic
retention time. Sivakumar et al. (2012) studied the effect of pH on biogas production from spoiled
milk. Experiments were conducted with substrate of different pH values (5-8) and reported that the
substrate with 7 pH resulted better biogas yield. Achmad et al. (2011) conducted experimental study
on the effect of C/N ratios (20, 25 and 30) on cattle feces and water hyacinth and reported that C/N
ratio of 30 produced highest methane compared to other C/N ratios. Abdel Hadi and Abd El-Azeem
(2008) investigated the effect of mixing, heating, organic total solids and digester type on biogas
production with buffalo dung as a substrate. Experiments were conducted in a 22 liter bench scale
batch anaerobic digester (horizontal and vertical types) and reported that the amount of biogas
production not only depends on the type of digester but also depends on other parameters like
mixing, heating, organic total solids and C/N ratio of the substrate.
In the present study, the effect of pH (5, 6, 7, 8 and 9) on biogas production was investigated
experimentally from the food waste through anaerobic digestion process using lab bench- scale batch
system. The experiment was carried out for a retention period of 30 days.
MATERIALS AND METHODS
Feedstock
Food waste used in this experimental study was collected from a hostel mess of National Institute
of Technology Calicut, Kerala, India. The food wastes obtained were shredded, mixed and stored
at 5C until it is introduced in the anaerobic digester. The solid concentration taken in all the
reactors were 7.5% total solids, found as optimum value from the previous experiments (Deepanraj
et al., 2014). Substrates with 5 different pH (5, 6, 7, 8 and 9) were prepared with the help of 1 N
sodium bicarbonate solution. The characteristics of the substrate used were determined before
and after digestion. For the entire experiments, cow dung was used as inoculum (10% inoculum to
feed ratio).
Experimental setup
Laboratory-scale anaerobic batch digesters made of glass vessel with total volume of 2 liter and
working volume of 1.6 liter was used in this experiment. The digesters were operated at ambient
(room) temperature in the mesophilic range with a hydraulic retention time of 30 days. Biogas
production from the digesters was measured daily by water displacement method. The volume of
water displaced from the flask was equivalent to the volume of gas generated. The reactor was
stirred using magnetic stirrer two times in a day.
Analytical methods
Characterization of feedstock is one of the most significant steps in the biogas production process.
Determining the general composition of the substrate (input feed) is essential for calculating the
quantity and composition of the biogas generated. The total solids (TS), volatile solids (VS), fixed
solids (FS) and chemical oxygen demand (COD) of the substrate and digestate were determined
as per the standard method (APHA., 1989). pH of the substrate and digestate was determined
using pH meter (pH-201, Lutron Electronic Enterprise, Taiwan). The methane and carbon-di-oxide
composition in the biogas were measured using Infrared gas analyzers (PIR-89, Technovation
Analytical Instruments, India).
Kinetic Study
The degradation of substrate in each reactor was assumed to follow a first order rate of decay. Thus,
the cumulative biogas production was assumed to follow the equation (Gunaseelan. 2004):
B = B0(1-e-kt)
Where B is the cumulative biogas production at digestion time t days. B0 is the biogas potential of
the substrate. k is the first order disintegration rate constant (biogas production rate constant). A
nonlinear least-square regression analysis was performed using Polymath 6.0 to determine B0, k, and
the predicted biogas yield. The coefficient of determination (R2) was also obtained from the analysis
with 95% confidence level.

800

RESULTS AND DISCUSSION

The characteristics of substrate and digestate before and after digestion process are given in Table 1
and 2. The pH of the substrate was adjusted to the required value (5-9) by adding 1 N sodium
bicarbonate solution. Figures 1 and 2 show the daily and cumulative biogas production over 30 days
retention period for the substrate with different pH respectively. Figure 1 show that the biogas gas
production was higher during initial days, and decreasing gradually as the days passes. The
maximum gas yield of 473 ml was obtained for pH 7 on the 6th day, followed by 430ml for pH 8 on the
8th day. Compared to pH 7 and 8, pH 5, 6 and 9 produced lower biogas production and degradation
efficiency. The results show that pH of the substrate has a significant effect on biogas production,
because it affects the activity of bacteria to destroy organic matter into biogas. A low pH in the
digester inhibits the activity of microorganisms involved in the digestion process particularly
methanogenic bacteria. Figure 3 shows the maximum biogas yield with respect to pH of the substrate.
The maximum cumulative biogas yield obtained by the reactor with pH 5, 6, 7, 8 and 9 are 4594, 5021,
5673, 5347 and 4889 ml. This shows that pH 7 resulted in higher biogas production followed by 8, 7,
9 and 6. Similar trend was observed by Budiyono et al. (2013) who has studied the effect of pH on
biogas production from food waste. The methane composition in the biogas produced with pH 5, 6, 7,
8 and 9 were determined to be 56.7, 58.6, 60.8, 60.1 and 59.4% (v/v) respectively.
Table 1. Characteristics of substrate
VS (g/l)
FS (g/l)
71.34
3.66

TS (g/l)
75

pH
5
6
7
8
9

COD (g/l)
69.39

Table 2. Characteristics of digestate

TS (g/l)
VS (g/l)
FS (g/l)

44.86
42.56
37.92
40.78
43.53

39.50
37.54
35.02
36.77
38.36

Fig.1. Daily biogas production

801

5.36
5.02
2.90
4.01
5.17

COD (g/l)

48.84
46.55
42.70
45.20
47.43

Fig.2. Cumulative biogas production

Fig.3. Maximum biogas production vs. pH of the substrate

Figure 4 shows the relationship between the experimental and predicted cumulative biogas
production with respect to retention time. The estimated kinetic parameters based on the first order
rate of decay were given in Table 3. All parameters were predicted from nonlinear least-square
regression analysis performed using Polymath 6.0 software with a confidence level of 95%. The
predicted maximum cumulative biogas production (B) for pH 5, 6, 7, 8 and 9 were 4765, 5250,
5948, 5603 and 5151 respectively. Maximum biogas production potential B0) predicted for pH 5, 6,
7, 8 and 9, were 5604, 6046, 6707, 6420 and 6116 respectively. The difference between the
experimental and predicted cumulative biogas production after 30 days for pH 5, 6, 7, 8 and 9
were 171, 229, 273, 256 and 263 ml respectively. For all the pH values, the predicted biogas
production is little bit higher than experimental value. The first order rate constant (k) and
coefficient of determination (R2) estimated from the analysis are given in Table 3.

pH
5
6
7
8
9

Table 3. Results of kinetic study using first-order kinetic model

Cumulative biogas
Cumulative biogas
Biogas
yield after 30 daysyield after 30 daysRate constant
Potential
Experimental
Predicted
(k)
(ml)
(ml)
(ml)

4594
5021
5675
5347
4889

4765
5250
5948
5603
5152

5604
6046
6707
6420
6116

802

0.0633
0.0675
0.0726
0.0687
0.0615

Coefficient of
determination
(R2)
0.9861
0.9852
0.9794
0.9790
0.9781

Fig.4. Comparison of cumulative biogas production

The VS, TS and COD removal efficiencies with respect to different pH is shown in Fig. 5. The TS
removal efficiency of the reactor with pH 5, 6, 7, 8 and 9 were 40.18, 43.25, 49.44, 45.62 and 41.96
respectively. The VS removal efficiency with pH 5, 6, 7, 8 and 9 were 44.63, 47.37, 50.91, 48.45 and
46.22% respectively. Similarly COD removal efficiency with pH 5, 6, 7, 8 and 9 were 30.14, 33.42,
38.93, 35.35 and 32.16 respectively. For all the cases, pH 7 achieved better degradation efficiency
followed by 8, 6, 9 and 5. Compared to TS and VS removal efficiencies, the COD removal efficiency
was low for all the cases because of the solid content available in the substrate.

Fig.5. TS, VS and COD removal efficiency

CONCLUSIONS
In the anaerobic digestion process, pH is a very important parameter. This study investigated the
effect of different pH (5, 6, 7, 8 and 9) on biogas production from food waste in an anaerobic batch
reactor with a retention time of 30 days. The results showed that pH 7 made favorable condition for
bacterial growth in the digester and produced better biogas yield compared to the others. Next to pH
7, pH 8 yielded better result followed by 6, 9 and 5. The degradation of TS, VS, and COD further
support and strengthen the reported results.
NOMENCLATURE
TS
Total Solids
VS
Volatile Solids
FS
Fixed Solids
COD
Chemical Oxygen Demand
DBP
Daily Biogas Production
CBP
Cumulative Biogas Production

803

REFERENCES
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biogas production from buffalo dung. MISR Journal of Agricultural Engineering, 25: 1454-1477.
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anaerobic digestion of jatropha and pongamia oil cakes. Applied Energy 93: 148159.
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yield from food waste in an anaerobic batch digester, International Conference and Utility
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pretreatment: A Review. IV th International Conference on Advances in Energy Research, Dec 1012, 2013, Mumbai, India.
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International Journal of Green Energy, 6: 117-142.
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Ghaly, A.E., D.R. Ramkumar, S.S. Sadaka and J.D. Rochon, 2000, Effect of reseeding and pH
control on the performance of a two-stage mesophilic anaerobic digester operating on acid cheese
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Gunaseelan, V.N., 2004, Biochemical methane potential of fruits and vegetable solid waste
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Gurung, A., S. W. Van Ginkel, W. C. Kang, N. A. Qambrani and Sang-Eun Oh, 2012, Evaluation
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805

Energy Consumption Analysis Of Fruit And Vegetable Hot Water Treatment

Equipment
Na Zhang, Zhao Yang*, Aiqiang Chen, Songsong Zhao
Key Laboratory of Medium-Low Temperature Energy Efficient Utilization of Ministry of Education, College
of Mechanical Engineering, Tianjin University, Tianjin 300072, China
Tianjin University, 92 Weijin Road, Nankai District,Tianjin, 300072, P. R. China
E-mails: zhaoyang@tju.edu.cn

Abstract
In order to improve the utilization of energy during the fruit and vegetable postharvest treatment, hot
water treatment equipment was constructed based on the principle of heat pump to prepare heat
treatment water of stable relatively high temperature (35~50). The treatment process was divided
into two stages of temperature rising and temperature keeping fruit and vegetable heat treatment
process, respectively. Cucumber was chosen as the heat treatment material. The temperature
distributions of fruit and vegetable treatment tank and cucumber internal tissue were measured.
The equipment operation parameters, such as energy coefficient of performance (COP) and etc
were explored under various compressor frequencies. Results show that, compare with the fruit and
vegetable heat treatment equipment of general electric heating system, the hot water treatment
equipment based on the principle of heat pump had the higher value of energy utilization rate.
During the temperature rising stage, time for the treatment water tank under various compressor
frequencies (30, 40, 50 HZ) reach to the final 40 were 36, 28 and 26 min, respectively, and the
average COP from high to low was 3.44 (40HZ), 3.19(50HZ), and 3.08(30HZ). During the hot water
treatment cucumber process, the compressor frequency with 30HZ expressed the minimum
temperature fluctuation range of cucumber internal tissue in the position of 4R/5, and 50HZ had the
maximum. In general, and compressor frequency with 40HZ exhibited obvious energy saving
potential during both the stage of temperature rising and keeping, and the lower the compressor
operating frequency, the smaller temperature fluctuation range of cucumber internal tissue in the
treatment of hot water. The interrelated conclusions can offer a reference for the build and
application of high efficient hot water treatment equipment.
Keywords: fruit and vegetable treatment equipment, COP, frequency, temperature distribution,
energy saving.
1. INTROUDCTION
With the growing pressure from consumers to reduce the quantities of postharvest chemicals
used for keeping fresh. Heat treatment, as a safe and effective physical method, had gain growing
interest. Postharvest heat treatment was first reported in 1992 for controlling decay on citrus fruit,
and now it was widely used in plant for the excellent performance in inhibiting the ripening process,
reducing insect disinfestations and inducing resistance to chilling injury (Paull et al., 2000).
According to the treatment medium, heat treatments are usually divided into three types: hot water
dips and sprays, vapor heat and hot air (Lurie , 1998).
Compared with hot vapor and air treatment, hot water dips treatment has a wide application in
commercial for the easier convenient production of hot water, especially in developed country. To
provide an equipment, which can produce stable relatively high temperature water (35~50), is the

806

important foundation for hot water treatment fruit and vegetable. Meanwhile, the specialized hot
water treatment equipment is very inadequate, and the existing equipments are mostly based on
the theory of electric heating. With the rapid development of economy and the increasing energy
demand in China, energy conservation draws more and more public attention. Compared with
those equipment with electric heating or other traditional gas to make hot water, air-source heat
pump water heater (ASHPWH) can provide the same hot water with two to three times higher
efficiency (Neksa et al., 1998; Ji et al., 2003; Ndoye et al., 2008), therefore, ASHPWH is gradually
used in residential and commercial residence for its significant economic benefit, high efficiency,
energy saving and environmental friendly. In previous studies, researches point out that the thermal
performance of the ASHPWH is influenced by refrigerants, ambient temperature, system structure,
water temperature, etc (Chen et al., 2009; Nuntaphan et al., 2009; Comakli et al., 2009; Zhang et al.,
2007; UNDP, 2005; Techarungpaisan et al., 2007; Ji et al., 2009; Morrison et al., 2004). Different
from the general ASHPWH used in residential or commercial building. The research of ASHPWH
used in hot water treatment fruit and vegetable is very poor.
Thus in this paper, in order to improve the utilization of energy during the fruit and vegetable
postharvest heat treatment, the hot water treatment equipment was constructed based on the
principle of hot pump. The operating characteristics were adopted through dynamic experiments to
analyze the performance of hot water treatment system. The treatment process was divided into
two stages of temperature rising and temperature keeping, respectively. Cucumber was chosen as
the heat treatment material. The temperature distributions of fruit and vegetable treatment tank and
cucumber internal tissue were measured. The equipment operation parameters, such as energy
coefficient of performance (COP) and etc were explored under various compressor frequencies.
The interrelated conclusions can offer a reference for the application and implementation of the hot
water pump system in the field of postharvest heat treatment.
Nomenclature
T

Temperature ()

Time (min)

Quantity of heat (KJ)

COP

Coefficient of performance

Ps

Mass of water (kg/s)

Pe

Specific heat of water (KJ/(kg k))

Electrical power consumption of compressor (KWh)

Compression ration

Suction pressure of compressor

Exhaust pressure of compressor
Operating frequency of compressor

2. EXPERIMENT SYSTEM AND PROCESS

2.1 Description of the experimental plant
Fig. 1 shows the schematic of the fruit vegetable hot water treatment system applied in this
study. The system is consisted of three subsystems, which including heat pump system, fruit and
vegetable hot water treatment system and automation control system.
The heat pump system is a type of air-source heat pump, with a compressor, a
variable-frequency drive of compressor, a condenser, an evaporator and an expansion valve, the
condenser type is plate heat exchanger, the rated power of compressor is 2.25 kw, and refrigerant
R22 is used as the working fluid in this heat pump system.
The fruit and vegetable hot water treatment system though the plate heat exchanger of heat
pump system to exchange the heat. And the hot water treatment system is consisted of a water

807

pump, a fruit and vegetable treatment water tank, a filter, and the joint plate heat exchanger with
heat pump system.
The automation control system is the important way to realize the control and monitor of the
heat pump system and fruit and vegetable hot water treatment system. The process of automation
control includes signal (temperature, pressure et al.,) acquisition, program calculation and result
execution. Fig.1 also shows the various locations of thermocouples and pressure gauges.

Fruit-vegetable hot water

treatment system
T

Heat pump system

Control
system

P
P

Fig. 1 Schematic diagram of fruit and vegetable hot water treatment equipment
1.

evaporator, 2. compressor, 3. condenser, 4. expansion valve, 5. filter, 6. 9. valve, 7. water pump, 8.

flow meter, 10. fruit and vegetable treatment water tank, 11. fruit and vegetable treatment basket, 12.
control cabinet, 13. Siemens PLC 200 modules ( CPU module and extension modules).

2.2 Test conditions and procedure

In this study, the tested operation state was divided into two stages of temperature rising and
temperature keeping (fruit and vegetable heat treatment process), respectively. The parameters of
equipment energy coefficient of performance (COP) and etc. were explored under various
compressor frequencies. The environment temperature of tested days was 121. The experiment
scheme for the temperature rising and keeping stages were according to table1. Cucumbers were
selected as the treatment test material in the temperature keeping stage. The total mass of
treatment water in tank and cucumber was 90 kg and 30 Kg, respectively. The mass flow rate of
treatment water pump was 0.34 kg/s, the temperature and temperature bandwidth of the fruit and
vegetable hot water treatment tank in the automation control program were set as 401, and the
initial water and cucumber temperature was 18.5 0.1.
The distributions of fruit and vegetable hot water treatment tank temperature and cucumber
internal temperature at 4R/5 radial direction were measured with T-type thermocouples (Tianjin
Zhonghuan Temperature Meters Co., Ltd., Tianjin, China), the measurement accuracy: 0.1, and
R is the radius of cucumber. The distributions of the compressor suction and exhaust pressure were
measured with pressure transmitters (Emerson Electric GmbH Co. OHG, Waibligen, Germany)
of 2 class.
Table.1 Experiment scheme for the temperature rising and keeping stages

808

Compressor frequency (Hz)

50Hz

40Hz

30Hz

Stage of temperature rising

Group R1

Group R2

Group R3

Stage of temperature keeping

Group K4

Group K5

Group K6

2.3 Date and calculate

Based on the measured temperatures, pressure and power consumption data, the quantity of
heat Q was calculated using the following equations:

Q MC (Tn1 Tn )
(1)
The equipment operating COP considering the electrical power consumption of compressors
was calculated as the following equations:

COPn

Q
W

(2)
And the electrical power consumption of compressor was measured by a multifunction meter
( Shanghai Changfang Electric Co., Ltd., Shanghai, China ).
The compression ration of compressor was calculated using the following equations:

Pe
Ps

(3)
3. RESULTS AND ANALYSIS
3.1 Stages of temperature rising
3.1.1 Temperature distributions of water in treatment tank
According to Fig. 2, the temperature distributions of water in the fruit and vegetable treatment
tank were increased with the operating time. The growth rate of the three groups R1, R2 and R3 all
remained a relative stable value, R3 had the minimum value, R1 and R2 showed a relative higher
value of growth rate, and R1 had the maximum value by a slight margin. The final time for the water
in treatment tank under various compressor frequencies (30, 40, 50 HZ) reach to the 40 was 36,
28 and 26 min, respectively. Result was in accordance with the tendency of temperature growth
rate. Quicker and time saving are the important elements in the process of postharvest hot
treatment, thus the operating frequency of compressor with 50 and 40 HZ performance better in the
speed than 30 HZ.

809

44
40

R1
R2
R3

Temperature ()

36
32
28
24
20
16

12

16 20 24
Time (mins)

28

32

36

40

Fig. 2 Temperature distributions of water in the fruit and vegetable treatment tank under various

frequencies
3.1.2 Dynamic compression ratio of hot water treatment system
The dynamic compression ratio of fruit and vegetable hot water treatment system was shown
in Fig. 3. The compression ratio distributions of the three groups can be divided into three stages:
the early slowly changing area, the middle quicker increasing area and the last slowly increasing
area, meanwhile, the higher compressor frequency, the shorter early slowly changing area.
Different from the tendency of decreased at first and increased later in groups R2 and R3, the
compression ratio of group R1 continuously increased at the early slowly changing area. And the
increase value of group R1 was higher than groups R2 and R3 in the middle quicker increasing
area. At the last slowly increasing area, the compression ratio from high to low was group R1, R2
and R3.
6.5
R1
R2
R3

Compression Ratio

6.0
5.5
5.0
4.5
4.0
3.5
3.0
0

12 16 20 24 28 32 36
Time (mins)
Fig. 3 Dynamic compression ratio of fruit and vegetable hot water treatment equipment under various

frequencies
3.1.3 COP and energy consumption of hot water treatment system
The dynamic coefficient of performance (COP) is one of the important performance index to
evaluate the heat pump system in the current GB /T 213622008 (Chinese National standards)
and JRA 4050-2001 (Japanese air conditioning industry standards). The dynamic COP of fruit and
vegetable hot water treatment system was shown in Fig. 4. At the beginning stage of operating, the
COP of the group R1 expressed the significant highest value, then group R2, and group R3 the

810

least. The dynamic COP of groups R1 and R2 had the similar tendency of shock down, and after 4
min, the COP values of groups R2 were higher than that of group R1 ( except the 22 min). Different
from the tendency of groups R1 and R2, the dynamic COP of group R3 shock increase at first, and
then shake down.
In order to compare the performance index of hot water treatment system more intuitive, the
average COP and total energy consumption of fruit and vegetable hot water treatment system
during the stage of temperature rising were calculated and shown in Fig. 5. The highest average
COP was appeared in group R2, and R3 the least. The average COP value of group R2 was 1.08
and 1.12 times of group R1 and R3. The total energy consumption of group R2 was 85% and 91%
of group R1 and R3.
Especially under the current situation of energy shortage, the energy consumption and
operating COP are the very important performance index to heat pump system. In general, the fruit
and vegetable hot water treatment system with the 40HZ compressor operating frequency had
better performance in energy saving than 30 and 50 HZ.

R1
R2
R3

Coefficient of Performance

7
6
5
4
3
2
1
0

12

16 20 24
Time (mins)

28

32

36

Fig. 4 Dynamic COP of fruit and vegetable hot water treatment equipment under various

frequencies
4.5
Total.Energy
Average.COP

4.0

4.0

3.5

3.5

3.0

3.0

2.5

2.5

2.0

2.0

1.5

1.5

1.0

1.0

0.5

0.5

0.0

0.0
30

40
Compressor Frequency (Hz)

Average COP

Total Energy Consumption (KWh)

4.5

50

Fig. 5 Average COP and total energy consumption of fruit and vegetable hot water treatment equipment
under various frequencies

3.2 Stages of temperature keeping (fruit and vegetable heat treatment process t)
3.2.1 The temperature distribution of cucumber internal tissue

811

According to Fig. 6, the temperature distribution of cucumber internal tissue at 4R/5 radial
direction under various compressor frequencies (30, 40, 50 HZ) expressed the similar trend. The
cucumber hot water treatment process could also divided into temperature rising stage and
temperature keeping stage. During the stage of temperature rising, the temperature distributions of
groups K1, K2 and K3 were highly similar, and time for the three groups reach to the 40 was all at
22 min. After that, the temperature of groups K1, K2 and K3 began to fluctuate around the 40,
and the fluctuation range from high to low was K1, K2, and K3. The highest temperature values of
cucumber internal tissue at 4R/5 radial direction under 30, 40 and 50 HZ were 40.75, 41.15 and
41.69, respectively.
Researches show that postharvest heat treatment has excellent performance in suppressing
softening of banana (Ummarat et al., 2011), enhancing self-defense capability of peach (Zhang et
al., 2011), inhibiting transformation of tomato carotenoids and discolor of peeled white asparagus
(Soto-Zamora et al., 2005; Siomos et al., 2010), et al. However, heat treatments with improper
temperature or time usually cause heat injury. Heat-treated spears at 50 for 10-25 min or 55 for
4-5 min appear clamminess (Siomos et al., 2005), Lydakis and Aked (2003) report that relatively
high temperature and long time treatment results in serious weight loss and browning, and the
study of Soto-Zamora et al. (2005) show that hot air treatment of tomatoes appear obvious negative
effect, such as severe losses of antioxidant components and the function for fruit coloring. Heat
treatment occupies a predominant position in the field of postharvest treatment for its positive effect,
while heat injury caused by improper treatment temperature also becomes the crucial obstacle to its
development and application. Thus controlling the temperature accuracy of cucumber internal
tissue in the process of hot water treatment is very important to the security of heat treatment. And
the results show that the lower compressor frequency, the higher controlling accuracy received.

Temperature()

40

35

K1
K2
K3

30

25

20
0

10

20

30

Time (mins)

40

50

60

Fig. 6 The temperature distribution of cucumber internal tissue at 4R/5 radial direction under various

frequencies
As shown in Fig.7, during the 1 h hot water treatment process, the start/stop count of
compressor under various frequencies was all 3 times. The energy consumption of compressor was
decreased with the increase of start/stop count, and the result was caused by the constant reduced
temperature difference between cucumber and treatment hot water. At the same time, the result of
energy consumption trend under various compressor frequencies was in accordance with the
previous stage of temperature rising, in the stage of temperature keeping, the energy consumption
of compressor with 40 HZ had the minimum value, and 50 HZ had the maximum value. The first,

812

Energy Consumption of Compressor (Kwh)

second, and third times energy consumption of K2 was 81%, 78% and 77% of K1.
0.24
K1
K2
K3

0.20

0.16

0.12

0.08
1

2
3
Start/Stop Count of Compressor
Fig. 7 The energy consumption of compressor during the temperature keeping stage under various

frequencies
4. CONCLUSIONS
(1) During the temperature rising stage, time for the treatment water tank under various compressor
frequencies (30, 40, 50 HZ) reach to the final 40 were 36, 28 and 26 min, respectively, and the
average COP from high to low was 3.44 (40HZ), 3.19(50HZ), and 3.08(30HZ).
(2) During the heat treatment cucumber process, the cucumber internal tissue temperature with
30HZ compressor frequency expressed the minimum fluctuation range, and 50HZ had the
maximum.
(3) Compressor frequency with 40HZ exhibited obvious energy saving potential during both the
stage of temperature rising and keeping, and the lower the compressor operating frequency, the
smaller temperature fluctuation range of cucumber internal tissue in the treatment of hot water.
Thus we can choose the optimum operating frequency based on the heat sensitivity of specific fruit
and vegetable.
ACKNOWLEDGMENTS
Supported by the National Natural Science Foundation of China (Grant No. 51276124), Research
Fund for the Doctoral Program of Higher Education of China (No.20130032130006)Science and
Technology Project of Tianjin City (Grant No. 12ZCDGGX49400).
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813

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refrigerant mixtures in heat-pumps using Taguchi method. Appl Energy. 86:24518.

Zhang J, Wang RZ, Wu JY., 2007. System optimization and experimental research on air source
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76(1-3). 147-152.
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815

Hydrothermal Carbonization (HTC): An Innovative Process For Low Quality

Lignocellulosic Biomass Conversion To Hydrochar For Replacing Coal
a

Harpreet S. Kambo , Animesh Dutta

School of Engineering, University of Guelph, Guelph, Ontario, N1G 2W1, Canada
a
b
kamboh@uoguelph.ca, adutta@guelph.ca

ABSTRACT
Biomass is an attractive feedstock for energy conversion. However, its application in industry
is very limited due to its poor physicochemical properties. Hence a thermal pre-treatment is a
highly necessary step for converting low quality lignocellulosic biomass to an energy dense
homogeneous solid fuel. The work presented in this study demonstrated the potentiality of
hydrothermal carbonization (HTC) of miscanthus feedstock for the production of carbon rich solid
fuel, referred as hydrochar, whose combustion characteristics are comparable to that of coal. The
effects of the operating conditions on mass yield, energy yield and higher heating values (HHVs)
were examined by varying reaction temperature (190, 225, and 260C), reaction time (5, 15, and
30mins) and feedstock to water ratio (1:6-1:12). The results showed that reaction temperature
remained the most significant parameter governing physicochemical properties of biomass.
Increasing reaction temperature reduces the mass yield where significantly augments the energy
density of solid product. The hydrochar samples produces at 260C had maximum energy density
of 26-30MJ/Kg, with 66-74% of raw miscanthus energy retained in the solid product. The results
from the fiber analysis indicates that the removal of hemicellulose is much faster in HTC and the
hydrophobicity of the solid product is significantly improved and therefore can be easily stored and
transported without processing any threat to biodegradation. In comparison the energy density,
grindability, and hydrophobicity of the solid samples produced via dry torrefaction (a conventional
thermal pre-treatment) was considerably lower than hydrochar samples, even if the reaction time
was kept much higher than HTC. Furthermore, the inorganic metallic composition of miscanthus
feedstock almost remained unaffected after dry torrefaction, however was significantly reduced
(40-80%) via HTC.
Keywords: Bioenergy, Biochar, hydrothermal carbonization, biomass, alkali and alkaline
composition

1.

INTRODUCTION:

The two primary concerns that world is facing today are sustainable energy production
and detrimental emissions from fossil fuels. Increasing total worlds population and tremendous
amount of pressure on demand and consumption are causing depletion in availability and
escalation in prices of fossil fuels. For instance, coal is the major source of energy production at
thermal power plant. Its reliability, maturity of technology, and its well understood nature by the
traditional electricity producers are the positive strengths favouring the use of coal. However,
burning coal causes smog, soot, acid rain, global warming, and toxic air emissions which include
the release of heavy metals, such as mercury and arsenic, found as trace elements in coal
(Finkelman et al., 2002). Such counterproductive consequence intensifies interest in seeking
alternative energy resources.
Recent research interests in biomass and using it as a substitute fuel for coal is gaining
signification attention (Bridgeman et al., 2010; Pimchuai et al., 2010). Biomass is a non-edible
renewable energy resource derived from living or recently living organic matter such as wood,
wood waste and agricultural residues. Biomass is the worlds fourth largest source of energy and
its billion ton availability can meet sustainable energy demand and production. However, owing to
its inferior physical and chemical properties such as low bulk density, hydrophilic nature, low
calorific value, poor grindability, and high alkali content in ash results highly inefficient handling
and combustion properties of biomass(Bridgeman et al., 2010; Demirbas, 2004). Raw biomass is
more likely to adsorb moisture and thus prone to biological deterioration, limiting its storage time
(Acharjee et al., 2011). High alkali and alkaline composition in biomass hinders its application as a
solid fuel. Presence of sodium and potassium along with sulphur causes highly undesirable effects
in terms of slagging, fouling and tendency to corrode equipment. Alkali metals react with sulphur to
form alkali sulphates which deposits on combustor surface and affecting heat transfer rates and

816

also resulting into the corrosion of turbine blades made from highly alloyed steels and super alloys
(Saddawi et al., 2011). Silica in biomass reacts to form alkali silicates, that melts or soften at low
temperatures (can be lower than 700C, depending on composition) and can result agglomeration
(Agblevor & Besler, 1996; Baxter et al., 1998). Calcium does not cause corrosion but can form
deposits that are very difficult to remove from turbine blades. When using biomass with high alkali
content for combustion, additives are often added to manage ash behaviour which can further
increase the operational expenses. Moreover, the lignocellulosic biomass is highly fibrous in
nature and is thus difficult to grind to small particles, where small fine particles are generally
required during gasification or co-firing with pulverized coal (Bridgeman et al., 2010). Therefore, to
overcome these aforementioned limitations, pre-treatment or preprocessing of biomass are highly
essential steps to improve its combustion properties and its effective utilization as a fuel source.
Dry torrefaction is a conventional thermal pre-treatment and is often proposed for
upgrading biomass properties (Acharya & Dutta, 2013; Pimchuai et al., 2010). During which
biomass is slowly heated in an inert atmosphere between 200-300C for 30 minutes to couple of
hours. The processes results into a hydrophobic solid product (denoted as biochar). The
grindability and HHV of biochar is little improved to some extent compared raw feedstock, but high
inorganics in ash still remains a challenge for biomass combustion. Also the process is highly
inefficient when dealing with a feedstock of high moisture content (Uslu et al., 2008).
A comparatively new approach of hydrothermal carbonization (HTC), also referred as wet
torrefaction, is performed around temperature of 180-260C. During which biomass is submerged
in water and is heated in a confined system under elevated pressure levels (2 to 6MPa) for 5 to
240 minutes(Libra et al., 2011). Lack of energy intensive drying processes, high conversion
efficiency, and relatively low operating temperature and residence time range are significant
advantages offered in HTC when compared to other conventional thermal pre-treatments (Reza et
al., 2012). The HTC process results into the formation of solid (hydrochar), liquid (bio-oil) and
gaseous (mainly CO2) products. The properties and percentage distribution of the final products
significantly depends upon process reaction conditions (Yan et al., 2010). Low percentage yield,
complex composition, and complicated separation and purification processes limits the utilization
of liquid and gaseous products from HTC process. Hydrochar is the primarily desired solid end
product in HTC process, which exhibits unique and significantly superior physicochemical
properties compared to biochar and have myriad value-added industrial applications (Titirici et al.,
2012).
To date very few studies have investigated the comparison of fate of inorganic
compositions in hydrochar and biochar. As the HTC process is carried out in presence of liquid
water, and therefore can wash away (fully or partially) these inorganic impurities from biomass into
liquid by-product stream. To confirm the validity of above mentioned hypothesis, the present study
was carried out to characterise hydrochar and biochar produced from purpose grown energy crop
(miscanthus). The physicochemical properties were characterized to evaluate the feasibility of
solid products from both the conversion processes for solid fuel application and their potentiality in
replacing coal from conventional pulverized-coal boilers (PCBs).
2. MATERIAL AND METHODS:
2.1.
Materials:
To evaluate the performance of HTC and dry torrefaction process, miscanthus biomass
feedstocks was considered in the study. Miscanthus feedstock was collected from a privately
owned farm in Ontario and was harvested in May, 2013. Prior to the experiments, biomass
feedstock was prepared for uniformity and was manually chopped into samples of length about 2025mm. The prepared samples were stored in sealed plastic bags until treatment. For the
comparison of raw and pre-treated miscanthus samples to conventional fossil fuel, a commercial
coal sample from industry was also analysed in this study.
2.2.
2.2.1.

Experimental Setup:
Hydrothermal Carbonization (HTC):

HTC of biomass was carried out using Parr 600ml bench top reactor fitted with glass liner
(762HC3) as shown in the figure 1. To analyze the effect of operating conditions, the experiment
was performed at different reaction temperatures (190, 225, 260C), residence times (5, 15, 30
minutes) and feedstock to water ratios (1:6 & 1:12 (w/w)). The temperature of the system was
controlled using Proportional-Integral-Derivative (PID) temperature controller. The reactor pressure
was not controlled in experiment and was kept autogenic with vapour pressure of water at the
corresponding temperature. As indicated by a pressure gauge attached to the reactor, the

817

pressure ranged from 180 to 720 psig. The temperature and the pressure profile in the reactor
during HTC experiments are shown in figure2.
Prior to the reaction each biomass samples were mixed with deionized water in different
ratios and was manually stirred for 2-3 minutes to ensure complete wetting. The reactor was
heated up to required temperature in about 20-30mins and was then maintained for a desired time
period. Later, to further quench the reactions, the reactor was immersed in cold water and was
cooled down to room temperature in about 5-7minutes. Once the inside temperature of reactor
dropped to room temperature, the pressure release valve was opened under the fume hood to
release gaseous products. The solid and liquid products were separated using filter paper
(20micron) and was collect for further analysis. The solid product was dried overnight at 103C
before analysis. To ensure repeatability, each experiment was repeated thrice.

Figure1. HTC experimental Setup

Figure2. Temperature and Pressure Profile for HTC experiment. Zone A: heating time, Zone
B: reaction time, Zone C: cooling time.
2.2.2.

Dry Torrefaction

Dry torrefaction experiments were performed using a quartz wool matrix (QWM) reactor
(see figure 3) that was designed and fabricated in machine lab at University of Guelph. The reactor

818

consists of a stainless steel tube heated by four electric heaters of 1.25KW capacity in close
contact with the reactor wall. The temperature of the reactor was controlled by two separate PID
controllers. The reactor consists of small perforated basket made of stainless steel attached to the
balance and was fitted with a ceramic crucible to hold sample.
For each run, miscanthus sample of about 5gm was placed inside the crucible. The reactor
was then heated to 260C with the heating rate of 10C/min and was maintained for 30mins.
During experiment, to prevent combustion, the reactor was continuously purged with nitrogen gas
(10ml/min) to maintain inert atmosphere inside the reactor. The nitrogen gas was passed through
the pre-heater (temperature controlled) before purging inside the reactor. After the desired reaction
period, the sample was cooled down to room temperature with the continuous flow of nitrogen
through the reactor. The remaining solid sample was collected and placed inside air sealed bag till
analysis.

Figure3. Torrefaction experimental Setup

2.3.
2.3.1.

Analytical Methods:
Proximate Analysis:
Proximate analysis (moisture & ash) of solid samples was carried out as per ASTM
standards. Measured amount of mass was place in muffle furnace (Thermo Scientific, F48055-60)
maintained at 1032C for at least 16hrs and was then moved to desiccator, containing silica gel,
for cooling. The samples were then re-weighed and the change in initial and final weight was
calculated as percentage moisture (ASTM-E871). The dried solid samples were then ignited at
575C for 5hrs in a muffle furnace to determine percentage ash (ASTM- E872).
2.3.2.

Higher heating Value:

The higher heating values (HHV) of raw and pre-treated solid samples were determined
using IKA C200 bomb calorimeter. All the samples were oven dried at 105C for 24hrs prior to
analysis.
2.3.3.

Hydrophobicity:
Thermal pre-treatments are often proposed to improve storage behaviour or
hydrophobicity of biomass. To confirm the validation of the above statement, pre-treated samples
were tested for equilibrium moisture content (EMC). EMC is defined as the moisture content of the
sample that is in thermodynamic equilibrium with the moisture in the surrounding atmosphere at a
given relative humidity, temperature, and pressure. To determine EMC of solid samples in this
study, both raw and pre-treated samples were exposed to rooms maintained at two different
humidity levels: 48-52% and 74-78% at 22-23C. After exposure of 24 hours to the controlled
environment, the samples were then dried in oven at 103C for 16hours. The change is weight was
then expressed as percentage moisture adsorbed (Eq. 1). Higher the moisture adsorbed, lower is
the hydrophobicity.
(1)

819

MC= Moisture content of the sample

Mwet = Final mass of the sample
Mdry = Mass of the oven dried sample
2.3.4.

Grindability:
Owing to high fibrous nature, pulverization of biomass is a highly energy intensive process.
Dry torrefaction pre-treatment has been widely discussed as a solution to improve the grindability
of biomass. To evaluate the performance of HTC on pulverization, grinding of the pretreated solid
samples was performed using planetary ball mill (Retsch PM100). Prior to grinding, samples were
sieved to particle size range of +850micorn to -1000micron. For each run, measured amount of
mass of pretreated samples were loaded into grinding bowl with five stainless steel balls (10mm).
The bowl was then placed in the ball mill operated at 420 rpm for 5minutes.
The grounded samples were collected and further evaluated for particle size distribution
(PSD) by using sieve shaker (Retsch AS200), with four different set of sieves (>500mm, 500
250mm, 250100mm and <100mm). The PSD was determined by the percentage weight retained
on each sieve. Higher the percentage weight retained on smallest sieve, higher and easier is the
grindability. For comparison, raw feedstock samples and a commercial coal sample was also
grinded using same procedure and measured for PSD. To ensure the repeatability, each
experiment was repeated thrice.
2.3.5.

Fiber Analysis:
Generally, biomass is divided into five main components: hemicellulose, cellulose, lignin,
hot water extractives and ash. A chemical analytical method was used to determine the
percentage of hemicellulose, cellulose, lignin and hot water extractive materials in raw and
pretreated samples (Harper & Lynch, 1981). Ash in samples was determined as per ASTM-E872
standard, described in section 2.3.1. Prior to analysis each samples were dried overnight at 103C.
2.3.6.

Scanning Electron Microscopy (SEM)

Both raw and pre-treated samples were mounted onto the surface of a standard aluminum
SEM stub using carbon tape. The samples were then placed into a Cressington 108Auto sputter
coater where a 10-nm gold film was deposited on the surface of sample to provide a conductive
coating. The samples were then placed in a scanning electron microscope (FEI Inspect S50). The
images were collected at an accelerating voltage of 20 kV with an aperture of 3.5 using an ETD
secondary electron detector.
2.3.7.

Inorganic Elemental Composition:

High alkali and alkaline composition in biomass is the biggest challenge when using it as
fuel source. To determine the effect of thermal pre-treatment on alkali and alkaline composition of
biomass, each sample was analyzed for inorganic composition. (Anderson, 1996). The testing was
performed at University of Guelph laboratory services (UGLS) using CEM-Mars Xpress microwave
digestion system and inductively coupled plasma atomic emission spectroscopy (ICP-OES)
system.

3.

RESULTS AND DISCUSSIONS

3.1.

Effect of Operating Conditions on Biomass Properties:

Table 1 shows the experimental design technique that was employed to study the effect of
three different operating parameters: reaction time, temperature, and ratio of feedstock to water,
during HTC process and their effect on physicochemical properties of biomass. Mass yield (Eq.2),
energy densification ratio (Eq.3) and energy yield (Eq.4) are the three important parameters that
were measured in this study and are expressed as:
(2)
(3)
(4)

820

Table1. Experimental Design for HTC Pre-treatment of Miscanthus Feedstock

Mass Yield
Energy Densification
Energy Yield
(%)
Ratio
Operating
Parameters
Feedstock to Water
Feedstock to Water
Feedstock to Water Ratio
Ratio
Ratio
Temperature
Time
1:6
1:12
1:6
1:12
1:6
1:12
(C)
(mins)
190

83.53

85.84

1.08

1.05

90.16

90.13

190

15

77.87

69.71

1.12

1.12

87.21

78.08

190

30

72.52

66.59

1.15

1.16

83.40

77.24

225

66.89

65.49

1.16

1.16

77.59

75.97

225

15

63.92

61.19

1.26

1.25

80.54

76.49

225

30

62.43

57.53

1.29

1.32

80.53

75.94

260

47.83

44.88

1.39

1.35

66.48

60.59

260

15

45.99

43.99

1.59

1.55

73.12

68.18

260

30

46.94

42.76

1.64

1.70

76.98

72.51

A Box-Behnken design and Analysis of Variance (ANOVA) method was used to analyze
the data and modelling HTC process in terms of reaction temperature, time and solid load and its
effect on mass yield, energy yield and HHV. According to the results shown in the table1 and
statistical analysis (ANOVA, at 95% confidence interval), it was found that the reaction
temperature remains the most significant and important parameter controlling the properties of
biomass. Reaction time is the second most affecting parameter. However, no significant effect was
found for varying solid load from 1:6 to 1:12. The statistical analysis of data using a model with
interaction terms, showed no-significant effect of interaction of variables except for reaction time
and temperature. Therefore the interpolation of variables can be done independently. Due to the
significant effect of reaction temperature, physical and chemical analysis (except for mass yield,
energy yield and HHV) of HTC pre-treated samples was performed for temperatures of 190C,
225C, and 260C, at 5mins reaction time and solid load of 1:6.
Similar results were also reported by another study (Reza, 2011). However, during which
no-significant effect of reaction time was reported and therefore contradicts the findings in this
study. This contradiction is most possibly due to the difference in levels of reaction times used in
the experiments. The present study was performed using three different levels of reaction times (5,
15, 30mins) where only two different levels (5 and 20mins) were used in experiments performed by
Reza, (2011).
3.1.1.

Effect on Mass Yield:

Table 1 shows the effect of reaction time and temperature on mass yield of biomass. As
expected, the mass yield considerably reduces with increase in reaction time and temperature, of
which reaction temperature remained the most prominent factor. Generally, the biomass with high
hemicellulose composition shows higher mass loss, due to least thermal stability of hemicellulose
among other polymer components in biomass (Garrote et al., 1999). To confirm the validity of
aforementioned statement, fiber analysis of samples was performed and the results are shown in
table2. Comparing to the results with literature (Garrote et al., 1999), miscanthus has high
percentage of hemicellulose composition in it compared to other woody and agricultural biomass
feedstocks.
Table2. Fiber analysis of Raw and Pretreated Miscanthus Samples

821

Pre-treatment

HTC
Torrefaction

Feedstock

Hemicellulose
(%)

Cellulose
(%)

Lignin
(%)

Hot water
Extractives
(%)

Ash
(%)

Raw

36.30

38.80

11.50

12.60

0.80

190C

5.77

56.94

15.61

21.14

0.54

225C

5.11

53.38

17.75

23.08

0.68

260C

0.97

27.50

30.57

39.99

0.97

260C

21.46

36.21

35.11

6.20

1.02

The strength of the effect of operating parameters on mass yield of miscanthus is better
represented by using linear model and a cube plot as shown in fig 4. It can be noticed that with
increase in reaction temperature from 190C to 260C, the mass yield of miscanthus was
considerably reduced by 30% at reaction time of 5mins and by 29.9% at reaction time of 30mins.
Where on the other hand (keeping the reaction temperature constant), with increase in reaction
time from 5 to 30mins, the mass yield of the miscanthus only reduced by 7.7% at 190C and by 7.6%
at 260C. No significant effect (<3%) was observed for the mass yield with increase in variation in
solid load.

Figure4. Linear Model Cube plot for Mass Yield vs Reaction time, temperature and ratio
Using the linear model relationship and ANOVA method for mass yield as function of
reaction temperature (T), time (t) and ratio of feedstock to water (R), the statistical equation (Eq. 5)
was derived with R-square value of 0.948.
( )

( )

( )

(5)

For the comparison to dry torrefaction process, miscanthus samples were torrefied using
QWM reactor. The effect of operating conditions on mass yield in both the conversion processes is
shown in the Fig.5. At the same reaction temperature, mass loss of miscanthus feedstock under
dry torrefaction process is considerably lower even if the process was carried out at significantly
higher residence time (30mins) compared to the one used for HTC process (5min). The difference
in mass loss of same feedstock in two different pre-treatment processes is mainly due to the
variation in extent of degradation of hemicellulose. Extent of degradation biomass polymer
significantly depends upon the reaction medium in which the process is carried out (Libra et al.,
2011).
To determine the extent of degradation of biomass polymers in of miscanthus under HTC
and dry torrefaction process, fiber analysis of both raw and pretreated samples was carried out
and the results are shown in table 2. It can be noticed that the degradation of hemicellulose in HTC
process is considerably higher and faster than under dry torrefaction process, even if the severity
of reaction was significantly higher in torrefaction (260C-30mins) compared to HTC (190C5mins). Decarboxylation, dehydration, de-carbonylation, de-methoxylation, intermolecular
derangement, condensation and aromatization etc. are some of the proposed chemical reactions
that take place during thermal pre-treatment of biomass. However, in HTC process due to the

822

presence of hot compressed water, the reaction mechanism is initiated by hydrolysis; resulting into
the cleavage of ether and ester bonds between monomeric sugars by the addition of one molecule
of water (Bobleter, 1994) and thereby reducing the activation energy levels of biomass polymers
(Libra et al., 2011). Thus the degradation of hemicellulose in HTC process is relatively higher than
in dry torrefaction process.

Mass Yield

Energy Yield

HHV
27
26

90

25
80
24
70

23

60

22
21

50
20
40

19

30

18
190

225

260

260

HTC-5mins
Torrefaction-30mins
Temperature (C)
Pre-treatment Process and Reaction Time
Figure5. Comparison of Mass yield, energy yield and HHV in HTC and Torrefaction
3.1.2.

Effect on HHV and Energy Yield:

In terms of HHVs of biomass polymers, lignin has the highest heating value and is in the
range of 23.3-26.6 MJ/Kg, followed by cellulose and hemicelluloses having HHV of about 17.617.9MJ/kg (Demirba, 2005). The thermal stability of biomass polymers from lease to most follows
the order: Hemicellulose<Cellulose<Lignin (Grnli et al., 2002). In hydrothermal process, due to
the presence of subcritical water, degradation of hemicellulose is rapid and takes place at fairly
lower temperature compared to in conventional dry pre-treatments like torrefaction, pyrolysis,
gasification etc. (Bobleter, 1994). Moreover, in hydrothermal processing, degradation of
hemicellulose and cellulose results into the formation of high quality intermediate products like 5Hydroxyl Methyl Furfural (HMF) which has several value-added applications in chemical industry
(Funke & Ziegler, 2010). The HHV of 5-HMF is about 22 MJ/kg, which is significantly higher than
that of hemicellulose and cellulose, and is close to that of lignin (Zhong et al., 2010). Small porous
structures are often obtained during hydrothermal conversion of biomass and these 5-HMF
particles may precipitate into the pores of hydrochar; further augmenting the energy densification
of solid product. These intermediate particles are characterised as aqueous soluble materials (hot
water extractives) during fiber analysis. Degradation of hemicellulose was found to increase with
increase in reaction temperature and almost complete degradation of hemicellulose can be
observed in case of HTC-pretreated miscanthus at 260C (Table 2). In biochemical industry, 5HMF is used as a product for the production of 2,5 Dimethyl-furan (DMF), whose heating value is
significantly higher (33.7 MJ/kg) than that of ethanol (26.9 MJ/kg) (Zhong et al., 2010).
The HHV and energy densification ratio increases with increase in reaction temperature
where the energy yield reduces with increase in reaction temperature. With increase in reaction
temperature from 190C to 260C at 5 minutes residence time, the HHV of miscanthus samples
increases from 19.93 to 25.72 MJ/Kg, corresponding to energy densification ratio of 1.08 to 1.39,
respectively. However, at same conditions, energy yield of pre-treated miscanthus samples
reduced from 90.16% to 66.48%. The significant drop in percentage energy yield of miscanthus

823

HHV (MJ/Kg)

Mass Yield (%) / Energy Yield (%)

100

samples directly correlates with the reduction in mass yield from 83.53 to 47.83% at 190C to
260C, respectively. With further increase in severity of reaction, i.e. highest reaction temperature
(260C) and highest residence time (30mins), the combustion properties (in terms HHV) of
hydrochar were surprisingly improved.
The strength of operating parameters on HHV was determined using linear model and is
represented by using cube plot as shown in Fig.6. It can be observed that with increase in reaction
temperature from 190 to 260C, the HHV of pre-treated miscanthus samples considerably
increased by 41% (18.56 to 26.38MJ/Kg) at reaction time of 5mins and by 35.9% (21.71 to 29.52
MJ/Kg) at reaction time of 30mins. Where on the other hand (keeping the reaction temperature
constant), with increase in reaction time from 5 to 30mins, the HHV of solid samples only
increased by 17.1% (18.56 to 21.75MJ/Kg) at 190C and by 12.05% (26.38 to 29.56 MJ/Kg) at
260C. No significant effect can be observed for HHV with increase in feedstock to water ratio. The
results from the model suggest that the HHV of feedstock is mainly controlled by operating
parameters in the order of: Temperature > Time> Solid load. Using the linear model relationship
and ANOVA method for HHV as function of reaction time (t), temperature (T) and solid load/ratio of
water to feedstock (R), the statistical equation (Eq.6) was derived with R-square value of 0.904.
( )

( )

( )

(6)

Figure6. Mean Model for Reaction time, temperature and ratio vs HHV
The strength of operating parameters on energy yield of miscanthus feedstock is
represented in Fig.7. Similar to the results from mass yield and HHV, energy yield of solid product
remains unaffected with change in reaction time and feedstock to water ratio. Results for the
energy yield are directly correlated with the product of mass yield and energy densification ratio.
Using linear model relationship and ANOVA method for energy yield as function of reaction time (t),
temperature (T) and solid load/ratio of water to feedstock (R), the statistical equation (Eq.7) is
derived with R-square value of 0.76.
( )

( )

( )

(7)

Figure7. Mean Model for Reaction time, temperature and ratio vs Energy Yield

824

In dry torrefied Miscanthus, very small percentage of hemicellulose degradation was

observed and significant portion of hemicellulose still remained in the solid product. Also, very
small percentage of aqueous soluble materials (hot water extractives) were characterised during
fiber analysis (Table 2). Moreover, so far no study has been confirmed for the formation of 5-HMF
during dry torrefaction. This explains the reason behind the lower mass loss and lower HHV of
solid product obtained during dry torrefaction compared to one from HTC (Fig.5). For the same
energy yield, pre-treatment condition requirements, i.e. reaction time and temperature, are
considerably lower for HTC (190C-5mins) when compared to dry torrefaction (260C-30mins).
Even though the lignin composition of dry torrefied miscanthus is higher than hydrochar samples,
still its HHV is not high. This could be related to its high hemicellulose and low aqueous soluble
material composition in dry torrefied miscanthus.
3.2.

Grindability:
The thermal pre-treatment of biomass alters the physical structure of biomass, reducing
its fibrous tenacious nature and thus making it much easier to grind compared to raw wood. Fig. 8
shows the particle size distribution of raw and pretreated miscanthus samples, and its comparison
with coal. The data indicates that the fraction of fine sized particles for miscanthus samples
increases in both the thermal pre-treatments pretreated and therefore is easier to grind as
compare to raw material. However, the miscanthus pretreated under HTC process has
pulverization and heating properties significantly higher than obtained for dry torrefied miscanthus.
Moreover, the properties of HTC pretreated miscanthus (260C-5mins) are very similar to that of
coal. The grindability (percentage fraction of fine particle) of hydrochar samples increases with
increase in HTC reaction temperature.

100-250m (%)

250-500m (%)

>500m (%)

HHV

100

28

90

27

80

26

70

25

60

24

50

23

40

22

30

21

20

20

10

19

18
190
Raw

225

260

HTC-5mins

260
Torref30mins

Coal

Temperature (C)
Pretreatment Process and Reaction Time
Figure8. Particle size distribution for raw and pretreated miscanthus samples and its
comparison with coal
Removal of hemicellulose from biomass results into destruction of lignocellulosic structure
of biomass via degradation and depolymerisation reaction mechanisms (Funke & Ziegler, 2010).
The destroyed structure has increased porous surface structure which is the main cause of
improved friability of the pretreated solid product. The structures of raw and pre-treated
miscanthus samples observed under SEM are shown in the Fig.9. The images of the samples
show the variation in structure with increase in reaction temperature. For the raw miscanthus, a
clearly well-defined structure can be observed. However, in case of pretreated miscanthus
samples the rupture and opening of pores is noticeable, and almost complete loss of structure can
be observed for the sample obtained at 260C. The pulverized HTC-pretreated samples has also
been reported to show spherical shaped particles which may further facilitate uidization process
during gasification processes (Tremel et al., 2012).

825

HHV (MJ/Kg)

Particle Size Distribution (%)

<100m (%)

Figure9. SEM images of HTC pretreated Miscanthus: (A) Raw, (B) 190C, (C) 225C, and (D)
260C
3.3.

Hydrophobicity:
EMC of material can be used as an indicator of hydrophobicity. The presence of high
moisture content in biomass can favors the fungal growth on it with time. Therefore, the rate of
biodegradation of biomass strongly depends upon its moisture content and the moisture content of
biomass further depends upon the atmospheric surrounding where it is stored and the
lignocellulosic composition biomass (Acharjee et al., 2011). For a lignocellulosic biomass, moisture
can be adsorbed in two types: non-bonded (present in cell wall) and bonded (hydrogen-bonded to
the hydroxyl groups of the cell wall). The non-bonded moisture increases with increase in relative
humidity where the bonded moisture does not, as the structural changes takes place in biomass
after thermal pre-treatment. Among polymeric composition of biomass, hemicelluloses have the
greatest capacity towards water adsorption; while lignin shows very little tendency for water
sorption (Acharjee et al., 2011). Hence, removal of hemicellulose (or percentage increase in lignin
content) from a solid product will lower its tendency to adsorb water and will make it more
hydrophobic in nature. A solid material with low moisture content can be stored easily without
possessing any threat to biological deterioration and the transportation of such material will be less
expensive, as there will be less water content to transport along with biomass (Yan et al., 2009).
The results for the hydrophobic behavior of raw and pre-treated solid samples are shown in the
table 3. Both, HTC and dry torrefaction, pre-treatment improves the hydrophobicity of biomass.
However, the solid materials obtained under HTC pre-treatment were found to be more
hydrophobic in nature than one obtained under torrefaction process. The hydrophobicity of the
HTC pre-treated samples increases with increase in reaction temperature. These finding are
directly correlated with the hemicellulosic composition of solid materials characterized under fiber
analysis (table 2). Also, the structural loss of solid samples, as shown in SEM images (Fig.9),
might have reduced the site availability for water sorption.
Table3. Hydrophobicity of Raw and Pre-treated Miscanthus Samples

Pre-treatment
Raw Miscanthus
HTC
HTC
HTC
Dry Torrefaction

Temperature
(C)

Time
(mins)

EMC (%)
(At R.H. =48-52%)

EMC (%)
(At R.H. =74-78%)

190
225
260
260

5
5
5
30

7.29
4.49
3.75
2.56
4.11

10.95
7.54
6.22
3.59
6.32

826

3.4.

Inorganic Analysis:
Lignocellulosic biomass has specific amount and different type of inorganic impurities in
its structure. Type of soil, growing condition and harvesting time can significantly affects the
inorganic composition of biomass (Kludze et al., 2012). These inorganic impurities are alkali and
alkaline metals such as calcium (Ca), magnesium (Mg), phosphorous (P), potassium (K), sodium
(Na), sulphur (S), iron (Fe) etc. that are left behind in the form of ash during biomass combustion.
In ash, these metals occurs in their oxide forms (Tortosa Masi et al., 2007), CaO, MgO, P2O5,
K2O, Na2O, SO3, Fe2O3, that shows various undesirable and notorious effects such as slagging,
fouling, klinker formation, corrosion etc. during biomass combustion (Baxter et al., 1998).
Generally, most of the inorganic impurities in lignocellulosic biomass are held in hemicellulose and
hot water extractives (Miles et al., 1996). Therefore, removal of hemicellulose from lignocellulosic
biomass will also reduce its inorganic composition. Furthermore, in HTC process due to the
formation of acetic acid in liquid by-product streams, acid reaction mechanisms takes place that
may solubilize and leach out these inorganic impurities (Lynam et al., 2011).
Under hydrothermal conditions, degradation/depolymerisation of hemicellulose and
cellulose takes place, causing the solid product to become porous (Funke & Ziegler, 2010). It has
been proposed that these porous structures may allow the leaching of previously held/bonded
inorganic impurities in the cross-linked matrix structure of biomass (Reza et al., 2013). However,
these porous structures obtained for hydrochars have significantly improved adsorption capacity
and are often used as a cheap alternate to powered activated carbons (PACs) in waste water
treatment industry (Regmi et al., 2012; Titirici et al., 2012). Therefore, hydrochar samples were
vigorously washed with acetone and de-ionized water in this study before inorganic analysis.
Raw

HTC-190

HTC-225

HTC-260

Torrefied-260

100
90

Inorgnaic Yield (%)

80
70
60
50
40
30
20
10
0
Calcium

Magnesium Phosphorous Potassium

Element Type

Sodium

Sulfur

Figure10. Inorganic yield of alkali and alkaline metallic composition of raw and
pretreated samples
Fig. 10 shows the effect of HTC and torrefaction pre-treatment on inorganic yield of
hydrochar and torrefied biomass. Inorganic yield was expressed as the ratio of inorganic
composition in pretreated solid material to the raw feedstock times the mass yield at a
corresponding reaction temperature. In Fig.10, it can be noticed that HTC process is able to
remove inorganic impurities from raw feedstock by 40-80%, and the removal capacity increases
with increase in reaction temperature. The unexpected trend observed in case of phosphorous
may be due to its interaction with porous structure of pretreated biomass even after vigorous
washing. Similar results were obtained by another study during HTC pre-treatment of corn stover
(Reza et al., 2013). In comparison, most of the alkali and alkaline metals remained high in dry
torrefied biomass, however the concentration level was found to be lower than the expected. This
might be due to the volatile behavior of such ash forming elements that plays major role in
gaseous and aerosol emissions (Obernberger et al., 2006).

827

Iron

CONCLUSION
Both hydrothermal carbonization and dry torrefaction are promising methods for upgrading
biomass and its conversion to an energy dense, homogeneous, friable and hydrophobic solid fuel.
However, for the same mass and energy yield, severity of operating conditions requirement (i.e.
reaction time and temperature) are significantly lower for HTC when compared to dry torrefaction.
Although, both the thermal pre-treatments reduced the EMC of solid product from that of raw
miscanthus but the solid obtained under HTC process is more hydrophobic in nature and therefore
can be stored and transported easily. Hydrothermally pre-treated biomass is highly friable in nature
and is much easier to grind to fine sized particles (<100m) compared to dry torrefied miscanthus.
Furthermore, HTC process is able to reduce the alkali and alkaline metal content of raw biomass
by 40-80% and thereby significantly reducing the problems of fouling and slagging in boilers during
combustion. HTC reaction temperature remained the most prominent parameter affecting the
extent of energy densification, grindability, hydrophobicity and inorganic removal capacity.
Most importantly, as the HTC process is carried out at the presence of water, therefore is
not affected by high moisture content of biomass and thus eliminates the pre-drying requirement
which is huge energy intensive and financial load for processes like dry torrefaction. The result
shows that HTC narrows the differences in fuel qualities and has potential to replace coal in
existing coal-fired power plants without any further modifications.
ACKNOWLEDGEMENT
We gratefully acknowledge the financial support from Ontario Ministry of Agriculture and
Food (OMAF), Ministry of Rural Affairs (MRA)-Highly Qualified Personnel (HQP) program, and
Natural Sciences and Engineering Research Council (NSERC) discovery.
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Energy & Fuels, 24(5), 2891-2899.

829

Development Of A Reduced N-Butanol/Biodiesel Oxidation Mechanism For A

Dual Fuel Engine
1

Xin Wang , Mingfa Yao , Haifeng Liu , Hu Wang , Zunqing Zheng

State Key Laboratory of Engines, Tianjin University, Tianjin 300072, China
2
Engine Research Center, University of Wisconsin-Madison, Madison, WI, 53705, USA
Corresponding author: Mingfa Yao, E-mail: y_mingfa@tju.edu.cn
1

ABSTRACT
A reduced chemical kinetic mechanism of the oxidation of n-butanol/biodiesel dual fuel has been
developed for a dual fuel engine simulation. The oxidation reaction pathway of n-butanol based on
the reduced kinetic mechanism by Wang et al. [Hu Wang, R. D. Reitz, Mingfa Yao, Combustion and
Flame, 160(2013)504-519] and several modifications were added. The main feature of the
modifications is consideration of the same species as the biodiesel mechanism. Then the n-butanol
mechanism was combined with an existing reduced mechanism for biodiesel oxidation. The final
mechanism consists of 157 species and 641 reactions. Validation of the mechanism was performed
with experiments of shock tube, jet-stirred reactor, constant volume chamber available in the
literature.
A KIVA code, coupled with the dual fuel mechanism, was used to simulate engine combustion. The
results showed good agreements with the experimental data of a dual fuel engine. The influence of nbutanol ratio on the oxidation of n-butanol/biodiesel dual fuel was studied. It was found that biodiesel
produced hydroxyl radicals when the in-cylinder temperature was above 700 k, and the hydroxyl
radicals were consumed by n-butanol. Therefore, the ignition delay time is extended with increasing
the n-butanol ratio. Moreover, the evolution of oxygen contained in the fuel structure was investigated.

Keywords: n-Butanol, Biodiesel, Reduced mechanism, Dual fuel, engines

1 INTRODUCTION
The increasingly stringent emission regulations have posed challenges to internal combustion engine
technology. The traditional mode of combustion has limited the improvement of thermal efficiency and
the decrease of nitrogen oxides and soot emissions. Therefore, experts world-wide are carrying out
research on new modes of combustion, such as homogeneous charge compressed ignition (HCCI),
premixed charge compression ignition (PCCI), partially premixed combustion (PPC) and reactivity
controlled compression ignition (RCCI) [1-4]. The control of in-cylinder fuel reactivity was achieved by
adjustment of fuel type, intake air temperature and pressure, injection strategy, EGR ratio and so on,
which realized the control of ignition and combustion process and is beneficial to high-efficient clean
combustion.
Biofuels are potential renewable, carbon neutral alternative to petroleum fuels and as a solution to the
energy crisis. Biodiesel and n-butanol are particularly attractive as they can be derived from a variety
of sources and costs lower. Biodiesel and n-butanol are both oxygenated fuel, which facilitates soot
emission reduction [5-8]. In our previous work, experimental studies were conducted to investigates
the combustion performance and emission characteristics in a modified single cylinder diesel engine
fueled with n-butanol/biodiesel dual fuel. The n-butanol is injected into the intake manifold with low
pressure and the biodiesel is injected into the cylinder. The different reactivity mixture can be obtained
by adjustment of the proportion of the fuels and the biodiesel injection timing. The effect of fuel
reactivity on combustion and emission characteristics have been investigated. The results showed
that ultra low NOx and soot emissions meanwhile highly-efficient could be achieved by varying the
biodiesel SOI(Start of Injection), EGR(Exhaust Gas Recirculation) rate and n-butanol ratio. When
EGR rate set at 40% and n-butanol ratio at 85% with reasonable biodiesel injection timing(-30CA
ATDC around)the indicated thermal efficiency reaches 47%, meanwhile the original NOx and soot
emissions stay ultra low.
To gain further insight into the combustion process of n-butanol/biodiesel dual fuel, it is essential to
construct the chemical kinetic mechanism for the oxidation of the dual fuel. The fundamental studies
of n-butanol oxidation have been conducted by several researchers. Dagaut et al. [9] developed a
detailed chemical mechanism for the high-pressure oxidation of n-butanol. This model was validated
by the experimental data obtained in a jet stirred reactor (JSR) at a pressure of 10 atm and a range of
equivalence ratios (0.52.0) and temperatures (8001150 K). Based on this mechanism, Sarathy et
al. [10] have made some modifications to provide better agreement with opposed-flow diffusion flame
data and JSR data at 1 atm. Black et al. [11] measured the autoignition delay times of n-butanol at
equivalence ratios of 0.5, 1 and 2 for n-butanol at pressures of 1, 2.6 and 8 atm at temperatures from
1100 to 1800 K in reflected shock experiments. A detailed chemical kinetic model was constructed

830

and validated against the delay times and also against jet-stirred reactor data measured by Dagaut et
al. [10] and Sarathy et al. [11] Harper et al. [12] developed a detailed mechanism for n-butanol
oxidation to predicted their experiments data of the pyrolysis of n-butanol. The mechanism is also
validated against recently published experimental data obtained in jet-stirred reactor, opposed-flow
diffusion flame and shock tube. Sarathy et al. [13] proposed a detailed model for the oxidation of four
isomers of butanol (1-, 2-, iso- and tert-butanol) including high-temperature and low-temperature
reaction pathways. The model well reproduced the low pressure premixed flat flame species profiles
obtained using molecular beam mass spectrometry (MBMS), premixed laminar flame velocity, rapid
compression machine and shock tube ignition delay, and jet-stirred reactor species profiles.
Due to the complexity of biodiesel and the size of its constituent molecules, it is more difficult to study
the combustion chemistry of biodiesel. In order to simplify biodiesel models, surrogate fuels with
shorter chain lengths are chosen for biodiesel combustion chemistry studies. In our previous work
[14], an experimental study has been carried out in a single-cylinder common-rail CI engine with
soybean biodiesel and two biodiesel surrogates containing neat methyl decanoate and methyl
decanoate/n-heptane blends. Tests has been conducted with various intake oxygen concentrations
ranging from 21% to approximately 9% at intake temperatures of 25 C and 50 C. The results
showed that the ignition delay and smoke emissions of neat methyl decanoate were closer to that of
soybean biodiesel as compared with methyl decanoate/n-heptane blends. A reduced chemical kinetic
mechanism for the oxidation of methyl decanoate has been developed [15]. The mechanism was
validated with experiments in shock tube, jet-stirred reactor, constant volume chamber and CI engine.
To the authors knowledge, the mechanism of the n-butanol-methyl decanoate has not been
discussed so far. So in this study, based on the previous biodiesel mechanism, a reduced n-butanol
mechanism was developed and combined with the biodisel mechanism, to construct a reduced
kinetic model for the oxidation of n-butanol and biodiesel dual fuel. This model is further validated
against ignition delay times measured in the shock tube, mole fraction measured in the jet stirred
reactor, combustion characteristics and emissions of the CI engine. The interaction of dual fuel in the
ignition process is investigated based on the variety mixture ratio. The reaction paths of oxygen
atoms in the two fuels are also discussed.
2 CONSTRUCTION OF KINETIC MODEL
2.1 THE N-BUTANOL SKELETAL MECHANISM FORMULATION
In our engine experiments, the n-butanol is injected into the intake manifold and have a long low
temperature process. Therefore, low-temperature reaction of n-butanol must be considered. The
reduction work was based on the detailed mechanism proposed by Sarathy et al [13]. The
mechanism includes high and low temperature reaction pathways of four isomers of butanol (1-, 2-,
iso- and tert-butanol). Species and reactions associated with 2-, iso- and tert-butanol are removed
from the detailed mechanism. A detailed kinetic mechanism consisting of 255 species and 1453
reactions is obtained.
Firstly, the detailed mechanism is simplified by the DRGEP(Directed Relation Graph with Error
Propagation) method [16,17]. It is important to choose the initial species for the DRGEP reduction.
According to the n-butanol reduced mechanism developed by Wang et al. [18], the important starting
species in the DRGEP reduction including C4H9OH, C3H7CHO, C3H6, C2H3OH, and C2H5 was
selected. While Reaction products including C4H9OH, O2, CO2 and H2O were added. The reduction of
the detailed mechanism was performed based on a large set of reaction states sampled within the
parameter space of pressure from 1 atm to 100 atm, equivalence ratio from 0.5 to 2.0, initial
temperature from 700 K to 1800 K for auto-ignition, and inlet temperature of 300 K for extinction in
perfectly stirred reactors (PSR). By allowing the worst case reduction error of approximately 30%, a
skeletal mechanism with 117 species and 663 reactions was obtained.
At the initial reaction of n-butanol, H atoms are abstracted by oxygen molecules, and C4H8OH
isomers and HO2 are produced. To reduce the number of species, it is necessary to remove the
isomers. C4H8OH-1 and C4H8OH-3 are left. There are several reasons, first, the skeletal mechanism
obtained by DRGEP method contains the two species, the other species are removed. Second, Black
et al. argue that the CH bond dissociation energies are is as follows: < < < < OH.
Furthermore, the rates of dehydrogenation of n-butanol with the temperature of 800 K and 1800 K are
shown in Fig. 1. At temperature of 800 K, the main step is the collision of the OH and HO2 radical with
n-butanol, for the formation of C4H8OH-1. When temperature increment to 1300 K, the most important
reaction is the OH attack on the fuel molecule, leading to the production of C4H8OH-1 and C4H8OH-3.

831

(a)

(b)
Fig.1. The rates of dehydrogenation of n-butanol (a. 800 K, b.1300 K ).

The following simplify is carried out by the reaction path and rate analysis. The main low temperature
reaction paths at 20% of n-butanol consumption are shown in Fig. 2. About 71% of n-butanol
converses to C4H8OH-1, and that of C4H8OH-3 accounts for 29%. There are two reaction paths of
C4H8OH-1 at low-temperature. 86% of C4H8OH-1 undergoes reaction (C4H8OH-1+O2 = NC3H7CHO +
HO2) to form the nC3H7CHO, the rest of C4H8OH-1 adds oxygen to form C4H8OH-1O2(RO2). Then the
C4H8OH-1O2 reacts by isomerization to C4H7OH-1OOH-3(QOOH). The reaction of C4H7OH-1OOH-3
is the second addition of O2 forming C4H7OH-1OOH-3O2. For the C4H7OH-1OOH-3O2(O2QOOH),
isomerization have been decided for C4OHKET1-3 and OH production. Decomposition reactions of
the C4OHKET1-3 lead to the formation of CH2OCHO, CH3CHO and OH radical. Unlike the C4H8OH-1,
at the second addition of O2 process of the C4H8OH-1, the C4H7OH-3OOH-1(QOOH) reacts with O2 to
produce the C4KET13 and HO2. Decomposition reactions of the nC4KET13 lead to the formation of
CH2CHO, CH3CHO and OH radical.

832

Fig.2. The main low temperature reaction paths of n-butanol.

When the temperature exceeds 1300 K, reactions of C-C chain scission of C4H8OH-1and C4H8OH-3
take place. The main reaction paths of n-butanol and biodiesel at temperature of 1300 K are shown in
Fig. 3. The C4H8OH-1 is decomposed into C2H3OH and C2H5, and decomposition reaction of the
C4H8OH-3 lead to the formation of C3H6 and CH2OH. Both of n-butanol and biodiesel are oxygenated
fuel, the same intermediate component will be produced in the pyrolysis process. When we make
further reaction path and rate analysis of the cracking products of C4H8OH-1and C4H8OH-3, even
unimportant intermediate components are retained if the intermediate components is the same to that
of the biodiesel mechanism. As can be seen from the Fig. 3, the same intermediate components of nbutanol and biodiesel mainly include C2H4C2H3CO,CH2CHO,CH2O and so on. Based on the above
reduction process, a skeletal mechanism with 71 species and 342 elementary reactions was
eventually obtained.

Fig.3. The main reaction paths of n-butanol and biodiesel at temperature of 1300 K.

2.2 THE COMBINED MECHANISM FORMULATION

When the n-butanol mechanism is added to the biodiesel reduced mechanism, repetitive species and
reaction will be appear. Part of the constants of element reaction are different between the two fuel.

833

The mechanism of biodiesel is more complicated, in order to ensure its integrity, repetitive species
and reaction are remove from the mechanism of the n-butanol. Therefore, the key constants of
element reaction of n-butanol are further adjustment to improve the prediction accuracy. By the
sensitivity analysis, the key constants of element reactions of dehydrogenation of n-butanol to
produce C4H8OH-1 and C4H8OH-3 should be adjusted. The pre-exponential factor A are multiplied by
1.4, as are shown in Table 1. The final mechanism consists of 157 species and 641reactions
Table 1. Changes made in the n-butanol sub-mechanism.
Reaction
A
nC4H9OH+OH<=>C4H8OH-3+H2O
1.141E+03
nC4H9OH+OH<=>C4H8OH-1+H2O
3.610e+03
nC4H9OH+HO2<=>C4H8OH-3+H2O2
2.760E-04
nC4H9OH+HO2<=>C4H8OH-1+H2O2
3.50E-05
nC4H9OH+O2<=>HO2+C4H8OH-3
2.000e+13
nC4H9OH+O2<=>HO2+C4H8OH-1
2.000e+13

n
2.87
2.890
4.760
5.260
0.000
0.000

E
-2.926e+03
-2.291e+03
1.185e+04
8.268e+03
4.980e+04
4.680e+04

Change A
1.60E+03
5.05E+03
3.86E-04
4.90E-05
2.80E+13
2.80E+13

3 VALIDATION OF PROPOSED MECHANISM

Due to the biodiesel mechanism in the dual fuel mechanism has not been changed, it is no need to
Verify the experimental data of pure biodiesel. The mechanism of pure n-butanol and n-butanol biodiesel dual fuel are validated with a variety of experimental data
3.1 PURE N-BUTANOL EXPERIMENTAL DATA VALIDATION
3.1.1 Ignition delay timings
Fig. 4 shows the modeling computations with the present model, the model of Sarathy et al. [13] with
the experimental data[19, 20] for the stoichiometric mixture, covering initial conditions with
temperatures of 7701250 K , pressures range from 10 atm to 80 atm. The present model shows
quite good agreement at high temperatures but over estimates the ignition delays of the lower
temperature regime.

Fig.4. T Oxidation of a n-butanol/oxygen/ nitrogen mixture in a jet stirred reactor at 1 atm and a residence time of 0.7 s.

3.1.2 Jet-stirred reactor

Dagaut et al. [9] studied the oxidation of a n-butanol/O2/N2 mixture in a JSR at atmospheric pressure,
between 800 and 1100 K. This study provided speciation data for the low-temperature oxidation of nbutnol (reactants, products and main intermediates). Fig. 5 presents a comparison between the
present skeletal model and the experimental data. The present skeletal model is in overall good
agreement with the experimental data.

834

Fig.5. Oxidation of a n-butanol/oxygen/ nitrogen mixture in a jet stirred reactor at 1 atm and a residence time of 0.7 s.
Experimental data [22] (symbols) and model computations (lines).

835

3.2 COMPRESSION IGNITION ENGINE

Experiments were conducted on a water-cooled direct-injection single-cylinder diesel engine
equipped with common-rail injection system. The experimental engine specification was described in
Table 2.
Fig. 6 shows the schematic diagram of the engine setup. Intake air was compressed, and then mixed
with recirculated exhaust gas. By using a throttle in the exhaust pipe, the exhaust back pressure was
adjusted to simulate the effect of a turbocharger. Injection was controlled by an electronic control
system. A pressure transducer (Kistler 6125A) was fitted flush with the wall of the cylinder head and
connected via a charge amplifier (Kistler 5011) to a data acquisition board in a computer. The cylinder
pressure data was recorded in half crank-angle increments, triggered by an optical shaft encoder.
Table 2. Engine Specification.
Engine type
Single cylinder, direct injection
Bore stroke

105 125 mm

Connecting rod length

210 mm

Displacement

1.08 L

Compression ratio

16:1

Speed

1500 rpm

Intake pressure

1.5 bar

Injection pressure

1000 MPa

Number of injector holes

Swirl ratio

1.6

Inlet Valve Close

-133 ATDC

Exhaust Valve Open

125 ATDC

1 Compressor; 2 Three-way valve; 3 Air flow meter; 4 Air tank; 5 Exhaust gas cooler; 6 Smoke meter; 7 Exhaust analyzer; 8
Pressure transducer; 9 Fuel injector; 10 Dynamometer; 11 Encoder; 12 Charge amplifier; 13 Air flow sensor
Fig.6. T Schematic of experimental setup.

The concentrations of CO2, CO, O2, NOx and HC in the exhaust gas were measured using a dynamic
multi-gas component measuring system (AVL SESAM-FTIR). The FTIR spectrometers use a wide
range of infrared wave lengths to simultaneously detect all spectral information available from the gas
sample. When the sample gas cell is filled with exhaust gas, each single exhaust gas component will
absorb infrared light at different wave length and depending on its concentration. This spectral
absorption will change the interferograms, which comprise the total information of the complete
spectral absorption of all gas components contained in the exhaust sample. This enables the
determination of the concentration of all infrared-active components of the exhaust gas sample.
Smoke was measured by a filter paper smoke meter (AVL 415S). The resolution of this smoke meter
is 0.001 FSN and the repeatability is less than 0.005 FSN + 3% measured value. Each measured
value presented here was an average result of three measurements.
The KIVA-3vr2 code, coupled with the Chemkin chemistry solver, was used to simulate the engine
operating conditions. The RNG k- model was used for modeling turbulence[21]. Spray droplet
breakup was modeled with the KH-RT spray breakup model[22]. NOx emissions are simulated by a
reduced NOx mechanism that was derived from the Gas Research Institute (GRI) NO mechanism[23].
A phenomenological multistep soot model was applied to predict the soot emissions.

836

The piston geometries and computational grids used for the simulations of the engine are shown in
Fig. 7. All the injectors of these engines are center-located and have 8 nozzles. Therefore, in order to
improve the computational efficiency, either 45 degree sector meshes were used in current
investigation. The cell numbers of the engine at bottom dead center were about 9500. The
computations were started from intake valve closure timing with an assumed uniform mixture
distribution in the cylinder and ended at the exhaust valve open timing.

Fig.7. T CFD grid.

Fig.8. Comparison of in-cylinder pressure traces and heat

release rate between experimental data and simulation results.

Fig.9. Comparison of emissions between experimental data

and simulation results.
.

Simulation study has been conducted with various n-butanol ratios. Fig. 8 and Fig. 9 compares the
pressure and emissions traces for various conditions. It is seen that the CFD simulations agree with
the experimental trends fairly well.
4 MODEL DISCUSSION
Due to the biodiesel mechanism in the dual fuel mechanism has not been changed, it is no need to
verify the experimental data of pure biodiesel. The mechanism of pure n-butanol and n-butanolbiodiesel dual fuel are validated with a variety of experimental data.
4.1 INTERACTION OF DUAL FUEL IN THE IGNITION PROCESS
As can be seen in in Fig. 8, with the increase of the proportion of n-butanol, ignition timing delays. To
better understand this trend, the effect of the ratio of n-butanol on the dual fuel ignition delay period is
calculate by use of the SENKIN model of the Chemkin package. The injection timing (-30CA ATDC)
of biodiesel is selected as the initial condition. Then the cylinder pressure is 25 bar, and cylinder
temperature is 800 K. The fuel used in the calculation contains neat n-heptane, neat n-butanol and a
binary mixture. The mole fractions of the initial material are shown in Table 3. The first three of fuelair equivalence ratio is fixed at 0.5. In comparison with the binary mixture, the 50% of neat biodiesel
was selected to understand the effect of n-butanol on the ignition process..
Table 3. The mole fractions of the initial material.

Biodiesel
n-butanol
O2
N2

100% Biodiesel
Mole fraction

100% n-butanol
Mole fraction

0.00673
0.20867
0.78460

0.01721
0.20647
0.77632

50% Biodiesel+
50% n-butanol
Mole fraction
0.00484
0.00484
0.20805
0.78227

50% Biodiesel
Mole fraction
0.00484
0.20805
0.78711

Computed temperature and species concentrations for auto-ignition of four kinds of fuel are shown in
Fig. 10. As can be seen in Fig. 10(a), pure biodiesel has significant cool-flame reaction, two stage
heat release process appears. At this stage, a large number of H2O2 radicals is generated. This is
because the OH radicals are produced by twice oxygen addition and dehydrogenation of biodiesel.

837

The low-temperature reaction more active and the HO2 radicals are generated. The H2O2 radicals are
generated through reaction HO2+HO2<=> H2O2+O2, and the system activity was reduced. When
temperature increases, ignition occurs when the H2O2 radicals begin to dissociate rapidly.
In Fig. 10(b), in the low-temperature process of n-butanol, there was little OH radicals generation
capacity. The HO2 radicals are mainly consumed by the dehydrogenation of n-butanol, leading to
generate less H2O2 radicals. So the ignition delay period of n-butanol is very long.
Comparison of the Fig. 10(b) and (c), when the biodiesel is added into the n-butanol, the ignition
delay is significantly shorter. Zhang et al. [24] considered that the OH radicals generated from the
biodiesel promote the dehydrogenation of the n-butanol. As can be seen from Fig. 10(c) and (d), at
the same mass fraction of bio-diesel fuel and oxygen, adding n-butanol will have shorter ignition
delay. The reason is, as Fig. 11 shows, at a low temperature process, the OH radicals generated from
the biodiesel are consumed by the n-butanol, and C4H8OH-1 is generated. The C4H8OH-1 radical
undergoes reaction (C4H8OH-1+O2 = NC3H7CHO + HO2) to form the HO2 radicals. The OH radicals
are more activity than the HO2 radicals. The dehydrogenation of n-butanol is mainly with the OH
radicals. A large number of HO2 radicals accumulate to generate the H2O2 radicals. Although
biodiesel consumption in Fig. 10(c) is lower than that of in Fig. 10(d), greater amounts of the H2O2
radicals are generated. When temperature increases, the period of richer H2O2 radicals dissociation
is shorter.

838

(a) Neat biodiesel at = 0.5,

(b) Neat n-butanol at = 0.5,

(c) Binary mixture at = 0.5,

(d) 50% Neat biodiesel
Fig.10. Computed temperature and species concentrations for auto-ignition of four kinds of fuel.

Fig.11. Schematic diagram of interaction of dual fuel in the ignition process.

4.2 THE REACTION PATHS OF OXYGEN ATOMS IN THE FUEL

839

Fig.12. The main reaction paths of oxygen atoms

Many researchers have found that oxygenated fuels can reduce the soot emissions of engine. Fig. 12
is the evolutionary paths of the two fuel. As can be seen from this figure, short-chain alcohols are
generated by C-C bond scission of n-butanol. Then dehydrogenation of short-chain alcohols
produces the formaldehyde which further generate CO. This is because that the bond energy of C-O
bond is greater than that of C-C, it is difficult to break the C-O bond. For the biodiesel, the oxygen
atoms of MD2J and MD8J will generate CO through the CH2O radicals. It is noteworthy that, the chain
scission of MD3J and MD6J will generate the CH3OCO radicals. The CO2 is generated through the
reaction CH3OCO = CH3 + CO2. As can be seen from Fig. 9, With the increase of the proportion of nbutanol, soot emissions of the engine is decreased. One important reason is that the one oxygen
atom in the n-butanol molecule combines a carbon to produce CO. Howerver, nearly 40% of the O
atoms in the biodiesel molecule, two oxygen atoms combine a carbon to produce CO2, which improve
the tendency of the conversion from the O atoms to soot.
4 CONCLUSIONS
A skeletal mechanism with 157 species and 641reactions for n-butanol-biodiesel oxidation was
developed. Based on the previous biodiesel mechanism, the skeletal mechanism of n-butanol was
added to the biodiesel mechanism. Repetitive species and reaction are remove from the mechanism
of the n-butanol, and he key constants of element reactions of dehydrogenation of n-butanol to
produce C4H8OH-1 and C4H8OH-3 are adjusted. Validated with the experimental data of shock tube
and jet-stirred reactor, Simulation results agree well with the ignition delay and the components
concentrations. A KIVA code, coupled with the dual fuel mechanism, was used to simulate engine
combustion. The results showed good agreements with the experimental data of a dual fuel engine
At the low-temperature process, the OH radicals generated by n-butanol are consumed by the
dehydrogenation of the n-butanol. By adding the n-butanol to the biodiesel, the H2O2 redicals
increase in the reaction system. Because of the greater bond energy of C-O, the one oxygen atom in
the n-butanol molecule combines a carbon to produce CO. Howerver, nearly 40% of the O atoms in
the biodiesel molecule are converted into CO2, which decrease the ability for soot reduction.
ACKNOWLEDGEMENT
The authors would like to acknowledge the financial supports provided by National Natural Science
Found of China (NSFC) through its project of 51125026 and 51320105008.
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842

Experimental And Numerical Studies On Residential Heating Equipment Burning

Biomass Briquettes
Du Cong

Liu Liansheng * Gou Xiang

Luo Jing

Ge Minghui

Zhang Xiaoyu

School of Energy and Enviroment Engineering, Hebei University of Technology, Tianjin

* Liu Liansheng@hebut.edu.cn

Abstract
Thermogravimetric-heating flow analyses of representative agricultural wastes of North China in
different heating rates were conducted with SDT-Q600, and the combustion kinetics of different
biomass were obtained based on the C-R method firstly. The heating rates influence
thermogravimetric process obviously. The combustion reactions of hemicellulose, cellulose and lignin
are considered to be parallel and independent in lower heating rate, while the combustion of char is
dependent. But in higher heating rate, the combustion processes of lignin and char present notable
time continuity. The volatiles combustion process is controlled by chemical reaction mechanism, and
the combustion of char is controlled by limiting surface reaction both phases mechanism. The
combustion mechanism changes with the increasing of heating rate and depends on the structure
characteristics of biomass to some extent.
Based on the analyses of energy rating, economical efficiency and combustion cycle of biomass
briquettes, residential heating equipment was designed. And the combination properties of heating
equipment were tested and the combustion process in combustion chamber was simulated. The
energy density and the low heating value of biomass briquettes are lower than anthracite, however
the energy rating of biomass briquettes is approximately equal to anthracite and the economical
efficiency is higher than anthracite. Because of the combustion cycle is just 20 minutes, delivering the
briquettes by automatic stoker enhances stability of the combustion process. The residential heating
equipment could work stably and abolish banking up process which was to lessen the tar
condensation and slag-bonding on heating surfaces. The thermal efficiency is about 72% and the
cooking heat efficiency is nearly 20%. Complex vortex structures in the combustion chamber caused
gases disturbance intensively, which was in favor of the burning of volatile matter.

Keywords: Biomass briquettes, combustion, combustion kinetics analysis, combustion mechanism,

heating equipment, mechanical.

0 INTRODUCTION
Biomass energy has received increasing attention worldwide with the depletion of traditional fossil fuel
source. In China, a series of electric-power/gas stations using gasification or direct combustion of

biomass fuel has been developed in the direction of large scale industrialization. However,
constrained by the dispersed distribution of biomass energy and consequently high cost of
acquisition, transportation and storage of the biofuels, the business outlook of these biofuel
power stations remain cloudy[1,2], and the strategy of large scale industrialized biomass energy has
not produced the planned effect.

843

Each year China produces 600 million tons of crop straw (equals to 380 million tons of standard
coal), 70% of which can be utilized as a source of energy. Twenty years ago in rural areas of North
China, crop straw had been used as the main fuel for cooking and heating, but with the improvement
of living standards during these years, most of these traditional low grade fuels have been replaced
and then wasted or burned directly in fields, causing atmospheric pollution and a whole series of
issues[3]. However recently, the development of straw briquette technique opens a possibility of using
these biomass energy cleanly and effectively: by compression molding, the physical density and the
power density of the biomass materials increased; therefore, with specially designed combustion
equipments, the straw briquette can be consumed locally and cleanly with reasonable efficiency. But
because the combustion behavior of crop straws is differ from each kind and vary widely from one
area to another, it is important to acquire detailed knowledge of the combustion kinetics of typical crop
straws for the reference of combustion equipment design. On the other hand, because of the high
burning rate of crop straw, a typical stoking cycle for a straw briquette boiler is within 20-30
minutes[4,5], which is much shorter than that of a coal boiler, and the design approach of the
combustion equipments for biomass fuel is inherently different from that of the coal.
In modeling the process of pyrolysis and combustion, the details of the activating energy, reaction
order, pre-exponential factor, the index of ignition behavior and the index of incomplete combustion
are usually studied by the general method of TG-DTG( Thermo Gravimetry and Differential Thermal
Gravimetry ) analysis. However, because of the parallel reactions and the competition between these
reactions in the pyrolysis and combustion of biomass, this process is so complex that no one single
kinetic model yet developed can explain the pyrolysis and combustion process entirely and precisely.
Therefore, based upon the comparison analysis of different kinetic models including single-step global
reaction model, multiple-step model and semi-global model, previous researchers found that the
multiple-step model with Coats-Redfern Equation may have the minimum deviation. Ma Xiaoqin et al
[6,7] and Jing Zhentao et al[8] individually analyze the cotton straw and wheat straw from Middle
China using the TG method which review that the combustion behavior of cotton straw is better than
that of the wheat. Atul Sharma et al [9] suggest that the order of reaction of the hemicellulose of the
rice hull oxidation is 1.5 and 2.0 for the fixed carbon ( FC ) content. At the heating rate of 20 C/sec in
the case of cane bagasse, research showed that the weigh loss occurs mainly above 550C and its
activating energy distinctly larger than other crops[10]. The thermodynamic analysis of various
Turkish crop straws show that the volatile content behave in a different way and the FC content burn
differently for different crops[8], and the country of origin usually affects the kinetic parameters.
Liu et al[11] and Ma et al[12] designed hand stoked residential heating boilers employ straw
briquette fuel with the load capacity of 87 kW and 200 kW respectively and analyzed the effect of
briquette size on the thermal efficiency and emission characteristics of the boiler; results show that the
thermal efficiency is 70% and the emission is comply with the national standard, but briquette size
greater than 40 mm causes the thermal efficiency to decrease. However with the their corresponding
heating supply area in the range of 1000-2500 m2 for the above boilers, they are not appropriate for
the individual farm user, and the short combustion cycle of briquettes, and thus the short handstoking intervals, destabilize the flame and increase the labor intensity.
North Europe countries such as Sweden and Norway maintain the leading position in the R&D of
biomass energy. Johansson et al [13] present a 6 kW biomass boiler with mechanical stokers and
wood pellet size 6-8 mm are conveyed into the furnace at the proper speed with the result of stable
combustion (Fig.1). However, the ash contend of crop straws is higher than that of wood and their ash

844

fusion temperature is lower, thus the clinkering of the straw combustion on the heating wall of the
combustion chamber decreased the thermal efficiency by 10% for the straw briquette fuel. Otherwise
the price of the compressed straw pellet ranges in 950~1000 per ton, exceeds the affordability of
the middle customer and limit the use of it.

aWater heating stove

bAir heating stove

Figure 1 Biomass boiler with mechanical stokers

[13]

Based on the above analysis, this paper focus on keen price briquettes fuel (450~550/ton ) and
developing proper residential heating boilers to explore new ways for north china farm of clean,
efficient and economical energy.
1 ENERGY EFFICIENCY ANALYSIS OF STRAW BRIQUETTE DIRECT COMBUSTION
The present work deals with the straw briquette size 303070 mm (Fig. 2) and made from
cotton and peanut straw, which are typical agricultural wastes in north china farms. The ultimate
analysis and proximate analysis of the briquette fuels are listed in Table 1, and are compared with the
typical heating coal used by north china farms, the Yangquan anthracite.
Table 1 Ultimate analysis and proximate analysis
Type of
fuel

ultimate analysis%
C

Qnet

proximate analysis%

FC

(MJ/kg)

Cotton

38.56

5.03

40.65

0.75

0.10

5.80

9.10

5.80

70.63

14.47

9.10

15.40

Peanut

39.17

4.91

36.37

0.78

0.03

6.83

11.89

6.83

63.49

17.79

11.89

14.27

Yangquan

65.65

2.64

3.19

0.99

0.51

8.00

19.02

8.00

7.85

65.65

19.02

24.42

anthracite[14]

It is shown in the table that the volatile content (VC) of the straw briquettes are significantly higher
than that of the coal and the Fixed Carbon(FC) are lower than that of the coal, and the low heating
value of the straw briquettes is 60% of the coal. However, the energy rate of the straw briquettes fuel
is approximately equal to that of the anthracite. The energy rate is defined as the amount of heat per
unit volume of flue gas under condition of complete combustion at stoichiometric ratio. Calculations
show that the energy rate of the cotton and peanut straw briquettes fuel is 3.22 MJ/Nm3and 3.40
MJ/Nm3 respectively, which is about 90% of the energy rate of the Yangquan anthracite (3.63
MJ/Nm3) . This answers the question whether the briquette fuels are applicable for residential heating
equipment: when using the high temperature flue gas to convect heat in the boiler, the heat transfer
effect are about the same for both briquette and coal fuel.
2 HEATING RATE OF STRAW BRIQUETTE FUELS IN COMBUSTION CHAMBER
The heating rate of the briquette fuel was obtained in a vented combustion chamber specially
designed for the experiment as illustrated in Figure 3. Once entered the high temperature combustion

845

chamber, the briquette temperature will increase rapidly by the heating of flame radiation. In Fig. 3,
experimental results show that the typical combustion cycle is 20 minutes. When the briquette fuel is
conveyed into the volatile flame, its temperature increases rapidly and the volatile fraction at the
surface of the briquette emit and then mix and burn, thus accelerating the volatile process and give
out smoke. Below 280 C, the temperature rising rate is 60 C/min; but above 280C, the temperature
rising rate is liable to be affected by the ventilation condition. The temperature rising rate is 80C /min
with forced ventilation, but without forced ventilation it decreased to 30 C/min. The volatile constituent
begins to burn at t=300 s in the condition of forced ventilation and burned out at t=720 s; and then in
the stage of coke combustion the temperature rising rate is zero (dT/dt=0 ) caused by the low FC
content of the fuel and the heat dissipation of the vented chamber.
800

600

temperature ( C )

700

500
400
300

Briquette in Flame
Forced draught
Natural draught

200
100
0
0

240

480

720

960

1200

t (s)

Figure 2 Straw briquette

Figure 3 Combustion of cotton straw briquette and the temperature curve

Therefore, hand stoking of residential heating boilers with briquette fuel and switching the fire
door too frequently will destabilizing the flame and increasing the labor intensity.
3 THERMOGRAVIMETRIC-HEATING FLOW ANALYSES
Having been compressed, the physical behavior of the straw, such as the physical density, water
affinity, angle of repose, friction coefficient varied accordingly, along with the emission and clinkering
behavior. According to the research of Fan et al[15,16], the amount of flying ash of the straw briquette
decreased greatly, and the clinkering rate decreased as well. But generally the modification of the
physical form does not have a significant effect on the combustion behavior of the fuel. In this section.
In this section, the TG-DTG curve is achieved using SDT Q600 simultaneous analyzer and the
thermo- kinetic parameter and reaction model is obtained and analyzed with the C-R method.
3.1 Regionalization of the weight loss process
Fig.4 illustrates the results of thermo gravimetry analysis of cotton straw briquette (left) and
peanut straw briquette (right) at the carrier gas flow rate of 100 ml/min which ensured the complete
combustion of the sample. According to our analysis, the weight loss process of cotton straws can be
divided into three regions: Region I is the drying region, which can be divided into two sub-regions (IA,
IB) according to the thermo gravimetry characteristic of the fuel. The temperature range of the
sub-region IA is 30-120C, in which range the TG curve descends slowly with temperature, owing to
the vaporizing of the water content, most of which are surface water. The peak value of the weightloss
curve occurred at T=80C. In Region IB (temperature range:120-200C), as the weightloss is
negligible, the TG, DTG curve is almost flat, but the temperature of the sample increased with the
heating process.

846

Figure 4 Thermo gravimetry analysis of cotton straw briquette(left) and peanut straw briquette(right)

Region II is the region of volatile matter emission and buring, with the corresponding
temperature ranged in 200-390C; three sub-regions can be found in this region: in the first
sub-region (II1), the DSC curve is below the zero line, thus the weightloss is mainly due to the
pyrolysis process of hemicellulose. Region II2 occurs at the point when the DSC curve rises above
the zero line and the sample begins to burn, causing the TG curve a rapid drop and the DTG curve a
rapid rise. The second peak of the DTG curve occurred at the third sub-region (II3), owing to the
combustion of the volatile contend of the lignin (VCL) . But according to the thermal analysis, the
combustion process of the VCL and the FC are overlaped, and with the heat peak of VCL combustion
merged into that of the FC combustion, the DSC and DTA curve rise rapidly in this region.These
results reveal that the process in Region II is mainly controlled by oxidative pyrolysis. Before
combustion, the sample pyrolysed firstly, but as the pyrolysis and buring of hemicellulose, cellulose
and lignin are partially overlapped, these reactions are coupled together in some degree, and it should
be noted that if the air flow is not actuated with the VC emission during the direct combustion process,
the emission of tar and soot will incease and prevent complete combustion.
Region III (390-520C) belongs to the char and FC oxidation: the weight loss ratio in this region
is far less than that of Regoin II, but according to the DSC curver, most of the heat of the cotton straw
combustion gives out in this region, due to the high lignin content of cotton straw which has a longer
growth cycle.
The weighloss process of the peanut straw briquette sample at the heating rate of 30 C /min
can be described with the 3-Region-Model as well ( Fig.4 right) , but because the straw compositions
are changed, the features of the regions varied accordingly: (1) the baseline deflection became
obscure in the TG curve of Region II3, and the small heat peak merged into a shoulder peak in the
DTG curve; thus the overlay of cellulose and lignin combustion forms the highest heat output as the
VC content is substantially larger than the FC content for peanut straw; (2) The total heat value ( by
means of integration of the DSC curve ) of the peanut straw is smaller that that of the cotton straw,
because of the higher ash contend due to the the addtion of clay during the briquetting process of the
peanut straw.
3.2 Influence of heating rate on the weight loss process of different straw
At the heating rate of 20C /min the regionalization of the weight loss process of the maize
straw is similar to that of the peanut. As shown in Figure 5, heating rate has a significant effect on the
thermal weightloss process of the briquette. Fig.5 shows the TG, DTG and DSC curve of the maize
straw at three different heating rates.

847

With the increase of the heating rate, the deflection of the baseline of the TG curve became
distinct and evidenced a shoulder in the DTG curve, resulting from the attenuated interactions of
cellulose and lignin combustion, and at the heating rate of 50 C /min the peak value of the DSC curve
rise higher. At the heating rate of 75 C /min, results show : 1) the baseline deflection of the TG curve
become more distinct; 2) the coupling effect of lignin and FC combustion is reinforced with the
gradient of the corresponding TG curve almost coincide to each other, and the continuity of these
weightloss process leads to the second peak in the DSC curve, which includes the heat output of both
reactions.

Weight(%)

200C DSC
500C DSC
750C DSC

40

30

20
15

1.0

10
5

20

1.5

25

0.5

200C DTG
500C DTG
750C DTG

2.0

Driv.weight (%/C)

60

Heat Flow(W/g)

80

Sample:Corn stalk
40
200C TG
500C TG
35
0
75 C TG

100

0
-5

0
0

200

400

600

800

1000

0.0

1200

Temperature (C)

Figure 5 Thermo gravimetry analysis of maize straw

Figure 6 TG, DTG and DSC curve of the maize

straw at different heating rates

Fig.7 is the weight loss-time curve based on Fig. 6. At a lower heating rate, the interactions of
hemicellulose, cellulose, lignin combustion is rather intensive, while the FC content burn almost
independently; but at higher heating rate, the coupling effect of lignin and FC combustion became
apparent. Actually the heating rate has a direct effect over the mechanism of combustion of the
various component of the fuel and gives rise to a distinct weightloss progress, which will be discussed
later in this paper. Furthermore, the increase of heating rate shorten the combustion time of the fuel,
and the sample burns out in 15 minutes at the heating rate of 75C /min, which is consistent with
above experiment in the combustion chamber. In conclusion, the key to a stable briquette fuel
combustion for small scale equipments is a smooth and stable fuel-feeding.

40

10

20

-10
60

1.0

0.5

60

20 C/min DSC
0
50 C/min DSC
0
75 C/min DSC

40
20

10

20

30

40

50

1.5

20
15

1.0

10
5

0.5

0.0
0

25

80

Deriv.Weight(%/ C)

20 C/min DSC
0
50 C/min DSC
0
75 C/min DSC

20

1.5

Weight(%)

60

30

20 C/min TG
0
50 C/min TG
0
75 C/min TG
0
20 C/min DTG
0
50 C/min DTG
0
75 C/min DTG

2.0

30

Deriv.Weight (%/ C)

20 C/min DTG
0
50 C/min DTG
0
75 C/min DTG

35

Sample: sunflower

40
Heat flow (W/g)

Weight(%)

80

100

2.0

20 C/min TG
0
50 C/min TG
0
75 C/min TG

Heat Flow(w/g)

Sample: Corn stalk

100

-5

0.0

0
0

200

400

600

800

1000

Temperature( C)

t (min)

Figure 7 Thermo gravimetry analysis of corn stalk

Figure 8 TG, DTG and DSC curve of sunflower

straw at different heating rates

Fig.8 is the TG, DTG and DSC curve of sunflower straw at different heating rates. The influence
of heating rate on the weightloss process is similar as in the case of Fig.6, except that the

848

time-continuity of the heat releasing of various components is more visible, superimposing a peak in
the DCS curve.
3.3 Combustion kinetic modeling of crop straws
Based upon the experimental results, the combustion kinetic behavior of the straw fuel can be
determined using C-R (Coats-Redfern) method. The C-R Equation can be written as

ln

g ( )
AR Ea
ln

Ea RT
T2

where Ea is the activation energy, A the pre-exponential index, T the absolute temperature, R
the gas constant and the heating rate; g() is the model function, which have different expressions
associated with the kinetic mechanism, particle size and shape, etc. as listed in Table 2; is the mass
conversion ratio:

m0 mt m0 m

where m0 is the initial mass of the sample, mt the mass of the sample at the time t ,mthe final
mass of the sample.
Taking 1/T as the abscissa and by means of linear regression analysis, the activation energy,
Ea, can be derived from the slope of the best fitting line of the curve ln [g() /T2] based on the TGA
data, and the pre-exponential index, A, can be obtained from the intercept of the line : ln(AR/Ea), as
R and are already known.
Table 2 Mechanism function
g kt

Symbol

One-way transport

D1

Two-way transport

1 ln 1

D2

Mechanism

Diffusion
mechanism

Three-way Jander transport

D3

1 1

1/3 2

1 2 3 1

D4

First order

ln 1

F1

Second order

1 1

F2

Third order

0.5 1

Two dimensions

1 1

R2

Three dimensions

1 1

R3

Ginstling-Brounshtein

2/3

equation
Chemical
reaction order

Limiting surface
reaction both phases

1/ 2

1/ 3

F3

3.4 Combustion kinetic of cotton straw

The following focus on the second region (Region II) of cotton straw, which is the most typical
crop in north China. Sub region 1st of Region II is the aerobic pyrolysis region, the Sub region 2nd
and 3rd of Region II belongs to the oxidation of volatile fraction.
In 1st, II, model D3 and D4 has the highest correlation coefficient: r=0. 9881 for D3 and 0. 9883
or D4, therefore the Three-way transport model is the optimum model for this region, which means
that the pyrolysis process is a diffusing controlled, interface fixed and solid state particle reaction
mechanism based upon three-way Jander transport. In region 2nd, II and 3rd, II, F1 model is the most
applicable model with the correlation coefficient r=0. 9515.

849

Table 3 Caculation results of different reaction mechanism

Region

Mech
anism

C min

correlation

A
-1

coefficient r

min

D4

235. 67

0. 9883

6. 288E+19

D3

243. 41

0. 9877

4. 477E+19

F1

114. 36

0. 9515

8. 805 E+6

IIC

F2

225. 96

0. 9481

7. 228E+17

III

R2

332. 97

0. 9942

1. 451 E+21

D2

659. 34

0. 9942

1. 529 E+45

D2

210.35

0.9983

F2

110.46

Region III

R2

1st

IIB

1st
50

Ea
kJ/mol

IIA

20

Caculation results

Temperatu

Mass loss

re range

rate

200-280

10. 5

290-380

64. 5

390-750

9. 5

3.270 E+17

200-280

11.0

0.9390

3.639 E+7

290-380

64.0

74.64

0.9873

3.677 E+1

390-700

9.5

D1

148.91

0.9959

1.604 E+11

200-290

12.0

F2

80.62

0.9919

4.588 E+4

290-390

39.0

F1

105.15

0.9923

1.451 E+4

400-650

31.5

Region II
2nd&3rd
Region II

Region II
75

2nd
Region II
3rd of
Region II
&Region III

In Region III, model R2 and D2 has the highest same correlation coefficient (r=0. 9942). But the
calculation result of Ea in D2 model is beyond reasonable range, thus model R2 is the acceptable
model.
3.5 Influence of heating rate on the kinetic parameter of cotton straw
As discussed above, the heating rate has a profound effect on the weightloss behavior of
cotton straw, for the basic reason of mechanism changing according to the heating rate. The
calculation results are listed in Table 3.
In Region 1st, II, the increase of heating rate leads to the acceleration of aerobic pyrolysis
within a shorter period of time, and the reaction mechanism is changed form the D4(3-way transport)
to the D2(2-way transport), even D1(1-way transport) , and Ea declined as well. In Region 2nd, II, the
reaction mechanism is changed from the First Order chemical reaction to the Second Order chemical
reaction. In other word, under the condition of rapid heating rate and prompt releasing of VC, the
effect of reactants concentration became stronger.
At the heating rate of 75C/min the combustion of lignin, char and FC exhibit the mechanism of
parallel reaction. Therefore in data analysis, the region of lignin combustion ( 3 rd, Region II) is
merged into Region III according to the trend of the TG and TSC curve. Region 1st and 2nd of II fits
into the D1 model and F2 model, respectively, and Region III fits into the F1 model, in which region the
combustion of lignin, cha and FC does not exhibit the mechanism of independent reaction and the
reaction rate is governed mainly by the reactants concentration.

850

In one word, the increase of heating rate makes the reaction mechanism varied accordingly in
each region, and Ea decreased in trend.
4 RESIDENTIAL HEATING EQUIPMENT DESIGN TEST AND SIMULATION
4.1 Equipment design & test
According to the living custom of north China farm, the residential heating equipment should
serve the demand of household heating and cooking, therefore, natural ventilation and gratefiring
structure are adopted in the design of briquette fuel boiler. The surface-area-heat-load is 220 kW/m3
and the volume-heat-load is 300 kW/m3 and the grate surface area is 0.04 m2 and the volume of the
combustion chamber is 0.024 m3 according to the design.
The overall structure of the heating equipment is shown in Fig.9, the briquette is conveyed into
the furnace through the inlet port on the top of the chamber by an automatic stoker and slides onto the
fire grate. The automatic stoker is worked by a push plate connected to a regulated speed motor and
the corresponding automatic control system. The heat loss can be reduced by use of firebricks round
the wall of the chamber and thus rising the combustion temperature and squeezing the volatile
constituent out of the fuel. The primary air is directed into the chamber through the bottom of it and
meet with the coke layer; the secondary air is passed through the vent holes uniform distributed in the
firebricks and burned with the volatile gas. The out wall of the chamber is surrounded by water tube
(0.05m3 of water) and the flue gas is passed through the funnel with certain angles to the chamber to
decrease its temperature and raise the thermal efficiency,
The flame shape from various angles is shown in Fig.10 .The main flame, colored in bright
yellow, fluctuates intensively, while the flamelet nearby the vent holes colored in blue, indicating a well
mix of the volatile matter and the secondary air. The burning briquette on the firegrate colored in dark
red. Fig 11 is the ash of the briquette after burning, with the carbon content less than 1-2% according
to TG analysis[17]. Ash removal work of the boiler is unnecessary because of the loose structure of
the briquette ash.

Figure 9 Heating equipment structure, funnel and stove

Figure 11 Briquette ash

Figure 10 Combustion experiment

The compositional analysis of the flue gas within a stoke cycle is shown in Fig.12. Before new
fuels are added into the chamber, the VC inside the chamber has been burned out and left a thin fuel
bed with low ventilation resistance, and the temperature of the chamber is relatively low and thus the
oxygen content is higher. When the new fuels are added, the CO and CmHn concentration increased

851

because of the quick emission of the volatile content; and then the temperature of the chamber
increased with the ignition of the volatile content, which reduced the O2 concentration, and the CO
and CmHn concentration dropped to the normal level but the NOx concentration increased. To sum
up, the CO and CmHn concentration ranged about 0.08% and 0.1% respectively and the NOx
concentration ranged about 130 ppm, fulfill the requirement of CO<1500ppm, NOx<150ppm
according to the industry standard.
3000

16
15
14

NOx
CO
CxHy

2500

O2
CO2

Concentration (%)

12
11
10
9
8
7
6
5
4

Concentration (ppm)

13

2000

1500

1000

500

2
1
0

9 10 11 12 13 14 15 16 17 18 19

Time (min)

9 10 11 12 13 14 15 16 17 18 19

Time(min)

Figure 12 Flue gas analysis

90

Temperture ( C)

75

60

45

t1
t2
t3

30

15

0
0

9 10 11 12 13 14 15 16 17 18 19 20

Time (min)

Figure 13 Indoor heating system

Figure 14 Supply water temperature curve

The indoor heating system is constructed as shown in Fig.13. The thermal efficiency of the
boiler is 74% according to the calculation based on the measuring data of the fuel rate, supply and
return water temperature and the circulating water rate. According to NB/T 34006-2011( General
Specification For Domestic Densified Biofuel Heating Stove) , experiment results show that when the
feed water temperature is 12C, at the circulating water rate of 60 kg/h, the leaving water
temperature fluctuated (Fig.14), which was caused by the combustion cycle fluctuation; but the
average temperature difference ranged within 70C and the positive equilibrium thermal efficiency of
72% is attained. For the main reason of the low feed water temperature (12C, colder than the
normal heating system), the combustion declined and reduced the thermal efficiency.
According to the measuring results of flue gas composition, ash carbon content and the boiler
surface temperature, the heat loss due to the incomplete solid combustion, the incomplete gas
combustion, the exhaust gas and the surface heat leakage is 1.5 %, 3.0 %, 20% and 0.5%,
respectively. Thus the reverse equilibrium thermal efficiency is 2=75%. But if the upper furnace gate
is opened for cooking demand simultaneously, the heating load capacity would be affected and the
cooking efficiency is about 20% according to the test, which basically satisfied the demand of a farm
household.

852

4.2 Numerical simulation

Simulation was conducted based on a simplified model of the boiler: the combustion chamber
takes the form of a cylindrical volume with vent holes on the firegrate; the primary air enter the
chamber through the 50 circular vent holes with 2 mm radius; the 16 vent holes of the secondary air
are of 5 mm radius; the fuels are carbon particles with 5 mm in diameter and the volatile constituent.
The inlet port area is 0.009m2 with the height of 0.05 m. and number of the unstructured grid of the
model is 352204. Model configurations are: k- turbulent model and non-premixed combustion;
one-step pyrolysis model, PDF model and Generalized Finite-Rate Model is used in the simulation of
the volatile pyrolysis and combustion, and the coke combustion, respectively; P1 radiation model for
the heat transfer in the combustion chamber.

Figure 15 Physical model

Figure 16 Velocity distributionm/s, streamline

and temperature distribution (Kon the X-Z plate

Figure 17 Mole concentrate on different plates

The simulation results show that the complex vortex of the gas phase intensified the
combustion inside the chamber. The high temperature regions concentrate on the mixing zone of the
coke and the primary air, and the mixing zone of the volatile constituent and the second air. The
average temperature of the chamber is 1200C, slightly higher than in the experiment, for the reason
that the surface heat flow rate is slightly lower in the simulation configuration than in the experiment.
The intense vortex disturbance of the gas flow and the high average temperature promotes the
emission and combustion of the volatile constituent, and CH4 burned out nearby downstream of the
flame bending plate, but the mole concentrate of CO and H2 are higher than in the experiment. As
mentioned above, the emission, ignition and combustion of the volatile constituent would take a few
minutes after the stoking of the straw briquette, therefore the actual combustion process is an
emission dominant, slow rate diffusion combustion; but the simulation simplified the fuel into a mixture
of carbon particles and volatile constituent, and the emission process of the volatile constituent was
ignored, thus the residence time of the volatile constituent decreased, and the intensity of CO and H2
combustion decreased. On the other hand, as the fuel was delivered into the chamber in a manner of
particle flow injection in the simulation, which configured differently with the actual fuel charging mode
in the experiment, thus the temperature and concentration distribution within the carbon layer are
asymmetric.

853

CONCLUSION
For the purpose of developing residential heating boilers and equipments using straw briquette

fuels, TG-DTG analysis under aerobic condition at different heating rates of the straws of several
typical crops in North China were conducted. Although the physical density and the power density of
the biomass are lower than that of the coal, the energy rate of the straw briquettes fuel is
approximately equal to that of the anthracite. Using C-R method in the DTG data processing, the
reaction mechanism of different temperature regions, the corresponding kinetic parameters and
combustion behavior were analyzed. The heating rates basically ranged in 20-80C/min, and the
increase of heating rate makes the reaction mechanism varied accordingly in each region, and Ea
decreased in trend. The indoor heating system is constructed and tested. According to the experiment
results, the system worked stably and no agglomeration of tar and slag-bonding on heating surfaces
occurred. The thermal efficiency of the heating equipment is 74%, the cooking efficiency is 20%, and
the emissions fulfill the requirement of the industry standard. Simulation results show that the complex
vortex structure of the gas phase intensified the combustion process and increase the emission of the
volatile constituent, and demonstrate that the structure design of the combustion equipment is quite
reasonable.
ACKNOWLEDGEMENTS
This research is supported by the Science and Technology Planning Project of Hebei Province, China
(13226604D-4), The Applied Basic Research Program of Hebei Province (13964503D) and the
Research Program of science and technology at Universities of Hebei Province (ZD2010122,
JH201110)
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855

TECHNOECONOMIC ANALYSIS OF BIODIESEL PRODUCTION: A CASE STUDY OF

JATROPHA CURCAS AND CALOPHYLLUM INOPHYLLUM
1

2,3

Hwai Chyuan Ong *, T.M.I. Mahlia , H.H. Masjuki , W.T. Chong , J. Milano

Department of Mechanical Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia

Department of Mechanical Engineering, Universiti Tenaga Nasional, 43000 Kajang, Selangor, Malaysia
3
Department of Mechanical Engineering, Syiah Kuala University, Banda Aceh 23111, Indonesia
* Corresponding author: Email address: onghc@um.edu.my, ong1983@yahoo.com,
Tel.: +6016-590-3110; Fax: +603-7967-5317 (H.C. Ong)

Abstract:
The world is confronted with fossil fuel depletion and environmental degradation. Biodiesel is one of the significant
solutions for oil shortage, global warming and air pollution that can be used in compression ignition engine without
any modification. The commercialization of biodiesel is yet to be undertaken at a large scale in many developing
countries. Besides the technological viability, the economic feasibility also plays a very important role on the biodiesel
development. Thus, this study focuses on techno-economic analysis of biodiesel production from non-edible oil as
biofuel for road transport. Life cycle cost and sensitivity analysis model are developed to analyse the biodiesel
production cost. The total production cost for a 50 ktons biodiesel production plant are $584 and $604 million for
jatropha curcas and calophyllum inophyllum biodiesel respectively over 20 years of life time. The largest economic
factor for biodiesel production is the feedstock and the variation in feedstock price will significantly affect the final
production cost. The payback period for jatropha curcas and calophyllum inophyllum biodiesel was found to be 1.90
and 1.98 years respectively. Besides, it is found that biodiesel fuel is competitive with fossil diesel when the subsidy
policy and tax exemption are implemented. As a final note, further studies and investigations on biodiesel production
and other limitation factors are needed to be carried out before the wider utilization of biodiesel fuel in the future.
Keywords: Techno-economic, Life Cycle Cost, Biodiesel, Alternative Energy, Sensitivity analysis.
INTRODUCTION
The continuing increase demand of energy consumption is needed for the industrialization, modernization and
development of the nation. This has led to the world confronted with fossil fuel depletion and environmental
degradation (Ong et al., 2012). Therefore, there is an urgent need to figure out the alternative energy resource that is
renewable, clean, reliable and yet economically feasible. Biodiesel is a solution for oil shortage, global warming and
air pollution that can be used in any compression ignition engine without any modification. Globally, there are huge
potential of biodiesel fuel and many researchers have been conducted on developing biodiesel as a potential energy
source for automobile fuels (Atadashi et al., 2011, Husnawan et al.,2009, Janaun et al., 2010, Reijnders et al., 2008,).
The world total biodiesel production in 2007 was reported to be 8.4 million tons and it is predicted to reach 150 million
tons by 2020 (Agra CEAS Consulting, 2010). However, the biodiesel fuel from edible oil like oil palm, rapeseed,
sunflower seed and etc faced the stiff competition between food and fuel. Thus, the focus is stiffed to non edible oil as
feedstock for biodiesel production such as jatropha, honge, calophyllum inophyllum, sterculia foetida, ceiba
pentandra and neem (Achten et al., 2010, Ong et al., 2011). Jatropha and calophyllum inophyllum oil is
geographically distributed around tropical Asia especially in Indonesia and Malaysia.
Although Malaysia is one of the biggest producers of biodiesel fuel, the commercialization of biodiesel is yet to be
undertaken at a large scale. Besides the technological viability, the economical feasibility also plays a very important
role on the biodiesel development. There are some researchers discussed the economical assessment of biodiesel
production from various feedstocks. The summary of these studies are shown in Table 1. Zhang et al. (Zhang et al.,
2003) studied the economic feasibility of four continuous processes to produce biodiesel from waste cooking oil. The
study discussed the biodiesel production cost and sensitivity analyses that affecting the economic viability of biodiesel
manufacture. Besides, Sakai et al. (Sakai et al., 2009) conducted the economic feasibility study on four batch
biodiesel production processes using homogeneous and heterogeneous alkali catalysts. A study of biodiesel
production cost model estimation was developed by Hass et al. (Haas et al., 2006). The model developed is flexible
to calculate the effects on capital and production costs variations in feedstock cost, type of feedstock employed as
well as changes in chemistry and technology process. Besides, You et al. (You et al., 2008) were analyzed and
assessed the economic costs of biodiesel production plants using alkali catalyst. Moreover, Ong et al. (Ong et al.,
2012) developed the life cycle cost model and assessed the sensitivity analysis for a biodiesel plant over 20 year life
time. On the other hand, Sotoft et al. (Sotoft et al., 2010) reported that production cost is $2.04/litre for biodiesel
produced from rapeseed oil using enzyme catalyst. Another study shows that the production cost of biodiesel a batch
process of 1 kton palm oil biodiesel production via biological catalyst is $2.30/litre (Jegannathan et al., 2011). In
general, it can be observed that biodiesel production using enzymes and biological catalysts are much more costly

856

and slower than alkali and acid catalysts. The higher production cost was due to the higher cost of the enzyme and
biological catalysts.
In the last decade, biodiesel production research has been focused on the election of the appropriate raw material
and optimization of production conditions (Blanco-Marigorta et al., 2012). However, variability in the feedstock, fossil
fuel price and the demand of biodiesel has given rise to instability within the industry. These factors have influenced
the economic viability of biodiesel at a global scale. Henceforth, this study is focuses on techno-economic analysis of
biodiesel production from non edible oil (jatropha curcas and calophyllum inophyllum) as biofuel. Besides, sensitivity
analysis, taxation and subsidy scenarios were also carried out to further understand the economical feasibility of
biodiesel production from non edible seed oil.
Table 1. Summary of techno-economical assessment for biodiesel production.
Plant
Feedstock
capacity
Catalyst and Method
Researchers
tons/yr
Waste cooking oil
8,000
Alkali catalyst
Zhang et al.
Waste cooking oil

1,452-14,520

Waste cooking oil

36,036

Waste cooking oil

150,480

Soybean oil

36,000

Rapeseed oil

8,000
30,000
100,000
8,000

Castor oil

8,650

Soybean oil

Batch, Alkali catalyst

Acid
preesterification
and alkaline catalyst
Homogeneous
base
catalyst
Sodium
methoxide
catalyst

Sakai et al.
Marchetti et
al.

Alkali catalyst

You et al.

Enzyme catalyst

Sotoft et al.
Santana et
al.

Alkali catalyst

Marchetti
Haas et al.

Continuous
Alkali
Ong et al.
catalyst
Batch,
biological Jegannathan
Palm oil
1,000
catalyst
et al.
a
Fixed capital cost (FCC), total capital investment cost (TCC), total manufacturing cost (TMC), net annual profit after
taxes (NNP), after-tax rate of return (ARR) and biodiesel break-even price (BBP)
Palm oil

50,000

METHODOLOGY
Design description
The life cycle analysis for biodiesel production starts from the feedstock seed acquisition and ends with biodiesel
consumption. The cycle can be divided into three specific phases, which are grouped as agricultural, production and
consumption processes as shown in Fig 1. This study focuses on the costs associated with the biodiesel production
phase with a typical production scheme shown in Fig. 2.
The method used in this research is two steps continuous acid (HCl) catalyst esterification and alkaline (NaOH)
catalyst transesterification processes. This process is regarded as economical and suitable method to convert crude
vegetable oil into fatty acid methyl ester (FAME). There are many studies conducted in the literature which present
technical aspects of the biodiesel production process via transesterification process. Acid catalyst esterification
process is required to reduce the FFA content to below 2% wt before the transesterification process. After that,
alkaline catalyst transesterification process is carried out to convert the crude oil into fatty acid methyl ester. The
reaction process significantly reduces the viscosity of the feedstock while maintaining a high rate of feedstock
conversion. Relative to the biological catalyst and supercritical processes, transesterification represents a low cost
and high conversion yield production technique.

857

Agricultural Phase

Feedstock Seeding

Fertilizer and Crop

Protection Products

Agricultural waste

Feedstock Crop Farming

Energy or Fuel

Emission to air, soil

and water

Feedstock Harvest

Production Phase

Plant Oil Extraction

Plant oil
Cake

Plant Oil Processing

Emissions
Methanol + NaOH

Transesterification

Consumption Phase
Biodiesel

Emission to air

Glycerol
Biodiesel Consumption

Fig. 1. Life cycle analysis diagram for biodiesel production.

Feedstock
Vegetable oil
Methanol

Esterification
Transesterification

Catalyst

Glycerin Separation

Methyl Ester

Glycerin

Methyl Ester Washing

Glycerin Neutralization

Fatty acids

Methyl Ester Drying

Methanol Recovery

Methanol

Biodiesel Distillation

Glycerin Drying

Biodiesel ASTMD6751

Glycerin

Fig. 2. Biodiesel production scheme diagram.

Life cycle cost
Life cycle cost analysis is the total cost of ownership of a plant or system by evaluating the economic benefit of the
plant. In this section, life cycle cost model for biodiesel production plant is developed and grouped into six categories
which are capital cost, operating cost, maintenance cost, feedstock cost, salvage value and by product credit. By
applying the following approach, the present value calculations are widely used in business and economics to
compare cash flows at different times. The life cycle cost in the form of a present value model yields is presented as
below,
= +

(1)

Capital cost
The capital cost takes into account are the required land area, building construction, equipment and instrumentations
for the biodiesel plant. Capital cost of the initial installation depends mainly on the biodiesel plant capacity. Based on

858

the study by Howell (Howell, 2005) the highest, average and lowest initial capital costs of biodiesel plant based on
plant capacity can be expressed in the following equation:

= 517.76 + 252928 + 3446300

(2)

= 430.13 + 205235 + 2696000

(3)

= 342.49 + 157542 + 1945700

(4)

Operating cost
Operating cost includes the cost of labour, utilities, laboratory services, factory expenses, supervision, administration,
transportation cost, all other materials and energy flows except those related to the crude feedstock oil (e.g. CPO,
CJO and CBO). Operating costs also include the costs associated with waste water treatment and sludge waste
processing to remove residual acids and any other contaminant (e.g. methanol and NaOH). Given their dependence
on production capacity, operating costs are calculated by setting a fixed cost per ton of biodiesel produced. Over the
life of the plant, total operating costs are,

(5)

Maintenance cost
The annual periodical maintenance and service cost is assumed to be a percentage of maintenance ratio (MR) to the
initial capital cost. This value is considered to be constant over the entire project lifetime. Maintenance costs are
calculated over the life time of the plant as,
=

(6)

Feedstock cost
The estimation of feedstock cost is based on the total feedstock consumption for biodiesel production process.
Therefore, annual feedstock consumption is determined by adjusting the plant capacity by the feedstock to biodiesel
conversion efficiency. The feedstock total consumption can be estimated using the following equation:
=

(7)

The price of feedstocks which are crude jatropha curcas and calophyllum inophyllum oil varies over time. In the
present study, feedstock prices are estimated considering the historical market price as a reference and an increment
with the annual growth rate. Thus, feedstock price is a function of feedstock reference price multiplied by an annual
growth rate over the year. This can be represented by the following equation:
= 1 +

(8)

The total feedstock cost is the multiplication of the total annual feedstock consumption and feedstock price on the
specific year. Based on this price, total cost of the feedstock over the life of the plant is given by,

(9)

Salvage value
The salvage value is the remaining value of the components and assets of biodiesel production plant at the end of
the project lifetime. In this study, it has been assumed that a depreciation rate occurs annually. The salvage value
model is based on the replacement cost rather than the initial capital cost. The salvage value can be expressed by
the following equation:
=

(10)

By product credit
Glycerine is the by-product generated during biodiesel production process. It can be sold as a useful by-product.
Calculation is based on the price of glycerine and its production volume which is determined by a plant capacity with
glycerine conversion factor. Thus, the by-product credit is the multiplication of glycerine price with the glycerine
produced. And, the by-product credit value over the life of the plant is given by,

859

(11)

Total biodiesel cost

Final biodiesel costs include the total life cycle cost, distribution cost and profit margin. The total distribution cost and
profit margin are 10% of biodiesel production cost. The total biodiesel cost can be estimated using the equation
below:
= 1.1

(12)

Final biodiesel unit cost

Final biodiesel unit cost is the total biodiesel cost converted into $ per litre of biodiesel fuel. The conversion unit is a
function of total biodiesel cost and density of biodiesel divided by annual production capacity. The final biodiesel unit
cost can be expressed by the following equation:
=

(13)

Biodiesel substitution ratio

Biodiesel and diesel fuels have different heating value or energy content. Thus, the substitution ratio of biodiesel to
diesel fuel is presented by applying the following equation:
=

(14)

Payback period
Payback period is the time taken to gain a financial return equal to the original investment cost, with the aid of which
the viability and feasibility of the investment can be evaluated. The payback method uses the ratio of capital cost over
annual earning as an approach to monitor the project. Taxes are the ratio of total biodiesel profit obtained. The
payback period is calculated by the following equations:
=

(15)

Whereby,
=

(16)

= 1.1

(17)

(18)

Data assessment and economical indicator

The lifetime of the project has been set to be 20 years. The plant was assumed to operate in 100% capacity during
the entire projects lifetime. The initial capital is considered to be paid by private investment and no loans have been
taken into account. It is assumed that the selling price of the produced biodiesel and glycerine does not vary over
time. Table 2 shows the summary of economic data and indicators used in this study.

860

Table 2. Summary of economic data and indicators.

Item
Data
Project lifetime
20 years
Plant capacity
50 ktons
Feedstock price:
Crude jatropha curcas oil
$700/ton
Crude calophyllum inophyllum oil
$800/ton
Depreciation model
10% annually
Operating rate:
Jatropha curcas biodiesel
$300/ton of FAME
Calophyllum inophyllum biodiesel
$300/ton of FAME
Maintenance cost
3% of capital cost annually
Replacement cost
$10 Million
Biodiesel conversion efficiency:
Jatropha curcas biodiesel
85%
Calophyllum inophyllum biodiesel
87%
Glycerine conversion factor:
Jatropha curcas biodiesel
10%
Calophyllum inophyllum biodiesel
8%
Tax ratio
15% of biodiesel profit
Glycerine price
$ 0.3/kg
Discount rate
8%
Sensitivity analysis
Sensitivity analysis is applied to predict the outcome of a decision if the situation turns out to be different compared to
the key prediction. Sensitivity analysis is an investigation to reveal the variation of the projected performance with
change in key assumptions on which the projections are based. It also enables examination of how uncertainty, for
example in international prices, can alter project outcomes. Important variables are crude feedstock oil price, discount
rate, initial capital cost, oil conversion yield and operating cost. Feedstocks price such as crude jatropha curcas and
calophyllum inophyllum oil are perhaps the most important. It follows the market value and can be expected to be
sensitive to global biodiesel production if growth in this sector occurs. Moreover, biodiesel production process and oil
yield play crucial roles in determining the biodiesel production cost.
RESULTS AND DISCUSSION
Life cycle cost analysis is used to estimate the biodiesel production cost over a lifetime of 20 years for a typical 50
ktons biodiesel plant using the input data shown in Table 2. The life cycle cost is driven by engineering details for
economic calculations to evaluate a project. The life cycle costs of biodiesel production from jatropha curcas and
calophyllum inophyllum oil are calculated based on Eq. (1). The following section shows the results of life cycle cost
assessment for jatropha curcas and calophyllum inophyllum oil based biodiesel production. The results are presented
in Fig. 3 and 4.
Life cycle cost of biodiesel production from jatropha curcas and calophyllum inophyllum are illustrated in Fig. 3. The
life cycle cost is shown in the present value by considering 8% discount rate. The results revealed that life cycle cost
of jatropha curcas and calophyllum inophyllum biodiesel production have almost similar trend with calophyllum
inophyllum biodiesel slightly higher than jatropha curcas biodiesel.
60
LCC ($ million)

50
40
30
20
10
0
1

Jatropha biodiesel

9 10 11 12 13 14 15 16 17 18 19 20
Year
Calophyllum inophyllum biodiesel

861

Fig. 3. Life cycle cost of biodiesel production over 20 years life time.
Fig. 4 illustrates the comparison and distribution of life cycle cost for jatropha curcas and calophyllum inophyllum
biodiesel. The largest share of life cycle cost of biodiesel production belongs to the feedstock price which is $438.6
and $470 million for jatropha curcas and calophyllum inophyllum biodiesel respectively, followed by operating, capital
and capital cost. Besides, the sale of by-products glycerine is a source of income which contributes $17.3 and $13.5
million over the life of the project for jatropha curcas and calophyllum inophyllum biodiesel respectively.

300

470.0

3.5

3.5

11.9

11.9

100

132.5

200
147.3

LCC ($ million)

400

438.6

500

Operating
cost

Jatropha biodiesel

(13.5)

Feedstock
cost

(17.3)

-100

(0.3)

(0.3)

Capital cost Maintenance Salvage value by product

cost
credit
Calophyllum inophyllum biodiesel

Fig. 4. Comparison of life cycle cost for jatropha curcas and calophyllum inophyllum production.
The summary of life cycle cost and payback period for biodiesel production are presented in Table 3. It is shown that
the total life cycle costs of biodiesel production are $601 and $617 million for jatropha curcas and calophyllum
inophyllum respectively without taking into account the glycerine credit. The largest economic factor for the life cycle
cost of biodiesel production is feedstock which is about 73% and 76% of total life cycle cost for jatropha curcas and
calophyllum inophyllum oil respectively. Moreover, the other important costs are operating costs such as labour cost,
utilities, laboratory, administration cost as well as other raw materials and chemical used in the process. The total
operating cost is ranged from 21.5% to 24.5% of the total life cycle cost. The sales of by-products are a source of
income and it contains around 2% of the biodiesel production cost. On top of that, the total biodiesel production life
cycle cost decreased to $584 and $604 million by taking into account the glycerine credit for jatropha curcas and
calophyllum inophyllum biodiesel respectively. Thus, the unit production cost of jatropha curcas and calophyllum
inophyllum biodiesel are calculated to be $0.503/litre and $0.525/litre respectively.
Payback period as an effective tool is used to determine the required time to recover the investment. This is very
important for financial management to monitor the recovery time of the project. The payback period for 50 ktons of
jatropha curcas and calophyllum inophyllum biodiesel production plant was found to be 1.90 and 1.98 years
respectively. Being less than one third of the 20 year project life, this result indicates that the project is economically
feasible.
Table 3. Summary of life cycle cost and payback period for biodiesel production.
Jatropha curcas biodiesel
calophyllum inophyllum biodiesel
$
%
$
%
Capital cost
11,882,425
1.98%
11,882,425
1.92%
Operating cost
147,272,211
24.51%
132,544,990
21.46%
Maintenance cost
3,499,902
0.58%
3,499,902
0.57%
Feedstock cost
438,583,834
72.98%
470,045,283
76.09%
Salvage value
260,841
0.04%
260,841
0.04%
by product credit
17,326,142
2.88%
13,542,272
2.19%
LCC (w/o by product credit)
600,977,532
617,711,759
Total life cycle cost
583,651,389
604,169,487
Production unit cost ($/litre)
0.503
0.525
Payback period (year)
1.90
1.98

862

Sensitivity analysis
Sensitivity analysis is used to predict the outcome of a decision if the parameter value turns out to be different
compared to the planned key prediction. Sensitivity analysis investigates the impact of input parameter variation on
the models conclusions.
Fig. 5 illustrates the sensitivity analysis results of jatropha curcas biodiesel production for five input variable of crude
jatropha curcas price, discount rate, oil conversion yield, operating cost and capital cost. The legends on the left of
the figure give the variation in the sensitivity variable from favourable, to planned and to unfavourable. The results
show that the highest impact belongs to crude jatropha curcas price. For instance, crude jatropha curcas with price of
$490/ton can decrease the life cycle cost to $452 million which is 23% reduction. However, increasing the price of
crude jatropha curcas to $910/ton will increase the total life cycle production cost to $715 million. Besides, the
discount rate also causes a huge impact on the life cycle cost which is followed by oil conversion yield and operating
rate. This implies that improvement of the biodiesel conversion process and lowering the operating rate could reduce
biodiesel production cost.

Fig. 5. Sensitivity analysis of life cycle cost for jatropha curcas biodiesel production.
Fig. 6 shows the sensitivity analysis results of calophyllum inophyllum biodiesel production for five input variable. The
legends on the left of the figure give the variation in the sensitivity variable from favourable, to planned and to
unfavourable. As expected, variation in the price of CBO represents the dominant impact on the life cycle cost;
second to this is the present value discount rate. For instance, the crude calophyllum inophyllum price of $560/ton
reduces the total life cycle production cost to $463 million. However, if the CBO price increases to $1040/ton, the total
life cycle production cost will be increased to $745 million. If the discount rate increases to 10% per annum, it causes
13% reduction in total life cycle production cost. Besides, oil conversion yield and operating cost also cause a large
impact on calophyllum inophyllum biodiesel production. Thus, the improvement in the biodiesel conversion processes
and greater operating efficiency can lead to a significant reduction in overall biodiesel production costs. However, the
effect of the initial capital cost on biodiesel production cost is small.

Fig. 6. Sensitivity analysis of life cycle cost for calophyllum inophyllum biodiesel production.

863

Taxation and subsidy scenarios on biodiesel fuel

Taxation and subsidy scenarios are presented for the final biodiesel cost in this section. Final biodiesel cost is the
total life cycle cost (biodiesel production cost), distribution cost and profit margin. Total distribution cost and profit
margin account to 10% of biodiesel production cost based on Eq.(13). The considered scenarios are total tax
exemption, 15% taxation, subsidy of $0.10/litre and $0.18/litre for biodiesel in comparison with fossil diesel price. The
$0.10/litre and $0.18/litre subsidy cost are chosen, based on the current subsidy costs for diesel and petrol fuel in
Malaysia. The considered fossil diesel price is based on $0.581/litre retail price of diesel fuel in Malaysia. There is a
difference in energy contents between the fossil diesel and biodiesel fuels. Therefore, a fuel consumption substitution
ratio of biodiesel to fossil diesel as shown in Eq.(14) has been taken into account for calculation.
Table 4 presents the comparison of the final jatropha curcas biodiesel price with fossil diesel at different taxation and
subsidy scenarios. The results show that the price of jatropha curcas biodiesel with tax exemption is $0.6/litre which
is $0.02 higher than diesel fuel. However, the final biodiesel price is compatible and lower than the fossil diesel price
when the subsidy is provided for biodiesel fuel.
Table 4. Jatropha curcas biodiesel taxation and subsidy scenarios at current production cost.
Jatropha curcas biodiesel
Fossil Diesel
Total tax
Subsidy
Subsidy
15% of tax
exemption
$0.10/litre
$0.18/litre
Biodiesel cost ($/litre)
0.553
0.553
0.553
0.553
Taxes/Subsidy ($/litre)
0.083
0.10
0.18
Total ($/litre)
0.553
0.636
0.453
0.373
0.581
Total cost ($/litre diesel)
0.602
0.692
0.493
0.406
0.581
Table 5 shows a comparison of final calophyllum inophyllum biodiesel price with fossil diesel at different taxation and
subsidy scenarios. It can be seen that the calophyllum inophyllum biodiesel price with subsidy of $0.10/litre and
$0.18/litre are compatible and even lower than the diesel fuel when the CBO price is $0.7/kg or below.
Table 5. Calophyllum inophyllum biodiesel taxation and subsidy scenarios at current production cost.
Calophyllum inophyllum biodiesel
Fossil Diesel
Total tax
subsidy
subsidy
15% of tax
exemption
$0.10/litre
$0.18/litre
Biodiesel cost ($/litre)
0.578
0.578
0.578
0.578
Taxes/Subsidy ($/litre)
0.087
0.10
0.18
Total ($/litre)
0.578
0.664
0.478
0.398
0.581
Total cost ($/litre diesel)
0.610
0.702
0.504
0.420
0.581
CONCLUSIONS
Biodiesel as a source of renewable energy with significant environmental benefits is considered as an alternative
energy for road transport. Besides the technical factors, economic impacts feasibility also plays an important role in
the development of biodiesel industry. Thus, techno-economic analysis of biodiesel production were analyzed and
evaluated for a lifetime of 20 years. The techno-economic model developed in this study can be adapted for other
biodiesel technology with minor modification. It has been found that the total life cycle cost of jatropha curcas and
calophyllum inophyllum biodiesel is $583 and $604 million respectively by taking into account the glycerine credit
over the project lifetime. On the other hand, the unit production cost of jatropha curcas and calophyllum inophyllum
biodiesel is reported to be $0.503/litre and $0.525/litre respectively. The largest economic factor for biodiesel
production is feedstock cost, which is equivalent to 73% and 76% of total life cycle cost for jatropha curcas and
calophyllum inophyllum biodiesel respectively. The payback period was found to be 1.90 and 1.98 years respectively,
while the calculated payback period is less than one third of the project life of 20 years and the results indicated that
biodiesel production plants are economically feasible. Sensitivity analysis revealed that crude feedstock oil cost is the
major contributor of biodiesel production cost. Biodiesel fuel is competitive with fossil diesel for the current production
costs when the subsidy policy and tax exemption are implemented. Therefore, further research and studies on
biodiesel production, subsidizing cost and other limitation factors are essential before the wider utilization of biodiesel
in the future.
ACKNOWLEDGEMENT
The authors would like to acknowledge the Ministry of Education of Malaysia and The University of Malaya,
Kuala Lumpur, Malaysia for the financial support under High Impact Research Grant (HIRG)
UM.C/HIR/MOHE/ENG/06 (D000006-16001) and UMRG RP022A-13AET.

864

NOMENCLATURE
BFP
biodiesel price, $/litre
BP
by product credit, $
CBO
crude calophyllum inophyllum oil
CC
capital Cost, $
CE
biodiesel conversion efficiency
CJO
crude jatropha curcas oil
d
deprecation ratio, %
FC
feedstock Cost, $
FP
feedstock Price, $/ton
FU
feedstock consumption, ton
GCF
glycerine conversion factor from crude oil
GP
glycerine price, $/kg
HVB
heating value of biodiesel fuel, MJ/kg
HVD
heating value of diesel fuel, MJ/kg
i
year
LCC
life cycle cost, $
MC
maintenance Cost, $
MR
maintenance Ratio, %
n
project life time, year
OC
operating Cost, $
OR
operating rate, $/ton
PC
annual biodiesel production capacity, ton/year
PP
payback period
RC
replacement cost
RP
feedstock reference price, $/ton
r
discount rate, %
s
growth rate of feedstock price, %
SR
substitution ratio of biodiesel fuel to diesel fuel
SV
salvage Value, $
TAX
annual total tax, $/year
TBS
annual total biodiesel sales, $/year
TPC
annual total production cost, $/year
TR
tax ratio, %
Greek letters

density, kg/m3
Superscripts
*$
All monetary unit is in US dollar
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866

REVIEW OF NON-EDIBLE BIOFUEL RESOURCES IN AUSTRALIA FOR SECOND

GENERATION (2G) BIOFUEL CONVERSION
A. K. Azad*, M. G. Rasul, M. M. K. Khan and Subhash C. Sharma
School of Engineering and Technology, Central Queensland University
Rockhampton, QLD 4702, Australia
e-mails: a.k.azad@cqu.edu.au/azad.cqu@gmail.com,
m.rasul@cqu.edu.au, m.khan@cqu.edu.au and s.sharma2@cqu.edu.au

ABSTRACT
The second generation (2G) biofuels are produced from non-edible feed stocks such as waste vegetable oils and fats,
non-food crops, forestry residues, various types of biomass sources. The 2G biofuels are not being produced
commercially yet in Australia because it requires more sophisticated processing equipment, more investment per unit
fuel production and large scale facilities than the first generation (1G) biofuel. However, 2G biofuel can overcome the
social, economic and environmental challenges without hampering our food cost and creating pressure on land use
because it is non-edible, biodegradable and can grow on marginal land. The literatures on non-edible energy
resources and their biofuel production facilities and present status are reviewed in this paper. The 2G biofuels market
status, future plans, government initiatives for 2G biofuel production and technological developments are presented
and discussed. Twenty five species available in Australia are selected from the literatures and their oil yield, fuel
characteristics; physical and chemical properties are described. Australias biofuel supply chain nexus from producers
to customers is developed where the elements namely primary resources, secondary resources, development and
production projects, processing, transport and storage, and finally end user or customer are considered as the main
part for the supply chain construction. Although, some research are available on 2G biofuel production, further study
using an appropriate supply chain with respect to given feed stocks is needed for producing 2G biofuel in a
commercial scale in Australia.
Keywords: 2G biofuels; Non-edible vegetable oils; Commercialized biofuel; Bioenergy; Energy conversion.
INTRODUCTION
Energy is a key driver for civilization. The energy comes from mostly petroleum sectors which is non-renewable and
gradually decreasing from the nature. Furthermore, more consumption of energy leads to serious environmental
pollution. Due to these reasons, renewable energy has become an important research field which can give fuel
security and save environment together. Worlds renewable energy resources are largely undeveloped. A large array
of renewable energy resources is available in nature. Biofuel like biodiesel is one of the most efficient forms of
renewable energy which can be an alternative for petroleum diesel in transport sector. Biodiesel can be made from
edible or non-edible oil seeds, animal fats, wood and wood waste etc. The literature reported that the biodiesel
comes from non-edible oil resources are defined as second generation (2G) biodiesel (Azad and Islam, 2012). The
first generation (1G) biodiesel comes from edible vegetable oil which faces socio-economic challenges like; it leads to
increase in food price and creates pressure on land (Azad and Uddin, 2013).
Second generation (2G) biodiesel can overcome the social, economic and environmental challenges without
hampering our food cost and creating pressure on land use because it is non-edible, biodegradable and can grow on
marginal land. The most important benefits for 2G biodiesel are that wide arrays of resources are readily available in
the nature. In Australia, renewables the majority of which is bioenergy (wood and wood waste, biomass and biogas),
accounts for 4% of the total energy consumption (Willcock et al., 2013). Australia is not only gifted with abundant,
high quality and diverse non-renewable energy sources but also has large, widely distributed renewable energy
sources like wind, solar, geothermal, hydroelectric, ocean energy and bioenergy resources. Australias renewable
energy resources are largely undeveloped (Puri et al., 2012, Che et al., 2013).
In this paper, Australias native species for 2G biodiesel production are reviewed and presented. The most
prospective species like Queen Palm (Syagrus romanzoffiana) are identified and their growth, distribution, available
oil extraction techniques, biodiesel conversion and characterize are outlined. The study also developed biodiesel
supply chain nexus from primary resources to end user/customer. The supply chain can be used in any other
countries in the world. The study also discussed the main advantages and disadvantages of biodiesel over petroleum
diesel.
AUSTRALIAN NATIVE SPECIES FOR 2G BIODIESEL PREPARATIONS
Australia has good potential of second generation (2G) biodiesel as a renewable source of energy. A wide array of
species is available for 2G biodiesel production. Some of the species, their oil content, distribution etc. are listed and
presented in Table 1. The species are arranged according to the descending order of their oil content.

867

Distribution

Plant type

Plant part

Table 1. Australian native species for second generation biodiesel production.

Non-edible source

Kernel

Oil Content
Seed
Kernel
(Wt%)
(Wt%)
49-61

41 - 52

Tree

Seed

45-50

Sea lemon
(Ximenia Americana)

Tree

Seed

30-50

Tree

25-50

Widespread throughout the tropics:

Africa, India and South East Asia
to Australia, New Zealand, Pacific
Islands, West Indies, Central and
South America
Australia, South America, from
northern Argentina to eastern
Brazil and west to eastern Bolivia.
Australia, Native to Africa and
Eurasia

Seed,
kernel

Queen palm
(Syagrus
romanzoffiana)
Castor oil plant
(Ricinus communis)

Tree

Northern Australia, Native western

Ghats in India, Fiji, Some region in
Eastern Asia

46.73

Karanja
(Pongamia pinnata)

Kernel

46.51

Tree

40-45

25-45

49

Tree

Seed

20-30

Seed

Herbaceous
annual

Seed,
kernel

2.8

Tree

Australia, Java, Malaysia, South

Asia etc.

Tree

10-45

Australia, Asia, Africa, Brazil.

Australia, East Africa, Southern

coastal India to Malaysia.

Shrub/tree

27-39

Widely grown and consumed

throughout the world including
Australia.
Australia, Native to India, Burma,
Bangladesh, Sri Lanka, Malaysia
Pakistan and Cuba, growing in
tropical and semitropical regions.
Australia, Southern China, India

Seed,
kernel
Seed

32 37

Australia, china, India, Japan,

Malaysia, and Pacific Islands
Australia, Turkey, Greece and
growing in tropical and semitropical
regions. It is originated in Mexico.

Legume
tree
Tree

Seed

Bengal almond
(Terminalia catappa)
Kukui Nut
(Aleurites
moluccana)
Beauty leaf tree
(Calophyllum
inophyllum)
Radish
(Raphanus sativus)
Neem
(Azadirachta indica)

White cedar
(Melia azedarach)
Pongam oil tree
(Millettia pinnata)
Tomato seed
(Solanum
lycopersicum)

References

(Atabani et al., 2013, Mohibbe Azam et al., 2005,

BGIR, 2004a, Mevy et al., 2006, Eromosele and
Eromosele, 2002, Eromosele and Paschal,
2003, Lin et al., 2011)

(Ashwath, 2010, Falasca et al., 2012, Coimbra

and Jorge, 2012, Coimbra and Jorge, 2011a,
Moreira et al., 2013a)
(Sujatha et al., 2008, Melo et al., 2008, Bajay et
al., 2009, Rajkumar and Freitas, 2008, Li et al.,
2010, Sarbyk et al., 2010, Berman et al., 2011,
Ashwath, 2010)
(Singh and Singh, 2010b, Mohibbe Azam et al.,
2005, Pinzi et al., 2009, Gui et al., 2008, Jean,
2009, Syers J.K., 2007, Razon, 2009, BGIR,
2004a)
(Oudhia et al., 2008, Pinzi et al., 2009, Singh
and Singh, 2010a, Moser, 2011, Canakci and
Sanli, 2008, BGIR, 2004b)
(Ashwath, 2010, Kibazohi and Sangwan,
2011a, Lima et al., Kibazohi and Sangwan,
2011b)
(Venkanna and Venkataramana Reddy, 2009,
Ong et al., 2011a, SathyaSelvabala et al., 2011,
Sanjid et al., 2013, Ong et al., 2011b)
(Moser, 2011, BGIR, 2004a, Atabani et al., 2013,
Domingos et al., 2008, Teixeira, 2005, Valle et
al., 2009, Lelivelt and Krens, 1992)
(No, 2011, Atabani et al., 2013, Singh and Singh,
2010b, Mohibbe Azam et al., 2005, BGIR,
2004a, Ragit et al., 2011, Wirawan, 2008, Jean,
2009)
(Atabani et al., 2013, Jean, 2009, Borges et al.,
2003, Stavarache et al., 2008)
(Subramanian et al., 2005, Chakrabarti and Ali,
2009, Kumar and Sharma, 2011)
(Atabani et al., 2013, No, 2011, Moser et al.,
2011, Giannelos et al., 2005, Panoutsou et al.,
2008)

868

Garden rocket
(Eruca sativa)

Foambark
(Jagera pseudorhus)
Koroch seed
(Pongamia glabra)

Mall-leaved plant
(Ochna serrulata)
Sandalwood
(Santalum album)
Chinese rain tree
(Koelreuteria
formosana)
Orange Jessamine
(Murraya exotica)
Sugar-apples
(Annona squamosal)

Quinine bush
(Petalostigma
pubescens)
Blue flax-lily (Dianella
caerulea)
Broad leafed palm
lily
(Cordyline
manners-suttoniae)
Atalaya Plant
(Atalaya hemiglauca)
Red silky oak
(Grevillea banksia)

Dwarf kurrajong
(Brachychiton
bidwillii)

Tree

Tree

Tree

Seed

Seed

Seed

Seed

22.17

24.49

31.16

33.6

34.01

(Ashwath, 2010, Rugkhla and Jones, 1998,

Chaturvedi et al., 2003, Anil et al., 2003, Misra
and Dey, 2013)
(Wirawan, 2008, Wirawan, 2007)

(Ashwath, 2010, Lin et al., 2014, Atkinson and

Riley, 2013)

(Ashwath, 2010, Bandi et al., 2012, Taylor et al.,

2003)
(Ashwath, 2010)

(Razon, 2009, BGIR, 2004a, Atabani et al.,

2013)

(Ashwath, 2010)

(Li et al., 2009, Chakrabarti et al., 2011, LIU

and ZHANG, 2006, LI et al., 2005, Qin et al.,
2010)

Australia, Caribbean, Central

America, Northern South America,
Western South America, Southern
South America, Pacific, Indonesia
Australia

Tree

Tree

Tree

Seed

Seed

Seed

Seed

13.85

15.62

15.84

18.66

21.13

(Ashwath, 2010)

(Ashwath, 2010)

(Ashwath, 2010, Wilson and Harrington, 1980)

(Ashwath, 2010)

(Ashwath, 2010)

(Ashwath, 2010, Grace et al., 2006, Burrows and

Burrows, 1992)

35

Tree

Seed

21.86

Australia and Tasmania

Tree

Seed

11.15

Seed

Australian, Canadian, British,

South African and New Zealand
English, Northwest of China, South
Asia, US,
Australia and New Guinea

Tree

Seed

15-20

Australia

Tree

Seed

Herbaceous
perennial

Naturally distributed in tropical Asia,

from India to Japan to Thailand to
Malaysia to north and north-Eastern
Australia to some Pacific islands.
Australia, New Zealand and South
Africa
Australia, China, India, Sri Lanka,
Indonesia, Malaysia, Philippines.
Australia, Taiwan

Tree

Seed

Australia, New Guinea, Southern

Africa, Swaziland, Mozambique
Australia

Tree

Australia, South and Southeast

Asia, China, USA

Tree

Australia

869

The review found that there is only a little work that has been done on high oil content species like Queen Palm
(Syagrus romanzoffiana), Foambark (Jagera pseudorhus), Mall-leaved plant (Ochna serrulata) and Quinine bush
(Petalostigma pubescens) etc. Among them queen palm (Syagrus romanzoffiana) appears to be more prospective
species which is discussed in this paper.
PROSPECTIVE SPECIES QUEEN PALM
The scientific name of the queen palm is Syagrus romanzoffiana. It is a naturalised species and is a widely cultivated
ornamental plant in Australia and overseas. The taxonomical or scientific classification of the species is presented in
Table 2. It originates from South America and is distributed from northern Argentina to eastern Brazil and west to
eastern Bolivia. Queen palm grows in a wide range of soils from costal sands to heavy cracking clay sand. It is grown
extensively in the city of Rockhampton, Australia and to the west as far as Alpha where the temperatures reach
sub-zero to high 40s and the rainfall ranges from 400 mm to 2000 mm (Falasca et al., 2012, Ashwath, 2010). Its
distribution map in Australia is presented in Figure 1. Queen palm is long living plant and fruits twice a year. It can
produce fruits throughout the year, if good supply of water is available. The fruit contains husk, hard shell and
unick-kernel. The kernel contents 41% to 52% of colourless oil. The oil has low acid value with density 0.94 g/ml
and kinematic viscosity 15.50 mm2/s. The oil contents mainly oleic acid and lauric acid which is non-edible. It can
be readily converted into biodiesel by base catalysts transesterification method. The oil extraction and biodiesel
conversion methods are briefly discussed below.
Table 2. Taxonomical/scientific classification of Queen Palm.
Taxonomical classification
Kingdom
Subkingdom
Infrakingdom
Division

Plantae
Viridaeplantae
Streptophyta
Tracheophyta

Subdivision
Infradivision
Class
Superorder
Order
Family
Subfamily
Genus
Species

Spermatophytina
Anqiospermae
Magnoliopsida
Lilianae
Arecales
Arecaceae
Arecoideae
Syaqrus
Syaqrus romanzoffiana

(a)

(b)

Figure 1. (a) Queen palm (Syaqrus romanzoffiana) tree and fruits, (b) Distribution map in Australia (ATLAS, 2013).
OIL EXTRACTION METHODS
Oil extraction is the first step for biodiesel preparation. The seed prepared for oil extraction by undergoing a
systematic process. The queen palm is similar to coconut in many respects. It has a hard shell bears small kernels

870

but does not content free water, unlike coconut. The shell and kernel of the seed can be separated before extracting
oil. On the other hand, entire seed can be grounded and used in oil extraction (Azad et al., 2012b). The separated
kernels can be sun dried with the required moister removed from it. After these pre-processing systems, the kernels
are ready for oil extraction with high oil yield. There are many oil extraction methods that are available in the literature
namely, mechanical extraction, chemical extraction, enzymatic extraction as seems in Figure 2.

Oil extraction
(Queen palm)

Mechanical oil extraction

Hot water extraction

Chemical oil extraction

Soxhlet extraction

Enzymatic oil extraction

Ultrasonication extraction

Figure 2. Different oil extraction techniques from the queen palm seeds/kernels (Atabani et al., 2012).
BIODIESEL CONVERSION METHODS
After oil extraction, raw or virgin oil is ready for biodiesel conversion. Lot of efforts has been made worldwide to
develop biodiesel conversion technology from vegetable oil. After conversion the properties of the vegetable oil can
be improved to become parallel to standard biodiesel properties. The crude/raw/virgin vegetable oil mostly has some
associated problems like high density, high kinematic viscosity, low volatility and polyunsaturated characteristics.
These problems can be overcomed by conversion of vegetable oil into biodiesel by different methods. The available
biodiesel conversion methods are namely dilution, thermal cracking, micro-emulsion and transesterification (Atabani
et al., 2013, Borugadda and Goud, 2012, Azad et al., 2013). The conversion methods are presented in Figure 3.

Biodiesel
conversion

Dilution

Blended fuel

Thermal cracking

Liquid fraction

Chemical cracking

Microemulsions

Homogeneous
catalysts

Catalytic
method

Alkaline
catalyst

KOH, NaOH

Acid
catalyst

H2SO4, HCL

Enzymes
Heterogeneous
catalyst
Transesterification
Supercritical method
Non-catalytic
method

Alcohole (Ethanol,
proponal, butanol)
BIOX co-solvent
process

Figure 3. Vegetable oil to biodiesel conversion methods.

871

Titanium silicate, alkaline

earth metal (MgO, CaO)

The literature reported that among different methods transesterification is the most economic and efficient method for
biodiesel conversion. Considerable study has been done on these methods, for instance Lin et al. (Lin et al., 2011)
studied different biodiesel conversion methods and summarized the advantages and disadvantages, which is
presented in Table 3.
Table 3. Comparison of different biodiesel conversion methods (Lin et al., 2011, Azad et al., 2012a).
Method
Dilution

Advantages
o Simple process.
o Directly blends with petroleum diesel

Disadvantages
o Higher density.
o Instability.
o Poor volatility.

Thermal cracking

o
o
o

Process is simple.
Less time consuming.
Pollution free (closed system).

o
o
o

High temperature required.

Expensive equipment
Low purity.

Chemical cracking

o
o
o
o

No catalyst required.
Less time consuming.
High conversion efficiency.
Good adaptability

o
o
o

High temperature and pressure required

Costly equipments required.
Energy intensive.

Transesterification

o
o
o
o

Good fuel properties (close to diesel).

High conversion efficiency.
Low cost.
Sustainable to industrial application.

o
o
o
o

Low free fatty acid and water content.

Pollutant/waste water produces.
Accompanied by side reactions.
Different by-products separation.

PROPERTIES OF THE BIODIESEL

The characterization of biodiesel fuel properties are an important and necessary step before engine application. The
property of the biodiesel varies with different feedstocks. Recently, some studies have been conducted on queen
palm (Moreira et al., 2013b, Coimbra and Jorge, 2011b). The authors studied the fuel characteristics of the queen
palm oil and biodiesel. The properties of the biodiesel from queen palm oil and the standard biodiesel is presented in
Table 4.
Table 4. Physio-chemical properties of the biodiesel produced from queen palm (Moreira et al., 2013b, Coimbra
and Jorge, 2011b, Ashwath, 2010).
Properties

UInit

Queen palm
biodiesel

Density at 20C
Kinematic viscosity at 40C
Cetane number
Acid value
Water content
Flash point
Ester content
Monoacylglycerols residue
Diacylglycerols residue
Pour point
Carbon residue

kg/m3
mm2/s
mg KOH/g
mg/kg
C
% mass
% m/m
% m/m
C
% m/m

870
3.16
0.08
453
98.50
0.29
0.06
-

Standard biodiesel
ASTM standard
EU standard biodiesel,
biodiesel, ASTM D6751
EN 14214
880
860-890
1.9-6.0
3.5-5.0
47
51
0.5
0.5
500 max
500 max
130
101
96.5 max
0.8 max
0.2 max
-15 to -16
0.050 max
0.30 max

ADVANTAGES AND DISADVANTAGES OF BIODIESEL

Biodiesel is renewable and alternative transport fuel. It is made from vegetable oils; it has some advantages over
petroleum diesel. It has some unavoidable disadvantages at the time of processing and uses in internal combustion
engine. Some of the advantages and disadvantage of biodiesel over petroleum diesel are presented in Table 5.

Table 5. Advantages and disadvantages of biodiesel over petroleum diesel (Atabani et al., 2012).
Advantages of biodiesel over petroleum diesel
1. Biodiesel is renewable, biodegradable, readily available, non-toxic,
non-flammable, eco-friendly, free from sulfur and aromatic content.

872

References
(Balat and Balat, 2010, Shahid and
Jamal, 2011, Kafuku and Mbarawa,
2010, Atadashi et al., 2010)

2.
3.
4.
5.

6.

7.
8.

Biodiesel has high combustion characteristics due to its 10-11%

more content of oxygen than petroleum diesel.
Biodiesel reduces ignition delay due to its higher cetane number
(about 60 to 65) than petroleum diesel (53).
Biodiesel has superior lubricity properties which can reduce engine
corrosion, wear, tear, and increase engine overall efficiency.
Biodiesel reduces CO2 emission by 78% on life cycle basis with
compared to petroleum diesel. It also reduces NOx and smoke with
free of soot.
Biodiesel can successfully run by B20 without any engine
modification. However, higher blends require some minor engine
modification.
Biodiesel has higher flash point above 100-170C which is safe for
transportation, distribution, storage and handling.
Biodiesel reduces the environmental effect and helps rural
development because it has good potential for rural employment.

Disadvantages of biodiesel over petroleum diesel

1. Biodiesel has lower calorific value than petroleum diesel. Due to low
energy content, it leads to an increase of fuel consumption of about
2% to10%.
2. Low engine speed and power, high price and high engine wear.
3.

Biodiesel conversion process is costly and time consuming.

4.

Biodiesel conversion has some environmental effect such as waste

disposal and waste water produce.
Biodiesel has some economic impact. It leads to increase food price
and create pressure on land.
Biodiesel causes excessive carbon deposition and gum formation.

5.
6.

(Balat and Balat, 2010, Balat, 2011,

Sharma et al., 2008, No, 2011)
(Mata et al., 2010, Yusuf et al., 2011,
Porte et al., 2010)
(Yusuf et al., 2011, Jena et al.,
2010b, Moser and Vaughn, 2010)
(Atadashi et al., 2010, Gerpen, 2005,
Ameer Uddin et al., 2013)
(Jain and Sharma, 2010, Atabani et
al., 2013, Azad and Uddin, 2013)
(Shahid and Jamal, 2011, Silitonga
et al., 2011)
(Jena et al., 2010a, Rashid et al.,
2009)
(Shahid and Jamal, 2011, Balat and
Balat, 2010, Ragit et al., 2011, Amir
Uddin and Azad, 2012)
(Yusuf et al., 2011, Singh and Singh,
2010b)
(Singh and Singh, 2010b, Balat and
Balat, 2010)
(Murugesan et al., 2009, Demirbas,
2008, Mondal et al., 2014)
(Yusuf et al., 2011, Carioca, 2010,
Batten and O'Connell, 2007)
(Atadashi et al., 2011, Li et al., 2009)

BIODIESEL SUPPLY CHAIN

The biodiesel supply chain is nothing but the lifecycle of biodiesel. Supply chain shows the nexus between the origin
of the resources and the customer or end user. Actually sun is the main and primary energy source. Plants and
animals are directly or indirectly nitrated by the sun, water and CO2. Stored energy of the secondary resources are in
many form like biomass, biogas and biofuel. Individual projects are needed for development and production of the
bioenergy from the secondary resources. Separate processing methods and technologies are required to convert into
useful form of energy. A typical biodiesel supply chain has been developed in this study and presented in Figure 4.

Figure 4. Biodiesel supply chain form primary resources to end user.

873

In the supply chain, bioenergy processing, transport and storage depends on types of feedstocks. In this stage
customer can get bioenergy in many forms like heat energy, electricity, biogas and biofuel. Biofuel such as biodiesel
is the most efficient form of bioenergy which can be used as an alternative transport fuel. Bioenergy in the form of
biodiesel can be easily stored, transported, exported and used. It can be used in industrial, commercial, residential
and transport sectors. Bioenergy sector is the most growing sector among other renewable energy sector in the world.
CONCLUSION
This paper reviewed the potential for 2G biodiesel production from Australian native non-edible energy resources.
The oil yield, fuel characteristics, physical and chemical properties of the Australian twenty five native species are
presented and discussed. The paper also studied the potential species like Queen Palm (Syaqrus romanzoffiana)
growth, habitat, distribution, production, oil extraction methods, biodiesel conversion techniques and characteristics of
biodiesel compared with petroleum diesel. The study developed and presented a biofuel supply chain for Australia
which can be applicable to other countries in the world. To the best of our knowledge, the review found no literature
on engine performance and emission study by using queen palm biodiesel. Further study is needed on the
prospective species like Queen Plan (oil content 41-52%) for biodiesel production, engine performance and emission
study.
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878

RHYLHZ OI BLRGLHVHO PURGXFWLRQ FURP MLFURDOJDH: A NRYHO SRXUFH OI GUHHQ(QHUJ\

A. K. Azad*, M. G. Rasul, M. M. K. Khan and Subhash C. Sharma
School of Engineering and Technology, Central Queensland University
Rockhampton, QLD 4702, Australia
e-mails: a.k.azad@cqu.edu.au/azad.cqu@gmail.com,
m.rasul@cqu.edu.au, m.khan@cqu.edu.au and s.sharma2@cqu.edu.au

ABSTRACT
Microalgae are the photosynthetic single-celled microorganism with a microscopic diameter of only 3-8 microns. It
has survived over 2.5 billion years due to its unique outer cell wall. The self-rejuvenation and rapid growth (4 new
cells every 17 to 20 hours) helps to produce lipids, proteins and carbohydrates in large amounts over a short period
of time by using CO2, sun light, sugar, N2, P, K as nutrient. These characteristics have drawn the attention of scientist
and engineers for possible production of green energy. This study reviews the available species in literatures, their oil
content, lipid content and lipid productivity per day as a prospective biodiesel source. Microalgae production
techniques, harvesting, oil extraction, conversion technologies underpinning biodiesel production are also outlined.
The review shows that microalgae biodiesel blends B20 produces engine performance closer to that of petroleum
diesel, and it reduce engine emission compared to diesel. It can be concluded that the algae biodiesel/green diesel
has the potential to become an alternative source of biodiesel to meet the increasing world energy demand.
Keywords: Microalgae, lipid content, oil extraction, algae-biodiesel.
INTRODUCTION
World energy demand increases gradually which mainly comes from the non-renewable resources. The energy
resources are limited and diminish simultaneously due to the high consumption of energy. More energy consumption
leads to polluting our environment. Due to these two main reasons worldwide scientist and engineers are paying
attention to find new, renewable, and ecofriendly energy resources which can meet the energy demand without
harming the environment. A lot of efforts have been made to search the alternative energy resources. A lot of
research efforts have been going on to meet the challenge of the fuel demand and environment protection
simultaneously. The researchers are engaged with finding new such resources and trying to exploit them to achieve
environment friendly alternate energy resources. Very recently scientists proposed microalgae as one of such
resources. This resource appears to be a low potency product but its growth rate and cost of production are the main
reasons that scientists are paying enormous attention. Algae have ability to convert CO2 into oil through
photosynthetic process (Hossain et al., 2008, Chisti, 2007, Mata et al., 2010). Microalgae are the oldest living
microorganism survived over 2.5 billion years. These are unicellular and their reproduction rate is very fast utilizing
environmental CO2, sun light and sugar that can produce lipids, proteins and carbohydrates in large amounts over
short period of time. Engineers and scientists are engaged with developing technologies that can help in converting
this biomass into diesel economically. The microalgae have some remarkable advantages to be used as a biodiesel
feedstock such as these are cultured to act as a low-cost raw material (feedstock), contain high energy per unit mass,
renewable, environmentally friendly and can contribute to reduce CO2 levels in the atmosphere by consuming for its
own reproduction it and converting it to diesel oil (Hossain et al., 2008).
The literature reports that microalgae have higher biomass and lipid productivity per unit area as compared to
conventional crops (Chisti, 2007, Demirbas, 2010, Amin, 2009). The comparison of the oil yield for biodiesel
resources per capita land size from variety of sources is presented in Table 1. Hossain has reported that microalgae
oil production is 7 to 31 times higher than that of palm oil (Hossain et al., 2008).
Table 1. Comparison of oil yield and land used of different biodiesel resources with microalgae (Chisti, 2007).
Feedstock
Corn (Zea mays)
Soybean (Glycine max)
Oil palm (Elaeis guineensis)
Microalgae (Chlorella vulgaris)

Oil yield (L/ha)

172
446
5950
58700

Required land for cultivation (M ha)

1540
594
45
4.5

Percentage of existing US cropping area

846
326
24
2.5

Microalgae can grow in a variety of conditions like, fresh water, marine water and treated industrial waste water by
taking very simple nutrition (Campbell, 2008, Mata et al., 2010). A large array of species is available throughout the
world and many of them have about 80% oil contents of the dry weight (Amin, 2009). A lot of research work has been
conducted to develop algae oil extraction techniques and conversion to biodiesel. The literature reported that the
higher lipid contents algae species are potential source of green diesel/algae biodiesel. Microalgae biodiesel is also
called green diesel because it has some remarkable environment friendly characteristics. The algae biodiesel is non-

879

toxic, non-corrosive, highly biodegradable and has no sulfur content (Demirbas and Fatih Demirbas, 2011). The
physio-chemical properties of the algae biodiesel are similar to the ordinary biodiesel which can meet the requirement
of the biofuel standard ASTM D6751. The literature also reported that the use of algae biodiesel in internal
combustion engine do not require major engine modification (Campbell, 2008, Mata et al., 2010). At the time of oil
extraction and conversion to biodiesel, no pollutant or waste is produced by the microalgae feedstocks. After oil
extraction, the bi-products or leftover materials is as good as soil fertilizer or can produce ethanol (Demirbas, 2011).
Moreover, microalgae cultivation for biodiesel production is economically viable than that of ordinary oil crop for large
scale production under suitable conditions and using appropriate technology (Hossain et al., 2008).
This paper reviews the microalgae species for biodiesel production and associated technologies for conversion of
lipid to biodiesel. The microalgae cultivation processes and harvesting methods are also outlined. The engine
performance tests and emission studies by using algae biodiesel as a green diesel product have also been reviewed
and presented in this work.
MICROALGAE SPECIES FOR BIODIESEL/GREEN DIESEL PRODUCTION
The microalgae were first used in food industries by the Chinese people over 2000 years. The development of
microalgae biotechnologies started from the middle of the twentieth century. Recently, a wide range of applications is
cited in the literature because it can be grown using undeveloped land and water which is not suitable for food
production. The lipid content of the microorganisms is the key factor to produce biodiesel from algae. Usually,
targeted species within the green algae including Chlorella vulgaris, Chamydomonas reinhardtii, Dunaliella salina etc.
are investigated due to their high lipid content (around 60-70%) (Liang et al., 2009, Scott et al., 2010, Metzger and
Largeau, 2005) and their high productivity (7.4 g/L/d for Chlorella vulgaris) (Chen et al., 2011). Table 2 presents the
previous studies conducted on the microalgae for biodiesel production. In the Table algae species are arrayed in
descending order of their oil content and lipid content in weight percentage of their dry weight.
Table 2. The spaces used for biodiesel production available in literatures
S. L.

Oil content
(wt% dry
mass)

Lipid content
(%, w/wdw)

Lipid
productivity
(mg/L/day)

References

50-77
64

35-55
25-75

Nitzschia laevis
Neochloris
oleoabundans
Chlorella vulgaris

69.1
35-65

29-65

90-134

63.2

5-58

11.2-40

6.

Parietochloris
incise

62

7.

Crypthecodium
cohnii
S. obiquus
Nannochloris sp.
Nannochloropsis
oculata
Nitzschia sp.
Scenedesmus
dimorphus
Monodus
subterraneus
Cylindrotheca sp.
Phaeodactylum
tricornutum
Chamydomonas
reinhardtii
Haematococcus
pluvialis
Dunaliella
primolecta
Tetraselmis sueica
Chlorella sorokiana
Monallanthus
salina
Dunaliella salina

56

20-51.1

35-55
50

11-55
20-56
22.7-29.7

60.9-76.5
84-142

45-47
16-40

16-47

39.3

16

30.4

(Meng et al., 2009, Yan et al., 2014)

(Metzger and Largeau, 2005, Banerjee et al., 2002, Rao et
al., 2007, Schenk et al., 2008, Meng et al., 2009, Yan et
al., 2014, Balat, 2011)
(Chen et al., 2008, Yan et al., 2014)
(Natrah et al., 2007, Yan et al., 2014, Mata et al., 2010,
Goiris et al., 2012)
(Scott et al., 2010, Yan et al., 2014, Tran et al., 2012b,
Tran et al., 2012a, Karimi et al., 2013, Singh and Sharma,
2013, Tran and Chang, 2013, Tsigie et al., 2012)
(Solovchenko et al., 2008a, Solovchenko et al., 2008b,
Merzlyak et al., 2007, Solovchenko et al., 2009, Yan et al.,
2014)
(Yan et al., 2014, De Swaaf et al., 2003, Jiang et al., 1999,
Ganuza et al., 2008, Balat, 2011)
(Yan et al., 2014, Lardon et al., 2009)
(Balat, 2011)
(Scott et al., 2010, Su et al., 2011, Khozin-Goldberg and
Boussiba, 2011, Crowe et al., 2012, Yan et al., 2014)
(Yan et al., 2014, Meng et al., 2009, Balat, 2011)
(Yan et al., 2014, Gouveia and Oliveira, 2009, Mata et al.,
2010)
(Yan et al., 2014)

16-37
20-30

18-57

44.8

(Meng et al., 2009, Yan et al., 2014)

(Balat, 2011)

1.
2.

3.
4.
5.

8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.

Name of
microorganisms
Microalgae
Schizochytrium sp.
Botryococcus
braunii

25.25
25

25

(Scott et al., 2010, Siaut et al., 2011, Kong et al., 2010, Li

et al., 2010)
(Scott et al., 2010, Razon and Tan, 2011)

23

23.1

(Scott et al., 2010, Balat, 2011)

15-23
22
> 20

8.5-23
19-22
20-22

27-36.4
44.7
-

(Balat, 2011)
(Yan et al., 2014, Wan et al., 2011)
(Balat, 2011)

14-20

6-25

116

(Scott et al., 2010, Yan et al., 2014, Natrah et al., 2007,

880

23.
24.
25.
26..
27.
28.
29.

30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.

Porphyridium
cruentum
Spirulina platensis
Isochrysis galbana
Bacterium
Arthrobacter sp.
Acinetobacter
calcoaceticus
Rhodococcus
opacus
Bacillus
alcalophilus
Yeast
Rhodotorula
glutinis
Rhodotorula
glutinis
Rhodosporidium
toruloides
Cryptococcus
albidus
Lipomyces starkeyi
Candida curvata
Fungi
Mortierella
isabellina
Humicola
lanuginosa
Mortierella vinacea
Aspergillus oryzae
M. ramanniana
Cunninghamella
japonica
Cunninghamella
echinulata
Mortierella alpina
C. bainieri
Mucor rouxii

19.3

9-18.8

34.8

Gouveia and Oliveira, 2009)

(Yan et al., 2014)

5-17
14.5

4-16.6
7-40

(Yan et al., 2014)

(Yan et al., 2014)

> 40
27-38

24-31
-

(Meng et al., 2009)

(Meng et al., 2009)

24-25

(Meng et al., 2009)

18-24

(Meng et al., 2009)

72

(Meng et al., 2009)

72

48-67.5

65

(Xue et al., 2008, Xue et al., 2010, Karatay and Dnmez,

2010)
(Li et al., 2007, Hu et al., 2009, Zhao et al., 2010, Zhao et
al., 2011, Wu et al., 2011, Wu et al., 2010)
(Meng et al., 2009)

64
58

(Meng et al., 2009)

(Meng et al., 2009)

86

(Meng et al., 2009, Yan et al., 2014, Fakas et al., 2009,

Chatzifragkou et al., 2010, Ruan et al., 2012)
(Meng et al., 2009, Yan et al., 2014)

66
57
54.2
50

46

(Meng et al., 2009, Yan et al., 2014)

(Meng et al., 2009, Yan et al., 2014)
(Yan et al., 2014, HC and CC, 1996)
(Yan et al., 2014, Sergeeva et al., 2008, Emelyanova,
1997, Lunin et al., 2013)
(Yan et al., 2014, Fakas et al., 2008)

42
38
32

Mucor
circinelloides
Mucor sp.

23

3-17

75

(Yan et al., 2014, Wynn et al., 2001)

(Yan et al., 2014, EM et al., 2010)
(Yan et al., 2014, Somashekar et al., 2003, Jeennor et al.,
2008, Jeennor et al., 2006)
(Yan et al., 2014, Wynn et al., 2001, Li et al., 2006, Zhang
et al., 2007)
(Yan et al., 2014, Somashekar et al., 2003)

Table 2 also presents wide array of microalgae, bacterium, yeast and fungi species and their oil and lipid
content. Research is ongoing on their growth, habituated, distribution, economic and environmental impact etc.
to find out suitable species for biodiesel production. As seen from the Table the main factors to consider in
selecting suitable species which are availability of the strain, growing methods, reason for growing and their
lipid content. The algae species cultivation technologies are briefly discussed below.
MICROALGAE CULTIVATION AND PRODUCTION TECHNIQUES
Microalgae are the fastest growing species. The growing microalgae requires light, water, nutrients, CO2 and growing
space temperature 20 C -30C. Microalgae capture CO2 and convert it to fuel by photosynthesis. They can capture
CO2 from three different sources namely, atmosphere, waste gas from heavy industry and soluble carbonates. A lot of
efforts have been made to enhance the productivity and the lipid content of some microalgae species by changing
the growing conditions. Scragg et al. (Scragg et al., 2003) studied on five ChlorellaI species in low nitrogen medium.
They found that Chlorella vulgaris gives the highest growing rate than other species. Microalgae can be grown in
using different methods and media. The main algae production mechanisms are namely, photoautotrophic,
heterotrophic and mixotrophic production. The photoautotrophic production is autotrophic photosynthesis. It is the
technically and economic feasible method for large-scale production of algae biomass (Brennan and Owende, 2010,
Borowitzka, 1997). There are two systems are available that have been deployed and these are based on open pond
and closed photobioreactor (PBR) technologies (Borowitzka, 1999). Heterotrophic production requires organic
nutrients like glucose to stimulate growth, while some algae strains can combine autotrophic photosynthesis.
Mixotrophic process is the combination of heterotrophic assimilation of organic compound (Brennan and Owende,
2010). The summary of the microalgae production technologies is presented in Figure 1.

881

Open pond
production system

Microalgae
production
technologies

Photoautotrophic
production

Closed
photobioreactor
system

Heterotrophic
production

Hybrid production
system

Mixotrophic
production

Fig. 1. Microalgae cultivation and production technologies

HARVESTING METHODS FOR ALGAE BIOMASS
Harvesting of algae biomass is the challenging phase of the microalgae production process in which one or more
solid-liquid separation steps are involved (Brennan and Owende, 2010, Wang et al., 2008). The process accounts 2030% of the total production cost (Brennan and Owende, 2010). The process involves some highly energy intensive
processes namely, flocculation, filtration, flotation and centrifugal sedimentation. The selection of harvesting
technique depends on the characteristics of microalgae i.e. size, density and the value of the target production
(Brennan and Owende, 2010, Olaizola, 2003). There are two stage processes namely; bulk harvesting and thickening
generally used technique for harvesting algae biomass. The harvesting processes are summarized and presented in
Figure 2.
Flocculation and
ultrasonic aggregation

Harvesting by flotation
Harvesting of algae
biomass
Gravity and centrifugal
sedimentation

Biomass filtration

Algae biomass
recovery techniques

Dehydration process

Extraction and
purification of microalgal
biomass

Extraction and purification

of biofuel
Extraction and purification
for algal metabolites

Fig. 2. Microalgae biomass harvesting and processing technologies

882

ALGAL BIODIESEL CONVERSION TECHNOLOGIES

This is the final stage for energy extraction from microalgae. There are two energy conversion techniques namely;
thermochemical conversion and biochemical conversion which are used to extract energy form the algal biomass.
The energy comes in different forms like gas, oil, heat or electricity etc. Thermochemical conversion process
thermally decomposes the organic components in biomass to yield fuel products. It can be achieved by different
process like direct combustion, gasification, thermochemical liquefaction and pyrolysis (Tsukahara and Sawayama,
2005, Miao et al., 2004). In biochemical conversion process, energy is converted from algal biomass into fuel by
anaerobic digestion, alcoholic fermentation and photobiological hydrogen production (Amin, 2009). The available
conversion processes are summarized and presented in Figure 3.

Gasification

Syngas

Thermochemical
liquefaction

Bio oil/ biodiesel

Thermal
cracking/Pyrolysis

Bio oil, Syngas, Charcoal

Direct combustion

Electricity

Anaerobic digestion

Methane, Hydrogen

Alcoholic fermation

Ethanol

Photobiological
hydrogen production

Hydrogen

Thermochemical
conversion

Algal biomass

Biochemical conversion

Fig. 3. Biodiesel conversion technologies from algal biomass (Brennan and Owende, 2010).
FUEL PROPERTIES OF THE MICROALGAE BIODIESEL/ GREEN DIESEL
The algal biodiesel/green diesel is one of the most efficient forms of energy from microalgae which can be used for
internal combustion engine. After conversion into biodiesel, it is required to know and assess the fuel properties of the
green diesel for IC engine application. More research work has been carried out on microalgae oil extraction,
biodiesel conversion and characterization of the biodiesel for engine performance test and emission study. For
instance, (Xu et al., 2006) studied on Chlorella protothecoids species for oil extraction and characterization of the
biodiesel from the microalgae. They found that the species contained 55.2% crude lipid which can be converted into
biodiesel. The biodiesel (B100) was characterized by a higher heating value of 41 MJ/kg, density of 0.864 kg/L and
viscosity of 5.2x10-4 Pa s at 40C. The literature reported that the heating values of the biodiesel differ from different
species of the microalgae. The properties of the biodiesel from microalgae is presented and compared with
petroleum diesel in Table 3. From the Table it can be observed that density of the algal biodiesel is in between the
limit of the ASTM standard biodiesel and slightly higher than petroleum based diesel.
The kinematic viscosity of the algae biodiesel is higher than the petroleum diesel and just above the range of the
standard biodiesel. It can be noted that the calorific value or heating value of the algal biodiesel is closed to the

883

petroleum diesel. The literature recorded that the heating value of the algal biodiesel is higher than that of any oil crop
biodiesel (edible or non-edible) (Azad and Islam, 2012, Mondal et al., 2014). Based on these facts conclusion can be
drawn that biodiesel has high potential to be used as a future alternative transport fuel.
Table 3. Comparison of fuel properties of the microalgal biodiesel/green diesel with petroleum diesel (Amin, 2009,
Xu et al., 2006, Haik et al., 2011).
Properties
Density
Viscosity (at 40C temp.)
Calorific value
Cloud point
Pour point
Flash point
Solidification point
Cold filter plugging point
Acid value
H/C ratio

Unit
Kg/L
mm2/s
MJ/kg
C
C
C
C
C
Mg KOH/g
-

Microalgae biodiesel
0.864
5.2
41.0
7
-6
115
-12
-11
0.374
1.81

Petroleum diesel
0.838
1.9-4.1
43.8
-15 to 5
-35 to -15
75
-50-10
-3.0 (max -6.7)
Max 0.5
1.81

ASTM biodiesel standard

0.86-0.90
3.5-5.0
-3 to -12
-15 to -16
Min 100
0 (Summer), <-15 winter
Max 0.5
-

The biodiesels are mostly content free fatty acid which affects adversely on the fuel properties. It also leads to
changes in engine characteristics such as injection timing, combustion, performance and exhaust emission (Ozsezen
et al., 2009, Azad and Uddin, 2013). The diesel engine performance and emission study have become important
research topics now-a-days. Considerable research has been carried out on diesel engine combustion, performance
and emission studies by using biodiesel and their blends form different edible and non-edible resources (Azad et al.,
2012b, Amir Uddin and Azad, 2012). The literature reported that use of biodiesel in IC engine can reduce emission
more than that using petroleum diesel (Azad et al., 2012a, Azad et al., 2013, Ameer Uddin et al., 2013). However, the
overall engine efficiency of the biodiesels is lower than that of petroleum diesel. The use of microalgae
biodiesel/green diesel in internal combustion engine has still not been fully studied. Although, many studies have
been undertaken on edible and non-edible vegetable oil produced biodiesel fuelled engine performance and emission
studies, there is little study undertaken on engine performance and combustion characteristics and exhaust gas
emission studies for algae biodiesel. Haik et al. (Haik et al., 2011) conducted an experimental study to use raw algae
biodiesel and its methyl esters in an indirect injection diesel engine. They studied the effect on engine speed, load,
injection timing of the algae biodiesel and engine compression ratio on the engine output torque, combustion
characteristics. They reported that the methyl ester properties of the algae biodiesel are similar to the petroleum
diesel and thus used algae biodiesel as a successful alternative fuel for single cylinder Ricardo diesel engine. So,
further studies are needed for improving optimum engine efficiency by modification of combustion of the IC engine.
CONCLUSION
The literature reveals that the microalgae biodiesel/green diesel is a potential renewable source of energy which is
cost effective, ecofriendly, and alternative to the petroleum diesel for internal combustion engine. Microalgae
production is most effective in terms of net energy balance and for mitigation of greenhouse gas related impacts. The
cultivation of microalgae in large scale for biodiesel production is also a feasible/ achievable option. It could also be a
great natural CO2 capturing mechanism. The review outlined the available cultivation and harvesting techniques and
the methods for biodiesel conversion form algal biomass. The Studies on characteristics of the algal biodiesel have
also been reported in this paper. Scant research on the biodiesel combustion, engine performance and emission
studies stresses the need for more research in this area before it could be accepted as a viable alternative source of
fuel for IC engines. Though, microalgae have highest oil yield per capita land area, among various oil crops, a large
volume of algal biomass is needed to extract oil for biodiesel conversion. Thus an economic analysis of its
reproduction and extraction of diesel from the feed stock is also recommended before commercial application of the
microalgae for biodiesel/ green diesel production could be considered.
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Rhodosporidium toruloides Y4. Journal of industrial microbiology & biotechnology, 37: 581-585.

888

One-Step Preparation For Iron-Doped Tio2 Nanotubes: Characterizations,

Sonocatalytic Activities And Reaction Kinetic Studies
1*

Yean-Ling Pang , Steven Lim , Hwai-Chyuan Ong , Wen-Tong Chong and Ahmad Zuhairi
2
Abdullah
1

Department of Mechanical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala

Lumpur, Malaysia
2
School of Chemical Engineering, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia
*
Email: pangyeanling@hotmail.com

ABSTRACT
Fe-doped titanium dioxide nanotubes (TiO2 NTs) were synthesized by a simple and
environmentally friendly one-step hydrothermal synthesis technique. The influences of iron doping
on the phase composition, microstructures, and optical properties of Fe-TiO2 were analyzed by the
methods of X-ray diffraction (XRD), transmission electron microscopy (TEM), UVvis diffuse
reflectance spectroscopy and nitrogen adsorption-desorption. The results showed that Fe3+ was
successfully introduced into the nanotubes. Appropriate Fe3+ doping can significantly enhance the
sonocatalytic activity of TiO2 due to narrower band gap energy, higher specific surface area, and
more active surface oxygen vacancies. Two kinetic models that were Langmuir-Hinshelwood
mechanism and apparent first-order reactions were proposed. It was found that the reactions were
fitted to the latter kinetic model as L-H model may not be valid when the reaction intermediates
effects prevail. The apparent first-order reaction rate constants of the degradation of catalyzed
reaction were higher than that obtained without catalyst. The calculated activation energy value for
ultrasonic degradation of Rhodamine B in the presence of Fe-doped TiO2 nanotubes was reduced
from 41.11 to 9.54 kJ/mol. Lower apparent activation energy was required to break the chemical
bonds of Rhodamine B in sonocatalytic degradation reaction, which will in turn reduce the reaction
time while enhancing the degradation rate.
Keywords: Fe-doped TiO2 nanotubes, sonocatalytic, Rhodamine B, characteristics, kinetic.
INTRODUCTION
It has been reported that more than 100,000 types of commercially available dyes exist and
an annual worldwide production of synthetic dyes of nearly 1 million tons has been reported in the
literature (Sinha et al., 2013). The estimated loss of organic dyes during dyeing processes is about
15-20% of the total world production of dyes (Ahmad et al., 2014). Hence, dye-containing
wastewater treatment has aroused worldwide interest among researchers. A basic xanthene dye
i.e. Rhodamine B was chosen as a target pollutant in this study. It is widely used as a colorant in
textile industries and it may cause detrimental harmful health effects i.e. irritation to the skin, eyes
and respiratory tract (Merouani et al., 2010).
Conventional treatment methods such as adsorption and filtration are ineffective in
mineralization of dye-containing wastewater as these methods only transfer organic dyes from
wastewater to another phase, creating secondary pollutant easily (Ahmad et al., 2014). In recent
years, the emerging of sonocatalytic degradation method to oxidize organic pollutants has
received great attention from researchers. Cavitation phenomenon occurred during ultrasonic
irradiation could results formation, rapid growth and implosive collapse of micro-bubbles in a liquid
(Zhai et al., 2013). As a result, chemical reactions will occur once the localized high temperature
and pressure thermally dissociated the water (H2O) molecule to form hydroxyl radicals (OH).
Many works shown that the presence of catalyst can increase the number of free radicals
generated, thereby increasing the degradation rate of the organic pollutants (Wang et al., 2008).
Titanium dioxide (TiO2) powder was adopted as sonocatalysts as it provides advantages such as
inexpensive, non-toxic, chemically stable and reusable (Tangestaninejad et al., 2008). TiO2
nanotubes with layered and hollow structure have become one of the most promising materials
among 1D TiO2 nanostructures. The presence of fewer interfacial grain boundaries and the inter
space charge layer of TiO2 nanotubes will facilitate electron transport throughout the 1D channel
(Yan and Zhou, 2011).
Chemical composition and optical properties of TiO2 nanotubes can be altered through
doping TiO2 with metal or non-metal ions. Iron ion (Fe3+) has been chosen in this study owing to
the radius of Fe3+ (0.64 ) being similar to that of Ti4+ (0.68 ) (Nasralla et al., 2013). Therefore, it
can be inferred that Fe ions might easily be incorporated with the crystal lattice of TiO2. In this
study, we have prepared Fe doped TiO2 nanotubes at molar ratio of Fe to Ti equal to 0.005. The
changes on morphology, crystallinity and surface area of the catalysts as well as sonocatalytic
activities of Rhodamine B will be discussed extensively.

889

In literature, sonolysis and sonocatalytic degradation of dyes can be described by either

apparent first-order or Langmuir-Hinsheldwood kinetics. The former kinetic has been used due to
its simplicity, but it could be affected by the initial organic concentration (Zhang et al., 2011b). This
behavior could be described in terms of modified Langmuir-Hinsheldwood model, which used to
determine the relationship between apparent first-order and initial dye concentration. However, the
extent of application of apparent first-order or Langmuir-Hinsheldwood kinetics to describe
sonocatalytic in different types of catalyst is yet to be explored. It is believed that this study provide
new insights for preparing highly sonocatalytic activity of TiO2 as well as the suitability of
application reaction kinetic models based on the experimental data.
EXPERIMENTAL
Materials and Methods
Rhodamine B (other name: C.I. Basic Violet 10; chemical class: xanthene; molecular
formula: C28H31N2O3Cl; molecular weight: 479.01 g/mol; IUPAC Name N-[9-(orthocarboxyphenyl)6-(diethylamino)-3H- xanthen-3-ylidene) was purchased from SigmaAldrich. Hydrochloric acid
(HCl, 37 % w/w), sodium hydroxide, (NaOH, 99 % w/w), tetra-n-butyl-orthotitanate (C16H36O4Ti or
Ti(OBu)4 for synthesis, 98 % v/v), ethanol (CH3CH2OH, 96 % v/v), hydrogen peroxide solution
(H2O2, 30 % w/w) and iron (III) nitrate nonahydrate (Fe(NO3)39H2O, 98 %) were obtained from
Merck. Meanwhile, potassium hydroxide (KOH, 98 % w/w) was purchased from System
Chemical Company. All the chemicals were used as received and distilled water was used
throughout the study. The ultrasonic irradiation source was obtained from an ultrasonic bath (Elma
Transsonic series TI-H5) to irradiate organic dyes, operated at fix frequency 35 kHz and output
power of 50 W. A general schematic diagram of experimental scheme is illustrated in Fig. 1.

Fig. 1: Schematic illustration of sonocatalytic degradation experiment apparatus

Preparation of Catalysts
In the present study, TiO2 NTs were prepared through sol-gel process followed by
hydrothermal treatment. Firstly, the Ti(OBu)4 was used as precursor to dissolve in ethanol solution
with a volume ratio of 4:1 for 1 h under constant stirring. Then, a known quantity of 0.1 M HCl was
added to control the pH of solution to prevent the precipitation of TiO2. The mixture was hydrolyzed
at room temperature under stirring for 2 h to obtain a transparent sol. Next, the sol was aged for 2
days at room temperature to obtain a dry gel. The resulting gel was dried in an oven and calcined
at 500 oC for 3 h. The obtained products denoted as TiO2 nanoparticles (NPs). TiO2 NTs were
synthesized using hydrothermal method which was reported by Bavykin et al. (2008). 3.0 g of
synthesized TiO2 NPs was mixed with 98 cm3 of 10 M NaOH and 2 cm3 of 10 M KOH solution in a
Teflon vessel and refluxed at 100 oC under constant stirring for 48 h. The resulted white powder
was thoroughly washed with 0.1 M of HCl until the washing solution reached pH 3. Then, it was
dried in an oven and calcined at a temperature of 300 oC for 2 h. To prepare the Fe-doped TiO2
nanotubes, appropriate amounts of Fe(NO3)39H2O were added to a mixture of TiO2 powder and
NaOH solution. The molar ratio of Fe to Ti used was 0.005. After that, the obtained products were
washed, filtered, dried in an over and calcined at 300 C for 2 h.
Characterization of Catalysts
The presence of tubular structures in the Fe-doped TiO2 NTs was confirmed by TEM
images taken using a Philips CM 12 transmission electron microscope equipped with an image
analyzer (Model Soft Imaging System, SIS 3.0) and operated at 120 kV. The elemental

890

composition of Fe-doped TiO2 NTs was analyzed using scanning electron microscope, which is
equipped with Oxford INCA 400 energy dispersive X-ray (EDX) system with operating voltages in
the range of 0.1 kV to 30 kV. X-ray diffractometer (Philips PANanalytical XPert PRO MRD PW
3040/60) with the integrated software, XPert High Score was used for analyzing the crystallinity,
phase structure and estimation of the crystallite size. UV-vis diffuse reflectance spectroscopy was
recorded on Perkin-Elmer Lambda 35 Ultravioletvisible (UVvis) Spectrometer in the wavelength
range of 190-1100 nm. A surface analyzer (Micromeritics, ASAP 2020) was used to determine the
surface area, pore size and pore volume of the catalysts through nitrogen adsorption-desorption
isotherm measurements at 77 K.
Sonocatalytic Degradation Study

Each reaction mixture was prepared by adding 2 g/L of TiO2 catalysts into 200 mL of
Rhodamine B solution. Then, the mixed solution was stirred for 30 min to make a good
dispersion of TiO2 catalysts. The beaker was placed inside the ultrasonic bath for 60 min and
o
the temperature was regulated at 30 2 C by adding ice periodically. After the sonocatalytic
reaction, the liquid sample was withdrawn and centrifuged at 4000 rpm to settle down the catalysts.
The concentrations of the samples were determined using AquamateTM Plus UVvis
spectrophotometer (Thermo Scientific Company) to monitor the degradation of Rhodamine B.
The chemical oxygen demand (COD) was conducted using commercially available test kits
provided by Hach Company based on the standard method of potassium dichromate oxidation in
the ranged of 0-150 mg/L (Hach, 2009). Samples were added into COD test tube that contained
potassium dichromate in acidic medium and heated at 150 oC for 2 h in a digestion reactor (Hach
Digital Reactor Block DRB 200). Oxidizable organic compounds would react and reduce the
dichromate ion (Cr2O72) to chromic ion (Cr3+). After cooling the COD test tubes to room
temperature, COD levels were measured by a colourimeter (Hach DR/890).
RESULTS AND DISCUSSION
Characterization of Catalysts
The morphological developments of the as-synthesized TiO2 NPs and TiO2 NTs were
investigated using TEM analysis. The analysis showed it was easy to find the needle-shaped
products (or nanotubes) since they were formed everywhere as shown in Fig. 2 (b)-(d). Fig. 2 (a)
demonstrate that the TiO2 particles had dimensions of about 15-25 nm, which were consistent with
the analysis of XRD result that will be described later. The TiO2 NTs had an average diameter of
10-15 nm with a layered, hollow structure and open ended. Their length ranged from several
hundred nanometers to several micrometers. These values were consistent with the reported
dimensions of TiO2 NTs (Erjavec et al., 2013). The unequally distributed layers in the left and right
side of wall shell tube indicated the formation mechanism of nanotubes. It could be considered that
nanotubes are formed by rolling-up the single-layer nanosheets rather than curving of several
conjoined nanosheets or direct production of multi-walled nanotubes (Deng et al., 2009). It can be
clearly observed that the Fe-doped TiO2 NTs catalysts showed nanotubular structures (Fig. 2 (d))
with sizes ranging from several hundred nanometers to several micrometers in length and openended. No Fe containing nanoparticles or clusters could be observed on the TiO 2 NTs. This result
suggested a possible substitution of Fe3+ for Ti4+ in the H2Ti3O7 lattice, rather than forming
coalescing metallic nanoparticles (Han et al., 2007). From EDX analysis, the atomic composition
for Fe-doped TiO2 NTs calcined at 300 oC was 26.63 % Ti, 72.91 % O, 0.10 % Na and 0.36 % Fe.
This demonstrated that the evidence for the presence of iron in Fe-doped TiO2 NTs. Elemental
ratio of O: Ti was higher than the stoichiometry ratio of TiO2 and it might be related to the
introduction of oxygen vacancies in the crystal lattice or surface of TiO2 NTs during Fe-doping
process (Abazovic et al., 2009).

(a)

(b)

891

(c)

(d)

Fig. 2: TEM images of (a) TiO2 NPs (b) TiO2 NTs-0, (c) TiO2 NTs-300 and (d) Fe-doped TiO2 NTs-300

Phase composition, crystallite size and crystallinity of TiO2 are reported to have great
influence on its sonocatalytic activity (Zhang et al., 2011a). Therefore, crystallinity study of the
samples had been conducted. Table 1 lists the calculated values of average crystallite sizes and
phase composition of TiO2 NPs, as-prepared TiO2 NTs, Fe-doped TiO2 NTs based on the highest
peaks that appear in Fig. 3. Fig 3 (a) shows the XRD pattern for raw TiO2 sample was mainly
composed of anatase phase of TiO2. Fig. 3 (b) shows two main peaks at 2 24.3 and 48.4
which can be readily assigned to the protonic trititanate (H2Ti3O7) phase (labeled as T), which is
consistent with previously reported finding (Cesano et al., 2010). After annealing TiO2 NTs at 300
o
C, the trititanate phase was transformed into anatase phase (labeled as A) as shown in Fig. 3 (c).
This profile was similar to the one reported by Deng et al. (2009) where there was no rutile or any
other phase present. Crystallite phase containing iron (i.e. iron oxide or FexTiOy) could not be
observed after Fe doped on TiO2 NTs. This might be ascribed to the substitutional doping where
Fe3+ substituted Ti4+ in the lattice of TiO2 NTs.

Table 1: XRD results of the annealed TiO2 NTs.

Samples
Average crystal size (nm)
Trititanate
Anatase
TiO2 NPs
21.0

TiO2 NTs-0
8.1

TiO2 NTs-300
14.9

Fe-TiO2 NTs-300
17.1

T: Trititanate
A: Anatase

Intensity (a.u.)

(d)
A

(c)

AA

AA

AA

AA

AA

70

75

(b)

Phase composition (%)

Trititanate
Anatase
100

100

100

100

10

15

(a)
20

25

30

35

40

45

50

55

60

65

80

Diffraction angle, 2 (degree)

Fig. 3: XRD pattern of (a) TiO2 NPs (b) TiO2 NTs-0, (c) TiO2 NTs-300 and (d) Fe-doped TiO2 NTs-300.

Fig. 4 shows the diffuse reflectance spectra of various TiO2 catalysts. The absorption edges
of TiO2 NTs shifted toward the shorter wavelength in comparison to the TiO2 NPs. This indicates
an increase in the band gap energy. By using Taucs relationship (Ganesh et al., 2012), the
indirect band gap energy values of the TiO2 catalysts were determined based on the diffuse
reflectance spectra. The estimated band gap energies of TiO2 NPs and as-prepared TiO2 NTs
were 2.92 and 3.04, respectively. The band gap energy of TiO2 NTs was larger than that of TiO2
NPs. Rodriguez-Gonzalez (2012) reported that this blue shift could be attributed to the difference
in the morphology, in which 3D tetragonal of anatase was transformed to 1D monoclinic of

892

trititanate phase. Meanwhile, Toledo Antonio (2010) presumed that the large amount of
physisorbed water remained in the inner and outer surface of TiO2 NTs and caused a blue shift to
the absorption edge as compared to that of the anatase phase. The band gap energies of TiO2
NTs-300 and Fe-doped TiO2 NTs were estimated to be about 3.03 and 2.70, respectively. The
reflectance spectra of Fe-doped TiO2 NTs slightly shifted towards longer wavelength (red shift) as
compared to that of un-doped TiO2 NTs (Fig. 4 (a)). These results revealed that the doped
elements involved were indeed incorporated into the lattice of TiO2 NTs, thus altered its crystal
structures. The reduction in the band gap energies of TiO2 NTs would enhance the catalytic activity.

4.0

[hvln(Rmax-Rmin)/(R-Rmin)]1/2 (eV)1/2

(b)
3.5
3.0
TiO2 NPs

Poly. (powder)

2.5

TiO NTs-0

2 per. Mov.
2 Avg. (NTs)

2.0

TiO NTs-300

3 per. Mov.
2 Avg. (300)

Fe-TiO2 NTs-300

Poly. (500)

1.5
1.0
0.5
0.0
1.4

1.6

1.8

2.2

2.4

2.6

2.8

3.2

3.4

3.6

3.8

Band gap energy (eV)

Fig. 4: (a) UVvis diffuse reflectance spectra and (b) band gap energy of various TiO2 catalysts.

The BET surface area, pore size and pore volume of the TiO2 NPs, as-prepared TiO2 NTs,
TiO2 NTs-300 and Fe-doped TiO2 NTs are listed in Table 2. The BET surface area of the TiO2 NPs
and as-prepared TiO2 NTs increased from 76.9 m2/g to 207.1 m2/g. The use of hydrothermal
alkaline treatment method to transform TiO2 powder to nanotubes resulted in a material with higher
surface area (about 100-400 m2/g) (Bavykin et al., 2008; Erjavec et al., 2013; Jiang et al., 2012).

Table 2: BET surface area, pore size and pore volume of various TiO2 catalysts.
Samples
BET surface area
Pore size (nm)
2
(m /g)
TiO2 NPs
76.9
9.43
TiO2 NTs-0
207.1
5.42
TiO2 NTs-300
155.4
5.61
Fe-TiO2 NTs-300
167.6
6.76

Pore volume (cm /g)

0.24
0.48
0.43
0.51

Fig. 5 (a) shows the nitrogen adsorption-desorption isotherms of the TiO2 NPs, as-prepared
TiO2 NTs, TiO2 NTs-300 and Fe-doped TiO2 NTs. According to the IUPAC classification, the
adsorption-desorption isotherms for Fig. 5 (a) were of the irreversible type IV (Kruk and Jaroniec,
2001). In such isotherm, the nitrogen adsorption on mesoporous solids generally proceeds via
monolayer followed by multilayer adsorption. The hysteresis loops in the samples of TiO 2 NPs is
categorized as types H1 (Kruk and Jaroniec, 2001). The H1 type hysteresis loop of TiO2 NPs with

893

sharp inflection at P/P0 range from 0.75 to 0.85 is a characteristic of mesoporous materials with
cylindrical pore geometry and high degree of pore size uniformity (Kruk and Jaroniec, 2001; Zhu et
al., 2009). On the other hand, it can be seen that TiO2 NTs-0, TiO2 NTs-300 and Fe-dopedTiO2
NTs-300 show H3 type of hysteresis loop N2 isotherms, indicating the character of disordered slitshaped pores (Morgado Jr et al., 2007). This suggested that the Fe3+ loading did not significantly
affect the mesoporous structure of the TiO2 NTs. The samples of TiO2 NTs-0 showed a hysteresis
loop at P/P0 between 0.5 to 1.0 to suggest the presence of mesopores (250 nm) and macropores
(>50 nm) (Lv et al., 2011). It is believed that the existing macropores are from the aggregation and
intercrossing of nanotubes that generated interparticle voids (Renden-Rivera et al., 2011). On the
other hand, the pore size distributions of various TiO2 catalysts are shown in Fig. 5 (b) and the
peak position of the distribution are listed in Table 2. TiO2 NPs showed monomodal pore size
distributions where it exhibited a rather narrow pore size distribution with a mean pore size of
about 10 nm. TiO2 NTs without annealing and TiO2 NTs-300 showed peaks at around 56 nm
which is related to the inner diameter of nanotubes (Toledo-Antonio et al., 2012).

Adsorbed volume (a.u.)

(a)

Fe-TiO2 NTs-300

TiO2 NTs-300

TiO2 NTs-0
TiO2 NPs
0.0

0.2

0.4

0.6

0.8

1.0

Relative pressure (P/P0)

0.09

(b)

Pore volume (cm3/g.nm)

0.08

nps
TiO

NPs

noTiO
calc

NTs-0

300
TiO

NTs-300

2
2

0.07

0.06

500
Fe-TiO2 NTs-300

0.05
0.04
0.03
0.02
0.01
0
1

10

100

Pore size (nm)

Fig. 5: (a) Nitrogen adsorption-desorption isotherm and (b) pore size distribution of various TiO2 catalysts.

Sonocatalytic Activities of TiO2 Catalysts

Sonocatalytic activity of TiO2 NPs, as-prepared TiO2 NTs, TiO2 NTs and Fe-doped TiO2 NTs
calcined at 300 oC were evaluated through the degradation of a basic dye i.e. Rhodamine B in an
aqueous solution under ultrasonic irradiation for up to 2 h (Fig. 6). TiO2 NTs showed higher
sonocatalytic activity than TiO2 NPs. Some researchers (Lee et al., 2007; Yu et al., 2006) claimed
that higher surface area of TiO2 NTs catalyst would allow more organic pollutant molecules to
adsorb onto the surface of the catalyst, while higher pore volume would result in more rapid
diffusion of various compounds. They reported that high surface area was the dominating factor in
determination of catalytic activity. Meanwhile, others pointed that the influence of crystalline and
surface defects of catalyst would determine the catalytic reaction rate (Testino et al., 2007). It has
been reported that TiO2 NTs exhibit a longer electron lifetime that TiO2 particles (Amano et al.,
2009). Amano et al., (2009) reported that long diffusion length and excellent transport of electrons

894

in the 1D structure of TiO2 NTs leading to the improvement in the separation probability of charge
carrier. Furthermore, the unique tubular structural characteristics of TiO2 NTs facilitated transport
of reactants towards the active sites of catalysts during the sonocatalytic reaction (Li et al., 2011).
However, the as-prepared TiO2 NTs showed lower catalytic activity as compared to that of TiO2
NTs-300 due to the low crystallinity of the structure with some defects which led to favorable
recombination of electrons and holes at defect positions (Fan et al., 2007).
In addition, appropriate amount of Fe3+ can act as shallow trapping sites for charge carrier
(holes and electrons) and improve charge transfer to degrade Rhodamine B (Yalcin et al., 2010). It
has been reported that a considerable part of OH will recombine to form H2O2 (Moumeni and
Hamdaoui, 2012). The possibility of Fenton reaction where the leached portion of Fe which was
soluble in the solution to react with H2O2 could not be ruled out. Hence, the resulting enhancement
effect in the degradation efficiency was actually the combined consequence between catalyst
surface area, crystallinity, band gap energy and the leached Fe into the solution at certain Fe3+
dopant concentration rather than merely on individual factor. Besides, the enhancement of the
degradation rate of Rhodamine B with the addition of H2O2 could be attributed to the additional
OH produced either through the reduction of H2O2 or the self-decomposition (Wang et al., 2008).
Meanwhile, the dissolved air could increase in the generation of additional highly reactive radicals
and nucleation sites for cavity formation (Ghows and Entezari, 2011), thereby, increases the
degradation efficiency of Rhodamine B.
120
NoNo

catalyst
2 NPs
NTs-0
TiO2 NTs-0
NTs
TiO2 NTs-300
FeFe-TiO NTs-300
2
Series6
Fe-TiO2 NTs-300
+ H2O2 + air
NPs
TiO

Degradation efficiency (%)

100

80

60

40

20

0
0

20

40

60
80
Irradiation time (min)

100

120

140

Fig. 6: (a) Sonocatalytic degradation efficiency of Rhodamine B using various TiO2 catalysts

At pH 7, the COD degradation efficiencies measured for the absence of catalyst, TiO2 NPs,
as-prepared TiO2 NTs, TiO2 NTs and Fe-doped TiO2 NTs calcined at 300 oC were 4 %, 12 %, 25 %,
30 %, and 40 %, respectively to indicate that the dye was yet to undergo complete mineralization
under the described conditions. The low degrees of mineralization recorded in the first few hours
for all the catalysts were attributed to the formation of colourless intermediates during ultrasonic
irradiation of Rhodamine B. Partial oxidation of organic molecules often form acidic intermediates,
usually carboxylic acids. These acid intermediates were rather difficult to be oxidized at the
beginning of the reaction (Mijangos et al., 2006). Besides, reducible species such as H2O2 that
was generated during the sonication of water could interfere with the COD test, leading to
erroneous COD results.
Kinetic study
In order to determine degradation of Rhodamine B in this study was either adsorption
controlled or solely sonocatalytic process, two types of kinetic models that are LangmuirHinshelwood adsorption kinetic (Eq. (1)-(2)) (Ghows and Entezari, 2013; Priya and Madras, 2006)
and first order kinetic expressions (Wang et al., 2008; Zhai et al., 2013) (Eqs. (3)-(4)) were used
for the verification. A plot of 1/r versus 1/C0 for different initial dye concentrations and apparent
first-order kinetic plots are shown in Fig. 7. From the intercept and slope of the straight lines, the
values of k, K and kapp could be obtained based on Eq. (2) or Eq. (4) and given in Table 3.
= =

=
d 1 +

(1)

895

where, r is the initial degradation rate (mg/L.min), k is the apparent rate constant (mg/L.min), K is
the equilibrium or adsorption constant (L/mg) and n corresponds to the ratio of the number of
adsorbed organic pollutant molecules in the interfacial region to the maximum number of the
adsorbable organic pollutant molecules.
Eq. (1) can be tested with experimental data after transforming it into a linear equation as
shown in Eq. (2).
1
1 1 1
=
. +

(2)

where, C0 is the initial concentration of organic pollutant in the bulk solution (mg/L).
When the initial organic content in a solution is low, the denominator term of Eq. (1) can be
neglected. Then, the reaction essentially follows an apparent first-order reaction, as shown in Eq.
(3).
=

d
= =
d

(3)

where, kapp (kapp = kK) is the apparent first-order rate constant (min-1).
After integrating, Eq. (4) is obtained.
ln

C0
= kapp .t
Ct

(4)

where, Ct is the concentration of the organic pollutant at ultrasonic irradiation time t (mg/L).
40
(a)
35

catalysts
2 NPs
2 NTs-300
Fe-NTs
Fe-TiO2 NTs-300
NPs
TiO

NTs-300
TiO

30

1/Rate (L.min/mg)

NoNo

25
20
15

10
5
0
0

0.02

0.04

0.06
0.08
0.1
1/Concentration (L/mg)

0.12

0.14

0.16

3.5
(b)
3

catalysts
NPs
NTs
TiO2 NTs-300
FeFe-TiO2 NTs-300
NPs
TiO2

2.5

ln (C0/Ct)

NoNo

2
1.5
1
0.5

20

40

60
80
100
Irradiation time (min)

120

140

Fig. 7: (a) Reciprocal plot of initial rate of ultrasonic degradation versus initial dye concentration of Rhodamine B and (b)
apparent first-order kinetic plots for sonocatalytic degradation of Rhodamine B using various TiO2 catalysts.
Table 3: Kinetic parameters of the ultrasonic degradation of Rhodamine B.
Experiment conditions
Langmuir-Hinshelwood
k
K (L/mg)
k/K
(mg/L.min)
Ultrasonic only
0.0510
0.1365
0.4/1
Ultrasonic + TiO2 NPs
0.1794
0.0423
4/1

896

0.9799
0.9752

Apparent first-order
2
kapp
R
(1/min)
0.0010
0.9933
0.0023
0.9945

Ultrasonic + TiO2 NTs-300

Ultrasonic + Fe-TiO2 NTs300

0.7008
2.5767

0.0154
0.0057

45/1
452/1

0.9800
0.9880

0.0093
0.0243

0.9832
0.9906

The coefficients of determination (R2) values for each case indicate that the degradation of
Rhodamine B by ultrasonic irradiation satisfactory followed an apparent first-order kinetic. Based
on the values for the ratio of k to K obtained using Langmuir-Hinshelwood adsorption kinetic,
indicated that the values of adsorption rate constants appear to be so negligible as compared to
rate constants. The kinetic was further verified for the ultrasonic degradation of Rhodamine B
under same experimental conditions as shown in Fig. 8. The sonocatalytic process in this study is
best described by the apparent first-order reaction rate rather than Langmuir-Hinshelwood
adsorption kinetic. It has been reported that the data analysis was performed with the initial
concentration changes are accompanied by a relatively short time of ultrasonic irradiation in the
Langmuir-Hinshelwood kinetic model (Ghows and Entezari, 2013). Hence, a longer ultrasonic
irradiation reaction can be described by an apparent first-order reaction.
In the case of sonolytic degradation of dye, k value might relate to the accumulation of dye
molecules in the interfacial region of cavitation bubbles (Okitsu et al., 2009). The k value for
sonocatalytic degradation by Fe-doped TiO2 NTs (2.5767 mg/L.min) was higher as compared to
other TiO2 catalysts. This k value might indicated the reaction rate for combined OH and direct
hole attack to organic compound (Priya and Madras, 2006). The higher value of K may implies the
blocking of the active sites of the catalyst due to strong adsorption of dye molecules on the catalyst
surface (Sivalingam et al., 2003).
The temperature dependence of kapp in a chemical reaction is generally assumed to follow
Arrhenius Law (Eqs. (5) and (6)) (Priya and Madras, 2006).
kapp = A exp (

Ea
)
Rg T

(5)

where, T is the reaction temperature (Kelvin), Ea is the activation energy (J/mol), A is the preexponential factor /Arrhenius proportionality factor (min1) and Rg is the universal gas constant
(8.314 J/mol.K).
Then, the apparent reaction rate constants at different temperatures were used to determine
the activation energy. Arrhenius equation (Eq. (5)) was then used to determine the activation
energy for the sonocatalytic degradation of Rhodamine B (Behnajady et al., 2008). Eq. (5) can be
linearlized to obtain Eq. (6):
ln kapp = ln A

Ea 1
( )
Rg T

(6)

897

Concentartion (mg/L)

Concentartion (mg/L)

48
46
44
42
40
38
36
34
32
30

Concentartion (mg/L)

Concentartion (mg/L)

51
50
49
48
47
46
45
44
43

50
45
40
35
30
25
20
15
10

50
45
40
35
30
25
20
15
10
5
0

Experiment
experiment
data

(a)

data

Apparent
first
apparent
first order

order

Langmuir
Hinshelwood
Langmuir
Hinshelwood

20

(b)

40
60
80
100
Irradiation time (min)

120

experiment
data
Experiment

140

data

apparent
first order
Apparent
first

order

Langmuir
Hinshelwood
Langmuir
Hinshelwood

20
(c)

40
60
80
100
Irradiation time (min)
experiment
data
Experiment

120

140

data

apparent
first order
Apparent
first

order

Langmuir
Hinshelwood
Langmuir
Hinshelwood

20

(d)

40
60
80
100
Irradiation time (min)

Experiment
experiment
data

120

140

data

Apparent
first
apparent
first order

order

Langmuir
Hinshelwood
Langmuir
Hinshelwood

20

40
60
80
100
120
140
Irradiation time (min)
Fig. 8: Comparison of experimental and predicted concentration of Rhodamine B (a) without catalyst (b) with TiO 2 NPs, (c) TiO2
NTs-300, (d) Fe0.005-doped TiO2 NTs after 30 min of adsorption.

Arrhenius plot could be obtained by plotting ln kapp versus 1/T which results a linear
relationship with an intercept of ln A and a slope of Ea/Rg. Linear relationships between ln kapp and
1/T in the temperature range of 303-318 K were observed as shown in Fig. 9. The slopes of the
straight lines correspond to the Ea of the ultrasonic degradation of Rhodamine B. The calculated Ea
values for ultrasonic degradation of Rhodamine B without catalyst, with TiO2 NPs, TiO2 NTs-300,
and Fe-doped TiO2 NTs-300 were 56.62, 41.11, 20.89 and 9.54 kJ/mol, respectively. It was found
that lower apparent activation energy was required to break the chemical bonds of Rhodamine B in
sonocatalytic degradation reaction, especially in the presence of Fe-doped TiO2 NTs. This would
reduce the reaction time while enhancing the degradation rate. Low apparent activation energy
also indicated that the effect of temperature on sonocatalytic degradation of Rhodamine B by
doped TiO2 NTs was not as significant as compared to that of non-catalytic reaction system. This
observation was consistent with other reported works using different catalysts or model dye

898

compounds (Priya and Madras, 2006). Fe-doped TiO2 NTs showed lower activation energy (9.54
kJ/mol) as compared to the activation energy obtained by Priya and Madras (2006) for the
ultrasonic degradation of Rhodamine B in the presence of combustion-synthesized TiO2 (13.8
kJ/mol).

1/Temperature (1/K)
0.0031
-6

0.00315

0.0032

ln kapp

-7

0.00325

0.0033

0.00335

ln kapp = -1,147.26 (1/T) - 4.02

R = 0.9958

-8
-9

ln kapp = -2,512.89 (1/T) - 0.45

R = 0.9578

-10
-11
-12

No
catalyst
No
catalyst

TiO2
NPs

NPs
NTs-300
Fe-TiO
Fe NTs
2 NTs-300

TiO2
NTs

ln kapp = -4,944.66 (1/T) + 6.13

R = 0.9735
ln kapp = -6,810.30 (1/T) + 11.63
R = 0.9476

-13
Fig. 9: Arrhenius plot of rate constant versus reciprocal of reaction temperature for ultrasonic degradation of Rhodamine B
without and with various catalysts.

CONCLUSIONS
An efficient Fe-TiO2 NTs sonocatalyst which is effective in the sonocatalytic degradation of
Rhodamine B has been successfully developed. The degradation of Rhodamine B in the presence
of Fe-TiO2 NTs was not depends on adsorption controlled but completely sonocatalytic. The
results showed that adsorption rate of Fe-TiO2 NTs was in the ratio of 1 to 452 of the rate of
reaction. Hence, the degradation obtained in this study was due to the properties of the
sonocatalyst. The catalysts showed narrower band gap energy (2.70 eV), high BET surface area
(167.6 m2/g) and more active surface oxygen vacancies. Meanwhile, leached Fe3+ could catalyze
Fenton-like reaction to improve the overall sonocatalytic activity. In addition, sonocatalytic
degradation of Rhodamine B was observed to behave according to an apparent first-order kinetic
model rather than described by Langmuir-Hinshelwood kinetic model.
ACKNOWLEDGEMENT
Financial supports provided by University of Malaya under UM.C/HIR/MOE/ENG/06 (D00000616001) and Universiti Sains Malaysia in the form of a Research Universiti (RU) Grant are gratefully
acknowledged.
NOMENCLATURE
A
Pre-exponential factor /Arrhenius proportionality factor, min1
C
Concentration of organic pollutant, mg/L
C0
Initial concentration of organic pollutant in the bulk solution, mg/L
Ct
Concentration of the organic pollutant at ultrasonic irradiation time t, mg/L
Ea
Activation energy, J/mol
k
Langmuir- Hinshelwood apparent rate constant, mg/L.min
kapp
Apparent first-order rate constant, min-1
K
Equilibrium or adsorption constant, L/mg
T
Reaction temperature, Kelvin
Rg
Universal gas constant, 8.314 J/mol.K
R2
Coefficients of determination, dimensionless
Greek Letters
n
Ratio of the number of adsorbed organic pollutant molecules in the interfacial region to the
maximum number of the adsorbable organic pollutant molecules, dimensionless

899

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902

SYNTHESIS AND PROPERTIES OF NOVEL MULTIBLOCK COPOLYIMIDES

CONSISTING OF BENZIMIDAZOLE-GROUPS-CONTAINING SULFONATED
POLYIMIDE HYDROPHILIC BLOCKS AND NON-SULFONATED POLYIMIDE
HYDROPHOBIC BLOCKS AS PROTON EXCHANGE MEMBRANES
Wei Li1, Xiaoxia Guo1, Jianhua Fang1*, Yan Yin2*
of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road,
Shanghai 200240, China. 2State Key Laboratory of Engines, Tianjin University, Tianjin 300072, China
*Corresponding author:Tel: +86-21-54747504; Fax: +86-21-54741297; E-mail: jhfang@sjtu.edu.cn

1School

ABSTRACT
A series of novel multiblock copolymers consisting of benzimidazole-groups-containing sulfonated
polyimide hydrophilic blocks (averaged block length = 20) and non-sulfonated polyimide
hydrophobic blocks (averaged block length = 5 or 10) have been synthesized via two-pot synthetic
procedures. The anhydride-terminated hydrophilic oligomer is synthesized by copolymerization of
excess 1,4,5,8-naphthalelnetetracarboxylic dianhydride (NTDA) with amine-terminated
polybenzimidazole
(PBI-NH2)
and
4,4-bis(4-aminophenoxy)biphenyl-3,3-disulfonic
acid
(BAPBDS), while the amine-terminated hydrophobic oligomers are synthesized by polymerization
of excess non-sulfonated diamines with NTDA or a fluorinated dianhydride. The resulting
multiblock copolymers can be cast into tough membranes indicating that reasonably high
molecular weights block copolymers have been obtained. The block SPIs exhibit microphaseseparated structure, whereas the random one is amorphous. Fentons test reveals that the block
copolymer membranes, in particular, those consisting of fluorinated hydrophobic blocks, are fairly
stable toward radical oxidation. Preliminary fuel cell tests are performed to evaluate the fuel cell
performance of the block copolymer membranes. The single cell equipped with the block
copolymer membrane of which hydrophobic block is prepared from NTDA and a fluorinated
diamine (averaged block length = 5) exhibits a peak output power density of 0.70 W/cm 2 at 90 C
and 92% relative humidity for H2/air which is comparable to that of Nafion 112.
Keywords: multiblock copolyimide, membrane, proton conductivity, radical oxidative stability, fuel
cell performance.
INTRODUCTION
Polymer electrolyte membrane fuel cells (PEMFCs) possess the merits of fast startup at room
temperature and high energy conversion efficiency and have been identified to be promising power
sources for vehicular transportation and for other applications which need clean, quiet, and
portable power. Proton exchange membrane (PEM) is one of the key components of a PEMFC
which functions as proton conductor, anode/cathode separator and electronic insulator. An ideal
PEM must meet the requirements of high proton conductivity, high mechanical strength, good
dimensional stability, and chemical resistance under harsh operation conditions of fuel cell
systems. Currently, the state-of-the-art PEMs are DuPonts Nafion, a perfluorinated polymer,
which has the merits of high proton conductivity and excellent chemical and electrochemical
stability. However some drawbacks such as high cost, low working temperature and high fuel
crossover limited their industrial applications. In the past decades a great many efforts have been
made to develop low cost and high performance hydrocarbon membranes as the alternative of
Nafion. Six-membered ring sulfonated polyimides (SPIs) are one of the most promising PEM
materials because of their excellent thermal stability, high mechanical strength and modulus, good
film-forming ability and structural diversity. The SPIs with optimal chemical structure and
morphology have been reported to exhibit high fuel cell performance and good long-term durability
at 90 C or lower temperatures have been reported by Okamotos group [1] and Watanabes group
[2].
The imide rings of the SPIs may undergo hydrolysis reaction leading to disclosure of imide rings
and cleavage of polymer main chains. The relationship between the chemical structure of the SPIs
and their hydrolytic stability has been well studied and it has been identified that the hydrolytic
stability can be greatly improved by using the sulfonated diamines with high basicity and/or the
dianhydrides with low electron affinity as the monomers [3-11]. The stability toward radical
oxidation is another important issue which greatly influence the fuel cell durability especially when
the fuel cells are operated at elevated temperatures (e.g. >110 C). Just like many other types of
hydrocarbon polymers, the SPIs generally show rather poor chemical stability toward radical
oxidation as compared with that of Nafion. Though the relationship between the polymer
structure and the radical oxidative stability has not been well discovered yet, we have previously

903

found that the incorporation of benzimidazole groups into polymer backbone were effective for
enhancing the radical oxidative stability of the SPIs [12,13].
Besides the chemical stability, proton conductivity is another key performance of a PEM. High
proton conductivity (minimum: 0.01 S/cm, ideal: 0.1 S/cm) under fuel cell operation conditions is
essential to achieve high performance of fuel cells. To achieve high proton conductivity, high ion
exchange capacity (IEC) is generally required. However, high IEC often causes excess swelling or
even dissolution of the membranes. To reduce swelling ratio while maintaining high IECs, many
approaches have been proposed such as ionic cross-linking [12-16], covalent cross-linking [12,1724], preparation of composite membranes [25-28] and block copolymerization [29-38]. It has been
recognized that the existence of ionic channels in PEMs can facilitate proton transport resulting in
high proton conductivity. To build up ionic channels, the PEMs are required to have the hydrophilichydrophobic microphase separated structure which can be achieved by block copolymerization
[35]. Hydrophilic blocks aggregate together yielding hydrophilic domains which may further form
ionic channels when they are effectively connected with each other. Up to date, many kinds of
multiblock SPIs have been developed [29-34], however, almost all the multiblock SPIs still lack of
sufficiently high radical oxidative stability. In this study, we report on the synthesis and properties of
a series of novel multiblock SPIs consisting of benzimidazole-groups-containing sulfonated
polyimide hydrophilic blocks and non-sulfonated polyimide hydrophobic blocks. The incorporation
of benzimidazole groups into the hydrophilic block is to enhance the radical oxidative stability of
the membranes, while a fluorinated dianhydride and a fluorinated diamine monomers are
synthesized for preparation of the hydrophobic blocks in order to enhance the hydrophobicity of
the hydrophobic blocks.
EXPERIMENTAL
Materials
Hexafluorobisphenol A, 4-chloro-1-nitrobenzene and Pd/C (10 wt%) were purchased from Acros.
4-Bromo-1,8-naphthalic anhydride was purchased QuZhou Rainful Chemical Co. Ltd. (China).
Bis(4-(3-aminophenoxy)phenyl) sulfone (BAPPS) was purchased from TCI. Dimethylsulfoxide
(DMSO), m-Cresol, 1-methylpyrrolidone (NMP), N,N-dimethylacetamide (DMAc), hydrazine
monohydrate and triethylamine (Et3N) were purchased from Sinopharm Chemical Reagent Co.,
Ltd. (SCRC, China). NTDA was purchased from Beijing Multi Technology Co., Ltd. (China) and
dried at 160 C in vacuum for 20 h before use. DMSO, NMP, DMAc and Et3N were distilled under
reduced (for DMSO, NMP and DMAc) or normal (for Et3N) pressure and dried over 4A molecular
sieves before use. Other materials were used as received. The BAPBDS was synthesized
according to a literature method [4]. The amine-terminated polybenzimidazole oligomer (H2N-PBI)
was synthesized via condensation polymerization of excess 3,3-diaminobenzidine (DAB) with
isophthalic acid (iPTA) in polyphosphoric acid at 190 C at the molar ratio of DAB/iPTA = 2/1 [13].
Monomer and Polymer Synthesis
Synthesis of 2,2-bis(4-(4-nitrophenoxy)phenyl)hexafluoropropane (BNPHF)
To a 100 mL three-necked flask equipped with a magnetic stirring device, a nitrogen inlet and a
nitrogen outlet, a Dean-Stark trap and a condenser were added 6.72 g (20 mmol) of
hexafluorobisphenol A, 1.60 g (40 mmol) of NaOH solid and 30 mL of methanol. After
hexafluorobisphenol A and NaOH were complete dissolved, the mixture were slowly heated to
80 C and kept at this temperature till the methanol was completely removed via the Dean-Stark
trap. The reaction mixture was allowed to cool to room temperature, and then 6.93 g (44 mmol) of
4-chloro-1-nitrobenzene and 25 mL of DMAc were added. The reaction mixture was reheated at
140 C for 4 h and 160 C for another 20 h. After cooling to room temperature, the resulting
solution mixture was poured into 200 mL of methanol. The white precipitate was collected by
filtration, washed with water and methanol thoroughly and dried at 80 C in vacuum. 8.68 g of
white product was obtained (yield: 75%).
Synthesis of 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane (BAPHF)
To a 100 mL three-necked flask equipped with a magnetic stirring device and a nitrogen inlet and a
nitrogen outlet were added 5.78 g (10 mmol) of NPPF, 0.25 g of Pd/C catalyst and 40 mL of
ethanol. The mixture was magnetically stirred at room temperature under nitrogen flow for 30 min,
and then heated to reflux. A mixture of 8 mL of hydrazine hydrate and 15 mL ethanol was added
dropwise within 4 h. After the addition of the hydrazine solution in ethanol, the reaction mixture
was kept refluxing for another 24 h. After cooling to the room temperature, the solution mixture
was filtered, and the filtrate was poured into 200 mL of deionized water. The white precipitate was
collected by filtration and thoroughly washed with deionized water. The crude product was purified

904

by recrystallization from the mixture of water and ethanol (1:1 by v/v) and dried at 80 C in vacuum.
4.15 g of white product was obtained (yield: 80%). FT-IR (KBr pellet): 3464, 3384, 3043, 1619,
1504, 1252, 1203, 1176, 1139, 1016, 964, 949, 928, 875, 837, 734, 701 cm-1.
Synthesis
of
4,4-(hexafluoroisopropylidenediphenylene-4,4-dioxo)-bis(1,8-naphthalic
anhydride) (HFBNA)
To a 100 mL three-necked flask equipped with a magnetic stirring device, a nitrogen inlet and a
nitrogen outlet, a Dean-Stark trap and a condenser were added 18.83 g (56 mmol) of
hexafluorobisphenol A, 4.48 g (112 mmol) of NaOH solid and 100 mL of methanol. After
hexafluorobisphenol A and NaOH were completely dissolved, the mixture were slowly heated to
80 C and kept at this temperature till the methanol was completely removed via the Dean-Stark
trap. The reaction mixture was allowed to cool to room temperature, and then 31.03 g (112 mmol)
of 4-bromo-1,8-naphthalic anhydride and 125 mL of DMAc were added. The reaction mixture were
reheated at 140 C for 4 h and 170 C for another 20 h. After cooling to room temperature, the
resulting solution was poured into 500 mL of methanol. The yellow precipitate was collected by
filtration and thoroughly washed with water and methanol. The crude product was purified by
recrystallization from the mixture of water and DMF (1:5 by v/v), and dried at 80 C in vacuum.
29.35 g of white product was obtained (yield: 70%). FT-IR (KBr pellet): 3074, 1774, 1737, 1594,
1580, 1507, 1468, 1430, 1402, 1343, 1303, 1253, 1176, 1112, 1074, 1022, 991, 967, 928, 897,
841, 840, 802, 779, 750, 727, 710 cm-1.
Synthesis of multiblock copolyimides
The multiblock copolyimides were prepared by two-pot procedures. The synthetic details are
described as follows using the multiblock copolyimide SPIBI20-b-NS05 as an example. Here, the
SPIBI refers to the hydrophilic blocks derived from NTDA, BAPBDS and H2N-PBI, while the NS
refers to the hydrophobic blocks derived from NTDA and BAPPS. The numerals 20 and 05 refer
to the averaged block lengths of the hydrophilic blocks and hydrophobic blocks, respectively.
To a 100 mL dry three-neck flask equipped with a magnetic stirring device, a nitrogen inlet and a
nitrogen outlet, and a condenser were added 2.0064 g (3.8 mmol) of BAPBDS, 0.1044 g (0.2
mmol) of H2N-PBI, 15 mL of m-cresol, 1.2 mL of Et3N and 1.2 mL of isoquinoline. The mixture was
stirred at room temperature under nitrogen flow to form a clear solution. Then 1.1256 g (4.2mmol)
of NTDA and 0.9768 g (8 mmol) of benzoic acid were added and the reaction mixture was stirred
at room temperature for 0.5 h followed by heating at 80 C for 12 h and 190 C for another 8 h
yielding anhydride-terminated SPIBI oligomer (hydrophilic block). The reaction mixture was cooled
to room temperature and stood by for next step reaction.
To another 100 mL dry three-neck flask equipped with a magnetic stirring device, a nitrogen inlet
and a nitrogen outlet, and a condenser were added 0.5190 g (1.2 mmol) of BAPPS, 0.2680 g (1
mmol) of NTDA, 0.2442 g (2 mmol) of benzoic acid, 7 mL of m-cresol and 0.3 mL of isoquinoline.
The mixture was magnetically stirred at room temperature under nitrogen flow for 0.5 h and then
heated at 80 C for 12 h and 180 C for another 8 h yielding the amine-terminated polyimide
oligomer (hydrophobic block). After cooling to room temperature, the solution mixture was
completely transferred to the flask where the foregoing anhydride-terminated SPI oligomer solution
was produced. Additional 5 mL of m-cresol was added to the flask and the reaction mixture was
magnetically stirred at room temperature under nitrogen flow. Subsequently the reaction mixture
was heated at 80 C for 4 h and 180 C for another 20 h to fulfill the block copolymerization. After
cooling to room temperature, the viscous solution mixture was poured into 150 mL of methanol.
The resulting fiber-like precipitate was collected by filtration, thoroughly washed by methanol, and
dried at 80 C for 10 h in vacuum.
Membrane Formation and Proton Exchange
The synthesized block copolyimides in their triethylammonium salt form were dissolved in m-cresol
to give ~7 wt% solutions. After filtration they were cast onto clean glass plates followed by drying
at 110 C for 6 h. The as-cast membranes were peeled off from the glass plates and dried in
vacuum at 200 C for 4 h. The membranes were soaked in hot methanol to remove any residual
solvent. Proton exchange was completed by soaking the membranes in 1.0 M sulfuric acid at room
temperature for 48 h. The resulting membranes were thoroughly washed with de-ionized water till
the rinsed water became neutral and finally dried in vacuum at 80 C for 10 h.
Measurements
H-NMR spectra were recorded on a Varian Mercury Plus 400 MHz instrument. FT-IR spectra were
recorded on a Perkin-Elmer Paragon 1000PC spectrometer. Reduced viscosity () was measured
in m-cresol at a polymer concentration of 0.5 g dL-1 with an Ubbelohde viscometer at 30 C.
Tensile measurements were carried out with an Instron 4456 instrument at room temperature and
1

905

50% relative humidity at a crosshead speed of 5 mm min-1. For each kind of membrane, three
samples were used for the measurements and the tensile stress and the elongation at break was
estimated by the averaged values of the three samples.
Ion exchange capacity (IEC) was measured by titration method. A dry membrane (~0.1 g) was
cut into small pieces and soaked in a saturated sodium chloride solution at room temperature for
three days. Then the samples were taken out and rinsed with deionized water three times. The
rinsed water was combined with the previous sodium chloride solution and then titrated with a 0.01
M sodium hydroxide solution using phenolphthalein as pH indicator.
Water uptake (WU) and swelling ratio (SW) measurements were carried out by immersing the
membranes (0.1 - 0.2 g per sheet) into deionized water at 80 C for 6 h. Then the membranes
were taken out, wiped with tissue paper, quickly weighed on a microbalance. WU was calculated
from the following equation:
WU = (W s W d)/W d 100 (%)

(1)

where W d and W s refer to the weight of dry and wet membranes, respectively.
The in-plane swelling ratio (l) and the through-plane swelling ratio (t) are calculated from the
following equations:
l = (ls ld)/ld

(2)

t = (ts td)/td

(3)

where ld and td are the length and thickness of the dry membrane, respectively, while ls and ts refer
to the length and thickness of the fully hydrate membrane.
Proton conductivity () was measured using a four-point-probe electrochemical impedance
spectroscopy technique over the frequency range from 100 Hz to 100 KHz (Hioki 3552) [3]. A
sheet of SPI membrane (proton form) and two pairs of blacken platinum plate electrodes were set
in a Teflon cell. The cell was placed in either a thermo-controlled humid chamber for measurement
at relative humidity (RH) lower than 100% or distilled deionized water for measurement in liquid
water. The resistance value was determined from high frequency intercept of the impedance with
the real axis. Proton conductivity was calculated from the following equation:
= D/(LBR)

(4)

where D is the distance between the two electrodes, L and B are the thickness and width of the
membrane, respectively, and R is the resistance value measured. For measurement in liquid water,
the dimensions in fully hydrated state were used.
Atomic force microscopy (AFM) was recorded on SII Nanonavi E-Sweep (Japan) at atmosphere.
Transmission electronic microscopy (TEM) was recorded on JEM-2010HT (Japan).
RESULTS AND DISCUSSION
Monomer Synthesis
A fluorinated diamine monomer BAPHF and a fluorinated dianhydride monomer HFBNA were
synthesized and used for preparation of the hydrophobic blocks. The BAPHF was synthesized via
two-step reactions (Scheme 1). In the first step reaction, 4-chloro-1-nitrobenzene reacted with
hexafluorobisphenol A in DMAc in the presence of stoichiometric amount of sodium hydroxide at
160 C for 20 h to yield the intermediate product BNPHF. In the second step reaction, the BNPHF
was reduced with hydrazine in ethanol in the presence of catalyst Pd/C to produce the desired
product BAPHF. Figure 1 shows the 1H NMR spectrum of the synthesized BAPHF. The broad peak
around 3.62 ppm is assigned to the protons of the amino groups. The peaks at 6.65-6.72 ppm are
assigned to the protons (H4) near the amino groups, the peaks in the range of 7.24-7.32 ppm are
attributed to the protons (H1) in the ortho position of the hexafluoroisopropylidene group, the
peaks around 6.85-6.94 ppm are ascribed to the rest of protons (H2 and H3). The peak
assignments are just consistent with the chemical structure of the BAPHF. The chemical structure
of the synthesized BAPHF is also confirmed by the FT-IR spectrum (not shown). The absorption
bands at 3464 and 3384 cm-1 are assigned to N-H stretch of the primary amino groups. The
characteristic absorption bands around 3043 (aromatic C-H stretch), 1623 and 1504 cm-1 (aromatic
C=C stretch) suggest the presence of aromatic rings. The strong absorption band at 1252 cm -1 is
attributed to the C-F stretch. .
The dianhydride monomer HFBNA was synthesized by reacting 4-bromo-1,8-naphthalic
anhydride with hexafluorobisphenol A in DMAc in the presence of stoichiometric amount of sodium
hydroxide at 160 C for 20 h (Scheme 2). The chemical structure of the synthesized HFDNA was
also confirmed by the 1H NMR spectrum (Figure 2). The doublet peaks at 8.80-8.76 ppm and the
doublet peaks at 8.69-8.65 ppm are assigned to the two kinds of protons adjacent to the anhydride

906

carbonyl groups (H4 and H5). The doublet peaks at 7.58-7.62 ppm are ascribed to the protons
(H1) adjacent to the hexafluoropropylidene group. The peaks from 7.31 to 7.06 ppm are caused by
the benzene proton (H2,H3) near ether. In the FT-IR spectrum (not shown) of the HFBNA, the
strong absorption bands at 1771 and 1737 cm-1 are assigned to the symmetric and asymmetric
stretching of carbonyl groups of 1,8-naphthalic anhydride. The absorption bands around 3074
(aromatic C-H), 1593 and 1507 cm-1 (aromatic C=C stretch) indicate the presence of aromatic
rings. The characteristic band of C-F stretch at 1252 cm-1 is also observed. The absorption band at
1022 cm-1 is assigned to the ether bond.

Figure 1. 1H NMR spectrum of the fluorinated diamine monomer BAPHF in DMSO-d6.

Scheme 1 Synthesis of the fluorinated diamine monomer BAPHF.

Scheme 2 Synthesis of the fluorinated dianhydride monomer HFBNA.

907

Figure 2. 1H NMR spectrum of the fluorinated dianhydride monomer HFBNA in CDCl 3.

Scheme 3 Synthesis of the anhydride-terminated sulfonated polyimide oligomer (hydrophilic block).

Synthesis of the Block Copolyimides

A series of multiblock copolyimides consisting of benzimidazole-groups-containing sulfonated
polyimide (hydrophilic blocks) and non-sulfonated polyimides (hydrophobic blocks) were
synthesized by two-pot synthetic procedures. In one pot, an anhydride-terminated sulfonated
polyimide oligomer was synthesized as the hydrophilic block source via the condensation
copolymerization of excess NTDA with BAPBDS and NH2-PBI in m-cresol in the presence of Et3N,
benzoic acid and isoquinoline at 190 C (Scheme 3). The oligomer was not isolated from the
solution mixture but directly used for next step reaction. The molar ratio of NTDA/BAPBDS/NH 2PBI was controlled at 21/19/1 resulting in an averaged block length of 20. The resultant
copolyimide oligomer is denoted as SPIBI20. In another pot, an amine-terminated non-sulfonated
polyimide was synthesized as the hydrophobic block source via the condensation polymerization
of excess aromatic diamine (BAPPS or BAPHF) with naphthalic dianhydride (NTDA or HFBNA) in
m-cresol in the presence of benzoic acid and isoquinoline at 180 C (Scheme 4). By varying the
dianhydride and diamine monomers and by controlling the monomer molar ratio at
diamine/dianhydride = 6/5 or 11/10, six kinds of hydrophobic oligomers were obtained which are
denoted as NS05, NS10, NF05, NF10, FF05 and FF10, respectively. Here, the NS, NF and FF
refer to the oligomers derived from NTDA and BAPPS, NTDA and BAPHF, and HFBNA and
BAPHF, respectively, while the numerals 05 and 10 refer to the averaged block lengths. Without
isolation, these amine-termianted hydrophobic polyimide oligomers were directly transferred to the
flask where the anhydride-terminated hydrophilic oligomer (SPIBI20) were synthesized to allow
further polymerization yielding various multiblock copolyimides (Scheme 5). The resultant block
copolyimides are denoted as SPIBI20-b-NSX, SPIBI20-b-NFX, SPIBI20-b-FFX, respectively, where
X is the average length of the hydrophobic block.

908

Scheme 4 Synthesis of the amine-terminated polyimide oligomers (hydrophobic blocks): a) NSy and
NFy series, b) FFy series.

Scheme 5 Synthesis of various sulfonated multiblock copolyimides.

Figure 3 shows the FT-IR spectra of the multi-block copolymers in their proton form. It can be
seen that these multi-block polymers show quite similar spectra because of their similar structure.
The characteristic absorption bands at 1710 cm-1 (asymmetric stretch of imide C=O), 1663 cm-1
(symmetric stretch of imide C=O) and 1350 cm-1 (C-N stretch) suggest the formation of imide
structure. The characteristic absorption bands at 1088 cm-1 (-SO2- asymmetric stretch) and 1020
cm-1 (-SO2- symmetric stretch) indicate the presence of sulfonic acid groups.

909

Figure 3. FT-IR spectra of the sulfonated multiblock copolyimide membranes in their proton.

The multiblock copolyimides synthesized in this study are well soluble in m-cresol but insoluble
in other organic solvents such as DMSO and DMAc. As showed in the Table 1, the reduced
viscosities of the multiblock copolymers are in the range of 1.0-1.5 g dL-1 at a polymer
concentration of 0.5 g dL-1 in m-cresol at 30 C. Transparent and tough membranes with the tensile
strength of 46-54 MPa were obtained by solution cast method indicating that reasonably high
molecular weight multiblock copolyimides have been successfully synthesized.
Table 1 Reduced viscosity () in m-cresol at 30 C and tensile properties of the block copolymers
Copolymer
Modulus
Tensile strength
Elongation at break (%)
Viscosityg
dL-1

(MPa)

(MPa

SPIBI20-b-NS05

1.5

500

48

44

SPIBI20-b-NS10

1.0

857

46

17

SPIBI20-b-NF05

1.2

699

54

30

SPIBI20-b-NF10

1.2

827

52

25

SPIBI20-b-FF05

1.3

448

53

49

SPIBI20-b-FF10

1.1

711

50

24

Table 2 IEC, water uptake at 80 C and swelling ratio (in-plane direction: l, through-plane direction: t)
at 80 C of block copolymer membranes
Copolymer
WU
IECmeq g-1
SR%
Theoreticala

Titration

(%)

SPIBI20-b-NS05

1.94

1.89

79

14

26

SPIBI20-b-NS10

1.68

1.53

68

10

22

SPIBI20-b-NF05

1.85

1.74

69

12

21

SPIBI20-b-NF10

1.54

1.42

53

10

17

SPIBI20-b-FF05

1.64

1.49

44

18

SPIBI20-b-FF10

1.28

1.27

36

12

2.24
1.90
95
18
35
SPIBI
a Calculated by deduction of the protons bonded with benzimidazole ring due to the strong acid-base
interaction.

IEC, Water Uptake and Swelling Ratio

910

The IEC, water uptake and swelling ratio values of the multiblock copolyimide membranes are
listed in Table 2. Because the chemical structures of the multiblock copolyimides contain both the
acidic sulfonate groups and the basic benzimidazole groups which interact with each other leading
to ionic cross-linking, the theoretical values of the IEC listed in Table 2 are obtained by deducting
the part of consumed sulfonate groups due to the ionic cross-linking (one sulfonate group reacts
with one benzimidazole groups). The IEC values obtained by titration are in the range of 1.89-1.27
meq g-1, which are similar or slightly lower than the theoretical ones probably because of the
incomplete ion exchange during the IEC measurement or experimental errors. Water uptake and
swelling ratio are mainly dependent on IEC and the membranes with higher IECs tend to exhibit
larger water uptake and swelling ratio. It seems that the nature (structure and length) of the
hydrophobic blocks have insignificant effect on water uptake and swelling ratio as compared with
that of IEC. This is probably because the hydrophilic blocks are much longer than the hydrophobic
blocks and therefore the former dominates the sorption and swelling behaviors of the membranes.
From Table 2 it can also be found that all the multiblock copolyimide membranes display an
anisotropic swelling behavior, i.e., the swelling ratio in through-plane direction is significantly larger
than that of in-plane direction. This is probably related to the rod-like structure of the polyimide
main chains which has been previously observed with many other SPI membranes [3, 22, 29-31].
Radical Oxidative Stability
Radical oxidation-induced degradation of polymer main chains has been identified to be one of the
major reasons that cause deterioration of proton exchange membranes in the fuel cell. Peroxide
radicals (hydroxyl and hydroperoxy radicals, etc.) are formed in fuel cells due to the oxygen
permeation through the membrane from the cathode side and reduction at the anode side [34].
Thus it is very important to develop the PEMs with high stability toward radical oxidation. The exsitu evaluation of radical oxidative stability of a PEM is usually performed by the Fentons test. In
this study, the Fentons test was performed by soaking the membranes in the Fentons reagent
(3% H2O2 + 3 ppm FeSO4) at 80 C and the radical oxidative stability was evaluated by the
elapsed time when the membrane samples started to dissolve or break into pieces ( 1), the
elapsed time when the membrane completely dissolved (2), and the weight loss after a fixed
period of soaking time (200 min). As shown in the Table 3, all the benzimidazole-groups-containing
multiblock copolyimide membranes exhibited much longer 1 and 2 than the benzimidazolegroups-free multiblock copolyimide membrane (SPIBI20-b-NS05). The former displayed only minor
or almost none weight loss, whereas the latter completely dissolved (100% weight loss). This
indicates that the radical oxidative stability has been significantly improved due to the incorporation
of benzimidazole groups. By comparing the radical oxidative stability of the benzimidazole-groupscontaining block copolymer membranes with that of the corresponding SPI membranes without
hydrophobic blocks (SPIBI), one can see that the radical oxidative stability was also improved due
to the incorporation of the inert hydrophobic blocks into the polymer main chains. Moreover, the
block copolymer membranes derived from the fluorinated monomers exhibited better radical
oxidative stability than those derived from the nonfluorinated monomers. The membranes derived
from the fluorinated dianhydride and fluorinated diamine (SPIBI20-b-FF05 and SPIBI20-b-FF10)
displayed the best radical oxidative stability. This is likely attributed to the presence of the highly
hydrophobic hexafluoroisopropylidene linkages in the hydrophobic blocks of the multiblock
copolyimides.
Table 3 Radical oxidative stability of various sulfonated polyimide membranes by the Fentons test at
80 C
Ionomer
IEC
Radical oxidative stability
(meq g-1)

1b (min)

2b (min)

Weight lossc (%)

SPIBI-b-NS2005

1.89

220

350

3.1

SPIBI-b-NS2010

1.53

240

350

2.9

SPIBI-b-NF2005

1.74

250

355

0.8

SPIBI-b-NF2010

1.42

260

360

0.5

SPIBI-b-FF2005

1.49

290

410

SPIBI-b-FF2010

1.27

300

420

SPIBI

1.90

200

270

5.8

SPI20-b-NS05a

NM

100

140

100

911

aThe

multiblock copolyimide consisting of the hydrophilic blocks synthesized from the BAPBDS and the
NTDA (averaged block length: 20) and the hydrophobic blocks synthesized from the BAPPS and the
NTDA (averaged block length: 5).
b and refer to the elapsed time when the membrane samples started to dissolved and completely
1
2
dissolved, respectively.
cSoaking time: 200 min.
NM: not measured.

Morphology
Morphology is an important issue associated with block copolymers. In the past decades many
efforts have been made on the development of block copolymers with hydrophilic-hydrophobic
phase separated structures in order to create effective ionic channels to facilitate proton transport.
In this study, the morphologies of the multiblock copolyimide membranes in their proton-form were
investigated by both AFM images (tapping mode) and TEM images. Figure 4 shows the AFM
images of the multiblock copolyimide membranes. The dark areas are attributed to the assemblies
of the hydrophilic segments because of the phase-lag effect resulting from the enhanced adhesive
forces between the tip and the hydrophilic surface of the samples [35], while the bright areas refer
to the hydrophobic domains. The AFM images suggest that all the multiblock copolyimide
membranes have microsphase-separated morphologies. This morphological structure was further
confirmed by the TEM images. Figure 5 shows the TEM images of the SPIBI20-b-NS05 and the
SPIBI20-b-FF05. The dark areas (width: ~20 nm) refer to the hydrophilic domains, while the white
areas refer to the hydrophobic domains.

(a)
(b)
(c)
(d)
Figure 4. AFM images of the sulfonated multiblock copolyimide membranes: (a) SPIBI20-b-NS05, (b)
SPIBI20-b-NF05, (c) SPIBI20-b-FF05 and (d) SPIBI20-b-FF10.

(a)
(b)
Figure 5. TEM images of the sulfonated multiblock copolyimide membranes: (a) SPIBI20-b-NS05 and
(b) SPIBI20-b-FF05.

912

Figure 6. Proton conductivity of various multiblock copolyimide membranes in deionized water as a

function of temperature.

Proton Conductivity
Proton conductivity is one of the most important performances of a PEM and is affected by many
factors such as IEC, temperature and morphological structure. Figure 6 shows the variation of
proton conductivity of the multiblock copolyimide membranes as a function of temperature in
deionized water. For all the membranes, the proton conductivity increases with an increase in
temperature. Generally, proton conductivity is mainly dependent on IEC, and the higher IEC, the
higher proton conductivity. However, at a given temperature the SPI-co-PBI-b-FF 2005 shows
significantly higher proton conductivity than the SPI-co-PBI-b-NS 2010 despite their similar IECs
(1.49 and 1.53 meq g-1). The same phenomenon is also observed with the SPI-co-PBI-b-FF 2010
and SPI-co-PBI-b-NF 2010. Although the former has a lower IEC (1.27 meq g-1) than the latter
(1.42 meq g-1), at a given temperature the proton conductivity of the former is even slightly higher
than that of the latter. This is likely attributed to the better microphase separation and the more
efficient connection of hydrophilic domains of the block copolymers of which hydrophobic blocks
consist of the fluorinated dianhydride and the fluorinated diamine moieties (SPI-co-PBI-b-FF 2010
and SPI-co-PBI-b-FF 2010). The plot of the natural logarithm of proton conductivity versus the
reciprocal of temperature reveals linear relationship between these two variables for all the
membranes (Figure 7). From the slope of each line, the apparent activation energies (Ea) of
proton conduction are calculated from Arrhenius equation. The multiblock colyimide membranes of
which hydrophobic blocks are derived from the fluorinated diamine and/or the fluorinated
dianhydride monomer show slightly higher Ea (14.3-15.4 kJ mol-1) than those derived from the
non-fluorinated monomers of which Ea values (11.2 and 12.0 kJ mol-1) are at the same level of
that (12 kJ mol-1) of Nafion112.

913

Figure 7. Arrhenius plots of proton conductivities of various multiblock copolyimide membranes in

deionized water.

Figure 8. H2/air fuel cell performances of the multiblock copolyimide membranes SPIBI20-b-NF05 and
the SPIBI20-b-FF05, the SPIBI and Nafion112. The fuel cells were operated at 90 C with external
humidification (anode: 92%, cathode: 82%) at 0.2 MPa.

Single Cell Performance

Preliminary H2/air fuel cell tests using four kinds of membranes, SPIBI20-b-NF05, SPIBI20-b-FF05,
SPIBI and Nafion112 as the electrolytes were carried out at 90 C under the external
humidification of 92% RH for the anode side and 82% for the cathode side, and the polarization
curves are illustrated in Figure 8. These membranes have approximately the same thickness (52 55 m). The open circuit voltage (OCV) values of these fuel cells are quite similar (0.96 - 0.97 V).
The single cell equipped with the SPIBI20-b-NF05 membrane shows fairly good fuel cell
performance with a peak power density of 0.70 W cm-2 which is comparable to those of the SPIBI
and Nafion112. However, the single cell equipped with the SPIBI20-b-FF05 membrane exhibits a
lower peak power density of 0.60 W cm-2 because of its lower proton conductivity. Nevertheless, at
the current density below 0.9 A cm-2 this fuel cell exhibits almost the same fuel cell performance as
the others.

914

CONCLUSIONS
A series of novel multiblock copolyimides consisting of benzimidazole-groups-containing
sulfonated polyimide hydrophilic blocks (averaged block length = 20) and non-sulfonated polyimide
hydrophobic blocks (averaged block length = 5 or 10) have been synthesized by two-pot synthetic
procedures. The resulting multiblock copolyimides could form tough membranes with microphaseseparated morphologies. They exhibited reduced swelling ratio and enhanced radical oxidative
stability in comparison with the corresponding SPI membrane containing no hydrophobic blocks
(SPIBI). Also, the presence of the polybenzimidazole unit in the polymer backbones was
responsible for the improvement in radical oxidative stability of the membranes. Preliminary fuel
cell tests revealed that the SPIBI20-b-NF05 membrane was a promising PEM which showed fairly
good fuel cell performance to H2/air with a peak power density of 0.70 W cm-2 at 90 C which was
comparable to that of Nafion112.
ACKNOWLEDGEMENTS
This study was supported by the National Basic Research Program of China (Grant No.
2014CB643600), Natural Science Foundation of China (Grant No. 51106111), and the Shanghai
Municipal Natural Science Foundation (Grant No. 13ZR1420200).
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916

Effects Of Dynamic Driving Cycle On The Performance Degradation Of Pem

Fuel Cell By Segmented Fuel Cell
Shan Jing

1, 2

1, 2*

Lin Rui

1, 2

, Cui Xin

1, 2

, Lin Xuwei

, Ma Jianxin

1, 2

Clean Energy Automotive Engineering Centre, Tongji University, Shanghai 201804, Shanghai,
China
2

School of Automotive Studies, Tongji University, Shanghai 201804, Shanghai, China

ABSTRACT
The in-situ segmented cell measuring technique can provide real-time, accurate current density
distributions and reflect the uniformity of the internal electrochemical reaction in the fuel cell. In this
study, the effects of the driving cycle, which is composed of idle condition, accelerated condition and
overload condition, on the durability of fuel cell were investigated. The cell was operated at 70
with 100% humidification for both electrodes in potential static mode. It was found from the I-V curves
that after 200 cycles the performance of fuel cell decreased obviously. With the segmented cell
technology, the local current density distributions were obtained. It showed that after 200 cycles, the
current density at the inlet region declined the most significantly while that of the middle region was
always above the mean current density. Meanwhile, electro-chemical impedance spectroscopy (EIS)
and cyclic voltammetry (CV) were used to characterize the impedance of fuel cell and the
electrochemical active area of cathode catalyst. SEM results revealed that crackle flaw appeared on
the inlet surface of the catalyst layer and the thickness of the MEA decreased distinctly. TEM results
showed that the Pt particle size grew up distinctly after the driving cycles.
Keywords: PEMFC, driving cycles, Current density distribution.

1.

INTRODUCTION
Proton exchange membrane fuel cell (PEMFC) is one of the most promising types of fuel cells

that can be used as a vehicular power source to replace gasoline and diesel internal combustion
engine. Increasing the durability of proton exchange membrane fuel cells (PEMFCs) is a major
challenge and a growing focus of research attention. So far there remains a wide gap between the
ideal and the reality of state-of-the-art PEMFC technology. For example, the durability of PEMFCs for
transportation application is far from the 5000h target for the full range of external environmental
conditions (-40 to +40), which is the minimum requirement for vehicles in practical use. To
improve the durability and lifetime of PEMFCs, a better understanding of failure modes is urgently
required[].
Tests are usually conducted at a steady state. We can get an overview of the effects of operating
conditions, including the reactant gas flows, humidification levels and temperatures on the fuel cell
performance and the corresponding morphological change of single fuel cells. However, the
steady-state method is impractical for large-scale application for its more time-consuming and costly
compared to accelerated stress tests (ASTs) like dynamic driving cycles. Dynamic driving cycles test
have been proven to be a valuable tool for significantly reducing the extent of experiments in life time
evaluation and degradation mode analysis[1]. Dynamic driving cycles changes much more
dramatically which would cause oxidant starvation, local hotspots and physical degradation. To
investigate the degradation mechanism of fuel cells, this study adopted driving cycles designed by
ourselves with reference to J10-15 road conditions in Japan. Printed circuit board (PCB)[2] technology
was adopted to measure the local current density distribution and to examine the changes of local

917

electrochemical reaction in degradation process. The PCB was inserted between the MEA and anode
current collector. Segmented flow field was arranged on the PCB with local current being collected by
each segment. The PCB technology has the advantage of being low cost and simple in manufacture
and thus being widely used in the fuel cell diagnosis field. In addition, scanning electron microscopy
(SEM) and transmission electron microscopy (TEM) were used in this study to investigate the
microstructure degradation mechanism of the catalyst layer.
2.

EXPERIMENT

2.1 Preparation of membrane-electrode assembly (MEA)

The membrane used in this experiment was bought from Wuhan Xinyuan Corporation. Anodic
catalyst and catholic catalyst with 0.4 mg cm-2 Pt obtained from Johns Manville Corporation were
coated on the membrane. The membrane thickness was 23m and the effective electrode area was
50 cm2.
2.2 Test conditions and dynamic driving cycles
The operating temperature was maintained at 70. Back pressures of anode and cathode were
kept at 0.2 bar. Reactant gases on both electrodes were 100% humidified by external humidifiers.
Other operating conditions were shown in Table 1. Stoichiometry of hydrogen and air were kept
constant at 1.2 and 2.5, respectively. Three channel serpentine flow fields[3] were applied on both
electrodes of the cell. In order to keep the MEA, the gaskets and the PCB in good contact, clamping
pressure of 8 bars was provided by cylinder compression.
Table.1 Operating conditions
Anode reactant gas

Hydrogen

99.99%

Humidity

100%

H2

1.2

Air

99.99%

Humidity

100%

Air

2.5

Clamping

Cylinder Compression force

8 bar

Backing pressure

Anode

0.2bar

Cathode

0.2bar

Cathode reactant gas

70

Cell temperature

The dynamic driving cycles were a simulation of the real internal engine vehicle working under
idle running, constant load running, variable load acceleration, full power running and overload
running conditions. Each cycle lasted for 20 min. The rated loading and overloading were set
respectively at 45A and 50A. Fig. 1a and 1b showed the evolution of current and voltage in one cycle,
respectively. Due to performance degradation, the aging tests were stopped after 200 cycles.
Nitrogen was passed through the anode and the cathode before air and hydrogen was passed
through the flow fields in order to eliminate the effects of the start-up phase on the performance of the
cell. After certain driving cycles, the performance of the cell was recorded by methods of I-V curve,
electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), etc. The current density
distributions were recorded during the whole testing process.

918

50

1000

900

Voltage / mV

40

Current / A

30

20

800

700

600
10

500
0
0

200

400

600

800

1000

1200

200

400

600

800

1000

1200

Time / s

Time / s

Fig. 1 Evolution of current (a) in a simulating driving cycle and response voltage (b) in one cycle
2.3 I-V curves
Fig. 1b demonstrates the transient voltages response to current densities. To observe the
performance degradation of the cell the polarization curve of the cell should be recorded. I-V curves
were measured under the same operating conditions, when the cell was activated and operated after
50 100, 150 and 200 cycles, respectively. Before recording the polarization curve, the cell was
operated at steady state for 20 min aiming to avoid any impact from recent chronological account of
the characterization measurements.
2.4 Electro-chemical impedance spectroscopy
The electro-chemical impedance spectroscopy (EIS)[4] of the cell was recorded to investigate the
following: the internal property of MEA including ohmic resistance, charge transfer resistance for the
oxygen reduction, mass transfer resistance of oxygen in the catalyst layer, and constant phase
element of the catalyst layer capacitance. EIS measurements of the cell were carried out using a
Zahner workstation at potentialstatic mode. It was conducted at a constant voltage of 0.7V with a
voltage disturbance of 5mV and frequency ranging from 100 mHz to 100 kHz. All impedance spectra
reported herein were measured between cathode and anode sides of the cell. Air was introduced to
the test electrode while hydrogen was introduced to the counter electrode. Due to the negligible
over-potential for hydrogen oxidation and reduction on platinum catalyst, the counter electrode was
also used as the reference electrode.
2.5 Cyclic voltammetry
Cyclic voltammetry (CV) measurement was conducted to calculate the electrochemical surface
area of MEA. As the electrochemical surface area (ESA) of cathode was measured, nitrogen was
introduced to the cathode, which was set as the test electrode. Hydrogen was introduced to the anode,
which was set as the reference electrode. After the open circuit voltage (OCV) decreased to 100mV or
below, the potential was scanned from 50mV to 1100mV versus the reversible hydrogen electrode
(RHE) at a rate of 20mV s-1. ESA was calculated from the CV results by dividing the charge (C)
corresponding to the area under the hydrogen desorption region by 210C as shown in Eq(1):

Se

0.1 Qr
mc

(1)

919

Where Se is the ESA, Qr is the integral area of hydrogen oxidation desorption peak in CV curve,
m is the loading of platinum, and c is the electrical charge associated with monolayer adsorption of
hydrogen on Pt surface.
2.6 Segmented cell technology
To investigate the current density distribution, the segmented printed circuit broad (PCB)
technology was adopted. The segmented flow field plate integrated with temperature sensors was put
between MEA and anode current collector plate. Temperature distribution of the cell was measured by
temperature sensors. The effects of PCB on the accuracy of measurement results depended on the
ratio of in-plane to out-of-plane electronic conductivity of electrodes, gas diffusion layers, and bipolar
plates. The coupling of the current density distribution at the anode and the cathode was found by R
Lins work[5], which can verify that the effects of the insertion of the PCB can be ignored. The current
density data of every segment was collected by Agilent 34970A, and presented by the Seglab
software. The experimental parameters, controlling devices and measuring devices are summarized
in Table 2.
Table 2 Measurement uncertainty
Source

Range

Error

Anode(H2)

1 SLPM

1% of full scale

Cathode(air)

2SLPM

1% of full scale

Gas mass

Alicat

flow controller

scientific

Cell

Xiamen Yudian

temperature
Electronic load

KIKUSUI PLZ-4W

Constant

50V/150A
150A

current(CC)

of

full

0.2%

of

full

scale

Constant

50V

voltage(CV)
Data logger

0.3%

scale
Aglient 34970A

DC voltage

100mV

6.5V

1V

26V

10V

190V

2.7 Scanning electron microscopy (SEM)

SEM micrographs of the catalyst layer were obtained by the JSM-5600LVSEM device to
investigate the effects of dynamic driving cycles on the microstructure of the electrodes, including the
changes in the catalyst layer surface and its cross-section, as well as the changes of catalyst particles
distribution. By comparing the MEA operated after dynamic driving cycles with the fresh MEA, the
microstructure changes of the MEA could be detected. Additionally the Energy Dispersive
Spectrometer (EDS) mappings of the MEA of different regions were obtained to investigate the
distribution of miscellaneous elements.
2.8 Transmission electron microscope (TEM)
To investigate the degradation of the catalyst, TEMs of the cathode and anode catalyst were
conducted on JEM 2010EX microscope at 200KV. Cu-Ka radiation was applied. The microstructure of

920

the Pt/C catalyst was examined using the HR-TEM technique. In addition, the particle size of Pt and
its distribution were analyzed.
3.

RESULTS AND DISCUSSION

3.1 Effects of dynamic cycles on single cell performance

Fig 2 shows the performance of the single cell before, during and after the driving cycles. From
the graph we can see that the performance degraded continuously. Additionally the OCV kept nearly
constant which meant that no perforation or delamination has occurred in the MEA. Fig 3 shows the
decline rates of current density during driving cycles at constant voltages of 0.6V and 0.8V
respectively. We adopted constant voltage mode to regulate the driving cycles while adopting the
current response to evaluate the degradation rate of the cell performance. Advantage of this method
lies in that a comparison between current density of each segment and average current density of the
whole cell is possible when evaluating the degradation rates of each segments. Disadvantage lies in
that due to the existence of connecting line between the load meter and the cell, voltage loss is
inevitable thus increase the test error. The current density decline rates at 0.6V and 0.8V were
1.7mA*cm-2/cycle and 0.21mA*cm-2/cycle respectively which means the performance degradation at
low voltage isfaster than that at high voltage.

1.0

36

fresh
50cycles
100cycels
150cycles
200cycels

0.8

32
28

Voltage / V

24
0.7

20
16

0.6

Power / W

0.9

12

0.5

8
0.4

0.3
0

200

400

600

800

1000

1200

Current density/ mA cm

1400

0
1600

-2

Fig. 2 Polarization and power curves of fresh MEA and those measured after 50,100, 150 and 200 cycles.

0.6V

1200

Current density / mA cm

-2

0.8V
1000

800

600

400

200
0

50

100

150

200

Cycles

Fig. 3 Average decline rate of current density during driving cycles at 0.6V and 0.8V, respectively.

3.2 EIS and CV measurement

921

The electrochemical impedance is a determinant of the performance of the fuel cell. The oxygen
reduction reaction at the cathode side is greatly affected by the conductivity of the electron and proton
of the catalyst layer. The EIS results would help us know more about the effects of driving cycle on the
performance of fuel cell. Fig.4 shows the EIS curves of the activated fuel cell and operated after 0, 50,
100, 150 and 200 dynamic driving cycles respectively. Its clear to see that the impedance of the cell
continued to increase with driving cycles. Before driving cycles, we could recognize a compressed
semicircle in EIS curves. With cycles going on, the real and the imaginary parts of the impedance
curves increased simultaneously. But the increasing rates were not constant. From 0 to 100 cycles the
impedance increased evenly and from 100 to 150 cycles the curve changed little while from 150 to
200 cycles the curve enlarged greatly.
Equivalent circuit (Fig.5) method was adopted to analyze the impedance results. Combined with
the Nyquist curve of the EIS results, we calculated the RHF, Rct2 and C2 in the equivalent circuit, as
shown in Fig 6. RHF is the integrated ohmic resistance of the membrane, catalyst layer and diffusion
layer, and Rct2 represented the cathode charge transfer resistance of the oxygen reduction reaction,
which corresponded to the diameter of the kinetic loop in the Nyquist curve. C2 is determined by the
catalyst layer where the oxygen reduction reaction took place. We knewfrom the graph that RHF didt
increase much which meant the dynamic cycles had little effects on the ohmic resistence and that
could be explained from the constant cylinder compression force and operating temperatures.
Meanwhile Rct2 showed obvious increase which meant the catalyst degraded after driving cycles.

0.008

fresh
50cycles
100cycles
150cycles
200cycles

-Im(Z)/Ohm

0.006

0.004

0.002

0.000
0.002

0.004

0.006

0.008

0.010

0.012

0.014

Re(Z)/Ohm

Fig. 4 Electro-chemical impedance spectroscopy (EIS) of fresh fuel cell and after 50,100,150 and 200 driving cycles,
respectively.

Fig.5 Equivalent circuit for impedance analysis.

922

10

1200

Rct
RHF2

1000

C2

600

mF cm

mOhm cm

-2

800
6

400

200
2
0
0

50

100

150

200

Cycles

Fig.6 The fitting results of the equivalent circuit during driving cycles.

CV test were conducted to investigate the variation of electrochemical active area during
dynamic driving cycles. CV curves were recorded in Fig.7. ESA of catalyst was calculated from the CV
data, and was presented in Fig.8. It was obvious that the ESA decreased with driving cycles. ESA of
cathode catalyst decreased from 708.1 to 614.8, 563.8, 460.2 and 368.2 cm2/mg with a decreasing
rate of 1.7cm2/mg per cycle after 50,100, 150 and 200 cycles, respectively.
Combined with the results of Fig.2 and Fig.3, we concluded that the electrochemical active area
of catalyst decreased with driving cycles while different decreasing rates should not be neglected. At
low voltage which meant high current density, the MEA could not provide enough active area for
electrochemical reaction, while at high voltage which meant low current density, the demand for the
electrochemical reaction active area was not as much. That explains why the performance degraded
much more severely at low voltage than at high voltage[6].

Fresh
50cycles
100cycles
150cycles
200cycles

600
400

I /mA

200
0

-200
-400
-600
0.0

0.2

0.4

0.6

0.8

1.0

1.2

Voltage / V

Fig. 7 Cyclic voltammetry (CV) curves of fresh MEA and those measured after 50,100, 150 and 200 cycles.

923

750

708.18
675

614.86

563.87

ESA/ cm /mg

600

525

460.24
450

368.26
375

50

100

150

cycles

200

Fig. 8 Electro-chemical surface area (ESA) of cathode catalyst layer after activated, 50,100, 150 and 200 cycles.

3.3 Current density distribution

Current density distribution reflects local electrochemical reaction and we adopted segmented
fuel cell technology to investigate the local degradation mechanism of MEA. A segmented bipolar
plate with 49 segments for single cell was used in the experiment and the area of each segment was
1.1cm2. The G1 and A1 segments were the entrance of hydrogen and air, respectively, and the A7
and G7 segments were the exit of hydrogen and air, respectively, as shown in Fig.9(a). Fig.9 shows
the evolution of current density distribution of the fuel cell during driving cycles operated at 0.6V.
Different color represented different current density value, which was indicated by the legend. The
average responding current density declined from 1090mA cm-2 to 830 mA cm-2 which meant serious
performance degradation .Combined with the current density distribution of each segment we
calculated the average decline rate to be 1.3mA cm-2/cycle. From Fig 9 it was found that current
density in all segments showed decline trend but the inlet area was more obvious especially D1
where the decline rate was 2.21mA cm-2/cycle. The downward trend in the middle area was not so
obvious with a decline rate of only 0.55mA cm-2/cycle. As to the outlet area especially the outlet of air,
segment A7 we observed the fastest current density decline rate of 3.02mA cm-2/cycle. So far we can
conclude that the performance in the inlet area degraded faster than the middle and outlet area. It was
worth mentioning that the current density in the middle area was always higher than the total average
current density. This phenomenon was not limited to 0.6V it equally applies to other voltage level.
Large amounts of water would be produced during the operation of fuel cells which would lead to
differentiated water content in different segments. Another explanation is that due to different velocity
of reactant gas water content vary accordingly[7].

a1cycle

b50cycles

924

c100cycles

d150cycles

e200cycles

Fig.9 Current density distribution at 0.6V after driving cycles (0, 50 100,150 and 200 cycle)

3.4 SEM analysis of MEA after operated under driving cycles

In order to investigate the performance degradation mechanism, the morphology of the catalyst
layer was analyzed by scanning electron microscope (SEM). Fig.10 shows the SEM results of the
morphology of the cathode catalyst in different areas after being activated and 200 driving cycles.
Differentiated morphology changes could be observed in different areas of the surface. Before the
driving cycles the surface of the catalyst layer was flat and compact without flaws. At 1000K times
magnification the catalyst particles and carbon support were evenly dispersed and displayed a flake
characteristic. After dynamic driving cycles the surface of the inlet area was rugged while the surface
of the middle and outlet area was relatively flat and compact except an obvious crack in the middle
area.

Fresh

inlet

middle

outlet

10K

100K

Figure.10. Scanning electron micrograph (SEM) of the surface layer of cathode catalyst

The thickness of the membrane and catalyst layer showed a consistent decrease after driving
cycles with the thickness of membrane decreasing from 22.94um to 17.3um.The catalyst layer
showed different scenarios on either side. At the inlet area of cathode catalyst layer obvious
delamination was observed with only a layer of 3.14um catalyst attached to the membrane.while the
rest of the catalyst agglomerated together. Fracture and cavity were also observed which seriously

925

degraded the catalyst. While in the middle and outlet area the cathode catalyst layer was relatively flat
and compact with thickness decrease of about 4.5um and 3um respectively. As for the anode catalyst
layer the thickness decrease was about 2-4um.

afresh

binlet

cmiddle

doutlet
Fig. 11 Cross-section of MEA morphology

There are two main reasons that would cause the thickness decrease of the membrane[8]. One
is the unstable mechanical stress caused by humidification cycles. The other is the chemical attack by
hydroxyl radicals produced during operation. 37% of the time of driving cycles was in OCV state when
hydrogen peroxide was largely produced which would cause serious fluoride loss and the membrane
thinning. Obviously the degradation of cathode was more serious. The reason might be that the
potential was high at the cathode where carbon was prone to be corroded. The possible reaction
mechanism might be described as Eq (2):

(2)
3.5 TEM analysis
The electrochemical reaction takes place at the interface of the catalyst layer and membrane.
The microscopic structure of the catalyst layer is critical for high efficiency of the electrochemical
reaction. In order to investigate the effects of driving cycles on the catalyst layer more thorough, TEM
technology was adopted to observe the microscopic structure of fresh catalyst layer and after driving

926

cycles Fig 12 displays the statistic of Pt particle size on the catalyst layer. Pt particle size was
distributed in a wide range. Before driving cycles most particles were distributed in the range of 2-4nm.
After driving cycles the particle size generally increased. Agglomeration occurred in some area with
the most serious to be nearly 8nm. By contrast it is not difficult to observe that the particle size
increase and agglomeration in the cathode was more serious than in the anode. It was because the
potential in the cathode was higher than that in the anode and high potential would cause Pt
dissolution which was followed by precipitation of surrounding Pt particles. We detected some carbon
support without catalyst particles on it which indicated that serious migration had occurred. According
to previous research[9], when the potential isbetween 0.65V and 1.1V, the dissolution rate of Pt
particle would increase with the increase of the potential. The reaction might be described as Eq (3)
and Eq (4):
Pt

Pt

(3)
Pt

Pt

(4)
It was also found that the amount of Pt particles at the cathode decreased. It was because Pt
particle migrated to other area[10], which also led to degradation of catalyst.

100

anode inlet

Particle number

80

60

40

20

0
1

Particle Diameter / nm

100

cathode inlet

Particle number

80

60

40

20

0
1

Particle Diameter / nm

(a) Anode inlet

(b) Cathode inlet

927

100

cathode middle

Particle number

80

60

40

20

0
1

Particle Diameter / nm

100

cathode outlet

Particle number

80

60

40

20

0
1

Particle Diameter / nm

(c) Cathode middle

(d) Cathode outlet

Fig. 12 Pt particle size statistic

4. CONCLUSIONS
In this study, the effects of dynamic driving cycles, which are composed of idle condition,
accelerated condition and overload condition, on the durability of fuel cell were investigated. The cell
was operated at 70 with 100% humidification for both electrodes in potential static mode. It was
found from the I-V curves that after 200 cycles the performance of fuel cell decreased seriously at
current density decline rates of 1.7mAcm-2/cycle at 0.6V and 0.21mAcm-2/cycle at 0.8V, respectively.
With the segmented cell technology, the local current density distributions were obtained. It showed
that after 200 cycles, the current density at the inlet region declined the most significantly while that of
the middle region was always above the total average current density. The electrochemical surface
area (ESA) decreasing rate was 1.18cm2mg-1/cycle. SEM results revealed that crackle flaw appeared
on the inlet surface of the catalyst layer and the thickness of the MEA decreased distinctly. TEM
results showed that the Pt particle size grew up distinctly after the driving cycles.

ACKNOWLEDGMENT
The authors gratefully acknowledge the financial support from National Natural Science
Foundation of China (No. 21276199), National Key Scientific Instrument and Equipment Development
Special Fund (2012YQ150256), The Young Talents "Climbing" Program of Tongji University, The
Fundamental Research Funds for the Central Universities and 111 Project (No. B08019).

928

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[5] Lin R, Cao CH, Ma JX, Gulzow E, Friedrich KA. Optimizing the relative humidity to improve the
stability of a proton exchange membrane by segmented fuel cell technology. International Journal Of
Hydrogen Energy. 2012;37:3373-81.
[6] Gutaz L, Escribano S, Sicardy O. Study by electron microscopy of proton exchange membrane
fuel cell membrane-electrode assembly degradation mechanisms: Influence of local conditions.
Journal of Power Sources. 2012;212:169-78.
[7] Qin Y, Li X, Jiao K, Du Q, Yin Y. Effective removal and transport of water in a PEM fuel cell flow
channel having a hydrophilic plate. Applied Energy. 2014;113:116-26.
[8] Ferreira-Aparicio P, Chaparro AM. Influence of the gas diffusion cathode structure on the
performance of an air-breathing proton exchange membrane fuel cell. International Journal Of
Hydrogen Energy. 2014;39:3997-4004.
[9] Bona D, Curtin DE, Pedrazzo F, Tresso EM. Using a Stack Shunt to Mitigate Catalyst Support
Carbon Corrosion in Polymer Electrolyte Membrane Fuel Cell Stacks During Start-Stop Cycling.
Journal of Fuel Cell Science and Technology. 2013;11:011010.
[10] Chung CG, Kim L, Sung YW, Lee J, Chung JS. Degradation mechanism of electrocatalyst during
long-term operation of PEMFC. International Journal of Hydrogen Energy. 2009;34:8974-81.

929

RESEARCH STATUS ON ENERGY RECOVERY FROM FOOD WASTE

Bahare Asefi1,2, Ma Hongzhi*1,2, Zhang Fengying1,2

1 Key Laboratory of Educational Ministry for High Efficient Mining and Safety in
Metal Mine, University of Science and Technology Beijing, Beijing 100083, China;
2 Department of Environmental Engineering, University of Science and Technology
Beijing, China, 100083
Abstract: The increased generation of food waste is a global and national problem. Energy
recovery is one of the effective solutions in food waste management. Food waste has a high
energy content which seems ideal to achieve dual benefits in terms of energy recovery and
waste stabilization. In this paper, a comparative scenario will be shown on energy utilization
from food waste and factors which affected the process. Methane is a gas with high
potential which can use for heating and cooking as a renewable energy, hydrogen is a
promising alternative to fossil fuel. Hydrogen can be generated by thermochemical,
electrochemical or microbial fermentation processes. Ethanol is a liquid fuel that can readily
be integrated into existing fuel supply systems and directly substitute fossil fuels in the
transportation sector. The key technology and characteristic of such energy sources from
food waste were summarized in this paper, which aimed to provide a theoretical analysis for
energy utilization for food waste.

Keywords: Food waste, methane, hydrogen, Ethanol

1.INTRODUCTION
Continuous economic activities, rapid urbanization, population growth and the rise of living
standards have greatly accelerated the generation of municipal solid waste (MSW).However,
the most content of MSW is food waste(FW).The urban population (UP) growth will produce
remarkable amounts of urban food waste (UFW) that will add more pressure on already
overloaded (FW) management systems of cities.
Food waste is composed of raw or cooked food materials .food waste includes food loss
before, during or after meal preparation in the household, as well as food discarded in the
process of manufacturing, distribution, retail and food service activities. It comprises materials
such as vegetable peelings, meat trimmings, and spoiled or excess ingredients or prepared
food as well as bones, carcasses and organs[1]. food waste has a high potential for utilization
as biodegradable substrate for biogas production.
Food waste is a heterogeneous substrate that can change depending on the season and
.

region Of most concern to many stakeholders is the impact food waste has on the generation
of greenhouse gas emissions such as methane and carbon dioxide. As food waste has a high
energy content, it seems ideal to achieve dual benefits to energy recovery and waste
[2]

stabilization . Food Waste management is a major challenge in urban areas throughout the
world, especially in the cities of developing countries

[3]

. Food waste management offers

opportunities to improve profits by conserving resources and improving environmental

performance[4].
Waste recently is more considered as a resource rather than garbage of no value [5]. Waste
as a resource, refers to resource recovery that can be converted into other material and
.

energy [6]. However, if methane is captured and used to generate electricity and waste is
converted into energy resources, then it will bring numerous climate benefits. Also, the energy
generation from waste can replace the dependence of fossil fuel to some extent and reduced

930

the emissions from fossil fuels. Furthermore, waste reuse and resource recovery can reduce
the volumes of total waste and reduced the cost of waste management, thus creating
economic opportunities.
2.THE FOOD WASTE COMPOSITION IN DIFFERENT COUNTRIES
2.1 To understand the waste composition is of great importance for its future utilization.
Table 2.1 showed the composition for food waste in different countries.
Table 2.1.Quantity of the Food and garden waste (%) composition in Taiwan and other countries in 2000 [7]
Country

Food and garden waste (%)

USA

23

Japan

34

Korea

25

Netherlands

39

Hong Kong

33

Singapore

50

Taiwan

31

Taiwan is the small densely populated country in the world; its 22.604 million residents (2002) .
The economy has grown rapidly during the last 20 years, resulting in a corresponding increase
in the amount of food waste. So Taiwan tried to reduce the amount of fw production. that the
amount of waste generated per capita per day in Taiwan was below 1 kg in 2000, while in all
other organization for economic cooperation and development (OECD) countries the amount
exceeded 1 kg. In Asia, between Singapore, Hong Kong, South Korea,and Taiwan, Taiwan had
the lowest food waste. The table 2.1, compares FW production in selected countries from 1980
to 2000 . The results show that other countries have also experienced a major and rapid
increase in waste production over the last 20 years. Taiwans accomplishments in reducing FW
are remarkable when compared to other countries. Taiwan aims was to reduce the total
amount of raw MSW by 25% by 2007, 40% by 2011, and 70% by 2020. Ways of achieving this
goal were related to recycling and reuse programs
The mandatory participation of the public in waste recycling was an important factor in Taiwan
Food waste composition in US 23%,japan 34%,Korea 25%, Netherlands 39%, Hong Kong 33%
Singapore 50%, Taiwan 31% were in total MSW. Food waste composition is considerably
higher than other composition in MSW composition. Food and garden waste comprises the
highest portion, followed by paper and plastics.
2.2 Compare of quantity of food waste at different country
Table 2.2. Food waste composition in different regions and cities
Food waste percentage %

China(Chongqing)

1998

69.3

2002

59.2

2003

Taiwan

Singapore
38.80

25

38.8

Japan(Kitakyushu)

[11]

10.7

6.7

Due to differences in economic development and standards of living Compared with these four

931

cites, the concentration of foods wastes in MSW respectively, food waste accounts for about
,

59% of total MSW in China 59.2% Taiwan 25% Singapore 38.8% ,Japan 10.7% in 2002, food
waste in Chongqing(china) are much higher than the other country [8]. F.W concentration in
.

1998 was respectively china 69.3% ,Singapore 38.80%. This increase of daily FW generation
per person with increased economic development and standard of living also occurs in other
cities in China such as Guangzhou, but Chinese people have a habit of preferring food that is
unprocessed and unpackaged. The result of this preference may mean that the proportion of
MSW that is made up of food waste will not decline significantly even as industry grows and
wealth increases. Even in the more developed Chinese cities such Guangzhou and Hong
Kong, food waste is higher when compared to most western countries [9].
The high concentration of food waste is related to Chinese eating habits; Chinese people
prefer their food unprocessed with little packaging. Due to the low amounts of packaging, this
preference leads to waste that has a higher proportion of organic food waste.
2.3 Comparison of produce food waste and inorganic components of the MSW
Table 2.3. MSW composition in different countries
Food waste

Miscellaneous

Paper

Plastics

Metal

China

49%

32%

8%

8%

1%

India

45%

48%

5%

3%

2%

Seri lanka

86%

2%

6%

4%

1%

thailand

54%

18%

10%

12%

3%

This study have been done about four countries of Asia: China, India, Sri Lanka and Thailand
This four country have been chosen due to the large population in China and India with wide
geographical variations while Sri Lanka and Thailand represent newly industrialized nations. In
2001, China had an economic growth of 7.3% in 2001,India 5.9%, Sri Lanka 4.9% and
Thailand 4.6%. All the four countries were experiencing a rapid economic growth and
urbanization. In the developing countries waste generated was similar but different regions
being dictated by the climatic, cultural, and industrial, infrastructural and legal factors, typical of
the developing countries where as the developed regions have a higher paper and cardboard
content. The waste composition from India indicates a comparable lower food but higher
inorganic (ash and dust) content. The lower values for paper, glass and plastic are due to the
intensive collection and scavenging by informal waste collectors [10]
The table shown In four country food waste had highest production in MSW, China 49%,India
45%,Serilanka 86%,Thailand 54%,srilanka was in the top ,the higher level of food waste
generation in Sri Lanka was due to increased consumption patterns as well as the movement
of the people from the rural areas to urban centers. In Thailand over 23% of the population is
urban and its rate of economic growth causes the higher value in food waste generation per
capita per day. In china the urban population is over 38% and the waste generation has been
increasing over the years. Food waste production is mainly due to economic disparity among
the population, economic status and population density.
3.ENERGY RECOVERY FROM FOOD WASTE

932

3.1 Methane fermentation from food waste

Due to the high organic concentration in side food waste, a lot of researcher has made
resource technology on it, particularly in methane fermentation, and to understand the
experimental conditions as well as the yield are very important. The yield of methane
compared with 3 others consider to temperature and hydraulic retention time .
The HRTs of methane production reactor were 150 days [11], 28 days [12] , 12days [13],
respectively.
The results indicate methane yield will increase with increase HRT. The yield of methane in
study for 150 days was 464 ml/g VS added with 2 stage fermentation, and higher than 240
ml/g VS added with Count 2 stage reactor reported and 223 ml/g VS added with Count 3 stage
.

reactor and close to 435 ml/g VS added with batch reactor . The results indicate that the
pH-phased two-stage process methane production is a suitable process for producing
methane simultaneously from F.W. The highest production shown 464ml/g vs in over 150 days
with 55c in 2stage fermentation reactor. However, if methane was captured and used to
generate electricity and waste was converted into energy resources, then it will bring
numerous climate benefits .
3.2 Produce methane from different organic waste
Table 3.1 Methane production characteristic from food waste
Substrate

T (C)

HRT(days)

Ch4 yield

Food waste

55C

90 days

57.39%

21

Chicken manure

55C

90 days

87.13%

21

SWWTP

55C

90 days

97.5 %

21

SWWTP: Sludge from waste water treatment plant

CN: Chicken manure
Production of methane from anaerobic digestion process at 55 C and HRT 90 days for
different substrate types is presented in table 3.1.The results showed that methane production
rate varies in percentage according to the type of waste substrate used. The highest methane
percentage (97.05%) was obtained for SWWT, while the CM and FW substrates yielded
methane rates of 87.13% and 57.39%, respectively.
In same period different yield showed it maybe related to biodegradability of organic fraction of
organic substrates. also the result showed effect of water added to the reactor cause produce
more methane and SRT(Sludge Retention Time)and type of waste have a remarkable effect,
with increase the SRT of waste methane production increased [14].

3.4.Biomethane yields from EU study compared to the literature.

Table .3.2
Substrate
SsFW

BMP yield

Retention time

(m3nCH4/tVS added)

(days)

467529

30 days

933

TEMP.range

37 1 C

25

SsFW

455456

30 days

36 1 C

26

ssOFMSW

300400

15 days

15 1 C

28

ssOFMSW

158-397

--

--

27

ssFW

401489

Source segregated food waste: SSFW

Bio methane yields from study in EU compared to the literature. the resource of biomethane
produced from food waste at a state level in the EU. Food waste makes up about 25% of
domestic household waste and 42% of commercial waste .It is estimated that approximately
178 kg/person/annum of food waste is generated in Ireland. The resource is dependent on the
quantity of food waste available for anaerobic digestion and the specific methane yield from
food waste. The upper bound BMP results for source segregated canteen food waste gave
specific methane yields of between 467 and 529 L CH 4 per kg volatile solids added.
Food waste is a quickly degradable substrate High methane yields from SSFW have also been
reported by other authors, However a detailed in the other study showed similar bio methane
yields from a large number of OFMSW samples which had all been through different
-1

pre-treatment processes (300400 L CH4 kg VS added).These findings indicated that the bio
methane yield was independent of the type of pre-treatment and source of OFMSW [15]. In
another studies methane yield from SSFW showed in 30 days, 36 1 C ,(455-456 CH4 kg
-1

VS added)

[16]

-1

-1

,BMP yield (158-397 CH4 kg VS added)[17],(401-489 CH4 kg VS added).

Reported biomethane yields from food waste can vary due to the heterogeneous nature of the
material and differences in food types between regions. Also operating temperatures,
bioreactor design and loading rate can significantly affect the results [18].
4.HYDROGEN PRODUCTION FROM FOOD WASTE.
4.1.Effect of substrate concentration to produce H2
Table 4.1.Hydreogen production from different substrate
Substrates

Concentration

Reactor

(g COD /L)

H2 yield

ml/g COD

Sucrose

4.5

Batch

234

29

NFDM

4.0

Batch

119

29

F.W

4.6

Batch

101

29

(NFDM): non-fat dry milk

As a sustainable and clean energy source with minimal or zero use of hydrocarbons, hydrogen
is a promising alternative to fossil fuel. Hydrogen can be generated by thermochemical,
electrochemical or microbial fermentation processes. hydrogen is alternative green energy.
Result in table 4.1 showed that hydrogen production potential and hydrogen production rate
increased with an increasing substrate concentration, the low pH (pH<4) inhibited hydrogen
production and resulted in lower carbohydrate fermentation at high substrate concentration.
The hydrogen yield from sucrose was found to be much higher than that from NFDM and food
waste due to higher carbohydrate content.

934

4.2.food waste as a carbon source to product hydrogen

Table . 4.2 Effect of different composition in food waste on hydrogen fermentation
5g/L

10g/L

20g/L

Starch

100

100

100

Flour

14.36

12.25

12.22

Corn

18.87

24.45

21.59

Potato

24.86

18.03

18.91

Mixed

11.71

Three raw materials- wheat, corn and potato- were tested for their ability to produce hydrogen
under the optimized conditions. Each three raw materials were then tested with varying
concentrations to compare the hydrogen producing efficiency with that of pure soluble starch.
Mixed raw material was also tested to obtain further insight of the possibility of utilizing food
waste for bio-hydrogen production by T. Onnurineus NA1.
5g/l: potato was the highest H2 production with 24.86%, 10g/L :corn was the highest H2
production with 24.45%, 20g/l: corn still had the highest H2 production. It shown corn was the
only raw material with an increase in H2 production, while H2 production steadily decreased
on flour and potato.
5.BIOETHANOL FEREMENTATION
The three largest producing countries/regions of transport biofuels are the US, Brazil, and the
European Union (EU). The US mostly produces ethanol from corn, Brazil ethanol from sugar
cane, and the EU mostly biodiesel from rapeseed. The rapid growth of biofuels sectors in the
US and EU stimulated growth in Asia, and many Asian countries have now set targets and
blending mandates to continue to increase their biofuels production. Total biofuels production
in Asia has grown more than five-fold since 2004, from just over 2 billion litres to almost 12
billion litres in 2008 .
Nippon Steel Engineering Co., Ltd. (NSE) was commissioned by the New Energy and
Industrial Technology Development Organization (NEDO) to carry out a project to
experiment recycling system test business to process food waste into ethanol from FY
2005 to 2009 as one of the seven projects in the Biomass Energy Regional System
Development Project.The idea for this system was developed by focusing on the large quantity
of carbohydrate content found in food waste. The facilities to produce ethanol and blend it into
gasoline were constructed in Kitakyushu Eco Town in Fukuoka Prefecture in 2007, The
ethanol production facility has a daily capacity to process 12 tonnes of food waste (the net
weight of 10 tonnes after removing trashes such as plastic bags) and produce 500 litres of
dehydrated ethanol. In addition to ethanol, it recovers approximately 700 kilograms of oil
(Bunker A equivalent) from plant and animal oil content of food waste [19] The overall flow of
the system included: Pre-treatment, separating trash such as plastic bags and boxes from
collected waste, scarification, converting to glucose by using amylase solid-liquid separation,
separating substance for fermentation from the solid remainder condensation, preparing
substance for fermentation ethanol fermentation, fermentation with flocculants yeast

935

(efficiency is high, no nutrient is necessary since the food waste itself contains enough
nutrition) Distillation/membrane separation: collection of ethanol.
Strengths of ethanol production from food waste include high rate of fermentation, compact
size of production facilities, and ease in handling and storage. It also has a high potential in
terms of energy efficiency as fat contents of food oil can also be collected during the process.

CONCLOUGEN
Different economic development and Food habits of the people has significant impact on the
food composition, food waste management can control the produce of food waste and give the
best technology to treat the food waste such as energy recovery. The results of this study
showed different behavior patterns of methane production from organic wastes .the highest
production shown in high rate of HRT, VS/TS and high temperature, 2 stage fermentation
reactor was also affective.
Methane production from food waste compare with SWWTP and CN showed high rate of
methane yield respectively SWWTP, CN, FW it maybe related to biodegradability of organic
fraction of organic substrates. and effect of water added to the reactor, also with increase the
SRT of waste methane production increased. finally type of waste have a remarkable effect.
the bio methane yield was independent of the type of pre-treatment and source of OFMSW.
Factors in hydrogen yield investigated with an increasing substrate concentration H 2 will
increase, the low pH (pH<4) inhibited hydrogen production and resulted in lower carbohydrate
fermentation at high substrate concentration. higher carbohydrate content produce high rate of
H2

To compare H2

Yield between wheat, corn and potato when using starch as

feedstock ,corn was the only raw material with an increase in H2 production, while H2
production steadily decreased on flour and potato. Strengths of ethanol production from food
waste include high rate of fermentation, compact size of production facilities, and ease in
handling and storage. It also has a high potential in terms of energy efficiency as fat contents
of food oil can also be collected during the process.
NOMENCLATURE
MSW

municipal solid waste

FW

food waste.

UP

urban population

UFW

urban food waste

OECD

economic cooperation and development

TS

total solid

VS

volatile solid

HRT

high retention time

SWWTP:

Sludge from waste water treatment plant

CN

Chicken manure

SSFW

Source segregated food waste :

NFDM

non-fat dry milk

EU

European Union

NSE

Nippon Steel Engineering Co., Ltd.

NEDO

New Energy and Industrial Technology Development Organization

936

Acknowledgement
The work was supported by International Science & Technology Cooperation
Program of China (2013DFG92600) and National Scientific Funding of
China(51008020, 51378003), Beijing Higher Education Young Elite Teacher Project.
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1.

Ms. Vronique Monier and Mr. Shailendra Mudgal, 2010, Preparatory study on food waste
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GyeongEun Yi, Lee Gyeong Je, Bio-hydrogen Production by Hyperthermophilic Archeon,

Thermococcusonnurineus NA1, Using Starch Containing Food Wastes. International
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Jin, J., Wang, Z. and Ran, S., 2006, Solid waste management in Macao: practices and
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Hui Y, Li'ao W, Fenwei S, Urban solid waste management in Chongqing: challenges and
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Zaman, A. U., 2010, Comparative study of municipal solid waste treatment technologies
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UNEP (2010). Waste and Climate Change: Global trends and strategy framework. United
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Li-Teh Lu and, Teng-Yuan Hsiao , 2006, MSW management for waste minimization in
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Renbi Bai, Mardina Sutanto The practice and challenges of solid waste management in
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Chung, S.S. and Poon, C.S., 1998, A comparison of waste management in Guangzhou
and Hong Kong. Resources. Conserv. Recycling 22:203216.

10. National Research Institute (NRI), Thailand. Municipal Solid Waste Management in
Thailand. Country Report, (2003).
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process for hydrogen and methane production from food waste, International Journal of
Hydrogen Energy 33:47394746.
12. Liu D, Liu D, Zeng RJ and Angelidaki I, 2006, Hydrogen and methane production from
household solid waste in the two-stage fermentation process. Water Res 40:22306.
13. Jung Kon Kim and Baek Rock Oh, 2006, Effects of Temperature and Hydraulic Retention
Time on Anaerobic Digestion of Food Waste. Journal of Bioscience and Bioengineering
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Methane Production during Thermophilic Digestion Process, International Journal of
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yield in source-sorted organic fraction of municipal solid waste. Waste Manage 3:40614.
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municipal waste streams. J Environ Manage 104:16674.

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17. Cecchi F, Traverso P, Pavan P, Bolzonella D and Innocenti L, 2003, Characteristics of the
OFMSW and behaviour of the anaerobic digestion process. Biomethanisation of the
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[Kitakyushu Environmental Technology Center] (official pamphlet), 2007

938

Effect of interaction between vortices and blades on

performance of H-Darrieus vertical-axis hydro turbine
Y. Wang1,2, X. J. Sun1,2, H. J. Zhang3, G. Q. Wu4, Y. Cao4, D. G. Huang1,2*
(1.University of Shanghai for Science and Technology, Shanghai, 200093)
(2. Shanghai Key Laboratory of power energy in multiphase flow and heat transfer, Shanghai
200093)
(3. Shanghai University, shanghai 200072)
(4. Nantong University, Nantong, 226600)
(Tel: 021-55897317, Email: dghuang@usst.edu.cn)
Abstract
Marine current is one of the renewable energy resources, and it shows wide distribution, huge
storage and inexhaustibility. Thus, the exploitation and utilization of marine current has gradually
attracted the world attention. The main way of utilizing marine current is electric power generation.
The hydro turbine which has similar principle of operation and blade structures as wind turbine
becomes an important energy conversion device to obtain marine current. Generally, the hydro
turbines can be classified into horizontal-axis type and vertical-axis type. Darrieus turbine is a
typical vertical-axis type hydro turbine which shows simple structure, convenient maintenance and
low sensitivity to the direction of incoming flow. However, by comparing with the horizontal-axis
type of hydro turbine, the Darrieus hydro turbine obviously has low energy conversion efficiency.
This paper numerically investigated the hydrodynamic performance of Darrieus hydro turbine
with different tip speed ratios. In addition, based on the aspect of vorticity, the performance and
principles of Darrieus hydro turbines were analysed and compared. The results show that vortices
structure on the blades has observable influence on the working performance of Darrieus hydro
turbine while it is operating with different tip speed ratios.
Key words marine current power; Darrieus hydro turbine; hydrodynamic performance; vortices
structure, numerical simulation

0 Intriduction
Marine current energy, which is one type of the renewable ocean energies, is from the kinetic
energy of seawater that flows horizontally. Generally, the marine current is worth to be exploited
and utilized when flows with velocities larger than 2m/s in submarine tunnel or areas with regular
seawater flowing caused by tide. Certainly, there has been a growing interest in the shortage of
fossil fuel and air pollution. The approaches to effectively exploit and utilize marine current have
already played an important role in energy strategy for many countries.
The main way of utilizing marine current is the electric power generation which has the same
principle as wind power generation. Both of power generation methods are designed to make use of
turbines or other types of energy conversion devices to do work as well as to transfer kinetic
energy into mechanical energy.
Nomenclature
1
939

a
Cm

sound velocity
torsion coefficient

velocity component along the z-axis

viscid flux in coordinate direction

Cp

energy efficiency

viscid flux in coordinate direction

inviscid flux in coordinate direction

inviscid flux in coordinate direction

inviscid flux in coordinate direction

enthalpy

h
J

n
p
Q

viscid flux in coordinate direction

Greek letters
preconditioner matrix
coordinate direction

coordinate transformation Jacobian matrix

rotating speed
pressure
primitive variable
reference velocity

intersection angle between y-axis and a

line that is generated from the center of
blade A to center of rotation
density

tip speed ratio

velocity component along the x-axis

coordinate direction

velocity component along the y-axis

coordinate direction

As a result, the electric generator can be driven and the electric energy then can be generated.
Usually, most of the hydro turbines developed and manufactured in the world have similar
structures as the hydro turbines. The hydro turbines are usually classified into two types including
the horizontal-axis type and the vertical-axis type. Darrieus hydro turbine is a typical vertical-axis
hydro turbine which makes use of lift force on the blade to do work. Beside, its electric generator,
which can be built above the water, has lots of advantages including simple structure, convenient
installation and simple maintenance. Consequently, the application of Darrieus hydro turbine
attracts the world attention, and many countries including England, Italy [2], China [3], Japan and
Canada have already conducted the investigation and development of the Darrieus vertical-axis
hydro turbine.
Compared with horizontal-axis hydro turbine, the vertical-axis hydro turbine generally has
relative low energy conversion efficiency which is about 20% to 30%. Research shows that the
performance of Darrieus hydro turbine with straight blades is closely related to tip speed ratio [4].
There is always an optimal tip speed ratio for hydro turbine to achieve the highest energy
conversion efficiency. When tip speed ratio is lower than the optimal value, the energy conversion
efficiency increases with the increase of tip speed ratio. On the other hand, when tip speed ratio is
higher than the optimal value, the energy conversion efficiency decreases with the increase of tip
speed ratio. Based on the aspect of vortex structure, this paper adopts the numerical method of
computational fluid mechanics (CFD) to analyze the interaction between vortex and blades for
Darrieus hydro turbine. Besides, the mechanism of how vortexes have influence on the energy
conversion efficiency for this type of hydro turbine is discussed.
1 Numerical methods and computational models
1.1 Numerical approach
A preconditioning algorithm has been developed. Based on the averaged Reynolds
Navier-Stokes equations in three-dimensional curvilinear coordinates, it utilizes pressure, velocity
and enthalpy (p, u, v, w and h) as the primal variables
2
940

(1)
where the primitive variable is , the coordinate transformation Jacobian matrix is . E, F and G are
the inviscid fluxes in the , and coordinate directions, respectively, and R, S and T are the viscid
fluxes in the , and coordinate directions, respectively. The turbulent viscosity is computed
using a two-layer algebraic eddy viscosity model or Baldwin-Lomax turbulence model. The
detailed expressions of preconditioner matrix, spatial and temporal discretized schemes can be
found in ref. [5].
The preconditioner matrix is described as follows
(2)
where , ,
Based on the preprocessing as shown above, the convergence rate was accelerated notably for
calculation of incompressible flow field [6].
1.2 Equation of State
The equations described above adopt two critical thermodynamic parameters as
unknown variables of fundamental equations. These two parameters include the pressure field p
which drives the moving of flow field and the enthalpy h which reflects the energy transformation
during flowing process. In order to close the above-mentioned equations, the equation which
shows the relation between thermodynamic parameter density and enthalpy h needs to be
introduced.
For any gas or liquid, the relation between density , pressure p and enthalpy h can be
obtained based on its thermodynamic properties: .
Meanwhile, the relation between sound velocity a, pressure p and enthalpy h as well as
relation between h , pressure p and enthalpy h can be obtained.
Based on the relation between above-mentioned state parameters, the governing equation can
be solved accordingly.
1.3 Validation
By means of simulations for classic supersonic flow field, transonic flow field, flow field with
low mach numbers, liquid flow field and even cavitation with phase transformation, it was found
that the results obtained from simulation with this method is close to the experiment results. In this
way, this method is suitable for better simulation of various complex flow fields [7].
1.4 Computational models
By adopting various turbulence models and comparing with experiment results, the
Spalart-Allmaras turbulence model is found to be the most suitable model for simulation of flow
field of Darrieus vertical-axis turbine. In this paper, by using high-resolution numerical simulation
combined with Spalart-Allmaras turbulence model, the two dimensional flow field of H-Darrieus
vertical-axis hydro turbine with three blades is investigated. In addition, the flow field
characteristic and energy efficiency of Darrieus vertical-axis hydro turbine are analyzed with
different tip speed ratios.
The NACA 0018 airfoil shape is adopted for the design of cross section of hydro turbine
3
941

blades. The length of blade chord is 200mm and the turning radius is 1000mm. As shown in Fig. 1,
Darrieus hydro turbine with 3 blades is adopted as object of study: the hydro turbine rotates in a
counterclockwise direction; the blade whose phase on z-axis is set as 0 is defined as the 1st blade;
the rest of blades are numbered successively according to the direction of rotation. In addition, the
flow direction is from left to right.
The whole computational domain is circular and can be divided in to three parts: the external
flow field domain, the rotor rotating domain and the rotor interior domain. In order to ensure the
mesh quality, the whole computational domain is divided into several parts for mesh generation
since the external flow field domain has static mesh which contains less details of flow field, and
the structured mesh is then applied; although there is static mesh in the rotor interior domain, the
mesh in interior domain has been refined as there are a large number of vortexes go through
around the rotor; since the rotor rotating domain includes the blades domain, it is necessary to
generate mesh for blades domain separately. Particularly, the blades domain adopts O type
structured mesh, and the mesh around the blades is refined to meet the wall boundary conditions
required by turbulence model. The whole computational domain which is ten times of rotor
diameter is large enough to ensure that the boundaries conditions have no influence on the
computational results.

(a) 2D hydro turbine computational domain

(b) Mesh topological structure around rotor

Fig. 1 Computational domain and the overall view of the 3-bladed turbine model mesh

When residual of calculation decreases for four orders of magnitude and the torque
coefficient of rotor appears regular periodic variation, the calculation can be considered as
converged. After that, the calculation is then continuously conducted for another cycle based on
this calculation result. In this calculation cycle, the torsion coefficient Cm with certain rotating
speed n is then decided by adopting the average value of torsion coefficient. Moreover, by
applying equations (1), the energy efficiency Cp for this type of Darrieus vertical-axis hydro
turbine can be calculated.
(3)
where is tip speed ratio.
2. Computational results and analysis
With different incoming flow velocities, Fig. 2 shows the variation curves for energy
4
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efficiency Cp and tip speed ratio . It can be observed that with the increase of incoming flow
velocities, the energy efficiency Cp of Darrieus hydro turbine increase accordingly. Moreover, with
certain incoming flow velocity, the energy efficiency rises firstly and then decreases with the
increase of tip speed ratio. For different incoming flow velocities, there is an optimal tip speed
ratio for hydro turbine rotor to achieve the highest energy efficiency. For instance, when flow
velocity equals to 2m/s and the optimal tip speed ratio is 2.2, the energy efficiency of hydro
turbine is the highest which is about 37%.

Fig. 2 Relation between energy efficiency and tip speed ratio

for Darrieus hydro turbine with different

incoming flow velocities

In Fig. 3, for Darrieus hydro turbine, the intersection angle between y-axis and a line which is
generated from the center of blade A to center of rotation is defined as . Meanwhile, during the
rotating process, the surface which always faces to the center of rotation is defined as internal
surface, while the other face on the blade is defined as external surface.

Fig. 3 Initial position of Darrieus rotor blades

When tip speed ratio equals to 1.6, blade A of Darrieus rotor rotates to different positions. Fig.
4 shows the vorticity around blade A. Generally, when the azimuth angle is 0, the incidence
equals to 0 correspondingly. There is large area of negative vortex at the front edge of internal
5
943

surface. This separated vortex turns to plump sickle shape and extrudes against to the positive
vortex which has similar length as blade chord at the tail part of blade internal surface. At this
position, the torsion on the center of rotation which is caused by lift force on the blade equals to 0,
and the value of torsion is negative due to the resistance from the blade. When blade rotates to
position with azimuth angle of 30, there is relatively high positive vortex structure on the blade
external surface. Moreover, the positive vortex on the tail part of the blade internal surface sheds
from the blade, and the negative vortex with plump sickle shape on the blade internal surface
sheds from the blade. However, there are still some negative vortex areas on the blade internal
surface, and the pressure on the blade external surface is larger than the blade internal surface.
When blade rotates to position with azimuth angle of 60, both of the positive and negative
vortexes shedding from the blade internal surface move to the downstream with the flow. At this
moment, the negative vortex on the blade internal surface becomes thinner and deviates to the tail
part of blade. In addition, the pressure difference between the blade internal and external surfaces
increases. When blade moves to position with azimuth angle of 90, there are relatively thin
negative vortex areas on the blade internal surface and at the tail part of blade, and there are also
relative thin positive vortex areas on the blade external surface and at the tail part of blade. In
addition, both of the negative and positive vortex areas extend to the rear of the blade. Based on
the pressure distribution of blade surface, it can be obtained that with the increase of incidence, the
blade surface pressure coefficient drops quickly, the pressure difference between the blade internal
and external surfaces rises continuously, and the work capability of blade increases accordingly.

(a)

(b)

6
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(c)

(d)

Fig. 4 Vorticity magnitude and the corresponding surface pressure distribution for the blade A (=1.6)

For this type of hydro turbine, when tip speed ratio increases to the optimal value of 2.2, for
single blade A of Darrieus rotor rotating to different positions, there are always thin and long
positive vortex areas on the external surface and at tail part of the blade, while there are always
thin and long positive vortex areas on the internal surface and at tail part of the blade, as showed
in Fig. 5. At this moment, there is no separation vortex on the blade surface. Based on the blade
surface pressure distributions at different positions, it can be observed that the pressure difference
between internal and external of blade surfaces increases continuously from position with azimuth
angle of 0. This indicates that the work capability of blade increases correspondingly. Moreover,
with the optimal tip speed ratio, blade A is no longer influenced by separation vortex shedding on
the surface of blade, and the pressure difference between internal and external of blade surfaces at
different positions is obviously larger than the results when tip speed ratio equals to 1.6. Therefore,
the work capability of blade is much higher when tip speed ratio is 2.2.

(a)

(b)

7
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(c)

(d)

Fig. 5 Vorticity magnitude and the corresponding surface pressure distribution for blade A (=2.2)

Fig. 6 shows the vorticity magnitude and velocity contour around Darrieus turbine when low
tip speed ratio equals to 1.6. Compared with Fig. 6, Fig. 7a shows that the rotational velocity of
the blade increases when tip speed ratio increase to 3.1, and there is a ring structure which is
formed by the coupling of blade and tail vortex at the tail part of blade. This type of structure has
obvious blockage effect on the coming flow which makes the fluid flow round the rotor, as
showed in Fig. 7b. In this way, the flow velocities at the center of rotor as well as in areas where
blades are running decrease and the energy efficiency of hydro turbine with high tip speed ratio
reduces accordingly.

(a)

(b)

Fig. 6 When =1.6, vorticity magnitude (a) and velocity contour plot (b) for Darrieus turbine

8
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(a)

(b)

Fig. 7 When =3.1, vorticity magnitude (a) and velocity contour plot (b) for Darrieus turbine

3. Conclusions
This paper numerically investigated the performance for two-dimensional H-Darrieus
vertical-axis hydro turbine with different tip speed ratios. In addition, the principles of how tip
speed ratios have influence on the energy conversion efficiency for this type of hydro turbine are
also analyzed from the aspect of vortex. With low tip speed ratio, most of the areas where Darrieus
hydro turbine blades operate are with high angle of attack. As a result of the separation vortex
shedding on the blade, the lift force acting on the blade decreases and the resistance from the blade
increases. Therefore, the hydro turbine shows poor performance. Besides, the low rotator rotating
speed may also result in the poor performance of hydro turbine. When blade operates with high tip
speed ratio, the blade as well as tail vortex of blade could generate a ring structure which has
blockage effect on the incoming flow. As a result, the fluid cannot flow though the turbine rotor
smoothly, and the performance of hydro turbine reduces obviously. In conclusion, there should be
an optimal tip speed ratio for the energy conversion efficiency to achieve the highest value.
References
[1] EC JOULE II. The exploitation of tidal and marine currents [R]. London: Commission of
European Communities, [EUR 16683 EN, JOU2-CT93-0355], 1996.
[2] Hongwei Liu, Shun Ma, Wei Li, Haigang Gu, Yonggang Lin, Xiaojing Sun. A review on the
development of tidal current energy in China [J]. Renewable and Sustainable Energy Reviews,
15(2): 1141-1146, 2011.
[3] http://www.pontediarchimede.com (Accessed 18/06/08).
[4] Weizhong Chen. Research on tip-speed ratio of vertical axis wind turbine [J]. Renewable
Energy Resources, 26 (5): 76-82. 2008.
[5] Diangui Huang. A preconditioning technology for fluid dynamics [J]. Journal of Engineering
Thermophysics, 26(4): 593-595, 2005.
[6] Diangui Huang. Zhuang Yueqing , Cai Ruizhong. A computational method for cavitational
flows based on energy conservation [J]. Journal of Mechanical Engineering Science, 221(11):
1333-1338, 2007.
9
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[7] Diangui Huang. A common unified computational fluid dynamic software and its validation [J].
Journal of Engineering Thermophysics, 33(10): 1699-1702, 2012.
[8] Qiemeng An. Numerical studies on blade-vortex interaction in a Darrieus Turbine [D].
Shanghai University, 2012.

10
948

Poster

949

WIND SPEEDS INTERVAL FORECASTS USING BACK PROPAGATION NEURAL NETWORK OPTIMIZED BY
CUCKOO SEARCH OPTIMIZATION ALGORITHM
a

Shanshan Qina, Ru Houa,*, Lin Shena, Jianzhou Wanga

School of Mathematics & Statistics, Lanzhou University, Lanzhou 73000, China.
*Corresponding authors contact email: hour12@lzu.edu.cn

ABSTRACT
The utilization of Wind energy, as a zooming technology in the field of renewable energies, has been highly regarded
around the world due to its low impact on environment and sustainable development. Accurate wind speed forecasting
is considerably significant to improve and optimize wind power generation, but it is still a tough work on account of the
unsteady and nonlinear characteristics of wind speed series. Additionally, quantification of uncertainties associated with
wind speed forecasts is essential for optimal management of wind farms and their successful integration into power
systems. However, traditional models for wind speed forecasting mostly focus on generating certain predictive values,
which cannot properly handle uncertainties. With the aim of quantifying potential uncertainties, a new model constructed
by the Cuckoo Search Optimization (CSO) algorithm based Back Propagation Neural Network (BPNN) is proposed to
establish wind speed interval forecasts (IFs) by estimating the lower and upper bounds. The quality of IFs is assessed
quantitatively by both the evaluation measures: IFs coverage probability (IFCP) and IFs normalized average width
(IFNAW). Moreover, to assess the overall quality of IFs comprehensively, a tradeoff between informativeness (IFNAW)
and validity (IFCP) of IFs is examined by an interesting criteria, coverage width-based criteria (CWC). As an applicative
study, wind speeds from Xinjiang Region are used to validate the CSO-based BPNN model. And the test results
demonstrate that the proposed model can construct higher quality IFs for short-term wind speed forecasts.
Keywords: Wind speed, interval forecasts (IFs), Cuckoo Search Optimization (CSO),
Back Propagation Neural Network (BPNN).
1. INTRODUCTION
Over the past few decades of rapid economic development and industrialization, China has become a large energy
consumption power. Fossil fuels, primary energy resources playing a crucial role in meeting energy demands, are nonrenewable resources that generate large amounts of greenhouse gases, which have caused an emerging crisis in
global climate warming (Wu et al., 2013). In recent years, wind energy has been receiving lots of attention due to the
focus on renewable and green energies (Kavak Akpinar et al., 2004). In terms of turbine installed capacity and energy
production, wind energy occupies the largest global share of renewable resources. The worlds wind energy production
is dominated by the USA, Germany, Spain, China, the UK, India, Canada, Italy, Portugal and France, which represent
approximately 86% of global wind power capacity(Nor et al.,2014). China, with its large reserves and wide distribution
of wind energy, has rapidly developed into the worlds fourth largest wind power market after the United States,
Germany and Spain.
Wind speed, with its intrinsically highly irregular and volatile series (Guo et al., 2011), is considered one of the most
difficult weather parameters to model and forecast due to its highly dependency on site topography and characteristic
(Bagiorgas et al., 2008). As wind speed is crucial not only for shipping, aviation, agriculture and environmental planning
(Abdel-Aal et al., 2009) but also for wind energy penetration into the electricity grid (Shi et al., 2011), the need for
accurate forecasting of wind speed becomes critical and urgent.
Many approaches have been developed to improve wind speed forecasting by organizations and institutes with
considerable experience in the field. Statistical and soft computing models are mainly utilized for short-term forecasting
and a physical model is applied for long-term forecasting (Huque et al., 2011). Physical methods are based on the lower
atmosphere or numerical weather prediction (NWP) utilizing weather prediction data such as pressure, temperature,
obstacles and surface roughness (Sanchez, 2006). Statistical methods draw on vast historical data without considering
meteorological conditions, which usually involves time series analysis and artificial intelligence (Chen et al., 2014). A
hybrid algorithm using linear prediction and Markov chain is adopted to facilitate very-short wind speed forecasting
(Pourmousavi et al, 2011). Spatial correlation approaches utilize multi-dimensional data from several study stations to
forecast wind speeds (Liu et al., 2012). Artificial intelligence models, including neural networks and support vector
machine (SVM), have been proliferating, attracting attention for accurate wind speed forecasting and improved
efficiency when compared to traditional time series models (Cadenas et al., 2007; Huque et al., 2011). Artificial neural
networks are data-driven, non-parametric models, which can be useful for wind speed forecasting because they can
capture subtle functional relationships existing in the empirical data even though the underlying relationships are
unknown or difficult to describe (Zhang et al., 2013). Classical neural network, Back Propagation Neural Network
(BPNN), has been studied extensively by researchers in time series forecasting and nonlinear identification. This
architecture provides considerable nonlinear mapping ability, which motivates the utilization of BPNN for short-term
wind speed interval forecasting in this study.

950

According to the above literatures, researches on wind speed forecasting is primarily driven by an individual or hybrid
model and then applied for decision-making. Those methods for wind speed forecasting mostly focus on generating
deterministic predictive values, while few of them handle the uncertainty of wind speeds properly. It was pointed out
that the purpose of most approaches is to make deterministic forecast, but knowledge about uncertainty is not directly
provided (Bremnes, 2006). However, the accuracy of deterministic forecasts is highly variable, and usually low on
average (Pinson et al., 2010). Actually, the predictive errors always exist regardless of forecasting model type, model
training methods and explanatory variables. From a practical view, an inherent and irreducible uncertainty, which results
in decision-making problematic or even prone to mistakes, exists in every forecasts generated by different models
(Pinson et al., 2010). As for decision maker, missing the uncertainty of wind speeds may result in some degree of risk
in the power system management. Therefore, quantification of uncertainties associated with wind speed forecasts is
essential for optimal management of wind farms and their successful integration into power systems.
Uncertainties of prediction can be properly quantified and represented using interval forecasts (IFs) and confidence
intervals (CIs), which describe the uncertainty in the prediction of a future realization of a random variable and an
unknown but fixed value, respectively (Meade et al., 1995). According to their definitions, IFs accounts for more sources
of uncertainty and is wider than the corresponding CIs (Heskes, 1997).
So far, methods based on Neural Networks have been examined by incorporating the uncertainty into the
deterministic forecasts to improve the credibility and reliability of the predictions in different domains, i.e., electricity load
forecasting (Khosravi et al., 2011), semiconductor industry (Liu, 2007), finical services (Benoit et al., 2009), and wind
power forecasting (Khosravi et al., 2011). Methods developed for NN-based IFs construction usually include Bayesian,
Bootstrap and mean-variance estimation techniques, which have been applied in many real case studies (Liu et al.,
2012; Nix et al., 1994). Despite their extensive application in real case study, those methods have their own weaknesses.
The Bayesian technique suffers from massive computational burden, and the Hessian matrix of the cost function is
required for calculation for IFs construction. While the main shortcoming of the Bootstrap is its computational cost for
large datasets (Ho et al., 2001). As for mean-variance method, it underestimates the variance of data, resulting in a low
empirical coverage probability (Ding et al, 2003).
The above three identified methods have been utilized for IFs construction in the literature. In traditional IFs
construction approaches, the major strategy is to minimize the predictive error, rather than to improve the quality of IFs,
being optimal in their key factors, such as width and coverage probability. While in the comparative case studies for IFs
construction, the coverage probability is taken as the only measure to evaluate the IFs quality (Papadopoulos et al.,
2001), which cannot completely describe the characteristics of constructed IFs.
In the present work, a cuckoo search optimization (CSO) algorithm is used for determining the optimal connection
weights for a BPNN structure, which estimates the Interval forecasts (IFs) associated with short-term wind speed
forecasting. The training and development processes of the proposed model are accomplished through approximating
the upper and lower bounds of IFs. As the objective function is nonlinear and complex, then a CSO algorithm is
conducted for its minimization. Moreover, quantitative measures are applied in experiments for unbiased and
comprehensive evaluation of the constructed IFs quality. Applicative experiments are conducted in an examined site of
Xinjiang region, China. Six-hourly wind speed series is collected for this region, over a period of from January 2013 to
October 2013 with 1252 samples. The constructed IFs are assessed from the perspectives of different training levels.
The test results show that the proposed model can construct higher quality IFs for short-term wind speed forecasting
at different levels.
The major contributions of this study are as follows:
A straightforward model for wind speed IFs construction is proposed.
CSO algorithm, with a strong searching ability, is initially integrated into BPNN structure.
Different levels of prediction tasks are implemented and compared together.
The test results from applicative cases are evaluated by coverage probability as well as width of intervals and
coverage width-based criterion CWC.
The rest of this paper is organized as follows. Section 2 describes the methodology used in this paper. Section 3
presents the proposed model and evaluation criteria. Case study and analysis are implemented in Section 4. Finally,
Section 5 outlines the conclusion.
2. METHODOLOGY
2.1. Wavelet De-noising (WD) technique
The wavelet de-noising technique is an effective tool for noise removal, which has been widely utilized in the fields
of signal processing, image processing and time series analysis (Zhang et al., 2013). In this study, the WDT is used to
de-noise and extract the essential feature from the original wind speed series with the characteristics of high frequency
and fluctuation.
WDT is based on the wavelet transform, which can be divided into two categories: Continuous Wavelet Transform
(CWT) and Discreet Wavelet Transform (DWT) upon that the wavelet are sampled continuously or discretely (Liu et al.,
2014). The CWT is defined as the convolution of a time series x(t ) with a mother wavelet function w(t ) (Zhang et al.,
2013):

951

CWTxw (b, a) xw (b, a)

1
t b
x(t ) w (
)dt

a
|a|

(1)

Where denotes the complex conjugate of w(t ) , b is a translation coefficient and a is a scale parameter. Let b k 2s
and a 1 2s , then the DWT can be defined as follows:
DWTxw (k , s) xw (

k 1
t k 2s
, s ) x(t ) w (
)dt
s
2 2
1 2s

(2)

where s and k are the scale and translation coefficient, respectively. But discrete in nature s and k belong to the integer
set.
Considering the discrete wind speed series, DWT is taken for data analysis. In this study, on the basis of soft
thresholding the wavelet de-noising technique is applied to filter out the noise from the original wind speed series.
Additionally, two main factors, levels of decomposition and wavelet basis function should be settled properly when
utilizing wavelet denoising technique. According to the wavelet de-noising literature, various wavelet functions are
adopted and each function has the corresponding application area due to their different resolution capability and
efficiency. This study adopts the db3, the daubechies wavelets filters of order 3 with high computing efficiency and
widely universality in time series analysis, to conduct the wavelet de-nosing process (Zhang et al., 2013). Furthermore,
pre-testing different decomposable levels with db3, level 3 seems to work best with most of the experimental data.
2.2. Back Propagation Neural Network (BPNN) of Multiple-inputs and Double-outputs
The Back Propagation Neural Network, which was developed by (Rumelhart et al., 1986) as a solution to the problem
of training multi-layer perceptron and was identified as the most common type of Artificial Neural Network (ANN) model,
has been widely used in many fields due to its ability of classification and linear or nonlinear mapping (Liu et al., 2012).
The basic structure of a BPNN with two outputs is shown in Fig.1, which consists of three layers, including input layer,
hidden layer and output layer. Each node in the input and hidden layer is connected to each of the nodes in the next
hidden or output layer. And all connection between nodes are directed, no connection between the nodes within the
same layer. In addition, each connection between nodes has a weighting factor associated with it. Normally, these
weights are modified using the Back-Propagation algorithm (BPa) during training process (Website, 1999).

Fig.1. The basic structure of a BPNN with two outputs.

Applying a BPNN model, the whole data sets are divided into three sets: training set, validation set and test set. The
training set is utilized to adjust the connection weights of BPNN. As for the validation set is used to determine the
optimal BPNN structure and other undetermined parameters. While for the test set, it is applied to evaluate the
performance of the BPNN model. Note that all the training data sets should be normalized, the same setting as test
sets for normalization (Quan et al., 2014).
In the training procedure, the BPNN model learns the relationship between the inputs and the outputs as the residual
between the desired outputs and the BPNN model outputs decreases. However, the training goal or iterative steps

952

should be set properly to terminate the training process for the reason that overly minimal training goal or excessive
training can cause over-learning, which indicates that the BPNN model extracts too individual information and cannot
be applicable to general cases (Liu et al., 2012).
2.3. Cuckoo Search Optimization (CSO) algorithm
Cuckoo search, an optimization algorithm developed by (Yang et al., 2009), was inspired by the obligate brood
parasitism of some cuckoo species by laying their eggs in the nests of other host birds (Website, 2014). Cuckoo Search
Optimization (CSO) algorithm idealizes such breeding behavior, and thus can be applied for various optimization
problems, which seems that it can outperform other Mataheuristic algorithms in application (Website, 2010)
For simplicity, the CSO algorithm uses the following simple representations that each egg in a nest represents a
solution, and a cuckoo egg represents a new solution. The aim is to use the new and potentially better solutions
(cuckoos) to replace a not-so good solution in the nests. Of course, this algorithm can be extended to the more
complicated case where each nest has multiple eggs representing a set of solutions. For simplicity in describing the
new CSO algorithm, we now use the following three idealized rules (Yang et al., 2010):

Each cuckoo lays one egg at a time, and dump its egg in randomly chosen nest;

The best nests with high quality of eggs will carry over to the next generations;

The number of available host nests is fixed, and the egg laid by a cuckoo is discovered by the host bird with a
probability pa (0,1) . Discovering operate on some set of worst nests, and discovered solutions dumped from
farther calculations.
For a maximization problem, the quality or fitness of a solution can simply be proportional to the value of the objective
function. When generating new solutions xi(t 1) , for say a cuckoo i , a Levy flight is performed.
xi(t 1) xi(t ) a Levy( )

(3)

where > 0 is the step size which should be related to the scales of the problem of interests. In most cases, we can
use = 1. The above equation is essentially the stochastic equation for random walk, but here the random walk via
Levy flights is more efficient in exploring the search space as its step length is much longer in the long run.
The Levy flight essentially provides a random walk while the random step length is drawn from a Levy distribution,
which can be defined as Eq.(4)
Levy ~ u t , (1< 3)

(4)

Some of the new solutions should be generated by Levy walk around the best solution obtained so far, which will
speed up the local search. However, a substantial fraction of the new solutions should be generated by far field
randomization and whose locations should be far enough from the current best solution, which will make sure the
system will not be trapped in a local optimum (Yang et al., 2010).
3. PROPOSED INTERVAL FORECASTs (IFs)
3.1. Evaluation indices of IFs
The quality of IFs needs to be assessed quantitatively by evaluation indices. IFs coverage probability (IFCP), a
significant characteristic of IFs, shows the probability of target values covered by the lower and upper bounds. IFCP is
defined as follows (Quan et al., 2014):
IFCP=

1 n
ci
n i 1

(5)

where n is the number of samples and ci 1 if the target value vi [ Li ,Ui ] , otherwise ci 0 . Li and U i are the lower
and upper bounds of the ith IF, separately. Theoretically, IFCP is a measure of validity of IFs constructed with an
associated confidence level. A larger value of IFCP implied more targets within the constructed IFs and vice versa.
The ideal value for IFCP is 100%, which indicates all targets are covered by IFs (Quan et al., 2014). However, the
quality of IFs is usually assessed by IFCP either without considering the width of IFs or vaguely presented. For example,
if the lower and upper bounds of IFs are chosen as the minimum and maximum values of the targets, then the perfect
value of IFCP is equal to 100%. Too wide IFs, which convey a little information, are useless for decision making.
Therefore, width of IFs is another key feature of IFs, which determines their informativeness. A quantitative measure,
IFs normalized average width (IFNAW), evaluates IFs from this aspect and is defined as follow (Khosravi et al., 2013):
1 n
(6)
(Ui Li )
nR i 1
where R , the range of underlying targets defined as the difference between their maximum and minimum values, is
used to normalize the IFs average width in percentage in the reason that IFNAW can be utilized for objective
IFNAW=

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comparisons, regardless of the magnitudes of the underlying targets or the techniques utilized for their construction.
Practically, narrow IFs are more informative than wide IFs, which means that the lower value of IFNAW, the more
informative of the forecasts.
From a practical point, a larger IFCP value with a smaller IFNAW value is the objective for high-quality IFs. However,
the two goals are conflicting due that amplifying the width of IFs always results in a increasing in IFCP and vice versa.
To quantitatively measure this event, therefore, a comprehensive index is required to address the both aspects and to
carry information about the width of IFs together with the corresponding coverage probability. A combinational index,
named coverage width-based criterion (CWC), is introduced by (Khosravi et al., 2011):
CWC IFNAW(1 (IFCP)e (IFCP ) )

(7)

where and are two hyper-parameters. The role of , denoting the pre-assigned IFCP which must be met,
corresponds to the nominal confidence level associated with IFs. As for , it is usually set to a large value to magnify
the difference between and IFCP, which can highly penalize the unsatisfied IFs. Applying such a reasonably
conservative strategy leads us to the following observation. On the basis of the CWC definition, if the pre-assigned
IFCP is not satisfied ( IFCP ), the exponential term are highly penalized. While IFCP is larger but approaches
( IFCP ), there exist two conflicting criteria. Expanding the widths of IFs will increase IFNAW and IFCP , which
simultaneously increase and decrease CWC , respectively. Additionally, as IFCP goes further away from , the
exponential term in Eq.(7) will gradually level off, resulting in the IFNAW criterion being dominant in CWC (Khosravi
et al., 2011). Therefore, a balance between IFCP and IFNAW should be examined. Here, (IFCP) is defined by the
following step function:
0 IFCP
(IFCP)
(8)
1 IFCP
According to the step function, the exponential term in Eq.(7) can be eliminated whenever IFCP thereby CWC
equal to IFNAW . Otherwise, the corresponding penalty will be accounted by CWC. Actually, the CWC measure tries to
find a tradeoff between validity ( IFCP ) and informativeness ( IFNAW ) of IFs.
3.2. Construction of wind speed interval forecasts model: WD-CSO-BPNN
In this paper, the proposed model, which incorporates the WD technique into a BPNN model based on CSO
optimization, is adopted for wind speed interval forecasts. The methodology used in the WD-CSO-BPNN model has
been briefly described in the above section.
Step 1: Wavelet de-noising. The original wind speed series are decomposed into a high-frequency component and lowfrequency component, which represent the noise signal and main features of the wind speed series, respectively. The
main purpose of wavelet de-noising is to remove the random disturbance and extract the major characteristics from
the original wind speed series.
Step 2: Data splitting and normalization. The available wind speed series after noise reduction are split into the training
set and test set, which are denoted as Dtrain and Dtest, respectively. The training data set is further split into input train
and output train sets, which are used for adjusting the connection weights of BPNN structure. While the test data set is
split into input test and output test sets, which are utilized to evaluate the performance of the proposed model. For
establishing BPNN, the training data sets as well as the input test sets need to be normalized with the same setting,
which can eliminate the influence of different scale data.
Step 3: Initialization. A BPNN structure with two outputs is shown in Fig.1. The number of connection weights of BPNN
is the size of a cuckoo egg in CSO algorithm, namely the dimension of optimized parameters. These initial weights can
be randomly assigned, while the parameter ( pa ) of CSO algorithm is set to be 0.25, an optimal value which has been
verified by (Yang et al., 2010).
Step 4: Optimization. The objective function of CSO algorithm is given as follows:
f objective =

1 n
)2 ]
[(Ui Uitrain )2 (Li Ltrain
i
n i 1

(9)

where n is sample size of Dtrain. The output training sets, U i and Li denote the upper and lower bounds of the training
sets, as for U itrain and Ltrain
, the corresponding fitting results of U i and Li . The optimized algorithm terminates if it
i
reaches the maximum iterations.
Step 5: BPNN construction. The best solution obtained by CSO algorithm is set to be the final connection weights of
BPNN training and construction. The terminal condition of network training is set as the reach of maximum iterations
or no further improvement.
Step 6: IFs construction for test data set. On the basis of the established optimal BPNN, the IFs of output test sets are

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generated by importing input test sets.

Step 7: Evaluation. The quality of IFs is assessed by IFCP and IFNAW measures, which present the validity and
informativeness of IFs, respectively. With the aim of comprehensive evaluation, CWC is calculated as well.
4. CASE STUDY AND ANALYSIS
This section presents the empirical study carried out to assess the effectiveness of the proposed method for wind
speed IFs construction. Structured in three subsections, the datasets utilized for conducting the experiments are
described in section 4.1. The results of wavelet de-noising are explained in section 4.2. Then applying the wind speed
series after noise elimination, the wind speed IFs model is built based on CSO-BPNN structure with two outputs. The
simulation and evaluation results are presented and discussed in section 4.3.
4.1. Data sets
Xinjiang region, accounting for more than one-sixth of Chinas total territory, possesses abundant wind resources
due to its geographical characteristics. Nine major wind zones are located in the region, which are Dabancheng,
Shisanjianfang, Alataw Mountain Pass, Turpan Grass Lake, Laofengkou of Tacheng, Erqisi River, Santang LakeNaomao Lake, Lop Nur and the southeastern Hami wind regions. In order to investigate the potential of wind power, it
is highly worthwhile to conduct interval forecasts of wind speeds in this region.
In this paper, the six hourly mean wind speed data observed in a representative site of nine major wind zones is
selected as an illustrative example to construct and evaluate the proposed model. To facilitate the following modeling,
we record the original wind speed series in this study site as {X}. The original wind speed series together with its
statistical measures, i.e., minimum, maximum and mean velocities and the standard deviations, are shown in Fig.2. As
demonstrated in Fig.2, the stand deviation is above 2.5, which implies the original wind speed series fluctuates severely,
with the minimum and maximum being 0.30 and 17.13 m/s, respectively. This can be intuitively observed from the
amplitude and frequency of the series fluctuation, which quickly changes from very high to low values and vice versa.

Fig.2. The original wind speed series together with the corresponding statistical measures: Mean, Std.dev, Min and
Max denote the average value, standard deviation, minimum and maximum of wind speeds, respectively.
4.2. Wavelet De-noising
In this subsection, DWT technique is used to decompose the raw wind speed series to remove the noise information
for further modeling. According to the literature, many kinds of mother wavelet functions are applied for discrete wavelet
de-noising. But every function gets the corresponding application area on the basis of the resolution capability and
efficiency. In this study, db3 is chosen as the mother wavelet function to decompose the original series into three levels,
with the wavelet de-noising process and results displayed in Fig.3. Here, the low-frequency, high-frequency in three
levels are recorded as {Xl}, {Xh1}, {Xh2} and {Xh3} series, respectively. From the Fig.3, it can be observed that the raw
series after noise reduction, which is recorded as {DX}, shows high similarity to {X}, presenting major fluctuation. Hence,
the {DX} is taken as the wind speed series to further model for efficiency.

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Fig.3. A brief process and result of Wavelet de-noising for wind speed series.
4.3. Data splitting and parameters selection.
Performance of IFs construction approach relies on the trained and CSO-optimized BPNN structure. Enough
freedom and feasibility of the approach are considerably significant to generate the optimal possible results (Khosravi
et al., 2011). Hence, single hidden layer BPNN with two output layers is chosen in this experimental study.
The purpose of this study is to quantify uncertainties associated with wind speed forecasts for study site. Due to the
complexity of wind speeds, there is no external available information, only the historical wind velocities are used to
complete the procedure of modeling and forecasting.
The wind speed IFs problem tries to obtain an estimates U (t k ) and L (t k ) , upper and lower bounds of wind speed
X (t k ) , based upon the previous p observations X (t ), X (t 1),..., X (t p 1) . According to this, a short-term wind speed
IFs problem is proposed.
For the case study, we split the 1252 wind speeds into training set (80%) and test set (20%). Furthermore, the training
set are further divided into input-training set and output-training set. Since the CSO-BPNN structure has two output
layers, representing the lower and upper bounds of the corresponding output-training set, then the output-training set
needs to be redefined as LU_output-training set, which is given by Eq.(10).
LU_output-training(i) [output-training(i) (1 ) output-training(i) (1 )] , (i 1,2,..., n)

(10)

where n is the number of the output-training set. , determining factor of the widths of the LU_output-training set, is
predesigned before model training, i.e.,10%, 15%, 20% and 30%. On the basis of the above four values, the model
training process is divided into 4 levels, which are level 1, level 2, level 3 and level 4, respectively. Fig.4 illustrates the
training sets clearly.

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Fig.4. The splitting process of training sets.

According to the four different training levels, the nominal confidence level in Eq.(7) is set to be 80%, 85%, 90%
and 95%, respectively. Furthermore, is chosen to be 50 as to highly penalize wind speed IFs with a coverage
probability less than the corresponding nominal confidence level. IFCP, IFNAW and CWC measure are selected to
examine the quality of constructed IFs.
4.4. Optimization and determination for connection weights of BPNN structure
In the CSO algorithm, each egg in a nest represents a solution, which is the connection weights of BPNN structure.
In this subsection, the convergence behavior of CSO algorithm is demonstrated in Figs.5, showing that the objective
function monotonically decreases with respect to iteration. The initial values of objective function are very large, but
they all decrease gradually as the iterations increase. In the early iterations, the objective function decreases drastically,
while it gradually plateaus as the optimization proceeds. For Figs.5 (a, c and d), the objective function values drop
rapidly in 20 iterations, which means the process with high convergence speed. While in Figs.5 (b), the objective value
continues to reduce step by step in 70 iterations. After the rapid reduction, however, the minimizations make little
improvement, which implies that the solution converges rapidly to a global optimum due to the strong searching
capability of the CSO algorithm. In this study, the number of iterations varies from approximately 100 to 200 based on
the different training levels. Once the iterations terminate, the best egg with the optimal connection weights can be
used for BPNN training in further step.

Fig.5. The convergence behavior of CSO algorithm.

4.5. Wind speed IFs results
The results for wind speed IFs based upon CSO-BPNN basically consist of three parts: training procedure, test

957

results and quality evaluation of IFs. The key factor for BPNN is connection weights, controller of BPNN structure,
which are determined by CSO algorithm in the above subsection. Considering different types of prediction problem, the
training process is conducted at four levels on the basis of four different LU_output-training sets defined by Eq.(10).
The final performance of the proposed model is examined by test set. For each case study, therefore, the corresponding
test results can be obtained upon the optimal CSO-BPNN structure at four levels. For better visualization, test results
for this case study are demonstrated in Figs.6-7.

Fig.6. Wind speed IFs results for different training levels.

Fig.7. Results comparison of wind speed IFs for different training levels.
From the above two figures, the shape of the IFs lines and the real test line are considerably similar to each other. It
indicates that the proposed model can well capture the characteristic of the fluctuation trend. While the width of the

958

constructed intervals from Figs.6 (a) to Figs.6 (d) are distinct from each other, gradually likely to become larger, due to
the different training levels, with the value being 10%, 15%, 20% and 30%, respectively. The smaller value, the
narrower output-training set, which leads to narrower wind speed interval forecasts (IFs). Different width of IFs results
in different cover probability. As seen from Figs.6 (a), the constructed IFs with the upper and lower bounds (two gray
lines) tight with each other, covers the real test samples in a poor percentage. The real test samples (black line) lie
without the constructed bounds (between gray lines) in relatively more cases than the other three levels. While for
Figs.6 (d), the width of IFs is largest, which implies the constructed IFs cover the real test sets in a great percentage.
The real test samples (black line) lie within the forecasting intervals (between yellow lines) in the overwhelming majority
of the cases.
As for Figs.6 (b and c), the widths of IFs are larger than those in Figs.6 (a) but smaller than those in Figs.6 (d). Fig.7
provides the whole results comparison, which can illustrate the constructed IFs clearly.
In order to quantitatively evaluate the quality of wind speed IFs constructed by the proposed model, the numerical
test results of all the cases are shown in Fig.8. Not only the coverage probability and average width of IFs (IFCP and
IFNAW) but also a comprehensive measure (CWC) are calculated. It is assumed that the constructed IFs are
theoretically valid if their coverage probability is larger than or equal to the corresponding nominal confidence level
(Khosravi et al., 2013). That is to say, violation of this condition leads to invalid IFs and destroys their credibility.
According to the results in Fig.8, the IFCP are larger than the corresponding nominal confidence level in the majority
of conducted experiments, and therefore the IFs are valid. Furthermore, a positive gap between IFCP and the
corresponding nominal confidence level highlights the capability of the proposed model for generating reliable IFs, such
as the IFCP at training level 1, 2 and 3, in which the CWC are equal to IFNAW. While there are some empirical case
that IFCP is not satisfactory, for example the IFCP at training level 4, in which the CWC is largely amplified.
It is significant to note that the coverage probability has a direct relationship with the training levels. As the training
level goes from level 1 to level 4, both the coverage probability and the width of IFs increase. High coverage probability
of IFs indicates that the IFCP measure for the test sample sets are very satisfactory applying the proposed model. On
the other hand, much wider of the constructed wind speed intervals implies less informative. Therefore, both the
conflicting index are balanced by a comprehensive measure CWC. As can be seen from Fig.8, on the condition that
the IFCP satisfy the corresponding confidence level for different training levels, the CWC is equal to the INFAW.
Otherwise, the it is enlarged by a penalty term defined in Eq.(7). Overall, CWC values are mostly less than 100, which
indicates that constructed IFs are valid and sufficiently narrow (Khosravi et al., 2011), and the proposed approach can
effectively establish a tradeoff between validity and informativeness.

Fig.8 Evaluation measures for constructed IFs for different nominal confidence levels.
5. CONCLUSIONS
Wind energy, a renewable and clean energy source, has become increasingly significant for sustainable energy
development and environmental protection. Reliable and accurate wind speed forecasts are vital for wind power
generation. However, the complexities of wind speed series pose great challenges to precise wind speed forecasting.
Considerable research effort has been devoted to generating deterministic wind speed forecasting values. However,
few studies have been conducted to handle the uncertainty of wind speeds properly, which may exert a certain degree
of risk in the operation of energy system.

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To overcome the deficiencies of deterministic forecasts to handle uncertainties, a newly proposed model called WDCSO-BPNN is adopted and developed to construct wind speed interval forecasts (IFs). Considering the high fluctuation
and volatility of original wind speed series, Wavelet de-nosing technique is applied to reduce high-frequency item. And
the series after noise elimination with the main feature of original wind speed series are utilized for model construction.
Additionally, Cuckoo Search Optimization (CSO) algorithm with a strong searching capability for parameter adjustment
is incorporated into BPNN for connection weights optimization, upon which the BPNN structure can be determined so
as to forecast wind speed intervals, lower and upper bounds of each point. Finally, the quality of wind speed IFs is
comprehensively examined by quantitative evaluation measures, which shows that the proposed WD-CSO-BPNN
model can construct higher quality IFs in a short time at different training levels with different forecasting tasks or
purposes.
This paper addresses the problem of uncertainty quantification for wind speed forecasts. From a theoretical
prospective, other statistical models like support vector machine (SVM) and artificial intelligence optimization algorithm,
such as particle swarm optimization (PSO), Genetic algorithm (Ga) and Simulated Annealing (SA), can be integrated
into together to generate uncertainty quantification and prediction intervals. While from a practical view, constructed
wind speed IFs, a complementary source of information on wind forecasts, can be efficiently utilized along with
predictive values by end users for decision-making due that uncertainties associated with wind speed forecasts are
quantified, and decision-makers can assess the probability of risk they bear when applying deterministic wind forecasts.
ACKNOWLEDGE
This work was supported by the National Natural Science Foundation of China (Grant No.71171102).

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ECONOMIC AND ENVIRONMENTAL ANALYSIS OF HYBRID POWER SYSTEM

FOR A SEMI-ARID REGION
Swarna K.S.V., GM Shafiullah, Amanullah MT Oo, Alex Stojcevski
School of Engineering, Faculty of Science, Engineering and Built Environment, Deakin University,
Geelong Australia
Email: ssrungar@deakin.edu.au

ABSTARCT
Growing demand of energy and the environmental consequences of fossil fuels have spurred
the search for renewable energies (RE) particularly wind and solar PV. The increased use of
renewable sources not only contributes to emission reduction but also improves energy
supply diversity, reduces energy crisis and cost of energy generation. Hence, renewable
energies represent a corner stone to steer our energy system in the direction of sustainability
and eco-friendly. This paper develops a Hybrid Power System (HPS) and investigates the
prospects of wind and solar energies for a semi-arid climatic region in Victoria. As a case
study, monthly mean global solar irradiation and wind speeds data have been collected from
Bureau of Meteorology (BOM) for Kilmore Gap weather station, North-Central Victoria, a more
prospective location considering both wind and solar energy generation. Hybrid Optimization
Model for Electric Renewable (HOMER) developed by National Renewable Energy
Laboratory (NREL) is used as a simulating tool in this analysis. This study also presents the
influences of storage system in the proposed HPS allowing energy to be stored in the storage
during high generation from RE sources with minimum load demand and released in to the
grid during peak hours. A comparison is drawn among different configurations of HPS with
and without storage considering both economical and environmental factors. Net Present
Cost (NPC) and Cost of Energy (COE) are compared for economic analysis whereas
Renewable Fraction (RF) and other emission factors are used for justifying environmental
analysis. From the optimization results it is observed that wind/grid and wind/PV/grid
connected systems are more feasible, contributing less GHG emissions and optimum COE
and NPC. Sensitivity results are also compared for performance variations due to wind speed
and solar irradiation and found that wind generation is more promising in this location due to
the a surplus availability of wind sources. It is also evident from the model results that energy
storage enhances contributions from RE sources and hence reduces GHG emissions further.
Keywords: Renewable Energy, Hybrid Power System, GHG Emission, Economical Analysis,
Environmental Analysis.
INTRODUCTION
Energy crisis has become a major issue throughout the world as most of the electricity is
generated from the traditional energy sources particularly coal. Continuous usage of
conventional sources not only increases the energy crisis but also contributes to Green
House Gas emissions[1-3].Despite differing reasons, it is clear that there is an emergency to
transit the present traditional power system to a viable one by integrating renewable energy
sources into the existing system[4, 5]. Hence, renewable energies represent a corner stone to
steer our energy system in the direction of reliability and sustainability[6, 7]. Victorian
government has set 20% renewable energy target representing a new bench mark for action
on climate change in Australia for sustainable future by 2020[8].From Victorian Climate
Change Action Plan it is evident that around 30,000 homes source their energy from
renewable power especially wind and solar PV as wind and solar are the fastest growing
pollution free technologies[9-11]. However, non availability of these renewable energy
sources all the time throughout the year has focused research area in Hybrid renewable
energy systems[12].
All over the world, there are many research literatures available on Integration of renewable
resources in to the grid considering different climatic conditions. For instance, in Australia,
Dalton [13]studied on the performance metrics of a stand-alone system of hotel in remote
tourist destinations in Queensland, hot arid region. From the case study, it was found that
integration of renewable sources in to the grid reduced the cost factors to 50% compared to

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conventional system and also contributed to the reduction of GHG emissions in to the
atmosphere. Moreover, Gang Lius[14] Economic and Environmental Modeling of a
Photovoltaic-wind-Grid HPS in hot arid Australia investigated the efficient ways to evaluate
renewable energies and reported that the assumed hybrid model in his analysis reduced the
Cost Of Energy (COE) to 0.256 $/kWh while the standard grid price was 0.3$/kWh. However,
based on the effective research done in different climatic regions the present study is focused
on a semi-arid region considering wind and solar as primary sources for grid integration.
In this paper, a feasibility study has been under taken to investigate the prospects of wind and
solar energies in Kilmore gap, North Central Victoria, a semi-arid region. The interest and
motivation for harnessing wind and solar PV for this location is due to their surplus availability
throughout the year when compared to the other locations in North Central region. Data have
been collected from Bureau of Meteorology (BOM) [15] from the available five weather
stations shown in Fig.1 and it is found that Kilmore Gap is the best suitable location for this
2
case study comparing its annual wind speed (6.94 m/s) and Solar irradiance (4.33 kWh/m /d)
with other locations. In order to ensure stable and continuous power a hybrid power system
including more than one type of energy component is introduced. This study also focuses on
the influences of storage system in the proposed hybrid system as the energy storage
enables the decoupling of electric generation from demand. Appropriate integration of
renewable energy sources with storage allows greater market penetration and emission
savings[16].

Fig.1. Solar and wind data comparisons in North-Central Victoria

FRAME WORK MODELING

The two important aspects to be considered while modeling the present research study are
economic and environmental factors. The economic indicators considered for the proposed
Hybrid power system are Net present cost (NPC) and Cost Of Energy (COE) whereas for
environmental assessment Renewable fraction is considered[14]. The detailed explanation
about these performance metrics are discussed below.
NPC and COE
HOMER uses the total NPC to represent the life cycle cost of the system. NPC is the present
value of all the cost of the system throughout the life time deducted by the cost of investment
and the operation of the system.
NPC ($) = TAC CRT
(1)
Where, TAC is the total annualised cost which is the sum of the annualised costs of each
system component. The capital recovery factor (CRF) is given by
N

CRF ($) = [ i (1+i)N] [(1+i) -1]

(2)

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Where, N is the number of years and i is the annual real interest rate (%)
Whereas cost of energy is defined as the average cost per kWh of electricity. For the best
optimum results NPC and COE values should be as low as possible making the configuration
more feasible.

Renewable Fraction
Environmental assessment can be made using the factor, renewable fraction. Renewable
fraction indicates the extent of renewable energy used by the system and it is defined as the
portion of the systems total annual electrical production originating from renewable power
sources. It is calculated by dividing the total renewable power production by the total energy
production. The fraction is in turn divided in to two components-photovoltaic fraction fpv and
wind fraction fw.
fpv=

Epv

Etot

fw.=

Ew

Etot

(3)
(4)
where, Epv. Ew, Etot are the respective total energy generations.
HYBRID RENEWABLE ENERGY POWER SYSTEM
Hybrid systems provide a high level of energy security and reliability through the integrated
mix of complementary generation methods, and often will incorporate a storage system to
ensure consistent supply. This section concentrates on system modeling, energy resources
used, electric load, standard grid and the converter. In this study a hybrid energy system is
designed with an integration of solar and wind power generation system. Fig. 2 shows the
Hybrid energy system modeling in HOMER and the renewable energy sources used in this
analysis are solar and wind resources. In this model, battery T-105 is used as a storage
device to release energy into the grid during peak hours. The following sections gives the
information for load, renewable energy resources and the other components used in the
hybrid power systems [17, 18].

Fig. 2 Hybrid renewable energy system with HOMER

Electric load
In the proposed HPS a typical load 1,629 kWh/d of Victoria State is considered for
simulation.Fig.3 shows the monthly average load profile and it can be clearly seen that the
load demand is more during the months of summer compared to winter and spring.

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Fig.3 Average Load profile for a year

Wind energy resource

Fig. 4 shows the graphical representation of wind speed level for Kilmore Gap location. From
the figure it is observed that the wind energy is maximum throughout the year except few
months maintaining an average wind speed of 6.94 m/sec.

Fig.4 Graphical representation of Wind variations

Solar energy resource

HOMER uses the daily solar resource inputs to calculate the PV array power for each hour of
the year. Fig. 5 shows the monthly average solar exposure levels with clearness index (CI).
The observed clearness index value is varied from 0.40 to 0.59 and the maximum solar
radiation observed is during months of December and January.

Fig.5 Average solar irradiance

Component Details
The components used in the proposed Hybrid system are Photovoltaic module, Aeolos s-H30
wind turbine, converter Trojan T-105 Battery and standard grid.
Photovoltaic
The capital cost for a 1.0 kW photovoltaic array considered in this study is $2100 with a
replacement cost of $2000. For optimum solution, the O&M cost is practically considered to
be zero. Search spaces of photovoltaic cells to be considered are from 0 to 300.
Wind turbine
For simulation Aeolos s-H30, 30 kW wind turbine is considered with a capital cost of $ 66,000
[19] and with zero O&M. For the simulation, the sizes to consider are 8, 10 and 12 and the
hub height used is 25m.
Power Converter
Converter serves the purpose of both rectifier and inverter. The DC energy from the
photovoltaic is converted into AC using an inverter. For 1 kW of energy, the installation cost is
considered to be $800 and the replacement cost is assumed to be $750.The life time is
assumed to be 20 years considering an efficiency of 90%.
Trojan T-105 Battery

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To conserve energy, separate storage system is considered in this analysis using a battery T105. The number of battery strings considered in this analysis are 300 and the batteries per
string are 4. The capital cost maintained is $ 210 and the nominal capacity of the battery is
1.35kWh.
Grid
Grid acts as backup component supplying energy to meet the demand load during surplus
energies. A standard grid price of 0.4$/kWh is maintained throughout the study for better
analysis.
RESULT ANALYSIS
This research paper provides the results in terms of optimization and sensitivity analysis for
the selected region using Homer simulation tool. Optimization results provide the economic
feasibility and environmental friendly information under specific meteorological conditions.
Whereas, sensitivity analysis is a measure that checks the sensitivity of a model while
changing the value of the parameters of the model useful in decision making and specific
model recommendations[20]. The present hybrid model has been simulated using wind speed,
solar irradiation, grid electricity price, NPC, COE and RF as sensitivity variables. Detailed
discussion is provided in the forth coming paragraphs.
Optimization results
Optimization results for a semi-arid region given the specific average wind speed 6.9 m/sec
2
and solar irradiation 4.33 kWh/m /d with a grid electricity price 0.4 $/kWh are summarized in
the Fig. 6.This figure also depicts the influences of storage system using a battery on the
measured performance metrics. For better analysis optimization, results are discussed
sepeartly with storage and with out storage.

Fig .6 Optimization results using HOMER for Kilmore Gap location

From Fig.6, when storage factor is not considerd it can be seen that , for a wind/grid
connected system the optimized COE and NPC are 0.197 $/kWh and $ 1,495, 861
respectively.In this case, the renewable fraction observed is around 0.87 contributing
maximum energy to grid compared to grid alone system. Moreover, Fig 6 shows one of the
highest renewable fraction 0.90 with a total NPC of $1,590,707 and COE of 0.209 $/kWh for
wind/PV/grid system. Whereas for a PV/grid connected system the observed COE and NPC
are 0.344 $/kWh and $ 2,612,334 respectively.
On the other hand, when storage is considered the observed NPC and COE for wind/PV/grid
connected system are 0.225 $/kWh and $ 1,709,572 respectively. The observed renewable
fraction in this case is around 0.94 meaning that higher proportion of renewable electricity
generation in to the grid during peak hours. Fig.6 also shows the economic performances of
optimized wind/grid system and PV/grid with storage. When the performance metrics of these
two hybrid systems are considered the observed renewable fraction is 50% more in a
wind/grid connected system compared to PV/grid connected system contributing more energy
to grid. NPC and COE for wind/grid and PV/grid connected systems are 0.225 $/kWh,
0.361$/kWh, $1,70,9572, $2,74,2765 respectively.

966

Fig.7 shows the monthly average electricity production for Kilmore location, North Central
Victoria. For a wind/PV/grid storage connected system wind energy has made maximum
contribution to the electricity production compared to other grid connected systems due to the
abundant wind energy resource in Kilmore location. From the simulation results the electricity
production from the wind turbine is observed as 1,244,270 kWh/y contributing 85% power to
grid whereas photo voltaic array contributes 9% and grid purchases are only 6%
approximately.

Fig. 7 Average electricity production

Fig.8 depicts the cash flow summary of Kilmore weather station and it is observed that for an
optimized wind/PV/battery/grid connected system most of the capital cost is required for
Aeolos s-H30 wind turbine compared to other resources.Hence provide higher wind energy
contribution in to the grid due to its abundant availability there is an vital need to sacrifice
financially with the high capital costs. However, the operating and maintenance expenditure is
quite low for renewable resources maximizing their usage in the grid for better optimization.

Fig. 8 Cash flow summary of different modules used in Homer Simulation

Table.1 shows the detailed performance measures of the studied system and it can be stated
that, wind/grid system is more feasible than any other systems resulting in less Cost of
Energy and Net Present Cost when storage is not considered. However, wind/PV/grid is also
identified as one of the optimum systems with appreciable performance metrics contributing
maximum renewable energy in to the grid. In addition, when storage is considered then it can
be observed that the amount of the renewable energy contribution is maximum to the grid
making it viable irrespective of the type of the systems connected. Hence, for Kilmore Gap
location, integration of wind in to the grid results in to more economical and feasible solution
contributing less GHG into the atmosphere compared to solar PV alone as it is available only
7 to 8 hours a day while wind is available all of the period.
Table 1. Performance metrics Comparisons

With out Battery

Type of
system

With Battery

NPC($)

COE($/Kwh)

RF

Wind/grid

1,495,861

0.197

0.87

Pv/grid

2,6123,34

0.344

Wind/Pv/grid

1,590,707

Grid only

3,040,311

COE($/Kwh)

RF

1,709,572

0.225

0.90

0.41

2,742,765

0.361

0.42

0.209

0.91

1,706,814

0.225

0.94

0.400

0.00

3,377,840

0.444

0.00

967

NPC($)

SENSITIVITY ANALYSIS
In this study sensitivity results are analysed using optimal system type and line graph
models.Fig.9 shows the sensitivity analysis in terms of optimal system type for Kilmore
weather station.For a fixed grid price, it can be oberved that wind/Pv/grid system is feasible
2
only when the solar irradiation is above 5.2kWh/m /d giving an optimal solution.From the
Fig.9 it can also be concluded that as the amount of integration of wind and solar generations
increases in to the grid there is a proportionate decrease in the total operating cost of the
system resulting a feasible solution for a hybrid power system.

Fig. 9 Sensitivity results using optimal system type

Fig.10 depicts the relation between the renewable fraction and the wind speed. As the wind
speed in the line graph increases from 6.0 m/sec to 8.0 m/sec there is a gradual rise in the
renewable fraction from 0.81 to 0.91 whereas there is a sharp decrease in levelized cost of
energy from 0.24 to 0.16 giving an optimum solution.

Fig. 10 Relation between renewable fraction and COE with wind speed

CONCLUSION
This paper mainly focuses on the Economic and Environmental Analysis of Hybrid Power
System for a Semi-arid Region. A Hybrid model is developed with storage for Kilmore Gap
location, North Central Victoria to identify the best available renewable energy resource in the
selected location. A comparison is made among different configurations and it is observed
wind/grid system is more feasible followed by wind/PV/grid connected systems due to the

968

maximum wind probability. Hence, wind generation is more promising in this location due to
the surplus availability of wind sources. From the optimization results, it is clearly evident that
integration of energy storage increases renewable fraction in to the grid resulting an optimum
and feasible solution. This fundamental study can be used by the utilities to facilitate largescale renewable energy integration into the grid. This study is still in its preliminary phase,
and further investigations are required in the following areas:

Research study can be extended using other residential and Industrial loads to
conserve energy generation.
More analysis with a larger volume of data considering transmission, distribution and
other socio-environmental factors

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[14]
[15]
[16]
[17]
[18]
[19]
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sources and integrating challenges in Victoria, Australia," in Power Engineering Conference
(AUPEC), 2013 Australasian Universities, 2013, pp. 1-6.
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government of Australia, vol. Victorian Climate Change White Paper - The Action Plan July
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T. Ackermann, Wind power in power systems vol. 140: Wiley Online Library, 2005.
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renewable energy systems," Renewable and Sustainable Energy Reviews, vol. 13, pp. 21112118, 2009.
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energy supply options for a large hotel," Renewable energy, vol. 33, pp. 1475-1490, 2008.
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renewable energya feasibility study in the Australian context," Renewable Energy, vol. 39,
pp. 183-197, 2012.

969

RENEWABLE ENERGY REGULATORY POLICIES IN CHINA BASED ON SYSTEM

DYNAMICS
Rui Wu, Yongxiu He
School of Economics and Management, North China Electric Power University, Beijing, 102206, China
E-mail: wurui0208@sina.cn

ABSTRACT
Along with global warming and the frequency of extreme weather, the worlds economy and energy
development faces severe challenges. Therefore, renewable energy has become an important
national choice to resolve environmental pollution and achieve sustainable development. Clarifying
the impact of renewable energy regulatory policies to electricity market operation and the relationship
among market bodies, is not only important to the further improvement of regulatory framework, but
also to the renewable energy development. This article establishes electricity supply subsystem,
energy conservation and social benefit subsystem under the complex generation structure. Taking
economic regulation, social regulation, antitrust regulation and other factors into consideration, it
simulates Chinas annual renewable energy market operation based on system dynamics from 2013
to 2030. The results show that Chinas existing renewable energy regulatory system is lack of market
adjustment mechanism and it just focuses on the regulation of corporate behavior on grid companies
that neglect other market players involved. Although it stimulated the development of renewable
energy to some certain extent, the economic regulation on the grid companies is inadequate in
incentives. This article proposes that China should take comprehensive consideration of renewable
energy development stages, electricity market trading mechanisms and other factors on electricity
regulatory requirements, actively explore suitable energy regulatory system mode for different period
of renewable development.
Keywords: System dynamics; Renewable energy; Complex generation structure; Electricity
market; Electricity regulation.
1 INTRODUCTION
At present, effective market regulation and policy support are important means to promote the
development of renewable energy in China. In-depth study of the existing regulatory policies for
renewable energy electricity market has significance to further improve the regulatory framework,
promote renewable energy development and realize the target of energy-saving emission reduction.
System dynamics was first produced by Professor Forrester in the 1950s. The SD model run by
analyzing the feedback loop structure behind the behavior, creating a system dynamic model
changing the state value of related variables in the structure, and then understanding the different
behavior of different strategies to accomplish optimization strategy. It is fit for policy analysis and
decision studies (Wang Q.F. et al., 2012). Since the 1990s, SD was gradually introduced into energy
power system and had a great advantage in the research of policy.
Zeng M. et al. (2012) studied the situation of electricity market supply and demand under the
condition of large-scale new energy grid-connected by developed a system dynamic(SD)model. He
in-depth analyzed the change of market bodies interest and verified the effectiveness of SD. Dai W.H
(2011) established a system dynamics model to study the harmonious development between rural
renewable energy, economy and ecological environment. She pointed out that the development of
renewable energy in rural areas has a significant effect on energy structure optimization, environment
protection, economic development promoting. Wang W. (2006) used SD method for transmission
price regulation applied research and intuitively displayed the advantages and disadvantages of
different regulatory methods. Andre Pina.et al. (2011) established a long-term policy dynamics
analysis model based on hourly electricity supply and demand, and pointing out that temporal
resolution modeling with high accuracy is important to improve efficiency and avoid invalid
investment. Hassan Qudrat-Ullah.et al. (2010) verified construct validity in dynamics policy analysis
modeling by way of exampling, noting that the construct validity tests may help to improve the overall
SD-type simulation model validity.
System dynamics simulation in policy has significant advantages. However, little research was on
power regulatory policy used by SD at present. This article applied SD method to the analysis of
renewable energy power regulatory policy, and simulating the electricity market operation under the
existing conditions of renewable energy regulation in China. Article is divided into the following parts:

970

1) Existing conditions of renewable energy market regulation in China was simply described;
2) Model of renewable energy grid-connected system was established based on CAS theory;
3) The effects of existing regulatory policy on electric market operation were quantitative analyzed;
4) Suggestions to perfect renewable energy regulatory were proposed based on research, hoping to
cause concerns of theorists and practitioners.
2 The current condition of renewable energy market regulation system in China
China has initially established the renewable energy regulatory system aiming at creating a
favourable market environment. Renewable Energy Law, Electricity Regulatory Ordinance,
Renewable Energy Prices and Cost-sharing Management Pilot Scheme ,Grid Enterprises
Purchase Renewable Electricity Regulatory Approach were the main legal basis for the current
renewable energy regulatory system. It covers renewable energy consumption and grid-connected
condition, power dispatching, electrical safety, energy conservation, etc. As shown in Fig.1.

Renewable Energy Law

Electricity Regulatory Related Documents

Electricity Regulatory Ordinance

Renewable Energy Power Regulation System

consumptive & grid-connected

Renewable
Renewable

Acquisition and settlement

power dispatching

energy generation

Priority

projects access condition

energy generators

scheduling situation of

The condition of grid enterprises

Purchase

renewable

energy

power grid electricity

renewable energy

Renewable energy grid security

Grid-connected conditions

Renewable Energy Prices and Costsharing Management Pilot Scheme",

"Grid Enterprises Purchase Renewable
Electricity Regulatory Approach etc.

Renewable

Data Retention

Record and preserve the case of

renewable energy information

energy electricity

settlement condition

operation

to provide service

Fig.1. Chinas Renewable Energy Electricity Regulatory System

3 Dynamic Tariff System Flow Diagram of renewable Energy markets

The interaction and mutual feedback among electricity market bodies constitute the complex causality
loop under the existing regulatory system, shown in Fig 2.

971

Electricity price+
+
Generating
capacity

Electricity
demand
-

Installed capacity of
renewable energy

Price elasticity of
electricitydemand

+
Thermal power
generation

Installed capacity
+
Technological advances
of power generation

+
Environmental
protection policies

Investment gains
+

+
Expected revenue of
new installed capacity
+
Electricity demand
growth
long-term marginal costs
of grid-connection

Investment in
power-grid construction

Renewable energy
power generation +

Fig.2. Causal Loop Diagram of electricity market in China

In order to clearly describe the complex operation of electricity market under existing renewable
energy regulatory system, three subsystems are established and various kinds of policy scenarios are
carried out to reflect the main quantitative and qualitative relationships between market bodies and
existing regulatory policy.

Variable

Table1. Main variable explanation

Variabl
Variable Explanation
e

Variable Explanation

Qdemand

Electricity demand in the internal and

external markets

Qprovide,1

Electricity demand in internal market

Qp , water

Hydroelectric power generation

Qp , wind

Total amount of wind power generation

Qp , fire

total amount of thermal power

generation

Qp , wind ,0 Wind power generation caused by the

internal electricity market

hwater

Hydropower generation Hours

Qp , wind ,1 Wind power generation caused by the

ICwater

Hydroelectric generating capacity

Qp , fire0

Thermal power generation cuased by

internal market demands

Vp , water

Output Coefficient of hydropower

unit

Qp , fire,1

Thermal power generation cuased by

external market demands

Qprovide,0 The total demand of electricity power

Qprovide

external market demands

in internal market

IC fire,4

Generating capacity of thermal power

unit 1#
Generating capacity of thermal power
unit 2#
Generating capacity of thermal power
unit 3#
Generating capacity of thermal power
unit 4#

IC fire, h

Generating capacity of heat supply unit

IC fire,1
IC fire,2
IC fire,3

V fire,1
V fire,2

Gross generation

Qp ,e

h fire,4

Generation hours of
unit 1#
Generation hours of
unit 2#
Generation hours of
unit 3#
Generation hours of
unit 4#

h fire,h

Generation hours of heat supply unit

h fire,1
h fire,2
h fire,3

Output coefficient of thermal power

unit 1#
Output coefficient of thermal power
unit 2#

f wind

972

Solar power generation

thermal power
thermal power
thermal power
thermal power

The proportion of wind power in

Bundled Wind & Fire

V fire,4

Output coefficient of thermal power

unit 3#
Output coefficient of thermal power
unit 4#

V fire, h

Output coefficient of heat supply unit

V fire,3

f fire

The proportion of thermal power in

Bundled Wind & Fire

Cc

Environmental pollution costs

Vsocial

Community environmental benefits of

Renewable energy

N co2

Total emission of CO2

N so2

N Nox

Total emission of NOx

N fenchen

Cco2

Environmental cost of unit CO2

CNox

Environmental cost of unit NOx

Vco2

Environmental value of reduce unit CO2

VNox

Environmental value of reduce unit

NOx

N co2 ,1

CO2 emission of 1# thermal power unit

N co2 ,2

N co2 ,3

CO2 emission of 3# thermal power unit

N co2 ,4

N co2 ,h

CO2 emission of heat supply unit

Vco2 , j

Pfire

Generation price of thermal power

Cwin d

C fire

Generating cost of thermal power

Pw

Cwind0

Initial generating cost of wind power

C fire0

Generating technology progress

multiplier of wind power

Initial generating cost of thermal

power

Rwin d

Unit electricity profits of wind power

Unit electricity profits of thermal power

Subwind

Unit electricity subsidy of wind power

Taxwind

Unit electricity tax of wind power

Taxnew,win d

Combined tax rate of wind power

Pwater

Generation price of hydropower

Taxnew,e

Combined tax rate of solar power

Cwater

Generating cost of hydropower

Taxwind

Wind power tax rate

Pwin d

Generation price of wind

Techwind

R fire

Sp

Cso2
C fenchen
Vso2

V fenchen

PS

Producer surplus

PSale

Total emission of SO2

Total emission of fenchen
Environmental cost of unit SO2
Environmental cost of unit fenchen
Environmental value of reduce unit
SO2
Environmental value of reduce unit
fenchen
CO2 emission of 2# thermal power
unit
CO2 emission of 4# thermal power
unit
Emission factor of thermal power unit
Generating cost of wind power
Purchase electricity price

The average purchase price

The average sale price

3.1 Power supply and demand balance model

In power supply and demand balance model, power supply is determined by power demand. The
total power demand is consist of power demand of the first, second and tertiary industries, residential
power demand and the emerging use of energy users. The total power supply is the sum of the
thermal power, hydropower, wind power and total outsourcing power.

973

<Time>

Total supply of
thermal power

Factor table for installed

hydro power capacity

Installed hydro
power capacity

Total supply of
hydro power

Hydropower
utilization hours

Installed wind
power capacity

Factor table for <Time>

hydropower utilization
<Time>
hours
Factor table for installed
wind power capacity

Proportion of thermal power

supply compared to
outsourcing power
Total
outsourcing
power

Total supply of
wind power
Wind power
utilization hours
<Time>

<Total power consumption of

third industry after factor
changes>
<Total power consumption
of residents after factor
changes>
Total electricity
demand after
<Total power consumption of
factor changes
secendary industry after factor
changes>

Total power
supply

<Total power consumption of

primary industry after factor
changes>

Factor table for wind

power utilization hours

Fig.3. Electricity supply and demand balance subsystem

Compared with the installed capacity of wind power, solar power installed capacity is relatively small.
To simplify the testing model, we default solar energy doesnt exist "disposable light" phenomenon
that can be consumed completely in the market.
Main equations of the system are as follows:

Qprovide Qdemand

Qp, wind Qp , wind ,0 Qp , wind ,1

Qp, water =hwater ICwater Vp , wind

3
4

Qp , fire,0 =IC fire, h h fire, h V fire, h IC fire, i h fire, i V fire, i

Qp,wind ,0 Qprovide,0 Qp , fire,0 Qp , water Qp ,e

Qp,wind ,1 Qprovide,1 f wind

Qp, fire,1 Qprovide,1 f fire

Qp, fire Qp, fire0 +Qp, fire1

i 1

3.2 Energy conservation and emission reduction subsystem

On one side, Energy conservation and emission reduction subsystem simulates pollution emission
condition in different scheduling models. On the other side, this subsystem aims to reflect the
pollution emissions reduction effect due to replacing fuel energy with electricity power (especially
clean energy power). Through environmental policies, the subsystem adjusts the energy generation
structure, reduces coal energy generation, increases clean energy generation, inhibits pollution
emissions.

974

Environmental
Environmental
Environmental Environmental
value of reduce
value of reduce value of reduce value of reduce
unit fenchen
unit CO2
unit SO2
unit NOx
CO2 emissions reduction
caused by the alternation of
Environmental
Environmental
Environmental
renewable energy power
cost of unit governance costs
cost of unit
Community environmental
Environmental
<CO2 emission of
SO2
CO2
benefits of Renewable
cost of unit
SO2 emissions reduction
thermal power unit>
NOx
energy
caused by the alternation of
<total amount of thermal
renewable energy power
Environmental cost Environmental
power generation>
Social costs
<SO2 emission of
pollution costs
of unit fenchen
Toner dust emissions from
environmental
NOx emissions reduction thermal power unit>
<Desulfurization
coal-fired power renewable energy
pollution
caused by the alternation of
costs>
<Total emission
alternative power reduction
renewable energy power
<NOx emission of
<Total
emission
<Denitration
of CO2>
thermal power unit>
of fenchen>
costs>
Renewable energy
Solar power
<Total emission <Total emission
<Cost of CCS>
power generation
<Average emissions
generation
of NOx>
of SO2>
of Toner dust> <Total amount of wind
power generation>

Fig.4. Energy conservation and emission reduction subsystem

Main equations of the subsystem are listed below:

Nco2 Nco2 ,1 Nco2 ,2 Nco2 ,3 Nco2 ,4 Nco2 ,5

Nco2 ,i Q provide ,i Vco2 ,i

10

Cc =Cco2 Nco2 Cso2 Nso2 CNox N Nox C fenchen N fenchen

11

Vsocial =(Vco2 Vso2 VNox V fenchen ) (Qprovide,wind Qprovide,e )

12

3.3 Social benefits subsystem

Social benefits subsystem includes producer surplus subsystem and consumer surplus subsystem.
However, we just take producer surplus situation into condition for consumer surplus have no
incremental impact on social benefits. Producer surplus subsystem describes social benefits
conditions of different types of power generation and grid enterprises.
Generating technology
<Wind power
learning indices
generating capacity> Unit electricity profits
Transmission
ofhydropower
Initial generating cost
incremental costs
Hydro
generation
of wind power
Generating technology progress
Electricity tax
multiplier of wind power
Unit electricity profits
of wind power

Generating cost of
Generating cost of hydropower
wind power

<Hydroelectric
power generation>

<Hydroelectric
power generation>
Purchase
electricity price
<Generation price of
hydropower>

Unit electricity tax of

The average
Combined tax rate
<Total amount of wind Generation price of
The average sale
wind power
<Total purchased
purchase price
Generation price power generation>
of wind power
hydropower
price
power>
of wind
Unit electricity subsidy
Incremental
Producer surplus
of
wind
power
costs
of hydropower
<Desulfurization
Producer surplus
<Generation price
Unit electricity
Generation price of
companies
of wind power
Unit electricity profits
costs>
companies
of wind>
profit
thermal
power
of thermal power
Producer surplus
<Denitration
of Power-grid
<Unit electricity subsidy
Producer surplus
enterprises
<total amount of thermal
costs>
Producer surplus
of wind power>
Generating cost of of themal power
power generation>
companies
electricity subsidy
thermal power
<Cost Unit
of CCS>
<Total amount of wind
of thermal power
Producer surplus
<Generation price of power generation>
of solar energy
<total amount of thermal
companies <Electricity demand in thermal power>
Desulfurization
Denitration costs
internal market>
power generation>
costs
Cost of CCS

Fig.5. Social benefits subsystem

Main equations of the subsystem are listed below:

Cwind =Cwind0 Techwind

13

Pwind Cwind Rwin d Taxwind Subwind

14

Taxwind =Rwin d Taxnew,wind (Cwind Rwind ) Taxwind

15

975

Swater ( Pwater Cwater ) Qprovide,water

16

Swind ( Pwind Cwind ) Qp,wind

17

Se ( Pe Ce ) Qprovide,e

18

Sgrid ( PSale PS ) Qdemand

19

S p =Swater +S fire +Swind +Se Sgrid

20

4. CASE STUDY
Province A is rich in renewable energy resources, and wind energy resources can be developed is
about 40 million kW. Therefore, this paper takes it as an analysis example and three main modules
are analyzed.
Table 1. Province A generation structure from 2015 to 2030

Unit: ten thousand kW

Power Source

2015

2020

2030

Thermal power capacity

2200

2900

4500

Hydropower capacity

900

1200

1600

Wind power capacity

1300

2000

3000

Solar power generation capacity

120

200

300

Total installed capacity

4520

6300

9400

4.1 Simulation of renewable energy electricity market running

Power supply and demand indices of province A is fall in the level of 1.261-1.401 from year2015 to
2030.Overall, power supply is always in the state of excess.
In 2014, the maximum load of the whole provincial transfer system is 15.4 million kW
approximately, and wind power grid electricity is about 11.765 billion kWh.
From the perspective of power balance, its hard enough to consumer 15.4 million kW wind power
merely in the internal market.
From the perspective of electricity supply and demand balance, assuming taken internally
balanced approach. According to the simulation results, the annual utilization hours of thermal
power respectively is 4224, 4643.85 hours in 2013,2015 without taking renewable energy
generation into consideration. Reverse, the annual utilization hours of thermal power
respectively is 3848, 3510.45 hours in 2013, 2015.
4.2 Economic regulatory policy Simulation
The impacts of economic regulatory policy on the electricity market mainly reflect in social benefits
subsystem module. It works through tariff policy, subsidy policy, tax policy, etc.

976

Producer
surplus

20

10
0

1
3

2
4

2
4

3
2

3
2

3
2

2
3

2
3

2
3

2
1
4

4
1

-10

1
1

-20
2011 2013 2015 2017 2019 2021 2023 2025 2027 2029
Time (Year)

:
1
1
1
1
1
1
1
1
Power grid
enterprises
Renewable
energy
enterprises

:generation

2
2
2
2
2
2
Hydropower
enterprises

: 3
3
3
3
3
3
3
3
Thermal
power
enterprises
: 4
4
4
4
4
4
4
4

Fig.6 producer surplus of electricity market body

According to the simulation results, the total social producer surplus declined with large-scale
renewable energy grid-connected. Social producer surplus of year 2015 is approximately 2.156 billion
RMB in total, of which thermal power, hydropower, renewable energy, power-grid enterprises
producer surplus respectively is -1.48, 10.12, 5.84, 7.08 billion RMB.
(1)Producer surplus of power grid enterprises
Along with the increasing of renewable energy percentage, producer surplus of power grid
enterprises is on the state of decline, shown in Figure 6. The main reason for this phenomenon is the
government merely setting subsidy subject to grid connection, and the current subsidy standards for
grid connection is insufficient to cover the funds grid enterprises invested to promote renewable
energy power in China.
(2)Producer surplus of renewable energy power companies
As shown in Figure 6, the producer surplus of renewable energy power companies keep rising under
the condition of the existing tariff, the new energy price subsidies and tax incentives.

Producer surplus of wind power companies

With the development of renewable energy generating technology, wind power generating
cost will drop. According to the simulation results, wind power electricity cost is about 0.265
yuan/kWh in 2015. Total producer surplus of renewable energy power companies have an
increasing trend, and the producer surplus of wind power companies is approximately 2.943
billion yuan in 2015, year2020 to 2030 it will accumulate 128.485 billion yuan.

Producer surplus of solar power companies

According to simulation, solar power electricity net profit has a trend to rise, and the
generating cost is about 0.865 yuan/kWh in 2015. Total producer surplus is about 1.43 billion
yuan in 2015, year2020 to 2030 it will accumulate 25.485 billion yuan.

(3)Producer surplus of hydropower companies

Producer surplus of hydropower companies also have a trend to rise, but the speed is much slower
compared with renewable energy generation companies. The main reason is hydropower generating
technology in China already has developed to a mature stage, the cost reduce will not obvious.

977

(4)Producer surplus of thermal power companies

As shown in figure 6, thermal power companies will have a decline in the total producer surplus. On
one side, the government will rise environmental requirements, so that thermal power companies
have to increase the technological input. On the other side, financial subsidies for desulfurization,
denitrification is inefficient to ensure the recovery of funds. In addition, the rapid development of
renewable energy squeezed the thermal power enterprise's market share to a certain extent.
4.3 Social regulatory policy simulation
Social regulation policy simulation is to analyze the effect of the implementation of "Three
Scheduling" and energy saving policies under background of large-scale renewable energy gridconnection market. In order to fully study the impact social regulation policies on electricity market
operation and environment, this paper set two scenarios to compare and analyze: traditional
scheduling and energy-efficient scheduling.
Traditional Scheduling (TS): Scheduling priority in upholding the principle of renewable energy, all
thermal power unit scheduled in accordance with the same number of hours.
Energy-efficient Scheduling (EES): Scheduling priority in upholding the principle of renewable energy,
according to the thermal power unit capacity for hierarchical scheduler.
(1) Impacts on the electricity market operation
The total
thermal power generation
Ten thousand kwh

10 M
7.5 M
1
2

5M

1
2

1
2

1
2

1
2

1
2

2
1

2
1

2
1

2.5 M
0
2011 2013 2015 2017 2019 2021 2023 2025 2027 2029
Time (Year)

Traditional
dispatching
:

Energy-efficient
: scheduling
2

1
2

1
2

1
2

1
2

1
2

1
2

1
2

1
2

1
2

The total wind

power

generation

Ten
thousand
kwh

6M
1

4.5 M
1

2
1

1
2

1
2

3M
1.5 M

2
1
2
1

1
2
1

2
1
2
1

2
1
1

0
2011 2013 2015 2017 2019 2021 2023 2025 2027 2029
Time (Year)

:
1
1
1
1
1
1
1
1
1
1
Traditional
dispatching
:
2 2 2 2 2 2 2 2 2 2
Energy-efficient
scheduling

Fig.7. (a) The total thermal power generation; (b) The total wind power generation

978

The total thermal power generation is decreased and renewable energy generation is increased
under the energy-efficient scheduling (Shown in Fig.7). Year2013 to 2015, the cumulative wind power
generating capacity increased 10.023 GWh, annually increased utilization hours is about 117.94.
(2) Impacts on environment

Environmental
pollution costs
4M

3.5 M
3M
2.5 M

1
2

1
2

1
2

1
2

1
2

1
2

1
2

1
2

2M
2011 2013 2015 2017 2019 2021 2023 2025 2027 2029
Time (Year)

Traditional
scheduling:

:
Energy-efficient
scheduling:
: 2

1
2

1
2

1
2

1
2

1
2

1
2

1
2

1
2

Fig.8. Environment pollution costs

Compared with traditional scheduling, the social cost of environmental pollution is reduced under
energy-saving scheduling, and the various pollutant emissions have a notable decrease.
4.4 Antitrust regulatory policy simulation
The calculation shows the proportion of renewable energy generation increased significantly from
year 2015 to 2030. Concretely, the renewable energy power generation increased about 24.5%, the
proportion is average increased 4.62% and electricity utilization hour has an average increase of 602.
4.5 RESULTS AND DISCUSSION
The main reasons for electricity oversupply in province A maybe belongs to the following situations:

The uncoordinated planning of power source and power-grid causing a bottleneck for
renewable energy power consumption.

The complexity of approval procedure has delayed the establishment of transmission

channel, and it is not conducive to renewable energy power configuration in a wider range.

Seen from economic regulatory policy simulation, under the condition of the existing tariff policies,
new energy tax and subsidy policies, renewable energy companies are able to achieve better social
benefits. However, the producer surplus of thermal power plants and power-grid companies is
decreased. Therefore, the government should make an appropriate adjustment ensure renewable
energy policies enable to mobilize the productive enthusiasm of them.
Seen from social regulatory policy simulation, energy-efficient scheduling has a big significance to the
social sustainable development. On one hand, it increases the amount of renewable energy to
promote its consumption. On the other hand, it reduces the thermal pollution to some extent and in
favor of energy reduction targets to realize.
Antitrust regulatory policy simulation shows that the implementation of Renewable portfolio Standard
(RPS) is significant to improve the renewable energy generation promotion, and plays a role in the
consumption of renewable energy power. China should step up research on RPS solutions to
promote renewable energy power configuration in a larger range.
4 CONCLUSIONS

979

This article constructs renewable energy grid-connection analysis model based on the theory of SD.
This model has applicability to stimulate electricity markets in different countries, regions and
developing stages. In addition, this article introduces SD approach into renewable energy electricity
regulatory policy studies. The regulation policies were simulated to study the impacts on electricity
market. The study found that although Chinas economic policies have promoted the development of
renewable energy market, it lacks an overall policy to run the whole concept of systemic regulation
and market adjustment mechanisms. To promote the healthy development of Chinas renewable
energy, a new regulatory policy system that adapting to market mechanisms should be established.
ACKNOWLEDGEMENT
The work described in this paper was supported by the National Natural Science Foundation of China
(Grant No. 71273089) and Beijing Natural Science Foundation of China (Grant No.9122022).
REFERENCES
[1]Wang QF. System Dynamics. Beijing: Tsinghua University Press; 1998:1-6.
[2]Li C, Zhou LS, Zeng M. New energy grid-connection and simulation of electricity markets based
on SD model. East China Electric Power 2012; 40:1676 -1679.
[3]Dai WH. Simulation of Renewable energy development based on system dynamics. Computer
Age 2011; 9:1 -3.
[4]Wang W, Zhang LZ, Cheng Y. Study of transmission price regulation based on system
dynamics. Electric Power System Protection and Control 2009; 37 (3):11-15.
[5]Pina A, Silva C, Ferrao P. Modeling hourly electricity dynamics for policy making in long-term
scenarios. Energy Policy 2011; 39:4692-4702.
[6]Qudrat-Ullah H, Seong BS. How to do structural validity of a system dynamics type simulation
model: The case of an energy policy model. Energy Policy 2010; 38:2216-2224.

980

OPTIMIZATION OF NEURAL NETWORK FOR A BIOMASS-FIRED BOILER STEAM

SYSTEM USING IMPROVED IMMUNE ALGORITHM
1,2

Xi Chen , Guangcai Gong

1, *

, Chenguang Wang , Xinshu Zhang , Siyue Gong

(1. College of Civil Engineering, Hunan Univ., Changsha 410082, China;

2. College of Information & Communication Engineering, Hunan Institute of Science and Technology,
Yueyang 414006, China)
E-mail: gcgong@hnu.edu.cn

ABSTRACT
This work focuses on the modelling of 14t/h small-scale biomass-fired boiler steam system based
on Neural Network (NN) and an improved immune algorithm is proposed to optimize the weight and
threshold values of the net. A steam NN prediction model is created according to the boiler running
data including feed rate, air pressure in wind chamber, steam flow, steam pressure. An Improved
Immune Algorithm (IIA) is employed to optimize the NN-model reducing prediction error. According to
the IIA, both antigen-antibody affinity and antibody concentration are taken to be the indexes
evaluating the expected reproductive probability (ERP) of individual. Furthermore, the influence
proportion from the two during the whole evolution stages is taken into account. A novel adjustment
factor (AF) is raised to regulate the influences proportion on ERP. By the computation based on IIA,
the optimal weight and threshold values of NN are obtained. Simulating models based on NN and
IIA-NN respectively, the results indicate that the later is more accurate than the former. The average
relative errors of steam pressure and steam flow reduce 3.69% and 5.24%, mean squared errors
(MSE) reduce 0.0206 and 0.4989 as well. Moreover, in comparison of IA, the success rate of
convergence, efficiency and optimal fitness based on IIA are much higher.
Keywords: biomass-fired boiler; steam system; Neural Network; Improved Immune Algorithm

981

INTRODUCTION
Recently, as a novel green power, small scaled biomass-fired boiler possessing high combustion
efficiency, great fuel flexibility, low emissions and rapid load change ability gained wide popularity in
heating system for steam production. Boiler steam system parameters influencing directly on
production efficiency is very important. On account of variety of biomass fuel and uncertainty in
combustion progress, it is a hard job to create a precise model for boiler steam system with nonlinear,
time-varying and multivariable-coupling characteristics by traditional methods.
In view of the problem illustrated above, the Artificial Intelligence (AI) is widely used in system
modeling and optimization. P. Ilamathi [1] created a model for unburned carbon in coal-fired boiler by
NN. J. Ma [2] proposed an optimal model of super-heater in coal fired power plant using Genetic
Algorithm (GA) and NN. The simulation results show the steady state error of superheated steam
temperature is reduced. A. Garg [3] presented a NN-model for natural circulation boiling water reactor.
Lately, Immune Algorithm (IA) became more and more popular in modeling and optimization as well. Y.
Gao [4] raised an immune genetic algorithm based neural net work model for flood disaster evaluation.
X. Chen [5] raised an industrial robot path planning method based on IA. G.L. Yuan [6] optimized the
PID parameters for boiler steam system using immune vaccine algorithm.
In this work, the prediction model of small scaled biomass-fired boiler steam system using
artificial neural network is given. An improved immune algorithm is proposed to optimize the
connected weight and threshold values of neural network. The prediction results between NN model
and IA-NN model are analyzed. The performances of classical IA and IIA are demonstrated.
1.

STUDY OBJECT
In this paper, the study project is a 14t/h small scaled biomass-fired boiler located in Zhuhai

City Guangdong Province. Fig.1 shows the external structure of it. During the test period, the boiler
run steadily, all the parameters shown in Table.1 kept in prescriptive ranges, no pollution blow-off and
no relief valves shut off. The biomass fuel is shown in Fig.2, the size and geometrical shape are
shown in Fig.3. The fuel composition and parameters are presented in Table2.

Fig.1. External structure

Fig.2. Biomass fuel

Fig.3. Geometrical

shape

Table1 Biomass Boiler main running parameter

Drum
pressure
MPa

Feed pressure
MPa

Feed

Steam

Exhaust gas

Excess air

Counter balance

temperature

mass flow

temperature

coefficient

thermal efficiency

()

t/h

()

982

(%)

0.91

1.30

94.7

13.98

119.7

1.4

88.99

Table2 Fuel composition and parameters

Fuel composition

Received basis net calorific value

Ash percentage%

kJ/kg

Sawdust

Mushroom dreg

15716

0.79

One months running data of boiler steam system is collected. The data is recorded every hour,
thus 24 groups data are recorded in a day. Totally, after being processed, 431 groups of data
available are obtained. Take one days data for example as is given in Table3.
Table3 Running data of boiler steam system
Time

Feed rate(t/h)

Air pressure in wind chamber (Pa)

Steam pressure (MPa)

Steam mass flow(t/h)

0:30

3.24

2330

14

1:30

3.024

2330

0.99

14

2:30

3.528

2420

0.93

16

3:30

3.348

2410

0.91

15

4:30

3.24

2300

0.9

15

5:30

3.24

2400

16

6:30

3.096

2410

0.95

13

7:30

2.736

2360

0.93

10

8:30

3.24

2420

0.91

12

9:30

3.24

2400

13

10:30

3.276

2400

0.97

14

11:30

3.6

2400

0.9

14

12:30

3.6

2400

0.97

14

13:30

3.6

2390

0.96

14

14:30

3.6

2400

0.9

15

15:30

3.78

2420

0.92

13

16:30

3.852

2410

0.89

14

17:30

3.96

2400

0.94

13

18:30

3.96

2400

0.98

12

19:30

3.96

2400

0.96

15

20:30

3.24

2440

0.96

15

21:30

3.24

2420

0.99

16

22:30

3.24

2480

0.96

16

23:30

3.24

2470

0.98

14

2.

DESIGNE OF IIA-NN

2.1 BP-NN
In accordance of the data collected, the inputs and outputs of steam system are established.
The input variables are feed rate and air pressure in wind chamber, outputs variables are steam
pressure and steam mass flow. In view of the empirical formula determining the number of hidden

983

note, 2-6-2 structure BP-NN is employed. In other words, there are one input layer (two nodes), one
hidden layer (six nodes), one output layer (two nodes). Fig.4 shows the topological structure of it. In
details, X 1 ,

X2

are the inputs and Y1 ,

Y2 are the outputs, ij and jk

represent the connected

weight between nodes of each layer. The BP-NN can be considered a nonlinear function, where
inputs and outputs are independent and dependent values.

X1

ij

Y1

jk

X2

Y2

Input layer

Hidden layer

Output layer

Fig.4 Neural network topological structure

2.2 Improved Immune Algorithm

Immune Algorithm is a novel optimization method able of overcoming the prematurity in
ordinary optimization, especially in optimization of multimodal function, using diversity in individual
generation and maintenance mechanism of immune system. In ordinary immune algorithm, both
antigen-antibody affinity and antibody concentration are taken to be the indexes evaluating the
expected reproductive probability (ERP) of individual. Because of the influence proportion from the
two is constant, it is possible that some excellent individuals generated during the whole evolution
steps will be lost. Consequently it is possible that the optimal solution will be missing, and the
algorithm convergence efficiency may be reduced. In this paper, an improved immune algorithm
(IIA) is proposed. In order to take the influences on ERP from the two illustrated before into account
respectively and preferentially in earlier and later evolution steps, an adjustment factor (AF) is
designed to raise the ERP of excellent individuals. The demonstration of IIA is as follows:
Step1. Analyse problem. Design proper expression for solution based on the analysis of problem
and solution characteristics.
Step2. Initialize the IIA parameter antibody population. Generate the initial population including

individuals created randomly and m individuals extracted from the memorial library.
Step3. Evaluate the individuals. Take the ERP as the index evaluating the individual.
Step4. Generate father population. List the initial population according to ERP in descending order,
and extract the top

N individuals as father population; similarly, save top m individuals in

memorial library.
Step5. Judge the end condition is reached or not. If yes, end computation; otherwise, continue next
step.
Step6. Generate novel population. According to the computation result of step4, take selection,
crossover, mutation operations on antibody population, get a new individual group. Add memorial
individuals saved from the memorial library to the new group, thus a novel generation is obtained.

984

Step7. Turn to Step3.

The generation of initial population:
If the memorial library is non-null, the initial population is generated on the basis of memorial
library, otherwise, generated from the feasible solution space randomly. All of the individuals is
coded in real number, and composed of four sections as follows: connected weights of input layer
and hidden layer nodes, thresholds of hidden layer nodes, connected weights of hidden layer and
output layer nodes, thresholds of input layer nodes. On account of the 2-6-2 structure of NN, the
length of individual is 32. Consequently, every individual includes 24 connected weights and 8
thresholds.
The solution diversity evaluation:
(1) Antibody-antigen affinity
The antibody-antigen affinity

Av

represents the ability of antibody to eliminate the antigen, in

this paper, it equal to individual fitness function Fv . The sum of the absolute values of error between
predicted and expected outputs of NN is served as the objective function Ev . The relationship
among the three is as follows:

Fv Av

1
Ev

(1)

where Fv is the individual fitness function,

Av is

the antibody-antigen affinity,

Ev is

the objective

function.

The antibody-antigen affinity

Av

can be expressed as:

Av

1
1 y1 o1 2 y2 o2

where

yi is the expected output of the i th node. oi is the predicted output of the i th node; 1 and

2 are constant.
(2) Antibody-antibody affinity
The antibody-antibody affinity

S v ,s

represents the similarity of antibodies. In this paper, the

location contiguous approach raised by S. Forrest [7] is employed to calculate the S v ,s . In fact, the
approach is a partial matching rule. The key is to establish the value of

able of representing the

threshold to judge affinity. If the number of match locations between two individual codes is R or
lager than R , the relationship of them can be judged as similarity. Otherwise, they are different. The
antibody-antibody affinity

S v ,s

can be described as:

985

S v,s

l v,s
L

(3)
where

lv , s

is the number of similar locations between antibody

v and s . L is the antibody length.

(3) Antibody concentration

The antibody concentration

Cv

is the proportion of similar antibodies in population. Formally:

Cv

1
N

N 1

s 1

Gv,s

(v s )

(4)
subject to:

1, S v,s T
G v,s
0, o t h e r
(5)

where N is the amount of antibody. T is the value of threshold set before.

(4) Expected reproduction probability(ERP)

Av and Cv . Formally:

The ERP of every individuals is determined by both

Cv

Av
(1 )e Cv
P
Av

(6)
where is a factor able of distributing the impact proportions on ERP between

Av and Cv .

According to eq.(6) the ERP of individual possessing higher fitness and lower concentration is
larger than others. In other word, the reproduction of individual with high fitness will be promoted,
while the one with high concentration will be suppressed. It is worth noting that with the progress of
algorithm, in the late evolution stage, the average fitness of individual is comparatively higher than
before. Thus the antibody concentrations influence proportion on ERP should be paid more
attention. Other than ordinary IA, in this work, the factor is defined as a variable, named
adjustment factor (AF). It can be illustrated as follows:

K1 e ( k K

2)

(7)
According to Fig.5, AF is reducing with the increasing of evolution generation k . In other
words, the individual ERP receives more influence from antibody-antigen affinity in the early
evolution stage, and more from antibody concentration in late evolution stage. Thus more excellent

986

individual can be obtained. On comparison with the ordinary IA, the convergence efficiency can be
increased and optimization result could be improved.

K1 e ( k K

2)

K1 e K2

K1

Fig.5 AF change with evolution generation

(5) Immune operation

Immune operation includes selection, crossover and mutation. In this paper, selection rate is
equal to ERP. The crossover and mutation operation is similar with GA [8-10], thus not discussed
here.
2.3 Immune optimization on NN
In view of ordinary NN modeling, the initial values of connected weight and node threshold are
obtained in the empirical approach or cut-and-trial method. Consequently, the NN convergence
efficiency and optimization result are usually not very well. In this paper, aiming at solving the
problems, the IIA illustrated above is employed to optimize the initial values of the network. The
IIA-NN algorithm flow chart is shown in Fig.6.

3.

SIMULATION RESULT

3.1 IIA-NN predicted result

The IIA parameter setting is as follows: the population size is 100, the evolution generation is
50, the crossover rate is 0.4, the mutation rate is 0.2. 1
as follows: K1

1 , 2 0.5 . The AF parameter setting is

0.4 , K 2 5.6 , 0.2 .Table.4 depicts the optimal result.

987

Part:Improved Immune Algorithm

Part: Neutral Network(NN)

Generate Initial
Antibody

Create NN Topological
Structure

Calculate Antibody
Affinity

Calculate Length of
Antibody
Generate
Memory Cell

End Condition
Achieved?

Obtain Optimal
Weight and Threshold

Calculate Error

Calculate Antibody
Affinity
Refresh Weight and
Threshold Value
Promotion and
Suppression on
Antibody Generating

N
End Condition
Achieved?

Selection Mutation
and Variation

Y
Output Result

Fig.6 IIA-NN algorithm flow chart

Table.4 Optimal initial values of connected weight and node threshold of IIA-NN
Connected weight of node between

Threshold of

Connected weight of node between

Threshold of

input layer and hidden layer

hidden layer node

hidden layer and output layer

output layer node

0.4326

1.5987

-2,8412

1.0791

-1.3354

2.9921

0.4821

0.9542

-2.5849

-1.4188

-0.8347

0.5613

1.7192

0.4832

1.9928

-2,1857

-0.9143

1.4391

1.7394

-1.6251

1.7482

0.6397

-2.8415

1.0312

0.2103

-0.8198

-1.0314

0.5849

-1.4024

0.7497

-0.5151

-2.7593

Moreover, the IIA-NN with optimal initial values of connected weight and node threshold is
trained by 431 groups of data. The data is divided into two parts including 351 groups training data

988

and 80 groups testing data. The testing data is employed to test the veracity of trained IIA-NN as
the prediction model. Fig.7 illustrates the simulation results. As is shown in Fig.7 (a) and (c), the
prediction result of steam pressure is perfect, and the maximum absolute error is less than 0.0416
MPa. According to Fig.7 (b) and (d), the prediction result of steam pressure is good, especially in
the prediction of 13 disturbance samples caused by fuel and uncertainty of combustion. While,
there are still some errors existed, through analysis, the main reason is the precision of test data of
steam mass flow is not precise enough. The precision of testing data is single digit, while the
prediction data is accurate to four decimal places. Therefore, the precision error cant be eliminated.

Comparison of Predicted and Experimental Steam Pressure

Comparison of Predicted and Experimental Steam Flow

15

Predicted
Experimental

Steam Flow(t/h)

Steam Pressure(MPa)

1.02

0.98
0.96
0.94
0.92

10

20

30

40

50

60

70

13
12
11
10

80

Predicted
Experimental

14

10

20

30

40

50

60

70

80

Samples
(a)

Samples
(b)

Absolute Error between Predicted and Experimental Steam Pressure

Absolute Error between Predicted and Experimental Steam Flow

1.5

Absolute Error(t/h)

Absolute Error(MPa)

0.06
0.04
0.02
0
-0.02
-0.04

10

20

30

40

50

60

70

1
0.5
0
-0.5
-1

80

10

20

30

Samples
(c)

40

50

60

70

80

Samples
(d)

Fig.7 prediction result and error

Training the predictive model based on ordinary NN with the same data, the predictive result
is compared with IIA-NN. Table.5 demonstrates that the performance of IIA-NN is better.
Table.5 Comparison of prediction errors based on IIA-NN and NN model
Steam

Prediction

Maximum

Maximum

Average relative error

Mean squared error

parameter

model

Absolute

relative

MSE

error

error

IIA-NN

0.041

3.92

1.92

0.0231

NN

0.074

7.45

5.61

0.0437

IIA-NN

1.296

9.25

4.73

0.6467

NN

2.261

14.494

10.16

1.1456

Pressure

Mass flow

Using the same data and parameter setting, simulate the optimizing progress 50 times based
on IIA and IA respectively, the results are listed in Fig.6. Apparently, using the IIA, the convergence
success rate, optimal individual fitness and convergence efficiency are higher. Moreover, the
time-consuming is less.

Table.6 Comparison of optimization based on IIA and IA

989

algorithm

Convergence

Average iteration times

frequency

4.

Average convergence

Average optimal

generation

fitness

IIA

49

0.096

20

76.7136

IA

46

0.121

33

68.8531

CONCLUSIONS
In this work, the novel modeling and optimization approach for prediction of biomass-fired

boiler steam parameters is proposed. IIA-NN was capable of learning the relationship between
inputs and outputs of steam system. The estimated outputs of the IIA-NN model agree well with the
experimental values. It offers an alternative for engineers to evaluate the effect of input disturbance
caused by fuel switching and air pressure variation. Although the IIA-NN does not give any
information about the mechanism that governs the simulated process, it may identify which input
variables may be significant for the process. In addition, the comparison result between IIA and IA
shows the former is more capable in neural network optimization. Future developments will focus
on the optimization of neural network using fuzzy rules combining with IIA.
NOMENCLATURE
AV antibody-antigen affinity
Fv

fitness function

Ev

objective function

Sv,s antibody-antibody affinity

Cv

antibody concentration

990

REFERENCE
[1] P. Ilamathi, V. Selladurai, K. Balamurugan, 2013, Modeling and Optimization of Unburned
Carbon in Coal-Fired Boiler Using Artificial Neural Network and Genetic Algorithm. Journal of
Energy Resources Technology 3: 145-150.
[2] J. Ma. Parameter Optimization of Boiler Steamwater System Model Based on Genetic
Algorithm and Artificial Neural Network [D]. Beijing: School of Energy, Power and Mechanical
Engineering, North China Electric Power University, 2009(in Chinese)
[3] A. Garg, P. S. Sastry, M. Pandey, 2007, Numerical simulation and artificial neural network
modeling of natural circulation boiling water reactor. Nuclear Engineering and Design 3:230-239.
[4] Y. Gao, Y. X. Chen, etc, 2006, Immune genetic algorithm based neural net work model for flood
disaster evaluation. Journal of Natural Disasters 1:110-114.
[5] X. Chen. Industrial robot path planning research based on immune algorithm [D].Hunan: School
of Information Technology and Engineering, Central South University, 2012(in Chinese)
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Control System Based on Immune Vaccine Algorithm. Journal of Chinese Society of Power
Engineering 4:285-289.
[7] S. Forrest, A. S. Perelson, 1994, Self-nonself Discrimination in a Computer. Research in
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Boston: Addison-Wesley Professional.
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Evolutionary Computation 2: 182 197.
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Application to a Coarse-Grained Model of RNA. Evolutionary Computation 3:147-152.

991

RESEARCH ON THE RELATIONSHIP BETWEEN SOLAR CELL POWER OUTPUT

AND THE THERMAL ENVIRONMENT WITH DIMENSIONLESS METHOD
*

Chenguang WANG

Guangcai GONG

Yingxing Wu

Xi Chen

College of Civil Engineering, Hunan University, Changsha, China

*

Corresponding email: gcgong@hnu.edu.cn

ABSTRACT
At present, most of the mathematical models of solar cell are mainly based on solid state physics
theory, and some other related researches are also based on this model. In this paper, a solar cell
power generation model is established from the viewpoint of energy balance using thermal physics
theory. Then, dimensionless method is derived to measure the correlation between solar cell power
output and thermal environment and a related non-dimensional formula is also given. At last, the
experimental data show that the none-dimensional formula possesses favorable commonality and
accuracy.
Keywords: solar cell, dimensionless method, heat transfer model
INTRODUCTION
As a kind of clean and renewable energy, the solar energy has been developed and applied widely.
Scholars all over the world have made expansion and a wealth of research on the characteristics of
solar cell. To study the characteristics of solar cell, most researchers prefer to study the
I-V characteristics of solar cell firstly, and then try to find out the output power characteristic curve.
Due to the typical physical meaning and the corresponding relations of process control, the
mathematical model of solar silicon cells has been widely recognized and applied by the majority of
researchers. By simplifying and analyzing the theoretical mathematical models, it would be easily to
carry out research on photovoltaic systems. M.K ADWI(M.K ADWI,2001) and many other
researchers(Z.Ouennoughi,2001;

M.Bashahu,1995;

Sharmat,1993;

EnginKiran,1999;

M.HaouariMerbah,2005; A.Ortiz-Conde,2006; V.Martinez,1998; A.Kaminski,1997) use the feature

points of three points provided by the manufacturer under STC(Standard Test Conditions) including
the short circuit point, open circuit point and the maximum power point to simultaneous solutions.
Then, they make some work such as omitting the shunt resistance and approximating the short
circuit current as photocurrent so as to simplify the current five-parameter equations as
three-parameter or two-parameter equations. In recent years, multi-purpose numerical fitting
methods are applied to determine the five parameters, such as the Monte Carlo method. But
because of the complexity of equations, the requirements of initial value is relatively higher and the
computation amount is relatively larger.
Meanwhile, many researchers have made a number of output characteristics models of solar cell
under different conditions of temperature and light intensity. King (King, D.L, 1998; King, D.L, 2000;
King, D.L, 2004) has proposed a model for predicting solar module output characteristics under
various conditions. Soto (De Soto W, 2006) has proposed a method which the output power could
be predicted only by the parameters provided by manufacturers. He assumes that the series
resistance doesnt change with temperature. However, the series resistance of the solar cell module

992

is strongly varies with the temperature (Jinlei Ding, 2005).

In this paper, a predictive model of solar cell output under different conditions of light and
temperature characteristics is proposed based on the five-parameter theoretic model and heat
transfer model. On the basis of this model, the application of non-dimensional analysis helps us to
derive solar dimensionless correlation battery output power and thermal environment parameters.
Thus it simplifies the tedious theoretical calculations and engineering applications. The
development of this method will be helpful to the photoelectric and photo-thermal integrated
application and design.

MODELS OF SOLAR CELLS

Structure model of solar cells

In this paper, our research object is a standard PV module which is made up of seven
layers of material including front glass panel, TPT layer, EVA layer, cell panel and back
panel, the structure of which is shown as Fig.1. The solar cell is placed surrounded with
the air and we just take it into consideration that the wind flows along the solar cell panel
parallel.

Fig.1. Sketch of the structure of solar cells

Five-parameter Theoretical Mathematical Model of Solar Cells

Fig.2 is the sketch of the equivalent circuit of solar cells. According to this sketch, an equation can
be conducted as Eq. (1). In this model, there are five parameters used to describe the I-V
characteristics of solar cells. They are IL, I0, Rs, Rsh and K1. This model has got been

extensively studied by researchers.

Fig.2. Sketch of the equivalent circuit of solar cells

993

Energy System Model of Solar Cells

According to the conservation of energy, there are the following equations as Eq. (2):

(2)
According to the sketch of the equivalent circuit of solar cells shown in Fig.2, it can be conducted the
following two equations as Eq. (3), Eq. (4):

(3)

(4)
For the solar cell, it also can be conducted the following equation shown as Eq. (5):

(5)
Thus, we get a mathematical model to describe the I-V characteristics of solar cells at any thermal
environment. It can be expressed as Eq. (6):

(6)
This model has a clear physical meaning, and it can reflect the output characteristics and heat
transfer characteristics of solar silicon cells in any light and temperature conditions.

PREDIGESTION OF MODEL AND THE NON-DIMENSIONAL ANALYSIS

Predigestion of model

Eq. (6) is a theoretical formula. To get the expected results, some mathematical software such as

994

MATLAB and ORIGIN can be used to calculate when some initial value were available. In this paper,
we simplifies the above theoretical model, after doing experiments and calculation, a new empirical
formula is conducted under the help of non-dimensional analysis method.
To simplify the model, some assumptions are made as follows:

1. After a period of operation of solar cells, the change of solar cells gradually slows down so that
it could be considered as the temperature change at unit of time is 0. Then we get :

(7)

2. It is supposed that the front panel temperature Tf is approximately equal to the back panel
temperature Tb

and they are both the multiple of the air temperature Tair , so is the sky

temperature Tsky . Then we can get:

(8)

(9)
It is also supposed that the temperature of solar cell T is the average value of the temperature
of front panel and back panel. Then we can get:

(10)

3. As the solar cell is placed surrounded with air, it can be considered that the heat transfer
coefficient of both front panel and back panel are equal. According to Watmuffs work, the
heat transfer coefficient can be defined as :

(11)
Thus, the Eq. (6) can be simplified as Eq. (12):

12

995

Non-dimensional analysis

When the non-dimensional analysis method is applied, it is recommended to find out all the
associated variables. The best way to find out all the key variables is to analysis the theoretical
formula.
According to the existed research, there are three formulas as follows (Messenger, 2004; A.Virtuani,
2003; Sehrode, 1998):

(13)

(14)

(15)
From the above equations Eq. (12) to Eq. (15), it is believed that there are mainly 20 independent
factors having influence on the solar cell photoelectric output power, namely: energy absorb ratio of
solar cell panel 1, effective light intensity S, area of solar panel A, heat transfer coefficient of solar
cell panel hb, Boltzmann constant K, diode ideality factor K1, panel temperature ratio K2, sky
temperature ratio K3, air temperature Tair, emission ratio of solar cell panel , PV output voltage U,

electronic charge q, reference air temperature Tref, band gap at reference condition Eg,ref, effective
light intensity at reference condition Sref , diode reverse saturation current at reference condition
I0,ref , equivalent series resistance at reference condition Rs,ref, equivalent parallel resistance at
reference condition Rsh,ref , and Stephen Pohl Seidman constant . And their influence on the solar
cell photoelectric output power Pout can be expressed as:

(16)
Buckingham theorem is adopted here to develop the correlation. Effective light intensity S, air
temperature Tair, area of solar panel A , electronic charge q and PV output voltage U are chosen as

the repeated parameters, with 5 fundamental dimensions, i.e. length, mass, time , temperature and
current. Then the 17 dimensionless parameters come as follows:

996

After regrouping

Then the dimensionless correlation results as: Eq. (17)

17
Which also can be rewritten as:

18
Where

which is a constant for a photovoltaic panels designated, is defined as the output efficiency of
solar cell, where b1, b2 and b3 are constants determined by experiments. And they are bounded by:
b1<0, b2>0, b3>0
Which is made according to the fact that the max output efficiency will increase when the light
intensity or the wind velocity is enlarged and decrease when the air temperature is enlarged.
Transfer the Eq. (15) with logarithmic treatment:

997

(19)
Then, based on the data cited from Zaiteng Zhais work (Zaiteng Zhai, 2008), the least squares
method is introduced to find the weights fitting for the correlation best.

Here, the heat transfer

coefficient of back panel of solar cell is defined as Eq.(11), and the wind velocity is set as 0. All the
cited data are shown in the Tab.1. Thus, the minimal norm least square results are obtained with
MATLAB after calculating 44 groups of data
b=0

-1.7683

Status =

0.9783

0.0275
923.5849

7.6542
0

0.0008

And the residual plots of the calculated results is shown as Fig.3.

Fig.3. Residual plots of the calculated results

According to the calculated results, we can get:

b1=-1.7683, b2=0.0275, b3=7.6542

Therefore, the Eq. (18) can be written as:

20
As the data cited from Zaiteng Zhais work are the maximum output power, the output voltage and
current at MPP, we can get a correlation based on the heat transfer coefficient of solar panel to
measure the maximum transfer efficiency of solar cell. That is:

(21)

998

Then, the method of correlation coefficient R, method of F-test and method of P-value test are used
to analyze the linear correlation of the regression results.

1. To evaluate the correlation coefficient R. The last calculated correlation coefficient R = 0.9783,
the absolute value of which is in the range of 0.8 to 1. So it can be judged that the regression
results between the independent variables and the dependent variable have strong linear
correlation, and the result shows a strong linear correlation between the selected factors and
the maximum output efficiency;

2. According to the calculated results, F = 923.5849> F1-0.05 (3,40) = 2.37, which shows a
significant linear correlation between the selected factors and the maximum output efficiency;

3. According to the calculated results, P = 0.0008 <0.05, which also indicates that it has a
significant linear correlation between the selected factors and the maximum output efficiency.
All of the three test methods mentioned above prove that the linear regression equation we are
about to get has a significant lineation. In the Fig.3, all the residuals are around 0, so we think this
formula has a certain accuracy.
Tab.1 Data cited from references to calculate
S

Pmax

Pmax

100

253

41.158

0.3957

16.2862

300

253

42.172

1.185

49.9738

100

263

39.215

0.3969

15.5644

300

263

40.265

1.1885

47.8550

100

273

39.277

0.3979

15.6283

300

273

38.364

1.1914

45.7069

100

283

35.346

0.3987

14.0925

300

283

36.47

1.1939

43.5415

100

293

33.42

0.3994

13.3479

300

293

34.584

1.1958

41.3555

100

303

31.5

0.3998

12.5937

300

303

32.706

1.1971

39.1524

100

313

29.603

0.3999

11.8382

300

313

30.839

1.1975

36.9297

100

323

27.71

0.3997

11.0757

300

323

28.984

1.197

34.6938

100

333

25.8333

0.3992

10.3127

300

333

27.142

1.1954

32.4455

100

343

23.964

0.3981

9.5401

300

343

25.31

1.1925

30.1822

100

353

22.116

0.3965

8.7690

300

353

23.506

1.188

27.9251

200

253

41.871

0.7907

33.1074

400

253

42.314

1.5789

66.8096

200

263

39.953

0.793

31.6827

400

263

40.413

1.5833

63.9859

200

273

38.041

0.795

30.2426

400

273

38.517

1.5872

61.1342

200

283

36.135

0.7967

28.7888

400

283

36.629

1.5904

58.2548

200

293

34.237

0.798

27.3211

400

293

34.749

1.5928

55.3482

200

303

32.348

0.7989

25.8428

400

303

32.878

1.5943

52.4174

200

313

30.469

0.7992

24.3508

400

313

31.017

1.5947

49.4628

200

323

28.601

0.7989

22.8493

400

323

29.169

1.5939

46.4925

200

333

26.746

0.7979

21.3406

400

333

27.335

1.5915

43.5037

200

343

24.906

0.796

19.8252

400

343

25.517

1.5874

40.5057

200

353

23.083

0.7931

18.3071

400

353

23.718

1.5811

37.5005

999

RESULTS AND DISCUSSION

As it shown in Fig.4, the maximum transfer efficiency of photovoltaic cell is not enough sensitive to
light intensity. Under the condition of same ambient temperature, the maximum transfer efficiency of
photovoltaic cell increases with the increasing of light intensity very slowly, it is almost unchanged.

Fig.4. Photoelectric Transfer Efficiency and Light Intensity

The transfer efficiency of solar cell is more sensitive to the air temperature, which is shown in Fig.5.
In this figure, under the same condition of light intensity, the transfer efficiency decreases drastically
as the temperature increases.

Fig.5. Photoelectric Transfer Efficiency and Environment Temperature

Here, we can see that the transfer efficiency is also very sensitive to the heat transfer coefficient of
solar panel. From the Fig.6, when the heat transfer coefficient of solar panel increases, the transfer
efficiency increases drastically. As the heat transfer coefficient increases, the heat took from the
surface by the air flow is more and the temperature of the panel and the air surrounding the panel is
lower so that the solar cell max transfer efficiency gets increased. That is to say, trying to increase
the heat power transferred from the surface solar panel is quite helpful to make full use of the solar
cell.

1000

Fig.6 Photoelectric Transfer Efficiency and Convective Heat Transfer Coefficient

To test the accuracy of this correlation, we choose another 10 groups of data random and calculate
with the Eq.(21). The calculate results are shown in the Tab.2 and Fig.7 as follows:
Tab.2 Test data and calculate results
Light

Maximum

Predicted

Relative
Error

IntensityW/

Environment

Max Output

Transfer

Maximum Transfer

TemperatureK

PowerW

Efficiency

Efficiency

500

273

76.4830

15.30%

15.28%

-0.10%

500

283

72.8856

14.58%

14.57%

-0.08%

600

253

100.2419

16.71%

16.66%

-0.27%

600

263

96.0119

16.00%

15.97%

-0.19%

700

293

96.7474

13.82%

13.81%

-0.05%

700

303

91.6162

13.09%

13.09%

0.04%

800

303

104.4412

13.06%

13.07%

0.09%

800

313

98.5246

12.32%

12.35%

0.27%

900

313

110.4766

12.28%

12.32%

0.35%

900

323

103.7827

11.53%

11.61%

0.65%

Fig.7 Accuracy test

From the Tab.2 and Fig.7, we can see that the relative error is very low, less than 1%, which means
that the Eq.(21) has high accuracy and versatility.

1001

CONCLUSIONS
In this paper, two major conclusions can be drawn: (1) based on the heat transfer theory and
electronic physics theory, we build an energy model of photovoltaic cell. Heat transfer
characteristics of the solar panel and I-V characteristics of photovoltaic cell are combined in this
model, the physical meaning of which is very clear. Based on this model, we can calculate the
output power of solar cell at any operation condition using some software such as MATLAB, Origin
and so on, when we are given some available initial values. (2) The model mentioned above is a
theoretical model and it is always difficult to get all the needed parameters when using the model to
analyze and design a photovoltaic system. A correlation with four dimensionless parameters has
been developed and modified to predict the maximum transfer efficiency of solar cell with
dimensionless analyses at. And the prediction average error between the test data and the modified
calculated value is less than 1% based on Eq. (21). Compared with the previous works, the factors
involving the thermal conditions and solar cell structures are all considered, including light intensity
S, air temperature Tair, and heat transfer coefficient of solar cell panel h. In addition, the correlation
of frost accumulation is of helpful for designing the integrated photoelectric and photo-thermal
system, thus increasing the overall efficiency of the usage of solar energy.
ACKNOWLEDGEMENTS
The authors are grateful for the financial support of National 863 Program of China, the Major
Science and Technology Projects of Hunan Province, China (No.2010FJ1013), the International
Science and Technology Cooperative in Project of China (No.2010DFB63830), the Key Technology
Research and Application of Department of Construction in Hunan Province, China (No.KY201111),
and Science and Technology Support Program of National "Twelve-Five" (No. 2011BAJ03B07).
NOMENCLATURE
A

area of solar cell panel, m2

heat transfer coefficient of solar cell panel, W/m2K

PV output currentA

IL

PV photocurrent A

I0

diode reverse saturation currentA;

PV output voltage V

electronic charge1.6X10-19C

Rs

equivalent series resistance

K1

diode ideality factor1K12

Boltzmann constant1.38X10-23 J/K

PV temperatureK

Rsh

parallel equivalent resistance;

energy absorb ratio of solar cell panel;

effective light intensity, W/m2;

Qpv

output power of solar cell, W;

Qpe

heat generated by Joule effect inside the solar cell, W;

Qs

heat caused by the heat conduction of solar cell panel, W;

1002

emission ratio of solar cell panel,

Stephen Pohl Seidman constant, 5.67X10-8 W/(m2k4)

Tair

air temperature, K

Tf

temperature of front panel, K

Tb

temperature of back panel, K

SUBSCRIPTS
f

front panel

back panel

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A method to determine the solar cell series resistance from

a single I-V characteristics curve considering its shunt resistance-new approach. Vacuum,
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[7]. A.Ortiz-Conde, F.J.Garcia Sanchez, 2006, New method to extract the model Parameters of
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National Laboratories, Albuquerque, NM, September5. (for Book)
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Performance characterization Procedure for Photovoltaic Arrays presented at the 2rd world
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1003

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1004

DEGRADATION CHARACTERISTICS OF MEMBRANE ELECTRODE ASSEMBLY

UNDER DRIVE CYCLE TEST PROTOCOL
a

b*

Cheng Wang , Jun Huang , Jianbo Zhang , Jianlong Wang , Zhongjun Hou

Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084, China;
State Key Laboratory of Automotive Safety and Energy, Tsinghua University, Beijing 100084, China
c
Sunrise Power Co Ltd, NERC Fuel Cell & Hydrogen Technol, Dalian 116025, China
* Corresponding author; email address: jbzhang@mail.tsinghua.edu.cn

ABSTRACT:
One of the key factors determining the lifetime of proton exchange membrane fuel cell (PEMFC)
is the degradation and eventually the failure of membrane electrode assembly (MEA). To assess
the long-term durability of MEA in fuel cells for vehicular applicatoin, this study adopted the
accelerating technique using drive cycle test protocol developed by Chinese NERC Fuel Cell &
Hydrogen Technology. The protocol includes starts/stops, idling and acceleration, simulating major
degradation processes in real automobile application. After 900 h of accelerated test, MEAs
performance declined from the initial 0.65 V to 0.58 V@500 mA cm-2, dropping by more than 10%
and giving an average voltage decay rate of 70 V h-1. To examine the underlying mechanisms for
the degradation, post-mortem analyses such as X-ray photoelectric spectroscopy (XPS), scanning
electron microscopy (SEM) and energy dispersive X-Ray spectroscopy (EDX) were carried out for
the MEA before and after 900 h drive cycle test. The post-mortem analyses indicate that the
thinning of the electrolyte membrane at H2 outlet region is the decisive factor leading to the
end-of-life of PEMFC, and the Pt catalysts loss and micro-structural damage of MEA are the
decisive factors for the performance degradation and stability deterioration of PEMFC.
Keywords: Proton exchange membrane; Fuel cells; Durability; Drive cycle test
1. INTRODUCTION
Due to their high-energy efficiency, high power density and environmental friendliness,
PEMFCs have been intensively developed as a promising electricity generation technology for both
vehicular and stationary applications (Barbir et al., 2005; Bernay et al., 2002; Wang et al., 2005).
Significant progresses in improving performance, cost-effective and durability have been achieved
over the past decades. However, the commercialization of fuel cell electrical vehicle is still
confronted with the prime issue of durability in PEMFC technology (Kang&Kim, 2010). The critical
component of the PEMFC, which is most likely to dictate the life of the PEMFC, is the MEA (Danerol
et al., 2011). To make the PEMFC vehicle technology commercially feasible, we must improve the
durability of MEA in the first place. Fuel cell power systems need to be as durable and reliable as
todays internal combustion engines, corresponding to a 5000 h life time under the practical
operating conditions in a real environment (including the cycling of dynamic load, dry/wet,
shutdown/startup and freeze/thaw) (Kang&Kim, 2010). So a prerequisite for the successful
commercialization of PEMFC for application in electrical vehicles is to increase their lifetime to 5000
h, but the harsh operating conditions make this target very challenging for current PEMFC
technologies. To mitigate the degradation and thereby increasing the lifetime of the PEMFC, it is
necessary to have an in-depth and comprehensive understanding of the degradation mechanisms.
Long-term durability tests are often required to explore the degradation mechanisms,
particularly for the development of new materials and new designs for fuel cell. However, operating
fuel cell under its normal conditions for several thousand hours is generally impractical and
expensive (Cleghorn et al., 2006). In ongoing R&D of fuel cell durability, accelerated stress test
(AST) methods are preferred to facilitate rapid learning about key durability issues, and about
various AST Protocols available in literature which are implemented to analyze the failure modes of
current fuel cell components (Yuan et al., 2011; Liu et al., 2013). It has to be noted that the existing
MEA degradation testing protocols may not be comprehensive enough to evaluate the effects of all
operating conditions that will be encountered during real automobile applications, more appropriate
protocols need to be developed. Among the durability test protocols such as the steady-state
durability test, the potential cycling durability test, and the start-up/shutdown cycling durability test,
the drive cycle test protocols are often adopted to assess the long-term durability of fuel cells for
vehicular applications and to compare stack performance with commercialization lifetime target.
The drive cycle protocol was constructed by converting internal combustion engine drive cycle to an
equivalent PEMFC engine drive cycle. This protocol involves stepping through a series of different
current draws typical of automotive loads.

1005

In this study, the durability test of a commercial MEA was operated up to 900 h using the drive
cycle test protocol developed by Chinese NERC Fuel Cell & Hydrogen technology. To identify the
major failure factors and decay mechanisms for MEA of PEMFC, post-mortem analyses such as
X-ray photoelectric spectroscopy (XPS), scanning electron microscopy (SEM) and energy
dispersive X-Ray spectroscopy (EDX) were applied for the MEA before and after 900 h dirve cycle
test. The results indicate that the membrane thinning, microstucture change and Pt catalysts loss
mainly contribute to the performance degradtion of the PEMFC.
2. EXPERIMENTAL
The life acceleraing test was performed in 25 cm2 single cell test fixture (Beijing RuiDaQi
Company) with polar plates, gold-plating copper current collectors and super hard aluminum
end-plates. The reactant gases flow fields of both anode and cathode were triple channel
serpentine channels machined into graphite plates (Shanghai Hong Feng Industrial Company
Limited) and were assembled in co-flow orientation. The channel depth, channel width, and rib
width of the serpentine flow field plate were all 1 mm. The cell was assembled with a commercial
MEA with a rim thickness of 100 m in the sealing area. In this study, the MEA consists of a CCM
(catalyst coating membrane, Hephas Energy Ltd.) based on a 20 mm composite membrane with
0.6 mg Pt/cm2, and two pieces of GDLs (gas diffusion layer, SGL 25BC). Fuel cell sealing was
achieved by the use of vulcanizing silicone on either side of the membrane. The fuel cell fixture was
fastened with eight lubricated bolts with an assembly torque of 6 Nm.

Figure 1. Load profile for fuel cell drive cycle test

Discharge load, cell temperature, reactant gas humidity and gas flow rate were all controlled by
a HS-150 Fuel Cell Test Equipment (Hephas Energy Co., Ltd.). The program code of the drive cyle
test protocol was input in the interface of test software of HS Fuel cell test equipment for
automatically measuring. During the accelerating life test of the MEA, the reaction gases were
introduced into cathode and anode of the cell respectively with a mode of parallel flow with RH 80%
pure hydrogen fuel and RH 80% fresh air. The temperature and reactant pressure of the cell were
maintained constantly at 70 C and ambient pressure respectively, reactants were
stoichiometrically controlled and were unsaturated at fuel cell temperature. To prevent water vapor
condensation on the surface of inlet pipe connecting the fuel cell, the reactant gases inlet pipe were
heated 10 C above the cell operating temperature. After assembly, the single cell was activated at
different current density for 3 times (Liu et al., 2014). After 22 h activation operation, accelerating
life test of the fuel cell started up.
The drive cycle protocol consists of four values of discharge current density: 147 mA cm-2, 500
mA cm-2, 588 mA cm-2 and 794 mA/cm-2 which simulate working conditions of starts/stops, idling
and acceleration in real automobile application, loading step-up rate is 0.0256A cm-2.s-1, and
loading step-down rate is 0.064A cm-2 s-1. Meantime, there are three types of stoichiometric number:
5 for cathode air flow at idle (147 mA cm-2), 3 for cathode air flow at other operating conditions (500

1006

mA cm-2, 588 mA cm-2 and 794 mA cm-2), 2 for anode hydrogen flow. The current density vs. time
for the fuel cell drive cycle test is shown in Fig. 1 as a quantitative measure, the MEA durability is
defined as the time it takes for the average cell voltage to decay by 10% from the initial voltage
when tested according to the above procedures.
During accelerating life test, the accelerating life test was interrupted approximately every 100 h
to conduct in-cell systematic electrochemical diagnostics including polarization curves, cyclic
voltammetry measurements, linear sweep voltammetry measurements and AC impedance
measurements, whose detail experiment conditions and results have been presented in the article
(Liu M.Y et al. 2014). Chemical and physical characteristics of the MEAs were investigated by XPS,
SEM combined with EDX before and after 900 h dirve cycle test. To take cross-sectional SEM
images of the MEAs, samples were prepared by cutting the MEAs in liquid nitrogen followed by
impregnating into epoxy and polishing with sandpaper. XPS analysis was performed to analyze the
chemical changes of the elements in the catalyst layers by using XPS (PerkinElmer model
PHI1600). The surface morphology and cross-sectional morphology of MEAs were observed using
a field emission SEM (JEOL JSM-6335F), and elements scanning on the surface of MEAs was
conducted with an EDX on a LEO-1530 microscope.

3. RESULTS AND DISCUSSION

3.1

Overall MEA performance change in the accelerating life test

The overall performance change of the fuel cell during the whole accelerating life test was
shown in Fig. 2, whose horizontal coordinate is the accelerating test cumulative time and vertical
coordinate is the voltage at a series of current density, i.e., 147 mA cm-2, 500 mA cm-2, 588 mA cm-2
and 794 mA cm-2. It could be seen from Fig. 2 that the overall MEA performances decayed
evidently with the test time. The initial performance of this fuel cell was 0.65 V@500 mA cm-2, but
the performance declined approximately to 0.58 V@500 mA cm-2 after 900 h. That is, the overall
working voltage vs. 500 mA cm-2 dropped 10%, corresponding to an average voltage decay rate of
70 V h-1, which is durability decay rate of the accelerating life test.

Figure 2. Overall voltages variation of the MEA during the accelerating life test.

One characteristic of the accelerating test is that: the cell voltages recover to a higher value
following the diagnostic interruption, then the cell voltages drops again when the accelerating life
test resume. This saw-tooth phenomenon has a typical period of approximately 100 hwhich is
exactly the interval for the diagnostics. In addition, as shown in Fig.2, the voltage decay rate is

1007

becoming steeper, and the stability decay rates between performance recoveries can be quite
different, moreover, the performance rebound depends on the magnitude of current density. When
compared to literatures (Ohyagi et al., 2011), the stability decay rate of this study is also relatively
high.
On one hand, the drop in the MEA performance is due not only to the irreversible decay
(durability) but also to the reversible decay (stability). The stability decay rate is calculated by
subtracting the durability decay rate from the total decay rate. On the other hand, the recovery of
the cell voltages is ascribed to the non-steady-state behavior of the fuel cell, especially, to the
recovery of the MEA. The stability of the MEA is typically concerned with the gas diffusion layers
sensitivity to operating conditions (i.e. water management), reversible material and transport
changes in catalyst layer (such as formation of PtO in cathode side, adsorption of trace toxic gases
or an increase in oxygen transport resistance as a result of the formation of liquid water barriers).
3.2

Change of gas diffusion layer

The GDL is composed of carbon paper and a water management layer coated on one side of
the carbon paper. The water management layer contacting with the CCM is exposed to tough
environmental conditions such as electrocatalysis, high temperature, water flow and electric
potential. To achieve a better understanding of the GDL degradation process, the water
management layer micostructure before and after the accelerating life test were illustrated by SEM.
Fig.3a and c show the surface of the fresh water management layer in the GDL, and Fig.3b and d
show these surfaces after the accelerating life test with different magnifications. Notably, collapse,
holes and thinning appeared on the water management layer surfaceas shown in Fig.3b and d after
the accelerating life test. Especially, the carbon fiber in carbon paper exposed to the surface of the
water management layer could be observed in Fig.3 d, which are mainly due to the carbon
corrosion and dissolution in Faraday water produced from electrochemical reactions in the CCM, at
the same time working with reaction gases, electrocatalyst and electric potential. Mechanical wear
of the carbon surface led to the loss of hydrophobicity in the GDL(Ha et al., 2011). Furthermore, the
loss of hydrophobicity and the damage of micro structure for mass transfer in the GDL result in an
increase in the electric contact resistance and a decrease in water diffusion and gas permeation.
Consequently, a reduction of the overall performance of the fuel cell and its stability decay were
observed in the above current-voltage curves. MEA stability decay calculated by subtracting the
durability decay from the total decay is typically related to the water mamagement layer. Stability
decay rate increases with the destruction of micro structure of water management layer in the MEA,
but the fuel cell performance can be recoverable after drainage from the CCM.

1008

Figure. 3. SEM images of the water management layer in GDL before and after accelerating life test
under different magnifications: (a) fresh GDL, magnification of 400; (b) used GDL, magnification of
400; (c) fresh GDL, magnification of 4000; and (d) used GDL, magnification of 4000.
3.3

Change of catalyst coating membrane

The CCM consists of a composite membrane with cathodic and anodic catalyst layer coated on
each surface. Fig.4 shows the SEM images of the cathode surface of both fresh CCM and
degraded CCM. Clearly, the catalyst layer is hardened after the drive cycle test, which means a loss

1009

of porosity. The collapse of these pores may be related to the decomposition of the Nafion ionomor
in the cathode. This speculation is to be validated using XPS measurement.

Figure. 4 SEM images for the cathode surface morphology of the CCM (magnification of 4000): (a)
fresh CCM; (b) used CCM.

Figure. 5 XPS measurement of the cathode surface for fresh and the used CCM
In order to quantify the chemical changes of the elements in the cathodic layers, XPS analysis
was performed as shown in Figure.5. The XPS analysis showed that platinum, sulfur, oxygen, carbon

1010

and fluorine were present on the surfaces of the catalyst layer samples both before and after 900 h
drive cycle test, which was based on their binding energy signature. However, remarkably, the relative
intensity of the F signal decreased. The elemental composition changes based on high-resolution
spectra are presented in Table 1. The surface concentration of platinum, sulfur and fluorine decreased
from 0.42% to 0.33%, from 0.80% to 0.60%, and from 52.20% to 39.70% respectively, while the
oxygen and carbon content increased from 5.60% to 7.10% and from 40.98% to 52.27%. The
oxidized states of platinum and carbon were found to substantially higher for the used samples. Both
XPS analysis and above SEM analysis reveal that the ionomer on the catalyst layer decomposed after
the accelerating test.
Table 1 Elemental compositon of the cathodic catalyst layer before and after the drive cycle test
Element

Surface composition (%)

before

after

Pt

0.42%

0.33%

0.80%

0.60%

5.60%

7.10%

52.20%

39.70%

40.98%

52.27%

Total

100%

100%

Anode

Anode

Cathode
Cathode

Anode

Cathode

Figure 6 cathodic surface SEM morphology and EDX of the CCM (magnification of 4000): (a) fresh
GDL; (b) used GDL; (c). EDX for used CCM

1011

Anode

Anode

Cathode

Cathode

Anode

Cathode

Figure.7 Cathodic surface SEM morphology and EDX of CCM (magnification of 4000): (a) fresh GDL;
(b) used GDL; (c). EDX for used CCM
Fig.6 and Fig.7 present cross-sectional images of the MEAs before and after the accelerating
test. The results show that the degradation of the membrane and cathodic catalyst layer are more
severe at the hydrogen outlet region. In terms of membrane thickness, after the accelerating test,
the membrane thicknesses at hydrogen inlet and outlet location are about 23 m and 19 m
respectively by simple average calculation. Both of them are lower than its original 25m thickness.
The larger reduction of the membrane thickness is attributed to higher water concentration at
hydrogen outlet location. The polymer backbone of the composite membrane preferentially reacts
as following : -CF2- + 2H2 -CH2- + 2HF . With water flooding circumstance, this reaction is
accelerated and subsequently followed by HO attack of the product CH2 group mainly at
cathode.
Furthermore, as one can see from Fig. 6.b and Fig. 7.b, the thickness of both cathodic layer
and anodic layer at the hydrogen inlet is almost unchanged, but those at the hydrogen outlet
location were reduced from 10 m to 6 m, from 5 m to 3 m respectively. This is due to the
carbon corrosion induced by high potentials and fuel starvation, especially in the presence of more
water and air at hydrogen outlet section.
Therefore, the membrane degradation and catatalyst layer reduction mainly ocurred at the
hydrogen outlet region of fuel cell.
EDX images collected from the used MEAs cross-sectional samples are shown in Fig.6c and
Fig.7c. The platinum element distribution was unraveled by platinum x-ray spectra characteristics in
the composite membrane after accelerating test. The results indicate that the dissolved Pt2+ species
in the catalyst layer diffuse into the composite membrane, and subsequently aggregate as particles.
It is well known that the voltage cycling lead to higher extent of the platinum dissolution than steady
state operation (Liu et al., 2013). The migration and agglomerate of Pt particles in the membrane,
leading to Pt catalyst surface loss, are significant contributors to the membrane failure as well as
during accelerating operation of fuel cell.

1012

4. CONCLUSIONS
In this study, we reported degradation characteristics of a proton exchange membrane fuel cell
using the drive cycle test protocol developed by Chinese NERC Fuel Cell & Hydrogen technology.
The accelerating life test on a commercial MEA was measured for 900 h. The cell performance
degraded at a rate of about 70 Vh-1 at a current density of 500 mA/cm2, corresponding to a
maximum total voltage loss of 70 mV throughout the test. The post-mortem analysis results indicate
that: 1) The loss of hydrophobicity and the damage of micro structure for mass transfer in GDL are
detected, which would cause an increase in the electric contact resistance and a decrease in water
diffusion and gas permeation; 2) membrane thinning and catatalyst layer reduction mainly ocurr at
the hydrogen outlet region of the fuel cell, and the non-uniform degradation accelerates the failure
of PEMFC; 3) the migration and agglomeration of Pt particles in the membrane results in the loss of
actives sites and are significant contributors to the membrane failure after the accelerating
operation of fuel cell.
ACKNOWLEDGEMENT:
This work was financially supported by the State Key Basic Science Research Project of China
(No.2012CB215401), the Program of Internatinal S&T Cooperation (2013DFG41460;
2013DFG60080) and National High Technology Research and Development Program of China
(No.2013AA110202).

REFERENCES:
Barbir F., 2005, PEM fuel cells: theory and practice. New York: Elsevier Academic Press;
Bernay C, M. Marchand, and M. Cassir, 2002, Prospects of different fuel cell technologies for
vehicle applications, Journal of Power Sources; 108: 139-152.
Cleghorn S.J.C., D.K. Mayeld, D.A. Moore, J.C. Moore, G. Rusch, T.W. Sherman, N.T. Sisofo, and
U. Beuscher, 2006, A polymer electrolyte fuel cell life test: 3 years of continuous operation, Journal
of Power Sources, 158:446454
Danerol A. S., C. Bas, L. Flandin, E. Claude, and N.D. Alberola, 2011, Influence of ageing in fuel
cell on membrane/electrodes interfaces. Journal of Power Sources, 196(7): 3479-3484.
Ha T., J. Cho, J. Park, K. Min, H. Kim, E. Lee, and J. Jyoung, 2011, Experimental study of the effect
of dissolution on the gas diffusion layer in polymer electrolyte membrane fuel cells, International
Journal of Hydrogen Energy, 36: 12427-12435.
Kang J., and J. Kim, 2010, Membrane electrode assembly degradation by dry/wet gas on a PEM
fuel cell, International Journal of Hydrogen Energy, 35:13125-13130.
Liu M.Y., C. Wang, F. Xie , and Z.Q. Mao, 2013, A polymer electrolyte fuel cell life test using
accelerating degradation technique, International Journal of Hydrogen Energy, 38:11011-11016.
Liu M.Y., C. Wang, J.B. Zhang, 2014, Diagnosis of membrane electrode assembly degradation with
drive cycle test technique, International Journal of Hydrogen Energy, in press (Reference:
HE13420).
Ohyagi S., T. Matsuda, Y. Iseki, T. Sasaki, and C. Kaito, 2011, Effects of operating conditions on
durability of polymer electrolyte membrane fuel cell Pt cathode catalyst layer, Journal of Power
Sources, 196: 37433749.
Wang C., Z.Q. Mao, F.Y. Bao, X.G. Li, and X.F. Xie, 2005, Development and performance of 5 kw
proton exchange membrane fuel cell stationary power system, International Journal of Hydrogen
Energy, 30:1031-1034.
Yuan X.Z., H. Li, S.S. Zhang, J. Martin J, and H.J. Wang, 2011, A review of polymer electrolyte
membrane fuel cell durability test protocols, Journal of Power Sources, 196: 9107-9116.

1013

A PARTIALLY IMPREGNATED AGGLOMERATE MODEL FOR THE PEM FUEL

CELL CATHODE CATALYST LAYER
1

Jun Huang , Cheng Wang , Jianbo Zhang

1.

1,*

Department of Automotive Engineering, State Key Laboratory of Automotive Safety and Energy,
Tsinghua University, Beijing 100084, P. R. China

2.

Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084, P. R. China
* Corresponding author; email address: jbzhang@mail.tsinghua.edu.cn

ABSTRACT
The catalyst layer in the cathode of a proton exchange membrane fuel cell (PEMFC) can be
treated theoretically as built up from an agglomerate of carbon-supported Pt catalysts, ionomer, and
pores. Previous models for the agglomerate assume that the pores between the carbon-supported
catalysts are fully impregnated by the ionomer, which may not be the case. In this work, a model for
the partially impregnated agglomerate is proposed and analytically solved while considering a
non-uniform overpotential in the agglomerate. The numerical analysis indicates that the
overpotential gradient is negligible compared with the oxygen concentration gradient. Primary
pores enhance the oxygen transport in the agglomerate significantly by Knudsen diffusion, and a
small fraction of primary pores lead to a remarkable improvement of the performance. Based on the
partially impregnated agglomerate model considering the primary pores, it is found that the inactive
core reduces the performance of the agglomerate remarkably.
Keywords: Proton exchange membrane fuel cell; Catalyst layer; Agglomerate model; Partially
impregnated;
1

INTRODUCTION
Cost is one of the biggest bottlenecks for the widespread use of PEM fuel cell vehicles, and it is

of especial importance to reduce platinum (Pt) loading in the catalyst layer (CL). Therefore, over the
past decades, various models have been developed to comprehend the complicated processes
inside the CL, so as to improve the utilization of the Pt, and reduce the Pt loading and cost. Among
all the models, the agglomerate model based on the morphology and function of the CL is widely
accepted as an appropriate simplification of the complex construction of the CL. Most previous
applications of the agglomerate model assumed that, the primary carbon-supported catalyst
particles were collected into a spherical secondary agglomerate which was fully impregnated with
solid polymer electrolyte, which is ionomer and especially the Nafion in most cases (Cetinbas, 2013;
Cetinbas, 2014; Jain, 2010; Yin, 2005). Having no gaseous phase pores in the agglomerate,
oxygen needs to be dissolved into the electrolyte and diffuse to the active sites inside the
agglomerate. In addition, most previous models assumed a uniform ionomer phase potential inside
the agglomerate, that is, a uniform overpotential distribution since the solid phase potential gradient
is negligible. However, Rao & Rengaswamy (2006) argued that signicant overpotential gradients
might exist across the ionomer film and inside the agglomerate core.
The gaseous pore-size distribution in the catalyst layer was determined by porosimetry with
varying the ionomer content (Kim, 2007). Fig.1 shows that most of the pores are in the 10100 nm

1014

range and part of them are in the <10 nm range, in addition, the volume of the pores decreases with
increasing the ionomer content in the catalyst layer. As suggested by Tominaka et al. (2009), the
pores in the <10 nm range are classified as primary pores, which exist inside the catalyst
agglomerates, and the pores in the 10100 nm range are regarded as secondary pores between
the agglomerates. The catalysts inside the primary pores where the ionomer phase can hardly
arrive at are considered to be inactive for the electrochemical reaction. However, these primary
pores are believed to be useful for the oxygen diffusion (Antolini, 2009). To the best knowledge of
the authors, none of the previous models takes into account the effect of the primary pores on the
oxygen diffusion inside the agglomerate.
Passalacqua et al. (2001) reported that, for low Naon content such as 14%, the polymer
electrolyte was insufcient to provide adequate electrolytic conductance inside the catalyst layer,
resulting in low catalyst utilization and high electrolyte resistance. Correspondingly, Yin (2005)
addressed this situation by proposing an agglomerate model in which there is no ionomer film on
the surface of the agglomerate. In this way, the oxygen diffuses directly to the active sites and
undergoes reactions upon reaching the agglomerate. However, Soboleva et al. (2010)
experimentally detected that the ionomer is more inclined to distribute on the surface of the
agglomerate. Therefore, the insufficient or obstructed impregnation of the ionomer will result in an
inactive core instead of the vanish of the ionomer film on the surface of the agglomerate as
assumed in Yins model. A multizone agglomerate model was introduced by Jain et al. (2010) to
examine the possible nonuniformly distributed reaction sites. The agglomerate with an inactive core
is one case of the multizone agglomerate model, however, the Jains model assumed no primary
pores.
The objective of this study is to examine the effect of the primary pores and the possible
inactive core on the performance of the agglomerate while considering the overpotential gradient.
In the model development section: (1) the conventional fully impregnated agglomerate (FIA) model
is modified by incorporating the overpotential gradient; (2) a model for the partially impregnated
agglomerate (PIA) having primary pores, through which the oxygen transports by Knudsen diffusion,
is presented. This model is named as PIA-I model; (3) a model for the partially impregnated
agglomerate having primary pores and an inactive core is investigated. This model is named as
PIA-II modeled. In the results and discussion section, we evaluate the effect of the overpotential
gradient, highlight the effect of the primary pores on the oxygen diffusion, examine the effect of an
inactive core, and compare these models. The last section summarizes the findings of this paper.
2

MODEL DEVELOPMENT

1015

Primary
pores

Nafion
Carbon
Pt

(a) Conventional fully

impregnated agglomerate

(b) Partially impregnated

agglomerate with
primary pores

(c) Partially impregnated

agglomerate with primary
pores and inactive core

Fig. 2. Schematic plot of: (a) conventionally fully

impregnated agglomerate, (b) partially impregnated
Fig. 1. Pore-size distribution inside the catalyst layer

agglomerate with primary pores, and (c) partially

with various ionomer contents (Kim et al., 2007).

impregnated agglomerate with primary pores and inactive

core.

Several assumptions are listed as follows for the subsequent deduction:

(1)

The agglomerate core is composed of homogenous mixture;

(2)

The agglomerate is assumed to be isothermal as a consequence of the sufficient heat

conduction rate (Cetinbas, 2013);

(3)

The agglomerate has a constant solid phase potential due to the high electron

conductivity;
(4)

The liquid water effect is neglected at the agglomerate scale;

(5)

The oxygen concentration in the gaseous phase outside the ionomer film is constant;

2.1 The conventional fully impregnated agglomerate model

Fig. 2 (a) shows a schematic plot for the conventional fully impregnated agglomerate model.
The agglomerate core with a radius of ragg is fully soaked by polymer electrolyte and surrounded by
an ionomer film with a thickness of f. Upon approaching the agglomerate, the oxygen has to be
dissolved in and diffused through the ionomer lm without any reaction. Then, the oxygen diffuses
into the agglomerate core while simultaneously undergoing reaction.
2.1.1

Conservation equations in the ionomer film

The diffusion of the oxygen in the ionomer film is expressed as:

Doco 0
(1)
where Do refers to the diffusivity of oxygen in the ionomer and is calculated as:

Do 3.1107 exp 2768 / T

(2)
The boundary conditions for Eq. (1) are as follows:
(1)

At the outer boundary facing the gaseous macropores, the dissolved oxygen

concentration is calculated from the Henrys law:

co r ragg f co0 Po / H
(3)

1016

where Po is the constant oxygen pressure in the gaseous phase surrounding the agglomerate, H is
the Henrys constant.
(2)

At the inner boundary between the ionomer film and the agglomerate core, the mass and

flux continuity of the oxygen concentration give:

co r ragg co r ragg

(4)

Doeff

co r ragg

co r ragg

r
(5)

where

e
is the volume fraction of the ionomer phase in the agglomerate core. Doeff is the
agg

effective diffusivity of oxygen in the ionomer phase and can be calculated by employing the
Bruggeman relation:
e
Doeff =Do agg

1.5

(6)
Since no reaction occurs in the ionomer film, the charge conservation equation is given by:

e e 0
(7)
where

e , e denote the proton conductivity and potential of the ionomer phase respectively.

In this study, the

at the surface of the agglomerate is set as an input parameter to

calculate the current generated inside the agglomerate. Therefore, the outer boundary condition for
Eq. (7) is:

e r ragg f e0
(8)
In addition, the continuity of

e and e at the interface between the ionomer film and the

agglomerate core constitute the other boundary condition:

e r ragg e r ragg
(9)

eeff

e r ragg
r

e r ragg
e

(10)
and,
e
eeff = e agg

1.5

(11)
2.1.2

Conservation equations in the agglomerate core

In the agglomerate core, as the oxygen diffuses while simultaneously undergoing reactions,
the conservation equation for the oxygen is:

1017

 Doeff co Rorr

(12)
The source term, Rorr , is the consumption rate of oxygen in the agglomerate and is determined
by the Faradays law:

Rorr apt kc co
(13)
apt is the total active area per volume of the agglomerate and is formulated as:

apt A0

m pt

tcl 1 cl
(14)

where A0 is the specific surface area of Pt, mpt the Pt loading, tcl the thickness of the CL, cl the
porosity of the CL.
kc is the first-order rate constant as a function of the overpotential within the agglomerate
following the simplified Butler-Volmer equation:
kc

i0,ref
4 Fco,ref

F
exp

RT

(15)
where i0,ref is the reference exchange current density, c0,ref the standard reference oxygen
concentration, the cathodic charge transfer coefficient, F the Faradays constant, R the universal
gas constant, T the temperature.
If one sets the oxygen electrode as the reference electrode, then, the uniform solid phase
potential s equals 0. In such a case, the local overpotential, , in the ButlerVolmer equation
numerically formulates as:

e
(16)
As mentioned, Eq. (4)-(5) constitutes one of the boundary conditions for Eq. (12), and the other
one is the zero concentration gradient at r=0:

co r 0
r

(17)
Writing the expression for the charge conservation inside the agglomerate core, we get:
eeff e 4FRorr

(18)
and the zero gradient at r=0 gives:

e r 0
r

0
(19)

In conclusion, applying Eq. (1), (7), (12), (18), together with the corresponding boundary
conditions, one can solve the oxygen concentration- and ionomer phase potential distribution. The
coupling between the concentration and potential in the controlling equations makes it difficult to

1018

obtain the exact analytical solution. However, on the basis of the simplifications as detailed in
appendix, we deduce an approximate analytical expression for the oxygen concentration and
ionomer phase potential, respectively, as shown in Tab.1.

Tab. 1. Expressions of the oxygen concentration and ionomer phase potential for the FIA model

Item

Oxygen concentration

ragg r ragg f

co r co0

0 r ragg

co r

1 =

Coefficients

1
p1 1
r ragg f
Do

r
sinh

r sinh
ragg
p4 co,ref ragg

apt i0,ref ragg 2

4 FDoeff co,ref

p3 e0

Potential of ionomer phase

F
RT

e r e0

e r

Fapt i0,ref ragg 2

2 =

RT eeff

p2 =

ragg f

p4 =

Do ragg f coth 1

Do ragg f +Doeff f coth 1

Do ragg f
co0
;
co,ref Do ragg f +Doeff f coth 1

The agglomerate current can be calculated by following equivalent equations:

2
I agg 4 ragg
4FDo
2
4 ragg
eeff

co r ragg

r
e r ragg
r

2
4 ragg
4FDoeff
r ragg

4 r 4FR
2

orr

co r ragg
r

2
4 ragg
e

e r ragg
r

dr

r 0

(20)
Therefore,

I agg 16 Fp1
(21)
2.2

The partially impregnated agglomerate model considering the primary pores

Fig. 2 (b) depicts a partially impregnated agglomerate with primary pores. Due to the

nano-scale of the primary pores, the oxygen diffusion process in these primary pores associates
with the collision of gas molecules with the pore wall, as a result, the Knudsen diffusion needs to be
considered (Djilali & Lu, 2002). Therefore, two parallel routes for the oxygen diffusion exist inside
the agglomerate: (1) the diffusion of the dissolved oxygen in the polymer electrolyte which can be
described by Ficks law; (2) the diffusion of the oxygen in the primary pores which follows the
Knudsen diffusion process. Therefore, the effective oxygen diffusivity, Doeff2 , is calculated as:
e
pp
Doeff2 = agg
Doeff + agg
Dkn

1019

p3

Do ragg f coth 1
2 eff RT co0
;
o
ragg
1
F co,ref
Do ragg f +Doeff f coth 1

1 =1e p3 2 = 2 e p3 ;

1 2co0 / co,ref

ragg
RT 2
r
p4 sinh

F 1 r sinh
ragg

p1 =Doeff co0 ragg

2 co0 ;
1 co,ref

p2

(22)
pp
where agg
is the volume fraction of the primary pores in the agglomerate, Dkn is the Knudsen

diffusion coefficient given by:

2
8RT
Dkn rpp
3
MO
(23)
where rpp is the mean radius of the primary pores and Mo denotes the molecular weight of oxygen.
After substituting the effective oxygen diffusivity with Doeff2 , as formulated in Eq. (23), the
analysis and deduced expressions for the conventional FIA model are the same for this PIA-I model
considering the primary pores,.
2.3

The partially impregnated agglomerate model considering an inactive core.

Fig. 2(c) shows the partially impregnated agglomerate model with an inactive core. Inside the

inactive core, no reaction occurs and the conservation equation for the oxygen formulates as:

Doeff co 0
(24)
Neglecting the overpotential distribution inside the agglomerate, one can deduce an analytical
expression for the oxygen distribution as shown in Tab. 2. In addition, the ignorance of the
overpotential gradient is to be verified in the section of 3.1. Similarly, the agglomerate current can
be calculated by Eq. (21).
Tab. 2. Expressions of the oxygen concentration for the PIA-II model
Inactive
Zone

part in the
agglomera

Active part in the agglomerate

Ionomer film

ric r ragg

ragg r ragg f

te
Radial
coordinat

0 r ric

Expressi

co r

co r p8

on

apt i0,ref ragg 2

eff
2
o

4 Fco,ref D

co0 ragg

Coefficie
nt

p6

agg

r sinh

r
p6 sinh
r

agg

Fe ;
exp

RT
coth
coth

ragg f

p5 Do co0 ragg

1 coth
ragg f

coth

coth

ric ;
ragg

r
p 1
1
p7 cosh co r co0 5

r
D
r
r

agg

o
agg f

agg

r
f

agg

coth

agg
f

1020

p7

coth
coth

p6

1 1

r
f

agg

agg
f

p8

p6
ragg cosh

sinh

RESULTS AND DISCUSSION

Simulations are conducted using the parameters in Tab. 3 to investigate whether the

distribution of the overpotential in the ionomer film and inside the agglomerate core can be ignored
or not, to explore how the primary pores in the agglomerate core affect the oxygen diffusion process,
and to explore what an inactive core will lead to. Parametric studies concerning the effect of the
volume fraction of primary pores, the effect of the ration, ric/ragg, are also presented.
Tab. 3. Parameters used in the simulation

Parameter

Value

Note
From Ref.

Temperature, T

353.15 [K]

(Cetinbas,
2013)

Oxygen pressure,
Po
Henrys constant,
H

From Ref.
1.5 [atm]

(Cetinbas,
2013)

0.3125

From Ref.

[atm

(Cetinbas,

m /mol]

2013)

Parameter

Value

Reference exchange

1.5*10

current density, i0,ref

[A/m ]

Reference oxygen

0.85

concentration, c0,ref

[mol/m ]

Mean radius of the

primary pores, rpp

Reference
-4

Calculated
from (Fofana,

2013)
Calculated
3

-9

from (Fofana,
2014)

2*10 [m]

Assumed

0.01

Assumed

Nafion volume
fraction in

0.4

agglomerate,

From Ref.

Volume fraction of

(Cetinbas,

the primary pores in

2013)

e
agg

Ionic conductivity,

2.633

[S/m]

Total active area

per volume of
agglomerate, apt
Thickness of the
ionomer film, f
Cathodic transfer
coefficient,

Calculated
from (Fofana,
2013)
6

9.08*10
[1/m]
-8

5*10 [m]

Calculated
from (Fofana,
2013)
Assumed

agglomerate,

Molecular weight of
oxygen, Mo

Radius of the inactive

core, ric
Radius of the
agglomerate, ragg

From Ref.
1

pp
agg

(Fofana,
2013)

1021

From Ref.
32 [g/mol]

(Fofana,
2013)

-7

Assumed

-7

Assumed

1*10 [m]

3*10 [m]

3.1

Overpotential distribution in the agglomerate

Fig. 3 shows the oxygen concentration profile in the ionomer phase and agglomerate core at a

series of overpotential. One can note the significant concentration gradient in the ionomer film
despite its small thickness. In the agglomerate core, the oxygen concentration decreases as a
consequence of consumption in the reduction reaction, and the gradient becomes steeper when the
overpotential is larger. Especially, the oxygen is consumed at the surface of the agglomerate core
when the overpotential exceeds 0.55 V. For this case, most of the catalysts inside the agglomerate
leave unused. In this view, designing a higher catalyst concentration toward the periphery of the
agglomerate core is benefit for high utilization of the catalyst, which is also suggested by Cetinbas
et al. (2013).
Regarding the ionomer phase potential, on the contrary, there is no remarkable gradient both in
the ionomer film and in the agglomerate core. This can be understood based on the following
expression which can be deduced from Eq. (A-5):
co

1
e
2

(25)
Order analysis gives: 2 10-3 1 . As a result, the gradient of the ionomer phase potential, i.e.,
the overpotential gradient, is negligible compared with the concentration gradient. This verifies the
assumption of uniform overpotential which is the common case in the literature. Accordingly, in the
two subsequent models, the overpotential gradient is ignored.

0.9

Potential of ionomer phase, / V

e

Oxygen concentration, c o / mol m -3

3
=-0.05V
=-0.15V
=-0.25V
=-0.35V
=-0.45V
=-0.55V
=-0.65V

0.5

1.5

2.5

agglomerate core

0.8

0
0

Ionomer film

Ionomer film

agglomerate core

3.5

Radial coordinate, r / m

0.6
0.5
0.4

=-0.05V
=-0.15V
=-0.25V
=-0.35V
=-0.45V
=-0.55V
=-0.65V

0.3
0.2
0.1

4.5
x 10

0.7

-7

0
0

0.5

1.5

2.5

3.5

Radial coordinate, r / m

Fig. 3. Oxygen concentration profile in the ionomer

Fig. 4. Ionomer phase potential profile in the

phase and agglomerate core.

ionomer phase and agglomerate core.

3.2

Caparison between the FIA model and PIA-I model regarding the effect of primary
pores on the oxygen diffusion

1022

4.5
x 10

-7

0
Fully flooded
Partially flooded, pp=1%
Partially flooded, pp=2%

Overpotential, , / V

-0.2

Partially flooded, pp=5%

-0.3
-0.4
-0.5
-0.6
-0.7
-0.8
0

1000

2000

3000

Current density, i

4000
agg

/Am

5000

Ionomer film
agglomerate core

Oxygen concentration, c o / mol m -3

-0.1

6000

-2

3
=-0.05V
=-0.15V
=-0.25V
=-0.35V
=-0.45V
=-0.55V
=-0.65V

0
0

0.5

1.5

2.5

3.5

Radial coordinate, r / m

4.5
x 10

Fig. 5. Comparison between the fully impregnated

Fig. 6. Oxygen concentration profile in the ionomer

agglomerate model and the partially impregnated

phase and agglomerate. The agglomerate core has

agglomerate model while varying the volume

primary pores with a volume fraction of 5%.

fraction of primary pores in the agglomerate.

Fig. 5 illustrates the comparison between the FIA model and the PIA-I model while varying the
volume fraction of primary pores in the agglomerate. It is clearly shown that the primary pores make
a big difference to the V-I curve. Even with a very small fraction of primary pores in the agglomerate
core, such as 1%, the performance of the agglomerate is much improved in the diffusion region of
the V-I curve. This improvement is attributed to the enhanced oxygen diffusion inside the
agglomerate. As shown in Fig. 6, the oxygen concentration profiles inside the agglomerate now
become much more uniform compared with Fig. 3. That is, the performance is limited by the
diffusion in the ionomer film instead of that in the agglomerate core. As a result, further increase of
the volume fraction only has a small effect on the performance, as shown in Fig. 5.
The almost uniform concentration profile may overthrow some conclusions drawn based on the
conventional FIA model. For example, Cetinbas et al. (2013) advocated concentrating the Pt
particles toward the periphery of the agglomerate core to reduce the diffusion lose and so as to
improve the catalyst utilization. Nevertheless, Fig. 6 shows that the diffusion loss in the
agglomerate is negligible, therefore, gradient Pt particles can hardly have an effect on the
performance.
One need to note that only the interconnected primary pores contribute to the oxygen diffusion,
while, in reality, some of the primary pores are isolated. Therefore, the improvement of oxygen
diffusion by the primary pores may be too optimistic in this study. A more sophisticated description
needs to consider the bottlenecks between primary pores. In this view, the pore-level direct
numerical simulation is preferred (Ji, 2010).
3.3

Effect of the ratio, ric/ragg, based on PIA-II model

1023

-7

0
-0.1

=1/3

Partially flooded with primary pores and an inactive core, r /r

=2/3

Partially flooded with primary pores and an inactive core, r /r

=2.5/3

ic agg
ic agg
ic agg

With an inactive core only, ric/ragg=2.5/3

-0.2

-0.3

-0.3

-0.4

-0.4

-0.5

-0.5

-0.6

-0.6

-0.7
-0.8
0

Fully flooded
With an inactive core only, ric/ragg=1/3

-0.1

Overpotential, , / V

Overpotential, , / V

-0.2

Partially flooded with primary pores

Partially flooded with primary pores and an inactive core, r /r

-0.7
1000

2000

3000

Current density, i

4000
agg

/Am

5000

6000

-2

-0.8
0

1000

2000

3000

Current density, i

4000
agg

/Am

5000

6000

-2

Fig. 7. The effect of an inactive core on the V-I

Fig. 8. The effect of an inactive core on the V-I

curve of the agglomerate while varying the ration,

curve of the agglomerate while varying the ration,

ric/ragg, based on the PIA-II model

ric/ragg, based on a partially impregnated

agglomerate model with an inactive core only, no
primary pores are considered.

Various studies have been concentrating on optimizing the ionomer content in the catalyst
layer based on the agglomerate model (Kamarajugadda& Mazumder, 2008). In these studies, a
homogeneous distribution of Nafion is always assumed in the agglomerate core. However, this
assumption can be violated since insufficient or obstructed impregnation of polymer electrolyte may
result in a partially impregnated agglomerate with an inactive core. Based on the PIA-II model, Fig.
7 illustrates the effect of an inactive core on the V-I curve of the agglomerate while varying the
ration, ric/ragg. An inactive core reduces the performance which is in consistent with the experimental
findings of performance loss at low ionomer content (Passalacqua, 2001). On the contrary, if one
neglects the primary pores in the agglomerate, the performance is inversely improved with an
inactive core, as shown in Fig. 8. This performance improvement is the consequence of the
enhancement of the oxygen diffusion in the agglomerate thanks to the inactive core. However, this
simulation result of performance improvement deviates from the experimental findings. In other
words, the consideration of the primary pores is necessary to correctly comprehend the processes
in the agglomerate.
4

CONCLUSION
In this study, we propose a partially impregnated agglomerate model to investigate the effect of

the primary pores on the oxygen diffusion, to explore the effect of the possible inactive core on the
performance of the agglomerate, and meanwhile, to examine the overpotential distribution inside
the agglomerate. The numerical analysis indicates that the overpotential gradient is negligible
compared with the concentration gradient, and the assumption of a uniform overpotential profile is
appropriate. Primary pores can significantly enhance the oxygen diffusion in the agglomerate, and a
small fraction of primary pores can improve the performance remarkably. Based on the partially
impregnated agglomerate model considering the primary pores, an inactive core, induced by
insufficient or obstructed impregnation of polymer electrolyte, reduces the performance. While,
neglecting the primary pores will lead to incorrect results.
ACKNOWLEDGEMENTS

1024

This work is supported by the MOST Program for International Science and Technology
Cooperation Project (No.2013DFG60080)
NOMENCLATURE
apt

Total active area per volume of agglomerate, [1/m]

Cathodic transfer coefficient

A0

the specific surface area of Pt, [m2/g]

Thickness of the ionomer film, [m]

c0

Oxygen concentration, [mol/m ]

e
agg

Nafion volume fraction in agglomerate

c0,ref

Reference oxygen concentration, [mol/m ]

pp
agg

Volume fraction of the primary pores in

agglomerate

Do

Diffusivity of oxygen in the ionomer, [m2/s]

cl

Porosity of the CL

Dkn

Knudsen diffusion coefficient, [m2/s]

Ionomer phase potential, [V]

Doeff

Effective diffusivity of oxygen in the ionomer, [m2/s]

Solid phase potential, [V]

Overpotential, [V]

Doeff,2 Effective diffusivity of oxygen considering the Knudsen

diffusion coefficient, [m2/s]
F

Faradays constant, [C/mol]

Ionic conductivity, [S/m]

Henrys constant, [atm m3/mol]

eeff

Effective ionic conductivity, [S/m]

i0,ref

Reference exchange current density, [A/m ]

Coefficient

kc

First-order reaction rate constant, [m/s]

ric/ragg

mpt

Pt loading, [g/m ]

Mo

Molecular weight of oxygen, [g/mol]

Coefficient

Po

Oxygen pressure, [atm]

Radial coordinate, [m]

ragg

Radius of the agglomerate, [m]

ric

Radius of the inactive core, [m]

rpp

Mean radius of the primary pores, [m]

Rorr

Source term, [mol/sm3]

tcl

Thickness of the CL, [m]

Temperature, [K]

apt i0,ref ragg 2

4 Fco,ref Doeff2

Fe
exp

RT

REFERENCES
Antolini, E., 2009, Carbon supports for low-temperature fuel cell catalysts. Applied Catalysis B:
Environmental, 88(1), 1-24.
Cetinbas, F. C., Advani, S. G., & Prasad, A. K., 2013, A Modified Agglomerate Model with Discrete
Catalyst Particles for the PEM Fuel Cell Catalyst Layer. Journal of The Electrochemical Society, 160(8),
F750-F756.

1025

Cetinbas, F. C., Advani, S. G., & Prasad, A. K., 2014, Three dimensional proton exchange membrane fuel
cell cathode model using a modified agglomerate approach based on discrete catalyst particles. Journal
of Power Sources, 250, 110-119.
Djilali, N., & Lu, D., 2002, Influence of heat transfer on gas and water transport in fuel cells. International
Journal of Thermal Sciences, 41(1), 29-40.
Fofana, D., Hamelin, J., & Bnard, P., 2013, Modelling and experimental validation of high performance
low platinum multilayer cathode for polymer electrolyte membrane fuel cells (PEMFCs). International
Journal of Hydrogen Energy, 38(24), 10050-10062.
Jain, P., Biegler, L. T., & Jhon, M. S. (2010). Sensitivity of PEFC models to cathode layer
microstructure. Journal of the Electrochemical Society, 157(8), B1222-B1229.
Ji, Y., Luo, G., & Wang, C. Y., 2010, Pore-level liquid water transport through composite diffusion media
of PEMFC. Journal of The Electrochemical Society, 157(12), B1753-B1761.
Kamarajugadda, S., & Mazumder, S., 2008, Numerical investigation of the effect of cathode catalyst layer
structure and composition on polymer electrolyte membrane fuel cell performance. Journal of Power
Sources,183(2), 629-642.
Kim, J. H., Kim, H. J., Lim, T. H., & Lee, H. I., 2007, Dependence of the performance of a
high-temperature polymer electrolyte fuel cell on phosphoric acid-doped polybenzimidazole ionomer
content in cathode catalyst layer. Journal of power sources, 170(2), 275-280.
Passalacqua, E., Lufrano, F., Squadrito, G., Patti, A., & Giorgi, L., 2001, Nafion content in the catalyst
layer of polymer electrolyte fuel cells: effects on structure and performance. Electrochimica Acta, 46(6),
799-805.
Rao, R.M., & Rengaswamy, R., 2006, Dynamic characteristics of spherical agglomerate for study of
cathode catalyst layers in proton exchange membrane fuel cells (PEMFC). Journal of power
sources, 158(1), 110-123.
Soboleva, T., Zhao, X., Malek, K., Xie, Z., Navessin, T., Holdcroft, S., 2010, On the micro-, meso-, and
macroporous structures of polymer electrolyte membrane fuel cell catalyst layers. ACS applied materials
& interfaces, 2(2), 375-384.
Tominaka, S., Goto, K., Momma, T., & Osaka, T., 2009, Ionic conductivity improvement in primary pores
of fuel cell catalyst layers: Electropolymerization of< i> m</i>-aminobenzenesulfonic acid and its effect on
the performance. Journal of Power Sources, 192(2), 316-323.
Yin, K. M., 2005, Parametric study of proton-exchange-membrane fuel cell cathode using an
agglomerate model. Journal of The Electrochemical Society, 152(3), A583-A593.

APPENDIX
Solution of the oxygen concentration and potential of ionomer phase in FIAM.
For the ionomer film, the oxygen concentration and potential of ionomer phase obey the
following formulations:
co r co0

p1
Do

1
1

r ragg f

1026

(A-1)

e r e0

p2 1
1

e r ragg f

(A-2)
For the agglomerate core, the dimensionless controlling equations are rewritten as:
2

co 2 co

1 exp e co
r 2 r r

(A-3)

e 2 e

2 exp e co
r 2 r r
2

(A-4)
where, c co r Fe r
o
e
co,ref
RT
That is,

2 co 1 e
co 1 e
2 2
2

0
r
r
r 2

(A-5)
Due to the consistency of both the controlling equation and boundary conditions, a linear
relationship between

e 2 co p3
1

co

and e can be established based on Eq. (A-5):

(A-6)
Substituting Eq. (A-6) into Eq. (A-3), we get:
2

co 2 co

1 exp 2 co p3 co
2
r r
r
1

(A-7)
Order analysis give: 2 10-3 , therefore,
1

2 co 2 co

1 exp 2 co p3 co e p3 1 2 co co e p3 1 2 co0 co

r 2 r r
1

(A-8)
Defining, 1 =1e p 2 = 2 e p 1 2co0 , we get:
3

2 co 2 co

2 co
r 2 r r

(A-9)
Applying the zero-gradient boundary condition at r 0 , we obtain the solution of Eq. (A-9):
co r p4

sinh r
r

(A-10)
Then, the ionomer phase potential follows:
e r

sinh r
2
p4
p3
1
r

$

1027

EFFECT OF RECIRCULATION VAPOR QUALITY ON PERFORMANCE OF A

DIRECT STEAM GENERATION SOLAR FIELD
*

Jie Sun , Qibin Liu and Hui Hong

Institute of Engineering Thermophysics, Chinese Academy of Sciences, Beijing 100190, China
*

sunjie@mail.etp.ac.cn

ABSTRACT
Direct steam generation (DSG) is one of the most promising technologies for the next-generation
concentrating solar power (CSP) plants. A hydraulic-thermal coupled model is proposed for
numerical study on performance of a single parabolic-trough DSG loop. The model has primarily
been validated by experimental data and then implemented to investigate the effect of recirculation
vapor quality (xrec=0.2~0.8) on performance of the DSG solar field under different direct normal
irradiance (DNI=200~1000 W/m2) conditions. It has been found that the pumping power (Pp) and
steam output (Mv) are more sensitive to xr under high DNI conditions while the field efficiency ()
and the flow pattern are more sensitive to xrec under low DNI conditions. The theoretically best
working condition emerges when xrec=0.8 and DNI=1000 W/m2, giving Pp=34.0 kW, Mv=1.43 kg/s
and =0.69 for a single loop. The results also indicate that the control strategy could be based on
xrec. A drop in xrec under high DNI conditions could lead to excessive pump consumption and
insufficient steam output while a high xrec under low DNI conditions results in potential failure due
to radial thermal stress problem in the receiver tube.
Keywords: solar energy, concentrating solar power (CSP), direct steam generation (DSG),
parabolic trough collector (PTC)
INTRODUCTION
In the last decades, the problems of increasing primary energy consumption, security of energy
supply and accelerating climate change have drawn worldwide attentions to renewable energy
sources. Solar energy has been widely recognized as one of the most competitive alternatives due
to the characteristics of green, low-cost and renewability. For example, the German Aerospace
Center (DLR), in a detailed study of the renewable energy potential of the MENA region plus South
European countries, estimated that concentrating solar power (CSP) plants could provide as much
as half the electricity consumption around the Mediterranean Sea by 2050 (International Energy
Agency, 2011) (see Fig. 1).
The CSP solar field is usually classified into one of the four basic categories based on the type of
solar energy collector, namely parabolic trough collector (PTC), parabolic dish collector (PDC),
heliostat field collector (HFC) and linear Fresnel reflector (LFR) (Barlev et al., 2011). The solar
energy collector is a heat-exchanging device that transfers solar radiation into thermal energy for
power generation. Generally a heat transfer fluid (HTF) is indispensable for a CSP solar field. The
concentrated solar energy is carried away in the form of thermal energy by the HTF; the HTF
transfers the thermal energy and evaporates the water for the steam turbine. The HTF serves as
intermediate for heat transfer, however, it also introduces disadvantages. Take the most prevailing
and mature PTC-CSP design for an example, the HTF is synthetic oil and it inherently has
environmental risks (fire and leaks) and degrading temperature limit of around 400 C. To avoid
HTF, direct steam generation (DSG) has been proposed and recognized as one of the most
promising technologies for the next-generation CSP application. In DSG technology, water is
directly used in the PTC to generate steam. Obviously, compared with HTF, the advantages for
DSG are (Fernandez-Garcia et al., 2010):
(1) Environmentally risks of fire and leakage are eliminated;
(2) The maximum temperature of the thermodynamic cycle can be increased over 400 C for
higher steam turbine efficiency;
(3) Overall plant efficiency is higher because the oil/steam heat-exchanger is unnecessary, which
also lower the investment;
(4) Plant configuration is simplified because the heat-exchangers and auxiliary synthetic oil
systems are eliminated;
(5) Operation and maintenance costs are reduced because there must be an auxiliary heating
system for synthetic oil and 3% must be replaced annually.
All the above advantages could potentially reduce the cost of the power produced by about 15%. A
schematically comparison between DSG and HTF power plant is shown in Fig. 2.

1028

However, there are also new challenges such as:

(1) The water flow must always be above the minimum threshold to avoid stratified flow in the
evaporation zone;
(2) Control systems are more complex and expensive;
(3) Higher operating pressure requires suitable hydraulic components, which cost more.

Fig. 1 Electricity generation from 2000 to 2050 and mix in 2050 in all MENA and South-European countries (International Energy
Agency, 2011).

Fig. 2 Comparison between DSG (left) and HTF (right) power plants (PTC-type) (Feldhoff, 2012).

Due to the characteristics of steam-water two-phase flow, the control of a DSG solar field is
distinctly different from a HTF solar field and the flow pattern should always be taken into serious
consideration. Generally, the flow patterns in a horizontal flow include bubbly flow, plug flow, slug
flow, wavy flow, stratified flow and annular flow (Collier and Thome, 1994) (see Fig. 3). Technically,
the stratified flow leaves the inner tube surface partially unwetted and thus has thermal stress risks
due to partially overheating in the dry region (see Fig. 4). Almanza et al.(Almanza et al., 1997,
Almanza et al., 2002) have shown that the thermal-stress-induced bending could cause a
deflection up to 6.5 cm for a 2.9 m long receiver tube. On the other hand, the annular flow gives an
ideal steam/water profile where the inner tube surface is wholly wetted (see Fig. 3). Therefore,
annular flow is the favorable flow pattern while stratified flow is the one to be avoided, which is one
of most important point the receiver design and control strategy should be based on.
Receiver design
Flores and Almanza (Flores and Almanza, 2004, Flores and Almanza, 2007) proposed a Cu-Fe
bimetallic receiver as a solution to the thermal-stress problem. Although the experimental results
showed good improvement in circumferential temperature profile that the maximum temperature
difference was reduced to 10 C. However, the high cost of the bimetallic tube is still a barrier.
Rojas and co-workers (Rojas and de Andres, 2004, Rojas and de Andres, 2006, Rojas et al., 2008)
introduced the re-construction of the steam-water profile by capillary effect. The inner tube surface
was machined with microchannels or porous coatings. Therefore, the wetting front rose due to
capillary pumping. Both numerical and experimental results showed that the angular liquid front
position could increase by 50 and approaching 180 for the best case. On the other hand, the
microchannels or porous coatings could also promote the nucleate boiling. Wang et al. (2013) also
benefitted the capillary effect to improve the wetting condition but in form of metal foam. They
numerically investigated the effects of layout, geometrical parameter and porosity of metal foam on
the flow resistance, heat transfer and thermo-hydraulic performance. It was found that the
maximum circumferential temperature difference decreased by about 45% when the optimum

1029

thermal performance was obtained, which could greatly reduce the thermal stress. However, the
above capillary-based methods demand higher processing standards, and thus higher cost.
Control strategy
According to the characteristic of two-phase flow, the stratified flow could be theoretically avoided
if the flow rate is maintained above the threshold (see Fig. 3). That is to say, the flow pattern
should be integrated with the system control strategy. Three basic DSG operation modes inlcude
once-through, injection and recirculation. The practical experience acquired through the DISS
project has verified the supremacy of recirculation mode over the other two due to high
controllability and thermohydraulic stability (Eck and Steinmann, 2002, Zarza et al., 2002, Zarza et
al., 2004). Therefore, the recirculation mode has been widely chosen as researching topic ever
since then. Valenzuela et al. (Valenzuela et al., 2005, Valenzuela et al., 2006) investigated the
control strategies of DSG solar field and presented details of the control scheme for recirculation
mode, for which the main objective was to obtain steam at constant temperature and pressure at
the outlet of solar field. It was found that the system is more stable, and consequently, easier to
control, at higher pressures (100 bar, 60 bar) than at lower pressures (30 bar), because the
thermodynamic properties (specific enthalpy, thermal conductivity, etc.) of the water and the steam
differ more at low pressure than at high pressure. However, high pressure and temperature could
cause higher risk of thermal stress problem. Eck and Steinmann (2005) built a themohydraulic
model of DSG solar field, which could be used for systematic assessment and optimization based
on the distributions of thermophysical parameter along the loop.
It is known from the above review that the thermal stress problem should be primarily avoided by
maintaining the flow rate at high level though surface-processing of receiver is an alternative for
low flow rate case. The control strategy must be specially built based on the thermohydraulic
characteristics of a DSG loop. On the other hand, the performance of a DSG solar field is highly
dependent on the control strategy. Since the vapor quality is a key characteristic parameter of twophase flow, the effects of vapor quality on the performance of a DSG solar field is investigated in
the present work.

Fig. 3 Map of two-phase flow patterns (Collier and Thome, 1994)

Fig. 4 Schematic of overheating problem in DSG receiver

(Feldhoff, 2012)

MODELLING
The present thermohydraulic model is based on the energy balance of the receiver tube as:

Qheatgain Qabsorbed Qheatloss

(1)

where Qheatgain , Qabsorbed and Qheatloss are the effective heat gain, absorbed radiation and heat loss,
respectively, W .
The equation for the absorbed solar radiation is:

Qabsorbed DNI cos( ) IAM opt field

(2)

1030

where DNI is the direct normal radiation, W/m2 ; is the angle of incidence, ; IAM is the
incidence angle modifier, -; opt is the optical efficiency accounts for losses due to receiver optics
and imperfections, -; field is the field efficiency accounts for losses due to field optics and
imperfections, -. The equation for IAM used in the present work is based on performance tests
conducted at Sandia National Laboratories on an LS-2 collector (Dudley et al., 1994), as:

IAM 1 0.000884 / cos( ) 0.00005369 2 / cos( )

(3)

To evaluate the solar field, the overall energy efficiency is defined as:

Qcollected / Qtotal

(4)

where Qtotal DNI Aa is the total radiation, W , Aa being the total aperture area, m 2 .
Based on the heat transfer analysis of receiver tube in Fig. 5, it is obtained that

Qheatgain Qabsorbed Qheatloss Q2-1, conv Q3-2, cond

(5)

Qheatloss Q3-4, conv Q3-4, rad Q4-5, cond Q5-6, conv Q5-6, rad

(6)

where Q2-1, conv is the forced convection between inner tube surface and the working fluid, W ;

Q3-2, cond is the heat conduction between outer and inner tube surfaces, W ; Q3-4, conv and Q3-4, rad the
natural convection and radiation between the outer tube surface and the inner glass envelop surface,
W ; Q4-5, cond is the heat conduction between inner and outer glass envelop surfaces, W ; Q5-6, conv
and Q5-6, rad are the natural/forced convection and radiation between the outer glass tube surface and
the ambient, W .

Q5-6, rad is calculated as:

Q5-6, rad D5l 5 (T54 T64 )

(7)

where l is the length, m ; D5 is the outer diameter of glass envelop, m ; is the StephenBoltzmann constant, 5.67 108 W/m2 K ; 5 is the emissivity of the outer glass envelop surface,
-; T5 and T6 are the temperatures of the outer glass envelop surface and ambient, K .

Q3-4, rad is calculated as:

Q3-4, rad l (T34 T44 ) / 1/ 3 (1/ 4 1)( D3 / D4 )

(8)

where D3 and D4 are the outer diameter of tube and inner diameter of glass envelop, respectively,

m ; 3 and 4 is the emissivity of the outer tube surface and inner glass envelop surface, -; T3 and
T4 are the temperatures of the outer tube surface and inner glass envelop surface, K .
The heat conduction is calculated by Fouriers law, as:

Qi - j , cond 2 lki j (Ti Tj ) / ln D j / Di , i=3, j=4 or i=5, j=6

where ki j is the conductivity of material, W/mK .

Q3-4, conv is neglected because the space between the outer tube surface and the inner glass envelop
surface is assumed to be vacuum.
The forced convection is calculated by Newtons law of cooling, as:

1031

(9)

Qi - j , conv Dlhi j (Ti Tj ) , i=2, j=1 or i=5, j=6

(10)

hi j ki j NuDi D5 , i=2, j=1 or i=5, j=6

(11)

where hi j is the heat transfer coefficient, W/m2 K ; ki j is heat conductivity of air, W/mK ; NuDi is
the Nusselt number based on Di .
When it is natural convection between the outer glass tube surface and the ambient, NuD5 is
calculated by Churchill and Chu correlation (Churchill and Chu, 1975), as:

0.387 Ra1/6

D5
0.6

9/16 8/ 27
1 0.559 / Pr5 6

NuD5

RaD5

(12)

g 5 6 T5 T6 D53

(13)

5 6 5 6

56 1/ T56

(14)

where T56 T5 T6 / 2 the characteristic temperature , K ; RaD5 is the Rayleigh number based on

D5 , ( 105 RaD5 1012 ); g is the gravity, g 9.81 m/s2 ; Pr5 6 is the Prandtl number based on T5 6 , ; 5 6 , 5 6 and 5 6 are the volume expansivity, thermal diffusivity and kinematic viscosity of air,
respectively, 1/K , m2 /s , m2 /s .
When it is natural convection between the outer glass tube surface and the ambient, NuD5 is
calculated by the following correlation (Cengel, 2006), as:

NuD5 CRenD5 Pr1/3

(15)

where Re D5 is the Reynolds number based on D5 , 0.4 ReD5 4 10 5 ; the values of C and n are
dependent on Re D5 . More details can be found in (Cengel, 2006).
The forced convection in receiver tube could be single-phase or two-phase. When it is single-phase
forced convection and the flow is laminar, NuD2 4.36 while if it is turbulent, NuD2 is calculated by
Gnielinski correlation (Cengel, 2006), as:

f 2 / 8 ReD -1000 Pr1 Pr1 0.11

0.5
1 12.7 f 2 / 8 ( Pr12/3 1) Pr1
2

NuD2

f 2 1.82log10 ReD2 1.64

(16)

(17)

where f 2 is the friction factor, -; the ranges of Prandtl and Reynolds numbers are 0.5<Pr1 2000
and 2300<ReD2 5 10 6 , respectively.
When two-phase forced convection is in the receiver tube, it becomes flow boiling problem
considering the phase-change. This is the most important flow type in a DSG solar filed. The heat
transfer coefficient h2 1 is calculated differently based on the Froud number Fr (Odeh et al., 1998,
Eck and Steinmann, 2005), which is defined as:

Fr

G2
l2 gDab,i

(18)

1032

if Fr 0.04 , h2 1 is calculated by Shah correlation (Stephen, 1992), as:

h2 1
x
3.9 Fr 0.24

hl
1 x

0.64

l

v

0.4

(19)

0.8

k G 1 x D1
0.4
hl 0.23 l
Prl
l
D1

where hl is the heat transfer coefficient assuming the tube is fully occupied by liquid, W/m2 K ; x is

(20)

vapor quality, -; l and v are the densities of liquid and vapor phases, respectively, kg/m3 .
if Fr 0.04 , h2 1 is calculated by Gungor and Winterton correlation (Gungor and Winterton, 1986,
Stephen, 1992), as:

h21 Ehl ShNB

0.12
r

hNB 55P

(21)

( log10 Pr )

0.55

0.5

0.67

(22)

Pr P / Pc

(23)
1.16

1.37 X

E 1 24000Bo

0.86

(24)

1.17 1
l

S (1 1.15 10 E Re

(25)

Bo q / rG

(26)
0.9

0.5

1 x v l
X

x l v

0.1

(27)

where Pc is the critical pressure of water, Pc 221 bar ; M is the molecular mass of water,

M 18 g/mol ; q is the heat flux, W/m2 ; Bo is the boiling number, -; r is the vaporization heat,
kJ/kg ; X is the Martinelli number, -; l and v are the dynamic viscosities of liquid and vapor
phases, respectively, Pa s .
In the simulation, the loop is discretized equally into N nodes. The outlet temperature of working fluid
in each section is calculated based on the heat gain. If the flow is single-phase, then

to,i Qheatgain,i / c p,i ti,i

(28)

where i is the node index, -; c p ,i is the isobaric thermal capacity of working fluid, J/kg K ; ti and to
are the inlet and outlet temperature of working fluid, o C .
If the flow is two-phase, then to,i is calculated according to the saturated pressure po,i , which is
determined based on the local pressure drop (Eck and Steinmann, 2005).
glass
envelop

solar radiation

receiver tube

heat gain

1033

heat loss

Fig. 5 Schematic of heat transfer analysis of receiver. (1) working fluid; (2) inner surface of receiver tube; (3) outer surface of receiver
tube; (4) inner surface of glass envelop; (5) outer surface of glass envelop; (6) ambient.

RESULTS AND DISCUSSION

Code validation
Based on the present thermohydraulic model, a code has been developed to simulate a single DSG
loop working in recirculation mode. The layout is shown in Fig. 6. The single loop is comprised of
10 collectors. The recirculation point is set between 8th and 9th collectors while an injection point is
set between 9th and 10th collectors to prevent overheating. The code is primarily validated by
experimental data from INDITEP project (Zarza et al., 2006). The collector configuration and
environmental and working conditions are listed in Table 1 and Table 2, respectively. A good
agreement between the present simulation results and experimental data can be seen in Fig. 7a.
In addition, the profile of local heat loss gradually increases in the preheating stage, then stays
constant in the evaporation stage, finally increases acceleratingly in the superheating stage. The
reason is that the vapor-solid convective heat transfer in the superheating stage is much weaker
than the liquid-solid convective heat transfer in the preheating stage and the evaporative heat
transfer in the evaporation stage (see Fig. 7b). The lower heat transfer coefficient and high
temperature difference in the superheating stage have proven this point. Accordingly, the profile of
local energy efficiency decreases in the preheating stage, keeps constant in the evaporation stage
while drops sharply in the superheating stage. The overall energy efficiency of the present
simulation is 65.7% while that of the experimental data is 65.2%. The above profiles have
indicated that from a heat transfer point of view, attention should be put on the superheating stage,
where potential enhancement could effectively improve the overall energy efficiency.
preheating

evaperation

superheating

vapor/liquid seperator

Fig. 6 Schematic of the present DSG recirculation loop (solid line: water; dash dot line: steam/water mixture; dot line: steam).
Table 1 Collector configuration
Overall length of a single collector (m)
Number of parabolic-trough modules
per collector
Gross length of every module (m)
Aperture (m)
Outer diameter of receiver tube (m)
Inner diameter of receiver tube (m)
Net collector aperture area per collector (m2)
Inner roughness factor of receiver tube (m)

Table 2 Environmental and working conditions

Direct solar irradiance
875 W/m2
Geographical longitude of the site
558 W
Geographical latitude of the site
3724 N
Incidence angle of solar radiation
13.7
Air temperature
20 C
Wind speed
1.5 m/s
Inlet water temperature
153 C
Inlet water pressure
80 bar
Outlet steam temperature
410 C
Outlet steam pressure
70 bar

98.5
8
12.27
6.76
0.07
0.055
548.35
4E-5

1034

(a) Comparison between the present simulation and

(b) Profiles of heat transfer coefficients, temperature differences,
experimental data (Zarza et al., 2006).
heat loss and energy efficiency.
Fig. 7 Code validation.

Investigation of recirculation vapor quality

In recirculation mode, the stability and efficiency of a DSG solar field is sensitive to the recirculation
vapor quality xrec . Ideally, xrec is supposed constant at an optimal value (Odeh et al., 1998). However,
the solar radiation continuously varies with time, the flow rate must be adjusted accordingly thus xrec
changes. The deviation of xrec is therefore unavoidable. The following part is to quantify the effects of

xrec on the stability and efficiency of a DSG solar field under different DNI conditions. The
recirculation vapor quality ranges from 0.2 to 0.8 while the DNI changes from 200 W/m2 to 1000
W/m2. The feed water temperature and pressure are constant at 124 C and 80 bar. The output
condition is fixed at the desired temperature 400 C. The simulation runs in an iterative way based on
a given combination of xrec and DNI. All the other thermohydraulic parameters are obtained
immediately when the iteration converges.
The pressure profiles under different conditions are shown in Fig. 8. Generally, the outlet steam
pressure decreases with decreasing xrec and increasing DNI. For a given combination of xrec and
DNI, the pressure gradient before recirculation point is higher than after and the pressure decreases
with increasing xrec because the liquid phase causes larger pressure drop than the vapor phase.
Specifically, the pressure profiles is much more sensitive to xrec in high DNI case (DNI=1000 W/m2)
than in low DNI case (DNI=200 W/m2) because the mass flow rate increases with increasing DNI.
The difference of pressure gradient before and after the recirculation point is smaller in higher xrec
and lower DNI case.
Since the condition of the feed water is fixed at 124 C and 80 bar, the inlet water temperature
depends on the condition of recirculating water, which is a part of the separated water. On the other
hand, since the outlet steam temperature is fixed at 400 C, the rest part of the separated water is
used to adjust the outlet steam temperature through injection. The temperature profiles under
different conditions are shown in Fig. 9. It is seen that the inlet water temperature decreases with
increasing xrec from 250 C ( xrec 0.2 ) to 150 C ( xrec 0.8 ). The range of preheating stage shrinks
with increasing xrec from about 347 m ( xrec 0.2 ) to about 276 m ( xrec 0.8 ). The steam
temperature drop at the injection point decreases with increasing xrec from about 80 C ( xrec 0.2 ) to
about 23 C ( xrec 0.8 ). Generally, the temperature profile is much more sensitive to xrec than to

1035

DNI. It is noted that in case of low xrec ( xrec 0.2 ) and high DNI (DNI=1000 W/m2) a remarkable
temperature drop exists in evaporation stage because of the friction-induced large pressure drop.

Fig. 8 Pressure profiles under different conditions.

Fig. 9 Temperature profiles under different conditions.

The mass flow rate profiles under different conditions are shown in Fig. 10. It is seen that the inlet
water mass flow rate increases with decreasing xrec and increasing DNI from 0.29 kg/s ( xrec 0.8 ,
DNI=200 W/m2) to 5.83 kg/s ( xrec 0.2 , DNI=1000 W/m2). However, apart from xrec and DNI, the
outlet steam mass flow rate additionally depends on both the mass flow rate and conditions of
injection. The outlet steam mass flow rate varies differently from the inlet water flow rate that it
increases with increasing xrec and DNI from 0.22 kg/s ( xrec 0.2 , DNI=200 W/m2) to 1.43 kg/s
( xrec 0.8 , DNI=1000 W/m2).
The energy efficiency is significantly affected by the heat loss. The energy efficiency profiles under
different conditions are shown in Fig. 11. Generally, the energy efficiency primarily increases with
increasing DNI and is also affected by xrec . The local energy efficiency in the preheating stage
increases with increasing xrec because it is liquid-solid convective heat transfer and higher mass flow
rate gives higher heat transfer coefficient. The local energy efficiency in the evaporation stage is
basically constant and solely dependent on DNI because the boiling heat transfer coefficient is very
high (~104 W/m2K). The local energy efficiency in the superheating stage drops sharply due to the
fact that the vapor-solid convective heat transfer is weak (~103 W/m2K) and the temperature is high
(>300 C) therefore the heat loss is large. Obviously, the superheating stage is a weak point in the
DSG loop in terms of heat transfer. Improvement could be focused on both heat transfer
enhancement internally and heat insulation externally of the receiver.

Fig. 10 Mass flow rate profiles under different conditions.

Fig. 11 Energy efficiency profiles under different conditions.

1036

For a more comprehensively parametric investigation, the pumping power and overall energy
efficiency are illustrated against xrec and DNI in Fig. 12 and Fig. 13, respectively. It is found that the
pumping power grows increasingly with decreasing xrec and increasing DNI. On the other hand, the
overall energy efficiency grows decreasingly with increasing DNI and seems not sensitive to xrec ,
especially in high DNI cases. To investigate the thermal-stress-induced risk, the flow pattern analysis
under different conditions is shown in Fig. 14. It is seen that the flow pattern is more likely to
experience stratified flow in higher xrec and lower DNI cases. For example, when xrec 0.8 and
DNI=200 W/m2, the flow pattern is predicted to be stratified where a high risk of thermal stress
problem exists. Note that the range of potential stratified flow also increases with increasing xrec ,
which even raises the risk. Based on the present simulations, the theoretically best working
condition emerges when xrec 0.8 and DNI=1000 W/m2, giving Pp=34.0 kW, Mv=1.43 kg/s and
=0.69. Taking all the above factors into consideration, it is recommended that the DSG recirculation
loop should be running with a high xrec in high DNI cases because a drop of xrec could cause
significant pump consumption; on the other hand, the DSG recirculation loop should be running with a
comparatively lower xrec in low DNI cases in order to keep the flow pattern away from stratified flow
and avoid the risk of thermal-stress-induced problem.

Fig. 12 Variation of pumping power ( Pp ) versus recirculation vapor

Fig. 13 Energy efficiency ( ) versus recirculation vapor quality ( xrec )

quality ( xrec ) and direct normal irradiance (DNI).

and direct normal irradiance (DNI).

Fig. 14 Flow pattern analysis under different conditions.

1037

CONCLUSIONS
In the present work, a hydraulic-thermal coupled model has been proposed for numerical study on
performance of a single parabolic-trough DSG loop. Before implementation, the proposed model
was validated by experimental data. The results also indicate that attention should be put on the
superheating stage, where potential enhancement could effectively improve the overall energy
efficiency. Then, the effect of recirculation vapor quality ( xrec 0.2 ~ 0.8 ) on performance of the
DSG solar field under different direct normal irradiance (DNI=200~1000 W/m2) conditions was
numerically studied. It has been found that the pumping power (Pp) and vapor output (Mv) are more
sensitive to xrec under high DNI conditions while the field efficiency () and the flow pattern are
more sensitive to xrec under low DNI conditions. The theoretically best working condition emerges
when xrec 0.8 and DNI=1000 W/m2, giving Pp=34.0 kW, Mv=1.43 kg/s and =0.69. The results
indicate that the control strategy could be based on xrec . Base on the present hydraulic and
thermal analysis, it is recommended that the DSG recirculation loop should be running with a high
xrec in high DNI cases because a drop of xrec could cause significant pump consumption. On the
other hand, the DSG recirculation loop should be running with a comparatively lower xrec in low DNI
cases in order to keep the flow pattern away from stratified flow and avoid the risk of thermal-stressinduced problem.
ACKNOWLEDGEMENT
Financial support from the Beijing Natural Science Foundation (3142021) is acknowledged.
NOMENCLATURE
total aperture area, m 2
Aa
Bo
the boiling number, C, n
coefficient
diameter, m
D
direct normal radiation, W/m2
DNI
the Froud number
Fr
friction factor, f

the gravity, g 9.81 m/s2

h
IAM
k
l
M
Nu
Pp

heat transfer coefficient, W/m2 K

incidence angle modifier, conductivity, W/mK
length, m
molecular mass of water, M 18 g/mol ; mass flow rate, kg/s
the Nusselt number, pumping power, kW

Pr
p
pc
pr
Q

the Prandtl number, pressure, bar

q
Ra
Re
r
T
t
X
x

heat flux, W/m2

the Rayleigh number, the Reynolds number, vaporization heat, kJ/kg
temperature, K
temperature, o C
the Martinelli number, vapor quality, -

critical pressure, bar

relative pressure, bar
energy flow, W

Greek Letters

thermal diffusivity, m2 /s
volume expansivity, 1/K

1038

opt

emissivity, energy efficiency, -

field

field efficiency, -

kinematic viscosity, , m2 /s
density, kg/m3

the Stephen-Boltzmann constant, 5.67 108 W/m2 K

Subscripts
1
2
3
4
5
6
absorbed
cond
cov
heatgain
heatloss
i

i
l
o
rad
rec
total
v

optical efficiency, angle of incidence,

dynamic viscosity, Pa s

related to working fluid

related to inner surface of receiver tube
related to outer surface of receiver tube
related to inner surface of glass envelop
related to outer surface of glass envelop
related to the ambient.
related to energy absorbed
heat conduction
convective heat transfer
related to eat gain
heat loss
inlet
index
liquid
outlet
radiative heat transfer
recirculation
total solar radiation
vapor

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1039

Feldhoff, F., 2012, Direct steam generation (DSG) technology overview, SFERA Summer School
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1040

KINETICS AND THERMODYNAMICS INVESTIGATION OF SUPERCRITICAL

REACTIVE EXTRACTION FOR JATROPHA CURCAS L. SEEDS IN BIODIESEL
PRODUCTION
1,2,

Steven Lim *, Yean-Ling Pang , Hwai-Chyuan Ong , Wen-Tong Chong and Keat-Teong Lee
Department of Mechanical Engineering, Faculty of Engineering, University of Malaya, Kuala Lumpur,
Malaysia
2
School of Chemical Engineering, Universiti Sains Malaysia, Penang, Malaysia
*E-mail: stevenlim@um.edu.my

ABSTRACT
Process intensification of biodiesel production from non-edible feedstock such as Jatropha
curcas L. (JCL) has been studied fervently in a bid to reduce the operational cost and
incorporating green chemistry elements throughout the process. Supercritical reactive
extraction is one of the promising process intensification for biodiesel production where
the extraction and reaction process proceed simultaneously in situ without any addition of
catalyst using solid seeds directly. In this study, the kinetics and thermodynamics
parameters of supercritical reactive extraction for JCL seeds in a batch reactor with
methanol were investigated through semi-empirical mathematical models. Supercritical
extraction was found to exhibit four different phases (lag, constant extraction, reduced
extraction and diffusion-controlled) and obeyed first order reaction kinetic. The estimated
values of diffusivity constant, Deff and Thiele modulus, showed that mass transfer inside
the particles were insignificant due to the high diffusivity of methanol in supercritical
conditions. Equilibrium constant, Ke was found to be higher than unity for three phases
which proved that the extraction of lipids was favored. Thermodynamics study showed that
the supercritical extraction process was feasible, spontaneous, highly endothermic and
irreversible. Transesterification reaction was discovered to follow pseudo first order rate
law and the activation energy, Ea was calculated to be 65.1 kJ mol-1. The estimated values
were comparable to other supercritical transesterification processes in the literature.
Transesterification process was subsequently simulated into three elementary steps
consisting of mono-, di- and triglyceride with the aid of Matlab software. Thermodynamic
parameters were also estimated for four different temperatures (240C, 260C, 280C and
300C). From the process parameters, kinetics and thermodynamics study, a suitable
mechanism describing the supercritical reactive extraction process was also proposed. The
results from this study enabled deeper understanding pertaining to the supercritical
reaction involving three phases (solid, liquid and gas) simultaneously.
Keywords: kinetics, mechanism, supercritical reactive extraction, Jatropha, biodiesel.
INTRODUCTION
Conventional method for the production of biodiesel from JCL and other types of oil seeds involve
various stages; oil extraction, purification (degumming, deacidification, dewaxing,
dephosphorization, dehydration, etc.) and esterification/transesterification. These processes
constitute a significant portion of the overall production cost while in the meantime, generate waste
streams which incurred additional loss of yield. Development of catalytic in-situ extraction,
esterification and transesterification or simply term as reactive extraction has the potential to cut
down the processing cost significantly while maintaining high product yield. The process differs
from the conventional biodiesel production process in which the oil-bearing material contacts with
alcohol directly instead of reacting with pre-extracted oil. In another words, extraction and
transesterification proceed in one single step, with alcohol acting both, as an extraction solvent
and a transesterification reagent. Therefore it eliminates the requirement of two separate
processes; the costly hexane oil extraction process and transesterification reaction process, thus
reducing processing time, cost and amount of solvent required.
Meanwhile, the utilization of supercritical fluids (SCFs) technology will eliminate the needs for
addition of expensive heterogeneous catalyst. SCFs are fluids above their critical temperature and
pressure with gas like diffusivities and liquid like viscosities. Their unique features enable SCFs to
form homogenous phase with the reactants and subsequently enhance the diffusion rates without
the aid of third-party catalyst. In addition, the usage of homogeneous or heterogeneous catalyst
results in a more complex process while requiring extra separation step post-reaction. Without
addition of catalyst, this can help to reduce product contamination and purification process thus
reduces the overall biodiesel production cost.

1041

In order to obtain the advantages of both processes, supercritical in situ extraction and
transesterification (SET) is developed which combines the application of reactive extraction with
SCFs. In this whole new intensification process, solid oil seeds will be reacted in situ with shortchain alcohol (methanol) to produce FAME under supercritical conditions without any addition of
catalyst. Theoretically, this process is able to enjoy ample of benefits from the combination process
while overcoming most of the weaknesses in the inherent biodiesel production system. Following
the previous works for SET process using JCL oil seeds, it is found that there is still lack of
fundamental studies pertaining to the process kinetics and mechanism (Lim and Lee, 2013).
Further understanding on the kinetics and thermodynamics behavior of SET process will be crucial
to explain their results in process study and up-scaling for commercial production. Therefore in this
study, mathematical models based on kinetics study were developed for both extraction and
reaction study together with thermodynamic parameters in order to predict the yield of products
according to different process conditions. Lastly, a relevant process mechanism representing SET
process based on the experimental observations and results was also proposed.
MATERIALS AND METHODS
Raw Materials
Raw JCL seeds with shell (planting-grade) investigated in this study were purchased from a local
plantation company in Malaysia (Misi Bumi Alam Sdn. Bhd.). They were kept in air-tight containers
placed within a proper ventilated cabinet away from direct sunlight prior to be used in the
experiment. Raw seeds were first manually de-shelled with pliers to obtain the white seed kernels.
Only seed kernels in good condition were retained and were subsequently ground into smaller
particles (50-80 m) using a mechanical grinder (Moulinex, France). Next, the seed samples were
subjected to heat treatment in a vacuum oven (Memmert, Germany, D-91126) at 75C, 3 kPa for
12 h. Pre-treated seed samples were then stored inside a desiccator before the reaction process.
The remaining moisture content of the seed kernels after heat-treated was 0.65 wt.% based on the
difference in weight compared to seed kernels dried at 105C, 3 kPa for 24 h. The available oil
content calculated was subsequently used as the reference for the calculation of process
responses (extraction and FAME yield) after the reaction.
Methanol (99.8% purity) was purchased from HmbG Chemicals, Germany. Analytical grade methyl
heptadecanoate which was used as the internal standard for gas chromatography (GC) FAME
analysis were purchased from Fluka Chemie, Germany. The other pure analytical standards for
GC, i.e., methyl palmitate, methyl stearate, methyl oleate, and methyl linoleate, were also
purchased from Fluka. All the listed chemicals are of analytical grades and were being used as
received without further purification. Distilled water was used where applicable for chemicals
preparation.
SET Process
SET was performed in a high-pressure isochoric batch reactor as described elsewhere (Mazaheri
et al. 2010). For a typical run, 15.0 g of pre-treated JCL sample was mixed with 75.0 ml of
methanol (152.8 mol ratio of methanol to oil) and added into the 450-ml reactor. When the
operating temperature reached the desired level (300C) (65 min after the initiation of heating), it
was held at that temperature for the duration of the reaction time (30 min) before quenching with
cooling water to room temperature. The reaction remained quiescent throughout the reaction,
without any external agitation. The reactor pressure was not an independent variable, but was
fixed according to the amount of reactants and the reaction temperature. After the reaction, the
product mixture removed from the reactor was first filtered to remove the solid residue. Next, 30.0
ml of n-hexane was added to the liquid product mixture and stirred for 30 min before being
transferred into a separation funnel. Two visible layers were formed upon settling by gravity for 30
min. The top, dark-brown layer mostly consisted of n-hexane and FAME, while the bottom darkcoloured layer contained a mixture of methanol, glycerol, and other polar compounds. The bottom
layer was decanted off, and the separation procedure was repeated twice. The top layers were
collected, and the solvent was separated from the FAME by using rotary evaporator (Buchi,
Switzerland, R-210). The final FAME samples were weighted as the total extracts obtained from
supercritical reactive extraction, and their subsequent volumes were also recorded. The extraction
efficiency was determined using Eq. (1). The solid residues after supercritical reactive extraction
were subjected to Sohxlet extraction with n-hexane to determine the amount of leftover oil inside
and validate against the extraction yield, Ee. All the experimental runs were performed in triplicate,
and the data variations were confined within 5%.

1042

Extraction yield, Ee (% w/w) =

(1)
Analytical Procedure
The concentration and composition of FAME were determined using a gas chromatograph (GC)
(Perkin-Elmer, Clarus 500) equipped with a NukolTM capillary column (15 m x 0.53 m; 0.5 m film
thickness) and flame ionization detector (FID). The details of the analytical procedure were
described in a previous work by the authors using pure methyl ester standards (Lim and Lee,
2013). The FAME yield was then calculated from Eq. (2).
FAME

yield,

Fy

(%

w/w)

=
(2)

Extraction
Based on the extraction yield collected from experimental data, two extraction mathematical
models were derived for comparison purpose. First, a simple empirical equation shown in Eq. (3)
was fitted to the experimental data (Esquivel et al., 1999). This was done by minimizing the value
of sum of square error (SSQ) using Microsoft Excel to determine the value of other constants
shown in Eq. (4).

(3)
where e is the ratio of the mass of recovered solute (g) in time t (min) to the initial mass of feed (g)
and elim is the maximum mass of recovered solute to the initial mass of feed in infinite extraction
time. Its adjustable parameter, b, does not have physical interpretation and may be a function of
mass flow rate, temperature and pressure.

(4)
where Xexp and Xpred are the experimental values and predicted values respectively. The second
mathematical model was modified from Eq. (5) (Sulaiman et al., 2013).

(5)
where dW A/dt is the rate of change of mass of solute (g/min); k.a is the volumetric mass transfer
coefficient (min-1); W A and W Ai are the mass of solute in solvent at time t and at equilibrium (g)
respectively. By taking into account that the value of k.a (min-1) is not constant and depended on
time, it was correlated as shown in Eq. (6).
k.a = kt
(6)
where k (min-2) is the apparent mass volumetric mass transfer coefficient. By substituting Eq. (6)
into Eq. (5) and integrating both sides from 0 to W A (g) and 0 to t (min), Eq. (7) was obtained.

(7)
Both mathematical models were then compared with the actual extraction experimental data. The
values of Thiele modulus, in Eq. (8) were calculated to determine the effect of internal mass
transfer resistance.

1043

(8)
where dp represents the particle diameter (m). Deff is the effective diffusivity (m2min-1).
In this equation, k.a which usually representing reaction rate constant is correlated to the mass
transfer coefficient by assuming that the spherical particle containing the solute is small and the
extraction is first order irreversible process (Giri and Sharma, 2000). The effect of internal mass
transfer resistance is negligible for any mass transfer process with value smaller than 2.
However, for value larger than 10, internal mass transfer limitation will play a main role in
extraction process. From the value of Thiele modulus, effectiveness factor, , which is correlated
to spherical particle, can then be calculated using Eq. (9).

(9)
For determining the effective diffusivity, Ficks second law is applied by assuming D eff remained
constant with the extraction yield, W A (g) at time t and initial yield at time 0, W 0 (g) (Pinelo et al.,
2006) as shown in Eq. (10).

(10)
Reaction
The rate of disappearance of triglycerides (TG) which was used as the reference for SET reaction
rate in this study, can be written according to Eq. (11). Due to the huge amount of methanol in this
process relative to the triglycerides, the concentration of methanol was assumed to be constant.
Thus, the rate of reaction becomes Eq. (12).

(11)

where rTG is the consumption rate of triglyceride (mol dm-3 min-1) , k is the reaction rate constant, CTG
and CMeOH are the concentration of triglycerides and methanol respectively (mol dm-3).

(12)
where k is the apparent reaction rate constant (min-1) . By taking natural logarithm on both sides,
the values of k for each temperature region and constant can then be determined through
minimizing the SSQ for predicted and experimental values of ln(-dCTG/dt) as shown in Eq. (13).

(13)
Activation energy and pre-exponential constant were then calculated through Arrhenius equation
by drawing the graph of 1/T vs ln k. For supercritical transesterification process in SET which
consists of 3 reversible elementary steps as shown in Fig. 1, the kinetic differential equations can
be derived as shown in Eqs. (14-18).

1044

dy1
dt

= k1 y1 + k2 y2 y5
(14)

dy 2
dt

= k3 y2 k2 y2 y5 + k1 y1 + k4 y3 y5
(15)

dy 3
dt

= k4 y3 y5 k5 y3 + k3 y2 + k6 y4 y5

(16)

dy 4
dt

= k6 y4 y5 + k5 y3
(17)

dy 5
dt

= - k2 y2 y5 k4 y3 y5 k6 y4 y5 + k1 y1 + k3 y2 + k5 y3
(18)

where y1, y2, y3, y4, and y5 are the concentrations (mol/dm3) of triglycerides, diglycerides,
monoglycerides, glycerol and FAME respectively. k1, k3 and k5 are the forward reaction rate
constants (min) whereas k2, k4 and k6 are the backward reaction rate constants (dm3/mol.min).
Ordinary Differential Equation (ODE45) solver available in Matlab (Version 7.0) was employed to
solve the differential equations. The process was divided into two parts; in the first part, the
reactants were being heated to the reaction temperature (0 < t < 70 min) while the second part
denoted the isothermal phase where reaction temperature was being held constant prior to
quenching (70 < t < 100 min). For the first part, the values of activation energy, Ea (kJ) and preexponential constant, A for all reaction rate constants were fixed according to calculated values
determined earlier. Subsequent values of pre-exponential constant were fine-tuned until the root
mean square error (RMSE) between predicted and experimental concentration values of both TG
and FAME were less than 5% as calculated from Eq. (19).

(19)
where n equals the total number of experimental points. If the value of RMSE is more than the
acceptable 5%, a new value was assigned according to Eq. (20).

1045

Fig. 1. Three reversible reaction steps for a typical transesterification process involving triglyceride with methanol where R1, R2
and R3 are fatty acid chains and k1, k2, k3, k4, k5 and k6 are the reaction constants (Ma and Hanna, 1999)

(20)
where Ai,new and Ai,initial are the new and initial values of pre-exponential constant respectively. The
tuning process was repeated for the values of activation energy, E a (kJ) in the second part
isothermal condition. After all the values had been obtained, the simulated results were validated
against experimental results to check for accuracy.
Thermodynamics of SET process
The process thermodynamics based on experimental data in this study was used to determine the
equilibrium constant, Ke, enthalpy, H (kJ mol-1), entropy, S (J mol-1) and Gibbs free energy of
activation, G (kJ mol-1). These data were crucial to interpret the behaviour of SET process under
various conditions. For the reversible reaction shown in Fig. 2, the equilibrium constant, Ke can be
calculated from Eq. (21).

(21)
where CG, CF, CTG and CMet (mol dm-3) are concentration of glycerol, FAME, triglyceride and
methanol respectively. kf and kr (min-1) are the rate constant for forward and reverse reaction
respectively. G can then be determined from Eq. (22).

(22)
where T is the reaction temperature (K) and R is the gas constant (J mol -1 K-1). A graph of ln Ke
against 1/T was then used to find the values of H and S from the slope and intercept
respectively.

Fig. 2. General equation for transesterification of triglyceride from lipid feedstock with methanol (Diasakou et al., 1998)

RESULTS AND DISCUSSION

Extraction
SET process was performed in a batch process with constant maximum heating rate. Due to the
large volume of reactants employed in the study, the non-isothermal condition at the initial of the
process might influence the corresponding kinetics and reaction activities. Fig. 3 shows the
reaction condition of the reactants under the proposed experimental parameters for the model
study (15.0 g JCL solid, 75.0 ml methanol, 300C, 30 min holding time). Fig. 4 shows the extraction
yield obtained from the experiment.

1046

Fig. 3. Temperature and pressure profiles of the reactants with time when heating commences

Fig. 4. Comparison of extraction yield with time for SET process for experimental data, simulation 1 and simulation 2

The first simulation of extraction yield data for SET process was based on the empirical model
from Eq. (3). elim was calculated as 2.0835 while b was 182.99 from the non-linear least square
method. The values of SSQ and RSME based on the 11 data points were 0.035 and 5.66%. Both
of the values were within acceptable range. The second simulation of extraction yield was
calculated based on the Eq. (7). The values of W Ai and k determined were 0.6769 and 0.001035
respectively. The calculated values for SSQ and RSME were 0.0016 and 1.19% respectively.
Comparison between the two simulated data points was done based on the correlation R2 with the
experimental data. Simulation 1 and simulation 2 yielded R2 values of 0.9558 and 0.9979
respectively. This shows that simulation 2 could represent the experimental data more adequately
than simulation 1. This was understandable since simulation 1 only employed a simple empirical
equation as representation. Even though it had lower accuracy compared to simulation 2, the
equation still provided reasonable prediction on the extraction yield of the SET process under the
designated experimental conditions. It is also important to study for the mass transfer within the
particle for the extraction process. The information derived could decide whether the extraction
process was controlled by internal or external diffusion. For internal diffusion controlled process,
the value of Thiele modulus, had to be greater than 10. Thiele modulus was depended on the
diffusivity factor, Deff. Based on Eq. (10), a plot of ln W A/W 0 vs reaction time, t was plotted to
determine Deff at three different phases which were constant extraction phase (CEP), reduced
extraction phase (REP) and diffusion-controlled phase (DCP).
Table 1 shows the values of parameters calculated using Eqs. (8) and (9). The radius of the solid
particle was assumed to be spherical and obtained from the particle size distribution analysis (not
shown). The extraction process was also assumed to be following Ficks diffusion law and
convective diffusion effects inside the particle pores were insignificant. From the calculated values
of and for the three extraction regions, it could be concluded that the extraction process was
not affected by mass transfer within the particle. The low value of Thiele modulus and
effectiveness factor proved that external diffusion played a greater role and the solvent diffused
well within the particle. This could be explained by the greater extraction efficiency of solvent at
supercritical condition which enabled the solvent to overcome most of the internal mass transfer
resistance. Thiele modulus was highest at CEP since the solvent had yet to achieve complete
supercritical condition. It reduced by almost 40% during REP where the extraction solvent was

1047

under supercritical phase and increased again during DCP when most of the outer solute had
been extracted.
Table 1. Calculated parameters for mass transfer phenomena in SET process

Parameters/Regions
Slope from graph
Coefficient of
determination (R2) for
slope
Diffusivity, Deff
Thiele modulus,
Effectiveness factor,

Unit
min-1
-

CEP
-0.02427
0.9689

REP
-0.06647
0.9936

DCP
-0.04659
0.9935

m2min-1
-

8.450x10-10
0.9011
1.799

2.314x10-9
0.5445
2.414

1.622x10-9
0.6504
2.226

The effective diffusivity, Deff, in this supercritical extraction process was well within the values
found from the literatures. Sulaiman et al., 2013 discovered an effective diffusivity of 7.26 x 10 -10
m2s-1 for oil extraction of solid coconut waste with hexane (Sulaiman et al., 2013). Riverchon et al.,
2000 found the values of effective diffusivity, Deff, to be in the range of 2.21 x 10-9 to 5.62 x 10-9 for
supercritical extraction of hiprose seed oil with CO2 (Reverchon et al., 2000). The variation of Deff
was discovered to depend on the particle size of the solute containing solid. This was also in
agreement with the supercritical CO2 extraction study performed by Valle and Uquiche, 2002 for
rosehip seeds (Valle and Uquiche, 2002). They calculated an average effective diffusivity of 3.00 x
10-9 for solid particle diameter of 0.29, 0.64 and 1.61 mm.. Table 2 shows the values of equilibrium
constant and thermodynamic parameters for three distinct phases in the extraction process
determined from the plot of ln Ke vs 1/T.
Table 2. Calculated thermodynamic parameters for mass transfer phenomena in SET process

Parameters/Regions
Equilibrium constant,
Ke
Gibbs free energy, G
Enthalpy of reaction,
H
Entropy, S

Unit
-

CEP
1.178

REP
14.17

DCP
58.60

kJ mol-1
kJ mol-1

-0.5751

-11.97
48.17

-19.40

J mol-1

114.57

Equilibrium constant, Ke was calculated based on the ratio of total solute in the solvent and total
solute remaining in the solid. As more amount of solute was being extracted into the solvent phase
with time, the equilibrium constant increased. Since Ke was higher than unity for all three phases,
extraction of solute into the solvent phase was favoured. Gibbs free energy was determined to be
negative which stated that the process was feasible and spontaneous. The calculated enthalpy of
the extraction process was positive which means that it was highly endothermic. This should be
understandable since supercritical extraction process usually requires maintaining high
temperature to be effective as extraction solvent (Amin et al., 2010). Higher extraction yield could
be obtained with increasing extraction temperature. The entropy of the process was also
calculated to be positive which indicated that the process was irreversible in agreement with the
literature (Meziane and Kadi, 2008). All the thermodynamic parameters calculated were assumed
that the products were at quasi-equilibrium with the reactants, exhibited ideal behavior, obey Vant
Hoff equation and the enthalpy/entropy of the system was constant with temperature.
Reaction
Without analyzing the concentration of triglyceride in the product sample, the concentration of
triglyceride was calculated based on the assumption that molecular weight of triglyceride was
three times of FAME. With the help of the CurveExpert Basic software (version 1.40), a Harris
model function of concentration of triglyceride, CTG to reaction time, t was created in Eq. (23).

(23)
The experimental and calculated values of k and are shown in Table 3. The increasing values of
k were corresponded to increasing reaction temperature with time. The value of alpha was found
to be 1.16 which was also the order of the reaction. This proved that SET process was pseudo first
order and possibly consisting of several elementary steps shown in Fig. 1 in agreement with the
literatures (Madras et al., 2004; Varma and Madras, 2006).

1048

Table 3. Experimental and calculated values for ln(-dCTG/dt)

Reaction
time, t (min)
10
20
30
40
50

ln (-dCTG/dt)
(experimental)
-6.6632
-5.6059
-5.5749
-6.0019
-6.5706

ln CTG

ln k

-1.9684
-2.0329
-2.5090
-3.1525
-3.8666

-4.3859
-3.2540
-2.6721
-2.3548
-2.0973

ln (-dCTG/dt)
(simulated)
-6.6632
-5.6059
-5.5749
-6.0019
-6.5701

60

-7.1467

-4.1434

-2.3854

-7.1789

70
80

-7.6865
-8.1806

-4.5328
-5.0308

-2.3854
-2.3854

-7.6294
-8.2056

1.16
SSQ
0.004921
RSME (%)
2.48
Correlation,
R2
0.9992

From the calculated rate constant, k, a plot of ln k vs reciprocal of reaction temperature, 1/T was
plotted through Arrhenius equation. A linear equation was created through linear regression to
obtain the value of the gradient and y-intercept with R2 value of 0.929. The preliminary activation
energy, Ea, calculated from the gradient is 65.13 kJ/mol while the preliminary pre-exponential
constant, A, derived from the y-intercept is 1.31x105 dm3 mol-1 s.
Since SET reaction might consist of several reversible elementary steps with diglycerides and
monoglycerides as the intermediate compounds, modeling study which included the elementary
steps was simulated in order to obtain a more thorough kinetic study of the SET process. The
simulation was performed with the aid of Matlab software (version R2008a). The preliminary values
of activation energy and pre-exponential constant determined from the one step modeling study
earlier were employed as the initial value in this simulation. The combined simulation result from
Matlab is shown in Fig. 5 detailing the concentration changes of triglyceride (TG), diglyceride (DG),
monoglyceride (MG), glycerol (GY) and FAME with respect to reaction time. From the figure, it can
be seen that concentration of DG and MG remained low throughout the reaction time. Their
concentrations only started to build up at 60 min reaction time but were quickly being converted to
FAME after another 10 min of reaction time upon reaching 300C reaction temperature. This
ensured that high FAME conversion could be achieved for SET process and the intermediate
concentrations were negligible in the final product. A comparison was done for both of the
simulation methods with the real experimental values of triglyceride and FAME concentrations
shown in Fig. 6. All of the simulated results were within 5% of the RSME error which implied that
the mathematical models could adequately represent the SET process.

Fig. 5. Combined simulation results from Matlab for concentration changes of triglyceride, diglyceride, monoglyceride, glycerol
and FAME with reaction time

1049

Fig 6. Comparison of concentration changes of triglyceride and FAME with time for experimental value (Exp), first simulation
with simplified equation (Sim 1) and second simulation with Matlab (Sim 2)

The equilibrium and thermodynamics values for SET process were calculated and tabulated in
Table 4 for four reaction temperatures (300C, 280C, 260C and 240C).
Table 4. Calculated thermodynamic parameters in SET process for reaction temperature 240 C, 260 C, 280 C, and 300 C.

Temperature/
Parameter
Equilibrium
constant, Ke
Gibbs free energy,
G
Enthalpy of reaction,
H
Entropy, S

Unit

240C

260C

280C

300C

0.04

0.14

0.70

2.13

kJ mol-1

13.73

8.71

1.64

-3.60

kJ mol-1

165.37

J mol-1

295.06

The value of Gibbs free energy for 300C was negative which indicated that the reaction was
feasible and spontaneous to produce FAME. SET process was most favorable at this temperature.
At 280C and below, G were positive which meant that the reaction was not really favorable and
will need elevated condition to obtain higher product yield (Ong et al., 2013). The enthalpy of the
reaction was highly endothermic which was understandable due to the supercritical nature of the
process. The entropy of the reaction also exhibited positive value which showed that forward
reaction dominated over backward process.
Proposed mechanism
A suitable process mechanism was proposed which explained all of the reactions occurred in SET
process and their respective discussions. A typical SET process was subjected to this discussion
at the following conditions: 15.0 g JCL solid, 75.0 ml methanol, 300C, 30 min holding time, 100
min overall reaction time (including heating). At the initial 10 min of heating started, no major
reaction took place due to the solid/liquid heterogeneous phase and high immiscibility between the
solvent, methanol and oil stored in the solid JCL seeds at near room temperature and pressure.
This was the lag phase of the SET process and surface extraction slowly took place as
temperature increased. Free, unbounded lipid content at the surface of the solid was being
diffused slowly into the liquid solvent phase.
The reaction time between 10 to 40 min was the constant extraction phase (CEP). During this
phase, the reaction temperature was between 80C and 220C. At the first part of the phase,
extraction of the lipid to the bulk liquid accelerated rapidly to an optimum point. Due to the
increment of reaction temperature and pressure, methanol was approaching subcritical condition
and its miscibility with non-polar lipid increased greatly. Outermost lipid content of the solid seeds
was being diffused slowly out to the bulk liquid. During the second part of the CEP phase, the
extraction rate remained stable at the maximum rate. The concentration of lipid in the bulk liquid
slowly built up together with the majority of polar solutes such as water molecules and FFA. From

1050

the inherent acidity of the FFA which acted as an autocatalyst, esterification of FFA to FAME began
slowly near the end of this phase. Cell walls rupturing and fragmentation also took place because
of the high thermal condition in the reactor which further promoted the extraction process.
The subsequent phase was the reducing extraction phase (REP) occurred between reaction time
40 min to 70 min. The corresponding reaction temperature during this phase was 220C to 300C.
At the first half of the phase, the rate of extraction of lipid to the bulk liquid slowly reduced. This
was mainly due to the buildup of high lipid concentration in the bulk liquid which reduced the
diffusivity gradient according to Ficks Law. Most of the outermost lipids had also been extracted
which left the remaining lipids which were concealed in the inner core of the solid particle. This
marked the initiation of internal diffusion of lipids to the bulk liquid. However, the decrement of
extraction rate was not significant due to the continuous cell wall rupturing from the thermal
reaction. For the reaction side, esterification of FFA continued to produce FAME reactively while
conversion of triglyceride molecules to diglyceride and monoglyceride began.
Due to the existence of water content in the reactants and from the product of FFA esterification,
hydrolysis of triglyceride also occurred to provide more FFA molecules for esterification process.
During the second half of the REP, the reaction started to enter supercritical conditions. Dielectric
constant of methanol dropped rapidly and miscibility between methanol and non-polar compounds
increased greatly. Extraction rate started to slow down since most of the solid volatile matter had
undergone thermal degradation into smaller polar and non-polar molecules.
Mechanism of thermal degradation in JCL seeds under SET process was assumed to be based on
the pyrolysis behavior of cellulose and lignin (Ishikawa and Saka, 2001; Matson et al., 2011). For
cellulose, its glucose chains will be cleaved and subsequently methylated by the methanol into
active methylated cellulose. Further depolymerization of the compound will yield methyl glucoside
and levoglucosan. Successive depolymerization and retro-aldol condensation will then decompose
the product into other smaller and more stable polar liquid products such as furfural. For lignin, it
first underwent thermal cleavage to produce solubilized lignin oligomers. Further depolymerization
process will reduce the active lignins into aromatic compounds before being hydrogenated and
methylated into other liquid products (Demirbas, 2000).
As SET process continued, the extraction yield would have almost reached the saturation level.
Due to the supercritical condition, transesterification of triglyceride to produce FAME proceed
rapidly. Hydrolysis of triglyceride remained constant due to the high amount of triglyceride
concentration in the bulk solution. The amount of diglyceride, monoglyceride, glycerol and FAME
started to buildup in the liquid phase. The last extraction phase was the diffusion-controlled phase
(DCP) which started at 70 min until the reaction was stopped and quenched at 100 min. At the
start of this phase, extraction process slowed dramatically since most of the solute had been
extracted and the majority of mass transfer resistance came from the internal diffusion from
remaining solid particle unaffected by thermal degradation. Reaction rate for transesterification
and hydrolysis of triglyceride started to slow down together due to the decreasing amount of
available triglyceride molecules. Most of the diglyceride and monoglyceride had been converted to
FAME.
The increasing amount of FAME also induced the side reaction, re-hydrolysis of FAME back to
aliphatic fatty acids. This reaction was also responsible for the decreasing FAME content in the
final product. Re-hydrolysis of FAME back into FFA was believed to proceed via direct nucleophilic
attack by sub-critical water molecules (Krammer and Vogel, 2000). At the end of this phase,
extraction process had come to near completion and its extraction rate was approaching zero. The
high thermal and pressurized condition enabled the lignocellulosic content from solid JCL seeds to
degrade into smaller molecular weight polar compounds dissolved in methanol bulk liquid. The
solid decomposition rate remained constant until the end of reaction.
For the reaction, most of the triglyceride molecules were depleted either by being transesterified
into FAME or hydrolyzed into FFA. The reaction attained equilibrium as the rate of triglyceride
transesterification and FFA esterification equaled the rate of re-hydrolysis of FAME. The increasing
amount of glycerol in the solvent phase was also responsible for the reducing rate of reaction. This
was further exacerbated by the initiation of thermal degradation of unsaturation esters originated
from linoleic acid. Thermal degradation of the unsaturated esters was assumed to follow a peroxy
radical chain mechanism (Lazzari and Chiantore, 1999). Fig. 7 summarized the proposed reaction
mechanism for SET process.

1051

Fig. 7. Time profile of changes of extraction and FAME percentage yield for SET process

CONCLUSIONS
Mathematical models based on the extraction and reaction in the SET process were successfully
formulated. The extraction process could be divided into four primary regions and the supercritical
transesterification process was found to obey pseudo first order kinetic rate with respect to
triglyceride concentration. Comparison with real experimental data proved that the models were
adequate and significant to represent the process and able to predict the process yields under the
designated process parameters. Lastly, a complete process mechanism describing the SET
process was also proposed based on the results kinetic modeling study. The fundamental
information obtained for SET process could be valuable for future biodiesel production studies.
ACKNOWLEDGEMENT
We are grateful for the funding from USM FRGS (6071233), Ministry of Higher Education and The
University of Malaya, Kuala Lumpur, Malaysia (UM.C/625/1/HIR/MOHE/ENG/15) (D000015-16001)
which fully supported this research.
NOMENCLATURE
Deff
effective diffusivity, m2/min
Ke
equilibrium constant, dimensionless
Ea
activation energy, kJ/mol
Ee
extraction yield, % w/w
Fy
FAME yield, % w/w
e
ratio of the mass recovered solute and initial mass of feed
k.a
volumetric mass transfer coefficient, min-1
WA
Mass of solute at time t, g
dp
particle diameter, m

effectiveness factor, dimensionless

rTG
consumption rate of TG, mol dm-3
H
enthalpy, kJ mol-1
S
entrophy, J mol-1
G
Gibbs free energy, kJ mol-1
A
Pre-exponential constant, dimensionelss
Greek Letters

Thiele modulus, dimensionless

order of reaction, dimensionless

REFERENCES
Amin, S. K., S. Hawash, G. E. Diwani and S. E. Rafei, 2010. Kinetics and Thermodynamics of Oil
Extraction from Jatropha Curcas in Aqueous Acidic Hexane Solutions Journal of American
Science 6(11): 293-300.
Demirbas, A., 2000. Mechanisms of liquefaction and pyrolysis reactions of biomass. Energy
Conversion and Management 41(6): 633-646.

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Diasakou, M., A. Louloudi and N. Papayannakos, 1998. Kinetics of the non-catalytic

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1053

NATURAL ZEOLITE MINERALS AS STORAGE OF SOLAR ENERGY

Oyku Bilgin
Authors' affiliations Sirnak University, Faculty of Engineering, Mining Engineering Department, Sirnak,
Turkey
e-mails: ykbilgin@yahoo.com, ykbilgin@atauni.edu.tr

ABSTRACT
Zeolites is a mineral group as a result of variation of volcanic ashes in the aquatic environment
millions of years ago consisting of alkaline and soil alkalines hydrated natural silicates. The most
important zeolite minerals are heulandite, chabazite, analcime, erionite, natrolite, philippsite,
mordenite. Zeolites have wide application areas. Zeolites important but uncommon usage is solar
storage. Solar energy is a kind of energy source used for heating house, heating ground and cooling,
providing to process heat in industry, watering in agriculture, drying and cooking. Solar energy
technologies are wall systems and roof systems which collecting heat, energy recovery, active solar
collection, solar repositories, solar collectors, satellite power systems. Studies have put forth
materials solar storage features which have adsorbent properties. Natural zeolite mineral is used in
solar storage depending on adsorption and ion change properties. Depending on temperature,
clinoptilolite and chabazite, heating and conditioning the small structures, in other words, it is
possible to use zeolites as heat changer. Also natural zeolite can keep the stored energy long time
and the stored energy have transferable feature.
Keywords: Energy storage, Solar energy, Usage area, Zeolite.

INTRODUCTION
Energy is an compusory necessity for human. Nonetheless, the conventional sources of energy fossil
fuels are just not enough to meet the constantly growing energy demand. Mankind has received a gift
which is solar energy from nature and from times immemorial man has tried to explore the use of this
large and plentiful energy source. Thus, solar energy seems to be the most promising renewable
energy source [1-3] and the usage of solar energy is very fascinating aspect of science. Zeolites
general chemical formula is Mx Dy [Alx+2y Sin-(x+2y)O2n].mH2O. In this formula, M formulates Na,
K or the other (+1) valency cations, D formulate Mg, Ca, Si, Ba and the other (+2) valency cations [4].
Zeolite, belonging to the alumina silicate group, literally means fusing rock. When heated, it
explodes and disperses. Zeolites is a mineral group as a result of variation of volcanic ashes in the
aquatic environment millions of years ago which consisting of alkaline and soil alkalines hydrated
natural silicates. Feldspar and the other alumino-silicates transformation is called zeolitization.
Natural zeolite that is more than 40 minerals are known. The most importants are clinoptilolite,
heulandite, chabazite, analcime, erionite, natrolite, fillipsit, mordenite. In addition, more than 150
synthetic minerals are also available. Zeolite minerals have alumino-silicate structure which
connected to each other by sharing oxygen atoms and consisting of tetrahedral AlO4 and SiO4s
extended unlimited three-dimensional system. Its structure is contained similarly honey comb or cage
and changeable cations and water. Micro-pores which are between its units combine with micro
windows and create one, two or three dimensional pore systems and canals. Displays of scanning
electron microscopy is shown in Fig. 1. The amount of space is between 20-50% of total volume.
Natural zeolites physical properties are shown in Table 1. Zeolite minerals the most important
feature is that molecular sieve that can easily enter this spaces and change place which arising from
liquid and gas molecules with soil alcaline ions. Zeolites have wide range usage areas. For example,
used in agriculture due to the properties such as ion change, water and gas storage, fisheries, water,
gas and radioactive wastes clening, drying, solar energy and gas storage, odor control, structural
component, good quality paper production and many fields [5].

1054

Fig. 1. Displays of scanning electron microscopy for zeolite mineral (clinoptilolite)

Table 2. The Arrangement of Channels

Zeolite

Pore
volume(%)

Heat
balance

Analcime
Chabazite
Clinoptilolite
Erionite
Heulandite
Mordenite
Philippsite

18
47
34
35
39
28
31

High
High
High
High
Low
High
Middle

Ion change
capacity
(meq/g)
4.54
3.84
2.16
3.12
2.91
4.29
3.31

Specific gravity
(g/cm3)
2.24-2.29
2.05-2.10
2.15-2.25
2.02-2.08
2.18-2.20
2.12-2.15
2.15-2.20

STRUCTURAL CHARACTERISTIC OF ZEOLITES

Adsorption Desorption Property
Adsorption is the adhesion of atoms, ions, biomolecules or molecules of gas, liquid, or dissolved
solids to a surface [6]. This process creates a film of the adsorbate (the molecules or atoms being
accumulated) on the surface of the adsorbent. It differs from absorption, in which a fluid permeates or
is dissolved by a liquid or solid (the absorbent) [7]. The term sorption encompasses both processes,
while desorption is the reverse of adsorption. It is a surface phenomenon. Similar to surface tension,
adsorption is a consequence of surface energy. In a bulk material, all the bonding requirements (be
they ionic, covalent, or metallic) of the constituent atoms of the material are filled by other atoms in
the material. Ion change capacities of zeolite are shown in Table 2. However, atoms on the surface of
the adsorbent are not wholly surrounded by other adsorbent atoms and therefore can attract
adsorbates. The exact nature of the bonding depends on the details of the species involved, but the
adsorption process is generally classified as physisorption (characteristic of weak van der Waals
forces) or chemisorption (characteristic of covalent bonding). It may also occur due to electrostatic
attraction [7].

Table 2. Ion Change Capasities Zeolites

1.50

1.75

2.00

2.25

Ion type
Na+
K+
Mg+2

Ion change capacity (meq/g)

2.50
2.75
3.00

3.25

3.50

3.75

4.00

0.075
0.127
0.040

0.080
0.136
0.043

0.086
0.147
0.046

0.092
0.156
0.049

Ion amount (g iyon/g zeolite)

0.034
0.057
0.018

0.040
0.068
0.021

0.046
0.078
0.024

0.052
0.088
0.027

0.057
0.098
0.030

1055

0.063
0.108
0.033

0.069
0.117
0.036

Ca+2
NH4+
Cs+4
Cu+2
Pb+2

0.030
0.028
0.049
0.048
0.155

0.035
0.033
0.058
0.056
0.181

0.040
0.037
0.066
0.064
0.207

0.045
0.042
0.074
0.071
0.233

0.050
0.047
0.082
0.079
0.259

0.055
0.051
0.091
0.087
0.285

0.060
0.056
0.099
0.095
0.311

0.065
0.061
0.107
0.103
0.337

0.070
0.065
0.115
0.111
0.363

0.075
0.070
0.123
0.119
0.389

Adsorption is present in many natural physical, biological, and chemical systems, and is widely used
in industrial applications such as activated charcoal, capturing and using waste heat to provide cold
water for air conditioning and other process requirements (adsorption chillers), synthetic resins,
increase storage capacity of carbide-derived carbons for tunable nanoporous carbon, and water
purification. Adsorption, ion change, and chromatography are sorption processes in which certain
adsorbates are selectively transferred from the fluid phase to the surface of insoluble, rigid particles
suspended in a vessel or packed in a column. Lesser known, are the pharmaceutical industry
applications as a means to prolong neurological exposure to specific drugs or parts thereof. Zeolites
are natural or synthetic crystalline aluminosilicates which have a repeating pore network and release
water at high temperature. Zeolites are polar in nature. They are manufactured by hydrothermal
synthesis of sodium aluminosilicate or another silica source in an autoclave followed by ion change
with certain cations (Na+, Li+, Ca2+, K+, NH4+). The channel diameter of zeolite cages usually
ranges from 2 to 9 (200 to 900 pm). The ion change process is followed by drying of the crystals,
which can be pelletized with a binder to form macroporous pellets. Zeolite is a tecto-silicate, its
structure is open which diferent the other tecto-silicates (felspar, quartz) and has a 3 dimensional
tunnel and cage system. This system provide to the molecules which small than its spaces and so
zeolites has a name that molecular sieve [5]. Zeolites are applied in drying of process air, CO2
removal from natural gas, CO removal from reforming gas, air separation, catalytic cracking, and
catalytic synthesis and reforming. Non-polar (siliceous) zeolites are synthesized from aluminum-free
silica sources or by dealumination of aluminum-containing zeolites. The dealumination process is
done by treating the zeolite with steam at elevated temperatures, typically greater than 500 C
(930 F). This high temperature heat treatment breaks the aluminum-oxygen bonds and the
aluminum atom is expelled from the zeolite framework.
Ion Change Feature
The template is used to format your paper and style the text. All margins, column widths, line spaces,
and text fonts are prescribed; please do not alter them. You may note peculiarities. For example, the
head margin in this template measures proportionately more than is customary. This measurement
and others are deliberate, using specifications that anticipate your paper as one part of the entire
proceedings, and not as an independent document. Please do not revise any of the current
designations.
C+A- +
Solid

BSolution

C+B- +
Solid

ASolution

(1)
Ion change that occur reversible between solution phase and insoluble solid phase (ion changer). For
example, in C-A+ ion changer M- is constant insoluble anion in the crystal structure and A+ is
replaceable cation. If the C-A+ ion changer put in a water solution which including B+ cations, this ion
change reaction (cation change reaction) occur. Refer to (1), ion chance. Ions total valencies are
equal to each other in ion change process from solid phase to solution, from solution to solid phase
and always system is neutral as electrically. Cations which inside crystal structure of zeolites, are
connected to tetrahedral structures with weak bonds and are replaced with solutions ions. Ion
changes amount is described with ion change capacity (ICC). ICCs measure is gram or changeable
mole concept per 100 g zeolite. Periodic working cooling system is illustrated in Fig. 2. Sometimes
can be used equivalent weight term instead of mole concept [5].

1056

0.080
0.075
0.132
0.127
0.414

Fig. 2. Periodic working cooling system [6]

Catalyst Feature
Natural zeolites are used as catalyst in some chemical reactions either as they are or as change
some properties. Zeolites have different characteristics than other catalyst materials. One of these
characteristic is Si and Al tetrahedrals specific and repetable sequences which in zeolites crystal
structure. In most cases, showing catalytic activity center points are cations locations in their
structures. The reason of zeolites usage as catalysts are to protect activeness, selectivity, chemical
stability and etc. properties long time, easy and repeatable regeneration and durable for external
influences such as heat and pressure [5].
Molecular Aieve Feature
Molecular sieving is defined as cations selective adsorbtion which depend on its physical properties
and electrical charge distribution. Porous structure which has uniform distribution allows specific
molecules adsorption which pass only from the pores in a solution. Molecules which is bigger than
the pore space stay out of zeolite. When zeolites are compared with the other minerals (active
carbon, silica gel etc.) which have molecular sieve feature, they are more advantageous for
molecular sieving [8]. Molecular sieving affected for heating of zeolite and its dehydratation.
Increasing of temperature cause deterioration of the crystal structure and proportionally with residual
temperature with amount of structural oxygen cause broadening the window. On the other hand
dehydratation cause change of cation settlement and electric load distribution. Dehydrated zeolites
adsorb polar molecules selectively such as H2O, CO2, and H2S [5].
USAGE AREAS OF ZEOLITES
Areas of usage for zeolites can be described under four main heads which are pollution control,
energy sector, agriculture and stockbreeding. Applications for pollution control are marginalizing
heavy metals like Pb, Cu, Zn, Cd and Hg from industrial waste waters, marginalizing ammonium
(NH4+) which has a toxic effect from city waste waters and drinking water, lowering water hardness,
regulating pH-conductivity and raising the quality of drinking water, purifying chimney gases, cleaning
up oil leaks, binding air pollutant gases such as SO2, CO, CO2, H2S, NH3, NOx, garbage disposal

1057

areas, metallurgy applications and marginalizing radioactive materials such as Cs, Sr, Rb from
nuclear wastes. Zeolites ion exchange, adsorption and molecular sieving properties are used for
these applications. Applications regarding naturalizing and drying of natural gases, heat storage,
oxygen generating, processing coal gases, separating industrial gas compounds such as CH4/N2 and
N2/H2, oil raffination and sun energy storage systems can be performed with the help of zeolites ion
exchange, adsorption, molecular sieving and catalyst properties. In agriculture and stockbreeding
zeolite with its ion exchange, adsorption and molecular sieving properties can be used as fertilizer
additive, in reclaiming soil by extracting excess water, conditioning soil for agriculture, preventing
washing off of plant nutrients, stabilizing pH on agricultural soil and regulating soil as carrier material
for pesticides, moisture and insect control in grain stores, preventing ripening and hardening in
fertilizers during storage, transferring nutrient ions on agricultural grounds, binding cations of
unwanted heavy metals such as Pb, Cd, Zn and Cu as additive for animal feed in cleaning ponds in
fish farms in order to provide enough oxygen, preventing effluvia in barns as cat soil, strengthening
bones, enhancing egg and bone development and bone meal applications [5]. Also zeolite with its ion
exchange, adsorption and catalyst properties are known to be used as filling material in paper
production for seeking uranium beds in mining as light component element and cement additive in
construction in water culture applications, powder detergent applications as defroster in highways
and many other industries such as medicine [9, 10].
STORAGE METHODS OF SOLAR ENERGY
Solar energy which not storaged as direct radiation energy, to use this energy it must be transformed
into other types of energies. Solar energy can be transformed into other forms with absorption,
pyrolysis and photovoltaic systems. This transforme energy is thermal or electricity energy forms. It
can be used or storaged with special methods to use later. Generally, energy storage is chemical
storage (thermochemical, electrochemical), mechanic storage (hydroelectricity), thermal storage
(sensible heat, latent heat).
Usage of Zeolites in Solar Energy Storage Systems
Solar energy is an energy clean, renewable, safe, available all over the world, transposable to
mechanic and electricity energy, for domestic usage, heating and cooling, industrial usage,
agricultural watering, drying and coking. Passive thermal systems, active solar collection systems,
solar ponds, collectors, satellite power systems are solar utilization areas [5]. According to zeolites
water exchange feature, in clinoptilolite and chabazite applications it seems possible to use zeolites
as heating and air-condition of small structures in other words heat changers to transfer solar energy
[11]. Energy is stocked similar as condensation-evaporation process. When gas is adsorbed on the
solid side, generally a heat discharge occur. The reverse process requires heat charging. Zeolite
material is dried with solar collectors hot air in water-zeolite system. When the zeolite is heated,
adsorbed water gave off. As a result of this process, air becomes filled with water. Vapor is
condensed with using a suitable heat changer and condensation heat is gave off. When zeolite
dehydrated it became potential for heat production. Water vapor is absorbed by zeolite and
adsorption heat is give off. Dry-warm air is obtained [12].
Storing Solar Energy Principle of Zeolites
Some examples about citation of journal articles, books and websites are shown below. Zeolites
have extremely nonlinear adsorption isotherms to water. The feature of adsorbing and desorbing
water makes zeolites a new type of material for storing solar energy and to be showed off. When
zeolites are heated, water molecules in it escape, and heat energy is stored in it in the meantime;
when water molecules are adsorbed again, the heat energy in zeolites is released. These two
processes can be shown by chemical equation as follow:
AmXpO2p nH2O = AmXpO2p+nH2O(endothermic)
(2)
AmXpO2p nH2O = AmXpO2p+nH2O
(endothermic)
(3)
When zeolites absorb heat and desorb crystal water molecules, the temperature of it does not vary,
therefore, this process belongs to the one of latent heat storage. So long as zeolites, of which water

1058

molecules are desorbed, keep apart water, the heat energy of it can be stored as long as you like.
The energy storing density of zeolites is higher than the aforementioned three types of ways of
storing energy. When the heat energy in zeolites is desorbed, we can control the speed of desorption
by controlling the speed of water absorption. Therefore, zeolites have better merits than the
aforementioned ways of storing energy.
CONCLUSIONS
Thermal energy is used which stored in natural zeolites are used in heating, drying and cooling
systems for storage the thermal energy long and short times which obtained from sun.
Thermochemical storage is used this process due to natural zeolites structure. Materials must have
some features to use in thermochemical storage process such as storage materials weight, effective
energy density, price of storage material, renewability feature, antitoxin effect, simply design.
Considering these properties, zeolites importance is understood than the other conventional storage
materials.

REFERENCES
[1] P. D. Galloy and F. Hayt, Pre cis dhistoire du temps pre sent: (19142002), De Boeck
Education, 6th ed., 2005.
[2] M. Asif and T. Muneer, Solar thermal technologies, In: Capehart BL, editor, Encyclopedia of
energy engineering and technology, 2007, pp. 1321.
[3] Y. D. Goswami, F. Kreith, and J. F. Kreider, Principles of solar engineering, 2nd ed., London,
Taylor & Francis, 2000.
[4] G. Gottardi, Mineralogy and chrystal chemistry of zeolites, natural zeolites; occurence,
properties, use, a selection of papers presented at zeolites, International Conference on the
Occurence, Properties, and Utilization of Natural Zeolites, Tucson, Arizona, USA, 1976, pp. 31-44.
[5] O. Bilgin, Investigation of the raw material properties of gordes zeolite ores and searching their
usability in different sectors, PhD dissertation, Department of Mineral Processing, 9 Eylul University,
Izmir, 2009.
[6]

C. Yamali, Mersin sun city and cooling systems, 5. Solar Energy Syposium, p. 273, 2011.

[7] Adsorption
from
Wikipedia,
the
Available:http://en.wikipedia.org/wiki/Adsorption.
[8]

free

encyclopedia,

(August,

2012)

D. W. Breck, Zeolites moleculer sieves, John Wiley&Sons, New York, 1974, pp. 771.

[9] O. Bilgin and U. Kokturk, Raw Material Properties of Gordes Zeolite Ores, The Journal of Ore
Dressing, vol. 11, pp.3345, 2010.
[10] E. Yorukogullari, Usage of natural zeolites as a solvent ice / snow on roads, Mining Journal,
pp. 40-42, 2005.
[11] Development plan for eight five-year, mining specialization commission report industrial raw
materials sub-commission general industrial minerals (mica-zeolite-meerschaum) working group
report,
(2001).
[Online].2.Available:http://www.dpt.gov.tr/DYS/DokumanAra.aspx?Enc=9311D34D022EB51F6CB54
291DAA7ADC64C86063F49652938.
[12] Z. Ayvaz. (March, 2004). Material of 21. Century: Zeolite. [Online]. 1. Available:
http://www.ekolojimagazin.com/?s=magazin&id=172.

1059

THE GEOTHERMAL ENERGY CONVERSION BETWEEN FLASH-BINARY AND

DOUBLE FLASH POWER SYSTEM
Yulie GONG a,b Chao LUO a,b*Qionghui XU a,b, Zhengneng LU a,bYuan YAO a,b
a Guangzhou Institute of Energy ConversionChinese Academy of SciencesGuangzhou 510640
GuangdongChinab Key Laboratory of Renewable EnergyChinese Academy of Sciences
Guangzhou 510640GuangdongChina.
E-mail:luochao@ms.giec.ac.cn (Chao Luo)

Abstract
To increase the energy conversion efficiency of geothermal resource, the paper proposes two-stage
geothermal power system, the thermodynamic performance between double flash and flash-binary
power system is compared basing on numerical simulation, the applicable conditions of different
power system are also discussed in the paper. The simulation result shows that, when the
geothermal resource temperature between 80-130, the net power output of two stage flash
geothermal power system is higher than flash-binary system by maximum value 19.4%; when the
geothermal resource temperature between 130-150, the net power output of flash-binary
geothermal power system is higher than two stage flash system by maximum value 5.5%. However,
the sum water gas production of double flash power system is 2-3 times than flash-binary power
system, which will cause the bigger volume of equipment and higher cost of power system. When
the temperature below 130, it is better to use the double flash system based on the net power
output and flash-binary power system based on the economy and power capacity. When the
temperature higher than 130, it is better to use double flash power system.

Keywords: geothermal power; two-stage flash; binary cycle; flash-binary power system; thermal
efficiency
1 Introduction
The geothermal resources are divided into low(90), medium (90~150) and high (

150) enthalpy (or temperature) resources, according to criteria that are generally based on the
energy content of the fluids and their potential forms of utilization. In China, most of the geothermal
resource temperature is less than 125 and widely distributed in coastal areas of southeastern

1060

China

[1]

. Most of geothermal resource is water- dominated or liquid-dominated geothermal

resource in this paper.

In china, new geothermal power plants were not built for 30 years because of technology and
government policy, and were only two commercial geothermal power plants were in operation, such
as Yangbajain power plant with 24.2 MW capacity and Fengshun power plant with 0.3 MW capacity
[2-3]

. However, many big corporations begin to invest the geothermal power projects during the

Twelfth Five-Year because of energy shortages and government energy policy in China, in
particular, two-stage geothermal power system become the research focus of Sinopec Star, State
Grid Corporation of China and other energy solution companies. There are two basic types of
two-stage geothermal power system, one is double flash power system, and another is flash-binary
power system.The thermal and exergetic efficiency of double flash system are analyzed by Ronald
Dipippo and Sadiq Zarrouk[4-5]. Mortaza also compared the exergetic efficiency between double
flash and flash-binary power system

[6-7]

. However, the power output, optimum flash temperature

and other performance of two-stage power system are not analyzed. The flash-binary power
system would increase the production compared with single flash power system, Denizli power
plant in Turkey gain 18% of power production by increasing a binary cycle system

[8]

. Lahendong

power plant in Indonesia was also flash-binary power system, which shows that there are optimal
evaporation pressure and flash pressure in the flash-binary system

[9]

. Net power output, energy

efficiency, exergy efficiency and thermal economics are also studied in theoretically

[10-11]

. When the

geothermal temperature is constant, sensitivity analysis shows that there is no significant effect
against the significant input variables on the output [12-13].
The more energy conversion stages, the more power output. However, the power output is finite
and the invest cost increases, when power energy conversion stage is added. As a result,
two-stage energy power conversion system is a best choice for countries in world. The object of this
research is to compare the performance of two-stage energy power system and give basis of
selected the type of the power system.
2 Calculations of two-stage geothermal power system
2.1 Double flash system

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Fig.1 schematic diagram of double flash system

Figure 1 shows the schematic diagram of double flash system, the geofluid from production well
is sent to the first separator, the primary separated steam enters the high-pressure cylinder of
turbine and the primary separated liquid flows into the flasher, the steam from the flasher enters the
low-pressure cylinder of turbine and the secondary flashing liquid is sent to injection well.

Fig.2 thermodynamic cycle of double flash system

The temperature-entropy (T-s) diagram of the double flash system is shown in Fig. 2. The
pressure and heat loss of the geofluid in the pipes were neglected. The sequence of processes

1062

begins with geofluid under pressure at state g, close to the saturation curve. The flashing process
g-1 and 1-2 generate a fractional amount of steam given by the quality, m1,D and m2,D, of the
2-phase mixture. Each flash is followed by a separation process. Thermodynamic process of
double flash system can be calculated as follow:
The optimum separator Kelvin temperature:
T1,op 3

Tg2Tc

t1,op = T1,op273.15 ()
The optimum flasher Kelvin temperature:
T2,op 3

TgTc2

t2,op = T2,op273.15 ()
Where Tg is geothermal water Kelvin temperature (K), Tc is condensation Kelvin temperature (K)
of flash system, t1,op is optimum separator Celsius temperature (), t2,op is optimum flasher Celsius
temperature ().
The amount of separator steam:

q m ,D(hg h1 ')
h1 " h1 ' 3

q m 1,D =

The fractional amount of separator steam:

m1,D

q m 1,D
h h1 '
g
4
q m ,D
h1 " h1 '

The amount of flasher steam:

q m 2,D

(q m ,D q m 1,D )(h1 ' h2 ')

h2 " h2 '

The fractional amount of flasher steam:

m 2,D

q m 2,D
(1 m1,D )(h1 ' h2 ')

6
q m ,D
h2 " h2 '

Highest net power output of double flash system:

Pnet,D

[q m 1,D (h1 "h3 ) (q m 1,D q m 2,D )(h4 h5 )](1 X )

oi m g
3.6

1063

Highest net power output per ton geofluid:

Ne ,D

[m 1,D (h1 "h3 ) (m 1,D m 2,D )(h4 h5 )](1 X )

oi m g
3.6

Where
qm,D is the mass flow rate of geothermal water (t/h), qm1,D, qm2,D is the mass flow rate of
separator and flash steam (t/h), hg, h1, h1, h2, h2, h3, h4, h5 and h6 are the enthalpy of geothermal
water at different states (kJ/kg), Pnet,D is the net power output of double flash system (kW), X is the
percentage of the plant self-consumption, oi is the isentropic turbine efficiency, m is the machinery
efficiency, g is the electrical efficiency.
2.2 flash-binary system

Fig.3 schematic diagram of flash-binary system

Figure 3 shows the schematic of flash-binary system, which includes single flash power system
and binary cycle system. The geofluid steam generated by flasher was used to promote turbine in
single flash system. After pressure dropping in flasher, the discharge geofluid liquid enters the
evaporator and exchanges heat energy with organic fluid which vaporized to promote turbine in
binary system. The processes and parameters can be confirmed qualitatively from figure 4 and 5.
The thermodynamic processes of flash and binary power system will be calculated separately

1064

according to Chinese geothermal resource. As electricity generated by geofluid, the calculation

formulas and performance indicators of the flash-binary system are as follows.
The optimum flash temperature of flash power system T1,

T1 TgTc (K) 9
t1 = T1273.15 ()
The optimum evaporation temperature of binary power cycle To1,

To1 T1Toc

(K)10

to1 = To1273.15 ()
Where Tg is geothermal water Kelvin temperature (K), Tc is condensation Kelvin temperature (K)
of flash system, Toc is condensation Kelvin temperature (K) of binary cycle, tg is geothermal water
Celsius temperature (), tc is condensation Celsius temperature () of flash system, toc is
condensation Celsius temperature () of binary cycle.
Obviously, to1 and t1 is associated through formula (10). After the optimum temperature to1 and t1
are fixed, system parameters could be calculated as follows.

1065

Fig.4 thermodynamic cycle of flash system

Fig.5 thermodynamic cycle of binary system

2.2.1 Flash subsystem

Based on flasher energy balance, the mass flow rate of flash steam can be calculated as follows
(Referring to Fig.3 and Fig.4):
The amount of flasher steam:

qm1

q m (hg h4 )
h1" h4

11

The fractional amount of flasher steam:

1066

q m (hg h4 )

qm1
h1" h4

12

Net power output of the flash subsystem:

Pnet 1

q m 1(h1 h2 )(1 X )
3.6

oimg

13

Where
qm is the mass flow rate of geothermal water (t/h), hg, h4, h1, h2, h3, h6 are the enthalpy of geothermal
water at different states (kJ/kg), Pnet1 is the net power output of flash subsystem (kW), net1 is the net
power output thermal efficiency of flash subsystem, X is the percentage of the plant
self-consumption, oi is the isentropic turbine efficiency, m is the machinery efficiency, g is the
electrical efficiency.
2.2.2 Binary cycle subsystem
Based on evaporator and preheater energy balance, the mass flow rate of organic working fluid
can be calculated as follows (Referring to Fig.3 and Fig.5):

qmo =

(qm -qm1 )(h4 -h6 )

(ho1 -ho5 )

14

Where
ho5=ho4wp, wp=(Po1Po4)vo4/(103 p), ho1, ho2, ho4, ho5 are the enthalpy of organic working fluid at
different states (kJ/kg), ho1 and ho6 are determined by the evaporation temperature to1; ho5 is
obtained from ho4 and compress work wp (kJ), namely, ho5=ho4wp; Po1 is the evaporation pressure
(Pa), Po4 is the condensation pressure (Pa), vo4 is the specific volume of condensation working fluid,
p is the working fluid pump efficiency.
Net power output of binary subsystem is defined as follows:

1067

Pnet 2

q mo [(ho1 ho 2 ) (ho5 ho 4 )](1 X )

oi m g
3.6
15

The net power output of flash-binary power system:

Pnet = Pnet1Pnet2 16

Net power output (kWh/t) per ton of geothermal water:

Ne

Pnet Pnet1 P net 2

qm
qm
qm

= Ne1Ne2 17

3 the results of two-stage power conversion system

The performances of the two-stage geothermal power system are compared when the geofluid
temperature ranges from 80 to 150. The cooling water inlet temperature is 20, the organic fluid
in binary subsystem is R245fa. The value of various efficiencies can be assumed as follow: X = 0.3

oi m g = 0.760.980.97 = 0.722. Numerical simulation is followed by Eq. from (1) to (17).

Fig.6 The influence of geothermal water temperature on net power output

Figure 6 shows the influence of geothermal water temperature on net power output of two stage
power system. From the figure, we can see that the higher geothermal temperature, the higher net

1068

power output. When the geothermal water temperature is 130, the net power output of double
flash system and flash-binary system are fairly close. When geothermal water temperature is
ranged from 80-130, the net power output of double power system is more than up to 19.5% of
flash-binary power system. However, When geothermal water temperature is ranged from
130-150, the net power output of flash-binary power system is more than up to 5.5% of double
power system.

Fig.7 The influence of geothermal water temperature on optimum flash temperature

Figure 7 shows the optimum flash temperature of the double flash and flash-binary power system.
For each choice of separator (or flasher) temperature, there will be a range of possible separator (or
flasher) temperature, one of which will yield the highest power output. Over the spectrum of
separator (or flasher) temperature, there will be corresponding separator (or flasher) temperature
that yields the highest power output which defines the optimum plant choices for both separator and
flash conditions. The higher optimal flash temperature, the higher flash pressure, and which will
ensure that the system will be operation not in negative pressure.

1069

Fig.8 The relationship between geothermal water temperature and fractional amount of
steam
For double flash system, the fractional amount of separator steam and flasher steam range from
3.5% to 8.8% and 3.1% to 6.8%; for flash-binary system, the fractional amount of flasher steam
range from 3.6% to 5.8%. When the geothermal temperature is below 130, flash pressure of the

double power system will be close to vacuumwhich will be result to bigger volume and higher cost
of power equipment. In contrary, the optimal flasher temperature of flash-binary system is higher
than double flash, which will help for minimizing the volume and cost of power equipment. when the
temperature below 130, it is better to use the double flash system based on the net power output
and flash-binary power system based on the economy and power capacity. When the temperature
higher than 130, it is better to use double flash power system.

1070

Fig. 9 the influence of flash temperature on power output of flash-binary system

For different geothermal water temperature in the flash-binary power system, the trend of
power output is drawn when the flash temperature ranges from condensation temperature to
geothermal water temperature basing on trial calculation. When the geothermal water temperature
is constant, the power output increases and then decreases with higher flash temperature. The
higher geothermal water temperature, the higher optimal flash temperature. figure 9 shows that the
optimal flash temperature are 60 and 125 when the geothermal water are 80 and 150.

4 Conclusions
Two-stage geothermal energy conversion power system is analyzed for enhancing the efficiency
the geothermal resource utilization in China. The conclusions as follow:
The increasing amount of flash-binary power system is bigger than double power system with
increasing geothermal water temperature. When geothermal water temperature is ranged from
80-130, the net power output of double flash power system is more than up to 19.5% of
flash-binary power system. However, When geothermal water temperature is ranged from
130-150, the net power output of flash-binary power system is more than up to 5.5% of double
power system.
The optimal flash temperature of flash-binary system is higher than the second flash system of
double flash system. When the temperature below 130, it is better to use the double flash system
based on the net power output and flash-binary power system based on the economy and power
capacity. When the temperature higher than 130, it is better to use double flash power system.

1071

Reference
[1] Keyan Zheng. Ying Dong. A Comparison on Geothermal Development between China and the
World [C]/ European Geothermal Congress 2013, Pisa, Italy, June, 2013.
[2] Chao Luo, Lichang Huang. Thermodynamic comparison of different types of geothermal
power plant systems and case studies in China [J]. Renewable Energy, 2012;48:155-160
[3] Keyan Zheng, Zaisheng Han. Steady Industrialized Development of Geothermal Energy in
China Country Update Report 2005-2009 [C]/ Proceedings World Geothermal Congress 2010,
Bali, Indonesia, April, 2010, paper no. 0136.
[4] Ronald Dipippo. Geothermal double-flash plant with interstage reheating: An updated and
expanded thermal and exergetic analysis and optimization[J]. Geothermics, 2013, 48:121-131
[5] Sadiq J Zarrouk, Hyungsul Moon. Efficiency of geothermal power plants: A worldwide review
[J]. Geothermics, 2014, 51:142-153
[6] Mortaza Yari. Exergetic analysis of various types of geothermal power plants [J]. Renewable
Energy, 2010, 35:112-121
[7] Joshua Clarke, James T. The constrained design space of double-flash geothermal power
plants [J]. Geothermics, 2014, 51:31-37
[8] Ahmet Dagdas, Reep Oztiurk. Thermodynamic evaluation of Denizli Kizildere geothermal
power plant and its performance improvement [J]. Energy Conversion and management,
46(2005):245-256
[9] Ari Darmawan Pasek, T.A. Fauzi Soelaiman. Thermodynamics study of flashbinary cycle in
geothermal power plant [J]. Renewable and Sustainable Energy Reviews, 2011,
15:5218-5223.
[10] EFSTATHIOS E, Michaelides. A binary-flashing geothermal power plant [J]. Energy, 1984,
9:323-331.
[11] Saeid Jalilinasrabady, Ryuichi Itoi. Flash cycle optimization of Sabalan geothermal power
plant employing exergy concept [J]. Geothermics, 2012, 43:75-82.
[12] H.Rosyid, R. koestoer. Sensitivity annlysis of steam power plant-binary cycle [J]. Energy, 2010,
35:3578-3586.
[13] Christoph Koch, Frank Cziesla. Optimization of combined cycle power plants using
evolutionary algorithms [J]. Chemical Engineering and Processing, 2007, 46:1151-1159.

1072

A NEW GAS CONCENTRATION DISTRIBUTION METHOD OF PROTON

EXCHANGE MEMBRANE FUEL CELL
Yu-Lin Wang1, Shi-Xue Wang1,2*
1. School of Mechanical Engineering, Tianjin University, 92 Weijin Road, Nankai, Tianjin, P. R.
China.
2. State Key Laboratory of Engines, Tianjin University, 92 Weijin Road, Nankai, Tianjin, P. R. China.
Corresponding authors contact email: wangshixue_64@tju.edu.cn

ABSTRACT

The cathode flow-field design of a proton exchange membrane fuel cell (PEMFC) determines its
reactant transport capacities to the catalyst layer and removal capacities of liquid water from the
fuel cell. In this study, the cathode flow-field is optimized for two halves by adding a sub channel.
Divided gas feeding fraction and sub channel inlet positions are numerically simulated to evaluate
cell performance using a three-dimensional, two-phase, and non-isothermal fuel cell model.
Numerical results illustrate that the new gas distribution design differs from the conventional
method in the liquid water distribution, the local current density generation and the output cell
performance. The position of sub channel inlet and gas feeding fraction of main channel play a
significant role in determining the removal of liquid water, the value of membrane resistance and the
transport of oxygen. It is found that when the distance of sub channel from main gas inlet is
equivalent to around 30% of the entire channel length, and the main-channel inlet gas feeding
fraction is about 30%, the cell will achieve higher output performance than that of a cell with straight
channel. A proposed scheme, finally, by optimizing the position of sub channel and gas feeding
fraction, is put forward.
Keywords: Proton exchange membrane fuel cell; water management; new cathode flow-field
design; liquid water saturation; cell performance.
INTRODUCTION
Proton exchange membrane fuel cell (PEMFC), which transforms the chemical energy to electrical
energy during the electrochemical reaction of hydrogen and oxygen with heat and water as
byproducts (Wang CY et al., 2004), is considered to one of the most promising renewable green
energy. During operation of a PEM fuel cell, water is mainly transported inside the membrane by
electro-osmotic drag(water molecules is dragged by the current-carrier protons from the anode side
to the cathode side through the membrane), and back diffusion(caused by the process in which
water is transferred into the membrane due to the water concentration gradient from the cathode to
the anode) (Yan Q et al., 2006). Hence if the transport rate of water exceeds the back-diffusion rate,
the membrane will become dehydrated, and result into a heavy resistance for high current
conducting. On the other hand, if water removal rate fails to keep up with the generation rate of
water by the cathodic reaction, flooding occurs in the cathode side, in this case, liquid water can
partially block the pores in the cathode gas diffusion layer, and reduce the accessibility of oxygen to
the catalyst layer. Therefore, to simultaneously ensure high membrane proton conductivity and
sufficient reactant delivery to reaction sites, water management has become one of the most
significant issues for high-performance PEM fuel cells (Jiao K. et al., 2011).
Mathematical modeling and simulations have been widely utilized in research to achieve a

1073

good understanding on the transport phenomena within a PEM fuel cell, and were deemed as an
effective tool for optimizing fuel cell performance (Liu HT et al., 2002). Yi and Nguyen TV (YI JS et
al., 1999) developed a two-dimensional isothermal model to evaluate the effects of various designs
and operating parameters on the performance of a PEM fuel cell. Fuller and Newman (Fuller TF et
al., 1993) created a quasi-two-dimensional, along-the-channel model with an assumption of
constant water diffusivity in the membrane to investigate water management problems in a PEMFC.
Voss HH (Voss HH et al., 1995) developed a relatively novel water management technique with
anode water removal to modify the water concentration gradient in the proton exchange membrane
to augment the back-diffusion of water from the cathode to the anode, where the water at the
cathode catalyst layer diffuses through the membrane and is removed via the anode reactant gas
stream. West and Fullers conclusion (West AC et al., 1996) showed that the two-dimensional effect
only slightly alters the half-cell potential for a given applied current, but significantly influences the
water management. Rowe and Li (Rowe A et al., 2001) carried out a two-dimensional simulation of
water transport in the PEMFC without external humidification. The results indicated that the amount
of water leaving the anode depends on the hydrogen stoichiometry, oxygen stoichiometry, current
density, and cell temperature. Meng and Wang (Meng H et al., 2005) also developed a two-phase
model to predict the cathode flooding effect on cell performance, and ultimately removed the
inability of prior two-phase models to correctly capture effects of the gas velocity or stoichiometry on
cell performance.
In the past decades, many efforts have been made on flow channel designs and humidification
methods. With decrease of reactant concentration and accumulation of liquid water in the
downstream channel, local performance reduces significantly, especially at high cell current density.
Water flooding generally occurs at the cathode side of the membrane. Accumulation of excess
water in the porous layer increases oxygen transport resistance, and hence, become an obstacle to
the transport of oxygen into the GDL and catalyst layers (Wang XD et al., 2008). Therefore, the
cathode flow-field design is a vital factor in determining reactant transport rates and for water
removal. Nguyen (Nguyen TV., 1996) first proposed the interdigitated flow channel design to avoid
flooding by the discharge liquid water out of the diffusion layer. Such type of flow channel is
characteristic of converting the transport of gases from diffusion to convection, whether the gas is
reactant coming into the catalyst or a product from the catalyst. Kumar and Reddy (Kumar A et al.,
2003) investigated the effect of flow-field design on the steady and transient state performance of
PEMFCs with serpentine, parallel, multiple parallel and discontinuous flow fields.
Although progress has been made in multi-dimensional modeling of two-phase transport
phenomena and flooding effects in PEM fuel cells, significant improvements are still needed,
particularly in the design of cathode flow-field.

1074

Fig.1. Schematic of PEMFC with sub channel design.

According to our study, a novel gas distribution method was developed to optimize a
straight-channel single cell, considering the characteristic that dry-out tends to occur in the
upstream area, and flooding in the downstream area of the cathode side. The cathode channel is
divided into two halves by adding a sub channel, as showed in Fig.1. Cathode reactant will be both
fed from main cathode channel inlet and the sub channel inlet. The relative humidity of reactant gas
supplied from main channel inlet is 100%, for sub channel is 0%. Divided gas feeding fraction and
sub channel inlet positions are numerically simulated to evaluate cell performance by a
three-dimensional, two-phase, and non-isothermal fuel cell model.
MODEL DEVELOPMENT

Computational domain

A straight-channel single flow field design is utilized to study the effects of new cathode flow-field
design on the cell performance, the transport of oxygen and the distribution of liquid water within a
PEM fuel cell. The computational domain is showed in Fig.2, because of symmetrical characteristic
along the Z-direction, a half cell is taken into account. The computational domain includes the flow
channel, bipolar plates, GDL, catalyst layer, membrane. The flow channel and the bipolar plates
had the same dimensions of 1.0 mm wide 1.0 mm high 100 mm long. The thicknesses of the
GDL, the catalyst layer and the membrane were 300 m, 10 m and 25 m, respectively.

Fig.2. Computational domain of PEMFC without sub channel design.

Basic assumptions and Governing equations

The basic assumptions of the present PEM fuel cell model (1) The cell is in a steady state; (2) All of
the gaseous species follow the ideal gas law; (3) The flow within the cell is incompressible and
laminar; (4) The pore distribution of the GDL, catalyst layer and membrane are isotropic.
The numerical model is developed based on the two-fluid method, which solve gaseous
(hydrogen, oxygen, water vapor, nitrogen) formation and liquid water formation separately. The
complete conservation equations of continuity and momentum of gaseous, species transport, liquid
water transport, water content in membrane, electron and proton transport, and energy are listed as
follows. First, conservation equations of gaseous transport are established.
Mass conservation:

1075

1 s g ug Sm

(1)

Momentum conservation:

1 s g ug ug 1 s pg ( 1 s ) Su

(2)

Species diffusion conservation:

(1 s)g u g X i g Di eff X i Si

(3)

Where Dieff is the effective diffusion coefficient of the i-th gaseous species, calculated by Dieff =
Di((1-s)). The mass source term Sm and the momentum source term Su are calculated as follows.

jc M H2 O jc M O2

SL

2F
4F

jM

Sm a H2 SL
2F

SL

Su

in cathode CL
in anode CL

(4)

in channels and GDLs

in ribs

g 2

1 s ug
k k

p rg

in GDLs and CLs

in channels and ribs

(5)

Where SL is the source term associated with the condensation of water vapor; kp and krg = (1-s)
3

are the permeability and the relative permeability of the porous material toward the gaseous

mixture.
The diffusion source term Si for gaseous species is calculated as follows.

SH2 O

jc
n

M H2 O M H2 O d im SL

2F
F
S

SH2

ja

M H2

2F

S O2

in cathode CL

(6)

elsewhere

in anode CL

(7)

elsewhere

jc
M O2
4F

in cathode CL

(8)

elsewhere

Quasi-thermodynamic equilibrium of liquid water and its vapor is assumed, so when the partial
pressure of the water vapor exceeds the saturation pressure, condensation of water vapor occurs,
and vice versa. The partial pressure of water vapor can then be calculated as follows.

pv

X H2 O g RuT

(9)

M H2 O

Where the parameter, pv, is the partial pressure of water vapor; the saturation pressure, psat, is
related to the temperature as follows.

log10 psat 2.1784 0.02953(T 273.15) 9.1837 105 (T 273.15)

1.4454 107 (T 273.15)

1076

(10)

Therefore, the source term, SL, associated with the condensation of water vapor is given by,

SL hpc M H2O p v psat

(11)

Where hpc is the evaporation-condensation coefficient:

hpc

p v psat
kc 1 s xH2 O
1 v
2 RuT
p psat

k s
l
e
2M H2 O

p v psat
1 v
p psat

(12)

Where the parameter, kc and ke, are the water vapor condensation rate coefficient, the liquid
water evaporation rate coefficient, respectively; and t xH2O is the molar fraction of water vapor.
Since the velocity of the liquid water is much lower than that of the gaseous mixture, the inertia
term in the momentum equation of the liquid water is negligible. Based on Darcys law, the water
transport equation is given as follow.

l kkl kp pc
l kkl kp

s SL
pg
s
l

(13)

The capillary pressure can be calculated by the Leverett-J function (Udell KS et al., 1985):
12

pc cos
k
p

pc cos
k
p

12

1.417 1 s 2.120 1 s
1.417s 2.120s

1.262 1 s

1.262s 3

90

(14)

90

(15)

Where is the surface tension of the water, and is the contact angle of water on the walls of
the pores in the porous material.
Based on the assumption that the membrane contains no unknown net water source, the liquid
water transport equation in the membrane is as follows.

D (

nd im
)0
F

(16)

Based on current conservation laws, the electron and proton transport equations are,

eff s Ss 0

(17)

m Sm 0
eff

(18)

The energy equations in this model are as follows.

g cp,g (1 s) ugT l cp,l sulT k eff T ST

(19)

Where cp,g and cp,l are the specific heats of the gaseous mixture and the liquid water,
respectively. The source term, ST, is given by,

is 2

eff

hfg SL

2
is
ST
hfg SL
eff

dU 0
im 2
j
(

T
)

dT
eff

im 2

eff

in ribs
in channels
in GDLs
in CLs
in membrane

1077

(20)

The source term ST takes into account the electrical work, Joule heating, and latent heat associated
with the phase change of the water. Table 1 presents the electrochemical and physical correlations,
and Table 2 presents the input parameters in the model. Table 1 is listed in (Meng H. 2007).
Table 2. Values of input parameters in the model.
Parameter

Value

unit

Parameter

Value

unit
5

Parameter

Value

0.6/0.3

DN2

2.210

mem

0.28

kc

5.0103

1/s

3.510-4

Ns/m2

kp,GDL

1.761012

m2

ke

1.0104

1/sPa

62.5

mN/m

1.7610

12

8.3145

J/molK

EW

1.1

kp,mem

1.8010

18

DH2

Ru

1.010

kg/m3

kg/mol

mem

1.9810

1.0106

A/m3

GDL,CLeff

5.0103

s/m

cH2eff

40.0

mol/m3

rib

2.0104

s/m

m2/s

CO2eff

40.0

mol/m3

CL

17.0

s/m

a/c

eff

aj0,a

9.73105

m2/s

aj0,ceff

DO2

2.73105

m2/s

DH2O

2.33105

DH2O

A/m

2.3310

m /s

unit

GDL/CL

kp,CL

m /s

8.010

1.0/1.0

hfg

2.310

kg/m3

J/kg

Boundary conditions

The inlet flow velocities, inlet temperature, and inlet compositions of the reactants at the anode and
the cathode flow channels assumed to be constant. The pressures are fixed at the anode and
cathode channel outlets. The solid walls are no-slip with zero flux boundary conditions. The liquid
water saturations and the velocities, mass fractions, momentum fluxes, and mass fluxes of the
gaseous species are all assumed to be continuous across the gas channels, the gas diffusion
layers, and the catalyst layers. On the surface of the anode current collector, the electronic phase
potential and the ionic phase potential satisfy s 0 , m x 0 , on the surface of the cathode
current collector, s Vcell and m x 0 . Additionally, on the interfaces between the membrane
and catalyst layers, the water and water flux should be continuous so,

0.043 17.81a 39.85a 2 36.0a 3

14.0 1.4 a 1
16.8

nd im
D
F

0 a 1
1 a 3

(21)

a3

n i

Deff X d m

M H O H2 O H2 O
F
mem
2

CL

(22)

Where a= pv/psat +2s is the water activity.

Numerical method

The PEM fuel cell model was solved by exploiting the user-coding capabilities of a commercial CFD
package, Fluent 13.0.0. Four user-defined scalars were introduced to solve the liquid water
transport equation, the equation for the water content in the membrane, and the electron and proton
transport equations, various source terms of conversion equations were taken into account.

1078

1.1

Experimental data [60]

Numerical prediction in present model

1.0

cell voltage (V)

0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

2
current density (A/cm )

Fig.3. Comparison of experimental and numerical polarization curve.

The model developed herein was validated by comparing experimental results presented in
(Yan WM et al., 2006). Fig.3 compares the simulated polarization curve with experimental data for a
fuel cell with the parallel flow channel design and an active area of 140140 mm2. The grid
independent study was carried out successfully.
RESULTS AND DISCUSSIONS
The cell performance is simulated by a three-dimensional, two-phase, and non-isothermal fuel cell
model, as is shown in Fig.1, the whole cathode channel length is defined as L, and the total
supplied cathode gas mass flux as F. When the position of the sub-channel inlet is set to be 30% of
the whole channel length from main inlet, and the gas mass flux from the main channel is assumed
to be 30% of the total supplied cathode gas mass flux, can simply defines as 0.3L-0.3F. In the
present work, three kinds of designs 0.3L-0.3F, 0.5L-0.5F, 0.7L-0.7F, are compared with
conventional method to evaluate cell performance using a 100 mm length flue cell. The operating
pressure of both gas distribution methods and conventional method are 1atm, fuel cell temperature
is assumed to be 50.

Analysis of the new gas distribution design

Fig.4 plots polarization curves that predicted by the conventional method and various designs of
sub channel inlet positions. At operating voltages >0.6 V, the two-phase model with various sub
channel designs predicted almost the same cell performance, because of the low electrochemical
reaction rate, so only limited amounts of oxygen or water are consumed or generated. However, in
the higher current density region, the cell performance follows the order: 0.3L-0.3F > conventional
method > 0.7L-0.7F > 0.5L-0.5F, resulting from the distribution of reactant gaseous
concentration, liquid water and membrane resistance

1079

1.1

0.5
RHa=100%

0.9

0.4

0.8

Conventional Method
0.3
0.3L-0.3F
0.5L-0.5F
0.7L-0.7F

0.7
0.6

0.2

0.5

Conventional Method
0.3L-0.3F
0.5L-0.5F
0.7L-0.7F

0.4
0.3

power (w/cm2)

cell voltage (V)

1.0

0.1

0.2
0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4

current density (A/cm2)

Fig.4. Polarization and power curves of fuel cells for conventional method and various designs of
sub channel inlet positions.
Fig.5 and Fig.6 plot the local current density distribution in the membrane and mass fraction of
oxygen distribution on the cathode GDL-CL interface for various designs of sub channel inlet
positions and conventional method at cell voltages = 0.4 V. In general, the values of local density
for all the three sub channel designs and conventional method decrease along the channel,
because the depletion of reactant gaseous concentration and accumulation of liquid water in the
downstream channel. In the upstream of sub channel inlet, on the account of the relative lower
reactant gaseous concentration than the conventional method, the new sub channel designs show
poorer local cell performances. Nevertheless, there is a jump of local current density under the
entrance of sub channel, for more oxygen was added to participate in the electrochemical reaction.

(a)

(b)

(c)

(d)

(d)

1080

(a)

(b)

(c)

Fig.5.Local current density distributions in the membrane for conventional method and various
designs of sub channel inlet positions at Vcell=0.4 V(Left Fig.): (a) conventional method; (b)
0.3L-0.3F; (c) 0.5L-0.5F;(d) 0.7L-07F.
Fig.6.Oxygen mass fraction distributions on GDL-CL interface for conventional method and various
designs of sub channel inlet positions at Vcell=0.4 V(Right Fig.): (a) conventional method; (b)
0.3L-0.3F; (c) 0.5L-0.5F; (d) 0.7L-07F.
Fig.7 plots membrane resistance curves along the channel. As previously mentioned, the
membrane resistance is in proportion to membrane water content. In this study, the membrane
water content is calculated by conservation equation (16), which is a result of mutual effect of
current density and water content. If the current density is high, the water transport from the anode
by electro-osmotic drag will exceed water transport to the anode by back diffusion from the cathode,
and the membrane will dryout (Nguyen TV et al., 1993). So, contrary to current density, the values
of membrane resistance rise up along the channel, because the reduction of water vapor content
due to electro-osmotic drag from the anode gas stream translates to a drop of water content in the
membrane.
membrane resistance (/cm2)

0.40
Conventional Method
0.3L-0.3F
0.5L-0.5F
0.7L-0.7F

0.35
0.30
0.25
0.20
0.15
0.10

RHa=100%

0.05
0.00

10

channel length (cm)

Fig.7. Membrane resistance curves along the channel for conventional method and various designs
of sub channel inlet positions at Vcell=0.4 V.
In the upstream of sub channel inlet, the current density of sub channel designs is lower than
that of conventional method, and water content in the cathode of the former is higher in quantity (as
is described in Fig.9), so the electro-osmotic drag is inferior to the back diffusion from the cathode,
thus, resulting into a relatively lower membrane resistance. There is also a jump under the entrance
of sub channel, for the introduction of dry reactant from sub channel increasing the current density,
and electro-osmotic drag become stronger, therefore the membrane is poorly hydrated from the
anode. Even though, in the downstream of the sub channel inlet, since the anode side of the design
0.7L-0.7Fand 0.3L-0.3F are well hydrated in the upstream of the sub channel inlet, the
membrane resistance is lower than that of conventional method, As for the design 0.5L-0.5F,
under the sub channel inlet, there exists a relatively sharp decline of water content, the back
diffusion sudden become much weaker, a slight increase of current probably results in membrane
resistance the highest.
Fig.8 and Fig.9 plot the current density curves in the membrane and water saturation
distribution on the GDL-CL interface for various cases at cell voltages = 0.4 V. Fig.9 reveals
significant difference of the saturation distributions or the saturation values between sub channel

1081

design and conventional method. Under the entrance of sub channel, the saturation level
remarkable higher than any other areas for higher cathodic reaction producing more water and
accumulation of liquid water from the upstream. However, in the downstream, the saturation values
decrease slowly, which is different from that of conventional method. Thus, the effective diffusion
coefficient of oxygen, DOeff2 DO2 1 s , is follow the order: 0.3L-0.3F> conventional method >

0.7L-0.7F > 0.5L-0.5F in the downstream. According to previous observation, the membrane
resistance values generally follow the order: conventional method > 0.5L-0.5F> 0.7L-0.7F >
0.3L-0.3F.Therfore the design 0.3L-0.3F predicts highest current density, while 0.5L-0.5F
produces the lowest.

Conventional Method
0.3L-0.3F
0.5L-0.5F
0.7L-0.7F

current density (A/m2)

16000
14000
12000
10000

RHa=100%

8000
6000

10

channel length (cm)

(a)

(b)

(c)

(d)

Fig.8. Local current density curves of membrane along the channel for conventional method and
various designs of sub channel inlet positions at Vcell=0.4 V.
Fig.9.Saturation distributions on the GDL-CL interface for conventional method and various designs
of sub channel inlet positions at Vcell=0.4 V: (a) conventional method; (b) 0.3L-0.3F; (c) 0.5L-0.5F; (d)
0.7L-07F.

Influencing factors of the new method on cell performance

As mentioned previously, the new method is characterized by an added sub channel, thus, the
position of the sub channel inlet, x/L, and the fraction of gas mass flux, Fmain/Ftotal, defined as mass
flux from the cathode main inlet to the total feeding gas mass flux, are assumed to have a
significant effect on the fuel cell output performance, which are discussed in this sector.
Fig.10 plots the effect of the sub channel inlet position at cell voltages = 0.4 V with the design
of nF-nL, which demonstrates the value of x/L is equivalent to that of Fmain/Ftotal. The current
density firstly increases, at about x/L = 0.3 (in Fig.10. n=0.3 also denotes Fmain/Ftotal = 0.3), reaches
the peak value, and then declines rapidly to the valley value at about x/L = 0.6 (in Fig.10. n=0.6 also
denotes Fmain/Ftotal = 0.6), however with the increase of x/L, the current density elevates again.
When x/L reaches 0.8, the current density reveals no significant difference between sub channel
design and the conventional method.

1082

1.16
Vcell=0.4 V

current density (A/cm2)

1.14

nL-nF

1.12
1.10
1.08
1.06
1.04
1.02
0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

n ( e.g. n=0.1 denotes design of 0.1L-0.1F )

1.16

current density (A/cm2)

Vcell=0.4 V
1.15

0.3L-nF

1.14

1.13

1.12

1.11
0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

mass flux ratio(Fmain/FTotal) n

Fig.10.Effect of various designs of sub channel inlet positions (x/L) on current density at Vcell=0.4 V.
Fig.11.Effect of various cathode gas feeding fractions, Fmain/Ftotal, on current density at Vcell=0.4 V
with sub channel inlet position, x/L=0.3.
Fig.11 plots the influence of the gas mass flux fraction, Fmain/Ftotal, on the output current density,
with the position of the sub channel inlet, x/L, setting at 30% of the entire channel length from the
main inlet. There only exists a peak but valley value for the current density with the changes of
Fmain/Ftotal, furthermore, differs from the effect of the sub channel inlet position, the current density
exerts no substantial fluctuation but smoothly changes. Which indicates the influence of the gas
feeding mass flux fraction plays a relative slighter role in determining the current density than that of
the sub channel inlet position under this design.
Based on above comparative analysis, the design0.3L-0.3Fcan yield a higher current density
by removal of excess water in the downstream, redistribution of the oxygen and water saturation in
the cathode channel. This new method not only reduces 70% of the water vapor supplied from the
main channel inlet, but also efficiently removes the excess water produced by the electrochemical
reaction. Furthermore, the humidified gas fed from the main inlet is sufficient to hydrate the
membrane.
CONCLUSIONS
A new cathode gas flow-field design, characterized by an added sub channel, was developed to
maintain an optimal water balance during the operation of a PEM flue cell, and thus to obtain a
higher cell performance, Comparative analysis of the new cathode gas flow-field design and
conventional method on the distribution of membrane resistance, liquid water saturation and local
current density were carried out.

1083

(1) Compared to the conventional method, the new cathode gas flow-field design varies
significant in the distribution of membrane resistance, liquid water saturation and local current
density, thus,

providing a potential for optimization design of a higher performance PEM

flue cell.
(2) The position of the sub channel inlet, x/L, and the fraction of gas mass flux, Fmain/Ftotal, from the
main inlet to sub channel inlet exert a strong influence on the fuel cell output performance.
However, the later one plays a relative slighter role under our design.
(3) The new cathode gas flow-field designs 0.3L-0.3F, can further extend current density, and
reduce the amount of water by 70%, adopted to humidify the reactant gas fed from cathode
inlet.
(4) Under the circumstance that the length of flue cell is100 mm and there exists only one single
sub channel along the main cathode channel, the position of the sub channel inlet, x/L, should
be at about 30% of the entire channel length from main inlet, and the fraction of gas feeding
mass flux, Fmain/Ftotal, should be near 30%.
ACKNOWLEDGMENTS
The authors are grateful for the financial support by the Joint Research Program between MOST &
JST (2013DFG60080).
NOMENCLATURE
a

water activity

cp

specified heat, J/kgK

mass diffusivity, m /s
2

Mm

membrane equivalent weight, kg /mol

nd

electro-osmotic drag coefficient

pg

gaseous mixture pressure, atm

water diffusivity in the membrane, m /s

pc

capillary pressure, atm

EW

equivalent weight of the membrane kg/mol

Ru

universal gas constant J/molK

Faraday constant, 96,487 C/mol, mass flux, kg/s

liquid saturation

Si

source term in the species equation

Sm

source in mass conservation

current density, A/m

hfg

evaporation latent heat of water, J/kg

3

transfer current density, A/m

Sj

source term in the phase potential equation

kc /ke

Condensation/ evaporation rate coefficient

Su

source term in momentum equation

kr

relative permeability of the liquid water

SL

source term for phase change of water

kp

permeability, m

ug

gaseous-phase velocity, m/s

krg

relative permeability of the gaseous mixture

Cell temperature, K

the total length of the cell, cm

Vcell

operating voltage, V

molecular weight, kg/mol

mass fraction

Variable denotes mass flux fraction and position of sub channel inlet

The length from the main channel inlet to the sub channel inlet

Greek

ionic phase potential, V

porosity

electronic phase potential, V

overpotential, V

xH2O

molar fraction of water vapor

water content in membrane

Subscripts

keff

effective thermal conductivity, W/mK

eff

effective

ks

thermal conductivity of solid matrix

gaseous phase

kf

thermal conductivity of fluids in the pores

i-th species of the mixture

1084

viscosity, kg/ms

liquid phase

viscous stress tensor

mem

membrane

density, kg/m

sat

saturation

electron conductivity, S/m

CL

catalyst layer

proton conductivity, S/m

GDL

gas diffusion layer

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Journal of the Electrochemical Society 140:1218-25.
Jiao K., Li X., 2011, Water transport in polymer electrolyte membrane fuel cells. Progress in Energy
and Combustion Science 37:221-91.
Kumar A., Reddy R. G., 2003, Effect of channel dimensions and shape in the flow-field distributor on
the performance of polymer electrolyte Membrane fuel cells. Journal of Power Sources 113:11-18.
Meng H., 2007, A two-phase non-isothermal mixed-domain PEM fuel cell model and its application
to two-dimensional simulations. Journal of Power Sources 168: 21828.
Meng H., Wang C. Y., 2005, Model of Two-Phase Flow and Flooding Dynamics in Polymer
Electrolyte Fuel Cells. Journal of the Electrochemical Society 152 (9):A1733-41.
Nguyen T. V., 1996, A gas distributor design for proton exchange membrane fuel cells. Journal of
the Electrochemical Society 143(5):L103-5.
Nguyen T. V., White R. E., 1993, A water and heat management model for proton exchange
membrane fuel cells. Journal of the Electrochemical Society 140(8):2178-86.
Rowe A., Li X., 2001, Mathematical modeling of proton exchange membrane fuel cells. Journal of
Power Sources 102(1-2):82-96.
Udell K. S., 1985, Heat transfer in porous media considering phase change and capillarity-the heat
pipe effect. International Journal of Heat and MassTransfer 28: 485-495.
Voss H. H., Wilkinson D. P., Pickup P. G., Johnson M. C., Basura V., 1995, Anode water removal: A
water management and diagnostic technique for solid polymer fuel cells. Electrochimica Acta
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Wang C. Y., 2004, Fundamental models for fuel cell engineering. Chemical Reviews 104: 4727-66.
Wang X. D., Duan Y. Y., Yan W. M., Peng X. F., 2008, Local transport phenomena and cell
performance of PEM fuel cells with various serpentine flow field designs. Journal of Power Sources
175:397-407.

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West A. C., Fuller T. F., 1996, Influence of rib spacing in proton-exchange membrane electrode
assemblies. Journal of Applied Electrochemistry 26:557-65.
Yan Q., Toghiani H., Wu J. X., 2006, Investigation of water transport through membrane in a PEM
fuel cell by water balance experiments. Journal of Power Sources 158: 316-25.
Yan W. M., Yang C. H., Soong C. Y., Chen F., Mei S. C., 2006, Experimental studies on optimal
operating conditions for different flow field designs of PEM fuel cells. Journal of Power Sources 160:
284-292.
Yi J. S., Nguyen T. V., 1999, Multi-component transport in porous electrodes of proton exchange
membrane fuel cells using the interdigitated gas distributors. Journal of the Electrochemical Society
146:38-45.
You L. X., Liu H. T., 2002, A two-phase flow and transport model for the cathode of PEM fuel cells.
International Journal of Heat and Mass Transfer 45: 2277-87.

1086

STUDY OF PATHWAYS TO MAXIMIZE ENGINE EFFICIENCY FOR FUTURE

ENGINES
Laihui Tong, Haifeng Liu, Mingfa Yao*, Zunqing Zheng
State Key Laboratory of Engines, Tianjin University, Tianjin, China
Corresponding author: Mingfa Yao, E-mail: y_mingfa@tju.edu.cn

Abstract:
The current indicated thermal efficiency of advanced internal combustion engines is limited in 50%.
How to further improve the engine efficiency will be a challenge in the future. In present study,
exploratory study was carried out using the 1-D engine simulation based on the first law of
thermodynamics. The energy distribution under assumed conditions and the extreme efficiency limits
of future engines was evaluated by using different parameters such as compression ratio, heat
transfer coefficient, combustion process, intake charge and fuels properties. Results indicate that
indicated efficiency was improved with the decrease of heat transfer, however only one thirds of the
saved heat transfer losses were converted to useful work while most of them were lost in exhaust. For
a specific heat transfer there was an optimal compression ratio for the indicated efficiency. Increasing
compression ratio reduced the energy lost in exhaust, however high compression ratio with high heat
transfer coefficient led to the increase of the heat transfer losses instead of useful work. High
compression ratio with reduced heat transfer coefficient could achieve a significant high efficiency, a
peak indicated efficiency of 65% was obtained at 100:1 compression ratio with adiabatic process.
Higher intake density and ratio of specific heats of intake charge, and shorter combustion duration
with CA50 close to top dead center increased efficiency significantly. However all these strategies with
extreme high compression ratio led to extreme high in-cylinder pressure and temperature, which is
unrealizable for engines with current mechanical and thermal capacity.
Keywords: efficiency, Heat transfer, first law of thermodynamics, losses.
INTRODUCTION
Currently, due to widespread application of vehicles, Transportation accounts for 28% of global
energy demand(Suzana Kahn Ribeiro, 2012), and 27.6% greenhouse gas emissions(including CO2,
Methane, Nitrous oxide, HFCs, PFCs) in 2012(Davis et al., 2003). In addition, the vehicle stock of the
world is still growing, especially in developing countries, such as China, India and so on. In a word,
the energy consumption by engines have caused a substantial negative impact on the ecological
environment and energy security. Since it is impossible to restrain the application of the vehicles,
improving the engines efficiency is the primary option to reduce energy consumption and greenhouse
gases emissions simultaneously.
Actually, improving efficiency has long been an objective of engine designers since the invention of
engines. After centuries of development, the efficiency of engines have been improved significantly.
Current production spark-ignition engines are working with top efficiency about 30%36%(Boretti,
2012), , compression-ignition engines (more commonly known as diesel engines) have long been
recognized as one of the most efficient power unit due to its relative high compression ratio, current
efficiency of diesel engines could achieve 40%47%. However, it is a great challenge to further
improve the efficiency with current designed engines architecture, even with very advanced control
strategies and combustion modes, the fuel energy conversion efficiency was just above 50%.
Recently, many countries and organizations have imposed fuel economy standards to cope with the
energy security and CO2 emission. According to the technology roadmap fuel economy of Road

1087

Vehicles issued by the International Energy Agency (IEA) cutting the average fuel economy of road
motorized vehicles by 30% to 50% by 2030(Cuenot, 2013). The trend of future standards are
increasing stringency as shown in figure 1.

Fig. 1. The trend of future CO2 emission standards for passenger cars (Icct, 2014)

For example, Europeans standards for passenger cars will reach 95g CO2/100 km by 2020(de Wilde
and Kroon, 2013). The goal of China national average fuel consumption is 6.9 L/100 km (equivalent to
about 165g CO2/100km) by 2015(AQSIQ[Administration of Quality Supervision, 2011), and the
proposed value will reach 5L/100 km (~120g CO2/100 km) by 2020(Administration of Quality
Supervision, 2014), reducing the average fuel economy of new vehicles by ~30% compare to 2013;
The targets of US CAFE is 109g/100km(i.e. 54.5mpg) in 2025 for cars and light trucks(EPA [U.S.
Environmental Protection Agency], 2011). However, the target will be a great challenge, according to
EPAs fuel economy estimates for all models with EPA rating in 2012, there are only 9.3% of the total
1041 surveyed vehicles in the market getting over 30mpg, among the most popular cars, there are
11.9% getting more than 30 mpg(Gillis and Cooper, 2013).
In order to cope with upcoming strict fuel economy standard in the future, much more fuel-efficient
vehicles should be developed, except for more efficient transmissions and auxiliary power systems
and improved aerodynamics and tires, the engines offers the most direct and effective path for the
improvement of fuel economy, because the engine losses account for about 67~72% losses of energy
for a typical light duty vehicle while in the city area the losses from engines will rise to 74%-75%
(DOE, 2012). How to improve the engines 30%-50% more efficient than today will be a massive
challenge for the internal combustion engines to fulfill the future standards. So, it is necessary to
assess the pathways to maximize engine efficiency, and estimate the potential of efficiency limits for
conventional engines.
Some researchers proposed that the fuel economy of traditional piston engines have the potential for
further improvement by 25% or more by supplementation with advanced combustion technology(Lu et
al., 2011). For this reason, global researchers have paid more attention to advanced combustion
modes. Among these, various low temperature combustion modes including HCCI, PCCI, PPC,
RCCI, etc. are all featured as relative low combustion temperature in a compression ignition engine,
have been demonstrated the great potential to achieve ever high efficiency, through the use of high
dilution by exhaust gases combined with relative intensified combustion allowed reaching peak gross
indicated efficiencies in the range of 54-56%. Vittorio Manente, Bengt Johansson and Per Tunestal in
Lund university showed gross indicated efficiencies higher than 50% for all the fuels tested ,with a
peak of 57% at 8 bar IMEP by applying this concept(Manente et al., 2010). RCCI strategy developed

1088

by researchers from the University of Wisconsin-Madison has demonstrated significant engine

efficiency improvements, peak gross thermal efficiencies in the range of 53-59% was achieved, nearly
20% improved fuel efficiency over conventional diesel, while meeting ultra-low emissions standards
without after-treatment system(Hanson et al., 2010; Splitter et al., 2011; Splitter et al., 2010). Derek
Splitter et al.(Splitter et al., 2011) analyzed and compared the energy flow of various combustion
strategies, the results showed that the efficiency improvement of dual-fuel RCCI were mainly resulted
from the decrease of heat transfer and exhaust losses.
According to the heat balance analysis with the first law of thermodynamics, Work output, heat
transfer losses and exhaust energy are the three approaches available for the fuel energy. In order to
increase the work output, the appropriate method is to translate the heat transfer losses or exhaust
energy into useful work. Be different from closed Carnot cycle, the actual engine cycle is an
open-cycle involves chemical reactions and gas exchange process, the in-cylinder heat transfer is not
thermodynamic required, and has the potential of producing more useful work. Since 1980s, low heat
rejection engines with thermal barrier coatings were investigated, the results showed that through
insulation of the cylinder walls, except for the decrease of heat transfer, also significantly decreases
the combustion irreversibilities, resulted in the improvement in the indicated efficiency and increased
exhaust availability. Primus et al. (Primus et al., 1984)demonstrated a 42% reduction in the heat
transfer losses in a low heat rejection engine, the reduced heat transfer losses resulted in a 3.7%
increase in the indicated work and also a 49% increase in the exhaust availability. Taymaz et
al.(Taymaz, 2006; Taymaz et al., 2003) compared the heat losses at different engine loads and
speeds with and without ceramic-coated diesel engine, a reduction in fuel consumption and an
increase in exhaust energy was found in a ceramic-coated engine, similar results were also obtained
in thermal barrier coating low heat rejection diesel engines(Parlak, 2005; Parlak et al., 2005).
Referring to the ideal cycle equations of the internal combustion engines, for constant volume
combustion

, the entire cycle is assumed adiabatic, the thermal efficiency are affected by

compression ratio significantly. Increasing the compression ratio could improve the engine efficiency
theoretically(Heywood, 1988). Murray H. Edson (Edson et al., 2012)made a theoretical analysis of the
ideal adiabatic Otto cycle engine ,the results showed that the engine thermal efficiency continued to
increase with compression ratio at least up to 300:1 for all the fuels considered (isooctane, benzene,
ethyl alcohol, and nitro methane), the achievable brake efficiencies typically lie between 70 and 80%
depends on the compression ratio. similar results also have been demonstrated by K-Y Teh, S L Miller
and C F Edwards (Edwards et al., 2008), in a free-piston research device demonstrating the feasibility
of achieving simple-cycle engine efficiencies approaching 60%, by employing extremely high
compression ratios, up to 60-100:1.
In the present work, we try to explore the potential approaches for improving efficiency based on
current engine configuration without radical modification. The main objective of this study is to
reevaluates the fuel energy distribution under assumed conditions and the extreme efficiency for
future diesel engines under assumed conditions. General performance computations were carried out
with a single cylinder engine model, the first law of thermodynamics was utilized to analysis the
distribution of fuel energy entering cylinder since we are not care about availability and inefficiencies
associated with the various processes. Some principle of the pathways to stretch engine efficiency
were proposed.

1089

SYSTEM DESCRIPTION AND THERMODYNAMIC MODEL

Simulations were carried out using the 1-dimensional engine simulation software, GT-Power. GT
-Power is based on 1-dimensional gas dynamics, representing the flow and heat transfer in pipes and
other components of an engine system.
A model of the single cylinder engine is built within GT-Power, and the engine model was developed
corresponding to a single cylinder diesel engine. Sub-models for flow in intake/exhaust system, fuel
injection, fuel vaporization and combustion, cylinder heat transfer et al. were combined with a
thermodynamic analysis of the engine to yield instantaneous in-cylinder parameters and overall
engine performance(GT Manual, 2004).
IN-CYLINDER HEAT TRANSFER MODEL
The in-cylinder heat transfer applied in the engine model is basically the Woschni GT model which is
recommended when measured swirl data is not available. The heat transfer losses consist convection
and radiation, under the normal conditions, In-cylinder radiation is usually only defined for diesel
engines. In order to compare the effect of heat transfer coefficient, Convection Multiplier and
Radiation Multiplier of Cylinder will be varied. A hybrid method transitions from linear to quadratic was
used for The Convection Temperature Evaluation which is the recommended method. In present
engine model, according to match experimental pressure data, the stock Convection Multiplier was
calibrated to 1.2 and Radiation Multiplier was set to the recommended value 1.0.
COMBUSTION MODEL
In present study, a user-Imposed combustion profile was applied, the combustion profile was acquire
from the experimental data of a typical diesel HCCI engine which was also used for the model
calibration, and the profile was then normalized to the fraction of fuel burned before being applied,
and the start of combustion in degrees crank angle was defined directly. The recommended option of
two-temp was applied, which indicates that temperature and composition will be independently
calculated for the burned and unburned gases in the cylinder chamber. The default combustion
duration from 1090% heat release was 27 degree crank angle, the combustion duration could be
adjusted through Crank Angle Array Multiplier.
ENGINE AND OPERATING CONDITIONS
To model the cylinder geometry, the bore, stroke, connecting rod length, wrist pin to crank offset,
compression ratio, and TDC clearance height are inputted into the program. The specifications of the
engine are shown in Table 1. The schematic diagram of GT-Power model was showed in figure 2, the
intake and exhaust valve lift was presented in figure 3.
In this study, all the simulations were carried out at the speed of 1500 rpm, the total mass of fuel
injected per cycle will be equal to equivalent 80 mg diesel. For studies of the compression ratio, heat
transfer coefficient, intake charge and fuel properties, a CA50 of 10CA ATDC and combustion
duration from 1090% heat release of 27CA was selected to represent the typical HCCI combustion
for simulations. While considering the effect of combustion phasing on best possible efficiency, a

1090

Figure 2. Schematic Diagram of GT-Power model

range of CA50 and combustion duration were identified. The exhaust pressure was regulated equal to
the inlet pressure.
Table 1. Engine specifications
Single cylinder 4-stroke

Number of Cylinders

Displacement

1.08L

Bore Stroke

105 125mm

Connecting road length

210 mm

Number of valve

Original compression ratio

16:1

Wrist Pin to Crank Offset

0 mm

TDC Clearance Height

1.2mm

Fuel injection system

Common rail

Valve Lift (mm)

Engine Type

Exhaust

10
9
8
7
6
5
4
3
2
1
0
90

180

270

360

Intake

450

540

630

Crank Angle (deg)

Figure 3. Exhaust and intake valve lift

The simulations are based on a set of assumptions and approximations which did not consider a few
engine characteristics. For example, combustion stability, cycle-to-cycle variations, knock and some
other abnormal combustion phenomena are not included here. In addition, exhaust emissions are not
in consideration. Because the focus of this study is not to understand the detail of combustion, rather,
the focus is just to detect and describe the thermodynamics characteristics based on successful
combustion. Of course, successful combustion is a challenge for some conditions, but this aspect is
beyond the scope of the current work.
RESULTS AND DISCUSSION:
THE EFFECT OF HEAT TRANSFER COEFFICIENY AND COMBUSTION RATIO

1091

Distribution of Fuel Energy(%)

100
90

Indicated Efficiency

80
70
60

34.60

50
40
30
20

25.67

22.77

39.73

1.2

10
0

36.47

38.63

Heat Transfer

Exhaust Energy

40.89

43.48

46.15

49.41

52.13

19.59

16.20

12.59

8.58

4.34

0.00

40.76

41.77

42.92

43.94

45.27

46.25

47.87

1.0

0.8

0.6

0.4

0.2

0.0

C=0
R=0

Convection&Radiation

C=
C=

R=1

R=1

Figure 4. Distribution of fuel energy

Figure 4. Distribution of fuel energyshows how the distribution of fuel energy changes with convection
multiplier calculated under the original compression ratio of 16 (The intake pressure is controlled at
1.3bar for premixed stoichiometric ratio), combustion inefficiencies are not discussed here because of
the near zero incomplete combustion (normally0.5%), and the unburned fuel energy was allocated
to useful exhaust energy. With the decrease of heat transfer coefficient, heat transfer losses reduced,
however only one thirds of the saved heat transfer losses were converted to useful work while most of
them were lost in exhaust. Compared to the normal convection multiplier of 1.2, the peak indicated
efficiency was increased to 47.87% from 39.73% under the adiabatic condition, the energy lost in
exhaust was increased to 52.1%. As shown in Figure 5, an increase of 90 K in the exhaust
temperature was observed, the gains of indicated thermal efficiency from the heat transfer losses are
not sufficient as expected even with adiabatic condition. Nearly 50% of the fuel energy was lost in the
exhaust. Meanwhile, the maximum in-cylinder temperature increased considerably with decreasing
heat transfer coefficient, the peak in-cylinder temperature was increased to above 2400K, partially
due to the stoichiometric combustion under the adiabatic condition.

2400

740

Exhaust Temperature (K)

Max Incylinder Temperature (K)

760

Max Incylinder Temperature

Exhaust Temperature

720

2350

700
2300

680
2250

660
1.2

1.0

0.8

0.6

0.4

0.2

0.0 C=0,R=0

Convection&Radiation

Figure 5.Maximum in-cylinder temperature and exhaust temperature as a function of heat transfer coefficient.

1092

60
55

50

C1.2/R1
C0.8/R1
C0.4/R1
C0/R1
C0/R0

Heat Transfer/%

Indicated Efficiency/%

65

50
45
40
35

40
30

C1.2/R1
C0.8/R1
C0.4/R1
C0/R1
0/0

20
10
0

20

40

60

80

100

40

60

80

100

Compression Ratio

20

40

60

Compression Ratio

80

100

Exhaust Energy/%

50

40

30

20

C1.2/R1
C0.8/R1
C0.4/R1
C0/R1
C0/R0
20

Compression Ratio

Figure 6. Distribution of fuel energy under different heat transfer coefficient as a function of compression ratio

Figure 6 shows the energy distribution change of fuel energy under different heat transfer coefficient
with compression ratio. Increasing compression ratio could reduce the energy lost in exhaust,
however it also led to the increase of the heat transfer losses when the cylinder was not heat
insulation (actually, heat transfer was inevitable) due to the a sharp rise in the peak in-cylinder
temperature. So, too higher compression ratio would result in a decrease in the indicated efficiency.
Heat transfer coefficient determines optimal compression ratio, as we can see in figure 6, an optimal
compression ratio existed for a given heat transfer coefficient, as the heat transfer coefficient
decreased, the corresponding optimal compression ratio for indicated efficiency increased. The peak
Indicated efficiency improved significantly with the decrease of heat transfer coefficient due to the
higher corresponding optimal compression ratio. For the normal heat transfer coefficient (convection
multiplier=1.2, radiation multiplier=1), a peak indicated efficiency of 44.7% was achieved with the
compression ratio of 30, while for the reduced heat transfer coefficient (convection multiplier=0.4,
radiation multiplier=1), the peak indicated efficiency was increased to 52% with the compression ratio
of 50.
THE EFFECT OF UNDER ADIABATIC PROCESS

1093

convection=0.2,Radiation=1

50
=0.95
=0.8
=0.71
=0.62
=0.58
=0.5

45
40
35
10

Exhaust Energy Percentage

60

Compression Ratio

100

30

convection=0.2,Radiation=1

55

=0.95
=0.8
=0.71
=0.62
=0.58
=0.5

50
45
40
35
30

convection=0.2,Radiation=1

=0.95
=0.8
=0.71
=0.62
=0.58
=0.5

25

Heat transfer

Indicated Thermal Efficiency

55

20
15
10
5

25
10

Compression Ratio

10

100

Compression Ratio

100

Figure 7. Energy distribution as a function of compression ratio for lean combustion with Convection multiplier=0.2,
Radiation=1

Figure 7 shows the indicated efficiency as a function of compression ratio for lean combustion with
equivalence ratio from 0.95 to 0.5, the convection multiplier was 0.2, about 80% reduction in the
in-cylinder heat transfer coefficient. The results at lean equivalence ratio appeared to agree with
stoichiometric condition as shown in figure 6, an optimal compression ratio existed for a given heat
transfer coefficient at stoichiometric condition, higher compression ratio resulted in the increase of
heat transfer losses. However, for different equivalence ratio, the corresponding compression ratio of
peak indicated efficiency was varied, with the decrease of equivalence ratio, the corresponding
compression ratio was reduced, while the peak indicated efficiency was higher even with a reduced
compression ratio, lean charges have more favorable specific heat ratios relative to stoichiometric
mixtures, and this leads to an improved indicated efficiency, at equivalence ratio of 0.5, a peak
indicated efficiency of 55.3% was achieved.

1094

Mconvection =0.2, Mradiation=1

2400

CR=50
CR=60
CR=70
CR=80

Max T In-cylinder (K)

2300
2200

2100

2000

1900

Maximum P In-cylinder (bar)

1000

1800

900

CR=50
CR=60
CR=70
CR=80

800
700
600
500
400
300
200

peak
indicated efficiency
0.5

0.6

0.7

0.8

0.9

1.0

Equivalence Ratio(-)

Figure 8. The influence of equivalence ratio on Maximum in-cylinder pressure and temperature

Figure 8 shows the influence of equivalence ratio on maximum in-cylinder pressure and peak in
cylinder temperature at different compression ratio, with Convection multiplier=0.2, Radiation=1. The
results showed that the peak in-cylinder temperature was mainly affected by equivalence ratio, much
leaner combustion could suppress the peak in-cylinder temperature effectively due to lean charges
have higher heat capacity relative to stoichiometric mixtures. However leaner mixture resulted in
higher in-cylinder pressure, as for the peak indicated efficiency achieved by equivalence ratio of 0.5 in
figure 7, the corresponding peak cylinder temperature was much lower with a relative moderate
in-cylinder pressure. Considering the mechanical and thermal capacity of current materials, extremely
lean mixtures would be favorable for higher indicated efficiency.
THE EFFECT OF INTAKE CHARGE COMPOSITION
Standard air is composed primarily of diatomic gases, about 78% of N2, 21% of O2, 0.93% of inert
gases. Many studies have showed that the intake fluids properties, such as specific heat Cp, specific
heat ratio =Cp/Cv and thermal conductivity of the gases, have a great effect on the indicated
efficiency(Laumann and Reynolds, 1978). The triatomic gases have a higher specific heat which is
known to be utilized in low temperature combustion to suppress the in-cylinder temperature, however
the of triatomic gases was relative lower.
Intake N2 replace by argon
Higher specific heat ratio could produce high peak cylinder pressures under adiabatic compression,
and maximum energy extraction during the expansion phase of the engine cycle. Considering the
equation of ideal engine cycle(Heywood, 1988),

a relative high specific heat ratio of the intake gas could improve the indicated efficiency theoretically.
Monatomic gases such as Argon, have a high specific heat ratio of more than 1.6, which is

1095

considerably more than the specific heat ratio of 1.4 for air. With the increase of argon ratio in the
intake charge, the of intake fluids increased. However, monatomic gases also provide a low Cp
which will lead to extreme high in-cylinder temperature which is undesired without insulation
(Killingsworth et al., 2010; Kuroki et al., 2010). The effect of intake on the energy distribution,
in-cylinder pressure and temperature were explored at the conditions of adiabatic and low heat
transfer separately.
60

70
65
60

Mass%
Ar=0%
Ar=20%
Ar=40%

55
50
45
40

adiabatic =0.67
20

40

60

80

Compression Ratio (-)

Indicated Efficiency (%)

Indicated Efficiency (%)

75

55

50

Mc=0.2,Mr=1 =0.67

40

100

Mass%
Ar=0%
Ar=20%
Ar=40%

45

20

40

60

80

Compression Ratio (-)

100

60
55
50
45
40
35
30
25
20
15

Mass%
Ar=0%
Ar=20%
Ar=40%
20

40

adiabatic =0.67
60

80

Compression Ratio (-)

Exhaust Energy Percentage (%)

Exhaust Energy Percentage (%)

Figure 9. Indicated efficiency for different Argon percentage with the change of compression ratio

100

60

Mc=0.2,Mr=1

55

Mass%
Ar=0%
Ar=20%
Ar=40%

50
45
40

=0.67

35
30
25
20
15

20

40

60

80

Compression Ratio (-)

100

Figure 10. Exhaust energy for different Argon percentage with the change of compression ratio

Figure 9 and Figure 10 shows the peak indicated efficiency and exhaust energy percentage for
different intake argon percentage with the change of compression ratio, the mass percentage of
intake O2 was kept constant to 23%, and intake pressure was varied to control the equivalence ratio
equal to=0.67 (calculated by all the oxygen in the cylinder).The left plots are assumed adiabatic
without heat transfer, the right plots are the results of low heat transfer cases with convection
multiplier of 0.2 and normal radiation multiplier of 1.
Under the adiabatic condition, the indicated efficiency presented a significant improvement with the
increase of intake argon percentage, that is the energy lost in the exhaust was reduced as shown in
left plot of figure 10, a peak indicated efficiency approaching 75% was obtained with 40% intake argon
percentage by employing extremely high compression ratios, showed an nearly 10% improvement
compared standard air without argon in the intake fluids. When there exist heat transfer, even was
fairly low compared to the normal heat transfer coefficient, the indicated efficiency showed a distinct
current, and the peak indicated efficiency was significant lower than the adiabatic cycles. The
indicated efficiency increased firstly, but then drops when the compression ratio above 40:1,
furthermore, with the increase of intake Argon ratio, the indicated efficiency was found to be more
sensitive to the compression ratio. The indicated efficiency peaks at 57% with 40% argon ratio, at

1096

about 40:1 compression ratio, at the same compression ratio and argon ratio with in-cylinder
adiabatic, the peak indicated efficiency was achieved to 69%.

Pressure Max (bar)

1500

2000

adiabatic =0.67

Mass%
Ar=0%
Ar=20%
Ar=40%

Mc=0.2,Mr=1 =0.67
1500

Pressure Max (bar)

2000

1000

1000

500
0

20

40

60

80

Compression Ratio (-)

500
0

100

Mass%
Ar=0%
Ar=20%
Ar=40%

20

40

60

80

Compression Ratio (-)

100

Figure 11. Maximum in-cylinder pressure for different Argon percentage with the change of compression ratio
3000

adiabatic =0.67

Mass%
Ar=0%
Ar=20%
Ar=40%

Temperature Max (K)

2800
2600

2600

Mass%
Ar=0%
Ar=20%
Ar=40%

Mc=0.2,Mr=1
=0.67

2400

2400

2200

2200
2000

2800

Temperature Max (K)

3000

20

40

60

80

Compression Ratio (-)

2000

100

20

40

60

80

Compression Ratio (-)

100

Figure 12. Maximum in-cylinder temperature for different Argon percentage with the change of compression ratio

The effect of intake argon ratio on the maximum in cylinder pressure and temperature were showed in
figure 11 and 12. Increase the intake argon ratio could produce high peak cylinder pressures,
especially above 40:1 compression ratio the enhancement became more obvious, under adiabatic
compression the maximum pressure was a little higher than the low heat transfer compression. At
40:1 compression ratio, the maximum in-cylinder pressure of 40% argon ratio was controlled in 400
bar, compared to the standard air working fluid with 0% argon ratio, the maximum in-cylinder pressure
was about 300 bar.
As we can see from figure 12, there was a significant increase in the peak in-cylinder temperature
with the increase of intake argon ratio, especially under adiabatic compression, the peak in-cylinder
was more than 2600K even at a low compression ratio. For the Carnot cycle, it is well known that
higher temperatures result in higher efficiencies. This is because the Carnot cycle is based on heat
engine concepts, as shown in the left plot of figure 12. An internal combustion engine, however, is not
a heat engine in practice, the heat transfer is inevitable, high in cylinder temperature will resulted in
the increase of heat transfer losses, and lower conversion of thermal energy to useful work.
Furthermore, higher in cylinder temperature will pose more severe challenges to the engines with high
thermal tolerance and durability. Besides advanced materials, some measures, such as high dilution
with high specific heat gases or excess air, should be taken to suppress the peak in cylinder
temperature in order to release the thermal load.
Intake N2 replace by CO2

1097

Contrary to monatomic gases, CO2 is characterized high specific heat which is beneficial for the
in-cylinder temperature control, however the specific heat ratio is lower.
Figure 13 shows how the energy distribution varied with CO2 percentage in the intake gas. Figure 14
shows the effect of CO2 percentage in the intake gas on the maximum in-cylinder pressure and peak
in-cylinder temperature.
For the calculations, N2 was replaced by CO2, the mass percentage of O2 in the intake gas was fixed
at 23%, and the equivalence ratio was kept constant to 0.57, at the same time a reduced heat
transfer coefficient was defined (Convection multiplier=0.2, Radiation=1)
20

58

CO2=0%
CO2=2%
CO2=5%
CO2=7%

Heattransfer (%)

Indicated Efficiency(%)

56
54
52

CO2=0%
CO2=2%
CO2=5%
CO2=7%

50
48
46
20

40

60

80

Compression Ratio

15

10

5
20

100

40

60

Compression Ratio

80

100

Exhaust Energy (%)

50

CO2=0%
CO2=2%
CO2=5%
CO2=7%

45
40
35
30
20

40

60

80

Compression Ratio

100

Figure 13. Energy distribution as a function of compression ratio for intake N2 replace by CO2 at reduced heat transfer coefficient
(Convection multiplier=0.2, Radiation=1)

Max Pressure (bar)

CO2=0%
CO2=2%
CO2=5%
CO2=7%

800

Maximum incylinder Temperature (K)

1950

1000

1900

600

CO2=0%
CO2=2%
CO2=5%
CO2=7%

1850

400
200
20

40

60

Compression Ratio

80

100

1800

20

40

60

Compression Ratio

80

100

Figure 14. The effect of intake N2 replace by CO2 on peak in-cylinder pressure and temperature at reduced heat transfer coefficient
(Convection multiplier=0.2, Radiation=1)

As we can see from figure 13, for different CO2 mass percentage, it showed a similar energy
distribution current with the variation of compression. With the increase of compression ratio, useful
exhaust energy decreased, heat transfer losses increased rapidly, the peak indicated efficiencies of all
different intake CO2 mass percentage were achieved at compression ratio 60:1. For a certain
compression ratio, higher CO2 replacement could depress the peak in-cylinder temperature
significantly due to higher specific heat of CO2, as shown in figure 14, thus reduced the in-cylinder
heat transfer losses, however depressed in-cylinder temperature would be bad for energy extraction
during the expansion phase of the engine cycle, which more energy was translated into exhaust. On

1098

the whole, there was a slight reduce in the indicated efficiency with the increase of intake CO2. A peak
indicated efficiency of 56% was achieved at 60:1 compression ratio without intake CO2 replacement,
the peak in-cylinder pressure was close to 550 bar. As for the 7% intake CO2, the peak indicated
efficiency was about 55.5%, with a significant reduced in-cylinder temperature.
THE EFFECT OF FUELS PROPERTIES
Different fuels properties have a significant impact on the process of the mixture preparation and
combustion thus the thermodynamically process and peak indicated efficiency. Methanol, isooctane
and hydrogen were compared with diesel fuel, for all the fuels, the total fuel energy entering cylinder
per cycle were kept equivalent to 80mg diesel fuel (i.e. 3424J/cycle), the corresponding mass flow
rate of fuels were showed in table 2. In the simulations, the intake pressure for all cases were kept
constant to 2.0bar. The results were showed in figure 15 and 16.
Table 2. Comparison of selected fuels properties and corresponding mass flow rate of fuels
Latent Heat of Vaporization

Stoichiometric air/fuel

Mass flow rate of fuel

(kJ/Kg)

(kJ/Kg)

ratio

(mg/cycle)

Diesel

42800

301

14.3

80

Methanol

21110

1109

6.47

162.2

Iso-octane

44344

510

15.2

78

Hydrogen

119940

34.3

23.94

C0/RO

Diesel
Methanol
iso-octane
H2

70
60

Exhaust Energy Percentage (%)

Lower Heating Value

Indicated Efficiency (%)

Fuel species

50

C0.2/R1

40
30

C1/R1
0

20

40

60

CR (-)

80

100

120

60

Diesel
Methanol
iso-octane
H2

50
40

C0/RO

30

C0.2/R1

20
10

C1/R1
0

20

40

60

CR (-)

80

100

120

Figure 15 Energy distribution as a function of compression ratio for different fuels at various heat transfer coefficient
1800

Diesel
Methanol
iso-octane
H2

C0/RO

1400
1200

2000

20

40

60

CR (-)

80

800

C1/R1

600
400
200

C1/R1
0

C0.2/R1

1000

C0.2/R1

1800

1600

C0/RO

Diesel
Methanol
iso-octane
H2

1600

Pressure Max (bar)

Temperature Max (K)

2200

100

120

20

40

60

CR (-)

80

100

120

Figure 16 Maximum in cylinder temperature and pressure for different fuels at various heat transfer coefficient

The figure 15 shows the energy distribution current of different fuels with the change of compression
ratio at three different heat transfer coefficient. In the figures, C1/R1 represent the normal heat
transfer conditions with convection multiplier=1, radiation multiplier=1. C0.2/R1 represent the low heat
transfer conditions convection multiplier=0.2, radiation multiplier=1. C0/R0 represent adiabatic

1099

conditions without convection and radiation. The figure 16 shows the maximum in cylinder
temperature and pressure of different fuels.
As shown in figure 15 and 16, with different heat transfer coefficient, the methanol showed a most
improved indicated efficiency and reduced exhaust energy percentage, the improvement was much
more significant with heat transfer, and hydrogen also got a higher indicated efficiency while the
isooctane was almost the same with diesel. However, from the figure 15 we can see that the indicated
efficiency was governed mainly by heat transfer coefficient and compression ratio. For example, with
reduced heat transfer coefficient C0.2/R1, the peak indicated efficiency of methanol was 58.6% at the
corresponding compression ratio 60:1, only showed 3% improvement in the indicated efficiency.
However, a peak indicated efficiency more than 70% was achieved with adiabatic condition, while the
peak indicated efficiency was only 49.1% with normal heat transfer and corresponding lower optimal
compression ratio.
However, compared to the improvement in indicated efficiency, the methanol suppressed the in
cylinder temperature even more significant, as shown in the left plot of figure 16. It was mainly due to
the much lower low heating value and higher latent heat of vaporization as shown in table 2.
Comparing to the diesel fuel, owning to the lower low heating value, the mass flow rate of methanol
injection was increased to 162.2 mg per cycle, meantime, the latent heat of vaporization was 2.6
times higher than diesel. For this reason, when the methanol was injected into the cylinder, more than
5 times of latent heat of vaporization per cycle resulted a reduction of 150 to 200 K on average in the
maximum in cylinder temperature, even with adiabatic compression at compression ratio 100:1, the
peak in cylinder temperature was limited in 2000 K. When heat transfer exist, the peak in cylinder
temperature was further reduced, which was favored to reduce the heat transfer losses.
THE EFFECT OF COMBUSTION PHASING
Combustion phasing including CA50 and combustion duration, have a significant effect on the energy
distribution. In the adiabatic cycles, a combustion phasing with a short combustion duration and CA50
close to the top dead center will be beneficial for the improvement of indicated efficiency theoretically.
Traditionally speaking, an engine with normal heat transfer, if the combustion phasing was intensified
excessively, however, would resulted in the increase of peak in-cylinder temperature and pressure, as
a consequence, the heat losses would be increased, especially when the CA50 was too advanced
before the top dead center. On the contrary, a poor combustion phasing with a retarded CA50 and
relative long combustion duration, the heat transfer would be decreased. However, when combustion
occurring at larger volumes, the energy extraction during the expansion phase of the engine cycle
was also deteriorated due to the decline in the degree of constant volume, and the energy loss in the
exhaust was increased, what is more, incomplete combustion will contribute significantly to the losses
with a too delayed and slow combustion.
Simulations were carried out to investigate the influence of combustion duration and CA50 on the
performance at different compression ratios with a low heat transfer coefficient, the convection
multiplier was set to 0.2 and radiation multiplier was set to the normal value 1. The mass rate of fuel
injection was 80 mg diesel fuel per cycle, the equivalence ratio was all kept constant to 0.57. The
results are shown in figure 17 and figure 18.
Figure 17 shows the effect of CA50 and combustion duration on energy distribution. The results
showed that the indicated efficiency was determined by combustion duration and CA50 together, a
short and intensified combustion increased the indicated efficiency, for a given combustion duration,
there exist an optimal CA50 range for the peak indicated efficiency, in this range, the combustion

1100

duration demonstrated a strong effect on the indicated efficiency. too early or late CA50 would lead to
the deterioration of the indicated efficiency, as shown in figure 17(a), especially when the CA50 was
before the optimal CA50 range, the indicated efficiency decreased rapidly with the advancement of
CA50, Figure 17(b) shows the effect of CA50 and combustion duration on heat transfer losses, we
can see that heat transfer increased significantly with the advancement of CA50, at an early CA50
range, the heat transfer was mainly dominated by CA50, at late CA50 range, a short combustion
duration could reduce the heat transfer losses for the moderate heat transfer timing. The exhaust
energy percentage was strongly effected by CA50, too late combustion phasing resulted in the
significant increase of energy lost in the exhaust. And a shorter combustion could decrease the
30 Indicated Efficiency(%) CR=50 Mc=0.2,Mr=1

54
25

56

57

20

Combustion Duration (CA)

Combustion Duration (CA)

exhaust energy.
51 49
52 50
53

55

58

15

51 54
48 52 55
10
49
50 53

59
60

-6 -4 -2 0

30 Heat Transfer(%) CR=50 Mc=0.2,Mr=1

8
25

15

20 18

10

24

16

14 12
6

22

-6 -4 -2 0

8 10 12 14 16 18

8 10 12 14 16 18

CA50 (CA ATDC)

CA50 (CA ATDC)

Combustion Duration (CA)

10

20

30 Exhaust Energy(%) CR=50 Mc=0.2,Mr=1

26

28

25
20

30

32

34

36

38 40

42

15

24

10

-6 -4 -2 0

8 10 12 14 16 18

CA50 (CA ATDC)

(a) Indicated efficiency

(b) Heat transfer losses

(c) Exhaust energy percentage

Figure 17. Effect of CA50 and combustion duration on energy distribution

Figure 18 shows the effect of CA50 and combustion duration on maximum in cylinder pressure and
temperature. As shown in figure 18(a), combustion duration had no significant effect on the maximum
in-cylinder pressure, the in-cylinder pressure was manly dominated by CA50, the maximum
in-cylinder pressure increased with the advancement of CA50 when the CA50 was before 10CA
ATDC, when the CA50 was retarded after 10CA ATDC, the maximum in-cylinder pressure was
almost remain unchanged with the delay of CA50. As shown in figure 18(b), the maximum in-cylinder
temperature was controlled by CA50 and combustion duration together, a late and long combustion
30 Max in-cylinder Pressure(bar) CR=50 Mc=0.2,Mr=1
25
20

490
640 540
590
740 690

15
10

790

440

-6 -4 -2 0

Combustion Duration (CA)

Combustion Duration (CA)

could suppress the maximum in cylinder temperature effectively.

Max in-cylinder Temperature(K) CR=50 Mc=0.2,Mr=1
30
1850
25
1950

20

2050
2150

15

2250

10
2450

2350

-6 -4 -2 0

8 10 12 14 16 18

8 10 12 14 16 18

CA50 (CA ATDC)

CA50 (CA ATDC)

1101

(a) Maximum in cylinder pressure

(b) Maximum in cylinder temperature

Figure 18. Effect of CA50 and combustion duration on maximum in cylinder pressure and temperature

CONCLUSION
In this paper, a commercially available cycle-simulation code was utilized for general performance
computations, results were analyzed from first law of thermodynamics perspective to investigate
pathways to maximize engine efficiency for future advanced high efficiency engines.
Some related strategies are considered in this study, including compression ratio, heat transfer
coefficient, equivalence ratio, intake fluids composition, alternative fuels and combustion phasing.
Following conclusions can be drawn from the study:
1. At the normal compression ratio, with the decrease of heat transfer coefficient, heat transfer losses
was reduced, only one thirds of the saved heat transfer losses were converted to useful work, the
energy lost in the exhaust increased significantly. The peak indicated efficiency was increased to
47.9% under the adiabatic condition while the energy lost in exhaust was increased to 52.1%.
2. Heat transfer coefficient determines optimal compression ratio, as the heat transfer coefficient
decreased, the corresponding optimal compression ratio for indicated efficiency increased, too higher
compression ratio would result in a decrease in the indicated efficiency due to the increase of heat
transfer losses. Additionally, higher compression would resulted in an extremely high in cylinder
pressure.
3. A lean combustion could decrease the heat transfer losses and exhaust energy, and the peak in
cylinder temperature was also suppresses effectively. A lean mixtures would be favorable for higher
indicated efficiency.
4. Increase the specific heat ratio of intake fluids through the N2 replace by argon, showed a
significant improvement in the indicated efficiency under the condition of adiabatic, while with a low
heat transfer coefficient, the peak indicated efficiency decreased significantly, due to the sharp rise in
the in cylinder temperature caused a significant increase in the heat transfer losses. The indicated
efficiency peaks at 57% with 40% argon ratio, at ~40:1 compression ratio. With the N2 replace by CO2,
the in cylinder temperature was suppressed while a peak indicated efficiency of 56% was obtained.
5. Methanol showed an excellence ability of decreasing the peak in cylinder temperature, and the
peak indicated efficiency was relative higher than other tested fuels.
6. Combustion phasing showed a significant effect on the energy distribution and maximum
in-cylinder temperature and pressure, a sharp and intensified combustion phasing was beneficial for
the improvement of the indicated efficiency, the optimal CA50 was about 4 to 8 CA ATDC for the
given eat transfer coefficient, too early combustion phasing would resulted in the increase of heat
transfer.
ACKNOWLEDGEMENT
The authors would like to acknowledge the financial supports provided by National Natural Science
Found of China (NSFC) through its project of 2013CB228402 and 51320105008.
NOMENCLATURE
ATDC

After Top Dead Center

CA50

Crank Angle of 50% Fuel Burned

CR

Compression ratio

Cp

Specific Heat at constant pressure, J/kgC

Cv

Specific Heat at constant volume, J/kgC

Convection Multiplier

1102

HCCI

Homogeneous Charge Compression Ignition

PPC

Partially Premixed Combustion

Radiation Multiplier

RCCI

Reactivity Controlled Compression Ignition

Greek Letters
specific heat ratio
equivalence ratio
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1104

OPERATING PRESSURE OPTIMIZATION OF A PEMFC POWER SYSTEM

a,b

a,

Xianguo Li , Yanzhou Qin , Qing Du , Mingzhe Fan , Yafei Chang , and Yan Yin *
a
State Key Laboratory of Engines, Tianjin University, Tianjin, China
b
Department of Mechanical and Mechatronics Engineering, University of Waterloo, Waterloo, ON,
Canada
*
Corresponding author: yanyin@tju.edu.cn

ABSTRACT
Proton exchange membrane fuel cell (PEMFC) is a promising clean energy conversion device.
PEMFC power system has great potential in the future power plants and automotive applications.
PEMFC stack and the air compressor are the two important components in a PEMFC power system,
and it is meaningful to study their properties and the system operating pressure optimization for better
system performance. In this study, the cathode operating pressure effect on the performance of a 20
kW vehicle use PEMFC stack is investigated using a fuel cell stack model, which is experimentally
validated. The compressor characteristics at various compressor speeds, including the compressor
outlet pressure, mass flow rate and efficiency, are obtained from the tested data. Then, the system
operating pressure optimization is carried out. It is found that both the stack power generation and the
compressor power consumption are increased with the system operating pressure increasing, and
the optimum system operating pressure is obtained in terms of the system net power generation. It is
also found that the compressor efficiency influences the optimum operating pressure and the
optimum operating pressure is increased with the compressor efficiency increasing.
Keywords: PEMFC power system, PEMFC stack, air compressor, operating pressure
optimization.
INTRODUCTION
Due to the growing concerns over the air pollution from the internal combustion engines (ICE) and
the depletion of the fossil fuel reserves, the proton exchange membrane (PEM) fuel cell (PEMFC),
which is an environment-friendly energy conversion device and uses the hydrogen as fuel, has
drawn considerable attention recently. PEMFC has high energy efficiency, rapid start-up, high
power density and zero emission features, making it a promising candidate in the transportation
applications.
The maximum output voltage of a PEMFC is determined by the thermodynamic law and is limited,
hence, in order to satisfy the power demand of a vehicle, PEMFCs must be connected in series to
form a fuel cell stack which is the key component of a fuel cell system. In a fuel cell stack
environment, due to the complexity of the flow network, the reactant gas and pressure distributions
may vary from cell to cell, leading to the difficulty in the water and thermal management and the stack
performance degradation. Therefore, the PEMFC stack design and operating parameters need to be
optimized for better stack performance. Since the fuel cell stack optimization by experiments is timeconsuming and expensive, the design and operating parameters of a PEMFC stack are usually
investigated by modeling. Baschuk and Li (2004) established a PEMFC stack model based on a
hydraulic network approach in which the mass and pressure distributions in the fuel cell stack were
determined by the hydraulic network analysis. They found that the performance degradation of the
cells in a stack was induced by the nonuniform mass flow rate distributions among the cells, and the
stack performance were improved through the design strategies of obtaining uniform mass flow rate
distributions among the cells, such as increasing the size of the manifold and decreasing the number
of channels per bipolar plate. Karimi et al. (2005) proposed a fuel cell stack design with a symmetric
double inlet-single outlet topology which benefited the uniform mass distributions among the cells and
improved the stack performance significantly. The temperature distributions among the cells in a stack
were predicted by Park and Li (2006), and the cooling water flow rate on the stack performance and
the pumping power required for the cooling water were also investigated. From the above studies
related to the PEMFC stack design and optimization, it indicates that the uniformity of the mass,
pressure and temperature distributions are achievable through the optimization of the design and
operating parameters of the PEMFC stack.
Besides the fuel cell stack, a vehicle use PEMFC system should also include the air system, the
hydrogen system, the cooling system, the start-up system, the DC/DC converter, etc. In the anode
hydrogen system, the reactant hydrogen can be provided by a high pressure hydrogen tank and in
this case the anode operating pressure is controlled by a pressure regulator; however, in the cathode
air system, the reactant is usually from the ambient air, and an air compressor or blower must be

1105

used to obtain the required pressure and reactant mass flow rate. For a vehicle use fuel cell stack,
the cell active area is large and the pressure drop across the flow channel is high, and hence an air
compressor is more commonly applied in a vehicle use fuel cell system, due to the limited pressure or
pressure ratio of a blower.
Although considerable amount of literatures can be found on the single fuel cell (Baschuk and Li,
2003; Um and Wang, 2006; Wu et al., 2010), fuel cell stack (Thirumalai and White, 1997; Karimi and
Li, 2006) and even the fuel cell system (Hussain et al., 2005; Gencoglu and Ural, 2009) performance
analysis and optimization, only a few studies have been focused on the air compressor for the fuel
cell system and the air compressor-fuel cell stack matching. Pei et al. (2006) numerically investigated
three types of compressing modes on the system performance based on a fuel cell stack model and
an existing speciality map of the compressor. They found that using the combination of a compressor
and a turbocharger in series is better than the other two modes which are using the electric
compressor alone and using the combination of the compressor and the turbocharger in parallel. Bao
et al. (2006) used a neutral network to treat the map of the compressor and turbine in the air system,
and three types of compressing systems were analysed, a single-level screw compressor, a screw
compressor combined with a turbocharger and a turbine combined with a separated electric
compressor. They found that with the help of the exhaust recycling by the turbocharger or the turbine,
the fuel cell system efficiency was enhanced by 3% compared to the system with the single-level
screw compressor. Their study also showed that the optimum cathode pressure was increased and
the optimum air stoichiometry manifested a concave trajectory as the fuel cell system net power was
increased. Zhao et al. (2012) analyzed the performance of a fuel cell system with a Rankine cycle for
recycling the waste heat from the fuel cell system operation. The power consumption of the air
compressor in their study was simply calculated from that of the isentropic compression divided by a
compressor isentropic efficiency. They found that with the stack operating pressure increasing, the
system overall efficiency was increased firstly, and decreased after the peak value, which indicates
that the optimum stack operating pressure exists for their fuel cell system operation.
In this study, the operating pressure effect on the performance of a 20 kW vehicle use PEMFC stack
is investigated by a fuel cell stack model which is experimentally validated. The characteristics of the
centrifugal compressor are obtained from the tested data. Then, the operating pressure optimization
is carried out using the system net power generation (system efficiency) as the criteria. The influence
of the compressor isentropic efficiency on the optimization is also investigated.
PEMFC STACK MODELING
PEMFC Performance Model
The PEMFC stack model used in this study consists of a one-dimensional single fuel cell model
developed by Baschuk and Li (2003) for the prediction of the cell performance. The single PEMFC
output voltage is predicted by the PEMFC performance model at the specified operating conditions. In
the PEMFC performance model, the cell output voltage is the result of the cell reversible voltage
subtracting the voltage losses or overpotentials from the cell components:

Ecell Erev Vact Vohm Vconc

(1)
where Ecell is the cell output voltage, Erev is the cell reversible voltage, Vact is the activation
overpotential, Vohm is the ohmic overpotential and Vconc is the concentration overpotential. The
reversible voltage is determined by the thermodynamic law and calculated from a modified version of
the Nernst equation:

E rev

G S

(T Tref
2F 2F

RT C H 2
)
ln ref
2 F C
H 2

C
O2
ref
C
O2

1
2

(2)
where G is the change in the Gibbs free energy, F is the Faraday constant, S is the entropy
change, T (K) is the fuel cell temperature, Tref is the reference temperature which equals to 298.15
K, R is the universal gas constant, CH2 and CO2 are the hydrogen and oxygen concentrations at the
electrode backing/ catalyst layer interface, CH2ref and CO2ref are the reference concentration of
hydrogen and oxygen in Nafion at the temperature of 25, and the values are 22.22 and 7.033 mol
m-3, respectively. G and S are calculated at the temperature of 298.15 K.

1106

The activation overpotential Vact is due to the catalyst layers. The activation overpotential consists of
the electrochemical kinetics, the electron and proton adsorption of both the anode and cathode
catalyst layer. The Ohmic overpotential Vohm is due to the proton and electron migration and it consists
of the Ohmic losses from the electron migration in the bipolar plates and electrode backing of both
the anode and cathode sides and the proton migration in the membrane and both the catalyst layers.
The concentration overpotential Vconc is due to the mass transport limitations of both the anode and
cathode sides, and Vconc becomes large when the reactant concentration is low in the catalyst layers
at large current densities. The details of the single fuel cell performance model can be found in the
literature (Baschuk and Li, 2003).
Fuel Cell Stack Model
The single cells in the fuel cell stack model are connected by a flow network, as shown in Fig. 1.
The cell and manifold are divided by the nodes into many branches. The reactant mass flow rate,
concentration, pressure and temperature distributions in each branch are controlled by applying
the mass and energy conservation laws at the nodes connecting the adjacent branches and are
solved iteratively based on the operating conditions at the stack inlet and outlet. Then, these
parameters for each single cell are exported to the fuel cell performance model for the cell voltage
calculation. The details of the fuel cell stack model and numerical procedures are shown
elsewhere (Karimi et al., 2005; Park and Li, 2006).
Model Validation

Fig. 1. Schematic of the flow network in the fuel cell stack model.

Table 1. The PEMFC stack design and operating parameters.

Components
Parameters
Width
Bipolar plate
Length
Thickness
Type of materials used
Effective working area
Cathode flow channel

Anode flow channel

Cooling channel

Width
length

Values
114 mm
410 mm
2 mm
metal
339 mm
92 mm

Channel length
Number of channel
Number of U-turn
Hydraulic diameter
Manifold
hydraulic
diameter
Channel length
Number of channel
Number of U-turn
Hydraulic diameter
Manifold
hydraulic
diameter
Channel length

1107

342 mm
67
0
0.44 mm
27.25 mm
342 mm
67
0
0.39 mm
20.43 mm
378.81 mm
9
4

Stack

Gas diffusion layer

Catalyst layer
Membrane

Number of channel
Number of U-turn
Hydraulic diameter
Manifold
hydraulic
diameter

1.333 mm
12.31 mm
120
1.05
0
2.0
80 %
1.6 atm
1 atm
333.15 K
338.15 K
0~1 Acm-2

Number of cell
Anode stoichiometry
Anode Relative Humidity
Cathode stoichiometry
Cathode Relative Humidity
Anode outlet pressure
Cathode outlet pressure
Inlet temperature
Outlet temperature
Current density

220 m
0.7
Cathode 10 m, anode 5

Thickness
Porosity

m
Pt/C

Thickness
Type of catalyst used

20 m
Nafion

Thickness
Type of membrane
The design and operating parameters of the fuel cell stack are shown in Table 1. It is found from
the modeling result that the voltage variations among the fuel cells in the fuel cell stack are small,
and also because only the

Fig. 2. Comparison of the model prediction with the

experimental data at the fuel cell stack operating conditions
given in Table 1.

Fig. 3. The degree of the cathode catalyst layer flooding

introduced in the fuel cell stack model for the result
comparison between the model prediction and the
experimental data

single cell experimental data is available at the present stage, therefore, the cell voltages from the
modeling are averaged and compared with the single cell experimental data for the model
validation. Figure 2 shows the comparison of the fuel cell polarization curves between the model
predictions and the experimental data. It is found that the predicted cell voltage agrees well with
the experimental data at small current densities, however, the predicted cell voltage is larger than
the experimental data at large current densities and the deviation between the predicted and
experimental cell voltage is increased as the current density is increased. For a PEMFC operated
at large current densities, the porous electrode may be flooded by the product liquid water, which
is not reflected in the fuel cell stack model. In order to reflect the flooding phenomenon in PEMFC,
a parameter representing the degree of the cathode catalyst layer flooding, lH2O, is introduced in
the PEMFC stack model. The flooding parameter lH2O physically means the ratio of the pores in the
cathode catalyst layer blocked by liquid water, which is shown in Fig. 3 for the present modeling.
The predicted cell voltage matches perfectly with the experimental data after the flooding is
introduced in the fuel cell stack model, as shown in Fig. 2.

1108

Effect of The Operating Pressure on The PEMFC Stack Performance

After the PEMFC stack model is validated, the effect of the operating pressure on the PEMFC
stack performance is predicted by the PEMFC stack model with the flooding effect. The current
density is fixed at 0.8 A cm-2 for the vehicle use PEMFC stack performance simulation and it is
assumed that the degree of flooding is maintained the same as that shown in Fig. 3 with various
stack operating pressures. In the fuel cell stack operation, the operating pressure is usually
controlled through regulating the pressure at the stack outlet, and hence the stack outlet pressure
is specified in the modeling. Figure 4 shows the average cell voltage and stack inlet pressure
variations with the stack outlet pressure. It is found that the average cell voltage is increased with
the stack outlet pressure increasing, due to the larger reactant concentration in the fuel cell at
larger pressure which decreases the activation and concentration overpotentials. However, for the
PEMFC stack and compressor matching, the stack inlet pressure or the compressor outlet
pressure is the optimization target, and the stack inlet pressure is referred to as the operating
pressure in this study. Therefore, the stack inlet pressure effect on the stack output power is
depicted in Fig. 5. In Fig. 5, the stack inlet pressure starts from 1.2 atm, since the pressure drop
across the fuel cell stack is 0.2 atm with the stack outlet pressure of 1 atm. It found that the stack
output power, which also represents the stack efficiency, is increased almost linearly with the
stack inlet pressure.
COMPRESSOR CHARACTERISTICS
The compressor characteristics are tested at various compressor speeds at the range of the
compressor outlet pressure of 1.1~1.7 atm. It is seen from Fig. 6 (a) that the compressor power
consumption is increased as the compressor speed is increased for the same compressor outlet
pressure, and it is also increased as the compressor outlet pressure is increased for the same
compressor speed. It is found from Fig. 6 (b) that the compressor mass flow rate is increased as the
compressor speed is increased for the same compressor outlet pressure, while it is decreased as the
compressor outlet pressure is increased for the same compressor speed.
The compressor isentropic efficiency shown in Fig. 6 (c) is calculated by the expression as follow:

comp

Ws
Wcomp

mair /( 1) ( R / M air )Tin ( Pout / Pin ) 1

Wcomp

(3)
where comp is the compressor isentropic efficiency, Ws is the compressor power consumption of the
isentropic process, Wcomp is the compressor electrical power consumption tested, mair is the mass flow
rate of the compressor,

Fig. 4. Stack average cell voltage and inlet pressure

variations with the stack outlet pressure.

Fig. 5. Effect of the stack inlet pressure on the stack output

power.

1109

Fig. 6. Compressor characteristics at the range of the compressor outlet pressure of 1.1~1.7 atm: (a) compressor power
consumption; (b) compressor mass flow rate; (c) compressor efficiency.

is the isentropic exponent, Mair is the molar weight of the air, Tin is the compressor inlet temperature,
Pout is the compressor outlet pressure, and Pin is the compressor inlet pressure. Pin and Tin are taken
as the ambient pressure and temperature at the compressor inlet, which are 1 atm and 299.15 K,
respectively. It is noticed from Fig. 6 (c) that the compressor efficiency is increased with the
compressor speed increasing at high pressure range, whereas it is the opposite at low pressure
range. It is also noticed that the compressor efficiency curve has a convex trajectory for the pressure
range tested except for the compressor speed of 3000 rpm, for which the compressor efficiency is
decreased monotonically as the compressor outlet pressure is increased.
OPERATING PRESSURE OPTIMIZATION
As mentioned earlier, as the PEMFC stack operating pressure is increased, the PEMFC stack power
generation is increased, as shown in Fig. 5, and the compressor power consumption is also
increased, as shown in Fig. 6 (a). Therefore, it is necessary to optimize the stack operating pressure
for the maximum system net power generation. Prior to the optimization work, it is pointed out that the
required air flow rate for the fuel cell stack operated at the

1110

Fig. 7. Effect of the system operating pressure on the system net power generation.

1111

Fig. 8. Effect of the compressor isentropic efficiency on the compressor power consumption. comp is the compressor isentropic
efficiency.

1112

Fig. 9. Effect of the system operating pressure on the system net power generation with various compressor efficiencies. comp is the
compressor isentropic efficiency.

current density of 0.8 A cm-2 must be satisfied by the air compressor. The required air mass flow rate
for the fuel cell stack operation is shown in Fig. 6 (b) by the dash line. The mass flow rates of the
compressor operated at various compressor speeds above the required mass flow rate are
considered to be feasible. In addition, since the compressor power consumption is increased with the
compressor speeds increasing for the same operating pressure, as shown in Fig. 6 (a), the
compressor speed should be as small as possible, provided that the required mass flow rate is
satisfied. Therefore, a two- mode speed operation of the compressor is proposed: the compressor
speed is 5000 rpm for the stack operating pressure equal to or below 1.4 atm; and the compressor
speed is 6000 rpm for the stack operating pressure above 1.4 atm. It is necessary to point out that the
required mass flow rate should be controlled precisely and the excess air from the air compressor is
discharged into the environment.
Figure 7 shows the effect of the operating pressure on the system net power generation. It is found
that the PEMFC system has the largest net power generation at the operating pressure of 1.2 atm,
corresponding to the stack outlet pressure of 1 atm of the unpressurized operating conditions. This
indicates that the increment in the compressor power consumption is greater than the increment in
the stack power generation, although the stack power generation is increased for a larger operating
pressure, leading to a negative system net power increment with the operating pressure increasing.
It is noticed in Fig. 6 (c) that for all the operating pressure and compressor speed range investigated,
the compressor efficiency is maintained low with the peak value less than 0.45, which possibly
explains the less economic for the large system pressure operation. Generally, the centrifugal
compressor efficiency, which could reach as high as 0.9, is much higher than the one tested in this
study. Without loss of generality, the compressor isentropic efficiency is specified artificially and used
for the compressor power consumption calculation based on Eq. (3), with the other compressor
characteristics maintained the same as the tested values. Figure 8 shows the influence of the
compressor efficiency on the compressor power consumption. It is clearly seen that the compressor
power consumption is decreased with the compressor efficiency increasing. It is shown in Fig. 9 that
the optimum operating pressure of the PEMFC system changes as the compressor efficiency is
changed. The optimum operating pressure is increased with the compressor efficiency increasing.
The optimum operating pressure is 1.2 atm for the compressor efficiency below 0.55; the operating
pressure is 1.3 atm for the compressor efficiency between 0.55 and 0.75; and the optimum operating
pressure is 1.4 atm for the compressor efficiency above 0.75.
CONCLUSIONS
In this study, the effect of the cathode operating pressure on the performance of a 20 kW vehicle use
proton exchange membrane fuel cell (PEMFC) stack is investigated by using a PEMFC stack model.
The characteristics of the air compressor used for the air supply are obtained from the tested data.
The operating pressure is optimized for the PEMFC system composed of the PEMFC stack and the
air compressor. It is found that the optimum operating pressure is 1.2 atm for the PEMFC system
investigated, corresponding to the unpressurized operating condition, due to the low compressor
efficiency. The effect of the compressor efficiency on the pressure optimization is also investigated,
and it found that the optimum operating pressure is increased with the compressor efficiency
increasing.

1113

ACKNOWLEDGEMENT
This work is financially supported by the National Basic Research Program of China (973 Program,
Grant No. 2012CB215506 and 2010CB234610) and the Natural Science Foundation of Tianjin, China
(Grant No. 11JCZDJC23500 and 11JCYBJC07400).
NOMENCLATURE
C
concentration, mol m-3
E
voltage, V
F
Faraday constant, C mol-1
G
change of Gibbs free energy, J mol-1
l
degree of water flooding
m
mass flow rate, kg s-1
M
molar weight, kg mol-1
P
pressure, Pa
R
universal gas constant, J mol-1 K-1
S
entropy change, J mol-1 K-1
T
temperature, K
V
overpotential, V
W
power generation or consumption, kW
Greek Letters

isentropic efficiency

isentropic exponent
Subscripts
act
activation
air
air
comp compressor
conc
concentration
H2
hydrogen
H2O
water
in
inlet
O2
oxygen
ohm
ohmic
out
outlet
ref
reference condition
s
isentropic process
Superscripts
ref
reference condition
REFERENCES
Bao C., M. Ouyang, and B. Yi, 2006, Modeling and optimization of the air system in polymer
exchange. Journal of Power Sources 156: 232-243.
Baschuk J. J. and X. Li, 2003, Mathematical model of a PEM fuel cell incorporating CO poisoning
and O2 (air) bleeding. International Journal of Global Energy Issues 20: 245-276.
Baschuk J. J. and X. Li, 2004, Modelling of polymer electrolyte membrane fuel cell stacks based
on a hydraulic network approach. International Journal of Energy Research 28: 297-724
Gencoglu M. T. and Z. Ural, 2009, Design of a PEM fuel cell system for residential application.
International Journal of Hydrogen Energy 34: 5242-5248.
Hussain M. M., J. J. Baschuk, X. Li, and I. Dincer, 2005, Thermodynamic analysis of a PEM fuel
cell power system. International Journal of Thermal Science 44: 903-911.
Karimi G., J. J. Baschuk, and X. Li, 2005, Performance analysis and optimization of PEM fuel cell
stacks using flow network approach. Journal of Power Sources 147: 162-177.
Karimi G. and X. Li, 2006, Analysis and modeling of PEM fuel cell stack performance: Effect of in
situ reverse water gas shift reaction and oxygen bleeding. Journal of Power Sources 159: 943-950.

1114

Park, J and X. Li, 2006, Effect of flow and temperature distribution on the performance of a PEM
fuel cell stack. Journal of Power Sources 162: 444-459.
Pei P., Y. Wu, and P. Li, 2006, Numerical prediction on an automotive fuel cell driving system.
International Journal of Hydrogen Energy 31: 361-369.
Thirumalai D. and R. White, 1997, Mathematical modeling of proton-exchange-membrane fuel-cell
stacks. Journal of The Electrochemical Society 144: 1717-1723.
Um S. and C. Y. Wang, 2006, Computational study of water transport in proton exchange
membrane fuel cells. Journal of Power Sources 156: 211-223.
Wu H., P. Berg, and X. Li, 2010, Steady and unsteady 3D non-isothermal modeling of PEM fuel
cells with the effect of non-equilibrium phase transfer. Applied Energy 87: 2778-2784.
Zhao P., J. Wang, L. Gao, and Y. Dai, 2012, Parametric analysis of a hybrid power system using
organic Rankine cycle to recover waste heat from proton exchange membrane fuel cell.
International Journal of Hydrogen Energy 37: 3382-3391.

1115

A study of biodiesel production, characterization and engine performance of

Manketti (Ricinodendron rautonemii) methyl ester and its blends as a potential
biodiesel
a

A.E. Atabani *, M. Mofijur , H.H. Masjuki , Irfan Anjum Badruddin , W.T. Chong , S.F. Cheng ,
S.W. Gouk

Department of Mechanical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala

Lumpur, Malaysia
b
Unit of Research on Lipids (URL), Department of Chemistry, Faculty of Science, University of Malaya,
50603 Kuala Lumpur, Malaysia

Abstract
Globally, there are more than 350 oil-bearing crops identified as potential biodiesel sources.
In this study, biodiesel production and characterization of Manketti (Schinziophyton
rautanenii) methyl ester and its blends with diesel were reported. The effect of Manketti
biodiesel blends (B5) on engine and emissions performance has also been investigated. A
single step of alkaline transesterification process has been used to produce biodiesel. It
has been found that biodiesel yielded a cloud, pour and cold filter plugging point of 1 C,
3 C and 5 C respectively. However, the kinematic viscosity of Manketti methyl ester is
8.3425 mm2/s. This is higher than the limit prescribed by ASTM D6751 and EN 14214. This
can be attributed to the high viscosity of the parent oil (132.750 mm2/s). Therefore, blending
of Manketti biodiesel with diesel can improve this property. The main findings of engine
performance and emissions showed that, at all engine speeds, B5 produced lower brake
power (1.18%) and higher BSFC (2.26%) compared to diesel. B5 increased the CO and HC
emissions by 32.27% and 37.5% respectively compared to B0. However, B0 produce 5.26%
higher NO emissions than B5 fuel.

Keyword:

Biodiesel

feedstocks,

Manketti

oil,

Transesterification,

Physico-chemical

properties, Blending, Engine performance.

Corresponding authors at: Department of Mechanical Engineering, University of Malaya, 50603 Kuala Lumpur,
1116

Malaysia. Tel.: +60122314659. E-mail address: a_atabani2@msn.com (Abdelaziz Emad Atabani).

CFD SIMULATION AND EXPERIMENTAL INVESTIGATION ON LIQUID FLOW

OUTSIDE EVAPORATION TUBES AND ITS INFLUENCE ON HEAT TRANSFER
QI Chun-hua, FENG Hou-jun,Lv Qingchun, Xu Ke*, Zhang Ming
Institute of Seawater Desalination & Multipurpose Utilization,SOA,Tianjin 300192, China
1# Keyan East Road, Nankai District, Tianjin
qi_chunhua@163.com

ABSTRACT
The liquid film flow has a significant impact on the distillation,which directly determine the heat
transfer coefficient. Aiming at a horizontal-tube falling-film evaporator, the effects of flow patterns and
heat and mass transfer on the vapor-liquid interface on the heat transfer process are studied in this
paper. The related data are acquired through both simulation and experiment. The volume of fluid
(VOF) model coupled with the user defined function (UDF) module was adopted for the simulation of
a liquid-vapor system. The experimental apparatus and its principal characteristics were introduced.
According to the method mentioned above, the droplets extended on the tube surface, flow patterns,
effect of liquid film state on heat transfer are tested. The results show good agreement between the
simulation and the experiment, both data having a deviation band within 10%.The computational
method adaptable to simulating liquid-steam flow is formed. The results of simulation and the
experiment both indicate that 0.08 kg/(ms) of sprinkling density is the breakpoint of liquid outside
tube from columnar flow to sheet flow, and the overall coefficient of heat transfer K at experimental
condition is up to 4.06kW/m2K.This value is of great significance in guiding the design of spraying
density of low-temperature multi-effect seawater desalination devices. In short ,the research should
be a basis for further improvement in the performance of heat transfer.
Keywords: falling-film evaporator, experimental investigation, VOF.
INTRODUCTION
Thin liquid films have significant advantages, such as low film flow rate, high heat transfer coefficient,
low energy consumption, and structural simple. Given these advantages, horizontal-tube falling-film
evaporators are widely used in the desalinization industries. Seawater is sprayed to the surface of the
tubes through a feeder, and then liquid film is formed outside the tubes, wherein liquid film is heated
to evaporative temperature by the vapor inside the tube.
Former studies involving heat transfer factor characteristics covered wide ranges of sprinkling density,
heat flux, temperature difference, and evaporation temperature, in which the effect of sprinkling
density on the heat transfer coefficient was critically discussed. The overall heat transfer coefficient is
almost independent of the sprinkling density in the smooth tube bundles; however, the evaporation
heat transfer coefficient increases slightly [1]. The sprinkling density is not one of the factors affecting
the evaporation-heat-transfer coefficient [2]. By contrast, Newson determined the heat transfer
coefficients of a horizontal tube falling-film evaporation equipment under sterile conditions and
showed that evaporation heat transfer coefficient increases with sprinkling density [3]. A close
relationship exists between sprinkling density and the evaporation heat transfer coefficient. That is, as
sprinkling density increases, the evaporation heat transfer coefficient initially decreases and then
increases after a certain value [4-7].
Different experimental studies on falling film heat transfer have inconsistent findings regarding the
effects of sprinkling density on the heat transfer coefficient. A critical review of falling-film evaporation
on horizontal tubes in 2005 indicated that the liquid distribution outside the evaporation tubes is one
of the factors that affect flow uniformity and dry out, especially in deep bundles [8]. The sprinkling
density resolves the flow patterns, which affect the evaporator performance. In general, thick films fail
to provide the advantages of thin liquid films in the bundle, thus affecting the heat transfer rate. Thin
films result in easy corrosion and scalability of metal tubes. Therefore, the effect of flow patterns is
significant for falling film evaporators; allowing better spray distribution and film thickness optimization
are very important.
Since the characteristics of falling films have drawn great attentions, the researches on the film
thickness have conducted by both theoretical and practical approaches in the past years. Nusselt[9]
first analyzed falling films theoretically, assuming a continuous sheet flow from tube to tube and
momentum effects on the falling films to be negligible. He derived the following expression for the film
thickness.

1117

Zhang et al. [10,11] presented theoretical and experimental investigations of the film thickness and
temperature profile on a vertical heated/cooled plate. Xu et al. [12] studied the flowing state in liquid
films outside horizontal tubes. Numerical methods based on the Computed Fluid Dynamic were also
applied to explore the construction and instability of the film [13,14]. Furthermore, a variety of
techniques have been employed to measure the film thickness. For example, double-fiber optical
probe [15], optical-electronic method [16], chromatic confocal imaging method and fluorescence
intensity technique [17], laser induced fluorescence[18], and laser focus displacement meter [19].
Most of above numerous theoretical and experimental studies considered a vertical tube or flat plate
as the test section. For a liquid film falling around a horizontal tube, it is not possible to utilize the
complex system to perform the measurements in a wide range of circumferential angles because of
geometrical restrictions. Hence, there are few researches on this issue reported in the literature so
that quantitative data of the film thickness around a horizontal tube are very limited. Displacement
micrometer was used to determine the distribution characteristics of the film thickness[20].
Measurements outside diameters varying from 20 to 32 mm, intertube spacings ranging from 10 to 40
mm, and film Reynolds numbers(Re) varying from 150 to 800. It is found that the distribution
characteristics of the film thickness are mainly affected by circumferential angle, intertube spacing
and film Reynolds number. However, the outside diameter has little influence on the film thickness.
Antonios D. Anastasiou[21]used a micro-Particle Image Velocimetry (l-PIV) to investigate the
thickness of the liquid film and for determining the shape of the interface in microreactors. and
experiments were conducted in two open inclined, rectangular microchannels with widths 1200 and
600m.
Above investigations showed the influence of the liquid flow rate on the film thickness and heat
transfer. However, modeling the mechanism of the flow pattern and the heat transfer over a horizontal
falling film tube needs more details. Mitrovic [22] studied experimentally the heat transfer and the
mechanism of the flow from a horizontal heated tube to a falling subcooled liquid film. The
experimental results indicated that the flow pattern not only depends on the film Re, but also on the
tube spacing. The study showed also that the transition from droplet mode to the jet mode occurred at
Reynolds numbers between 150 and 200, while transition from the jet mode to the sheet mode
occurred at Reynolds between 315 and 600 using water. Other experimental observations refered by
Hu and Jacobi [23] for the flow characteristics and mode transitions The review study of Ribastki and
Jacobi [24] covered the available literature about horizontal type falling film type evaporators, focusing
on the technical difficulties of the process. The study also covered the flow pattern studies and the
experimental parameters that affect the heat transfer performance on plain single tube, enhanced
surfaces and tube bundles.
Despite that local and foreign researchers have conducted numerous studies on the liquid flow
outside heat transfer tube and its influence on heat transfer, and obtained significant achievements,
but there are still some limitations. For instance, the physical probe used in experiments affects the
distribution of liquid film on heat transfer tubes surface, so errors exist in the results. In order to
compensate the experimental shortcomings, many researches employed numerical simulation to
study process of liquid flow outside heat transfer tube. Morales-Ruiz et al [25] adopted improved
SIMPLE algorithm to study the envaporation outside heat transfer tube and condensation process
inside tube in refrigeration systems evaporator, and the simulated results are consistent with the
experimental results. Moalem [26] theoretically analyzed the laminar liquid film thickness by
calculation, and achieved analytical solutions. In most current reports, 2D model is used to study the
fluid distribution outside heat transfer tube. However, in such model, liquid thickness is unchangeable
in Z direction, which is inconsistent with the actual situation; because when each droplet drops onto
heat transfer tube, there is sputtering effect, resulting in the incorrect and incomplete reflection of
liquid film distribution on heat transfer tube in 2D model, neither the thickness distribution of tubewinding liquid film. In this paper, FLUENT software is adopted, and UDF custome programming
estabishes applicable 3D mathematical and physical model, to investigate the state and thickness
distribution of liquid film outside heat transfer tube. Besides, the influence of flow patterns on
envaporation and heat transfersimulation of falling-film outside horizontal tube by means of simulation
and experimental research. We have obtained the optimal sprinkling density parameters of seawater
desalination envaporator, which are of great significance in increasing envaporation efficiency and
optimizing envaporator design. In this paper, a method of combing simulation and experiments is
provided for studying liquid films flowing state and for the reference of optimizing falling-film
evaporator.

1118

SIMULATION METHODS
The Fluent software was used to investigate the flow characteristic and heat and mass transfer
process in seawater desalination equipment. A transient numerical simulation was applied to obtain
the time-dependent flow characteristics. The volume of fluid (VOF) model coupled with the user
defined function (UDF) module was adopted for the simulation of a liquid-vapor system. The k-
turbulence model was employed to describe the turbulence outside the tube.
Physical model
Simulation of the flow and heat transfer in a horizontal-tube falling-film evaporator is difficult to
perform. In this study, a single tube model was used (Figure 1).

Fig.1 Schema of the simulated a single tube

A 19 mm tube was placed in the center of the cube calculation area, and the seawater inlet was a
2 mm hole at the center of the upper side of the tube. The section perpendicular to the tube can be
used as a respective plane to analyze the results.
Model equations
The CFD modeling involves numerical solutions of the conservation equations for mass, momentum,
and energy. These equations for incompressible flows can be written as follows:
Mass conservation:

u 0
t

(1)

Momentum conservation:

u
uu g P
t
(2)

Energy conservation:

e
u e P Keff T eff u
t

(3)

Where

2
3

u u T uI

(4)

In the present study, the RNG version of a k- turbulence model with enhanced wall function for the
near-wall treatment was used to model the turbulent flow regime. The following equations were used
for this purpose:

eff C

k2

k
kui eff k ui j ui

t
xi
xi k xi
x j xi x j

1119

(5)

(6)

2
2

ui eff C1 ui j ui C2

t
xi
xi xi
k u j ui u j
k
k

(7)

Where

C 3

ui u j
1 / 0
k
2

2
E
E
and
,
,

E
E

0
.
5

ij
ij
ij
x

1 3
j xi

(8)

The VOF model was applied in this study to monitor the liquid-vapor interface, in which q represents
the volume ratio of the q phase (vapor phase), the liquid-vapor interface can be identified by the
continuous function in Eq. (9), and the q phase volume can be obtained using Equation (10).
n
1 q q

q q uq S q m pq m qp
q t
p 1

(9)
n

p 1

1
(10)

m pq

m qp

Where Sq is the source, with a default value of zero.

and
represent the mass transfer
from p to q and from q to p, respectively. The value of q for incompressible fluid is constant. Density
and viscosity were determined using the following equations:

L L (1 L ) G

(11)

L L (1 L )G

(12)
The evaporation was described using Equation (13):

L L x A
( L L u L x A L L x A ) S LG
t

(13)

Where SLG is the source of mass transfer, and G and L are the mass transfer coefficients of
vapor and liquid phases, respectively, which can be calculated via the following equation:

D Dt

(14)
Where D is the molecular diffusion coefficient and Dt is the turbulent mass transfer diffusivity
coefficient.

Dt

Sct

DL 7.4 10 8

(15)

(M B ) T
B v 0.6 A
1/ 2

(16)

1120

Mesh Methods and boundary condition

In the modeling part of the present study, the modeled domain that consists of a tube and a box was
meshed into almost 200,000 tetrahedral cells. Figure 2 and Figure 3 show the example of the
meshed configuration of single-tube and multi-tube respectively. The regions in the bath close to the
tube wall were meshed into smaller control volumes to obtain more precise prediction results [27].

Fig.2 The Meshed Configuration of the Bath

Fig.3 Multi-tube heat transfer model and a grid of discrete structures in evaporator

(1) Inlet boundary condition

The inlet boundary condition is velocity boundary condition, and the inlet velocity refers to the
operating range of spraying density of actual low-temperature multi-effect device, while the flowing
direction is perpendicular to inlet plane, and the velocity is 0.09 m/s, 0.2 m/s, 0.5 m/s and 0.8 m/s.
(2) Outlet boundary conditions
There are two types of outlet boundary referred in this paper. One is the outlet of liquid water and the
other is the outlet of secondary steam. The outlet of liquid water is set to be wall boundary condition,
while the outlet boundary of secondary steam is taken as pressure outlet 0 kPa (gauge pressure).
(3) Heat transfer tube surface boundary
The distribution of liquid on heat transfer tube is greatly linked with its surface tension. In the
simulation, the contact angle of fluid and the surface of heat transfer tube is 30o. Besides, according
to the actual working condition, the wall temperature is set to be 2 to 3 C higher than feed liquid
temperature.

1121

EXPRIMENTAL INVESTIGATION
Experimental equipment
Figure 4 shows the experimental apparatus used in this study. The principal characteristics of the
apparatus are reported elsewhere [28].

Fig.4 Experimental distillation apparatus

Fig. 5 Heat transfer tubes in evaporation(The upper three rows being liquid distribution)

Heat transfer tubes are 29 smooth aluminum brasses with 19 mm of outer diameter, being 890 mm
long, with 0.75 mm of wall thickness, 800 mm of effective heat transfer length. They are arranged in
the shape of regular triangle at six rows and six lines, as is shown by Fig.5. The upper three rows are
for liquid distribution and the lower three rows (14 tubes) are for heat transfer, as is indicated by Fig.5,
so as to make sure of the stable flow of seawater outside the tube, making the experimental
conditions be closer to the actual engineering working conditions; liquid distributor is a cuboid
container with the upper part unsealed, under the bottom of which there is evenly distributed spraying
holes of 2 mm. The evaporator is equipped with windows of which insulation cover is easy to
disassemble. During the experiment, 3D imaging measurement system of film real-time tracks,
photographs and records gas and liquid interfaces, and then analyzes the images and signals, so as
to collect the changes of flowing state of liquid film outside the tube and the liquid film thickness. The
measurement system is fixed on 2-layer platform with tripod, which is shown by Fig.4. It is 300 mm
away from evaporator sight glass and in the same horizontal line as test heat transfer tube. A stable
surface light source direct shines experimental pieces to reduce the influence of light on experimental
data. The addition of light burning substances into liquid and sheet beam illumination increases the
contrast ratio of liquid film. The measurement system adopts Phantom V12.1 high-performance color
image acquisition system produced by American Vision Research Inc, and its maximum shooting
speed is 680,000 frames / second. The time interval of signal collection is set by collection program,
and the data are stored in specific documents. The film thickness is measured with PCC 1.3
measuring function of Phantom.
Its flow diagram of the experiment system is shown in Figure 6.

1122

Fig.6 Schematic Diagram of Experiment System

The experiment system mainly consists of an evaporator, an electric boiler, circulating pumps, heat
exchangers, vacuum pumps, condensate metering devices, etc. The experimental procedure is as
follows. First, the vacuum pumps (Nos. 10 and 11) are started to create a given vacuum for the
system. Second, the circulating pumps (Nos. 4 and 5) are operated and the fluid is pumped into the
evaporator (No. 2). The fluid passes through a regulating valve and flows into the liquid feeder, from
which the fluid is supplied at the desired flow rate in the form of discrete droplets or individual jets. At
the same time, the saturated steam generated by the electric boiler (No. 1) comes into the bundle of
tubes and condenses inside the horizontal tubes. The heat transfer then goes between the falling film
evaporation outside the tube and primary steam condensing inside the tubes. The secondary vapor
from the falling film evaporation is condensed in the condenser (No. 6), with its condensates precisely
measured by a metering device (No. 8). The condensing part of the primary steam flows to the
electric boiler after being measured by a flow meter. The non-condensing part of the primary steam
then enters the condenser (No. 7) and is condensed fully, with its condensation measured by a
metering device (No. 9).
Non-condensable gases are extracted by the vacuum pump from the tube side and shell side of the
evaporator. The vacuum pumps not only extract the non-condensable gases during system operation,
but also create an initial vacuum when the system is started.
The experiments were conducted using Al-brass tubes (outer diameter: 19 mm) and heated by
internal saturated steam. The experimental work of falling films down on the horizontal tubes was
carried out to obtain basic data and principle similar to that in the desalination experiment. A sight
glass with an insulating cover exists in the shell of the evaporator, and the cover can be easily
removed. When the liquid flows from one horizontal tube to another below it, the liquid flow can be
instantly photographed through the sight glass using a high-speed camera (PhantomV12.1) with a
maximum frame rate of 680,000 fps.
Data reduction
The primary steam condensation heat transfer can be calculated as:

Q1 G1

(17)

The heat absorption equation of the falling film evaporation is shown as:

Q2 G2 ( I i )

(18)

The heat transfer temperature difference between vaporization and condensation is defined as:

t t1 t2

(19)

Where t1 is the saturated steam temperature inside the tube and is equated with the steam inlet
temperature of the evaporator. It can be adjusted by the electric boiler control. t2 is the feed liquid

1123

temperature, namely, the evaporation temperature. In this experiment, the heating unit is located in
the circulating water tank, and the feed liquid is pumped into the evaporator for falling film evaporation
until it is heated to saturated temperature.
The heat flux equation is shown as:

Q G1
(kW/m2)

s
d 0 L

(20)

The average heat flux is defined as:

Q1 Q1
2

(kW)
(21)

The average deviation can be calculated as:

Q1 Q1
Q

(22)
The formula for the total heat transfer coefficient is defined as:

Q
(kW/m2K
)
F tm
(23)

F (

d0 di
)L
2

(24)

NUMERICAL RESULTS AND COMPARISION WITH THE EXPRIMENTAL RESULTS

Flow patterns
The flow rate can affect the flow pattern of liquid in the equipment. Figure 7 shows an image of the
flow character at different velocities (0.09 m/s to 0.8 m/s), in which the liquid phase is shown in red
(shows the light in Figure 7) and the vapor phase is shown in blue (shows the deep in Figure 7).

Fig.7 Flow patterns at different velocity

The evaporation of a liquid falling on horizontal tubes depends on the processes that generally
govern the evaporation kinetics and the shape and area of the liquid-vapor interface. The latter is
known as a function of flow patterns. Whether droplets, columns, or a liquid sheet forms at moderate
tube spacing mainly depends on the flow rate and the physical properties of the liquid[29]. Based on
the simulation results, the flow pattern is droplet when the flow rate is lower than 0.1 m/s [<0.023
kg/(ms)], the droplet-jet pattern appears when the flow rate is between 0.1 m/s and 0.3 m/s [0.023
0.05 kg/(ms)], the jet pattern appears when the flow rate is between 0.3 m/s and 0.65 m/s [0.05
0.10 kg/(ms)], and the sheet pattern occurs when the flow rate is higher than 0.65 m/s.
The experimental images of different flow patterns are given in Fig. 8. The numerical simulation and
experimental results were in good agreement.

1124

Fig.8 Flow patterns at different velocity (experimental results)

Fig. 7 and Fig.8 indicate that when inlet velocity is 0.5m/s, that is, sprinkling density is 0.08 kg/(ms),
the liquid film evenly wraps the external wall of heat transfer tube and membranously flows; besides,
the liquid film fluctuates to certain degree. This state guarantees liquid film to completely cover the
external heat transfer tube, maximizing the effective heat transfer domain of heat transfer tube with
the best heat transfer effect [30].
Liquid droplet results
According to the simulation results of 4.1, as for smooth alumina brass with 19 mm, when inlet
velocity is 0.5 m/s, that is, sprinkling density is 0.08 kg/(ms), flow pattern is columnar at certain
speed, and liquid film evenly covers the external wall of heat transfer tube and flows membranously.
Here is the simulated process of droplets dropping when sprinkling density is 0.08 kg/(ms), and it is
compared with experimental results, so as to further verify the 3D mesh model of low-temperature
multi-effect seawater desalination, and then to get the calculation method for simulating liquid dropletsteam two-phase flow.
Fig. 9 is the phase distribution at different time points. The inlet droplets drop onto heat transfer tube
and disperse, spread to the tube bottom and finally condense to be droplets at the lower tube. It took
about 7.6 ms for droplets from contacting heat transfer tube to its spreading on tube surface.

Fig. 9 The holdup rate distribution of droplets outside heat transfer tube at different moments (The red color refers to liquid
phase domain, while blue represents gas phase domain, and the inlet velocity is 0.5 m/s)

Figure 10 shows the experimental images of a liquid droplet above the tube at different moments.
These images were captured by a high-speed camera (1280 800 pixels/frame; 680,000 fps). The
droplets extended on the tube surface as a circular image, and it took approximately 8ms from
touching the tube to fully extending on the tube surface, which is basically consistent with 7.6ms of
numerical simulation. The error of simulation results is about 5%.

1125

Fig.10 Process of the liquid droplet and extend on the tube surface

Fig.11 Comparison of process of the liquid extend on the tube surface between simulation results and experimental results

The droplet extending process was also observed in the simulation results. As shown in Figure 11,
the simulation image of the droplet extending on the tube surface is circular, which is in agreement
with the experimental image. And the error of simulation time of dropping and spreading is about 5%.
It demonstrates that the mathematical and physical model established by simulation computation can
correctly reflect the process of liquid droplets dropping and the flowing of liquid films spreading
outside heat transfer tube. These results also indicate that the simulation method is suitable for this
process.
Liquid film thickness
4.5

mm

4.0

Experimental data
Numerical simulation data

1.0
0.8
0.6
0.4
0.2
0.0

20

40

60

80

100

120

140

160

180

/()

Fig. 12(a) The distribution of liquid film around

Fig. 12 (b) The distribution of thickness of

liquid film
the outside the tube with =0.08 kg/(ms)

outside the tube

Fig. 12(a) shows that liquid film distributes around the tube, but has an uneven thickness at different
angles of circumference, which is characteristic of thick liquid film at the top and bottom and thin in
the interspace. The top angle of circumference of heat transfer tube is defined to be 0o and the lower
one 180o. Fig.12(b) is the thickness distribution of liquid film at different angles of circumference.

When 0< <90, the increase of tube-winding angle leads to gradual thinning of liquid film which
becomes 0.34 mm at 90o; later, due to gravity, liquid condenses again at the lower tube and the film
thickens which becomes 0.43mm at 135o and 3.7 mm at 180o. It is mainly caused by the liquid
condensation at tube bottom. It is consistent with literature [31]. Compared with the measure values,
the error of simulated thickness of liquid film outside tube is 10%.

1126

Effect of liquid film state on heat transfer

According to the above-mentioned numerical analysis method, the numerical simulation of the
evaporation rate is conducted under different flow patterns, such as droplet, droplet-jet, jet, and sheet
flow. The result of this numerical simulation is compared with the experimental data obtained from the
above experiment system.
Figure 13 shows a comparison between the experimental and numerical simulation results on the
effect of sprinkling density on the heat transfer coefficient when the evaporation temperature and the
temperature difference are 70 and 3 C, respectively. In Figure 13, the abscissa () and the ordinate
(K) stand for the sprinkling density [kg/(ms)] and the total heat transfer coefficient [kW/(m2K)].

Fig.13 Comparison between numerical simulation and experiment about effects of spray density on heat transfer
coefficient

As is manifested by the figure above, with the increase of sprinkling density , the overall coefficient of
heat transfer first increases, then reduces and finally increases; when it exceeds certain value, the
influence of sprinkling density on overall coefficient of heat transfer gradually decreases, which is the
same as the manifestation in literature [32-33].
As sprinkling density increases, the total heat transfer coefficient K initially increases, then decreases,
and finally increases again (Figure 11). The effect of sprinkling density on the heat transfer coefficient
gradually weakens when the sprinkling density is more than 0.08 (kg/ms). The values vary between
0.008 (kg/ms) 0.05 (kg/ms); thus, the heat transfer coefficient initially increases and then
decreases. In the experiment, large dry-out areas are found on the surface of the tube when the
spray density is very small and the liquid is dripping in a discontinuous droplet flow pattern between
the upper and lower tubes. Thus, evaporation is mainly conducted through tube wall heat conduction,
and the heat transfer coefficient is very low. As the spray density increases, the liquid outside tubes
also increases. As a result, the liquid flows in the droplet-column pattern in which the convective heat
transfer is enhanced. Accordingly, the completely wetted perimeter surface of the tube is maintained
well, and the heat transfer coefficient is improved significantly. However, when spray density
increases more than a certain value, the thickness of the liquid film alongside the tube circumference
increases sharply. As a result, the thermal resistance is enhanced, and the heat transfer coefficient is
decreased gradually.
When the spray density varies between 0.05 (kg/ms) 0.08 (kg/ms), the total heat transfer
coefficient improves stably. These results mirror what was seen by Shen et al.[34]. The reason is that
when the spray density is beyond 0.05 (kg/ms), the liquid flow may take the form of circular jets, and
falling film evaporation may occur. When the spray density further increases, the velocity of the liquid
flow and the fluctuation of the liquid film outside the tube are increased, thereby enhancing the

1127

convective heat transfer. Thus, the total heat transfer coefficient increases constantly, reached 4.06
kW/m2K.
When the spray density is more than 0.08 (kg/ms), the liquid outside the tube flows in the pattern of
continuous sheet. The total heat transfer coefficient becomes stable, and the effect of spray density
weakens gradually. The reason is that the increase in thickness of the liquid film outside the tube
leads to increased thermal resistance, which takes the dominance and makes against the heat
transfer.
Therefore, 0.08 kg/(ms) of sprinkling density is used in designing falling-film evaporator of seawater
desalination to avoid regional dry boiling of external wall of heat transfer tube, making liquid film
outside tube be at membranous evaporation state; under the precondition of saving pump power
consumption, a big heat transfer coefficient is guaranteed, while the operating efficiency of falling-film
evaporator is increased.
A comparison between the experimental data and numerical simulation results is shown in Figure 11.
The experimental data and numerical simulation results on the curve reflects the similar variation of
the spray density versus the heat transfer coefficient. However, the numerical analysis results are
higher than the experimental data, with a deviation within 6.5%. When the spray density increases
beyond 0.108 (kg/ms), the heat transfer coefficient of the numerical analysis is lower than that of the
experimental data. This finding may be attributed to the inadequate assumption and accuracy of grid
generation in the numerical simulation.
CONCLUSIONS
(1)In this study, a detailed numerical model of thermal and fluid flow phenomena is developed to
simulate the liquid flow outside a horizontal-tube falling-film evaporator. The flow patterns obtained by
PhantomV12.1 high-speed camera during the experiments are compared with the numerical results.
The numerical results provide accurate predictions of the flow patterns, as done in the computer
model.
(2)The numerical results are compared with the experimental results. Both results present the same
trend, with both data having a deviation band within 10%. And then the computational method
adaptable to simulating liquid-steam flow is formed.
(3) 0.08 kg/(ms) of sprinkling density is the breakpoint of liquid outside tube from columnar flow to
sheet flow, and external tube stays at membranous evaporation state, while surface liquid acerbates
renewing, and the overall coefficient of heat transfer K at experimental condition is up to 4.06
kW/m2K. In the precondition of saving pump power consumption, a big heat transfer coefficient is
guaranteed, and the operating efficiency of falling-film evaporator is increased, which is of great
significance in guiding the design of spraying density of low-temperature multi-effect seawater
desalination devices.
(4)CFD and experiments are used to study the effects of heat transfer. The liquid flow outside the
tube and the vapor-liquid interface, which are the thermal resistance to control, significantly affect
heat transfer. Future studies should focus on the liquid flow and the vapor-liquid interface.
(5)The heat transfer process of low-temperature multi-effect seawater desalination is complex,
consisting of the evaporation process on the surface of heat transfer tube and the condensation
process inside heat transfer tube. The research in this paper primarily focuses on the single tube
model of evaporation process outside heat transfer tube. Multi-tube model is needed in future study
on liquid distribution and its influence on evaporation and condensation heat transfer process, as well
as the effect of heat transfer size and arrangement on liquid distribution and heat transfer process.
ACKNOWLEDGEMENT
The authors are grateful for the support of special fund for research institutes of the Ministry of
Science and Technology No. 2013EG149277. This paper is also supported by National Natural
Science Foundation of China (NSFC ) No. 51209044.
NOMENCLATURE
G1
flow rate of primary steam condensate, kg/s

latent heat of vaporization of primary saturated steam, kJ/kg

G2
flow rate of secondary steam condensate, kg/s
I
enthalpy of secondary saturated steam, kJ/kg

1128

di
do
F
L
t

t
K

enthalpy of saturated water at corresponding temperature, kJ/kg

the density of condensate, kg/m3
tube inner diameter, m
tube outer diameter, m
heat transfer area, m2
length of heating zone, m
temperature, C or K
flow density, kg/ms
temperature difference, C
total heat transfer coefficient, kW/m2K

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1130

Measurement and Prediction of Compressive Behaviour of Membrane

Electrode Assembly in Proton Exchange Membrane Fuel Cell
Yinqi Shen, Sogol Roohparvar, Xianguo Li
Department of Mechanical & Mechatronics Engineering, University of Waterloo
200 University Avenue West, Waterloo ON, Canada N2L 3G1
Xianguo.li@uwaterloo.ca

ABSTRACT

The compressive behaviour of membrane electrode assembly (MEA) is one of the most significant
factors contributing to the mechanical degradation in polymer electrolyte membrane fuel cells.
Studying the compressive behaviour of different components in MEA during regular cell operation is
therefore essential for the understanding of the mechanical degradation mechanisms. A fully
automated compression testing apparatus is used for the stress-strain relation. Scanning electron
microscope (SEM) testing is conducted on both new and compressed GDL. The compression curve
for the raw GDL has four piecewise linear regions. In addition, the effects of temperatures on the
stress-and-strain relations are not statistically significant. According to the SEM testing, compressive
load results in fragmented carbon fibers, cracks and pinholes. Also, it makes the carbon fibers bind
more tightly.
Keywords: PEM fuel cell, stress-strain relation, mechanical degradation, SEM.
INTRODUCTION
Polymer electrolyte membrane (PEM) fuel cell is a promising alternative power source for
transportation and stationary application, because of its low operating temperature, high power
density and zero/low emission (Li, 2005; Sieniutycz et al, 2013). However, before their widespread
use, a number of technical challenges need to be overcome, including durability (Moss, 2009). Fuel
cell durability is mainly influenced by three factors: mechanical, thermal, and chemical degradation.
Mechanical degradation is of particular importance because it results in microstructural changes in
the membrane electrode assembly (MEA) which consequently leads to the cell performance decay
(Wu et al, 2008). Recently, many longer-term durability studies show that these microstructure
changes occur mainly because of inappropriate compressive force, including hygro-thermal stress
and the cell assembly (or clamping) force. Studying the compressive behaviour of different
components in MEA during regular cell operation is therefore essential for the understanding of the
mechanical degradation mechanisms.
MEAs have to be sufficiently durable to withstand mechanical stresses during assembly process and
regular or randomly changing operating conditions. MEA contains at least five layers: two gas
diffusion layers (GDLs), two catalyst layers and one membrane layer. There are mainly two kinds of
MEAs, GDL-based MEAs and CCM (catalyst-coated membrane)-based MEAs. In GDL-based MEA,
the catalyst is coated on the gas diffusion layer, while the catalyst is directly applied onto the PEM in
CCM-based MEAs (Koraishy et al, 2009). Compared with GDL-based MEA, CCM-based MEA
provides significantly higher performance in terms of lower contact resistance between the catalyst
layers and the PEM, and lower catalyst loading without sacrificing the cell performance; hence it is
the choice of industry (Tang et al, 2007). During the cell operation, the MEA undertakes several
functions, namely, providing a place for the electrochemical reaction, offering an ionic conductive
path, serving as an electronic insulator, and acting as a gas barrier to prevent mixing of anode and
cathode gases.
Studying the compressive behaviour of MEA helps to understand the mechanism of mechanical
degradation and cell performance decay. Because of the clamping force and hygro-thermal stresses,
MEA is compressed during cell operation, which might lead to cracking, pinholes, delamination, and
thickness variations (Wilkinson et al, 2009). These microstructural changes can deteriorate its
functions and consequently reduce the cell performance. In addition, most of the critical material
parameters in terms of performance such as electrical and thermal conductivity, gas permeability and
diffusivity highly rely on compressive behavior of MEA (Dubau et al, 2014). Further, to date, many
studies are concentrated on the mechanical modelling of different components in MEA of PEM fuel
cell. However, the reliability of the modelling largely depends on the accuracy of mechanical
properties of MEA components. Currently very few data about MEA mechanical properties can be
found in open literature.

1131

Several studies are available on the effects of steady-state compression on GDL. Most of them linked
the compression with the porosity, pore size distribution, material electrical resistance and electrical
contact resistance. However, the behaviours of CCM and membrane under steady-state compression
have not been studied in-depth. In addition, the impact of cyclic compression on different components
in MEA still remains unclear. Rama et al. studied the causes and effects of cell performance decay
and related this performance degradation with the failure in different components of PEM fuel cells.
They mentioned that over-compression and inhomogeneous compression on GDLs result in mass
transport losses, because the porosity, hydrophobicity, and gas permeability decrease during stack
assembly or regular cell operation (Rama et al, 2008). Bazylak et al. studied the effect of
compression on the microstructural changes of the GDL using scanning electron microscopy (SEM).
They proposed that due to the surface roughness, small compression leads to non-uniform stress
distribution which finally results in anisotropy damage to the GDL. Further, compression contributes to
the breakup of fibers and deterioration of the PTFE coating (Bazylak et al, 2007). Nitta et al.
investigated the effect of inhomogeneous compression of GDL caused by the channel/rib structure of
flow-field plate. Compared to the GDL under the rib which is as thick as the gasket, the deformation of
GDL under the channel is quite small. Additionally, gas permeability, in-plane and through-plane bulk
electric conductivities and contact resistances at interfaces are studied. It is found that although
compression improves bulk conductivity, it reduces gas permeability and contact resistance, and that
inhomogeneous compression contributes to significant variation of mass and charge transport
properties in GDL (Nitta et al, 2007).
El-kharouf et al. conducted a complete ex-situ characterisation measurement on commercial GDLs.
The results illustrate that substrate structure significantly affects the mechanical and electrical
properties of the GDL. Also, the roughness of the surface, permeability and porosity of the GDL are
largely determined by the micro-porous layer structure. In addition, PTFE coating increases the GDLs
hydrophobicity and permeability; however, the decrease of the overall porosity and resistivity are
attributed to it. Lee et al. investigated the impact of compression and GDL on the cell performance.
Three types of GDLs were used. They indicated that the optimum is related to the gasket thickness
and the measured compression pressure. Further, the changes in porosity and electrical contact
resistance of the GDL result in the change of cell performance (El-Kharouf et al, 2012). Sadeghi et al.
studied the effect of unsteady/cyclic compression on the thermal and structural properties of GDLs.
They argued that during the loading and unloading process, a significant hysteresis exists in
properties, such as total thermal resistance, thermal contact resistance, effective thermal conductivity,
thickness and porosity. In addition, the geometrical, mechanical and thermal parameters can reach a
steady state and remain unchanged. The highlight of their study is that the thermal contact resistance
is the dominant component of the GDL total thermal resistance with a significant hysteresis resulting
in up to a 34% difference between the loading and unloading cycle data (Sadeghi et al, 2010).
Kleemann et al. studied the local compression distribution in the GDL and its associated effect on
electrical material resistance. The influence of GDL compression on electrical properties and contact
effects is also determined. Additionally, they experimentally measured the mechanical properties,
(such as Youngs modulus, the shear modulus, and Poissons ratio for in-plane and through-plane
resistance) of both fibrous paper and non-woven GDLs (Kleemann et al, 2008). Zhou et al. employed
finite element method to probe the impact of the clamping force on the electrical contact resistance
and the porosity of the GDL. The GDL was assumed to be a porous elastic material. They proposed
that the porosity is not uniform and the smallest porosity is located at the middle of flow-field plate rib
(Zhou et al, 2006). Escribano et al. focused on the relation between thickness reduction and
compression. They stated that the thickness values for the second loading were smaller and their
variation over the range of compressions was smoother. The research on the behaviours of CCM and
membrane under steady-state compression is very limited in the open literature (Escribano et al,
2006). Poornesh et al. experimentally studied the mechanical properties of catalyst layer at nanoscale. They classified the catalyst layer as graded material, and proposed that its mechanical
properties are as a function of its depth. In addition, the gradation in catalyst layer leads to greater
amount of plastic energy dissipation, indicating its enhanced ductility (Poornesh et al, 2009).
So far, from the literature review it can be seen that there are some studies focusing on the
compression experiments of GDL. However few of them measure the mechanical properties of GDL.
In addition, almost all the experiments are under room conditions. However, the mechanical
properties of GDL under operating conditions (like 90% relative humidity; 85oC) are much more
important. Further, the compressive behaviors of CCM and MEA have been fully studied in open
literature. Therefore, the aim of the present paper is to study the compressive behavior of GDL, CCM
and MEA under steady-state compression with operating conditions (different relative humidities and
temperatures). Additionally, the effects of cyclic compression on different components in MEA under
operating conditions are investigated. Finally, in order to clarify microstructural changes of

1132

compressed CCMs and GDLs, scanning electron microscope testing is conducted on both fresh and
compressed samples.
Experimental Setup
A fully automated compression testing apparatus is used for the measurements. As illustrated in
Fig 1, the apparatus consists of two calibrated electrolytic iron fluxmeters, a Velmex steeper, and a
Honeywell Sensotec load. The sample (GDL or CCM) is compressed between two calibrated
fluxmeters. This machine can provide a series of prescribed clamping pressures. The compression
force can be up to 100lbs which is controlled by the stepper motor. It also offers feedback of
sample thickness at 1.2m per step. Sample compression pressure is measured by the load cell.
In order to measure the properties under certain temperature and relative humidity, an
environmental chamber is used. The heat is provided on the lower portion of the test apparatus by
an electric heater, and the upper portion is heated by a constant temperature thermal bath. The
environmental chamber is connected with a fuel cell automated test station, which provides
humidified air with desired temperatures. The effects of temperature and relative humidity will be
tested.
The thickness reduction is calculated by the movements of the fluxmeters. For room condition
experiments, first the stepper motor compresses the fluxmeters to a set of desired pressures and
record position at each. Then a sample is placed between the fluxmeter surfaces and compressed
to the first compression pressure in the set. When steady state is reached, the data acquisition
system can automatically record the compression pressure, and stepper motor position. Finally
current sample thickness is determined by subtracting the position of the stepper motor from the
previously recorded position without the sample in place. After the procedure, the stepper motor
compresses the sample to the next desired pressure and the measurement procedure is repeated.
On the other hand, for the experiments with certain relative humidity and temperature, it is
essential to minimize the thermal expansion in the apparatus components, thereby preventing it
from affecting the thickness measurements. Therefore, an additionally warm-up procedure is
required. The upper and lower fluxmeters are initially set to touch each other without a sample in
between. By doing this, the joint temperature is raised to the desired level.

Fig.1. Schematic of the compression testing apparatus

Scanning Electron Microscope SEM Analysis

Commercial CCMs (Nafion 112, manufactured by Solvicore) and raw GDLs (SPECTRACARB
2050-A) are used in the experiments, as shown in Table 1. Because the GDL and CCM are very
thin, experiments are performed on five GDLs and ten CCMs in order to reduce the random error.
In order to elucidate microstructural changes of compressed CCMs and GDLs, scanning electron
microscope testing is conducted on both fresh and compressed CCMs and GDLs. In order to
preserve the spatial relationships among the cross section of the CCM and GDL, the sample is
submerged in liquid nitrogen, before being cut. JEOL JSM6464 Scanning electron microscope is
utilized in the experiments.

1133

Table 1. Cell properties.

Cell components
CCM
GDL (uncompressed, anode & cathode)

Properties
Membrane type
Thickness
Porosity

Value
Nafion 112
230 m
0.75

Results and DISCUSSION

(a) four piecewise linear regions

(b) uncertainty
Fig 2. Stress and strain compressive relation of GDL at room conditions
Fig 2. illustrates the stress-strain compression relation at room conditions, which is obtained from
measurements of the thickness change as a function of load in the compression tests. Normally, the
contact pressure used in practical PEM fuel cells is about 1MPa. For this study, contact pressure
over a wider range between 0 MPa and 4.4MPa was used to conduct measurements on
rectangular GDLs (1cm*1cm) in contact with fluxmeter with circular surface. Progressively
increasing force is applied over the selected range. In order to minimize the random error, 15 sets
of replicate tests are conducted for each GDL to obtain the compression curve. Fig 2(a). illustrates
the compression curve for the GDL sample in which four piecewise linear regions maybe identified
in the ranges of 0-0.09 MPa, 0.09-0.23 MPa, 0.23-1.11MPa, and 1.11-4.4 MPa. The compressive
modulus in each of the fourth ranges is determined as the slope of the best fit straight line through
the data in the respective range. Origin programme is used to complete this procedure.
Compressive modulus values for CCM and the MEA are obtained in the same way. Table 2.
summarizes the compressive modulus of the GDLs as function of the relevant pressure range. It
can be seen that the difference between them are quite small. Also, Fig 3. shows the compressive
curves with different temperatures. The differences between them are very small which may result
from the experimental uncertainty.

6
o

Stress (MPa)

5
4

25 C
o
45 C
o
65 C
o
85 C

3
2
1
0
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40

Strain

Fig 3. Stress and strain compressive relation of GDL with different temperatures

1134

Table 2. Compressive modulus of GDL under different temperatures

0~0.09
oC

Compressive modulus (MPa)

25
45 oC
65 oC
85 oC

2.18
2.67
3.63
4.27

Pressure range (MPa)

0.09~0.2
0.23~1.1
3
1
6.31
11.01
6.78
11.67
5.53
11.08
7.76
11.47

1.3~4.4
17.55
17.46
16.69
16.82

(a) new GDL

(b) Used GDL (4.7 MPa)

Fig 4. Front surface of the raw GDL without PTFE coating

(c) Used GDL (10.6 MPa)

(a) new GDL

(b) Used GDL (4.7 MPa)

Fig 5. Cross section of the raw GDL without PTFE coating

(c) Used GDL (10.6 MPa)

Figures 4 and 5 show the surface and cross sectional view of the fresh and compressed GDL. To
minimize the random measurement errors, several scans are performed at various locations of the
surface. As shown in Fig 4, the GDL is porous material. The carbon fibers randomly connect with
each other. When the GDL is subjected to compressive stress, the surface profile changes. In
addition, the carbon fibers in new GDL are intact, while in compressed GDL they become
fragmented. As illustrated in Figs 4(b) and (c), cracks and pinholes develop in compressed GDL.
SEM characterization on the cross section of the new GDL indicates that the carbon fibers layers
with each other to form a certain thickness. As reflected in Figs (b) and (c), due to the compressive
load, the carbon fibers bind more tightly.
CONCLUSIONS
The compression curve for the raw GDL has four piecewise linear regions.
The effects of temperatures on the stress-and-strain relations are not statistically significant.
According to the SEM testing, compressive load results in fragmented carbon fibers, cracks
and pinholes.
Compression makes the carbon fibers bind more tightly packed.
ACKNOWLEDGEMENT
The financial support of this project by Automotive Partnership Canada (APC): Catalysis Research
for Polymer Electrolyte Fuel Cells (CaRPE-FC), is gratefully acknowledged.
REFERENCES
Bazylak A., D. Sinton, Z. S. Liu, N. Djilali, 2007, Effect of compression on liquid water transport
and microstructure of PEMFC gas diffusion layers. Journal of Power Sources 163:784-792.

1135

Dubau L., L. Castanhyeira, F. Maillard, M. Chatenet, and O. Lottin, 2014, A Review of PEM Fuel
Cell Durability: Materials Degradation, Local Heterogeneities of Aging and Possibile Mitigation
Strategies. John Wiley & Sons.
El-kharouf A., T. J. Mason, D. J. L. Brett, B. G. Pollet, 2012, Ex-situ characterisation of gas
diffusion layers for proton exchange membrane fuel cells. Journal of Power Sources 218:393404.
Escribano S., J. F. Blachot, J. Etheve, A. Morin, R. Mosdale, 2006, Characterization of PEMFCs
gas diffusion layers properties. Journal of Power Sources 156:8-13
Kleemann J., F. Finsterwalder, W. Tillmetz, 2009, Characterisation of mechanical behaviour and
coupled electrical properties of polymer electrolyte membrane fuel cell gas diffusion layers.
Journal of Power Sources, 190:92-102.
Li X., 2005, Principles of Fuel Cells. New York: Taylor & Francis.
Moss j. A., 2009, Observation of a Polymer Electrolyte Membrane Fuel Cell Degradation Under
Dynamic Load Cycling. Worchester Polytechnic Institute, Bachelor Thesis.
Nitta I., T. Hottinen, O. Himanen, M. Mikkola, 2007, Inhomogeneous compression of PEMFC gas
diffusion layer Part I. Experimental. Journal of Power Sources 171:26-36.
Poornesh K. K., C. D. Cho, G. B. Lee, Y. S. Tak, Gradation of mechanical properties in gas
diffusioin electrode. Part 1: Influence of nano-scale heterogeneity in catalyst layer on
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hydrogen-fuelled polymer electrolyte fuel cells. Journal of Power Energy 222:421-441.
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Sieniutycz S., and J. Jezowski, 2013, Energy Optimization in Process Systems and Fuel Cells.
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Power Sources 184:104-119.

1136

ANALYSIS ON MEA CAPTURE CO2 SYSTEM ENERGY CONSUMPTION

CHARACTERISTICS UNDER THE IMPACT OF OPERATING PARAMETERS
CHANGED AND ENERGY-SAVING POTENTIAL PATHWAYS EXPLORE
Liangxu Liu, Hailong Li, Jun Zhao, Li Zhao, Jinyue Yan
Authors' affiliations
Authors' addresses
Authors' e-mails:

ABSTRACT (FONT, ARIAL, SIZE 9.5, BOLD)

The high cost and energy consumption of large-scale CO2 capture is one of the bottlenecks to be
widely employed in the project for CCS technology. In this study, Aspen plus and Matlab was used to
take simulation on absorption-desorption process. Through this, search for the reboiler heat load
properties when operating conditions changed. Then take the optimization on the capture process.
Amine physical data packet AspenPlus it had was used, and Ratefrac Module which is based on the
flow rate non-equilibrium model was selected. The results show that MEA solution exists maximum
concentration make the energy consumption to be the lowest, this value is lower than the theoretical
maximum concentration. According to the results, the lowest energy consumption mass concentration
is about 53wt%. There exists optimum lean solution CO2 load make the energy consumption to be
lowest in certain capture conditions, in the conditions of this article, the best value is 0.32. Absorber
outlet temperature risen when the temperature of lean MEA solution and flue gas increased, this
made sensible heat reduced, then reboiler heat demand decrease, last energy consumption was
reduced. But at the same time, Liquid-gas ratio increased proportionally. When the value of Liquidgas ratio is too high it makes the sensible heat increased too, then reboiler heat demand increased.
When pressure is 1.0atm and solution inlet temperature is 55.7C, Lowest reboiler heat load is
3249.94kJ/kgCO2, Liquid-gas ratio increase by 5.5% compared to inlet temperature is 40C. When
pressure is 1.0atm and flue gas inlet temperature is 60.1C, Lowest reboiler heat load is
3198.37kJ/kgCO2, Liquid-gas ratio increase by 1.6% compared to inlet temperature is 40C. Rise the
temperature can reduce heat load, but Liquid-gas ratio increased simultaneously, water consumption
increased. The results can provide basis for system operation optimization.
Keywords: CO2 capture, regenerate energy, operating parameters, stripper load

1137

ANALYSIS ON MEA CAPTURE CO2 SYSTEM ENERGY CONSUMPTION

CHARACTERISTICS UNDER THE IMPACT OF OPERATING PARAMETERS
CHANGED AND ENERGY-SAVING POTENTIAL PATHWAYS EXPLORE
a

Liangxu Liu , Hailong Li , Jun Zhao , Li Zhao , Jinyue Yan

Key Laboratory of Efficient Utilization of Low and Medium Grade Energy, MOE(Tianjin University)
a
b
92 Weijin Road, Nankai District, Tianjin, P.R.China. Sweden

ABSTRACT
High cost and energy consumption of large-scale CO2 capture is one of the bottlenecks for it to be
widely employed in the project on CCS technology. In this study, Aspen plus and Matlab was used to
take simulation on absorption-desorption process. Through this, search for the reboiler heat duty
properties when operating conditions changed. Then take the optimization on the capture process.
Amine physical data packet that AspenPlus it had was used, and Ratefrac Module which is based on
the flow rate non-equilibrium model was selected. The results show that MEA solution exists
maximum concentration that make the energy consumption to be the lowest, this value is lower than
the theoretical maximum concentration. According to the results, the lowest energy consumption
mass concentration is about 53wt%. There exists optimum lean solution CO2 load make the energy
consumption to be lowest in certain capture conditions, in the conditions of this article, the best value
is 0.32. Absorber outlet temperature risen when the temperature of lean MEA solution and flue gas
increased, this made sensible heat reduced, then reboiler heat demand decrease, at the last, energy
consumption was reduced. But at the same time, Liquid-gas ratio increased proportionally. When the
value of Liquid-gas ratio is too high it makes the sensible heat increased too, then reboiler heat
demand increased. When pressure is 1.0atm and solution inlet temperature is 55.7C, lowest reboiler
heat load is 3249.94kJ/kgCO2, Liquid-gas ratio increased by 5.5% compared to inlet temperature is
40C. When pressure is 1.0atm and flue gas inlet temperature is 60.1C, Lowest reboiler heat load is
3198.37kJ/kgCO2, Liquid-gas ratio increase by 1.6% compared to inlet temperature is 40C. Rise the
temperature can reduce stripper heat load, but Liquid-gas ratio increased simultaneously, water
consumption increased too. The results can provide basis for system operation optimization.
Keywords: CO2 capture, regenerate energy, operating parameters, stripper load
INTRODUCTION
China's energy supply mainly depends on carbonaceous resources, and the utilization of it was very
low. This made a large number of consumption of resources, also increased CO2 emissions. It is a
big problem for china to protect the environment. The effect to solve this problem is not significantly
only by improving energy efficiency. Thus we must employ carbon capture and storage technology. In
the whole process of CCS, energy consumption and investment costs are the most important
questions, it accounts for 80% of the whole process consumption (Adeyemo, 2010).
High cost and energy consumption of large-scale CO2 capture is one of the bottlenecks to be widely
employed in the project for CCS technology. Generally, CO2 concentration in exhaust gas of coalfired power plant approximately 10-15%, in Natural Gas Power Plant it is lower, about 3-5%, but the
flow of Natural Gas Power Plant exhaust gas is larger than the coal-fireds. A study of International
Energy Agency (IEA) shows that, Energy consumption was about 0.37 - 0.51 MWh/tCO2 in CCS
process, it equivalent to nearly 40-50% of the power plant output (Ziaii, S., 2009). That is, if 90%
CO2 were captured would make the efficiency of energy conversion system drop 4-8% (Liu, Y.,
2011).
Due to the advantages of fast chemical reaction, high carrying capacity and low price to absorption
CO2, Monoethanolamine (MEA) or its derivatives had been used to absorb CO2 from the flue gas in
some power plant. But because of its high energy consumption of stripper, its application range is
limited. So, many academics devote their times on it to reduce the stripper energy demands.
Desorption operation is the major energy consuming processes. The biggest problem for MEA
solution capture CO2 system is the high energy consumption to desorption the rich liquid. Anusha
Kothandaraman (Kothandaraman, A., 2009) had taken simulations on absorption-desorption model
about energy consumption of stripper use Aspen plus RateSep model. Hes result shows that, it will
result in 20% decrease in the efficiency of the power plant output when we setting CO2 capture
system on it, and 62% of which are consumed in the stripper heat demand.
Thus how to reduce energy consumption for CO2 capture process is worth to study. We can
according to the analysis result employ the energy reasonably, reduce the investment costs to the
lowest, and under the high efficiency of power output reduce energy consumption.

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In this study, Aspen plus and Matlab was used to take simulation on absorption-desorption process.
Through the simulation, search for the reboiler heat load properties when operating conditions
changed. Then take the optimization on the capture process.
MEA CO2 CAPTURE PROCESS
Typically flow charts of CO2 capture processes shown in Figure 1. After desulfurization and
desquamation, flue gases entering the absorber form bottom of the column, at the same time, MEA
solution into the absorber from the top.
They countercurrent in the absorber, carry on heat and mass exchange, also take chemical reactions.
After removal CO2, the gas gets out from the top of the column. Rich solution gets into the desorber
from the middle of the column, and to be regenerated in the desorber after exchange heat in the lean
- rich solution heat exchanger. In the desorber, the rich solution was heated in the bottom by stripper,
to make water vapor evaporated and bring the CO2 out to the top of the column as stripping gas.
On top of the column, a condenser was provided, water vapor was condensed into liquid in it and
reflux back to desorber, and then high purity of CO2 was collected from the top. In the bottom of the
column, rich solution was regenerated into lean solution, then flow out and was pushed into lean-rich
heat exchanger, and the temperature of the lean solution from the desorber can reach to 100-120C
(Rochelle, G. 2009). After heat exchange in rich-lean solution heat exchanger, lean solution was
further cooled in coolers to make the temperature value equals to inlet temperature value. MEA
solution cycling in the system and keeping capture CO2.

Fig1 Typical flow charts of CO2 absorption process

The initial investment and electricity cost will rise substantially when added CO2 chemical capture
and storage system into the coal-fired power plants, and the efficiency of the output will be reduced,
then leading to CO2 capture cost increased. We can optimize the operating parameters to minimize
CO2 capture costs and energy needed. In CO2 capture system, operating parameters are: MEA
concentration, temperature of absorbent solution and flue gas into the absorber, CO2 load of lean
solution, stripper pressure and temperature and reflux ratio etc. To solve the problem of large energy
consumption of regeneration, we can contribute to improve and develop capture equipment, optimize
capture process and operating parameters. About equipment can refer to references(Shao, P., 2013.
Le Moullec, Y. 2013. Kuramochi, T., 2010). In this paper, only to analyze operating parameters and
optimization measures.
PROCESS SIMULATION MODEL BASED ON ASPEN PLUS AND MATLAB
In this paper, use amine physical data packet take simulations on MEA capture CO2 process which
AspenPlus it has. Absorber and desorber column are select Ratefrac Module which is based on the
flow rate non-equilibrium model.
In the calculation, we select Elecnrtl model to calculate the amine solution chemistry changes, the
calculate model description a weak electrolyte thermodynamics system (Zhang, Y., 2010). Physical
parameters are look up in Aspen Plus when MATLAB simulation conducted.

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Fig2 Flow charts of CO2 absorption in the simulation

Figure 2 is the Flow chart in this simulation. For convenient, change the cycle processes into the
order process.
For accurate, a mixer was Added into, use FORTRAN language restrict the flow and CO2 load of lean
solution be required Value. In the study, set CO2 capture rate is 90% that of CO2 content in the flue
gas. That is, 90% of CO2 in flue gas was absorbed in the absorber and all of them are regenerated in
the desorber. MEA is recycled when the system is running.
Table 1. Table of boundary constraints in simulation
Content
Value Unit
ow rate of ue gas
500
m3/h
N2 composition of the ue gas
87
vol%
O2 composition of the ue gas
3
vol%
CO2 composition of the ue gas 10
vol%
degree of CO2 removal
90
wt%

Table 1 shows the boundary conditions of the simulation, these initial parameters are constant in
simulation and other operating parameters are changed such as temperature and pressure etc..
The following assumptions were made in simulation:
1. Ignore the degradation of MEA and the corrosion to the equipment
2. Liquid and gas distributed evenly in each part of the column
3. Process does not include drying, compression, transportation and storage and others in simulation.
4. To description the utilization of thermal energy, and reduce the complexity of the simulation, flue
gas doesnt include NOx, SOx, solid particles and other pollutants.
ENERGY SIMULATION AND CALCULATION MODEL
The regeneration energy is calculated using a mass and energy balance for the stripper. When
doesnt consider the heat loss of pipeline and other equipment (Merkel, 2010. Oyenekan, 2006.).
Rich solution into desorption column after exchange heat in lean-rich solution heat exchanger, and its
temperature was increased toT2 before into the column, then rich solution was heated to boiling by
stripper in the bottom. High temperature lean solution which outlet from the bottom of the column
exchange heat in lean-rich solution exchanger, the temperature of it reduced, but, it still higher than
the temperature into the absorber T4. So, in cooler it had been cooled into the need value, in figure 1
is T4. This heat cannot be recycled, and the value equals to the latent heat of rich solution that
heated in the stripper, that is, temperature difference (T3-T4) is provided by stripper. Reboiler also
needs to provide chemical reaction heat to generate CO2 from the solution. To desorption CO2, we
use water vapor as stripping steam, so, reboiler need to heat the water into vaporization too.
In summary, reboiler heat load include solution sensible heat, chemical reaction heat and vaporization
latent heat.
Regeneration energy can be shown as following (Oyenekan, 2006. Kishimoto, 2011. Oexmann,
2010.):
Qregeneration Qvapor Qreaction Qsensible
(1)
Qvapor nH 2O ,V

H vap

H liq

dH

(2)
Treg

o
Qreaction nCO2 (H abs
R

T0

cP
dT )
R

(3)
Treg

Qsensible

Tst ,in

(mslvent mCO2 )cP dT

(4)
According to Daltons law, nH 2O ,V nCO2

PH 2O
PCO2

Where: Qvapor is the heat of water vaporization (W), Qreaction is the heat of reaction (W), Qsensible is
the sensible heat (W), nH 2O ,V is the vaporized water molar ow rate at the stripper top (mol/s),
is the enthalpy of water saturated liquid at the stripper top temperature (J/ mol),
enthalpy of water saturated vapor at the stripper top temperature (J/mol),

nCO2

H va p

H liq

is the

is the captured CO

2 molar ow rate (mol/s), H is the heat of reaction at standard condition (J/mol of CO 2

captured), R is the universal gas constant (MJ/molK), T0 is the temperature of standard condition
o
abs

(K), Treg is the solvent regeneration temperature (K),

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cP

is the overall specic heat capacity

(J/kgK), Tst ,in is the stripper inlet temperature (K), mslvent is the solvent mass ow rate (kg/s), mCO2
is the captured CO2 mass ow rate (kg/s), PH O the partial pressures of water vapor in the gas
phase at the stripper top outlet (Pa), PCO2 the partial pressures of CO2 in the gas phase at the
stripper top outlet (Pa).
2

RESULTS AND DISCUSSION

IMPACT OF MAXIMUM MEA CONCENTRATION ON STRIPPER HEAT DUTY
CO2 absorption rate increases with the concentration of MEA solution improved (Raksajati, 2013).
Finally, tends to a constant value, for the impact of gas-liquid mass transfer and reversible reaction
equilibrium conditions. If we keep the flow of CO2 in flue gas and absorption rate to be constant, with
the increase of MEA concentration, lean and rich solution CO2 concentration both were increased. If
we do not consider degradation of MEA, the concentration of it had a maximum value. At this value,
the water in the solution completely changed into vapor, the amount of water vapor just can strip out
the CO2. Because of the balance of CO2 partial pressure is different in different regeneration
pressure; the value of maximum concentration in different regeneration pressure is not the same.
At maximum concentration, water completely changed into vapor and totally stripping out, so:
nCO2 M MEA
nCO2 R k
(1 wmax )
M H 2O wmax

Where: R is the reflux ratio, k is the liquid-gas ratio, M MEA is the molar mass of MEA (g/mol),
M H 2O is the molar mass of H2O (g/mol), is the difference between lean and rich solution CO2
load (mol/mol MEA,

wmax is the mass fraction of MEA (g/g).

The results shown in Fig1 were conducted in MATLAB.

Fig 3 MEA maximum concentration curves under different regeneration pressures

As shown in Figure 3, in Standard atmospheric pressure, the theoretical maximum concentration of

MEA can reach to 87.3%. With the increasing of pressure, the theoretical maximum concentration
increased too. This is because, the equilibrium of CO2 partial pressure would reduce when
regeneration pressure was rose, and the minimum of reflux ratio would drop too, on this condition, the
required of water vapor to stripping CO2 out is reduced. So, the need of water was dropped. Pressure
increase and MEA concentration increase are generally to be proportional. At 2atm, the theoretical
maximum concentration is about 89.8%.
However, the regeneration energy is not always decline with the MEA concentration increases. This is
because, it is difficult for water to evaporated completely when it at the theoretical minimum value. So,
there is an optimum value of MEA concentration make the stripper heat load to be the minimum.

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Fig 4 Curves of stripper heat duty in different MEA concentrations

F As shown in Figure 4,, when the concentration is less than 55wt%, the stripping heat duty for
capture per unit CO2 is reduced gradually with the increasing of MEA concentration.
This is because, with the increase of MEA concentration, per unit solution can carry more CO2, to
absorb the same amount of CO2 required less absorbent solution. That is sensible heat Qsensible
reduced, thereby the total energy consumption reduced. However, when the concentration is greater
than 55wt%, the amount of water in solution is too less to be evaporated. So, more heat needed.
Therefore, when the concentration is greater than 55wt%, the stripping heat duty increased gradually.
According to the result, at 1atm, the maximum concentration that makes the stripper duty to be lowest
is 53.3wt%, the minimum heat duty is 2.638MJ/kgCO2. At 1.4atm is 53.5wt% and 2.5978MJ/kgCO2,
and 1.7atm is 54.7wt% and 2.558MJ/kgCO2.
Of course, it is not the higher the better for MEA concentration in reality operation. With the increasing
of concentration, MEA degradation, metal corrosion and adverse reactions are increased. These not
only reduce equipment life, but also increase MEA loss. The best value requires experimental
verification.
IMPACT OF LEAN CO2 LOAD AND DESORPTION DEGREE ON STRIPPER HEAT DUTY
In order to be able to recycling the absorbent solution, CO2 absorbed in the absorber need to be
desorption totally in desorber. Lean CO2 load not only determine both the circulation flow and
absorption capacity but also determine the depth of regeneration. Therefore, it is necessary to know
which value is the best for lean solution to make the stripper duty be the lowest.
Figure 5 is the result conduct by Aspen plus. MEA concentration are 20wt%30wt% and 40wt%.

Fig 5 Curves of stripper heat duty in different lean solution CO2 load

As shown in Figure 5, when MEA concentration is constant, stripper heat load increase first then
decrease with the increase of lean solution CO2 load. When the concentration are 20wt%, 30wt%
and 40wt%, the lean load of them all are 0.32 that make the stripper heat duty is the minimum. Rich
solution CO2 load is generally about 0.47. So, only when CO2 load changes from 0.47 to 0.32 in
desorber column, the stripper heat duty could be the lowest. This is because, the higher of CO2 load
the higher of solution flow, and the lower of CO2 load the more difficult of water to evaporate.
When lean solution CO2 load is greater than 0.20, heat duty becomes smaller with the increasing of
MEA concentrations, due to the less solution flow required to capture the same amount of CO2.
IMPACT OF LEAN SOLUTION AND FLUE GAS TEMPERATURE ON STRIPPER HEAT DUTY
The impact of lean solution temperature

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When the temperature of solution increased, the saturated CO2 load for rich solution would reduce,
this is because, in high temperature the MEA absorption capacity decreases, then solution circulation
flow increased.
The simulation was conducted in Aspen plus as shown in figure 6. Because gas flow would change
very large when pressure changed, we adjust the gas flue flow to make CO2 mass flow is constant.

Fig.6 Curves of the lean solution temperature changed impact on liquid-gas ratio

As shown in Figure 6, System liquid-gas ratio soared when the temperature of lean solution rose. As
shown in figure 4, when the temperature is 40, the liquid-gas ratio of system is 3.99, and when the
temperature is 60, the liquid-gas ratio is 4.22. In this 20 difference, Liquid-gas ratio had been
increased by 5.5%. This made sensible heat Qsensible increase inevitably.
With the solution temperature increased, the reaction speed is increased, and the viscosity of the
solution is dropped, temperature difference is decreases. All of these are advantages for CO2 capture
and energy consumption reduces.
However, the increase of temperature also leads to circulating solution volume increased, then lead to
the reboiler heat load increases.
So, there is an optimal temperature for inlet absorb column solution, in this temperature, the stripper
heat duty is the lowest.
Three states had ben simulated as shown in figure 7, 1.0atm, 1.4atm and 1.7atm. in the simulation
make the intake flue gas temperature Keep at 40.

Fig.7 Curves of the stripper heat load when lean solution temperature changed

As shown in Figure 7, when the temperature of the lean solution less than about 60 , with the
increase of temperature, the stripper load dropped slowly. When the temperature higher than 60,
the stripper load elevated.
Lean solution temperature rose caused the temperature difference (T3-T4) dropped, and the heat
caused by it was greater than the heat caused by solution flow rose, so the total heat was reduced.
But with the lean solution temperature rose and more than 60, the heat caused by temperature
difference dropped was less than the heat caused by the solution flow rose, so the total heat
becomes rise.
Simulation results show that, the minimum heat load is 3249.94MJ/kgCO2 when the temperature is
55.7 at 1.0atm,
the minimum heat load is 3180.17MJ/kgCO2 when the temperature is 62.3 at 1.4atm and the
minimum heat load is 3132.25MJ/kgCO2 when the temperature is 60.4at 1.7atm.
The impact of flue gas temperature

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MEA and CO2 is an exothermic chemical reaction, therefore, when the temperature is too high, it is
negative for reaction, but can reduce the temperature difference (T3-T4).
The law of it is similar to the solution temperature increase as described above.

Fig.8 Curves of flue gas temperature changed impact on liquid-gas ratio

As shown in Figure 8, System liquid-gas ratio increasing slowly when the temperature of lean solution
rose.
When the flue gas temperature is 40 , liquid-gas ratio is 3.99, and 60 is 4.06.
In this 20 difference, Liquid-gas ratio had been increased by 1.6%. This made sensible heat
Qsensible increase slowly.
The liquid-gas ratio increased by lean solution temperature rose is large than by flue gas temperature
rose.
So, Circulating solution flow that changed by solution temperature is higher than by flue gas when at
a same temperature difference.
That is why the curves in figure 8 are gentler than the curves in figure 6.
With the flue gas intake temperature rose, chemical reaction rate increased, and then the liquid
temperature that outlet from the absorber bottom increased, circulating solution temperature
difference decreased. This is an advantageous for reboiler heat load drop. But it leads to the
circulating fluid flow increased at the same time.
So, the same conjecture as the solution temperature changed, there is an optimal temperature for
inlet absorb column flue gas, in this temperature, the stripper heat duty is the lowest.
Three states had ben simulated as shown in figure 9, 1.0atm, 1.4atm and 1.7atm. in the simulation
make the intake solution temperature Keep at 40.

Fig.9 Curves of the stripper heat duty when flue gas temperature changed

As shown in Figure 9, the tendency of heat duty changes with the flue gas temperature rise is similar
to figure 7 shown. When the temperature of the lean solution less than about 60 , with the increase
of temperature, the stripper load dropped at any one of the three pressure shown in figure 9.
When the temperature higher than 60, the stripper load elevated.
The flue gas temperature rose caused the temperature difference (T3-T4) dropped, and the heat
caused by temperature difference dropped was greater than the heat caused by the solution flow
rose, so, the total heat was reduced.
But with the flue gas temperature rose and more than 60 , the heat caused by temperature
difference dropped was less than the heat caused by the solution flow rose, so the total heat
becomes rose.

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Simulation results show that, the minimum heat load is 3198.37MJ/kgCO2 when the temperature is
60.1 at 1.0atm,
the minimum heat load is 3119.98MJ/kgCO2 when the temperature is 60.3 at 1.4atm and the
minimum heat load is 3058.95MJ/kgCO2 when the temperature is 58.0at 1.7atm.
From the above can be concluded that, When less than 60 , heat duty reduce speed that caused
by increase of flue gas temperature is less than caused by increase of solution temperature. This is
because, liquid-gas ratio increase speed that caused by increase of flue gas temperature was less
than caused by increase of solution temperature, and the sensible heat Qsensible is less too. So, the
heat duty caused by increase of flue gas temperature decline faster, and the heat duty caused by
increase of solution temperature decline gently.
CONCLUSIONS
1. MEA concentration exist theoretical maximum concentration and the optimal concentration that
make the stripper heat duty lowest. According to the calculation result, the concentration make the
stripper heat duty to be lowest is 53wt% without considering the degradation and corrosion.
2. Lean solution CO2 load determine the stripper heat duty and regeneration degree of rich solution in
desorber, therefore, there exist an optima value for it to make the stripper heat duty to be the lowest.
According to the calculation result, the values of them all are 0.32 at the concentration of 20wt%,
30wt% and 40wt% when the CO2 mole concentration is 10% in flue gas.
3. When solution and flue gas temperature rose, latent heat of solution decreased, and Liquid-gas
ratio increased. So, there existence an intermediate value of the inlet solution and flue gas
temperature. That is when they are both 60C, the stripper heat duty is the lowest.
NOMENCLATURE
Q
heat, w
cp
specific heat, J/kgk
h
heat transfer coefficient, W/m2k
T
temperature C
m
mass ow rate (kg/s)
n
molar ow rate (mol/s)
M
molar mass (g/mol)
P
pressure or partial pressure(Pa)
GREEK LETTERS

CO2 load (mol/mol)

SUBSCRIPTS
reg
regeneration
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