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Energy Sources, Part A: Recovery, Utilization, and

Environmental Effects

ISSN: 1556-7036 (Print) 1556-7230 (Online) Journal homepage: http://www.tandfonline.com/loi/ueso20

Sustainable Green Diesel: A Futuristic View


A. Demirbas & K. Dincer
To cite this article: A. Demirbas & K. Dincer (2008) Sustainable Green Diesel: A Futuristic View,
Energy Sources, Part A: Recovery, Utilization, and Environmental Effects, 30:13, 1233-1241, DOI:
10.1080/15567030601082829
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Date: 17 June 2016, At: 00:16

Energy Sources, Part A, 30:12331241, 2008


Copyright Taylor & Francis Group, LLC
ISSN: 1556-7036 print/1556-7230 online
DOI: 10.1080/15567030601082829

Sustainable Green Diesel: A Futuristic View


A. DEMIRBAS1 and K. DINCER2
1

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Sila Science, Trabzon, Turkey


Selcuk University, Konya, Turkey
Abstract The energy sources have been split into three categories: fossil fuels,
renewable sources, and nuclear sources. Energy new and renewable resources will
play an important role in the worlds future. There are several reasons for biofuels
to be considered as relevant technologies by both developing and industrialized
countries. They include energy security reasons, environmental concerns, foreign
exchange savings, and socioeconomic issues related to the rural sector. The term
modern biomass is generally used to describe the traditional biomass use through
the efficient and clean combustion technologies and sustained supply of biomass
resources, environmentally sound and competitive fuels, heat, and electricity using
modern conversion technologies. Modern biomass can be used for the generation
of electricity and heat. Biofuels as well as green diesel produced from biomass by
Fischer-Tropsch synthesis are the most modern biomass-based transportation fuels.
Green diesel is a renewable replacement to petroleum-based diesel. Biomass energy
conversion facilities are important for obtaining bio-oil by pyrolysis. Pyrolysis is
the most important process among the thermal conversion processes of biomass.
There are four different ways of modifying vegetable oils and fats for use as diesel
fuel, such as pyrolysis, dilution with hydrocarbons (blending), emulsification, and
transesterification.
Keywords bio-syngas, energy system, green diesel, modern biomass, sustainability

Introduction
The demand for energy is increasing at an exponential rate due to the exponential growth
of world population. Advanced energy-efficiency technologies reduce the energy needed
to provide energy services, thereby reducing environmental and national security costs
of using energy and potentially increasing its reliability (Demirbas, 2006a).
In general, a sustainable energy system includes energy efficiency, energy reliability,
energy flexibility, energy development and continuity, combined heat and power (CHP)
or cogeneration, fuel poverty, and environmental impacts. The environmental impacts of
energy use are not new. For centuries, wood burning has contributed to the deforestation of
many areas. On the other hand, the typical characteristics of a sustainable energy system
can be derived from political definitions. A sustainable energy system can be defined
also by comparing the performance of different energy systems in terms of sustainability
indicators (Alanne and Sari, 2006). Because, by definition, sustainable energy systems
must support both human and ecosystem health over the long term, goals on tolerable
emissions should look well into the future. They should also take into account the publics
tendency to demand more (UNDP, 2000).
Address correspondence to Prof. Ayhan Demirbas, P.K. 216, 61065 Trabzon, Turkey. E-mail:
ayhandemirbas@hotmail.com

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A. Demirbas and K. Dincer

Figure 1. Main parts of an energy system.

An energy system is made up of an energy supply sector and energy end-use


technologies. The object of the energy system is to deliver to consumers the benefits that
energy offers. Energy plays a vital role in our everyday lives (UNDP, 2000). The energy
system commonly consists of energy resources and production, security, conversion, use,
distribution, and consumption. Figure 1 shows the main parts of an energy system.
The energy sources have been split into three categories: fossil fuels, renewable
sources, and nuclear sources. Energy resources will play an important role in the worlds
future. Renewable energy resources such as biomass, solar, geothermal, and wind energy
have the potential to supply a considerable portion of energy requirements in the coming
years. Renewable energy refers to fuel sources more consistently available than their
fossilized counterparts. Energy conversion mainly consists of thermochemical and biochemical conversion technologies, power plant, fuel refinery, and energy storage. Energy
security means the availability of energy at all times in various forms, in sufficient
quantities, and at affordable prices. Energy use is closely linked to a range of social
issues, including poverty alleviation, population growth, and urbanization.

Global Energy Scenarios


Worldwide energy consumption has increased 17-fold in the last century and emissions
of CO2 , SO2 , and NOx from fossil fuel combustion are primary causes of atmospheric
pollution (Ture et al., 1997). Known petroleum reserves are estimated to be depleted
in less than 50 years at the present rate of consumption (Sheehan et al., 1998). In
developed countries, there is a growing trend towards employing modern technologies
and efficient bio-energy conversion using a range of biofuels, which are becoming costwise competitive with fossil fuels (Puhan et al., 2005).
Renewable resources are more evenly distributed than fossil and nuclear resources,
and energy flows from renewable resources are more than three orders of magnitude
higher than current global energy use. Todays energy system is unsustainable because
of equity issues as well as environmental, economic, and geopolitical concerns that have
implications far into the future (UNDP, 2000).

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According to International Energy Agency (IEA), scenarios developed for the USA
and the EU indicate that near-term targets of up to 6% displacement of petroleum fuels
with biofuels appear feasible using conventional biofuels, given available cropland. A 5%
displacement of gasoline in the EU requires about 5% of available cropland to produce
ethanol, while in the USA 8% is required. A 5% displacement of diesel requires 13% of
USA cropland, 15% in the EU (IEA, 2004).
The recent commitment by the U.S. government to increase bio-energy three-fold in
10 years has added impetus to the search for viable biofuels. The EU have also adopted
a proposal for a directive on the promotion of the use of biofuels with measures ensuring
that biofuels account for at least 2% of the market for gasoline and diesel sold as transport
fuel by the end of 2005, increasing in stages to a minimum of 5.75% by the end of 2010
(Hansen et al., 2005). Advantages of biofuels are the following: (a) Biofuels are easily
available from common biomass sources; (b) They represent a carbon dioxide cycle in
combustion; (c) Biofuels have considerable environmentally friendly potential; (d) There
are many benefits to the environment, economy, and consumers in using biofuels; and
(e) They are biodegradable and contribute to sustainability (Puppan, 2002).
Figure 2 shows the main biomass conversion processes. Biomass can be converted to
biofuels such as bioethanol and biodiesel and thermochemical conversion products such
as syn-oil, bio-syngas, and biochemicals. Bioethanol is a fuel derived from renewable
sources of feedstock, typically plants such as wheat, sugar beet, corn, straw, and wood.
Bioethanol is a petrol additive/substitute. Biodiesel is better than diesel fuel in terms of
sulfur content, flash point, aromatic content, and biodegradability (Bala, 2005).
If the biodiesel valorized efficiently at energy purpose, so would it benefit the
environment and the local population: job creation, provision of modern energy carriers to
rural communities, avoidance of urban migration and reduction of CO2 and sulfur levels
in the atmosphere. Biofuels include energy security reasons, environmental concerns,
foreign exchange savings, and socioeconomic issues related to the rural sector.
Figure 3 shows the shares of alternative fuels compared to the total automotive fuel
consumption in the world as a futuristic view. Hydrogen is currently more expensive than
conventional energy sources. There are different technologies presently being practiced
to produce hydrogen economically from biomass. Biohydrogen technology will play a

Figure 2. Main biomass conversion processes.

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A. Demirbas and K. Dincer

Figure 3. Shares of alternative fuels compared to the total automotive fuel consumption in the
world. (Source: Demirbas, 2006b.)

major role in future because it can utilize the renewable sources of energy (Nath and
Das, 2003).

Green Diesel Fuel from Bio-syngas via Fisher-Tropsch Synthesis


Gasification technologies provide the opportunity to convert renewable biomass feedstocks into clean fuel gases or synthesis gases. The synthesis gas includes mainly hydrogen and carbon monoxide (H2 C CO) which is also called bio-syngas. Bio-syngas is a
gas rich in CO and H2 obtained by gasification of biomass. Hydrogen can be produced
from biomass via two thermochemical processes: (1) gasification followed by reforming
of the syngas, and (2) fast pyrolysis followed by reforming of the carbohydrate fraction
of the bio-oil. In each process, water-gas shift is used to convert the reformed gas into
hydrogen.
In the steam-reforming reaction, steam reacts with hydrocarbons in the feed to
predominantly produce bio-syngas. Steam reforming can be applied to various solid
waste materials, including municipal organic waste, waste oil, sewage sludge, paper mill
sludge, black liquor, refuse-derived fuel, and agricultural waste.
The Fischer-Tropsch synthesis (FTS) for the production of liquid hydrocarbons from
coal-based synthesis gas has been the subject of renewed interest for conversion of coal
and natural gas to liquid fuels (Jin and Datye, 2000). The use of iron-based catalysts is
attractive due to their high FTS activity as well as their water-gas shift reactivity, which
helps make up the deficit of H2 in the syngas from modern energy-efficient coal gasifiers
(Rao et al., 1992). The interest in use of iron-based catalysts stems from its relatively
low cost and excellent water-gas shift (WGS) reaction activity, which helps to make up
the deficit of H2 in the syngas from coal gasification (Wu et al., 2004; Jothimurugesan
et al., 2000; Jun et al., 2004).
The FTS-based gas to liquids (GTL) technology includes three processing steps:
syngas generation, syngas conversion, and hydroprocessing. In order to make the GTL

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technology more cost-effective, the focus must be on reducing both the capital and the
operating costs of such a plant (Vosloo, 2001). For some time now, the price has been
up to $60 per barrel. It has been estimated that the FT process should be viable at crude
oil prices of about $20 per barrel (Jager, 1998; Dry, 2004). The current commercial
applications of the FT process are geared at the production of the valuable linear alpha
olefins and of fuels such as LPG, gasoline, kerosene, and diesel. Since the FT process
produces predominantly linear hydrocarbons, the production of high quality diesel fuel
is currently of considerable interest (Dry, 2004). The most expensive section of an FT
complex is the production of purified syngas, so its composition should match the overall
usage ratio of the FT reactions, which in turn depends on the product selectivity (Dry,
2002).
The Al2 O3 /SiO2 ratio has significant influences on iron-based catalyst activity and
selectivity in the process of FTS. Product selectivities also change significantly with
different Al2 O3 /SiO2 ratios. The selectivity of low molecular weight hydrocarbons increases, and the olefin-to-paraffin ratio in the products shows a monotonic decrease
with increasing Al2 O3 /SiO2 ratio. Table 1 shows the effects of Al2 O3 /SiO2 ratio on
hydrocarbon selectivity (Jothimurugesan et al., 2000). Recently, Jun et al. (2004) studied
FTS over Al2 O3 - and SiO2 -supported iron-based catalysts from biomass-derived syngas.
They found that Al2 O3 as a structural promoter facilitated the better dispersion of copper
and potassium and gave much higher FTS activity. The reaction results from FTS with
balanced syngas are given in Table 2 (Jun et al., 2004).
More recently, there has been some interest in the use of FTS for biomass conversion
to synthetic hydrocarbons. Biomass can be converted to bio-syngas by non-catalytic, catalytic, and steam gasification processes. The bio-syngas consists mainly of H2 , CO, CO2 ,
and CH4 . The FTS has been carried out using CO/CO2/H2 /Ar (11/32/52/5 vol%) mixture
as a model for bio-syngas on co-precipitated Fe/Cu/K, Fe/Cu/Si/K, and Fe/Cu/Al/K
catalysts in a fixed-bed reactor. Some performances of the catalysts that depended on
the syngas composition are also presented (Jun et al., 2004).
To produce bio-syngas from a biomass fuel, the following procedures are necessary:
(a) gasification of the fuel, (b) cleaning of the product gas, (c) usage of the synthesis gas

Table 1
Effects of Al2 O3 /SiO2 ratio on hydrocarbon selectivity

Hydrocarbon
selectivities,
wt%

100
Fe/6
Cu/5
K/25
SiO2

100
Fe/6
Cu/5
K/3
Al2 O3 /22
SiO2

100
Fe/6
Cu/5
K/5
Al2 O3 /20
SiO2

100
Fe/6
Cu/5
K/7
Al2 O3 /18
SiO2

100
Fe/6
Cu/5
K/10
Al2 O3 /15
SiO2

100
Fe/6
Cu/5
K/25
Al2 O3

CH4
C2 4
C5 11
C12 18
C19C

6.3
24.5
26.8
21.9
20.5

8.7
27.8
27.6
21.2
14.4

10.4
30.8
32.2
15.8
11.0

10.7
29.9
33.9
15.0
10.6

14.3
33.4
40.0
6.0
6.1

17.3
46.5
31.0
4.9
0.4

Reaction condition: 523 K, 2.0 MPa, H2 /CO D 2.0, and gas stream velocity: 2,000 h
Source: Jothimurugesan et al. (2000).

1.

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A. Demirbas and K. Dincer


Table 2
Reaction results from FTS with balanced syngas (H2-supplied bio-syngas)

CO C CO2

CH4

C2 C4

C5 C7

C8C

Olefin
selectivity,
%, in C2 C4

0.3

12.6

39.2

21.9

26.3

84.9

Conversion, %
CO
82.9

CO2

Hydrocarbon distribution, C mol%

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Reaction conditions: Fe/Cu/Al/K (100/6/16/4), CO/CO2 /Ar/H2 (6.3/19.5/5.5/69.3), 1 MPa,


573 K, and 1,800 mL/(gcat h).
Source: Jun et al. (2004).

to produce chemicals, and (d) usage of the synthesis gas as energy carrier in fuel cells.
Figure 4 shows the production of diesel fuel from bio-syngas by FTS. Bio-syngas is a
gas rich in CO and H2 obtained by gasification of biomass.

Diesel Fuel from Vegetable Oil by Decarboxylation


A sustainable biofuel has two favorable properties, which are availability from renewable
raw material and its lower negative environmental impact than that of fossil fuels. As an

Figure 4. Green diesel and other products from biomass via Fisher-Tropsch synthesis.

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alternative fuel, vegetable oil is one of the renewable fuels. Vegetable oil is a potentially
inexhaustible source of energy with an energetic content close to diesel fuel.
There are four alternative fuels that can be relatively easily used in conventional CI
engines: vegetable oil, biodiesel, Fischer-Tropsch (FT) diesel, and dimethyl ether (DME).
The vegetable oils, such as palm, soybean, sunflower, peanut, and olive oils as alternative
fuels, can be used for diesel engines. The vegetable oils as alternative engine fuels are all
extremely viscous, with viscosities ranging from 10 to 20 times greater than petroleum
diesel fuel. The major problem associated with the use of pure vegetable oils as fuels
for diesel engines are caused by high fuel viscosity in compression ignition. The direct
use of vegetable oils in fuel engines is problematic. Due to their high viscosity and low
volatility, they do not burn completely and form deposits in the fuel injector of diesel
engines.
The use of vegetable oils as alternative renewable fuel competing with petroleum was
proposed in the beginning of the 1980s. The advantages of vegetable oils as diesel fuel
are liquid nature portability, ready availability, renewability, higher heat content (about
88% of No. 2 petroleum diesel fuel), lower sulfur content, lower aromatic content, and
biodegradability.
The viscosity of the distillate was 10.2 mm2 /s at 311 K, which is higher than the
ASTM specification for No. 2 diesel fuel (1.94.1 mm2 /s) but considerably below that of
soybean oil (32.6 mm2 /s). Used cottonseed oil from the cooking process was decomposed
with Na2 CO3 as catalyst at 725 K to give a pyrolyzate containing mainly C8 20 alkanes
(69.6%) besides alkenes and aromatics. The pyrolyzate had lower viscosity, pour point,
and flash point than No. 2 diesel fuel and equivalent heating values. The cetan number
of the pyrolyzate was lower than that of No. 2 diesel fuel (Bala, 2005; Sang et al., 2003).
Vegetable oils may be resources for fuels as petroleum alternatives. There are four
different ways of modifying vegetable oils and fats to use them as diesel fuel, such
as pyrolysis (cracking) and dilution with hydrocarbons (blending, emulsification, and
transesterification). Figure 5 shows the use of vegetable oils as petroleum alternative
fuels. The saponification and pyrolysis of sodium soap of vegetable oil proceeds as
follows:
Saponification:
Vegetable Oils or Fats ! NaOH C RCOONa C Glycerin

(1)

Pyrolysis of Na-soaps:
2RCOONa C .1=2/O2 ! R R C Na2 CO3 C CO2

(2)

The soaps obtained from the vegetable oils can be pyrolyzed into hydrocarbon-rich
products, according to Eq. (2), with higher yields at lower temperatures (Demirbas,
2002).

Figure 5. Use of vegetable oils as petroleum alternative fuels.

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A. Demirbas and K. Dincer

The vegetable oils can be converted to petroleum compounds by effectively separating the carboxylic group without breaking the hydrocarbon chain. Hot compressed
water is one of the candidates for treating the oils to produce petroleum (long chain
hydrocarbon) because of its capability to hydrolyze triglyceride into free fatty acid and
glycerol without catalyst (Holliday et al., 1997; King et al., 1999). However, a free fatty
acid is stable in subcritical water (Holliday et al., 1997). Thus, to develop the petroleum
recovery process from oils, decarboxylation of a free fatty acid is a key reaction.

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Conclusion
A sustainable energy system includes energy efficiency, energy reliability, energy flexibility, fuel poverty, and environmental impacts. A sustainable biofuel has two favorable
properties, which are availability from renewable raw material and its lower negative
environmental impact than that of fossil fuels. The term modern biomass is generally
used to describe the traditional biomass use through the efficient and clean combustion
technologies and sustained supply of biomass resources, environmentally sound and
competitive fuels, and heat and electricity using modern conversion technologies.
Biofuels as well as green diesel produced from biomass by Fischer-Tropsch synthesis
are the most modern biomass-based transportation fuels. Green diesel is a renewable
replacement to petroleum-based diesel. Pyrolysis is the most important process among
the thermal conversion processes of biomass. The vegetable oils can be converted to
petroleum compounds by effectively separating the carboxylic group without breaking
the hydrocarbon chain.

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