Você está na página 1de 69

Contents

Contents....................................................................................................................................................1
Symbols and abbreviations....................................................................................................................3
Summary..................................................................................................................................................5
Samenvatting...........................................................................................................................................6
1 INTRODUCTION................................................................................................................................7
1.1 Main introduction.........................................................................................................................9
1.2 Objectives and thesis outline.....................................................................................................10
2 SUSTAINABILITY METRICS..........................................................................................................11
2.1 One dimensional sustainability metrics..................................................................................13
2.1.1 Thermodynamics: Energy and Exergy.............................................................................13
2.1.2 Ecology: Life cycle analysis................................................................................................16
2.1.3 Economics: Costs of investment and labor......................................................................16
2.2 Multidimensional metrics..........................................................................................................17
2.2.1 Cumulative exergy consumption......................................................................................17
2.2.2 Extended exergy accounting..............................................................................................17
3 NON-RENEWABLE AND RENEWABLE FUELS........................................................................21
4 PROCESSES........................................................................................................................................25
4.1 The gas to liquid process...........................................................................................................27
4.2 The biomass to liquid process...................................................................................................31
5 RESULTS.............................................................................................................................................35
5.1 The gas to liquid process...........................................................................................................37
5.1.1 Exergy analysis.....................................................................................................................38
5.1.1 Exergy analysis.....................................................................................................................39
5.1.2 Capital cost analysis............................................................................................................43
5.1.3 Labor analysis.......................................................................................................................44
5.1.4 Environmental remediation exergy..................................................................................45
5.1.5 Extended exergy analysis...................................................................................................45
5.2 The biomass to liquid process...................................................................................................48
5.2.1 Exergy analysis.....................................................................................................................48
5.2.2 Capital analysis....................................................................................................................52
5.2.3 Labor analysis.......................................................................................................................53
5.2.4 Environmental remediation exergy..................................................................................53
5.2.5 Extended exergy analysis...................................................................................................54
6 DISCUSSION AND RECOMMENDATIONS...............................................................................55
Acknowledgement................................................................................................................................59
References..............................................................................................................................................61
Appendix 1: Spreadsheet of calculation of exergetic efficiency.....................................................65
Appendix 2: Exergetic values of the components............................................................................69

1
2
Symbols and abbreviations

Symbols

A yearly write-off of the investment [€]


C capital flux of the process [€]
C0 velocity [m/s]
C1 cost for apparatus at scale 1 [€]
C2 cost for apparatus at scale 2 [€]
CEx cumulative exergy [J/mol]
CF cost factor [-]
Ein exergy of the input [J/s]
Einput exergy input in a society [J]
Einput,sector exergy input in a sector [J]
Eout exergy of the output [J/s]
EQ thermal exergy [J/s]
W
E exergy due to work interaction [J/s]
g gravitational acceleration [m/s2]
h enthalpy [J/mol]
h0 enthalpy at environmental conditions [J/mol]
I irreversibilities [J/s]
i interest rate [-]
Kcap capital conversion factor [J/€]
Klab labor conversion factor [J/hr]
M2 monetary circulation in a society [€]
min molar flux in [mol/s]
mout molar flux out [mol/s]
N life time of the plant [years]
P the investment [€]
Q heat [J/s]
s entropy [J/mol/K]
s0 entropy at environmental conditions [J/mol/K]
SC1 scale 1 [-]
SC2 scale 2 [-]
SF scale factor [-]
T temperature (of the heat) [K]
T0 environmental temperature [K]
WHprocess total man hours needed for the process [hr]
WHsector number of labor hours in a specific sector [hr]

3
Z0 height [m]
ε specific exergy [J/mol]
εch chemical exergy [J/mol]
εin specific exergy of the input [J/mol]
εout specific exergy of the output [J/mol]
ηex exergetic efficiency [-]

Abbreviations

BTL Biomass to liquid


CBS Central bureau of statistics of the Netherlands
CCF Capital conversion factor
CEE Capital exergy equivalent
CExC Cumulative exergy consumption
CSTR Continuous stirred tank reactor
EE Extended exergy
EEA Extended exergy accounting
ERE Environmental remediation exergy
FE Feedstock exergy
FT Fischer Tropsch
GTL Gas to liquid
LCA Life Cycle Analysis
LEE Labor exergy equivalent
SETAC Society of Environmental Toxicology and Chemistry
WGS Water gas shift

4
Summary

Sustainability is becoming more and more important these days. The area in which
sustainable development could play a major role is in that of transportation fuels.
The scarcity of the common energy carriers like oil and gas makes sustainable
development more attractive. To meet the growing demand in all the developed
countries and especially in the developing countries like China and India, alternative
fuels are becoming more and more important. Biodiesel is such an alternative fuel.
The major advantage of biodiesel over petroleum diesel is its environmental
friendliness. The European Union stated that in 2020 the diesel must contain 10%
biodiesel so the market for biodiesel will increase.

In order to quantify the sustainability of a process, multi-dimensional metrics was


developed. The short-coming of the one-dimensional metrics was the fact that is only
tells you something about the efficiency, the investment costs, the labor it took or the
pressure the process had on the environment. In order to assemble all these aspects
conversion factors were needed to convert all aspects into one (preferably exergy)
unit. Therefore, capital, labor and environmental conversion factors had to be
calculated. Now, the efficiency of these four aspects, for instance, could be stated as
one number. This theory in combination with the concept of Cumulative Exergy
Consumption (CExC) was called Extended Exergy Accounting (EEA).

Two processes are analyzed with the use of EEA. The first process is the gas to liquid
(GTL) process in which natural gas is processed with use of a reformer. The Fischer-
Tropsch produces the biofuels and waste. In the separation train the different
fractions are separated from the tail gas. The second process is the biomass to liquid
(BTL) process, which is a renewable process. In the BTL process poplar wood is dried
and gasified. After the Fischer-Tropsch reactor and the gas cleaning unit the different
fractions are separated in the separation train.

Three different efficiencies are calculated: the exergetic efficiency and the EEA
efficiency with use of two different capital conversion factors. When the two
processes, the gas to liquid and the biomass to liquid, are compared the first thing
that stands out are the better efficiencies of the gas to liquid process. The C/H ratio
has a large influence on the CO 2 emission and thus on the EEA. In wood the C/H
ratio is 2.5 times larger than in natural gas. But if the emission of CO 2 is the BTL
process is assumed to be a part of the carbon dioxide cycle the EEA efficiency will
rise but will still be smaller than the GTL process EEA efficiency.

5
Samenvatting

Duurzaamheid is tegenwoordig steeds belangrijker aan het worden. Duurzaamheid


kan een belangrijke rol gaan spelen op het gebied van transport brandstoffen. De
schaarste van de heden ten daagse meest gebruikte energie dragers zoals olie en
aardgas maakt duurzame ontwikkeling attractiever. Om aan de vraag naar energie
van de ontwikkelingslanden zoals China en India te kunnen voldoen zullen
alternatieve brandstoffen steeds belangrijker worden. Biodiesel is een dergelijk
alternatieve brandsof. Het grootste voordeel van biodiesel boven normale diesel is de
milieuvriendelijkheid. De Europese unie heeft afgesproken dat in 2020 de normale
diesel 10% biodiesel moet bevatten, hiermee zal de markt voor biodiesel stijgen.

Om de duurzaamheid van een proces te kunnen kwantificeren zijn multi-


dimensionale metriek ontwikkeld. De tekortkoming van ééndimensionale metriek is
het feit dat het alleen iets verteld over de efficiency, de investeringskosten, de arbeid
die het kost of de druk dat het proces uitoefent op het milieu. Om al deze aspecten te
assembleren zijn conversiefactoren nodig om alle aspecten in één (het liefste exergie)
eenheid om te rekenen. Hiervoor zijn kapitaal, arbeid en milieu conversiefactoren
berekend. Met gebruik van deze conversiefactoren kan de efficiëntie in één getal
samengevat worden. Deze theorie is in combinatie met het concept van de
Cumulatieve Exergie Consumptie (CExC) te definiëren als Extended Exergie
Accounting (EEA).

Twee processen zijn met behulp van de EEA geanalyseerd. Het eerste proces is het
proces van aardgas naar vloeibare brandstof (GTL). Het aardgas wordt eerst
behandeld met een ‘reformer’ waardoor syngas ontstaat. De Fischer-Tropsch reactor
produceert de vloeibare fracties en afgas. In de scheidingstrein zorgen de
destillatietorens ervoor dat de fracties gescheiden worden. Het tweede proces is het
proces van biomassa naar biodiesel (BTL). Dit is een ‘renewable’ proces. In het BTL
proces wordt eerst populierhout gedroogd waarna het vergast wordt. Na de Fischer-
Tropsch reactor en de gasverschoner worden de verschillende fracties gescheiden in
de scheidingstrein.

Drie verschillende efficiënties zijn berekend: de exergetische efficiëntie en de EEA


efficiëntie met twee verschillende kapitaal conversiefactoren. Wanneer de twee
processen, GTL en BTL, worden vergeleken is het belangrijkste wat opvalt de betere
efficiëntie van het GTL proces. De C/H verhouding van de ingaande stromen heeft
een grote invloed op de CO2 emissie en dus ook op de EEA efficiëntie. De C/H
verhouding van hout is 2.5 keer zo groot als de C/H verhouding van aardgas. Maar
als de emissie van CO2 in het BTL proces gezien kan worden als een gedeelte van de
koolstofdioxide cyclus zal de EEA efficiëntie stijgen. De EEA efficiëntie van het BTL
proces zal dan echter nog wel steeds kleiner zijn dan die van het GTL proces.

6
1 INTRODUCTION

7
8
1.1 Main introduction
The concept of sustainable development is becoming more and more relevant for
politicians nowadays than it was thirty years ago. Why? Maybe because Al Gore
made a documentary about what greenhouse gases do with our environment. He
showed us the correlation between the concentration of greenhouse gases in the
atmosphere and the mean temperature on earth. Both are rising with an increasing
slope. Why does he have to tell us what is going wrong with the environment when
almost three hundred years ago, in 1713 a German tax accountant and mining
administrator, Hans Carl von Carlowitz, already told us that sustainability was
important. To von Carlowitz, sustainability means cutting only as much timber as
was regrowing, with forestry having to ensure that soil fertility was maintained or
even increased [1].He was the first one mentioning sustainable development in the
scientific literature.

In the early 60’s the visionary Rachel Carson came with her alert called Silent Spring
[2], but it was the Brundtland commission in 1987 who settled down the idea of
sustainable development in the whole scientific community with their report ‘Our
Common Future’. The Brundtland commission defined sustainable development as
development that “meets the needs of the present without compromising the ability of
future generations to meet their own needs.”

The area in which sustainable development could play a major role is in that of
transportation fuels. The scarcity of the common energy carriers like oil and gas
makes sustainable development more attractive. To meet the growing demand in all
the developed countries and especially in the developing countries like China and
India, alternative fuels are becoming more and more important. Biodiesel is such an
alternative fuel. The major advantage of biodiesel over petroleum diesel is its
environmental friendliness. The European Union stated that in 2020 the diesel must
contain 10% [3] biodiesel so the market for biodiesel will increase.

Many people think biodiesel is sustainable but is it really sustainable? When


biodiesel is made from wood and large amounts of timber are cut in the Amazon-
area and no new plants are planted, it would not be sustainable. So, just as von
Carlowitz said, when you want to make biodiesel out of timber, you have to make
sure that new plants are planted there; otherwise you do not have sustainable
development.

In order to quantify the sustainability of a process, multi-dimensional metrics was


developed. The short-coming of the one-dimensional metrics was the fact that it only
tells you something about the efficiency, the investment costs, the labor it took or the
pressure the process had on the environment. In order to assemble all these aspects
conversion factors were needed to convert all aspects into one (preferably exergy)
unit. Therefore, capital, labor and environmental conversion factors had to be
calculated. Now, the efficiency of these four aspects, for instance, could be stated as

9
one number. This theory in combination with the concept of Cumulative Exergy
Consumption (CExC) was called Extended Exergy Accounting (EEA).

Now, with the use of EEA, different processes can be analyzed by calculating their
total efficiency. Processes can be compared with the notice that the financial, labor,
exergetic as well as the environment aspects are considered, instead of just one of
these

1.2 Objectives and thesis outline

Main Objective

The main objective is to calculate and compare the efficiencies of gas to liquid and
the biomass to liquid process by using the concept of EEA.

Research activities

The research is a theoretical desk study involving no practical experiments.

In order to compare the two processes, Aspen flow sheets were made for exergy
calculations. The investment and transportation costs were calculated to say
something about the financial efficiency of the two processes. Beside that also labor
and environmental efficiencies were calculated to come to an overall efficiency.

Thesis Outline

In chapter two the background of sustainable metrics is presented. The concepts of


Exergy, Energy, Life cycle analysis (LCA), economical metrics, CExC and EEA are
explained in more detail. In chapter three, more information is given about the need
for energy, renewable fuels (biomass based) and non-renewable fuels (natural gas).
Chapter four presents the two processes which were analyzed and gives some more
background information about them. Chapter five shows the results of the EEA of
the two processes and in chapter six, the results are discussed and recommendations
are made.

10
2 SUSTAINABILITY
METRICS

11
12
These days, sustainability is a frequently used word. But how can you measure
sustainability? The sustainability of a process is not only based on the
thermodynamic efficiency but also on how large the investments are, how many
people you need for your process and the impact on the environment. However,
these four different terms have all different units. The energy is expressed in for
instance Joules, investment costs in Euros, labor costs in man hours and
environmental costs in kg CO2 emission. In order to add all these components multi-
dimensional sustainability metrics are needed.

2.1 One dimensional sustainability metrics

To come to multidimensional sustainability metrics, first a couple of one-dimensional


sustainability metrics has to be explained.

2.1.1 Thermodynamics: Energy and Exergy

Traditional methods of thermal system analysis are based on the first law of
thermodynamics. To calculate the heat transfer between the thermal system and the
environment, energy balances are used. These methods are based on energy
conservation, which states that in a thermal system the energy entering the system is
equal to the energy leaving to the environment. These energy flows can be mass or
heat flows. No energy can be lost. However, we want to know something about the
quality of the energy and something about the internal losses. The second law of
thermodynamics tells us something about the irreversibilities of energy by
introducing the concept of entropy. Clausius said about entropy: The entropy of an
isolated system which is not in equilibrium, will tend to increase over time, approaching a
maximum value at equilibrium [4]. Based on the second law of thermodynamics Rant
introduced the term exergy in 1956 [5], but the concept was developed by J. Willard
Gibbs in 1873 [6]. The exergy of a thermal system tells something about the quality of
the energy and will dissipate in every real process.

In order to carry out an exergy analysis, an exergy balance over a control region has
to be made.

13
Thermal energy reservoirs
Surface Control

Output of matter
Input of matter

Shaft Work
Figure 1:Control region

In this control region there is a part of incoming matter entering the control region:

∑E in = ∑ε in min (eq.1)

in which means:
Ein : exergy of the input [J/s]
εin : specific exergy of the input [J/mol]
min : molar flux in [mol/s]

And there is a part of outgoing matter leaving the control region:

∑E out = ∑ε out mout (eq.2)

in which means:
Eout : exergy of the output [J/s]
εout : specific exergy of the output [J/mol]
mout : molar flux out [mol/s]

14
When heat enters the control region, its thermal exergy is defined by:

T0
∑E Q
= ∑ Q ( 1_
T
) (eq.3)

in which means:
EQ : thermal exergy [J/s]
Q : heat [J/s]
T0 : environmental temperature [K]
T : temperature of the heat [K]

Shaft work is defined as EW

in which means:
EW : exergy due to work interaction [J/s]

The formula for specific exergy is

_ _ _
C 02
ε = (h h0 ) T0 ( s s0 ) + ε ch + + gZ 0 (eq.4)
2
in which means:
ε : specific exergy [J/mol]
h : enthalpy [J/mol]
h0 : enthalpy at environmental conditions [J/mol]
T0 : environmental temperature [K]
s : entropy [J/mol/K]
s0 : entropy at environmental conditions [J/mol/K]
εch : chemical exergy [J/mol]
C0 : velocity [m/s]
g : gravitational acceleration [m/s2]
Z0 : height [m]

Within real processes the exergy entering the control region is always larger than the
exergy leaving the control region. The difference is due to irreversibilities. And thus
the overall balance looks like

∑E in + ∑EQ = ∑E out + EW + I (eq.5)


in which means:
I : irreversibilities [J/s]

and where

I = Π * T0 (eq.6)
in which means:
π : Entropy production [J/s/K]

15
The exergy efficiency will be calculated as follows:

∑E + E
out
W

ηex = (eq.7)
∑E + ∑E
in
Q

in which means:
ηex : exergetic efficiency [-]

2.1.2 Ecology: Life cycle analysis

Life Cycle Analysis (LCA) has been defined by Society of Environmental Toxicology
and Chemistry (SETAC) as an objective process to evaluate the environmental burdens
associated with a product, process or activity, by identifying and quantifying energy and
materials used and waste released to the environment, and to evaluate and implement
opportunities to effect environmental improvements [7]. It is a typical cradle to grave
analysis. It starts with the resources needed for the process and stops with the final
products. It does not only consider the feedstock for a process but also at the
resources used for manufacturing the machines which are used during the process. It
really takes every step into account.

The LCA looks at the impact of a new process or product on the environment but it
tells you nothing about the economical part of a process. It is a one-dimensional
analysis.

2.1.3 Economics: Costs of investment and labor

When a process is economically evaluated the profitability is calculated and, for


instance, a cost-benefit analysis is made. The investment costs for the apparatus are
analyzed and it is predicted how much will be sold. It is hard to predict the life time
of a plant so assumptions have to be made. Expenses have to be made to hire
operators, so they will be included in the analysis, too. With all these costs and
benefits investors can predict whether they could invest in the project or they should
rather put their money on a bank. If the rate of return is smaller than the interest rate
the investors could get at a bank, they will not invest in the project. In the end the
investors will only respond to a value which has a good perspective for them
without considering the impact the process has on the environment. So there should
be a multi dimensional metrics system to evaluate projects with each other and not
only on money basis.

16
2.2 Multidimensional metrics

In order to put some of these analyses listed above together various people tried to
invent a new concept for multi-dimensional sustainability metrics.

2.2.1 Cumulative exergy consumption

Szargut and Moris tried to combine the life cycle analysis with the exergy analysis
and called it Cumulative exergy consumption (CEsC). Szargut defined CExC of a
product as: The sum of the exergy of natural resources consumed in all links of a
technological network that starts with these resources and leads to the product under
consideration.[8]

This two-dimensional analysis is a typical from well to wheel analysis. For example,
when you have a process in which biomass has to be transported, the CExC would
include the fuel (energy) needed for the transport.
So the cumulative exergy of a component is not the same as the specific exergy of the
component but the specific exergy times a cost factor:

CEx = ε .CF (eq.8)

in which means:
CEx : cumulative exergy [J/mol]
ε : specific exergy [J/mol]
CF : cost factor [-]

In this study the CEx of natural gas is needed and the value of the cost factor of
natural gas is 1.04. [9]

2.2.2 Extended exergy accounting

In extended exergy accounting, Sciubba [10] tried to combine the four different
factors (exergy, economics, labor and environment). So this concept tells you more
about the economics of a process and not only about the thermodynamics and
environmental issues like the CExC.
He stated that:

EE=FE+CEE+LEE+ERE (eq.9)

in which:
EE = Extended exergy [GJ/hr]
FE = Feedstock exergy [GJ/hr]
CEE = Capital exergy equivalent [GJ/hr]
LEE = Labor exergy equivalent [GJ/hr]
ERE = Environmental remediation exergy [GJ/hr]

17
Feedstock exergy

Feedstock exergy is nothing more than the CExC of the process streams. This is all
the material streams entering and leaving the process. When you make an exergy
analysis of a project you would only take this term into account.

Capital exergy equivalent

The capital exergy equivalent (CEE) term takes the costs into account. These costs are
in Euros and if they have to be added to the feedstock exergy, the unit should be in
joules. Therefore a capital conversion factor is needed. The capital conversion factor
is a factor with the unit J/Euro. These costs are for the write-off of the investment at
the beginning and the transport and energy costs.

The capital conversion factor states how much it cost to produce one unit of exergy.
It can be calculated for a whole country [11] or for different sectors like the energy or
industry sector. The capital conversion factor for different sectors has never been
calculated. In the present study, the extended exergy efficiency is calculated with this
value and compared to the extended exergy efficiency calculated with the capital
conversion factor of the whole country, to determine the influence of this new value.

The capital conversion factor of a whole country is calculated as follows:


Einput
K cap = (eq.10)
M2
in which means:
Kcap : capital conversion factor [J/€]
Einput : exergy input in a society [J]
M2 : monetary circulation in a society [€]

With this capital conversion factor the CEE can be calculated as follows:

CEE = C * K cap (eq.11)

in which means:
C : capital flux of the process [€]

For the calculation of the capital conversion factor for a sector, the total input of
exergy in the sector is divided by the monetary value of the goods which are
imported in that sector calculated with values of the central bureau of statistics (CBS)
[12].

The investment of a new plant is spread over large number of years. The value of
money decreases in time with the interest rate and because the investment costs for
each year are needed, a business economic formula is needed.

18
i (1 + i ) N
A= P _ (eq.12)
(1 + i ) N 1
in which means:
A : yearly write-off of the investment [€]
P : the investment [€]
i : interest rate [-]
N : life time of the plant [years]

Some prices for apparatus are for a specific scale. When another scale is needed it can
not linearly be adapted. For this problem a scale factor has been introduced. Scale
factors can have different values but the most common value for a scale factor is 0.6
[13]. This means that if an apparatus is twice as big the price will be 1.52 times
higher. The formula with the scale factor is given below:

SC1 SF
C1 = C 2 (eq.13)
SC 2
in which means:
C1 : cost for apparatus at scale 1 [€]
C2 : cost for apparatus at scale 2 [€]
SC1 : scale 1 [-}
SC2 : scale 2 [-}
SF : scale factor [-]

Labor exergy equivalent

The LEE term is about labor. This term contains all labor that is done, that could be
all kinds of labor concerning the process, for example wood collecting or operating a
power plant. Labor is expressed in man hours but joules are needed, so a labor
conversion factor is has to be used. This factor can be calculated for every sector
because the number of man hours and the total exergy of every sector is known [11].

The labor conversion factor of a sector is calculated as follows:

E input ,sec tor


K lab = (eq.14)
WH sec tor
in which means:
Klab : labor conversion factor [J/hr]
Einput,sector : exergy input in a sector [J]
WHsector : number of labor hours in a specific sector [hr]

19
With this labor conversion factor the LEE can be calculated as follows:

LEE = WH process * K lab (eq.15)

in which means:
WHprocess : total man hours needed for the process [hr]

Environmental remediation exergy

The last term, Environmental remediation exergy (ERE) is also the most difficult term
in the formula to evaluate. This is the exergy you need to convert all waste streams to
components which have zero impact on the environment. So the waste stream has to
be broken up into components which are in equilibrium with the natural
environment.

20
3 NON-RENEWABLE AND
RENEWABLE FUELS

21
22
This master thesis is all about two different processes. One is renewable and the
other is non-renewable. This chapter explains why new energy forms are needed and
shows some present-day available processes. Four popular processes will be
discussed and two of them will be analyzed in the remaining part of this thesis.

Need for energy

The need for energy increased in time. Before mankind learned how to make a fire
for preparing food, food was the only energy use in that time. This is about 1 million
years ago. 100,000 years ago the Neanderthals used heat for preparing food. They
also used fire for making spears and other tools. This increased the energy need with
25% to 0.25 kW/capita [14]. 7000 years ago the Homo sapiens started the
development of agriculture and cattle breeding and that increased their energy need
with 100% to 0.5 kW/capita. In the Middle Ages mankind needed more energy
because more and more energy was needed for agriculture and melting of bronze for
instance. In this time the people began to transport themselves with animal or sailing
ships, this also increased the need for energy. The total energy need increased with
350% to 1.75 kW/capita. In the industrial time the transport part of the energy need
growths one order of magnitude with the invention of the dynamo in 1875. The
energy need increased with 210% to 3.7 kW/capita. At this time we need about 11.1
kW/capita. Industry and transport are the largest part of this value. In many
developing countries the energy use is still considered lower than 1 kW/capita. If
these countries become developed and use the same amount of energy we use the
total need for energy will be 5 times larger. So people have to think about the future
and the sources for future energy or else we have a big problem.

At this moment, a large part of the energy


production comes from the non-renewable fuels
(see figure 2 [15]). Only 8% (2006) is renewable.
With a growing energy demand from mainly the
developing countries and decreasing oil supply
the scream for more renewable fuels has to be
heard. In the past some new processes for
renewable and non-renewable fuels were invented
and the most important will be discussed.

The first two processes are renewable and the last


two are non-renewable.

Process 1: Biomass  Hydrogen Figure 2: World Energy Production

Hydrogen from biomass is one of the most popular sustainable processes because
biomass is hundred percent renewable and the waste of burning hydrogen is pure
water. A disadvantage of hydrogen is the need for a new infrastructure like new
pump stations for hydrogen. Another disadvantage is the low energy density of
hydrogen. Even when it is liquefied it has an energy density of 27% of that of

23
present-day fuels like gasoline. Hydrogen from fossil fuels is still cheaper than from
biomass but with the depletion of fossil fuels in the future this will change. It is
important to construct a hydrogen infrastructure before the oil resources will deplete
or else it will cause a major energy crisis.
Van de Heijden analyzed a couple of biomass to hydrogen conversion processes and
concluded that these conversion processes are comparable to hydrogen from fossil
fuel qua exergetic efficiency [16].

Process 2: Biomass  Bio liquids

This process is already worldwide used with many different sorts of biomass. In
Brazil for instance, they use all kinds of waste material to make biodiesel [17].
Some recent studies indicated that the use of Fischer-Tropsch technology for biomass
conversion to synthetic hydrocarbons may offer a promising and carbon neutral
alternative to conventional diesel, kerosene and gasoline [17, 18].

A lot of exergy analyses are already done on these sorts of processes by Prins [19]
and Loonen [20].

Process 3: Methane  Hydrogen

Since hydrogen is more and more the fuel of the future [21], processes in which
hydrogen is formed in an easy way are interesting. Today, 95% of the hydrogen is
produced by steam-methane reforming [16]. Rosen [21] investigated the steam-
methane reforming process and his results can be used to analyze this process
further.

Process 4: Methane  liquid fuels

This process is better known as gas-to-liquid (GTL). Shell has started a GTL plant in
Bintulu, Malaysia in 1993, that has current capacity of 14,700 barrels/day [22] and is
about to start a plant in Qatar for 140,000 barrels/day [23]. The fuel, just like
biodiesel, is practically sulfur and aromatics-free and makes significantly less vehicle
emissions of local air pollutants like hydrocarbons, carbon monoxide, particulates
and nitrogen dioxide in comparison with traditional diesel fuel [24]. Methane is still a
low density gas so pipeline constructions for transporting it over large distances
would be a problem but this will cause a drive to develop new liquefying techniques
[25].

In the remaining part of this master thesis process 2 and 4 will be further analyzed in
order to determine their efficiency.

24
4 PROCESSES

25
26
In this chapter the processes will be described. The first process is the gas to liquid
process. After this process, the biomass to liquid process will be described

4.1 The gas to liquid process

The process is divided into 7 units. The reformer, gas cooler, compressor, water-gas-
shift reactor, Fischer-Tropsch reactor, separators and power plant. Figure 4 illustrates
the division of the process-units.

Reformer
A non-renewable fuel is used for this process. The gas used for this process is not
only methane; it contains also 0.5% carbon monoxide [26]. A mass flow of 200 ton gas
per hour is used. The oxygen needed for the reformer is formed in the air separation
unit where the oxygen is separated from the nitrogen. Before these streams go to the
reformer they will be heated to 1100 °C. In this analysis a catalytic auto thermal
reformer is used. This reformer produces a better H 2/CO ratio than other reformers
[26]. To simulate this in Aspen a Rgibbs reactor is chosen. In the reformer the
following overall chemical reactions take place.

2CH 4 + 3O2 ⇒ 2CO + 4 H 2 O (eq.16)

CH 4 + H 2 O ⇔ CO + 3H 2
(eq.17)
CO + H 2 O ⇔ CO2 + H 2
(eq.18)

The first reaction is the partial combustion of methane. The second reaction is the
steam reforming reaction and the third is the shift reaction.

Gas Cooler
Before the gas is going to the multi stage compressor is has to be cooled to 240 °C.

Compressor
The reactions in the Fischer-Tropsch reactor take place at a pressure of 30 bar.
Therefore a compressor is needed. In a multistage compressor 3 stages are used. First
the pressure is increased to 3 bar and the stream will be cooled before it goes to the
next stage. There the gas pressure will be increased to 10 bar and cooled down
afterwards. In the last stage the gas pressure is increased to 30 bar and also cooled
afterwards.

Water-gas-shift reactor
To form long hydrocarbons the H2/CO ratio has to be 2.03. To increase the current
ratio to 2.03 a water-gas shift (WGS) reactor is used. To simulate this reactor in Aspen
a REquil reactor is chosen.

27
Fischer-Tropsch reactor
The Fischer-Tropsch reactor is a continuous stirred tank reactor (CSTR) operating at
a constant temperature of 240 °C and at a pressure of 30 bar. To simulate this reactor
in Aspen a RStoic reactor is chosen. The authors of [26] assume that the essence of the
Fischer-Tropsch synthesis is described by the next reaction.

nCO + (2n + 1) H 2 ⇒ C n H 2 n + 2 + nH 2 O (eq.19)

The water gas shift reaction can be neglected. To predict the product distribution of
the Fischer-Tropsch reactor the Anderson-Schulz-Flory distribution is used. This
model assumes a chain growth mechanism. In this distribution an alpha is defined.

In

Figure 3: ASF distribution


figure 3 [27] the ASF distribution is displayed. The value of alpha is considered
constant at 0.95. The division of the different hydrocarbons is a result of the
algorithm Prins [19] wrote. The conversion of H2 is 80% and is a realistic assumption
when a fixed bed reactor with three slurry reactors in series is used. [26]

Separators
To separate the water from the rest, a mechanical separator is used. This separator
separates the stream into a water phase, an organic liquid phase and an organic gas
phase. The water phase is separated from the water free stream. After the water
separator, the water free stream will be cooled to 150 K to separate the CO, H 2 and
methane from the heavier components. The CO, H 2 and methane rich stream is
recycled to the FT inlet stream. The remaining part goes to the distillation train.
Before it goes into the first distillation column, it is cooled to 310 °C. In the first
distillation column the heavy hydro carbons are separated from the lighter hydro
carbons. The first product stream is the residue from distillation column 1. This
stream contains C18H38 to C24H50 (soft waxes). The distillate is cooled down and goes
directly into the next distillation column. The residue of this distillation column is
also product stream and contains C9H20 to C17H36 (middle distillates). The distillate is
cooled down before is goes to the last distillation column where the light hydro
carbons are separated from the flue gas. The residue of distillation column 3 contains
C4H10 to C8H18 (nafta). The tail gas contains CO, CO 2, CH4, H2, C2H6 and C3H8 which is
sent to the power plant.

28
To give more insight into the distillation train, table 1 shows the conditions of each
separator.

Table 1: Separator conditions


Pressure Temperature [K]
[bar] Inlet Outlet (bottom) Outlet (top)
Flash 30 150 150 150
Distillation column 1 2 583 641 488
Distillation column 2 1 413 463 324
Distillation column 3 1 253 294 186

Power plant
In the power plant the tail gas is used to make electricity by using an electrical turbo-
generator. The exergetic efficiency of the power plant is estimated on 40%.

29
Reformer Gas cooler Compressor WGS F-T reactor
4

1
14

ASU
3
5 6 7 8 9 10 11 12 13

Heater 1 Cooler 1 Compressor Cooler 2

Reformer WGS F-T Water-Separator


2
17

Figure 4: Process flow sheet GTL


Power plant

Separators 15
23 22
27 18 16

Cooler 5
Heater 2 Cooler 3
Distillation Column 3 21 20
Flash
26 19
Power plant
Cooler 4

Distillation Column 2
25

Distillation Column 1
24

30
4.2 The biomass to liquid process

The biomass to liquid process has already been analyzed by Tamara Loonen [20].
However, she only performed an exergy analysis. In this master thesis an extended
exergy analysis was made for this process. The process is divided into 10 units as
figure 5 illustrates.

Drying
Most wood has a moisture content of about 50%. If the wood is not dried before it
goes to the gasifier, much more energy will be needed to remove all the water from
the wood in the gasifier, which will decrease the efficiency of the whole process. So
for this process a dryer is needed. There are different sorts of dryers on the market.
For a flash dryer the particles will be too big. A disk dryer is not designed for a large
flow of biomass and a super heated steam dryer is too expensive [28]. Therefore, a
drum dryer would be the best for this process, although it needs a big space and it
brings a great fire hazard.

Table 2: The composition of


For this process poplar wood is used. The composition
poplar
of poplar wood is showed in table 2 [29]. The flow of
Element Mass % Mol % wood is 1000 ton per hour. In the dryer the moisture
C 49.10 31.823 content decreases to 20%. The steam that is produced
H 6.00 46.333 can be used for heating other streams.
O 44.30 21.552
N 0.48 0.267 In Aspen this drying unit is modeled with a Rstoic
S 0.02 0.005 reactor. In this dryer the following reaction is modeled
Cl 0.10 0.022 to separate the water from the biomass.
Total 100 100

Biomass  0.0555084 H2O. (eq.20)

The precise value of 0.0555084 results in a dry wood content of 20%.


This trick is necessary for modeling the dryer. The heat duty of the dryer is 0 and it
runs at 1 bar. The water will evaporate in the heater.

Gasifier
The dry biomass goes into the Gasifier, which operates at 1 bar and 900°C. Air is
used to gasify the wood. In Aspen, the gasifier is modeled with a decomposer
(Ryield reactor) followed by a Rgibbs reactor. The Ryield reactor degrades the wood
into the elements. Subsequently, the elements are gasified in the Rgibbs reactor. The
reactor runs auto thermal. The reactions that take place in the reactor are:

31
2C + O2 ⇔ 2CO (eq.21)
C + O2 ⇔ CO2 (eq.22)
C + CO2 ⇔ 2CO (eq.23)
C + H 2 O ⇔ CO + H 2 (eq.24)
(eq.25)
C + 2 H 2 ⇔ CH 4
(eq.26)
CO + H 2 O ⇔ CO2 + H 2
(eq.27)
CH 4 + H 2 O ⇔ CO + 3H 2 (eq.28)
2 H 2 + 2CO ⇔ CO2 + CH 4
Gas cooler
Before the gas flows to the gas cleaning unit it has to be cooled down to 150°C.

Gas cleaning
In the gas cleaning unit a filter is installed to remove condensed products like salts
and tars. The filter is modeled in Aspen with a Ssplit unit. All solid particles are
separated from the rest. HCl and NH 3 will be removed in the scrubber with the use
of water. This unit is modeled by a Radfrac unit with 6 plates. It runs at 1 bar and has
a pressure drop of 0.2 bar.

Compressor
In this model, an isentropic compressor is used. It compresses the gas to 25 bar. After
leaving the compressor the gas is cooled down to 330°C.

WGS Reactor
The shift reaction is modeled by a Requil reactor. For the reaction see section 4.1
Also here, a H2/CO ratio of 2.03 is needed to form desired hydro carbons. The WGS
reactor has a pressure drop of 0.5 bar.

CO2 removal
First, the gas is cooled to 10°C and this unit has a pressure drop of 0.5 bar. This
separation process contains two steps. In the first step the CO 2 is stripped with use of
an amine, like DMEA. In the second step these two components are separated by
phase separation at high temperatures. Total separation of the CO2 is assumed.

Fischer Tropsch reactor


This unit is the same as the Fischer Tropsch reactor in the gas to liquid process so this
will not be further explained. The conversion of each reaction depends on the
Anderson-Schulz-Flory (ASF) distribution.

32
Hydro carbon separators
The first distillation column is a flash separator. The liquid is separated from the gas.
In the second distillation column, which also is a flash separator, the gas is
cryogenically separated at -73°C.

Power plant
The tail gas is sent to the power plant and will be combusted to produce electricity
and CO2.

33
Gas cooler Gas cleaning
Dryer
Gasifier
2 9
Compressor
5 11
7 8 Spray tower

Cooler Filter 13
6 Gasifier
1 3 10
Heater
4

Compressor

Dryer 12
Decomposer

Figure 5: Process flow sheet BTL


25 14

Power plant
Power plant Cooler 2

22
Distillation column 2 CO2 Separator 15

21 20 18 17
24 Distillation column 1

Cooler 3

F-T reactor Shift reactor 16

Hydro carbon separators 19


23 F-T reactor
WGS reactor
CO2 Separator

34
5 RESULTS

35
36
5.1 The gas to liquid process

Table 3 and 4 show the process conditions and composition of all streams.

Table 3: Process conditions and composition of light component streams


Stream number 1 2 3 4 5 6 7 8 9 10 11 12 13
Temperature K 298 298 298 298 298 1373 1373 513 513 521 321 513 298
Pres ure bar 1 1 1 1 1 1 1 1 30 30 30 30 30
Total Flow kmol/hr 30000.0 12413.4 6300.0 23700.0 18713.4 18713.4 37069.5 37069.5 37069.5 37069.5 74132.4 50704.1 50704.1
Total Flow kg/hr 865511.9 200000.0 201592.4 663919.5 401592.4 401592.4 401592.4 401592.4 401592.4 401592.4 1415245.2 1415245.2 1415245.2
O2 6300.0 0.0 6300.0 0.0 6300.0 6300.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
N2 23700.0 0.0 0.0 23700.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
CO 0.0 71.4 0.0 0.0 71.4 71.4 12345.8 12345.8 12345.8 12133.3 47118.0 35403.8 35403.8
CO2 0.0 0.0 0.0 0.0 0.0 0.0 53.7 53.7 53.7 266.2 266.2 266.2 266.2
CH4 0.0 12342.0 0.0 0.0 12342.0 12342.0 14.0 14.0 14.0 14.0 2066.5 2183.5 2183.5
H2O 0.0 0.0 0.0 0.0 0.0 0.0 218.3 218.3 218.3 5.8 5.8 11720.0 11720.0
H2 0.0 0.0 0.0 0.0 0.0 0.0 24437.8 24437.8 24437.8 24650.3 24650.3 0.0 0.0
C2H6 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 24.6 117.3 117.3
larger hydro carbons 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1.1 1013.4 1013.4

Stream number 14 15 16 17 18 19 20 21 22 23 24 25 26 27
Temperature K 298 298 150 150 144 583 488 413 324 253 641 463 294 186
Pres ure bar 30 30 30 30 2 2 1.8 1.2 1 1 2 1 1 1
Total Flow kmol/hr 11720.0 38984.1 38984.1 37062.9 1891.5 1891.5 1689.9 1689.9 1291.4 1291.4 201.6 398.6 329.9 961.4
Total Flow kg/hr 211138.3 1204106.9 1204106.9 1013652.8 189623.3 189623.3 130422.0 130422.0 58959.9 58959.9 59201.3 71462.1 27826.6 31133.3
O2 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
N2 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
CO 0.0 35403.8 35403.8 34984.7 389.4 389.4 389.4 389.4 389.4 389.4 0.0 0.0 0.0 389.4
CO2 0.0 266.2 266.2 0.0 266.2 266.2 266.2 266.2 266.2 266.2 0.0 0.0 0.0 266.2
CH4 0.0 2183.5 2183.5 2052.5 131.0 131.0 131.0 131.0 131.0 131.0 0.0 0.0 0.0 131.0
H2O 11720.0 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
H2 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
C2H6 0.0 117.3 117.3 24.6 92.7 92.7 92.7 92.7 92.7 92.7 0.0 0.0 0.0 92.7
larger hydro carbons 0.0 1013.4 1013.4 1.1 1012.0 1012.0 811.0 811.0 412.0 412.0 201.6 398.6 329.9 82.2

37
Table 4: Process conditions and composition of
heavy component streams

Stream number 1 12 13 15 16 17 18 19 20 21 2 23 24 25 26 27
C3H8 1. 83. 83. 83. 83. 1. 82. 82. 82. 82. 82. 82. 0. 0. 0. 82.
C4H10 0. 75.3 75.3 75.3 75.3 0. 75.3 75.3 75.3 75.3 75.3 75.3 0. 0. 75.3 0.
C5H12 0. 69. 69. 69. 69. 0. 69. 69. 69. 69. 69. 69. 0. 0. 69. 0.
C6H14 0. 65.4 65.4 65.4 65.4 0. 65.4 65.4 65.4 65.4 65.4 65.4 0. 0. 65.4 0.
C7H16 0. 61.5 61.5 61.5 61.5 0. 61.5 61.5 61.5 61.5 61.5 61.5 0. 0. 61.5 0.
C8H18 0. 57.9 57.9 57.9 57.9 0. 57.9 57.9 57.9 57.9 57.9 57.9 0. 0. 57.9 0.
C9H20 0. 54.6 54.6 54.6 54.6 0. 54.6 54.6 54.6 54.6 0. 0. 0. 54.6 0. 0.
C10H2 0. 51.6 51.6 51.6 51.6 0. 51.6 51.6 51.6 51.6 0. 0. 0. 51.6 0. 0.
C1 H24 0. 48. 48. 48. 48. 0. 48. 48. 48. 48. 0. 0. 0. 48. 0. 0.
C12H26 0. 46.2 46.2 46.2 46.2 0. 46.2 46.2 46.2 46.2 0. 0. 0. 46.2 0. 0.
C13H28 0. 43.8 43.8 43.8 43.8 0. 43.8 43.8 43.8 43.8 0. 0. 0. 43.8 0. 0.
C14H30 0. 41.5 41.5 41.5 41.5 0. 41.5 41.5 41.5 41.5 0. 0. 0. 41.5 0. 0.
C15H32 0. 39.3 39.3 39.3 39.3 0. 39.3 39.3 39.3 39.3 0. 0. 0. 39.3 0. 0.
C16H34 0. 37.3 37.3 37.3 37.3 0. 37.3 37.3 37.3 37.3 0. 0. 0. 37.3 0. 0.
C17H36 0. 35.4 35.4 35.4 35.4 0. 35.4 35.4 35.3 35.3 0. 0. 0. 35.3 0. 0.
C18H38 0. 3 .5 3 .5 3 .5 3 .5 0. 3 .5 3 .5 0. 0. 0. 0. 3 .5 0. 0. 0.
C19H40 0. 31.8 31.8 31.8 31.8 0. 31.8 31.8 0. 0. 0. 0. 31.8 0. 0. 0.
C20H42 0. 30.2 30.2 30.2 30.2 0. 30.2 30.2 0. 0. 0. 0. 30.2 0. 0. 0.
C21H4 0. 28.6 28.6 28.6 28.6 0. 28.6 28.6 0. 0. 0. 0. 28.6 0. 0. 0.
C2 H46 0. 27.2 27.2 27.2 27.2 0. 27.2 27.2 0. 0. 0. 0. 27.2 0. 0. 0.
C23H48 0. 25.8 25.8 25.8 25.8 0. 25.8 25.8 0. 0. 0. 0. 25.8 0. 0. 0.
C24H50 0. 24.5 24.5 24.5 24.5 0. 24.5 24.5 0. 0. 0. 0. 24.5 0. 0. 0.
38
5.1.1 Exergy analysis

Before an extended exergy analysis is made, a classical exergy analysis is made to


detect the major irreversibilities.

In the appendix 1 the spreadsheet for the exergy analysis is displayed. In this chapter
only the results are showed. In table 5 the heat and work of the different units are
displayed.

Table 5: Heat and work for all units


Name of process unit Heat [G/hr] Thermal Exergy [GJ/hr] Work [GJ/hr]
Air separation unit 0 0 -1221
Heater 1 1071 838.5 0
Reformer -357 -279.5 0
Cooler 1 -992.2 -641.6 0
Compressor 0 0 -881.5
Fischer-Tropsch -1462.8 -613.1 0
Cooler 2 -954.4 -400 0
Cooler 3 -263 -97.3 0
Heater 2 224.6 109.8 0
Cooler 4 -35.7 -9.9 0
Cooler 5 -14.8 -1.9 0
Reboiler Dist 1 445 170.4 0
Condenser Dist 1 418.8 223.7 0
Reboiler Dist 2 115 7.6 0
Condenser Dist 2 110 39.2 0
Reboiler Dist 3 78.9 21.8 0
Condenser Dist 3 75.4 1.2 0
The diagram in figure 6 shows the irreversibilities of each unit at a reformer
temperature of 1100 °C (standard conditions).

Irreversibilities versus the different units

2500.0

2000.0
Irreversibilities (GJ/h)

1500.0

1000.0

500.0

0.0
Reformer Gas cooler Compressor WGS FT Separators Powerplant
Units

39
Figure 6: Irreversibilities versus the different units

The standard conditions were chosen with a reformer temperature of 1100 °C. To
compare, other reformer temperatures were applied and the accompanying
irreversibilities were calculated. Table 6 shows the irreversibilities for the different
temperatures for each unit. The chosen temperatures, are 800, 900, 1000, 1100, 1200
and 1300°C. Below 800°C, kinetic problems will appear and that means that the
reaction time will increase. Above 1300°C the high temperatures needs too much
energy.

Table 6: Irreversibilities for different temperatures


Irreversibilities [GJ/hr] Reformer Gas cooler Compressor WGS Fischer-Tropsch Separators Power plant
800 C 2128.71 22.7 542.0 16.9 1340.5 204.8 767.3
900 C 2146.69 33.0 562.9 6.9 653.0 296.6 443.2
1000 C 2161.72 33.6 569.0 3.5 563.7 377.2 358.4
1100 C 2174.20 38.6 570.7 2.8 531.2 303.9 336.7
1200 C 2185.62 43.9 571.0 2.7 510.8 207.1 319.4
1300 C 2199.21 47.3 646.3 2.9 507.2 207.2 318.0

Figure 7 displays a graphical view of the irreversibilities for each unit at various
temperatures.

2500

2000
Irreversibilities [GJ/hr]

800 C
1500 900 C
1000 C
1100 C
1000 1200 C
1300 C

500

0
Reformer Gas cooler Compressor WGS Fischer- Separators Power plant
Tropsch

Figure 7: Irreversibilities for different units at various temperatures

As figure 8 shows, the reformer has the largest irreversibilities, and the
irreversibilities of the gas cooler and the WGS reactor are very small. To determine
the influence of the temperature, the graph is normalized by dividing the
irreversibilities by the irreversibilities at 1100 °C.

40
7.00

Irreversibilities/Irreversibilieties at 1100 C [-]


6.00

5.00
800 C
900 C
4.00
1000 C
1100 C
3.00
1200 C
1300 C
2.00

1.00

0.00
Reformer Gas cooler Compressor WGS Fischer- Separators Power plant
Tropsch

Figure 8: Normalized irreversibilities for different units at various temperatures

As figure 8 shows the reformer temperature has only a small influence on the
irreversibilities of the reformer itself. The irreversibilities of the gas cooler increase
with temperature. This is expected because the temperature difference to cool down
increases and so do the irreversibilities of the gas cooler. The irreversibilities of the
WGS reactor are negligible. The H2/CO ratio is almost on its target before the WGS
reactor so not much will happen in the WGS reactor. The peak value at 800°C says
nothing because the values of the WGS reactor are negligible and a small difference
in the amount of irreversibilities will make a large difference in the normalized
value. The Fischer-Tropsch reactor exergy dissipation decreases with increasing
temperature. This can be explained by the fact that the recycle stream is much bigger
because there is less conversion into reaction products. Furthermore, it needs more
energy to be heated in the reactor. The separators show an optimum. That is because
of a double effect. At a higher temperature more products are formed and also the
exergy dissipation will be higher. But at the lower temperature, more tail gas is
formed and this gas needs to be heated so more exergy will be dissipated here at low
temperatures. At the power plant the irreversibilities are higher at low temperatures
because the flow through the power plant is higher and with a constant efficiency of
40% the irreversibilities will be higher.

The graph of figure 9 the total irreversibilities are displayed versus the reformer
temperature

41
5500.0

Total irreversibilities [GJ/h]


5000.0

4500.0

4000.0

3500.0

3000.0
800 900 1000 1100 1200 1300

Reformer temperature [C]

Figure 9: Total irreversibilities versus the reformer temperature

This graph shows that 1200°C for the reformer is the temperature with the smallest
irreversibilities. Figure 10 displays the efficiency as function of the temperature.
According to that graph 1300°C for the reformer is the temperature with the largest
efficiency. This is because of a greater input of exergy in the process with 1200°C. The
irreversibilities are absolute; the efficiencies give a better view on the process because
they are relative.

0.62

0.6

0.58

0.56
Efficiency [-]

0.54

0.52

0.5

0.48

0.46

0.44
800 900 1000 1100 1200 1300
Reform er tem perature [K]

Figure 10: Exergetic efficiency versus reformer temperature

42
5.1.2 Capital cost analysis

For the capital analysis the investment costs for the different units are needed. Only
the prices of the largest apparatuses are calculated because the prices of for instance
heaters or coolers are negligible. For the yearly write-off an interest rate of 15 % is
assumed and the plant will operate for 30 years. This is calculated with equation 12.

Table 7: Capital costs


  Total investment Yearly write-off Cost/hr
Air separation unit € 470,000,000.00 [26] € 71,581,093.15 € 8,171.36
Reformer € 54,000,000.00 [30] € 8,224,210.70 € 938.84
Multistage compressor € 187,000,000.00 [31] € 28,480,137.06 € 3,251.16
WGS reactor € 57,000,000.00 [32] € 8,681,111.30 € 990.99
FT reactor € 57,000,000.00 [32] € 8,681,111.30 € 990.99
Distillation column 1 € 1,900,000.00 [31] € 289,370.38 € 33.03
Distillation column 2 € 1,700,000.00 [31] € 258,910.34 € 29.56
Distillation column 3 € 800,000.00 [31] € 121,840.16 € 13.91
Power plant € 21,000,000.00 [31] € 3,198,304.16 € 365.10
Total costs € 850,400,000.00 € 129,516,088.54 € 14,784.94

Conversion to exergetic units


To convert the economic value into exergetic units the capital conversion factor
(CCF) is needed. The CCF of the Netherlands, K cap=15.7 MJ/ €=0.0157 GJ/€ [11].
Because this process can be allocated as a conversion process, the CCF has to be
calculated for the conversion sector. As additional information the CCF for the
transportation and extraction sector are calculated. To calculate the CCF, the input
exergy into the sector is needed. The input of exergy into these sectors is mainly
composed to the input of energy carriers like gas or electricity. The prices for the
different energy carriers can be looked up in the database of the central bureau of
statistics (CBS) in the Netherlands. The CCF is calculated by dividing the total input
of exergy by the total value of the energy carriers.

Conversion sector

Table 8: Total input of money in the conversion sector


Conversion sector Energy [GJ/y] Price per GJ [€] Monetary value [mln]
Crude Oil products 1904000000 14.89 € 28,350.56
Crude Oil 2358000000 5.69 € 13,417.02
Natural Gas 410000000 4.96 € 2,033.60
Electricity 3900000 14.2 € 55.38
Electricity 82600000 14.2 € 1,172.92
Other 104000000 5 € 520.00
Hard Coal 598000000 5.3 € 3,169.40
Total     € 48,718.88

43
The total input of exergy into this sector per year is 5805.73 PJ [11]. So the CCF for the
conversion sector is 0.119 GJ/ €. This value is almost eight times the national value so
in the conversion sector each unit of exergy converted is almost eight times more
valuable than the average of exergy conversion in the Netherlands.

Transportation sector

Table 9: Total input of money in the transportation sector


Transportation sector Energy [GJ/h] Price per GJ [€] Monetary value [mln]
Crude Oil products 458000000 14.89 € 6,819.62
Electricity 5870000 14.2 € 83.35
Total     € 6,902.97

The total input of exergy into the transportation sector per year is 504.52 PJ [11]. So
the CCF for the conversion sector is 0.073 GJ/ €. This value of the CCF is less than the
value for the conversion sector meaning that in the transportation sector each unit of
exergy converted is less valuable than a unit of exergy converted in the conversion
sector

Extraction sector

Table 10: Total input of money in the extraction sector


Extraction sector Energy [GJ] Price per GJ [€] Monetary value [mln]
Crude Oil 4221000000 14.89 € 62,850.69
Natural Gas 2711000000 4.96 € 13,446.56
Natural Gas Condensate 300000000 4.96 € 1,488.00
Electricity 1000000 14.2 € 14.20
Other 2000000 5 € 10.00
Total     € 77,809.45

The total input of exergy into the extraction sector per year is 7673.34 PJ [11]. So the
capital conversion factor for the extraction sector is 0.099 GJ/ €.

The total costs for the plant are € 14,784.94 per hour. The capital conversion factor is
0.119 GJ/ €. So the capital exergy equivalent (CEE) is 1,759.41 GJ/hr. With the national
CCF the CEE would be 232.12 GJ/hr.

5.1.3 Labor analysis

For the labor analysis the total number of man hours for the process is needed. The
value for the conversion sector can be calculated with the value found in [11]. For
the process 20 people are necessary. This means that per hour 20 man hours are
needed. In the conversion sector people work 70 million hours per year. In this sector
5805.73 PJ is converted. Therefore, the labor conversion factor is 83.30 GJ/hr. So the
labor hours converted to labor exergy is 1658.78 GJ/hr.

44
5.1.4 Environmental remediation exergy

Calculating the
environmental Table 11: Worldwide capacity of carbon sequestration
remediation exergy Sequestration option Worldwide capacity
(ERE) is very Ocean 1000 GtC (Gigaton of carbon)
difficult. There are
Deep saline formations 100-1000GtC
many ways to
calculate it. The way Depleted oil and gas reservoirs 100 GtC
it is calculated here Coal seams 10-100 GtC
is the total emission Terrestrial 10 GtC
of CO2 times the
Utilisation <1 GtC/year
cost for CO2 capture
and sequestration (CCS). CCS is a short sighted method for decreasing the CO 2
emission. CCS captures the CO2 and injects it in geologic or oceanic sinks. In table 11
the worldwide capacity for sequestration is showed [33].

The costs can be converted to exergy units with the CCF. At the different
temperatures, different amounts of CO 2 will be emitted. Therefore, for every
temperature of the reformer, the ERE has to be calculated. Table 12 shows the ERE as
function of the reformer temperature. The cost for carbon capture and sequestration
is $ 48-102 per ton CO2 [34]. So, on average the cost per ton CO2 are $ 75 or € 55.

Table 12: CO2 emission at different reformer temperatures


Reformer CO2 emission CO2 emission CO2 emission CO2 emission
temperature [kmol/h] [ton/hr] [€/hr] GJ/hr]
800 °C 2629.5 115.7 6363.4 757.2
900 °C 1540.6 67.8 3728.3 443.7
1000 °C 1291.2 56.8 3124.7 371.8
1100 °C 1218.6 53.6 2949.0 350.9
1200 °C 1114.4 49.0 2696.9 320.9
1300 °C 1109.7 48.8 2685.5 319.6

5.1.5 Extended exergy analysis

Now, all the extended exergy accounting (EEA) terms are calculated. In table 13 the
data is summarized and the EEA efficiency is calculated.

45
Table 13: EEA efficiency at different reformer temperatures
Total exergy IN Total exergy OUT EEA
Reformer [GJ/hr] [GJ/hr] Efficiency
temperature FE CEE LEE ERE FE [-]
800 °C 10111.9 1759.4 1658.8 757.2 5071.8 0.355
900 °C 9721.0 1759.4 1658.8 443.7 5561.7 0.409
1000 °C 9750.4 1759.4 1658.8 371.8 5666.2 0.418
1100 °C 9652.4 1759.4 1658.8 350.9 5677.2 0.423
1200 °C 9613.2 1759.4 1658.8 320.9 5755.6 0.431
1300 °C 9627.7 1759.4 1658.8 319.6 5787.9 0.433

As the diagram in figure


Pie diagram of the division of the four terms at 1100 C
11 shows, the feedstock calculated with the CCF of the conversion sector
exergy has the largest
influence on the efficiency ERE
LEE
with a value of 72%. The 3%
12%
capital and labor part are
both much smaller with 13
CEE
and 12 % respectively. The
13%
influence of the
environmental
remediation is almost
negligible with 3%. FE
72%
The same calculation will
be done for the process,
but with the CCF of the Figure 11: Pie diagram of the division of the four terms at 1100 C
Netherlands instead of calculated with the CCF of the conversion sector
that of the conversion sector.

Table 14: EEA efficiency at different reformer temperatures with use of the CCF of the
Netherlands
Total exergy IN Total exergy OUT EEA
Reformer [GJ/hr] [GJ/hr] Efficiency
temperature FE CEE LEE ERE FE [-]
800 °C 10111.9 232.1 1658.8 99.9 5071.8 0.419
900 °C 9721.0 232.1 1658.8 58.5 5561.7 0.477
1000 °C 9750.4 232.1 1658.8 49.1 5666.2 0.485
1100 °C 9652.4 232.1 1658.8 46.3 5677.2 0.490
1200 °C 9613.2 232.1 1658.8 42.3 5755.6 0.498
1300 °C 9627.7 232.1 1658.8 42.2 5787.9 0.501

46
As the diagram in figure
12 shows, the influence Pie diagram of the division of the four terms at 1100
of the feedstock exergy C with the CCF of the Netherlands
increases and the
LEE ERE
influence of the CEE and
the ERE become almost 14% 0%
CEE
negligible. So the effect
2%
of the CCF on the
extended exergy is large,
the EEA efficiency
increases with 7%
because of the low
exergetic costs of the
capital and the
environment. FE
84%

Figure 12: Pie diagram of the division of the four terms at 1100 C with
the CCF of the Netherlands

47
5.2 The biomass to liquid process

Table 15 shows the process conditions and compositions of some important streams.

Table 15: Process conditions and composition of some important streams


Discription After Gasifi er After WGS After FT Product steam 1 Product stream 2 Tail gas
Stream number 7 17 21 23 24 25
Temperature [C] 900 330 240 240 -73 -73
Pressure [bar] 1 24 22.5 22.5 22.5 22.5
Total fl ow [kmol/hr] 72000.45 67971.69 43097.81 115.38 8486.33 34486.34
H2O 9085.50 864.00 7483.50 1.62 7483.50 0.00
H2 12505.50 16956.00 3393.00 0.00 1.76 3388.50
CO 12834.00 8352.00 1737.00 0.00 50.04 1683.00
CO2 7348.50 11641.50 0.00 0.00 0.00 0.00
N2 30217.50 30150.00 30150.00 0.68 751.50 29394.00
H2S 1.58 1.44 1.44 0.00 1.35 0.09
Cl2 7.07 5.94 5.94 0.00 5.85 0.09
CH4 0.81 0.81 17.96 0.00 1.98 15.98
C2H6 0.00 0.00 16.29 0.00 12.60 3.69
C3H8 0.00 0.00 15.48 0.00 15.08 0.05
C4H10 0.00 0.00 14.72 0.00 14.67 0.86
C5H12 0.00 0.00 13.95 0.00 13.10 0.09
C6H14 0.00 0.00 13.28 0.00 13.14 0.00
C7H16 0.00 0.00 12.60 0.00 12.56 0.00
C8H18 0.00 0.00 11.97 0.09 11.88 0.00
C9H20 0.00 0.00 11.39 0.09 11.25 0.00
C10H22 0.00 0.00 10.80 0.14 10.67 0.00
C11H24 0.00 0.00 10.26 0.23 10.04 0.00
C12H26 0.00 0.00 9.77 0.36 9.41 0.00
C13H28 0.00 0.00 9.27 0.50 8.73 0.00
C14H30 0.00 0.00 8.78 0.63 8.15 0.00
C15H32 0.00 0.00 8.37 0.99 7.25 0.00
C16H34 0.00 0.00 7.92 1.40 6.53 0.00
C17H36 0.00 0.00 7.56 1.76 5.81 0.00
C18H38 0.00 0.00 7.16 2.16 4.95 0.00
C19H40 0.00 0.00 6.80 2.66 4.14 0.00
C20H42 0.00 0.00 6.48 3.15 3.29 0.00
C21H44 0.00 0.00 6.17 3.56 2.57 0.00
C22H46 0.00 0.00 5.85 3.87 1.98 0.00
C23H48 0.00 0.00 5.54 4.14 1.40 0.00
C24H50 0.00 0.00 5.27 4.28 0.99 0.00
C25+ 0.00 0.00 83.34 83.12 0.23 0.00

5.2.1 Exergy analysis

This paragraph summarizes the results of the exergy analysis made by Tamara
Loonen [20].

The graph in figure 13 displays the irreversibilities for the different units at standard
conditions. The standard conditions are: Gasifier temperature is 900 °C, dry wood
content is 80% and α is 0.95.

48
3000.0

2500.0
Irrersibilities [GJ/hr]

2000.0

1500.0

1000.0

500.0

0.0

l
r

t
r

FT
r

ng

n
S

an
fie
ye

so

ov

io
G
ol

i
i

pl
at
Dr

es
an

W
as

Co

till

r
pr

re
cle
G

we
s
as

Di

Po
as

Co

CO
G

Units

Figure 13: Irreversibilities versus different units at standard conditions

The gasifier has the largest irreversibility and the other irreversibilities are hard to
compare because of the high value of the irreversibility of the gasifier. In figure 14,
the irreversibility of the gasifier is excluded, in order to compare the others.

1000.0

900.0

800.0
Irreversibilities [GJ/hr]

700.0

600.0

500.0

400.0

300.0

200.0
100.0

0.0
r r
ng
r S al FT n nt
ye ol
e i so G ov t io la
Dr Co an res W m illa rp
cle p re s t
we
as m 2 Di o
G as Co CO P
G
Units

Figure 14: Irreversibilities versus different units at standard conditions without the gasifier

As figure 14 as well as 15 shows, after the gasifier, the power plant has the largest
irreversibilities because it has an efficiency of 40%. The WGS reactor, gas cleaning
and the compressor unit have the smallest irreversibilities with respectively 1, 4 and
5 % of the irreversibilities without the gasifier, so they are almost negligible.

49
Irreversibilities divided over the units without the gasifier

Dryer
Power plant 11%
26%
Gas Cooler
16%

Gas cleaning
4%
Distillation Compressor
15% WGS 5%
1%
CO2 removal
FT
9% 13%

Figure 15: Irreversibilities divided over the units without the gasifier
Dry wood content
In figure 16 the graph is displayed in which the dry wood content is varied. Dry
wood contents of 70, 80 and 90% are chosen. Gasifier temperature and α were at
standard conditions.

3000

2500
Irreversibilities [GJ/h]

2000
70%

1500 80%
90%
1000

500

er er r ng r S al FT
n nt
ry ifi le
ni so G ov tio la
D a s oo a r es W ill a p
G C cl
e p re
m
ist er
as as om w
G G C O2 D P o
C

Figure 16: Irreversibilities versus the different units at various dry wood contents

Figure 17 shows the total irreversibilities at the different dry wood contents. The
graph shows a decrease in irreversibilities with an increase of dry wood content. This

50
can be
6800
explained by

Total irreversibilities
the fact that 6600

with a higher 6400


dry wood 6200
content the 6000
total flow of
5800
mass will be
5600
less. There is
70% 80% 90%
less work
needed for the Dry wood content
compressor
because of the
smaller gas Figure 17: Total irreversibilities versus different dry wood contents
volume. Moreover, there is less gas needed in the gasifier. However, in the dryer
more energy is needed. In the shift reactor more CO 2 will be formed because there is
more steam needed to apply to the H2/CO ratio. But in the gasifier less CO2 is formed.
The total emission of CO2 will be less at higher dry wood contents. Precise
simulations to calculate the total CO2 emission needed for the ERE were not
performed.

Gasifier temperature
In figure 18 the graph is displayed in which the gasifier temperature is varied.
Gasifier temperatures of 700, 800, 900 and 1000°C are chosen. Dry wood content and
α were at standard conditions.

3000
Irreversibilities [GJ/h]

2500
700 C
2000
800 C
1500
900 C
1000
1000 C
500

er er er g or S al FT io
n nt
ry s ifi ol n in ss G ov at p la
D a o a e W ll
G C cl
e pr re
m
ist
i er
as as om 2 w
G G C O D Po
C

Figure 18: Irreversibilities versus the different units at various gasifier temperatures

Figure 19 shows the total irreversibilities at the different gasifier temperatures. The
graph shows an increase in irreversibilities with an increase of gasifier temperature.
This can be explained by the fact that there is less syngas produced at higher
temperatures. For the gasifier more air is needed at high temperatures. The increase
in irreversibilities in the gas cooler is caused by the larger temperature difference and
the larger flow of products through the gas cooler because of the larger air stream.

51
The decrease of irreversibilities in the Fischer-Tropsch reactor is caused by the
decrease of
6600

Total irreversibilities [GJ/hr]


products that are
6400
formed there. With
6200
less products less
6000
reaction heat is
5800
produced which 5600
results in a smaller 5400
irreversibility. 5200
5000
Precise simulations 700 C 800 C 900 C 1000 C
to calculate the Gasifier temperature [C]
total CO2 emission
at the Fischer-
Tropsch reactor for Figure 19: Total irreversibilities versus gasifier temperatures
different temperatures, needed for the ERE, were not performed.

Table 16a and 16b shows the efficiencies at the different conditions.

Table 16: (a) Exergetic efficiency at different dry wood contents (b) Exergetic efficiency at
different gasifier temperatures
Dry wood content Efficiency
70% 0.334
80% 0.380
90% 0.406
Gasifier temperature Efficiency
700 °C 0.457
800 °C 0.401
900 °C 0.380
1000 °C 0.352

So the best conditions would be 90% dry wood content and a gasifier temperature of
700°C. The efficiency at the best conditions is regrettably not calculated in [20].

5.2.2 Capital analysis

The wood used in this process is recovered in Canada. This wood has to be
transported to Western Europe, so energy (and thus money) is needed to transport
the wood. In [30] costs for short range and long range transport are given. Short
range transport is needed because all the wood has to be collected at the harbor from
different biomass sources. An average distance of 186.9 km is calculated [30] for the
short range transport and 6000 km is assumed for the long range transport over sea
by a long range carrier.

52
The cost for the short range transport is 1.8 €/GJ moved. The cost for the long range
transport is 0.2 €/GJ moved [30]. The energy density of wood is 9.4 GJ/ton. Table 17
displays the total cost for the transport for 1000 ton wood/hr.

Table 17:Transportation costs


  Costs [€/hr]
Transport by truck ( 186.9 km) 16920
Transport by long range boat ( 6000 km) 1880
Total transportation costs 18800

Table 18 shows the investment cost for all the apparatuses.

Table 18: Total investment costs


  Total investment Yearly write-off Cost/hr
Dryer € 5,678,000.00 € 864,760.53 € 98.72
Gasifier € 54,000,000.00 € 8,224,210.70 € 938.84
Compressor € 187,000,000.00 € 28,480,137.06 € 3,251.16
WGS reactor € 57,000,000.00 € 8,681,111.30 € 990.99
FT Reactor € 57,000,000.00 € 8,681,111.30 € 990.99
Power plant € 1,900,000.00 € 289,370.38 € 33.03
Total costs € 362,578,000.00 € 55,220,701.26 € 6,303.73

So the total capital cost is € 18800+ € 6304= € 25104/hr. With a capital conversion
factor of 0.119 GJ/€ the CEE is € 25104 /hr * 0.119GJ/€= 2987 GJ/hr. When the CCF of
the Netherlands is used the CEE would be € 25104* 0.0157GJ/€= 394 GJ/hr

5.2.3 Labor analysis

For the labor analysis the total man hours for the process are needed. The value for
the conversion sector can be calculated with the value found in [11]. Also for this
process 20 people will be necessary. So the labor exergy is the same as for the gas-to
liquid process and will be 1658.78 GJ/hr

5.2.4 Environmental remediation exergy

In this process (at standard conditions) there are two points where CO 2 emission
takes place. In the CO2 removal unit the CO2 is removed and in the power plant CO 2
will be formed. In the CO2 removal unit the amount of CO2 removed is 11641.5
kmol/hr. In the power plant 1706.4 kmol CO 2/hr is emitted. So in total 13347.9
kmol/hr of CO2 is emitted. This is equal to 587 ton CO 2 per hour and with a price of €
55 for the carbon capture and sequestration this emission costs € 32302 per hour.
With a capital conversion factor of 0.119 GJ/€ the environmental remediation exergy
is 3844 GJ/hr.

53
5.2.5 Extended exergy analysis

As table 19 and figure 20 show the influence of the CEE (calculated with the CCF of
the conversion sector), LEE and the ERE terms are not negligible in this case. These
terms have a large influence on the efficiency.

Table 19: EEA efficiency at different gasifier temperatures


Gasifier Total exergy IN     Total exergy OUT EEA
temperature FE CEE LEE ERE FE efficiency
700 °C 10107.0 2987 1658.8 3844.0 4617.0 0.248
800 °C 9982.4 2987 1658.8 3844.0 4005.0 0.217
900 °C 9893.3 2987 1658.8 3844.0 3762.0 0.205
1000°C 9777.2 2987 1658.8 3844.0 3438.0 0.188

The feedstock part is in this


process only the half of the Pie diagram of the division of the four terms for
the biomass to biodiesel process at standard
total exergy. The ERE part is
conditions
much larger compared with
ERE
the gas to liquid process. This
21%
is because of the high CO 2
emission in this process. The
ERE part of the other gasifier
temperatures are not totally LEE
FE
correct because the CO2 9%
54%
emission is not calculated at
these temperatures. Three
quarters of the CEE term is CEE
due to the transportation cost. 16%

When in the future the


biomass can be found in
Western Europe the CEE term Figure 20: Pie diagram of the division of the four terms for
will shrink to 750 GJ/hr and the biomass to biodiesel process at standard conditions
the EEA efficiency will
increase 3%.

54
6 DISCUSSION AND
RECOMMENDATIONS

55
56
In table 20 the exergy efficiency and extended exergy accounting efficiency are
summarized for the gas to liquid and the biomass to liquid processes. The efficiencies
are showed at the best conditions. For the gas to liquid process at a reformer
temperature of 1300 °C and for the biomass to liquid process the gasifier temperature
of 700°C and a dry wood content of 20%.

Table 20: Summary of the efficiencies When the two processes, the gas to
  GTL BTL liquid and the biomass to liquid, are
compared the first thing that stands
Exergetic efficiency 60.1% 45.7%
out are the better efficiencies of the gas
EEA (conversion sector) 43.4% 24.8%
to liquid process. The total input of
EEA (NL) 50.1% 28.8% feedstock exergy is almost the same
but the total output is smaller in the biomass to biodiesel process. This is because of
the larger stream of tail gas going into the power plant. The power plant has a
relatively small efficiency so the larger the stream into the power plant the smaller
the output of feedstock exergy.

The second remarkable point is the large ERE value in the biomass to biodiesel
process. This has a large impact on the efficiency so if this value can be reduced by
more research this would certainly help to improve the efficiency. In the biomass to
liquid process much more CO2 is emitted than in the gas to liquid process. This is
because of the element distribution of the feedstock. In methane, the hydrogen to
carbon ratio is 4. In wood the hydrogen to carbon ratio is 1.46. So relatively the wood
contains much more carbon. And if the carbon can not be used for forming a liquid,
it is emitted. This explains the large value of the ERE in the biomass to liquid process
in comparison with the gas to liquid process.

In the CEE and the LEE these processes are comparable, the biomass to biodiesel
process has a larger CEE but when in the future the biomass can be collected in
Western Europe the CEE value could decrease with 75%. One required condition for
the decrease of the CEE is that the large amount of wood should be located in one
place - and not distributed as in Canada – then the transport cost would be
negligible.

The large difference between the capital conversion factor of the Netherlands and the
capital conversion factor of the conversion sector has also a little influence on the
EEA efficiency. Until now, no one has calculated with the capital conversion factor
of a specific sector. This makes the calculations in this thesis very new, so much more
research on this topic is needed to tell if these numbers have an acceptable value

Until this point in this master thesis the CO2 emission of the biomass to liquid
process is calculated and used for calculating the EEA efficiency. But if you take a
deeper look into the CO2 cycle it could be stated that the biomass to liquid process is
CO2 neutral. The CO2 that is emitted during the process is captured during the
process of photosynthesis. So if the process is CO 2 neutral the ERE term has to be

57
zero and the efficiency would increase with 6.5% to 31.3%. This is a relative increase
of 20%, so this can not be ignored.

But at this time, the EEA efficiency of the gas to liquid process is still better than the
EEA efficiency of the biomass to biodiesel process. With more research the EEA
efficiency of the biomass to liquid process should increase. In the end the fact is that
natural gas sources will deplete, so the change has to be made to biomass.

58
Acknowledgement

This study was performed at and supported by the environmental technology group
of the department of Chemical engineering and Chemistry of the Eindhoven
University of Eindhoven, the Netherlands.

I would like to thank dr. ir. Krzysztof Ptasinski for giving me the opportunity to
perform this graduate internship at his group. Furthermore I want to thank
everybody of Matrix 1.40 for their support and advice.

59
60
References

[1] Ulrich Grober, Der Erfinder der Nachhaltigkeit (German), Die Zeit Nr. 48/
25.11.1999, page 98

[2] J. García-Serna, L. Pérez-Barrigón, M.J. Cocero, New trends for design towards
sustainability in chemical engineering: Green engineering, Chemical Engineering
Journal 133 (2007) 7–30.

[3] http://www.greencarcongress.com/2007/03/eu_leaders_agre.html

[4] Clausius, R. (1865). "Mechanical Theory of Heat - with its Application to the
Steam Engine and the Physical Properties of Bodies." London: John van Voorst.

[5] Z. Rant (1956). "Exergie, ein neues Wort fur "Technische Arbeitsfahigkeit"
(Exergy, a new word for "technical available work")". Forschung auf dem Gebiete des
Ingenieurwesens 22: 36–37.

[6] J.W. Gibbs (1873). "A method of geometrical representation of thermodynamic


properties of substances by means of surfaces: reprinted in Gibbs, Collected Works,
ed. W. R. Longley and R. G. Van Name (New York: Longmans, Green, 1931)".
Transactions of the Connecticut Academy of Arts and Sciences 2: 382–404.

[7] http://www.setac.org/

[8] J. Szargut, D.R. Morris, Cumulative exergy loss associated with the production of
lead metal, Int. J. Energy Res. 14 (6) (1990) 605–616.

[9] M.N.Koymans, Inquiry into possibilities for applications of exergy-based methods


on sector level, The performance of the Dutch energy sector, MSc Thesis, Eindhoven
University of Technology, Eindhoven, 2002.

[10] Enrico Sciubba, From Engineering Economics to Extended Exergy Accounting:


the path from “Monetary cost” to “Resource-Based Value”, ECOS, 2001, Istanbul.

[11] M. van der Stelt, Performance of the Dutch Society, MSc Thesis, Eindhoven
University of Technology, Eindhoven, 2006.

[12] CBS 2003 Online database of statistics, www.stat.cbs.nl

[13] Waren D.Seider, J.D.Seader, Daniel R. Lewin (1999). Product and process design
principles, Wiley

[14] Earl Cook, The flow of energy in an Industrial society, Scientific American, 224, 3
(Sept. 1971, p.134

[15] www.forestinfo.org/Discover/images/Energy.gif

61
[16] Simon van der Heijden, Exergy Analysis of Hydrogen Production Methods from
Biomass, MSc Thesis ,Eindhoven University of Technology, Eindhoven, May 2005.

[17] Analysis of the sustainability of using wastes in the Brazilian power industry,
Luciano Basto Oliveira, Maria Silvia Muylaert de Araujo, Luiz Pinguelli Rosa,
Martha Barata, Emilio Lebre La Rovere, renewable and sustainable energyreviews,
13 September 2006

[18] http://icischemicalbusines.com

[19] Mark J. Prins, Thermodynamic analysis of biomass gasification and torrefaction,


Eindhoven University of Technology, Eindhoven, 2005.

[20] Tamara Loonen, Exergie-analyse van de productie van Fischer-Tropsch


vloeistoffendoor vergassing van biomassa (Dutch),MSc Thesis ,Eindhoven University
of Technology, Eindhoven, mei 2001.

[21] M. A. Rosen, Thermodynamic investigation of hydrogen production by steam-


methane reforming, October 1990.

[22] http://www.shell.com

[23] http://icischemicalbusines.com

[24] Focus on Catalysts Volume 2003, Issue 10 , October 2003, Page 7.

[25] Martin Wietschela,_, Ulrike Hasenauera, Arend de Groot, Development of


European hydrogen infrastructure scenarios—CO2 reduction potential and
infrastructure investment, Energy Policy 34 (2006) 1284–1298

[26] Carmine L.Iandoli, Roger Hansen, Signe Kjelstrup, Exergy analysis of a gas to
liquid plant, December 2006

[27] http://www.ecn.nl/fileadmin/ecn/units/bio/Biomassa/ft-figure.jpg

[28] Wade A. Amos, Report on Biomass Drying Technology, National Renewable


Energy Laboratory, November 1998.

[29] R. van Ree, A. Faaij, B. Meuleman, ‘Long term perspectives of biomass


integrated gasification with combined cycle technology, ECN and Utrecht
University, 1998.

[30] Oscar P.R. van Vliet, André P.C. Faaij, Wim C.Turkenburg, The future of Fischer-
tropsch diesel production in a well-to-wheel perspective: a carbon and energy flow
analysis, Utrecht University, Copernicus Institute, 2006

62
[31] Aspen Icarus 2004

[32] Carlo N. Hamelinck, André P.C. Faaij, Herman den Uil, Harold Boerrigter,
Production of FT transportation fuels from biomass; technical options, process
analysis and optimization and development potential, Energy 29 (2004) 1743–1771.

[33] Caleb Stewart, Mir-Akbar Hessami, a study of methods of carbon dioxide


capture and sequestration––the sustainability of a photosynthetic bioreactor
approach, Energy Conversion and Management 46 (2005) 403–420.

[34] John Davison, Performance and costs of power plants with capture and storage
of CO2, Energy 32 (2007) 1163–1176.

[35] http://www.exergie.nl/ExergieSchat%20internetversie%201.0.html

63
64
Appendix 1: Spreadsheet of calculation of exergetic efficiency

In table 21 the spreadsheet is displayed which is used to calculate the exergetic


efficiency.

Table 21: Spreadsheet of calculation of exergetic efficiency


Reformer
Inlet Outlet
Stream Component Flow Exergy Stream Component Flow Exergy
kmol/hr GJ/hr kmol/hr GJ/hr
1 O2 6300.0 0.0 4 N2 23700.0 17.1
N2 23700.0 0.0 7 CO 12345.8 3644.3
2 CO 71.4 19.6 CO2 53.7 2.8
CH4 12342.0 10236.7 CH4 14.0 12.2
Total IN 10256.3 H2O 218.3 7.6
H2 24437.8 6178.2
W (ASU) -1221.0 GJ/hr Total OUT 9862.2
Q (reformer) -357.0 GJ/hr
Qex (reformer) -279.5 GJ/hr
Q (heater) 1071.0 GJ/hr Irreversibilities 2174.2 GJ/h
Qex( heater) 838.5 GJ/hr Rendement 0.799

Gas Cooling
Inlet Outlet
Stream Component Flow Exergy Stream Component Flow Exergy
kmol/hr GJ/hr kmol/hr GJ/hr
7 CO 12345.8 3644.3 8 CO 12345.8 3414.4
CO2 53.7 2.8 CO2 53.7 1.2
CH4 14.0 12.2 CH4 14.0 11.6
H2O 218.3 7.6 H2O 218.3 2.6
H2 24437.8 6178.2 H2 24437.8 5762.1

Total IN 9845.1 Total OUT 9191.9

Q (heater) -992.2 GJ/hr Irreversibilities 38.6 GJ/h


Qex( heater) -614.6 GJ/hr Rendement 0.996

Compressor
Inlet Outlet
Stream Component Flow Exergy Stream Component Flow Exergy
kmol/hr GJ/hr kmol/hr GJ/hr
8 CO 12345.8 3414.4 9 CO 12345.8 3518.5
CO2 53.7 1.2 CO2 53.7 1.6
CH4 14.0 11.6 CH4 14.0 11.8
H2O 218.3 2.6 H2O 218.3 4.4
H2 24437.8 5762.1 H2 24437.8 5966.5
Total OUT 9502.8
Total IN 9191.9
Irreversibilities 570.7 GJ/h
W (compressor) -881.5 GJ/hr Rendement 0.938

65
WGS
Inlet Outlet
Stream Component Flow Exergy Stream Component Flow Exergy
kmol/hr GJ/hr kmol/hr GJ/hr
9 CO 12345.8 3518.5 10 CO 12133.3 3459.1
CO2 53.7 1.6 CO2 266.0 8.2
CH4 14.0 11.8 CH4 14.0 11.8
H2O 218.3 4.4 H2O 5.8 0.1
H2 24437.8 5966.5 H2 24650.3 6020.8

Total IN 9502.8 Total OUT 9500.0

Irreversibilities 2.8 GJ/h


Rendement 1.000

FT Reactor
Inlet Outlet
Stream Component Flow Exergy Stream Component Flow Exergy
kmol/hr GJ/hr kmol/hr GJ/hr
10 CO 12133.3 3459.1 12 CO 35403.8 10089.8
CO2 266.0 8.2 CO2 266.2 8.1
CH4 14.0 11.8 CH4 2183.5 1834.3
H2O 5.8 0.1 H2O 11720.0 236.9
H2 24650.3 6020.8 H2 0.0 0.0
17 CO 34984.7 9976.5 C2H6 117.3 176.4
CH4 2052.5 1676.9 PROPA-01 83.3 180.1
H2 0.0 0.0 N-BUT-01 75.3 211.9
C2H6 24.6 37.0 N-PEN-01 69.9 242.8
C3H8 1.1 2.4 N-HEX-01 65.4 270.1
N-HEP-01 61.5 293.0
Total IN 21192.7 N-OCT-01 57.9 314.0
N-NON-01 54.6 332.4
N-DEC-01 51.6 346.6
N-UND-01 48.8 360.1
N-DOD-01 46.2 371.7
N-TRI-01 43.8 380.8
N-TET-01 41.5 387.7
N-PEN-02 39.3 392.9
N-HEX-02 37.3 396.5
N-HEP-02 35.4 398.7
N-OCT-02 33.5 399.6
N-NON-02 31.8 399.4
N-EIC-01 30.2 412.3
N-HEN-01 28.6 409.4
N-DOC-01 27.2 405.7
N-TRI-02 25.8 401.2
N-TET-02 24.5 396.2

Total OUT 20048.5


Q (FT) -1462.8 GJ/hr
Qex( FT) -613.1 GJ/hr Irreversibilities 531.2 GJ/h
Rendement 0.974

66
Separators
Inlet Outlet
Stream Component Flow Exergy Stream Component Flow Exergy
kmol/hr GJ/hr kmol/hr GJ/hr
12 CO 35403.8 10089.8 14 H2O 11720.0 10.5
CO2 266.2 8.1 24 N-HEP-02 0.0 0.4
CH4 2183.5 1834.3 N-OCT-02 33.5 402.7
H2O 11720.0 236.9 N-NON-02 31.8 403.1
H2 0.0 0.0 N-EIC-01 30.2 416.4
C2H6 117.3 176.4 N-HEN-01 28.6 413.7
PROPA-01 83.3 180.1 N-DOC-01 27.2 410.3
N-BUT-01 75.3 211.9 N-TRI-02 25.8 406.1
N-PEN-01 69.9 242.8 N-TET-02 24.5 401.3
N-HEX-01 65.4 270.1 25 N-NON-01 54.6 331.9
N-HEP-01 61.5 293.0 N-DEC-01 51.6 347.4
N-OCT-01 57.9 314.0 N-UND-01 48.8 360.0
N-NON-01 54.6 332.4 N-DOD-01 46.2 371.2
N-DEC-01 51.6 346.6 N-TRI-01 43.8 380.2
N-UND-01 48.8 360.1 N-TET-01 41.5 387.2
N-DOD-01 46.2 371.7 N-PEN-02 39.3 392.5
N-TRI-01 43.8 380.8 N-HEX-02 37.3 396.4
N-TET-01 41.5 387.7 N-HEP-02 35.3 398.3
N-PEN-02 39.3 392.9 26 N-BUT-01 75.3 210.7
N-HEX-02 37.3 396.5 N-PEN-01 69.9 241.5
N-HEP-02 35.4 398.7 N-HEX-01 65.4 268.6
N-OCT-02 33.5 399.6 N-HEP-01 61.5 292.0
N-NON-02 31.8 399.4 N-OCT-01 57.9 312.8
N-EIC-01 30.2 412.3 27 CO 389.4 107.4
N-HEN-01 28.6 409.4 CO2 266.2 29.8
N-DOC-01 27.2 405.7 CH4 131.0 108.8
N-TRI-02 25.8 401.2 H2 0.0 0.0
N-TET-02 24.5 396.2 C2H6 92.7 138.5
PROPA-01 82.2 176.8
Total IN 20048.5
17 CO 34984.7 9976.5
CH4 2052.5 1676.9
Q (heaterB8) -954.4 GJ/hr H2 0.0 0.0
Qex( heaterB8) -400.0 GJ/hr C2H6 24.6 37.0
Q (heaterB20) -263.0 GJ/hr C3H8 1.1 2.4
Qex( heaterB20) -97.3 GJ/hr
Q (heaterB10) 224.6 GJ/hr
Qex( heaterB10) 109.8 GJ/hr
Q (heaterB12) -35.7 GJ/hr
Qex( heaterB12) -9.9 GJ/hr
Q (heaterB15) -14.8 GJ/hr Total OUT 19809.2
Qex( heaterB15) -1.9 GJ/hr
Q (RebB4) 445.0 GJ/hr
Qex(RebB4) 170.4 GJ/hr
Q (CondB4) 418.6 GJ/hr
Qex(CondB4) 223.7 GJ/hr
Q (RebB11) 115.0 GJ/hr
Qex(RebB11) 7.6 GJ/hr
Q (CondB11) 111.0 GJ/hr
Qex(CondB11) 39.2 GJ/hr
Q (RebB14) 78.9 GJ/hr
Qex(RebB14) 21.8 GJ/hr
Q (CondB14) 75.4 GJ/hr Irreversibilities 303.9 GJ/h
Qex(CondB14) 1.2 GJ/hr Rendement 0.985

67
Powerplant
Inlet Outlet
Stream Component Flow Exergy Stream Component Flow Exergy
kmol/hr GJ/hr kmol/hr GJ/hr
27 CO 389.4 107.4 Electricity 224.5
CO2 266.2 29.8 Total OUT 224.5
CH4 131.0 108.8
H2 0.0 0.0 CO2 1218.6
C2H6 92.7 138.5
PROPA-01 82.2 176.8
Irreversibilities 336.7 GJ/h
Total IN 561.2 Rendement 0.400

68
Appendix 2: Exergetic values of the components
In table 22 the exergetic values which were necessary for the exergy calculations are
displayed [35]. The boxes in grey were not necessary.

Table 22: Exergetic values of different components at various conditions


Exergy (GJ/kmol)
Temperature [K] 298 1073 1173 1273 1373 1473 1573 513 513 521 150 298 641 463 294 186
Pressure [bar] 1 1 1 1 1 1 1 1 30 30 30 30 2 1 1 1
N2 0.0007196
CO 0.2750017 0.2874273 0.2899117 0.2925031 0.2951833 0.2979343 0.3007374 0.2765661 0.2849932 0.2850946 0.2851663 0.275854
CO2 0.0395626 0.0436467 0.0479213 0.052364 0.0569584 0.0616959 0.0221175 0.0305461 0.0306988 0.1118049
CH4 0.829421 0.8530742 0.8586646 0.8646622 0.8710232 0.8777062 0.8846738 0.8316744 0.8400822 0.8402422 0.8170061 0.8304362
H2O 0.025031 0.0281723 0.0314987 0.0349969 0.0386541 0.0424575 0.0117923 0.0202162 0.020336 0.0008993
H2 0.2458236 0.2480585 0.2503908 0.2528136 0.2553204 0.2579049 0.2357864 0.2441504 0.2442488 0.2441144 0.2350336
C2H6 1.504461 1.5030558 1.4935815
C3H8 2.1629722 2.1606768 2.150903
C4H10 2.8152823 2.7998027
C5H12 3.4726536 3.4545413
C6H14 4.1287121 4.105984
C7H16 4.767478 4.751938
C8H18 5.4237563 5.4020827
C9H20 6.0830118 6.0737101
C10H22 6.7116911 6.7282426
C11H24 7.3721606 7.3719454
C12H26 8.0402384 8.028981
C13H28 8.6967306 8.6827116
C14H30 9.3452852 9.3333379
C15H32 9.9913862 9.9831754
C16H34 10.635549 10.63168
C17H36 11.277773 11.367619 11.27885
C18H38 11.918058 12.021172
C19H40 12.556406 12.673672
C20H42 13.660645 13.797639
C21H44 14.294423 14.447655
C22H46 14.926262 15.096618
C23H48 15.556164 15.744526
C24H50 16.184126 16.391381

69

Você também pode gostar