Produccion de Hidrogeno 2

SIMULATION AND OPTIMIZATION OF ETHANOL AUTOTHERMAL
REFORMER FOR FUEL CELL APPLICATIONS
MUHAMAD SYAFIQ BIN ADAM
UNIVERSITI TEKNOLOGI MALAYSIA
SIMULATION AND OPTIMIZATION OF ETHANOL AUTOTHERMAL

REFORMER FOR FUEL CELL APPLICATIONS
MUHAMAD SYAFIQ BIN ADAM
A report submitted in partial fulfilment of the

requirements for the award of the degree of
Bachelor of Engineering (Chemical)
Faculty of Chemical Engineering and Natural Resources Engineering

Universiti Teknologi Malaysia
NOVEMBER 2006
iii
To my beloved mother and father
iv
ACKNOWLEDGEMENTS
Alhamdullilah. Finally my first thesis was finished. Thanks to God because

all of His merciless and the knowledge that was given, I did my work successfully.
An honour and respect to the Prophet Muhamad SAW. Peace be upon him.
I would like to thank to my supervisor; En. Mohd Kamaruddin. A word thank

you cant describe all of his guidance and encouragement that showed to me during
the progresses of this thesis. All the knowledge that I learned from him will come in
handy at the future.
I also wanted to thank my family for the moral support. Especially to my

parents, for effort and support those drive me to this level. This thesis was dedicated
to them.
Finally, to all of my friends that contributed to this thesis. Thank you very
much to all of them that help me either direct or indirect.
ABSTRACT
Fuel cell application from hydrogen was one of alternative energy that
being studied and widely accepted in industry. This case study focused on
optimization of hydrogen production for fuel cell applications. In this case study,
ethanol was chosen as a raw material and with autothermal reforming as a process of
produce hydrogen. Using a commercial dynamic flow sheeting software, HYSYS
3.2, the process of hydrogen production was successfully simulated. In this research,
fuel processor consists of an autothermal reactor, three water gas shift reactors and a
preferential oxidation reactor was successfully developed. The purpose of this case
study is to identify the effect of various operating parameters such as air-to-fuel
(A/F) ratio and steam-to-fuel (S/F) ratio to get the optimum hydrogen production
while made carbon monoxide lower than 10 ppm. From the results, an optimum A/F
and S/F ratio are 5.5 and 1.5, respectively to produce 34 % of hydrogen and 10.055
ppm of CO. Under these optimum conditions, 83.6% of fuel processor efficiency was
achieved.
vi
ABSTRAK
Penggunaan sel bahan api daripada hidrogen merupakan salah satu tenaga
yang masih dikaji dan diterima dalam kebanyakan industri. Kajian ini memfokuskan
tentang pengeluaran hidrogen untuk penggunaan sel bahan api secara dinamik.
Dalam kajian ini, etanol dipilih sebagai bahan mentah dan pembentukan autoterma
(auto thermal reforming) merupakan proses untuk menghasilkan hidrogen. Dengan
menggunakan perisian HYSYS 3.2, proses pengeluaran hidrogen ini berjaya
dilakukan secara simulasi. Dalam kajian ini, pemproses minyak mengandungi reaktor
autoterma,, tiga reaktor anjakan air gas dan reaktor pilihan pengoksidaan telah
berjaya dihasilkan. Kajian ini bertujuan untuk mengenalpasti kesan pengandelaian
parameter yang berlainan seperti ratio udara-ke-minyak (A/F) dan ratio stim-keminyak (S/F) untuk mendapatkan pengeluaran hydrogen yang optimum sementara
CO dihasilkan rendah dari 10 ppm. Daripada keputusan ujikaji, nilai ratio A/F dan
S/F yang optima adalah 5.5 dan 1.5 masing-masing. Dengan ratio tersebut,34%
hydrogen dan 10.055 ppm CO dapat dihasilkan. Dibawah keadaan pengoptimaan ini,
sebanyak 83.6 % kecekapan pemproses minyak didapati.
vii
LIST OF CONTENTS
CHAPTER
II
TITLE
PAGE
Tittle Page
Declaration
ii
Dedication
iii
Acknowledgements
iv
Abstract
Abstrak
vi
List of Contents
vii
List of Figures
xi
List of Tables
xiii
List of Symbols
xiv
INTRODUCTION
1.1
Background Research
1.2
Problems Statement
1.3
Research Objective
1.4
Scopes of study
1.5
Thesis Organizations
LITERATURE REVIEW
2.1
Introduction
2.2
Hydrogen Production for Fuel Cell Application in
General
2.2.1
Natural Gas
viii
2.2.1.1 Methane
2.2.1.2 Ethane
2.2.1.3 Propane
2.2.1.4 Butane
2.2.2 Alcohol
2.2.3
2.3
2.4
III
2.2.2.1 Methanol
10
2.2.2.2 Ethanol
10
2.2.2.3 Propanol
11
Petroleum Fractional
12
2.2.3.1 Kerosene
12
2.2.3.2 Gasoline
12
2.2.3.3 Diesel
13
Hydrogen Production for Fuel Cell from Ethanol
13
2.3.1
Steam Reforming
14
2.3.2
Partial Oxidation
15
Steam Reforming of Ethanol for Hydrogen

Production
16
2.5
Optimization simulation of Hydrogen Production
17
2.6
Summary
17
METHODOLOGY
3.1
3.2
Research Tools
18
3.1.1
18
Aspen HYSYS
Research Activities
19
3.2.1
Data Collection
19
3.2.2
Base Case Stoichiometry
19
3.2.3 Base Case Validation
21
3.2.4
21
Auto-thermal Reactor Optimization
3.2.5 Heat Integration
21
3.2.6
Carbon Monoxide Clean Up
22
3.2.6.1 Water Gas Shift
22
3.2.6.2 Preferential Oxidation
22
Plant Wide Optimization
23
3.2.7
ix
3.3
IV
3.2.7.1 ATR Optimization
23
3.2.7.2 Water Gas Shift Optimization
23
3.2.7.3 Preferential Oxidation Optimization
24
3.2.8
Temperature and Component Profile
24
3.2.9
Fuel Processor Efficiency
24
Summary
25
SIMULATION AND OPTIMIZATION OF HYDROGEN

PRODUCTION PLANT FROM ETHANOL FOR FUEL CELL
APPLICATION
4.1
Process Description of Hydrogen Production from

Ethanol
4.2
4.3
26
Modelling and Simulation of Hydrogen Production

From Ethanol for Fuel Cell
27
4.2.1
Thermodynamic Properties
31
4.2.2
Physical Properties
32
4.2.3
Integration Algorithm
33
4.2.4
Mathematical Modelling of the Reactor

Operating
33
4.2.4.1 Linear and Non-Linear System
33
4.2.4.2 Material Balance
34
4.2.4.3 Component Balance
35
4.2.4.4 Energy Balance
36
4.2.5
Degree of Freedom Analysis
38
4.2.6
Analysis of Optimization Response
38
Summary
39
RESULTS AND DISCUSSION

5.1
Results for Base Case Study
40
5.2
Results for Validation
43
5.3
Results for Heat Integration
44
5.4
Results for Carbon Monoxide Clean Up
46
5.4.1
46
Water Gas Shift
5.5
VI
5.4.2 Preferential Oxidation
47
48
5.5.1 ATR Optimization
49
5.5.2
Water Gas Shift Optimization
50
5.5.3
Preferential Oxidation Optimization
53
5.6
Temperature Profile of fuel Processor System
55
5.7
Component Profile of the Fuel Processor System
56
5.8
57
5.9
Summary
57
CONCLUSION AND RECOMMENDATIONS

6.1
Summary
58
6.2
Conclusion
59
6.3
Recommendation
59
REFERENCES
61
APPENDIX
APPENDIX A Final result of simulation HYSYS 3.2
66
xi
LIST OF FIGURES
FIGURE NO.
TITLE
3.1
Algorithm for methodology.
4.1
The operation conditions for the major unit
PAGE
25
operation
27
4.2
The whole plant system by Aspen HYSYS 3.2
29
4.3
HYSYS simulation environment
30
4.4
Reactor operating
35
4.5
Block diagram of the simulation of hydrogen

plant using Aspen HYSYS 3.2
39
5.1
Process flow diagram of the base case
41
5.2
The heater attachment on the ATR reactor
45
5.3
The heaters at the feed streams were exchange

with the heat exchanger
46
5.4
The WGS reactor
47
5.5
The PROX reactor
48
xii
5.6
Temperature of ATR vapour for varies air feed

molar flow
5.7
Molar flow of CO and H2 effluent for varies

air feed molar flow
5.8
51
Temperature to ATR outlet for varies water feed

molar flow
5.10
50
Molar flow of CO and H2 effluent for varies

water feed molar flow
5.9
49
52
CO Molar flow in PROX effluent for varies air

feed molar flow
54
5.11
Temperature profile for the whole unit operation
55
5.12
H2 and CO profile for the whole unit operation
56
xiii
LIST OF TABLES
TABLE NO.
TITLE
PAGE
4.1
Physical property of the component
32
5.1
Molar flow of ATR effluent for base case
43
5.2
Validation for simulation effluent compare

with calculated effluent
5.3
Effluent molar flow after water gas shift

reaction for each reactor
5.4
52
Molar flow of the effluent after optimization

for ATR,HTS, MTS and LTS.
5.7
48
Molar flow of the effluent before optimization

for ATR,HTS, MTS and LTS.
5.6
47
Effluent molar flow after preferential

oxidation reaction
5.5
44
53
Molar flow of the effluent before and after

optimization for PROX
54
xiv
LIST OF SYMBOLS
Heat transfer area
Parameter, cubic equation of state
Parameter, cubic equation of state
Concentration
Volumetric flow rate
Local acceleration of gravity
Molar or specific enthalpy
Step size
Kinetic energy
Mass flow rate
MW
Molecular weight
Nm
Number of independent variables
Nom
Number of manipulated variables with no steady state effect
Noy
Number of variables that need to be controlled from Nm
Nss
Number of variables needed to be specified
Absolute pressure
Po
Reference pressure
Pci
Critical pressure, species i
Pri
Reduced pressure, species i
Heat
Qr
Heat generated by reaction
Universal gas constant
Rate of reaction
Time
Internal energy
Volume
xv
Process Variable
Greek letters
Function, cubic equation of state
Error
Viscosity
Density
Potential energy
Acentric factor
Abbreviations
ATR
Auto thermal reforming
ca.
at approximate
CO
Carbon Monoxide
CO2
Carbon Dioxide
et al.
et alias: and others
etc.
et cetera
H2
Hydrogen
HTS
High Temperature Shift
LTS
Lower Temperature Shift
PROX
Preferential Oxidation
MTS
Medium Temperature Shift
WGS
Water Gas Shift
CHAPTER
INTRODUCTION
1.1
Background Research
Hydrogen was expected to become an important energy carrier for

sustainable energy consumption with a significantly reduced impact on the
environment. Hydrogens benefit and disadvantages differ from the fossil fuels
common place in advanced energy utilizing society. It is because characteristics of
hydrogen that cheap, easy to obtain, high efficiency, virtually silent operation and
less pollutant emissions. (Fuel cell store website, 2006)
From that perspective, researcher over the world tries to make use the
hydrogen as an alternative energy by converting into fuel cell. Hydrogen as fuel cell
technology currently needed in large quantities, and is projected to be the fuel of
choice for a number of advanced technologies that are being pursued. Fuel cell will
supply the energy that a global society requires to support the growing number of
people that demanding on fuel cell technology using hydrogen. (Fuel cell store
website, 2006)
For that purpose, some fossil fuels which have high hydrogen to oxygen ratio
were the best candidates to produce hydrogen. The more hydrogen present and the
fewer extraneous compounds was the idea to get it. One of the methods which
commonly being used was the steam reforming. Other established methods include
partial oxidation of residual oil, coal gasification, water electrolysis and etc. The new
2
technologies such as high-temperature electrolysis of steam, thermal cracking of
natural gas, thermo chemical water splitting, solar photovoltaic water electrolysis,
and plasma decomposition of water is still investigated its efficiency. These
technologies can be classified as thermal, thermo chemical, electrochemical,
photochemical, and plasma chemical methods. (Fuel cell store website, 2006)
Seven common fuels are the postulated hydrogen sources studied in this work
alcohol, natural gas, gasoline, diesel fuel, aviation jet fuel, and hydrogen itself.
Among the bio-fuel candidates for carriers of hydrogen, ethanol is of particular
interest because its low toxicity, low production costs, the fact that is a relative
clean fuel in terms of composition, relatively high hydrogen content and availability
and ease of handling. Hydrogen can be obtained directly from ethanol by two main
processes; partial oxidation and steam reforming. (Fuel cell store website, 2006)
1.2
Problem Statement
In reality, chemical plants are never truly at steady state. Feed and
environmental disturbances, heat exchanger fouling, and catalytic degradation
continuously upset the conditions of a smooth running process. Optimization
simulation can help researcher to make better design, optimize, and operate process
or refining plant. In this research, ethanol is the main focus to study the steady state
behaviour. Furthermore, the optimization is the main case study that will make more
yield selectivity hydrogen. The important of this study is to identify design
parameters and also to estimate fuel processor efficiency.
1.3
Research Objectives
The main objective of this research is to simulate and optimize the hydrogen
production plant for fuel cell application using ethanol via autothermal reformer.
3
1.4
Scope of Study
To achieve above objective, several scopes has be drawn:

i.
Base case simulation development

By using Aspen HYSYS 3.2, hydrogen production simulation plant was
being developed with data from Akande et al. (2005)
ii.
Base case simulation validation

From base case simulation that being developed with Aspen HYSYS 3.2, it
was validated using theoretically data from total reactions stoichiometry
coefficient.
iii.
ATR optimization
ATR was optimizing by optimized the air feed molar that enter the ATR
while monitoring the production of hydrogen and carbon monoxide (CO) in a
certain range of temperature.
iv.
Heat integration
This system is used to increase the efficiency of the plant by using heat
exchanger to cool down the ATR vapour out with the hot stream from the
feed.
v.
Carbon monoxide clean up

Carbon monoxide that produced by the total reaction in ATR need to be
reduced their concentration by introducing water gas shift reaction and
preferential oxidation reactions.
a.
Water gas shift

Equilibrium reactors were placed to the plant to convert CO into carbon
dioxide (CO2). Three reactors were needed for conversion with water
gas shift (WGS) reaction as the main reaction.
4
b.
Preferential oxidation
To maximum reducing CO, preferential oxidation (PROX) reaction was
introduced.
vi.
Plant wide optimization

It was develop to optimized all the reactors used in the plant developed using
Aspen HYSYS 3.2 and to reduced CO concentration to the specific
requirement.
a.
ATR optimization
Its used to optimize the ATR temperature outlet for heat integration.
b.
Water gas shift optimization

Its used to optimize water molar flow to the ATR and reduces the CO
concentration with WGS reaction.
c.
Preferential oxidation optimization

It was formed to maintain the amount of air into PROX reactor that
reduced the CO concentration to the specification.
vii.
Temperature and component profile

The profile of temperature and components for every unit operations involve
in this research was analyzed.
1.5
Thesis Organizations
This thesis involves the conclusion of the several tasks to achieve the
objective. Chapter Two is discuss about the literature survey that related in synthesis
of hydrogen for fuel cell applications.
In this chapter, internal researched of
hydrogen production using ethanol by autothermal reforming was been concentrated.

This chapter is the major chapter because the development of the of hydrogen
production are based on the literature survey that we had researched.
5
Chapter Three is about the methodology for the methods that we need in
scope. Fundamentally, there are five methods that we carried out. The next chapter;
Chapter Four, is optimization simulation of hydrogen production plant from ethanol
for fuel cell application. We are using Aspen HYSYS 3.2 as a simulator to simulate
the plant.
Chapter Five is the results and discussion based on the methodology that we
use and developed from chapter four. Finally, Chapter Six is the conclusion all what
we have done in this entire thesis.
CHAPTER II
LITERATURE REVIEW
2.1
Introduction
In this chapter, a general hydrogen production using natural gas, alcohol and
petroleum fractional of gas as an input will be reviewed. It is meant to provide a list
of hydrogen had been produced by a specific class of hydrocarbon such as natural
gas and alcohol. Methane, ethane, propane and butane are some example of natural
gas. (Fuel cell store website, 2006)
Alcohol can also be used to produce hydrogen with a different condition

either used a same method or not. The different between those methods was higher
selectivity of hydrogen. Methanol, ethanol and propanol were some of them.
Petroleum fractional such as kerosene, gasoline, and diesel too will produce
hydrogen by using same method like reforming. From this review, some significant
journal will be taken as references. (Fuel cell store website, 2006)
2.2
Hydrogen Production for Fuel Cell Application in General
Fuel cell requires hydrogen as its fuel source for generating power. Hydrogen
used in secondary power units is produced in a fuel processor by the catalytic
reforming of hydrocarbons. Diesel, jet fuel, gasoline, as well as natural gas, are
7
potential fuels that all have existing infrastructure of manufacture and distribution,
for hydrogen production for fuel cell applications. (Fuel cell store website, 2006)
2.2.1
Natural Gas
The lack of a hydrogen infrastructure and the unsolved hydrogen storage

problem has initiated the development of compact fuel reformers that are able to
produce a hydrogen-rich gas from fuels such as hydrocarbon. Methane, due to its
large abundance and high H: C ratio is an ideal source of hydrogen. Ethane, propane
and methane are the family of natural gas which they produce hydrogen-rich too.
(Liu et al., 2002)
2.2.1.1 Methane
Fernandez et al. (2005) discussed and studied the hydrogen production by

sorption enhanced reaction process simulated by a dynamic one-dimensional pseudohomogenous model of a fixed-bed reactor, where a hydrotalcite-derived Ni catalyst
has been used as steam reforming catalysts.
Galvita and Sundmacher (2005) said that almost CO-free hydrogen gas, can
be produced by a novel steam reforming process of methane in a fixed bed reactor
which contains two different catalysts layers which go through a periodic
reduction/re-oxidation cycle.
The fluidized bed reactor was proposed by Lee et al. (2004) in order to
overcome the reactor plugging problem due to carbon deposition, which was resulted
in the shut-down of the fixed bed reactor system. Several kinds of activated carbons
were employed as the catalyst to examine the reaction activity.
8
Oxidized diamond is proposed by Nakagawa et al. (2004) as an effective
catalyst support material for decomposition of methane. Oxidized diamondsupported Ni catalyst produced a high yield of hydrogen by the decomposition of
methane at 823 K.
Bingue et al. (2004) describes that transient filtration combustion waves

formed in a porous matrix of randomly arranged alumina pellets are studied
experimentally for rich and ultra-rich methane/air waves with oxygen enrichment
and depletion.
2.2.1.2 Ethane
The catalytic decomposition of ethane was studied by Chin et al. (2005) over
a Ni/SiO2 catalyst at temperatures ranging between 450 and 650 C.
Wang et al. (2003) proved that formation rates of the more valuable
hydrocarbons and hydrogen are remarkably enhanced by selective permeation of
hydrogen product in the membrane reactor. It was also found that formation rate of
methane as a side product is effectively suppressed by selective permeation of
hydrogen though the membrane tubes.
The key reactions forming the higher hydrocarbons involved addition of

radicals to unsaturated bonds (Shebaro et al., 1997). Recent model calculations for
association reactions in hydrocarbon pyrolysis and flames have emphasized the role
of chemically activated association and isomerization in overcoming entropic
inhibitions, particularly for benzene formation.
9
2.2.1.3 Propane
Aartun et al. (2005) compared Rh-impregnated alumina foams and metallic

micro channel reactors upon production of hydrogen-rich syngas through short
contact time catalytic partial oxidation (POX) and oxidative steam reforming (OSR)
of propane.
Resini et al. (2005) compared the both catalyst and suggest the palladiumbased catalyst, the steam reforming of propene is faster and more selective than
steam reforming of propane.
Silberova et al. (2005) investigated partial oxidation and oxidative steam

reforming of propane over 0.01 wt.% Rh/Al2O3 foam catalysts and concluded high
selectivity to hydrogen was obtained for both reactions.
2.2.1.4 Butane
Avci et al. (2003) found the major difference between the two catalysts at 648
K, at which Pt-Ni/-Al2O3 showed superior performance in terms of selective
hydrogen production that resulted in lower carbon dioxide and methane formation.
2.2.2
Alcohol
Alcohols as fuel have been proven to be effective in the near complete

elimination of emissions of benzene, olefins, complex hydrocarbons and SO2. In
particular, methanol and ethanol are now seriously considered as a source for fuelcell-powered vehicles. While propanol too produce high selectivity of hydrogen with
various support of certain catalysts. (Wanat et al., 2005)
10
2.2.2.1 Methanol
Basile et al. (2005) showed that the methanol reforming (MR) gives methanol
conversions higher than traditional reactors (TRs) at each temperature confirming the
good potential of the membrane reactor device for this interesting reaction system.
Liu et al. (2004) described that prepared catalysts showed high activity and
selectivity towards hydrogen formation and explained their catalytic performances
during oxidative methanol reforming for the production of hydrogen reaction
conditions.
Xu et al. (2004) found that the alkali-leached Ni3Al powders show a high
catalytic activity for the methanol decomposition and made rate of hydrogen
production increases rapidly with increasing reaction temperature.
2.2.2.2 Ethanol
Both Vaidya and Rodrigues (2005) said that this production is simple and
cheap and hence steam reforming of ethanol to produce hydrogen for fuel cells is
attractive. The entire process of ethanol steam reforming coupled with selective CO2
removal by chemisorptions will enable production of high-purity H2 and hence is
very promising.
Aupretre et al. (2005) conclude that Rh is the most active metal in the steam
reforming reaction, especially in ethanol steam reforming (ESR)but the conditions
plead in favor of a support that is non-acidic and moderately basic.
A reaction mechanism is proposed by Mattos and Noronha (2005b) to explain

the catalytic tests. The effects of reaction conditions and catalyst reducibility on the
11
performance of the Pt/CeO2 catalyst in the partial oxidation of ethanol were
described.
H2 production and CO2/COx ratio obtained over Ni-based catalysts supported

on Al2O3 are compared by Fierro et al. (2005) with those obtained over NiCu/SiO2
and Rh/Al2O3 catalysts and suggest that its provided very good activity and
selectivity for ethanol partial oxidation reaction with high selectivity to H2.
A series of Pt catalysts supported on alumina modified by Ce and/or La were

discussed by Navarro et al. (2004) involving the production of hydrogen by oxidative
reforming of ethanol. When both ceria and lanthana were present on the support
substrate the platinumceria interaction was diminished, reducing the promoter effect
in the production of hydrogen by oxidative reforming of ethanol.
2.2.2.3 Propanol
CeO2 resulted in the highest selectivity and fairly higher stability for the
steam reforming among the supported Rh catalysts. Mizuno et al. (2003) concluded
that Rh=CeO2 is actually superior to any other catalyst for the steam reforming of
IPA.
Wanat et al. (2005) have shown that different alcohols have very different
selectivity in catalytic partial oxidation at short contact times even at high
temperatures. Rapid adsorption of alcohols as alkoxy species leads to complete
dissociation to H2 and CO. 2-Propanol gave lower conversions and less H2 and CO
than the other alcohols, but produced the most chemicals.
12
2.2.3
Petroleum Fractional
The Polymer Electrolyte Membrane (PEM) fuel cell requires hydrogen as its
fuel source. In order to avoid storing high-pressure hydrogen, the fuel can be
generated in an onboard fuel processor. For transportation applications, the primary
focus is on reforming gasoline, because a production and distribution infrastructure
already exists. For auxiliary power units, the focus is on reforming both gasoline (for
automotive applications) and diesel (for trucks and heavy-duty vehicles). For
portable power generation, the focus has been on reforming natural gas and liquefied
petroleum gas. (Cheekatamarla and Lane, 2005)
2.2.3.1 Kerosene
The auto thermal reforming of desulphurised kerosene was examined with a

15 kW (based on the lower heating value of Jet fuel) test rig. Lenz and Aicher (2005)
successfully performed experiment at steam to carbon ratios of S/C = 1.52.5 and air
to fuel ratios of = 0.240.32.
Suzuki et al. (2000) was discussed about long sustained run of hydrogen
production using HD-kerosene was successfully achieved on the CRI-101CE catalyst
(Ru/CeO2Al2O3). Highly dispersed Ru/Al2O3 catalyst can be obtained by using
ruthenium trichloride and aqueous ammonia in the catalyst preparation.
2.2.3.2 Gasoline
A numerical model of a simple reforming system, based on a partial oxidation

process, has been developed by Minutillo (2005) and tested it using the experimental
data of a plasma-assisted reformer. The conversions of methane, propane, heptane,
toluene and gasoline to hydrogen have been investigated and a thermodynamic
13
analysis of the reforming system has been conducted by means of the AspenPlus
software.
Otsuka et al. (2002) proposed and investigated a new technology using

gasoline as a fuel for solid polymer electrolyte fuel cell through the decomposition of
gasoline range alkanes into hydrogen and carbon and figured the method can supply
high purity hydrogen without CO and CO2.
2.2.4
Diesel
In order to show efficient catalysts for hydrogen generation from diesel

autothermal reforming Cheekatamarla and Lane (2005) showed that bimetallic
catalysts exhibited superior performance to the commercial catalyst and the
monometallic counterparts which showed that the enhanced stability is due to a
strong metalmetal and metalsupport interaction in the catalyst.
The reforming process efficiency has been shown by Tsolakis and Megaritis
(2004) to improve considerably with water addition up to a certain level after which
the adverse effects of the exothermic water gas shift reaction become significant.
Methanol, natural gas, gasoline, diesel fuel, aviation jet fuel, ethanol, and
hydrogen are compared by Brown (2001) for their utility as hydrogen sources for
proton-exchange-membrane fuel cells used in automotive propulsion.
2.3
Hydrogen Production for Fuel Cell from Ethanol
Fuels containing hydrogen generally require a fuel reformer that extracts

the hydrogen from any hydrocarbon fuel; ethanol for example. Ethanol appears as an
attractive alternative to methanol since it is much less toxic, offers a high octane
14
number, a high heat of vaporization and a low photochemical reactivity. There was
several method of producing hydrogen using ethanol. Steam reforming was the
popular way to produce follow by partial oxidation.
2.3.1
Steam Reforming
Oxidative steam reforming of ethanol for hydrogen production in order to

feed a solid polymer fuel cell (SPFC) has been studied over several catalysts at on
board conditions (a molar ratio of H2O/EtOH and of O2/EtOH equal to 1.6 and 0.68
respectively) and a reforming temperature between 923 and 1073 K. Two Ni (11 and
20 wt.%)/Al2O3 catalysts and five bimetallic catalysts, all of them supported on
Al2O3, were tested by Fiero et al. (2005).
By using high temperatures, low pressures and high water-to-ethanol ratios in

the feed favour hydrogen production. Vaidya and Rodrigues (2005) Ni, Co, Ni/Cu
and noble metal (Pd, Pt, Rh)-supported catalysts to produce hydrogen by using steam
reforming. They said that this entire process of ethanol steam reforming coupled with
selective CO2 removal by chemisorptions will enable production of high-purity H2
and hence is very capable.
Akande et al. (2005) were estimated the effects of catalyst synthesis method
(i.e. precipitation (PT), co-precipitation (CP) and impregnation (IM)), Ni loading and
reduction temperature on the characteristics and performance of Ni/Al2O3 catalysts
for the reforming of crude ethanol for H2 production. The result showed the type of
species generated by the synthesis method, the PT catalysts were more reducible than
the CP and IM catalysts.
Comas et al. (2004) analysed ethanol steam reforming with and without the
presence of CaO as a CO2 sorbent. They founds Both processes show the same
behaviour with pressure and water to ethanol ratio, atmospheric pressure and water to
15
ethanol relations higher than three are favourable conditions for higher hydrogen
productions without carbon formation.
Sun et al. (2004) proved that the catalyst Ni/Al2O3 exhibits relative lower
activity for ethanol steam reforming and hydrogen selectivity. But they found that the
catalysts Ni/Y2O3 and Ni/La2O3 exhibit relative high activity for ethanol steam
reforming at 250 C with a conversion of ethanol of 81.9% and 80.7%, and a
selectivity of hydrogen of 43.1% and 49.5%, respectively. When temperature
reached 320 C, the conversion of ethanol increased to 93.1% and 99.5% and the
selectivity of hydrogen was 53.2% and 48.5%.
From the endurance tests Freni et al. (2003) founded out at low gas hourly
space velocity (10,000 h-1) for 630 h showed that Ni/MgO catalyst possesses
adequate characteristics to be proposed as an efficient catalytic system for the
production of hydrogen for MCFC by steam reforming of ethanol.
Liguras et al. (2002) found that, under certain reaction conditions, the 5%
Ru/Al2O3 catalyst is able to completely convert ethanol with selectivity toward
hydrogen above 95%. They found it from investigated of the active metallic phase
(Rh, Ru, Pt, Pd), the nature of the support (Al2O3, MgO, TiO2) and the metal loading
(05 wt.%).in the temperature range of 600850 C .
2.3.2
Partial Oxidation
The performance of Pt/Al2O3, Pt/ZrO2, Pt/CeO2 and Pt/Ce0.50Zr0.50O2

catalysts as the support were being studied upon on each individuals catalyst. Mattos
and Noronha (2005a) showed that the support plays an important role on the products
distribution of the partial oxidation of ethanol.
16
From the effect of reaction conditions and catalyst reducibility on the
performance of the Pt/CeO2 catalyst, Mattos and Noronha (2005b) found that at low
conversions, the ethanol dehydrogenation dominates, forming acetaldehyde, whereas
at high conversions the decomposition of ethanol is favoured, producing CH4, H2,
and CO.
2.4
Steam Reforming of Ethanol for Hydrogen Production
Akande et al. (2005) reported that the effect of catalyst synthesis method, Ni
loading and reduction temperature on the characteristics and performance of
Ni/Al2O3 catalysts were estimated. They investigated that which method will
produces highest selectivity hydrogen yield.
The feed for this process was crude ethanol. Based on this composition, the
general equation representing the reforming of crude ethanol can be represented as in
equation below.
C2:12H6:12O1:23 + 3:01H2O 2:12CO2 +6:07H2
(2.1)
Upon experiment of synthesis catalysts, three methods of synthesis: coprecipitation, precipitation and impregnation were investigated. The reactor used to
obtain experimental data was BTRS model number 02250192-1 supplied by
Autoclave Engineers, Erie, PA, USA. Crude ethanol was delivered to the reactor
chamber by means of a HPLC pump regulated at the desired flow rates. The
reactions were carried out at atmospheric pressure and reaction temperature of 400
C. The product mixture during reaction was passed through a condenser and gas
liquid separator to separate the gaseous and liquid products for analysis.
As a result of the type of species generated by the synthesis method, the PT

catalysts were more reducible than the CP and IM catalysts. Catalysts prepared by
precipitation generally exhibited lower crystallite sizes of NiO species than the
corresponding catalysts prepared by co-precipitation. The catalysts prepared by
17
impregnation had the largest crystallite sizes except IM10 which had the smallest
crystallite size. In terms of H2 yield, CP15 gave the highest yield because the CP
catalysts gave the highest H2 selectivity as compared to corresponding catalysts
prepared by precipitation and impregnation.
2.5
Optimization Simulation of Hydrogen Production
Based on the literature reviews that have been done, there were few
researchers did on optimization simulation of hydrogen production using ethanol as a
raw material for fuel cell application. However, some of them did research
hydrocarbon on simulation. Jimnez (2006) using Aspen HYSYS to study the
viability of using a new catalyst to Methanol to a hydrogen rich product gas and
compare their production potential. Ozdogan et al. (2005) shows by using
hydrocarbon fuel as source in HYSYS 3.1 to compare two liquid hydrocarbon fuels.
They studied the effect of average molecular weights of hydrocarbons, on the fuel
cell processing efficiency.
2.6
Summary
Generally, there are many articles and journal on hydrogen production for
fuel cell application but when we are grouping that journal, we can conclude that,
there are three major groups that can synthesis hydrogen for fuel cells. Three of them
are natural gas, alcohol and petroleum fraction.
Additionally, there are many
processes that produce hydrogen such as steam reforming, autothermal reforming,

partial oxidation reforming, etc. Focus of this literature survey is to find a research
about ethanol as an input for hydrogen production by autothermal reforming. There
are a researchers had done the research about ethanol but a few had done research it
in simulation.
18
CHAPTER
METHODOLOGY
3.1
Research Tools
This research was carried out using various computational tools. Aspen
HYSYS 3.2 simulator was used for process flow sheeting to provide data regional
analyses. Aspen HYSYS 3.2 simulator was also used to perform the new process
model control structure for H2 production using ethanol as a raw material for fuel cell
application.
3.1.1
Aspen HYSYS
HYSYS was a product of AEA Technology, which is now part of Aspentech

Engineering Suite (AES). HYSYS has been chooses as the process simulator for this
research because of two main advantages over the other software packages. It can
interactively interpret commands as they entered one at a time. Other requires
execution after new entries. HYSYS has the unique feature that information
propagates both in forward and reverse directions, performing back-calculation in a
non-sequential manner. The bi-directionality often makes iterative calculations
unnecessary and the solution is fast.
19
3.2
Research Activities
3.2.1
Data Collection
From theoretical analysis and the report that have been done by Akande et al.
(2005), variables, variables relationship, approximate correlations, dynamic
characteristic and etc., about hydrogen production from ethanol is collected. Other
journal that related to this case study was collected too. Fierro et al. (2005) elaborate
the reaction that might be occurring while ethanol steam reforming reaction was
reacted. Vaidya et al. (2005) show that some reaction that using by ethanol. Reaction
such as ethanol steam reforming, ethanol cracking, and the others were collected to
comparable.
3.2.2
Base Case Stoichiometry
Vaidya et al. (2005) showed that the reaction is strongly endothermic and
produces only H2 and CO2 if ethanol reacts in the most desirable way.
CH 3CH 2 OH + 3H 2 O 6 H 2 + 2CO2
(H = 174kJmol-1)
(3.1)
However, other undesirable products such as CO and CH4 are also usually
formed during reaction.
CH 3CH 2 OH + H 2 O 4 H 2 + 2CO
(H = 256kJmol-1)
CH 3 CH 2 OH + 2 H 2 2CH 4 + H 2 O
(H = -157kJmol-1) (3.3)
(3.2)
Total oxidation of ethanol to H2 and acetaldehyde respectively, the main

reactions are being given by:
CH 3 CH 2 OH + 0.5O2 CH 3 CHO + H 2 O (H = -175kJmol-1) (3.4)
20
Other reactions that can also occur are: ethanol dehydrogenation to

acetaldehyde, ethanol dehydration to ethylene, ethanol decomposition to CO2 and
CH4 or CO, CH4 and H2.
CH 3CH 2OH C2 H 4O + H 2
CH 3 CH 2 OH C 2 H 4 + H 2 O
CH 3 CH 2 OH 0.5CO2 + 1.5CH 4
CH 3 CH 2 OH CO + CH 4 + H 2
(H = 68kJmol-1)
(3.5)
-1
(H = 45kJmol ) (3.6)
(H = -74kJmol-1) (3.7)
(H = 49kJmol-1)
(3.8)
They suggested the occurrence of several reactions: acetaldehyde formed by

dehydrogenation of ethanol is decomposed to CH4 and CO or undergoes steam
reforming.
(H = -21kJmol-1)
(H = 180kJmol-1)
(3.9)
(3.10)
CH 4 + 2 H 2 O CO2 + 4 H 2
CH 4 + H 2 O CO + 3H 2
C 2 H 4 + 2 H 2 O 2CO + 4 H 2
(H = 160kJmol-1)
(H = 210kJmol-1)
(H = 210kJmol-1)
(3.11)
(3.12)
(3.13)
C 2 H 6 + 2 H 2 O 2CO + 5H 2
(H = 350kJmol-1)
(3.14)
C 2 H 4 O CO + CH 4
C 2 H 4 O + H 2 O 2CO + 3H 2
Water reforms the C1 products to hydrogen.
In addition, the following reactions occur when O2 is present:

CH 4 + 2O2 CO2 + 2 H 2 O
(H = -800kJmol-1) (3.15)
CH 4 + 0.5O2 CO + 2 H 2
(H = -36kJmol-1)
CH 4 + O2 CO2 + 2 H 2
(H = -320kJmol-1) (3.17)
CO + 0.5O2 CO2
(H = -280kJmol-1) (3.18)
C + O2 CO2
(H = -390kJmol-1) (3.19)
(3.16)
Other reaction:
CH 4 C + 2 H 2
(H = 75kJmol-1)
(3.20)
21
3.2.3
C2 H 4 + H 2 C2 H 6
(H = -140kJmol-1) (3.21)
C 2 H 4 2C + 2 H 2
(H = -52kJmol-1)
(3.22)
Base Case Validation
Validation was done by comparing the mole fraction of the effluent by

calculation from total reaction and the mole fraction of the effluent of the ATR as
simulated in Aspen HYSYS 3.2 simulation.
3.2.4
Autothermal Reactor Optimization
Optimization for ATR was done by varies the feed air molar to get the best
flow rate of air when entered the ATR. Two case studies have been developed in this
optimization. The first one is about to monitor the molar flow rate of CO and
hydrogen at ATR vapour stream after varying the air molar flow rate. The second
case study is to monitor the temperature at the ATR vapour stream after varying the
air flow rate within the same range as the first case study. The optimize air molar
flow rate need to be above 700C when flow out at the ATR vapour stream. This is
for usage of heat energy in heating the feed stream.
3.2.5
Heat Integration
All hot and cold streams were systematically arranged to build system heat
integration. By apply a heat exchangers to a process, the heat from ATR vapour
stream was being cooled down by the feed stream; water, air, and ethanol. This can
really save a lot of energy and achieve target required.
22
3.2.6
Carbon Monoxide Clean Up
Carbon monoxide is a dangerous gas that should be aware and not profitable.
Several reactions may produce it as main product or by-product. So, the cleaning
method is required need and converts it to other relevant component. Water gas shift
and preferential oxidation can reduce CO and are being used in this research entirely.
3.2.6.1 Water Gas Shift
Water gas shift is the first stage to reduce the CO after reaction in ATR. CO
will be converted into hydrogen and carbon dioxide when mixed with steam. There
were three equilibrium reactors that being attached after stream that flow out from
ATR reactor. The first reactor is called high temperature shift (HTS), followed by
medium temperature shift (MTS) and end with low temperature shift (LTS). Stream
from ATR vapour will entered this entire three equilibrium reactor, and will react on
this reaction:
CO + H 2 O CO2 + H 2
(H = -42kJmol-1)
(3.23)
3.2.6.2 Preferential Oxidation
The next stage CO cleans up was preferential oxidation reactions. The

conversion reactor was attached after WGS stage. It was performed in order to
reduce the CO concentration out of the LTS to the ppm levels required for the fuel
cell. The PROX reactor was modelled as a conversion reactor based on two reactions
to oxidize CO. the reactions were
CO + 0.5O2 CO2
(H = -280kJmol-1) (3.24)
H 2 + 0.5O2 H 2 O
(H = -240kJmol-1) (3.25)
23
3.2.7
Plant wide optimization was being done to optimize the usage of the reactors
for the whole plant. ATR optimization optimized the stream out ATR reactor, water
gas shift optimization optimized the HTS, MTS and LTS reactors and preferential
oxidation optimization optimized the PROX reactor.
3.2.7.1 ATR optimization
ATR optimization was studied by monitoring the temperature at the ATR

stream out. The temperature of the stream must be above than 700 C. These was
important because it will affect the heat exchanger network if the required
temperature not in right conditions. The case study one was optimizing the air flow
and set the range of the molar flow rate that can be manipulated. The next case study
was to monitor the highest hydrogen that can be choosing in the range of air molar
flow rate in first case study.
3.2.7.2 Water Gas Shift Optimization
WGS optimization was conducted by varying the water feed molar flow rate
to get the best water feed molar flow rate to optimized the efficiency of the reactors
except for PROX reactor. For this optimization, case study three developed to
monitor the CO and hydrogen concentration in each reactor except PROX after
varying water feed molar flow rate. While case study four was developed to monitor
the temperature of HTS inlet after varying the water molar feed rate within the same
range as case study three. The optimized water molar flow rate was taken at the point
where the temperature for HTS inlet is above 100C.
24
3.2.7.3 Preferential Oxidation Optimization
PROX optimization was conducted by varying molar flow rate of air in the
additional air stream that directed to PROX reactor. The purpose was to reduce the
concentration of CO in PROX effluent to approximately 10 ppm while making sure
that the effluent temperature is in range 60C to 100C. Case study five was
developed to monitor the CO concentration in PROX vapour stream after varying the
air molar flow rate in the new air stream in a certain range.
3.2.8
Temperature and Component Profile
By looking at the temperature and component profile, we investigated the

behaviour of every unit operations. This is needed to find out the different for each
reactor and their effect. Next, the conditions like the temperature and the component
on overall plant also were studied well.
3.2.9
The system fuel processor efficiency can be calculated by :

(Lenz and Aicher , 2005)
(n
H2
LHV H 2 + nCO LHVCO

nCxHyOz LHVCxHyOz
(3.26)
25
3.3
Summary
This chapter basically show the methodology that need to accomplish. The
method are describe in detail from stoichiometry mathematical analysis calculation,
base case development with HYSYS, validation, heat integration model, clean up
model, plant wide optimization, components and temperature analysis to fuel
processor efficiency. All of them are systematically do as a Figure 3.1.
Stoichiometry Mathematical Analysis

Input
Base Case Development with HYSYS
Heat Integration Model
Clean Up Model
Plant Wide Optimizations
Temperature and Component Analysis
Figure 3.1 : Algorithm for methodology.
Output
Validation
26
CHAPTER V
SIMULATION AND OPTIMIZATION OF HYDROGEN PRODUCTION

PLANT FROM ETHANOL FOR FUEL CELL APPLICATION
4.1
Process Description of Hydrogen Production from Ethanol
The process simulation package Aspen HYSYS 3.2 has been used along with
conventional calculations in this study. Figure 4.1 presents the investigated operation
conditions for major fuel processing units (ATR, HTS, MTS, LTS, and PROX). The
selection of these operating conditions are based on theoretical studies aiming at
producing hydrogen rich and carbon monoxide poor mixtures in an efficient manner
at acceptable conversions.
It started from the feed stream; ethanol, air and steam at 1 atm enter the ATR
reactor. Then the outlet stream will enter WGS reactor. There were three reactor in
WGS section; HTS, MTS and LTS. Finally, the outlet entered the PROX reactor and
the product was ready to enter fuel cell.
27
Ethanol
Air
Steam
100C
100C
70C
ATR
reactor
WGS
reactor
PROX
reactor
To Fuel
Cell
Air
Figure 4.1: The operation conditions for the major unit operation
4.2
Modelling and Simulation of Hydrogen Production from Ethanol for

Fuel Cell
The hydrogen production from ethanol for fuel cell was simulated using
HYSYS software as a figure 4.2 shows it. Typically, the simulation process takes the
following stages:
i.
Preparation Stage
a) Selecting the thermodynamic model
b) Define chemical components
ii.
Building Stage
a) Adding and define streams
b) Adding and define unit operations
i. Auto-thermal reforming reactor
ii. Water gas shift reactor
1. High temperature shift reactor
2. Medium temperature shift reactor
3. Low temperature shift reactor
iii. Preferential oxidation reactor
c) Connecting streams to unit operations
d) Add auxiliary unit
i. Heater
28
ii. Cooler
iii. Heat exchanger
iii.
Execution
a) Starting integration
b) Optimization the whole plant
Figure 4.2: The whole plant system by Aspen HYSYS 3.2
29
30
HYSYS simulator is made up of four major parts to form a rigorous

modelling and simulation environment.
i) A component library consisting of pure component physical properties.
ii) Thermodynamic packages for transport and physical properties
prediction.
iii) Integrator for dynamic simulation and/or solver for steady-state
simulation.
iv) Mathematical modelling of unit operation.
For this study, each of above components is described in below.
Physical
Property
Library
Integrator
/ Solver
HYSYS
Simulation
Environment
Unit
operation
Model
Figure 4.3: HYSYS Simulation Environment
ThermoDynamic
Package
31
4.2.1
Thermodynamic Properties
In order to define the process, the thermodynamic property packages used to

model steady-state of ethanol must be specified. The feed for the hydrogen
production is considered to be relatively ideal mixture of ethanol and oxygen.
Ethanol is the primarily characterized as a C2H5OH. The Peng-Robinson Equation of
State (EOS) is used to model the thermodynamics of hydrogen production for both
steady-state and dynamics operations (HYSYS Reference, 2000):
P=
ai (T )
RT
Vi bi (Vi bi )(Vi + bi )
(4.1)
The terms;
ai (T ) =
(Tr i ; i ) R 2Tci 2
Pci
bi =
RTci
Pci
(4.2)
(4.3)
Where according to Peng Robinson (1976);
= 1 2 , = 1 + 2 , = 0.45724 , = 0.07779 , Z c = 0.30740 .

Therefore,
(Tr i ;i ) = [1 + (0.37464 + 1.54226i 0.26992i 2 )(1 Tr 1 / 2 )]2
For dynamics modelling of hydrogen production, the Peng-Robinson

Equation of state was found to simulate hydrogen production faster than the real
time. When performing the dynamics simulation, Aspen HYSYS permits a user
selected thermodynamics calculation procedure.
32
Additionally, the allowable maximum and minimum temperature and

maximum pressure over which dynamics are calculated and is user defined in Aspen
HYSYS. For the Aspen HYSYS model the default values were selected. Usually the
default minimum and maximum temperature value in flow sheet, respectively. The
maximum pressure was selected to be 1 atm above the highest pressure in the flow
sheet (HYSYS reference, 2000).
4.2.2
Physical Properties
Components that entered the ATR for the process hydrogen production was
ethanol, water and air. Additionally, the component such as carbon monoxide, carbon
dioxide, hydrogen, nitrogen, oxygen, acetaldehyde, ethylene, methane and carbon
need to define in HYSYS environment. All components are present in room
temperature. The pure component properties of the feed stock are listed in Table 4.1.
Table 4.1: Physical property of the component

Component
Ethanol
Oxygen
Water
Nitrogen
Carbon
Monoxide
Carbon dioxide
Hydrogen
Acetaldehyde
Methane
Ethylene
Carbon
Molecular formula
C2H4OH
O2
H2O
N2
MW(kg/kmol)
46.069
31.999
18.015
28.014
(kg/m3)
795.98
1137.68
997.99
806.37
BP (C)
78.25
-183.95
100.00
-195.80
CO
CO2
H2
C2H4O
CH4
C2H4
C
28.010
44.010
2.016
44.05
16.04
28.05
12.01
799.39
825.34
69.86
777.00
299.39
383.23
1642.06
-191.45
-78.55
-252.60
19.85
-161.52
-103.75
-
MW was the molecular weight, was density and BP was boiling point. The
densities were taken at 25C.
33
4.2.3
Integration Algorithm
A dynamic model is represented by a set of ordinary differential equations

(ODEs) in Aspen HYSYS. In order to solve the model, an implicit Euler method is
used to integrate the ODEs. The fixed step size implicit Euler method explains here
is known as the rectangular integration. It can be described by extending a line slope
zero and length h (the step size) from tn to tn+1 on a f(Y) versus time plot. The area
under the curve is approximately by a rectangle of length h and height fn+1(Yn+1) in a
function of the following form (HYSYS Documentation, 2000).
Yn +1 = Yn +
t n +1
f (Y )dt
, where :
tn
dY
= f (Y )
dt
(4.4)
To provide a balance between accuracy and speed, Aspen HYSYS employs a

unique integration strategy. The volume, energy and speed composition balances are
solved at different frequencies. Volume balances are defaulted to solve at every
integration step, whereas energy and composition balances are defaulted to solve at
every 2nd and 10th integration step, respectively. The integration time step can be
adjusted in Aspen HYSYS to increase the speed or stability of the system. The
default value of 0.5 second was selected.
4.2.4
Mathematical Modelling of the Reactor Operating
4.2.4.1 Linear and Non-Linear Systems
A linear first-order Ordinary Differential Equation (ODE) can be described as

follows:
dY
+ Y = Kf (u )
dt
(4.5)
34
In a non-linear equation, the process variable Y may appear as a power,

exponential, or is not independent of other process variables. Here are two examples:
dY
+ Y 3 = Kf (u )
dt
dY
+ YY2 = Kf (u )
dt
(4.6)
(4.7)
The great majority of chemical engineering processes occurring in nature are

nonlinear. Nonlinearity may arise from equations describing equilibrium behaviour,
fluid flow behaviour, or reaction rates of chemical systems. While a linear system of
equations may be solved analytically using matrix algebra, the solution to a nonlinear set of equations usually requires the aid of a computer.
4.2.4.2 Material Balance
The conservation relationships are the basis of mathematical modelling in

HYSYS. The dynamic mass, component, and energy balances that are derived in the
following section are similar to the steady-state balances with the exception of the
accumulation term in the dynamic balance. It is the accumulation term which allows
the output variables from the system to vary with time. The conservation of mass is
maintained in the following general relation:
Rate of accumulation of mass = mass flow into system - mass flow out of system
35
Figure 4.4: Reactor operating
d ( oV )
= Fi i Fo o
dt
Where:
Fi = the flow rate of the feed entering the reactor tank
i = the density of the feed entering the reactor tank
Fo = the flow rate of the product exiting the reactor tank
o = the density of the product exiting the reactor tank
V = the volume of the fluid in the reactor tank
4.2.4.3 Component Balance
Component balances can be written as follows:
Rate of accumulation of component j =

Flow of component j into system
- Flow of component j out of system
+ Rate of formation of component j by reaction
(4.8)
36
Flow into or out of the system can be convective (bulk flow) and/or
molecular (diffusion). While convective flow contributes to the majority of the flow
into and out of a system, diffusive flow maybe come significant if there is a high
interfacial area to volume ratio for a particular phase. For a multi-component feed for
a perfectly mixed tank, the balance for component j would be as follows:
d (C joV )
dt
= Fi C ji Fo C jo + R jV
(4.9)
Where:
Cji = the concentration of j in the inlet stream
Cjo = the concentration of j in the outlet stream
Rj = the reaction of rate of the generation of component j
For a system with NC components, there are NC component balances. The

total mass balance and component balances are not independent; in general, you
would write the mass balance and NC-1 component balances.
4.2.4.4 Energy Balance
The Energy balance is as follows:

Rate of accumulation of total energy =
Flow of total energy into system
- Flow of total energy out of system
+ Heat added to system across its boundary
+ Heat generated by reaction
- Work done by system on surroundings
37
The flow of energy into or out of the system is by convection or conduction.

Heat added to the system across its boundary is by conduction or radiation. For a
CSTR with heat removal, the following general equation applies:
d [(u + k + )V ]
= Fi i (u i + k i + i ) Fo o (u o + k o + o ) + Q + Q r ( w + Fo Po Fi Pi )
dt
(4.10)
Where:
u = Internal energy (energy per unit mass)
k = Kinetic energy (energy per unit mass)
= Potential energy (energy per unit mass)
V = the volume of the fluid
w = Shaft work done by system (energy per time)
Po = Vessel pressure
Pi = Pressure of feed stream
Q = Heat added across boundary
Qr = Heat generated by reaction: DHrxnrA
Several simplifying assumptions can usually be made: The potential energy

can almost always be ignored; the inlet and outlet elevations are roughly equal. The
inlet and outlet velocities are not high; therefore kinetic energy terms are negligible.
If there is no shaft work (no pump), w=0.
The general energy balance for a 2-phase system is as follows:

d
[ vVv H + l Vl h ] = Fi i hi Fl l h + Fv v H + Q + Q r
dt
(4.11)
38
4.2.5
Degree of Freedom Analysis
There are two types of degree of freedom. The first one is dynamic degrees of
freedom, Nm (m denotes manipulated). Nm is usually easily obtained by process
insight as the number of independent variables that can be manipulated by external
means. In general, this is the number of adjustable valves plus other adjustable
electrical and mechanical devices. Second is steady state degrees of freedom, Nss
which is the number of variables needed to be specified in order for a simulation to
converge. To obtain the number of steady state degrees of freedom we need to
subtract from Nom which is the number of manipulated variables with no steady state
effect and Noy which is the number of variables that need to be controlled from Nm
As a result equation 4.12 is obtained
N ss = N m ( N om + N oy )
(4.12)
In any process simulation work, it is essential that the degrees of freedom

analysis be carried out to determine the number of variables to be specified.
4.2.6
Analysis of Optimization Response
The case study for certain section of plant was selected; an optimization
analysis will carry out to show the efficiency of the plant wide. Selected process
inputs were changed when the process had been optimized. Corresponding process
outputs were monitored to get the scope required.
39
4.3
Summary
Basically, this chapter is about the development of the simulation using

Aspen HYSYS 3.2. All the data that gathered from literature surveys are used. For
the simulation of HYSYS, the equation of state that used is Peng-Robinson to
calculate the stream physical and transport properties. Mass and energy balances
have established for all cases. A block diagram about the simulation of hydrogen
plant using Aspen HYSYS 3.2 is shown in Figure 4.3.
Enter Aspen HYSYS 3.2
C2H4OH
O2
N2
Selecting thermodynamic model

# Peng-Robinsion
Define chemical component
Adding & define stream

Adding & define unit operation
ATR reactor
CO2
H2O
H2
CO
01 Ethanol
01 Air
03 water
Optimization
Start integration
WGS reactor
Optimization
Adding & define unit operation
PROX reactor
Plant wide optimization

Figure 4.5: Block diagram of the simulation of hydrogen plant using Aspen HYSYS
3.2
40
CHAPTER V
RESULTS AND DISCUSSIONS
5.1
Results for Base Case Study
The base case of this study was developed by introducing all the raw
materials which were ethanol, air and water into a single autothermal reactor (ATR)
in vapour phase. The feed were entered the ATR in a different stream as shown in
Figure 5.1. Since ethanol and water are in liquid phase at room temperature; 25 oC,
these two materials need to be converted to gas phase first. This process was done
by heating the materials with heaters until 100 oC as the ethanol and water boiling
point are 78.4 oC and 100 oC, respectively. Air too was being heat up to 100 oC to
increase the rate of reaction. The reactor was set up to be operated at 1 atm. The
molar flow rate of the raw materials is being evaluated from the total reactions of all
reactions that occur in the reactor with basis of 100 kgmole/hr of ethanol.
41
Figure 5.1: Process Flow Diagram of the Base Case
Thermodynamic aspects of ethanol steam reforming have received a fair

amount of attention in the literature review by Vaidya et. al. (2006). The reaction is
strongly endothermic and produces only H2 and CO2 if ethanol reacts in the most
desirable way. The basic reaction scheme; (3.1) and (3.2), was as follows:
CH 3CH 2 OH + 3H 2 O 6 H 2 + 2CO2
CH 3CH 2 OH + H 2 O 4 H 2 + 2CO
In autothermal conditions, conversion of ethanol gives rise mostly to the
production of acetyldehyde which has been detected as the only product till complete
conversion of both ethanol and oxygen. However, after total oxygen conversion, H2
is also produced. Total oxidation of ethanol to H2 and acetaldehyde respectively, the
main reactions (3.4) are being given by:
CH 3 CH 2 OH + 0.5O2 CH 3 CHO + H 2 O
42
Other reactions that can also occur are: ethanol dehydrogenation to

acetaldehyde (3.5), ethanol dehydration to ethylene (3.6), ethanol decomposition to
CO2 and CH4 (3.7) or CO, CH4 and H2 (3.8).
CH 3CH 2OH C2 H 4O + H 2
CH 3 CH 2 OH C 2 H 4 + H 2 O
CH 3 CH 2 OH 0.5CO2 + 1.5CH 4
CH 3 CH 2 OH CO + CH 4 + H 2
At low temperature in steam reforming conditions, acetaldehyde too reacts
and produces CO and H2 (3.10).
C 2 H 4 O + H 2 O 2CO + 3H 2
When O2 occur, methane will react and turn out total oxidation; (3.15), and
partial oxidation; (3.16) and (3.17).
CH 4 + 2O2 CO2 + 2 H 2 O
CH 4 + 0.5O2 CO + 2 H 2
CH 4 + O2 CO2 + 2H 2
Steam reforming of methane will give more production of hydrogen. The

reactions of the process; (3.22) and (3.19) are given by:
C 2 H 4 2C + 2 H 2
2C + 2O2 2CO2
All of the chemical reactions are assumed to occur adiabatically under

conversion conditions. All these 13 reactions are reacting in an autothermal reactor
(ATR) in vapour phase. Total reaction for all the reactions (5.1) are given as:
7CH 3CH 2 OH + 5.5O2 + 2 H 2 O 6CO2 + 8CO + 23H 2
(5.1)
43
From the total reaction, the feed ratio that should be introduced into the
reactor is 7:5.5:2 for ethanol over oxygen over water. Taking basis 100 kgmole/hr of
reactant ethanol, the flow rate for oxygen and water is 78.5714 kgmole/hr and 28.57
kgmole/hr respectively. This will make the air flow rate is 374.1597 kgmole/hr. The
flow rate of the ATR effluent is given in Table 5.1:
Table 5.1: Molar Flow of ATR Effluent for Base Case

Master Component
Molar Flow (kgmole/hr)
Ethanol
Oxygen
Nitrogen
295.5783
Water
69.2490
Carbon monoxide
129.6610
Carbon dioxide
43.4019
Hydrogen
259.3220
Ethylene
Acetaldehyde
Methane
Carbon
5.2
Result for Validation
Validation was done by comparing the mole fraction of the effluent by

calculation from total reaction and the mole fraction of the effluent of the ATR as
simulated in Aspen HYSIS 3.2 simulation.
44
Table 5.2: Validation for simulation effluent compare with calculated effluent
Master Component
Calculated
Simulated
Error
Ethanol
Oxygen
Water
0.0869
Carbon monoxide
0.1387
0.1626
0.0239
Carbon dioxide
0.1040
0.0544
0.0496
Hydrogen
0.3987
0.3253
0.0734
Nitrogen
0.3586
0.3708
0.0122
Ethylene
Acetaldehyde
Methane
Carbon
From Table 5.2, errors for all components are very small, ranging from 1.2%7.3%. Since the errors are small, we can conclude that the simulation model
developed using Aspen HYSYS 3.2 is valid and can be used as a real plant for
further analysis.
5.3
Results for Heat Integration
The feed stream was basically in a room temperature condition; 25C.

The temperature required to enter the ATR reactor was 100C. In order to achieve
this target, three heaters were installed to the feed stream. Figure 5.2 show the
diagram of the heater being attached. The outlet temperature from ATR was above
700C, so we can apply the heat exchanger network.
45
Figure 5.2: The heater attachment on the ATR reactor
Heat exchanger network from three cold stream and hot stream was being
applied. Heat exchanger HE1, HE2, and HE3 was replaced for heater-1, heater-2 and
heater-3. Figure 5.3 shows the ATR reactor after heat integration. The hot streams
from ATR vapour out will cooling down by cold stream from stream ethanol, water
and air. All these stream was entered the heat exchanger at room temperature; 25C,
and out to 100C. The temperature ATR vapour stream was cooled from 763.3 C to
497.5 C before entering WGS.
46
Figure 5.3: The heaters at the feed streams were exchange with the heat exchanger.
5.4
Results for CO Clean Up
CO needs to be cleans up for the safety. The CO was produced in ATR. This
component was unprofitable and dangerous to environment, needs to be cleans up by
using water gas shift reaction and preferential oxidation reactions.
5.4.1
Water Gas Shift
The ATR effluent was passed through ATR cooler to cool down its
temperature to the desired HTS inlet temperature. The HTS was performed the water
gas shift reaction (3.23) in which CO was converted to meet the specification. Then
the outlet from HTS was being cool to enter MTS reactor. This process was repeated
until to LTS reactor. Figure 5.4 show the WGS reactor being attached after outlet
ATR reactor. The Table 5.3 shows the molar flow of the component out of all
reactors involved. From the water gas reaction, the composition of CO decreased
47
from 16.27% to 7.6%. Meanwhile the composition of hydrogen was increased from
32.53% to 41.20%.
Figure 5.4: The WGS reactor
Table 5.3: Effluent molar flow after water gas shift reaction for each reactor
Master
ATR
HTS
MTS
LTS
Nitrogen
295.5390
295.5390
295.5390
295.5390
Water
69.2453
2.8729
0.1864
0.1596
Carbon
129.6629
63.2925
60.6040
60.5772
Carbon dioxide
43.3924
109.7628
112.4513
112.4781
Hydrogen
259.3257
325.6961
328.3846
328.4114
Component
monoxide
5.4.2
Preferential Oxidation
Effluent from the LTS was cooled down first to the required PROX inlet
temperature. Preferential oxidation reactions, (3.24) and (3.25) took place in PROX
conversion reactor. CO was oxidized to CO2 and the H2 was oxidized to H2O,
simultaneously. Additional air was attached to the PROX reactor with zero molar
flow as shown in Figure 5.5. This extra air stream was needed in the optimization.
48
Figure 5.5: The preferential oxidation reactor
Table 5.4: Effluent molar flow after partial oxidation reaction

Master Component
After LTS
After PROX
Nitrogen
295.5390
295.5390
Water
0.1596
0.1596
Carbon monoxide
60.5772
60.5772
Carbon dioxide
112.4781
112.4781
Hydrogen
328.4114
328.4114
5.5
Plant wide optimization was set to optimize the hydrogen production while
minimize the CO concentration with several constraints.. WGS optimization
optimized the water molar flow rate and increase the water gas shift reaction in HTS,
MTS and LTS while PROX optimization optimized the air molar flow in PROX air
feed stream and decrease the concentration of CO to ppm level required for the fuel
cell in the PROX reactor.
49
5.5.1
Result for ATR Optimization
Optimization for ATR was done by varying the air molar flow rate to get the
best flow rate of air to be introduced into the ATR. Two case studies were developed
in order to do this optimization. The first case study was developed to monitor the
temperature at the ATR vapour stream after varying the air molar flow rate from 100
kgmole/hr to 1500 kgmole/hr. The second case study was developed to monitor the
molar flow rate of carbon monoxide and hydrogen after varying air molar flow rate
within the range that was chosen from first case study. The optimized air molar flow
rate was taken at temperature of the ATR vapour stream is above 700 oC. This is
because the heat from the stream can be used later for heat integration.
The results for case study one and case study two are presented in Figure 5.6
and Figure 5.7. From Figure 5.6, the temperature out of ATR is over 700 oC only
after the molar flow rate of air greater or equal 350 kgmole/hr. With that air molar
flow rate range, the hydrogen and CO molar flow rate was monitored. From figure
5.7, the flow rate of hydrogen produced by the ATR is decreasing when of air molar
flow rate greater than 350 kgmole/hr. Then it began constant after 550 kgmole/hr.
1200
temperature
ATR out - Temperature C
1000
800
600
400
200
0
100
350
600
850
1100
air - Molar Flow kgmole/h
Figure 5.6: Temperature of ATR vapour for varies air Feed molar flow
1350
50
135
270
CO
Master Comp Molar Flow (Hydrogen) kgmole/h

.
Hydrogen
125
250
120
240
115
230
110
220
105
210
Master Comp Molar Flow (CO) kgmole/h
130
260
100
100
350
600
850
1100
1350
Figure 5.7: Molar flow of CO and H2 effluent for varies air feed molar flow
The air molar flow rate was chosen at temperature 760C which is 370
kgmole/hr. This is suitable flow rate because at this rate hydrogen molar flow rate
begin to decrease. At that slope, hydrogen is 259.322 kgmole/hr.
5.5.2
Water Gas Shift Optimization
In WGS optimization, one case study was developed to optimized value of

feed water molar flow to reduce concentration of CO through water gas shift
reaction. Figure 5.8 shows the result of case study where the concentration of H2 and
CO after ATR was monitored. Another case study was developed to know how
temperature of the effluent will affect the water molar flow and the result was shown
in Figure 5.9.
51
Water molar flow rate was optimized from 30 to 300 kgmole/hr. As we can
see from Figure 5.8, the H2 show an increasing slope and the increasing is a bit
slower at 388 kgmole/hr. The optimum water molar flow rate was taken when H2 at
its higher molar flow rate. So, the value of water molar flow rate that was chosen was
150 kgmole/hr. At this point, H2 produced the greatest flow rate and CO reduced the
lowest flow rate. At that state, temperature was 250.1C as a Figure 5.9 show it.
Comp Molar Flow (CO) kgmole/h
370
Hydrogen
CO
360
350
340
330
320
30
70
110
150
190
230
270
water - Molar Flow kgmole/h
Figure 5.8: Molar flow of CO and H2 effluent for varies water feed molar flow
380
Comp Molar Flow (H2) kgmole/h
390
52
500
400
ATR out - Temperature C
450
350
temperature
300
250
200
150
100
50
30
70
110
150
190
230
270
Figure 5.9: Temperature to HTS for varies water feed molar flow
Table 5.5 compares the effluent produced by ATR, HTS, MTS and LTS
before and after WGS optimization being done. The increasing in water molar flow
rate did not affect the reactions in ATR, so the effluent of ATR did not change except
for steam. Other reactors show the same similarity, which were CO and steam being
reduced and H2 and CO2 were increased. From the ATR to LTS, CO was reduced
from 13.53% to 0.02% and H2 was increased from 27.05% to 40.56%.
Table 5.5: Molar flow of the effluent before optimization for ATR, HTS, MTS and
LTS.
Component
ATR
HTS
MTS
LTS
Nitrogen
295.5390
295.5390
295.5390
295.5390
Water
69.2453
2.8749
0.1864
0.1596
CO
129.6629
63.2925
60.6040
60.5772
CO2
43.3924
109.7628
112.4513
112.4781
Hydrogen
259.3257
325.6961
328.3846
328.4114
53
Table 5.6: Molar flow of the effluent after optimization for ATR,HTS, MTS and
LTS.
Component
ATR
HTS
MTS
LTS
Nitrogen
295.5390
295.5390
295.5390
295.5390
Water
190.6743
72.6090
61.4964
61.3008
CO
129.6629
11.5976
0.4850
0.2894
CO2
43.3924
161.4577
172.5703
172.7659
Hydrogen
259.3257
377.3910
388.5036
388.6992
5.5.3
Preferential oxidation optimization
Figure 5.10 show the result of the concentration of CO in ppm after varying
the air molar at PROX reactor. The concentration of CO in PROX was required
under 10 ppm. After being optimized, air molar flow was setup at 550 kgmole/hr,
where the 10.055 ppm and the temperature at 112.6 C. Table 5.7 compare the
effluent of PROX reactor after optimization was achieved. The concentration of H2
was decreased from 42.31 % to 34.02% because H2 was reacted with O2 in PROX to
produce H2O
54
200
CO molar flow - ppm
160
120
CO
80
40
0
100
250
400
550
700
850
1000
1150
1300
1450
Figure 5.10: CO Molar flow in PROX effluent for varies air feed molar flow
Table 5.7: Molar flow of the effluent before and after optimization for PROX
Component
PROX
Before
After
Nitrogen
295.5390
434.50
Water
61.3008
81.0109
CO
0.2894
0.0109
CO2
172.7659
199.9891
Hydrogen
388.6992
368.9891
55
5.6
Temperature Profile of Fuel Processor System
Figure 5.11 presents the temperature profile for the whole process starting
from the temperature of raw materials feed into the reactor until the temperature of
PROX vapour. The temperatures start up with 100 oC. The temperature rose up after
flow out from ATR (955.8 oC ). Then the temperature occurred at ATR will be used
to heating the raw materials by heat integrations process. The temperature slowly
cooled down to 100 oC during the heat integration process. At the first WGS reactor
(HTS), the temperature raise to 240.4 oC but then was set to cool at 100 oC before
enter the MTS reactor. After flow out from MTS reactor, the temperature rises just a
little and that same goes to LTS reactor. The temperature of effluents feed into the
prox reactor were set to 70 oC. Finally the temperature of prox vapour is at 112.6 oC.
1000
Temperature , C
800
600
400
200
AT
R
i
AT
R
o
H
E1
H
E2
H
E
H 3
TS
C
o
H
TS
M o
TS
C
o
M
TS
LT o
SC
o
LT
PR So
O
Xc
o
PR
O
X
fe
ed
Unit operations
Figure 5.11 : Temperature profile for the whole unit operation
56
5.7
Component Profile of Fuel Processor System
Figure 5.12 shows the profile of CO and H2 component through the whole
plant. The main objective of this study was to maximize the production of H2 and in
the same time to reduce the concentration of CO as lower as possible. Therefore, it is
important to monitor concentrations of H2 and CO. The behaviour of the two
component profile was very different after ATR. This happened because CO was
being clean up in the plant where WGS reaction converted it into CO2 and H2 while
PROX reaction converted CO and H2 into CO2 and H2O with presence of O2. The
molar flow of CO was 0.0109 kgmole/h which was 10.055 ppm of the PROX outlet
and H2 molar flow was 368.9891 kgmole/h.
400
350
H2
300
250
CO
H2
200
Molar
flow , 150
kgmole/h
100
50
Figure 5.12: H2 and CO profile for the whole unit operation
CO
PROX
PROXco
LTSo
LTSCo
MTSo
HTSo
MTSCo
unit operation
HTSCo
HE3
HE2
HE1
ATRo
57
5.8
From equation (3.26), the fuel processor efficiency of plant was calculated. In
this study, with the water optimization at 150 kgmole/hr and air optimization at 550
kgmole/hr, the calculated fuel processor system efficiency is about 83.6%.
5.9
Summary
From this chapter, all the scope from earlier chapter had we did it. The result
is based on the requirement in the scope. The simulation was successfully developed.
From the ATR reactor through the heat integration, WGS reactor and finally reach
PROX reactor, the main product; H2, was produced.. By optimize the water and air
molar flow rate, we achieve to reduces the CO concentration and produces 34% H2.
58
CHAPTER V
CONCLUSIONS AND RECOMMENDATIONS
6.1
Summary
Ethanol was simulated and optimized to produce H2 for fuel cell application.
Many researched been search a lot the usage of H2 for fuel cell application. By try to
produce it from different material such as natural gas, alcohol and nafta, many result
can be conclude. This case study is about using simulation to optimization the
ethanol to get the highest selectivity yield H2 by using Aspenplus HYSYS 3.2.
Ethanol, water and air were the inlet stream that through in this plant. From
the validation of the stoichiometry , there were 13 reactions that add on this entire
plant which are total oxidation (TOX), partial oxidation (POX), steam reforming
(SR), and cracking in this processes and three reactions occurred for the clean up of
carbon monoxide at the WGS and PROX reactor.
Using 100 kgmole/h of ethanol as basis, the plant was achieved to produce
the main product which is theH2 that produced about 368.9891 kgmole/hr. For the
first reactor that is at the ATR reactor, hydrogen that produced after the optimization
was 259.3257 kgmole/hr. After the stream through three WGS reactor and being
optimization by water molar flow rate the H2 molar flow rate was increased to
328.4114 kgmole/hr. Then, for the last reactor that is PROX reactor, the air
optimization made once again the H2 molar flow rate increasing
59
For this plant, optimization is one of this case study scopes. By optimizing
the water and air on the WGS reactor and PROX reactor, the CO been reduces to
minimum concentration. Meanwhile, the H2 was produced to highest flow rate.
6.2
Conclusions
A number of important observations were noted based on the analysis of

results as presented in the previous chapter. The main contributions of this research
to the simulation of hydrogen production plant for fuel cell applications, which also
represent the view developments in this field, are the following:
1. The simulation of hydrogen production plant model using autothermal
reforming of ethanol had been successfully developed using Aspen HYSYS
3.2.
2. The optimum A/F and S/F ratios are 5.5 and 1.5 respectively to produce 34%
hydrogen and 10.055 ppm of CO.
3. With optimum parameter above, 83.67.% of fuel processor efficiency was
achieved
6.2
Recommendations
In the future works, it is recommended to study and integrate the following

aspect:
1.
Purification of H2
By using water gas shift reaction and preferential oxidation, the component
that can be reduced was only CO. To get 100% yield of H2, other components need to
60
observe. CO2, N2, and H2O are the final component that flow out with H2 .In order to
get rid of them, a new reactor or new study case need to carry out.
2.
Water management
Water was one of the components that flow out from the reaction that had
been stimulated. The recovery of sufficient water in the stream is needed to avoid
from exhaust stream. Furthermore, this recovery depends on the factor as exhaust
temperature, exhaust pressure, air feed rate and fuel processor efficiency. With all
these, one of the objectives of the fuel processor system can maintain self-sufficiency
with respect to water needs.
3.
Energy integration basis

Economical factor was the solution to archive a high efficiency fuel processor.
In order to do that, energy integration was the good choices. It can be conduct by
maximize the recovery of waste heat from various portions of the fuel processor and
minimizing the number of heat exchangers and complexity of the systems. Waste
process heat is utilized to generate the steam needed in the process. Steam is required
for the autothermal reformer.
61
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APPENDIX A
Final result from Simulation Aspen HYSYS 3.2
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SIMULATION AND OPTIMIZATION OF ETHANOL AUTOTHERMAL

REFORMER FOR FUEL CELL APPLICATIONS

MUHAMAD SYAFIQ BIN ADAM

UNIVERSITI TEKNOLOGI MALAYSIA

SIMULATION AND OPTIMIZATION OF ETHANOL AUTOTHERMAL

MUHAMAD SYAFIQ BIN ADAM

A report submitted in partial fulfilment of the

Faculty of Chemical Engineering and Natural Resources Engineering

To my beloved mother and father

Alhamdullilah. Finally my first thesis was finished. Thanks to God because

I would like to thank to my supervisor; En. Mohd Kamaruddin. A word thank

I also wanted to thank my family for the moral support. Especially to my

Hydrogen Production for Fuel Cell Application in

Hydrogen Production for Fuel Cell from Ethanol

Steam Reforming of Ethanol for Hydrogen

Optimization simulation of Hydrogen Production

Base Case Stoichiometry

3.2.3 Base Case Validation

Auto-thermal Reactor Optimization

3.2.5 Heat Integration

Carbon Monoxide Clean Up

3.2.6.1 Water Gas Shift

3.2.6.2 Preferential Oxidation

Plant Wide Optimization

3.2.7.1 ATR Optimization

3.2.7.2 Water Gas Shift Optimization

3.2.7.3 Preferential Oxidation Optimization

Temperature and Component Profile

Fuel Processor Efficiency

SIMULATION AND OPTIMIZATION OF HYDROGEN

Process Description of Hydrogen Production from

Modelling and Simulation of Hydrogen Production

Mathematical Modelling of the Reactor

4.2.4.1 Linear and Non-Linear System

4.2.4.2 Material Balance

4.2.4.3 Component Balance

4.2.4.4 Energy Balance

Degree of Freedom Analysis

Analysis of Optimization Response

RESULTS AND DISCUSSION

Results for Base Case Study

Results for Validation

Results for Heat Integration

Results for Carbon Monoxide Clean Up

Water Gas Shift

5.4.2 Preferential Oxidation

Plant Wide Optimization

5.5.1 ATR Optimization

Water Gas Shift Optimization

Preferential Oxidation Optimization

Temperature Profile of fuel Processor System

Component Profile of the Fuel Processor System

Fuel Processor Efficiency

CONCLUSION AND RECOMMENDATIONS

Algorithm for methodology.

The operation conditions for the major unit

The whole plant system by Aspen HYSYS 3.2

HYSYS simulation environment

Block diagram of the simulation of hydrogen

Process flow diagram of the base case

The heater attachment on the ATR reactor

The heaters at the feed streams were exchange

The WGS reactor

The PROX reactor