SIMULATION AND OPTIMIZATION OF ETHANOL AUTOTHERMAL REFORMER FOR FUEL CELL APPLICATIONS

MUHAMAD SYAFIQ BIN ADAM

UNIVERSITI TEKNOLOGI MALAYSIA

PSZ 19:16 (Pind. 1/97)

UNIVERSITI TEKNOLOGI MALAYSIA

BORANG PENGESAHAN STATUS TESIS

JUDUL: SIMULATION AND OPTIMIZATION OF ETHANOL AUTOTHERMAL REFORMER FOR FUEL CELL APPLICATION SESI PENGAJIAN: 2006/2007 Saya: MUHAMAD SYAFIQ BIN ADAM (HURUF BESAR)

mengaku membenarkan tesis (PSM/Sarjana/Doktor Falsafah)* ini disimpan di Perpustakaan Universiti Teknologi Malaysia dengan syarat-syarat kegunaan seperti berikut : 1. 2. 3. 4. Tesis adalah hakmilik Universiti Teknologi Malaysia Perpustakaan Universiti Teknologi Malaysia dibenarkan membuat salinan untuk tujuan pengajian sahaja. Perpustakaan dibenarkan membuat salinan tesis ini sebagai bahan pertukaran antara institusi pengajian tinggi. **Sila tandakan (3 )

SULIT TERHAD

(Mengandungi maklumat yang berdarjah keselamatan atau kepentingan Malaysia seperti yang termaktub di dalam AKTA RAHSIA RASMI 1972) (Mengandungi maklumat TERHAD yang telah ditentukan oleh organisasi/badan di mana penyelidikan dijalankan)

3
WW

TIDAK TERHAD
Disahkan oleh

P (TANDATANGAN PENULIS) Alamat Tetap: No. 32, Jln SG 10/11, Taman Seri Gombak, 68100 Batu Caves, Selangor. Tarikh : 15th November 2006 (TANDATANGAN PENYELIA)

O___

Engr. Mohd. Kamaruddin bin Abd Hamid Nama Penyelia Tarikh : 15th November 2006

CATATAN:

* **

Potong yang tidak berkenaan Jika Tesis ini SULIT atau TERHAD, sila lampirkan surat daripada pihak berkuasa/ organisasi berkenaan dengan menyatakan sekali sebab dan tempoh tesis ini perlu dikelaskan sebagai SULIT atau TERHAD. Tesis dimaksudkan sebagai tesis bagi Ijazah Doktor Falsafah dan Sarjana secara penyelidikan, atau disertai bagi pengajian secara kerja kursus dan penyelidikan atau Laporan Projek Sarjana Muda (PSM).

I hereby declare that I have read this report and in my opinion this report is sufficient in terms of scope and quality for the award of the degree of Bachelor of Engineering (Chemical).

Signature Date

: :

. Engr. Mohd. Kamaruddin Abd. Hamid 15th November 2006

Name of Supervisor :

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

ii

I declare that this thesis entitled Simulation and Optimization of Ethanol Autothermal Reformer for Fuel Cell Applications is the result of my own research except as cited in the references. The thesis has not been accepted for any degree and is not concurrently submitted in candidature of any other degree.

Signature : Name Date : :

.. Muhamad Syafiq bin Adam 15th 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.

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LIST OF CONTENTS

CHAPTER

TITLE

PAGE

Tittle Page Declaration Dedication Acknowledgements Abstract Abstrak List of Contents List of Figures List of Tables List of Symbols

i ii iii iv v vi vii xi xiii xiv

INTRODUCTION 1.1 1.2 1.3 1.4 1.5 Background Research Problems Statement Research Objective Scopes of study Thesis Organizations 1 2 2 3 4

II

LITERATURE REVIEW 2.1 2.2 Introduction Hydrogen Production for Fuel Cell Application in General 2.2.1 Natural Gas 6 7 6

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 2.2.2.1 Methanol 2.2.2.2 Ethanol 2.2.2.3 Propanol 2.2.3 Petroleum Fractional 2.2.3.1 Kerosene 2.2.3.2 Gasoline 2.2.3.3 Diesel 2.3 Hydrogen Production for Fuel Cell from Ethanol 2.3.1 2.3.2 2.4 Steam Reforming Partial Oxidation

7 8 9 9 9 10 10 11 12 12 12 13 13 14 15

Steam Reforming of Ethanol for Hydrogen Production 16 17 17

2.5 2.6

Optimization simulation of Hydrogen Production Summary

III

METHODOLOGY 3.1 Research Tools 3.1.1 3.2 Aspen HYSYS 18 18 19 19 19 21 21 21 22 22 22 23

Research Activities 3.2.1 3.2.2 Data Collection Base Case Stoichiometry

3.2.3 Base Case Validation 3.2.4 Auto-thermal Reactor Optimization

3.2.5 Heat Integration 3.2.6 Carbon Monoxide Clean Up 3.2.6.1 Water Gas Shift 3.2.6.2 Preferential Oxidation 3.2.7 Plant Wide Optimization

ix

3.2.7.1 ATR Optimization 3.2.7.2 Water Gas Shift Optimization 3.2.7.3 Preferential Oxidation Optimization 3.2.8 3.2.9 3.3 Temperature and Component Profile Fuel Processor Efficiency

23 23 24 24 24 25

Summary

IV

SIMULATION AND OPTIMIZATION OF HYDROGEN PRODUCTION PLANT FROM ETHANOL FOR FUEL CELL APPLICATION 4.1 Process Description of Hydrogen Production from Ethanol 4.2 Modelling and Simulation of Hydrogen Production From Ethanol for Fuel Cell 4.2.1 4.2.2 4.2.3 4.2.4 Thermodynamic Properties Physical Properties Integration Algorithm Mathematical Modelling of the Reactor Operating 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 4.2.5 4.2.6 4.3 Degree of Freedom Analysis Analysis of Optimization Response 33 33 34 35 36 38 38 39 27 31 32 33 26

Summary

RESULTS AND DISCUSSION 5.1 5.2 5.3 5.4 Results for Base Case Study Results for Validation Results for Heat Integration Results for Carbon Monoxide Clean Up 5.4.1 Water Gas Shift 40 43 44 46 46

5.4.2 Preferential Oxidation 5.5 Plant Wide Optimization 5.5.1 ATR Optimization 5.5.2 5.5.3 5.6 5.7 5.8 5.9 Water Gas Shift Optimization Preferential Oxidation Optimization

47 48 49 50 53 55 56 57 57

Temperature Profile of fuel Processor System Component Profile of the Fuel Processor System Fuel Processor Efficiency Summary

VI

CONCLUSION AND RECOMMENDATIONS 6.1 6.2 6.3 Summary Conclusion Recommendation 58 59 59

REFERENCES

61

APPENDIX APPENDIX A Final result of simulation HYSYS 3.2 66

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LIST OF FIGURES

FIGURE NO.

TITLE

PAGE

3.1 4.1

Algorithm for methodology. The operation conditions for the major unit operation

25

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

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5.6

Temperature of ATR vapour for varies air feed molar flow 49

5.7

Molar flow of CO and H2 effluent for varies air feed molar flow 50

5.8

Molar flow of CO and H2 effluent for varies water feed molar flow 51

5.9

Temperature to ATR outlet for varies water feed molar flow 52

5.10

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 44

5.3

Effluent molar flow after water gas shift reaction for each reactor 47

5.4

Effluent molar flow after preferential oxidation reaction 48

5.5

Molar flow of the effluent before optimization for ATR,HTS, MTS and LTS. 52

5.6

Molar flow of the effluent after optimization for ATR,HTS, MTS and LTS. 53

5.7

Molar flow of the effluent before and after optimization for PROX 54

xiv

LIST OF SYMBOLS

A a b C F g H h k

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 Molecular weight Number of independent variables Number of manipulated variables with no steady state effect Number of variables that need to be controlled from Nm Number of variables needed to be specified Absolute pressure Reference pressure Critical pressure, species i Reduced pressure, species i Heat Heat generated by reaction Universal gas constant Rate of reaction Time Internal energy Volume

m MW Nm Nom Noy Nss P Po Pci Pri Q Qr

R

r t
u V

xv

Process Variable

Greek letters
Function, cubic equation of state Error Viscosity Density Potential energy Acentric factor

Abbreviations ATR ca. CO

CO2 Auto thermal reforming at approximate Carbon Monoxide Carbon Dioxide et alias: and others et cetera Hydrogen High Temperature Shift Lower Temperature Shift Preferential Oxidation Medium Temperature Shift Water Gas Shift

et al. etc.
H2 HTS LTS PROX MTS WGS

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 CH 3 CH 2 OH + 2 H 2 2CH 4 + H 2 O (H = 256kJmol-1) (3.2)

(H = -157kJmol-1) (3.3)

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)
-1

(3.5)

(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.
C 2 H 4 O CO + CH 4 C 2 H 4 O + H 2 O 2CO + 3H 2

(H = -21kJmol-1) (H = 180kJmol-1)

(3.9) (3.10)

Water reforms the C1 products to hydrogen.

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) (H = 350kJmol-1)

(3.11) (3.12) (3.13) (3.14)

C 2 H 6 + 2 H 2 O 2CO + 5H 2

In addition, the following reactions occur when O2 is present:

CH 4 + 2O2 CO2 + 2 H 2 O CH 4 + 0.5O2 CO + 2 H 2 CH 4 + O2 CO2 + 2 H 2 CO + 0.5O2 CO2 C + O2 CO2

(H = -800kJmol-1) (3.15) (H = -36kJmol-1) (3.16)

(H = -320kJmol-1) (3.17) (H = -280kJmol-1) (3.18) (H = -390kJmol-1) (3.19)

Other reaction:
CH 4 C + 2 H 2

(H = 75kJmol-1)

(3.20)

21

C2 H 4 + H 2 C2 H 6
C 2 H 4 2C + 2 H 2

(H = -140kJmol-1) (3.21) (H = -52kJmol-1) (3.22)

3.2.3

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 2 + 0.5O2 H 2 O

(H = -280kJmol-1) (3.24) (H = -240kJmol-1) (3.25)

23 3.2.7 Plant Wide Optimization

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

Fuel Processor Efficiency

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 Output

Base Case Development with HYSYS

Validation

Heat Integration Model

Clean Up Model

Plant Wide Optimizations

Temperature and Component Analysis

Figure 3.1 : Algorithm for methodology.

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

100C Ethanol Air Steam ATR reactor

100C WGS reactor

70C 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.

Integrator / Solver HYSYS Simulation Environment

Physical Property Library

Unit operation Model

ThermoDynamic Package

Figure 4.3: HYSYS Simulation Environment

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 RTci Pci

(4.2)

bi =

(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

tn

f (Y )dt

, where :

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

(4.6) (4.7)

dY + YY2 = Kf (u ) dt

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

(4.8)

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

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

Selecting thermodynamic model # Peng-Robinsion Define chemical component

C2H4OH O2 N2

CO2 H2O H2 CO
01 Ethanol 01 Air 03 water

Adding & define stream Adding & define unit operation ATR reactor 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 + 2 H 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 Ethanol Oxygen Nitrogen Water Carbon monoxide Carbon dioxide Hydrogen Ethylene Acetaldehyde Methane Carbon Molar Flow (kgmole/hr) 0 0 295.5783 69.2490 129.6610 43.4019 259.3220 0 0 0 0

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 Ethanol Oxygen Water Carbon monoxide Carbon dioxide Hydrogen Nitrogen Ethylene Acetaldehyde Methane Carbon Calculated 0 0 0 0.1387 0.1040 0.3987 0.3586 0 0 0 0 Simulated 0 0
0.0869 0.1626 0.0544 0.3253

Error 0 0 0.0239 0.0496 0.0734

0.3708 0 0 0 0

0.0122 0 0 0 0

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 Component Nitrogen Water Carbon monoxide Carbon dioxide Hydrogen 43.3924 259.3257 109.7628 325.6961 112.4513 328.3846 112.4781 328.4114 295.5390 69.2453 129.6629 295.5390 2.8729 63.2925 295.5390 0.1864 60.6040 295.5390 0.1596 60.5772 ATR HTS MTS LTS

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 Nitrogen Water Carbon monoxide Carbon dioxide Hydrogen After LTS 295.5390 0.1596 60.5772 112.4781 328.4114 After PROX 295.5390 0.1596 60.5772 112.4781 328.4114

5.5

Plant Wide Optimization

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 1000 . ATR out - Temperature C 800 600 400 200 0 100 350 600 850 1100 1350 air - Molar Flow kgmole/h

Figure 5.6: Temperature of ATR vapour for varies air Feed molar flow

50

270 Hydrogen Master Comp Molar Flow (Hydrogen) kgmole/h . 260 CO

135 . 130 Master Comp Molar Flow (CO) kgmole/h 125 120 115 110 105 100 100 350 600 850 1100 1350 air - Molar Flow kgmole/h

250

240

230

220

210

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.

390 . 380 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 . Comp Molar Flow (H2) kgmole/h

Figure 5.8: Molar flow of CO and H2 effluent for varies water feed molar flow

52

500 450 400 350 300 250 200 150 100 50 30 70 110 150 190 230 270 air - Molar Flow kgmole/h temperature . ATR out - Temperature C

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 Nitrogen Water CO CO2 Hydrogen ATR 295.5390 69.2453 129.6629 43.3924 259.3257 HTS 295.5390 2.8749 63.2925 109.7628 325.6961 MTS 295.5390 0.1864 60.6040 112.4513 328.3846 LTS 295.5390 0.1596 60.5772 112.4781 328.4114

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Table 5.6: Molar flow of the effluent after optimization for ATR,HTS, MTS and LTS. Component Nitrogen Water CO CO2 Hydrogen ATR 295.5390 190.6743 129.6629 43.3924 259.3257 HTS 295.5390 72.6090 11.5976 161.4577 377.3910 MTS 295.5390 61.4964 0.4850 172.5703 388.5036 LTS 295.5390 61.3008 0.2894 172.7659 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

160 . CO molar flow - ppm 120 CO 80 40 0 100 250 400 550 700 850 1000 1150 1300 1450 air - Molar Flow kgmole/h

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 Nitrogen Water CO CO2 Hydrogen PROX Before 295.5390 61.3008 0.2894 172.7659 388.6992 After 434.50 81.0109 0.0109 199.9891 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

800 Temperature , C

600

400

200

0
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

Molar flow , 150 kgmole/h

200

CO H2

100 50 0 ATRo HE1 HE2 HE3 HTSCo HTSo MTSCo MTSo LTSCo LTSo PROXco CO PROX

unit operation

Figure 5.12: H2 and CO profile for the whole unit operation

57 5.8 Fuel Processor Efficiency

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.

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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

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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

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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.

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APPENDIX A Final result from Simulation Aspen HYSYS 3.2

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