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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)

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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:

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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

Muhamad Syafiq bin Adam 15th 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 : : ……………………..

iii To my beloved mother and father… .

An honour and respect to the Prophet Muhamad SAW. to all of my friends that contributed to this thesis. A word thank you can’t describe all of his guidance and encouragement that showed to me during the progresses of this thesis. Especially to my parents. En. Finally. I would like to thank to my supervisor. .iv ACKNOWLEDGEMENTS Alhamdullilah. Thanks to God because all of His merciless and the knowledge that was given. Finally my first thesis was finished. I did my work successfully. I also wanted to thank my family for the moral support. This thesis was dedicated to them. Peace be upon him. Thank you very much to all of them that help me either direct or indirect. for effort and support those drive me to this level. Mohd Kamaruddin. All the knowledge that I learned from him will come in handy at the future.

Using a commercial dynamic flow sheeting software. 83.6% of fuel processor efficiency was achieved.v ABSTRACT Fuel cell application from hydrogen was one of alternative energy that being studied and widely accepted in industry.055 ppm of CO. In this case study. Under these optimum conditions.5.5 and 1. three water gas shift reactors and a preferential oxidation reactor was successfully developed. HYSYS 3. an optimum A/F and S/F ratio are 5. the process of hydrogen production was successfully simulated. In this research.2. . ethanol was chosen as a raw material and with autothermal reforming as a process of produce hydrogen. 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. fuel processor consists of an autothermal reactor. respectively to produce 34 % of hydrogen and 10. This case study focused on optimization of hydrogen production for fuel cell applications.

5 dan 1. tiga reaktor anjakan air gas dan reaktor pilihan pengoksidaan telah berjaya dihasilkan. Dalam kajian ini. Dalam kajian ini. Dibawah keadaan pengoptimaan ini. Dengan menggunakan perisian ‘HYSYS 3. sebanyak 83. Dengan ratio tersebut. Daripada keputusan ujikaji. nilai ratio A/F dan S/F yang optima adalah 5.. proses pengeluaran hidrogen ini berjaya dilakukan secara simulasi.055 ppm CO dapat dihasilkan. pemproses minyak mengandungi reaktor autoterma.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. 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.5 masing-masing.34% hydrogen dan 10.2. .6 % kecekapan pemproses minyak didapati. etanol dipilih sebagai bahan mentah dan pembentukan autoterma (auto thermal reforming) merupakan proses untuk menghasilkan hidrogen.

1 1.4 1.2.vii 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 I INTRODUCTION 1.1 2.1 Natural Gas 6 7 6 .3 1.2 Introduction Hydrogen Production for Fuel Cell Application in General 2.5 Background Research Problems Statement Research Objective Scopes of study Thesis Organizations 1 2 2 3 4 II LITERATURE REVIEW 2.2 1.

2.1.3.3 Hydrogen Production for Fuel Cell from Ethanol 2.1 2.viii 2.3 Diesel 2.5 Heat Integration 3.3 Petroleum Fractional 2.2 Ethanol 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 2.1 Methanol 2.2 Data Collection Base Case Stoichiometry 3.6.2.3.2.3 Propanol 2.3.1.1 Water Gas Shift 3.2 2.3 Propane 2.5 2.2 Gasoline 2.3.6 Carbon Monoxide Clean Up 3.6 Optimization simulation of Hydrogen Production Summary III METHODOLOGY 3.2.2.1 Methane 2.1 Research Tools 3.2 Preferential Oxidation 3.4 Auto-thermal Reactor Optimization 3.2.2.2.1 3.1 3.2.2.2.2.2.2.3.2 Aspen HYSYS 18 18 19 19 19 21 21 21 22 22 22 23 Research Activities 3.7 Plant Wide Optimization .6.1 Kerosene 2.1.3 Base Case Validation 3.2 Alcohol 2.2.2 Ethane 2.2.1.2.2.2.2.1.2.2.2.4 Butane 2.2.

1 Linear and Non-Linear System 4.2.2.3 5.4.3 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 4.2 4.1 Process Description of Hydrogen Production from Ethanol 4.7.4.4.2.2.2.4 Energy Balance 4.2 Modelling and Simulation of Hydrogen Production From Ethanol for Fuel Cell 4.7.4.ix 3.4.2.9 3.2 Water Gas Shift Optimization 3.1 Water Gas Shift 40 43 44 46 46 .4 Thermodynamic Properties Physical Properties Integration Algorithm Mathematical Modelling of the Reactor Operating 4.2 5.3 Preferential Oxidation Optimization 3.1 ATR Optimization 3.7.2.2 Material Balance 4.3 Component Balance 4.1 5.2.3 Degree of Freedom Analysis Analysis of Optimization Response 33 33 34 35 36 38 38 39 27 31 32 33 26 Summary V RESULTS AND DISCUSSION 5.2.2.2.2.2.2.5 4.1 4.2.3 4.6 4.8 3.4 Results for Base Case Study Results for Validation Results for Heat Integration Results for Carbon Monoxide Clean Up 5.

5.1 6.x 5.2 5.4.9 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 6.2 Preferential Oxidation 5.5 Plant Wide Optimization 5.8 5.2 66 .1 ATR Optimization 5.3 5.5.2 6.3 Summary Conclusion Recommendation 58 59 59 REFERENCES 61 APPENDIX APPENDIX A Final result of simulation HYSYS 3.7 5.6 5.5.

TITLE PAGE 3.2 29 4. The operation conditions for the major unit operation 25 27 4.xi LIST OF FIGURES FIGURE NO.2 The whole plant system by Aspen HYSYS 3.1 Process flow diagram of the base case 41 5.5 Block diagram of the simulation of hydrogen plant using Aspen HYSYS 3.5 The PROX reactor 48 .1 Algorithm for methodology.2 39 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 Reactor operating 35 4.3 HYSYS simulation environment 30 4.1 4.4 The WGS reactor 47 5.

10 CO Molar flow in PROX effluent for varies air feed molar flow 54 5.xii 5.11 Temperature profile for the whole unit operation 55 5.6 Temperature of ATR vapour for varies air feed molar flow 49 5.12 H2 and CO profile for the whole unit operation 56 .9 Temperature to ATR outlet for varies water feed molar flow 52 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.

MTS and LTS.5 Molar flow of the effluent before optimization for ATR.4 Effluent molar flow after preferential oxidation reaction 48 5. TITLE PAGE 4. 53 5.1 Physical property of the component 32 5.xiii LIST OF TABLES TABLE NO.2 Validation for simulation effluent compare with calculated effluent 44 5.1 Molar flow of ATR effluent for base case 43 5. 52 5. MTS and LTS.HTS.HTS.3 Effluent molar flow after water gas shift reaction for each reactor 47 5.6 Molar flow of the effluent after optimization for ATR.7 Molar flow of the effluent before and after optimization for PROX 54 .

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 .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.

H2 HTS LTS PROX MTS WGS . etc.xv Y Process Variable Greek letters α ε μ ρ φ ω 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.

Hydrogen as fuel cell technology currently needed in large quantities. (Fuel cell store website. some fossil fuels which have high hydrogen to oxygen ratio were the best candidates to produce hydrogen. water electrolysis and etc. The more hydrogen present and the fewer extraneous compounds was the idea to get it. 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. 2006) For that purpose. Other established methods include partial oxidation of residual oil. easy to obtain. One of the methods which commonly being used was the steam reforming. coal gasification.CHAPTER Ι 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. researcher over the world tries to make use the hydrogen as an alternative energy by converting into fuel cell. virtually silent operation and less pollutant emissions. high efficiency. and is projected to be the fuel of choice for a number of advanced technologies that are being pursued. It is because characteristics of hydrogen that cheap. The new . Hydrogen’s benefit and disadvantages differ from the fossil fuels common place in advanced energy utilizing society. (Fuel cell store website. 2006) From that perspective.

1. Furthermore. partial oxidation and steam reforming.2 technologies such as high-temperature electrolysis of steam. gasoline.2 Problem Statement In reality. photochemical. thermo chemical water splitting. Optimization simulation can help researcher to make better design. Hydrogen can be obtained directly from ethanol by two main processes. (Fuel cell store website. aviation jet fuel. relatively high hydrogen content and availability and ease of handling. 2006) 1. chemical plants are never truly at steady state. the fact that is a relative clean fuel in terms of composition. optimize. In this research. ethanol is of particular interest because its low toxicity. and hydrogen itself. (Fuel cell store website. and plasma chemical methods. thermal cracking of natural gas. the optimization is the main case study that will make more yield selectivity hydrogen. low production costs. These technologies can be classified as thermal. Feed and environmental disturbances. and plasma decomposition of water is still investigated its efficiency. diesel fuel. and catalytic degradation continuously upset the conditions of a smooth running process. 2006) Seven common fuels are the postulated hydrogen sources studied in this work alcohol. The important of this study is to identify design parameters and also to estimate fuel processor efficiency. solar photovoltaic water electrolysis. thermo chemical. electrochemical. . and operate process or refining plant. heat exchanger fouling. ethanol is the main focus to study the steady state behaviour. natural gas. Among the bio-fuel candidates for carriers of hydrogen.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.

2.4 Scope of Study To achieve above objective. hydrogen production simulation plant was being developed with data from Akande et al. 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. . (2005) ii. 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. Water gas shift Equilibrium reactors were placed to the plant to convert CO into carbon dioxide (CO2). v.2. Base case simulation development By using Aspen HYSYS 3. Three reactors were needed for conversion with water gas shift (WGS) reaction as the main reaction. iv.3 1. it was validated using theoretically data from total reactions stoichiometry coefficient. iii. a. several scopes has be drawn: i. Base case simulation validation From base case simulation that being developed with Aspen HYSYS 3. 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.

preferential oxidation (PROX) reaction was introduced. 1. a. vi.4 b. ATR optimization It’s used to optimize the ATR temperature outlet for heat integration. Plant wide optimization It was develop to optimized all the reactors used in the plant developed using Aspen HYSYS 3. Chapter Two is discuss about the literature survey that related in synthesis of hydrogen for fuel cell applications. Water gas shift optimization It’s used to optimize water molar flow to the ATR and reduces the CO concentration with WGS reaction. internal researched of hydrogen production using ethanol by autothermal reforming was been concentrated. c. In this chapter. Preferential oxidation To maximum reducing CO. This chapter is the major chapter because the development of the of hydrogen production are based on the literature survey that we had researched.2 and to reduced CO concentration to the specific requirement. . b.5 Thesis Organizations This thesis involves the conclusion of the several tasks to achieve the objective. vii. Preferential oxidation optimization It was formed to maintain the amount of air into PROX reactor that reduced the CO concentration to the specification. Temperature and component profile The profile of temperature and components for every unit operations involve in this research was analyzed.

We are using Aspen HYSYS 3. there are five methods that we carried out. Chapter Four. Fundamentally.5 Chapter Three is about the methodology for the methods that we need in scope. Chapter Six is the conclusion all what we have done in this entire thesis. Chapter Five is the results and discussion based on the methodology that we use and developed from chapter four.2 as a simulator to simulate the plant. is optimization simulation of hydrogen production plant from ethanol for fuel cell application. Finally. The next chapter. .

Hydrogen used in secondary power units is produced in a fuel processor by the catalytic reforming of hydrocarbons. (Fuel cell store website.1 Introduction In this chapter. propane and butane are some example of natural gas. It is meant to provide a list of hydrogen had been produced by a specific class of hydrocarbon such as natural gas and alcohol. The different between those methods was higher selectivity of hydrogen. From this review. Diesel. Petroleum fractional such as kerosene. some significant journal will be taken as references. 2006) 2. a general hydrogen production using natural gas. ethanol and propanol were some of them. Methane. jet fuel. (Fuel cell store website.6 CHAPTER II LITERATURE REVIEW 2. ethane. Methanol. gasoline. alcohol and petroleum fractional of gas as an input will be reviewed.2 Hydrogen Production for Fuel Cell Application in General Fuel cell requires hydrogen as its fuel source for generating power. 2006) Alcohol can also be used to produce hydrogen with a different condition either used a same method or not. and diesel too will produce hydrogen by using same method like reforming. are . gasoline. as well as natural gas.

1 Methane Ferna´ndez et al.2. . which was resulted in the shut-down of the fixed bed reactor system. (2004) in order to overcome the reactor plugging problem due to carbon deposition. 2006) 2. Galvita and Sundmacher (2005) said that almost CO-free hydrogen gas. for hydrogen production for fuel cell applications. The fluidized bed reactor was proposed by Lee et al. (Fuel cell store website. Ethane. where a hydrotalcite-derived Ni catalyst has been used as steam reforming catalysts.1. 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. Several kinds of activated carbons were employed as the catalyst to examine the reaction activity. 2002) 2. propane and methane are the family of natural gas which they produce hydrogen-rich too. (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. (Liu et al.7 potential fuels that all have existing infrastructure of manufacture and distribution.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. due to its large abundance and high H: C ratio is an ideal source of hydrogen..2. Methane.

particularly for benzene formation. 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.1. 1997).. . The key reactions forming the higher hydrocarbons involved addition of radicals to unsaturated bonds (Shebaro et al. 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. (2005) over a Ni/SiO2 catalyst at temperatures ranging between 450 and 650 °C. Wang 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.8 Oxidized diamond is proposed by Nakagawa 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. Bingue 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.2 Ethane The catalytic decomposition of ethane was studied by Chin et al.2.

2.% Rh/Al2O3 foam catalysts and concluded high selectivity to hydrogen was obtained for both reactions. 2. methanol and ethanol are now seriously considered as a source for fuelcell-powered vehicles. olefins. (2003) found the major difference between the two catalysts at 648 K.2.4 Butane Avci et al. (2005) investigated partial oxidation and oxidative steam reforming of propane over 0.9 2.01 wt.. 2005) .2. While propanol too produce high selectivity of hydrogen with various support of certain catalysts. Silberova et al. the steam reforming of propene is faster and more selective than steam reforming of propane. Resini et al.1. In particular. (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. (2005) compared the both catalyst and suggest the palladiumbased catalyst.2 Alcohol Alcohols as fuel have been proven to be effective in the near complete elimination of emissions of benzene.3 Propane Aartun et al. at which Pt-Ni/γ-Al2O3 showed superior performance in terms of selective hydrogen production that resulted in lower carbon dioxide and methane formation. complex hydrocarbons and SO2.2. (Wanat et al.1.

2. Aupretre et al. Xu et al.1 Methanol Basile et al. The effects of reaction conditions and catalyst reducibility on the . 2. 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. (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.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. (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. Liu 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. A reaction mechanism is proposed by Mattos and Noronha (2005b) to explain the catalytic tests. especially in ethanol steam reforming (ESR)but the conditions plead in favor of a support that is non-acidic and moderately basic. (2005) conclude that Rh is the most active metal in the steam reforming reaction.10 2.

2. Wanat et al. When both ceria and lanthana were present on the support substrate the platinum–ceria interaction was diminished. A series of Pt catalysts supported on alumina modified by Ce and/or La were discussed by Navarro et al. (2005) have shown that different alcohols have very different selectivity in catalytic partial oxidation at short contact times even at high temperatures. Mizuno et al. reducing the promoter effect in the production of hydrogen by oxidative reforming of ethanol.3 Propanol CeO2 resulted in the highest selectivity and fairly higher stability for the steam reforming among the supported Rh catalysts. (2005) with those obtained over Ni–Cu/SiO2 and Rh/Al2O3 catalysts and suggest that its provided very good activity and selectivity for ethanol partial oxidation reaction with high selectivity to H2.11 performance of the Pt/CeO2 catalyst in the partial oxidation of ethanol were described. 2-Propanol gave lower conversions and less H2 and CO than the other alcohols. . Rapid adsorption of alcohols as alkoxy species leads to complete dissociation to H2 and CO. H2 production and CO2/COx ratio obtained over Ni-based catalysts supported on Al2O3 are compared by Fierro et al. (2003) concluded that Rh=CeO2 is actually superior to any other catalyst for the steam reforming of IPA.2. but produced the most chemicals. 2. (2004) involving the production of hydrogen by oxidative reforming of ethanol.

the focus is on reforming both gasoline (for automotive applications) and diesel (for trucks and heavy-duty vehicles). based on a partial oxidation process.5 and air to fuel ratios of λ = 0.2. The conversions of methane.5–2. has been developed by Minutillo (2005) and tested it using the experimental data of a plasma-assisted reformer. propane. Suzuki et al.3. Highly dispersed Ru/Al2O3 catalyst can be obtained by using ruthenium trichloride and aqueous ammonia in the catalyst preparation.3 Petroleum Fractional The Polymer Electrolyte Membrane (PEM) fuel cell requires hydrogen as its fuel source.2. 2. the focus has been on reforming natural gas and liquefied petroleum gas.2. 2005) 2.2 Gasoline A numerical model of a simple reforming system. For portable power generation.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.24–0. In order to avoid storing high-pressure hydrogen. Lenz and Aicher (2005) successfully performed experiment at steam to carbon ratios of S/C = 1. heptane.12 2. (Cheekatamarla and Lane. (2000) was discussed about long sustained run of hydrogen production using HD-kerosene was successfully achieved on the CRI-101CE catalyst (Ru/CeO2±Al2O3). toluene and gasoline to hydrogen have been investigated and a thermodynamic . the primary focus is on reforming gasoline. the fuel can be generated in an onboard fuel processor. For transportation applications. because a production and distribution infrastructure already exists. For auxiliary power units.32.3.

Methanol.13 analysis of the reforming system has been conducted by means of the AspenPlus software. ethanol for example.3 Hydrogen Production for Fuel Cell from Ethanol Fuels containing hydrogen generally require a “fuel reformer” that extracts the hydrogen from any hydrocarbon fuel.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 metal–metal and metal–support interaction in the catalyst. diesel fuel. natural gas. 2. 2. Otsuka et al. offers a high octane . ethanol. 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. (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. gasoline.2. and hydrogen are compared by Brown (2001) for their utility as hydrogen sources for proton-exchange-membrane fuel cells used in automotive propulsion. aviation jet fuel. Ethanol appears as an attractive alternative to methanol since it is much less toxic.

%)/Al2O3 catalysts and five bimetallic catalysts. Akande et al.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. 2. The result showed the type of species generated by the synthesis method.68 respectively) and a reforming temperature between 923 and 1073 K. Ni/Cu and noble metal (Pd. co-precipitation (CP) and impregnation (IM)). (2004) analysed ethanol steam reforming with and without the presence of CaO as a CO2 sorbent. Co.3. 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.e. all of them supported on Al2O3. Pt. By using high temperatures. Steam reforming was the popular way to produce follow by partial oxidation.14 number. Ni loading and reduction temperature on the characteristics and performance of Ni/Al2O3 catalysts for the reforming of crude ethanol for H2 production.6 and 0. precipitation (PT). (2005). a high heat of vaporization and a low photochemical reactivity. low pressures and high water-to-ethanol ratios in the feed favour hydrogen production. They founds Both processes show the same behaviour with pressure and water to ethanol ratio. atmospheric pressure and water to . Rh)-supported catalysts to produce hydrogen by using steam reforming. There was several method of producing hydrogen using ethanol. Two Ni (11 and 20 wt. Vaidya and Rodrigues (2005) Ni. were tested by Fiero et al. (2005) were estimated the effects of catalyst synthesis method (i. the PT catalysts were more reducible than the CP and IM catalysts. Comas et al.

the nature of the support (Al2O3. From the endurance tests Freni et al. Pt/ZrO2. Liguras et al. Sun et al. 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. (2003) founded out at low gas hourly space velocity (10. Mattos and Noronha (2005a) showed that the support plays an important role on the products distribution of the partial oxidation of ethanol. the 5% Ru/Al2O3 catalyst is able to completely convert ethanol with selectivity toward hydrogen above 95%.1% and 49.1% and 99.%). Pt/CeO2 and Pt/Ce0. . under certain reaction conditions. (2004) proved that the catalyst Ni/Al2O3 exhibits relative lower activity for ethanol steam reforming and hydrogen selectivity.2 Partial Oxidation The performance of Pt/Al2O3.15 ethanol relations higher than three are favourable conditions for higher hydrogen productions without carbon formation.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. They found it from investigated of the active metallic phase (Rh. 2.50Zr0. Pt. TiO2) and the metal loading (0–5 wt. the conversion of ethanol increased to 93.50O2 catalysts as the support were being studied upon on each individual’s catalyst.5%. (2002) found that.3. When temperature reached 320 °C. MgO.7%. Pd). and a selectivity of hydrogen of 43.2% and 48.9% and 80.5% and the selectivity of hydrogen was 53.in the temperature range of 600–850 °C . Ru.5%. respectively.

Catalysts prepared by precipitation generally exhibited lower crystallite sizes of NiO species than the corresponding catalysts prepared by co-precipitation.4 Steam Reforming of Ethanol for Hydrogen Production Akande et al. USA. producing CH4. The catalysts prepared by . Mattos and Noronha (2005b) found that at low conversions. forming acetaldehyde. C2:12H6:12O1:23 + 3:01H2O → 2:12CO2 +6:07H2 (2. PA. the ethanol dehydrogenation dominates. Crude ethanol was delivered to the reactor chamber by means of a HPLC pump regulated at the desired flow rates. and CO. The feed for this process was crude ethanol. The product mixture during reaction was passed through a condenser and gas– liquid separator to separate the gaseous and liquid products for analysis. They investigated that which method will produces highest selectivity hydrogen yield. 2. As a result of the type of species generated by the synthesis method. Ni loading and reduction temperature on the characteristics and performance of Ni/Al2O3 catalysts were estimated. The reactions were carried out at atmospheric pressure and reaction temperature of 400 °C. three methods of synthesis: coprecipitation.16 From the effect of reaction conditions and catalyst reducibility on the performance of the Pt/CeO2 catalyst. Based on this composition.1) Upon experiment of synthesis catalysts. precipitation and impregnation were investigated. the general equation representing the reforming of crude ethanol can be represented as in equation below. whereas at high conversions the decomposition of ethanol is favoured. H2. the PT catalysts were more reducible than the CP and IM catalysts. (2005) reported that the effect of catalyst synthesis method. The reactor used to obtain experimental data was BTRS model number 02250192-1 supplied by Autoclave Engineers. Erie.

2. there are three major groups that can synthesis hydrogen for fuel cells. CP15 gave the highest yield because the CP catalysts gave the highest H2 selectivity as compared to corresponding catalysts prepared by precipitation and impregnation.17 impregnation had the largest crystallite sizes except IM10 which had the smallest crystallite size.6 Summary Generally. Ozdogan et al. There are a researchers had done the research about ethanol but a few had done research it in simulation. alcohol and petroleum fraction. Jiménez (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. . They studied the effect of average molecular weights of hydrocarbons. 2. there were few researchers did on optimization simulation of hydrogen production using ethanol as a raw material for fuel cell application. we can conclude that. partial oxidation reforming. In terms of H2 yield. on the fuel cell processing efficiency. some of them did research hydrocarbon on simulation. autothermal reforming. Additionally. Focus of this literature survey is to find a research about ethanol as an input for hydrogen production by autothermal reforming. there are many articles and journal on hydrogen production for fuel cell application but when we are grouping that journal.1 to compare two liquid hydrocarbon fuels. there are many processes that produce hydrogen such as steam reforming. etc. However.5 Optimization Simulation of Hydrogen Production Based on the literature reviews that have been done. Three of them are natural gas. (2005) shows by using hydrocarbon fuel as source in HYSYS 3.

1 Aspen HYSYS HYSYS was a product of AEA Technology. HYSYS has the unique feature that information propagates both in forward and reverse directions. HYSYS has been chooses as the process simulator for this research because of two main advantages over the other software packages. performing back-calculation in a non-sequential manner. It can interactively interpret commands as they entered one at a time.1. The bi-directionality often makes iterative calculations unnecessary and the solution is fast.2 simulator was used for process flow sheeting to provide data regional analyses.1 Research Tools This research was carried out using various computational tools. which is now part of Aspentech Engineering Suite (AES). Aspen HYSYS 3. Other requires execution after new entries.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. Aspen HYSYS 3.18 CHAPTER ΙΙΙ METHODOLOGY 3. . 3.

(2005) elaborate the reaction that might be occurring while ethanol steam reforming reaction was reacted. variables. about hydrogen production from ethanol is collected.4) .2) (∆H° = -157kJmol-1) (3. Other journal that related to this case study was collected too.2 Research Activities 3.2. approximate correlations. Vaidya et al.2 Base Case Stoichiometry Vaidya et al.5O2 → CH 3 CHO + H 2 O (∆H° = -175kJmol-1) (3. ethanol cracking.1 Data Collection From theoretical analysis and the report that have been done by Akande et al. dynamic characteristic and etc. (2005). CH 3CH 2 OH + 3H 2 O → 6 H 2 + 2CO2 (∆H° = 174kJmol-1) (3. Reaction such as ethanol steam reforming.1) However. 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) (3.3) Total oxidation of ethanol to H2 and acetaldehyde respectively. 3. variables relationship.2.. other undesirable products such as CO and CH4 are also usually formed during reaction. and the others were collected to comparable. (2005) showed that the reaction is strongly endothermic and produces only H2 and CO2 if ethanol reacts in the most desirable way. Fierro et al. the main reactions are being given by: CH 3 CH 2 OH + 0.19 3. (2005) show that some reaction that using by ethanol.

6) (∆H° = -74kJmol-1) (3. ethanol dehydration to ethylene.5CH 4 CH 3 CH 2 OH → CO + CH 4 + H 2 (∆H° = 68kJmol-1) -1 (3. 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 → 0.9) (3. 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) (3.14) C 2 H 6 + 2 H 2 O → 2CO + 5H 2 In addition. 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. CH4 and H2.19) Other reaction: CH 4 → C + 2 H 2 (∆H° = 75kJmol-1) (3.5O2 → CO + 2 H 2 CH 4 + O2 → CO2 + 2 H 2 CO + 0.12) (3.16) (∆H° = -320kJmol-1) (3.13) (3.5CO2 + 1.17) (∆H° = -280kJmol-1) (3.20 Other reactions that can also occur are: ethanol dehydrogenation to acetaldehyde.8) They suggested the occurrence of several reactions: acetaldehyde formed by dehydrogenation of ethanol is decomposed to CH4 and CO or undergoes steam reforming.15) (∆H° = -36kJmol-1) (3. ethanol decomposition to CO2 and CH4 or CO. the following reactions occur when O2 is present: CH 4 + 2O2 → CO2 + 2 H 2 O CH 4 + 0.11) (3.5O2 → CO2 C + O2 → CO2 (∆H° = -800kJmol-1) (3.20) .18) (∆H° = -390kJmol-1) (3.7) (∆H° = 49kJmol-1) (3.5) (∆H° = 45kJmol ) (3.10) Water reforms the C1 products to hydrogen.

By apply a heat exchangers to a process.22) 3.21) (∆H° = -52kJmol-1) (3. 3. air. 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.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. and ethanol.2. 3. The optimize air molar flow rate need to be above 700°C when flow out at the ATR vapour stream.2.21 C2 H 4 + H 2 → C2 H 6 C 2 H 4 → 2C + 2 H 2 (∆H° = -140kJmol-1) (3. 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.5 Heat Integration All hot and cold streams were systematically arranged to build system heat integration.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. . water.2 simulation. This is for usage of heat energy in heating the feed stream. This can really save a lot of energy and achieve target required. the heat from ATR vapour stream was being cooled down by the feed stream. Two case studies have been developed in this optimization.

Water gas shift and preferential oxidation can reduce CO and are being used in this research entirely.2. followed by medium temperature shift (MTS) and end with low temperature shift (LTS).5O2 → H 2 O (∆H° = -280kJmol-1) (3.6 Carbon Monoxide Clean Up Carbon monoxide is a dangerous gas that should be aware and not profitable. There were three equilibrium reactors that being attached after stream that flow out from ATR reactor.2. Several reactions may produce it as main product or by-product.1 Water Gas Shift Water gas shift is the first stage to reduce the CO after reaction in ATR. and will react on this reaction: CO + H 2 O ⇔ CO2 + H 2 (∆H° = -42kJmol-1) (3. It was performed in order to reduce the CO concentration out of the LTS to the ppm levels required for the fuel cell.6. CO will be converted into hydrogen and carbon dioxide when mixed with steam. The PROX reactor was modelled as a conversion reactor based on two reactions to oxidize CO.6. Stream from ATR vapour will entered this entire three equilibrium reactor.24) (∆H° = -240kJmol-1) (3.22 3. the cleaning method is required need and converts it to other relevant component.25) . The conversion reactor was attached after WGS stage. 3. So. the reactions were CO + 0.2.23) 3.2 Preferential Oxidation The next stage CO cleans up was preferential oxidation reactions.5O2 → CO2 H 2 + 0. The first reactor is called high temperature shift (HTS).

. For this optimization. water gas shift optimization optimized the HTS. 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.23 3. 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. 3. ATR optimization optimized the stream out ATR reactor.7 Plant Wide Optimization Plant wide optimization was being done to optimize the usage of the reactors for the whole plant. 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. The optimized water molar flow rate was taken at the point where the temperature for HTS inlet is above 100°C. The case study one was optimizing the air flow and set the range of the molar flow rate that can be manipulated.2. MTS and LTS reactors and preferential oxidation optimization optimized the PROX reactor.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. These was important because it will affect the heat exchanger network if the required temperature not in right conditions.2. case study three developed to monitor the CO and hydrogen concentration in each reactor except PROX after varying water feed molar flow rate.7.

2. 2005) η= (n H2 LHV H 2 + nCO LHVCO nCxHyOz LHVCxHyOz ) (3.9 Fuel Processor Efficiency The system fuel processor efficiency can be calculated by : (Lenz and Aicher .2.26) .24 3. the conditions like the temperature and the component on overall plant also were studied well. Next.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. 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. 3. This is needed to find out the different for each reactor and their effect.7.2.8 Temperature and Component Profile By looking at the temperature and component profile. we investigated the behaviour of every unit operations. 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 60°C to 100°C.

All of them are systematically do as a Figure 3.25 3. plant wide optimization. The method are describe in detail from stoichiometry mathematical analysis calculation.1 : Algorithm for methodology. 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. components and temperature analysis to fuel processor efficiency. clean up model. heat integration model. .3 Summary This chapter basically show the methodology that need to accomplish.1. validation. base case development with HYSYS.

There were three reactor in WGS section. Then the outlet stream will enter WGS reactor. ethanol. Figure 4. the outlet entered the PROX reactor and the product was ready to enter fuel cell.26 CHAPTER ΙV SIMULATION AND OPTIMIZATION OF HYDROGEN PRODUCTION PLANT FROM ETHANOL FOR FUEL CELL APPLICATION 4. and PROX). It started from the feed stream. air and steam at 1 atm enter the ATR reactor.1 presents the investigated operation conditions for major fuel processing units (ATR. HTS. MTS and LTS.2 has been used along with conventional calculations in this study. 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. MTS. Finally. . LTS.1 Process Description of Hydrogen Production from Ethanol The process simulation package Aspen HYSYS 3. HTS.

Building Stage a) Adding and define streams b) Adding and define unit operations i. Water gas shift reactor 1. Medium temperature shift reactor 3. Preparation Stage a) Selecting the thermodynamic model b) Define chemical components ii. Low temperature shift reactor iii.1: The operation conditions for the major unit operation 4. the simulation process takes the following stages: i. Heater .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. High temperature shift reactor 2. Auto-thermal reforming reactor ii.2 shows it.27 100°C Ethanol Air Steam ATR reactor 100°C WGS reactor 70°C PROX reactor To Fuel Cell Air Figure 4. Typically. Preferential oxidation reactor c) Connecting streams to unit operations d) Add auxiliary unit i.

28 ii. Execution a) Starting integration b) Optimization the whole plant . Cooler iii. Heat exchanger iii.

Figure 4.2 29 .2: The whole plant system by Aspen HYSYS 3.

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. Integrator / Solver HYSYS Simulation Environment Physical Property Library Unit operation Model ThermoDynamic Package Figure 4. iv) Mathematical modelling of unit operation.30 HYSYS simulator is made up of four major parts to form a rigorous modelling and simulation environment. For this study. each of above components is described in below.3: HYSYS Simulation Environment .

. the Peng-Robinson Equation of state was found to simulate hydrogen production faster than the real time.45724 . σ = 1 + 2 .1 Thermodynamic Properties In order to define the process. Ethanol is the primarily characterized as a C2H5OH.2) bi = (4.37464 + 1. ε = 1 − 2 . ωi ) R 2Tci 2 Pci ΩRTci Pci (4. The feed for the hydrogen production is considered to be relatively ideal mixture of ethanol and oxygen.26992ωi 2 )(1 − Tr 1 / 2 )]2 For dynamics modelling of hydrogen production.3) Where according to Peng Robinson (1976). 2000): P= ai (T ) RT − Vi − bi (Vi − εbi )(Vi + σbi ) (4. 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.07779 . Ω = 0.ωi ) = [1 + (0. Therefore.30740 . When performing the dynamics simulation. ψ = 0.2.54226ωi − 0.1) The terms. the thermodynamic property packages used to model steady-state of ethanol must be specified.31 4. ai (T ) = ψα (Tr i . Z c = 0. α (Tr i . Aspen HYSYS permits a user selected thermodynamics calculation procedure.

32 Additionally.39 383.1. 2000).2 Physical Properties Components that entered the ATR for the process hydrogen production was ethanol.39 825. Table 4.60 19.25 -183.01 799.015 28. All components are present in room temperature.98 1137. the component such as carbon monoxide.95 100. carbon dioxide.05 12.2.52 -103. methane and carbon need to define in HYSYS environment. ethylene.68 997. acetaldehyde. For the Aspen HYSYS model the default values were selected.55 -252. 4.010 2.014 ρ(kg/m3) 795.999 18.010 44. the allowable maximum and minimum temperature and maximum pressure over which dynamics are calculated and is user defined in Aspen HYSYS. The maximum pressure was selected to be 1 atm above the highest pressure in the flow sheet (HYSYS reference.80 CO CO2 H2 C2H4O CH4 C2H4 C 28. water and air. The densities were taken at 25°C. .00 299.00 -195. Usually the default minimum and maximum temperature value in flow sheet. Additionally. respectively. nitrogen. The pure component properties of the feed stock are listed in 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) 46.45 -78.34 69.04 28. oxygen.99 806.069 31.06 -191.86 777.23 1642.016 44. ρ was density and BP was boiling point.05 16.85 -161.75 - MW was the molecular weight. hydrogen.37 BP (°C) 78.

whereas energy and composition balances are defaulted to solve at every 2nd and 10th integration step. 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). respectively.2.5 second was selected. 4. The volume.33 4.4) To provide a balance between accuracy and speed.3 Integration Algorithm A dynamic model is represented by a set of ordinary differential equations (ODEs) in Aspen HYSYS. The integration time step can be adjusted in Aspen HYSYS to increase the speed or stability of the system. The default value of 0. Yn +1 = Yn + t n +1 tn ∫ f (Y )dt . Volume balances are defaulted to solve at every integration step. In order to solve the model.5) .2. Aspen HYSYS employs a unique integration strategy. 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.4 Mathematical Modelling of the Reactor Operating 4. where : dY = f (Y ) dt (4.1 Linear and Non-Linear Systems A linear first-order Ordinary Differential Equation (ODE) can be described as follows: τ dY + Y = Kf (u ) dt (4.2. energy and speed composition balances are solved at different frequencies. 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.4.

4. the process variable Y may appear as a power.7) τ dY + YY2 = Kf (u ) dt The great majority of chemical engineering processes occurring in nature are nonlinear. component. or reaction rates of chemical systems. The dynamic mass. While a linear system of equations may be solved analytically using matrix algebra.4. or is not independent of other process variables.2. Nonlinearity may arise from equations describing equilibrium behaviour. 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.34 In a non-linear equation. fluid flow behaviour. exponential. the solution to a nonlinear set of equations usually requires the aid of a computer. 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 .2 Material Balance The conservation relationships are the basis of mathematical modelling in HYSYS.6) (4. Here are two examples: τ dY + Y 3 = Kf (u ) dt (4. It is the accumulation term which allows the output variables from the system to vary with time.

Flow of component j out of system + Rate of formation of component j by reaction .2.3 Component Balance Component balances can be written as follows: Rate of accumulation of component j = Flow of component j into system .35 Figure 4.8) Where: Fi = the flow rate of the feed entering the reactor tank ρi = the density of the feed entering the reactor tank Fo = the flow rate of the product exiting the reactor tank ρo = the density of the product exiting the reactor tank V = the volume of the fluid in the reactor tank 4.4: Reactor operating d ( ρ oV ) = Fi ρ i − Fo ρ o dt (4.4.

4 Energy Balance The Energy balance is as follows: Rate of accumulation of total energy = Flow of total energy into system . 4.Work done by system on surroundings . the balance for component j would be as follows: d (C joV ) dt = Fi C ji − Fo C jo + R jV (4. in general. there are NC component balances.4.2. While convective flow contributes to the majority of the flow into and out of a system.Flow of total energy out of system + Heat added to system across its boundary + Heat generated by reaction . The total mass balance and component balances are not independent.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. you would write the mass balance and NC-1 component balances. diffusive flow maybe come significant if there is a high interfacial area to volume ratio for a particular phase.36 Flow into or out of the system can be convective (bulk flow) and/or molecular (diffusion). For a multi-component feed for a perfectly mixed tank.

11) . The general energy balance for a 2-phase system is as follows: d [ ρ vVv H + ρ l Vl h ] = Fi ρ i hi − Fl ρ l h + Fv ρ v H + Q + Q r dt (4. The inlet and outlet velocities are not high. the inlet and outlet elevations are roughly equal.10) Where: u = Internal energy (energy per unit mass) k = Kinetic energy (energy per unit mass) φ = 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. Heat added to the system across its boundary is by conduction or radiation. If there is no shaft work (no pump).37 The flow of energy into or out of the system is by convection or conduction. therefore kinetic energy terms are negligible. For a CSTR with heat removal. the following general equation applies: d [(u + k + φ )V ] = Fi ρ i (u i + k i + φ i ) − Fo ρ o (u o + k o + φ o ) + Q + Q r − ( w + Fo Po − Fi Pi ) dt (4. w=0.

Corresponding process outputs were monitored to get the scope required. In general.12 is obtained N ss = N m − ( N om + N oy ) (4. Selected process inputs were changed when the process had been optimized.38 4.12) In any process simulation work. this is the number of adjustable valves plus other adjustable electrical and mechanical devices.2. an optimization analysis will carry out to show the efficiency of the plant wide. Second is steady state degrees of freedom. it is essential that the degrees of freedom analysis be carried out to determine the number of variables to be specified. The first one is dynamic degrees of freedom. Nm is usually easily obtained by process insight as the number of independent variables that can be manipulated by external means.2. 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 4.6 Analysis of Optimization Response The case study for certain section of plant was selected.5 Degree of Freedom Analysis There are two types of degree of freedom. . Nm (m denotes manipulated). 4. Nss which is the number of variables needed to be specified in order for a simulation to converge.

2.3. A block diagram about the simulation of hydrogen plant using Aspen HYSYS 3. Mass and energy balances have established for all cases.39 4. All the data that gathered from literature surveys are used.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 4.2 is shown in Figure 4. For the simulation of HYSYS.5: Block diagram of the simulation of hydrogen plant using Aspen HYSYS 3. the equation of state that used is Peng-Robinson to calculate the stream physical and transport properties.2 . Enter Aspen HYSYS 3.3 Summary Basically. this chapter is about the development of the simulation using Aspen HYSYS 3.

1. The feed were entered the ATR in a different stream as shown in Figure 5. 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. respectively. air and water into a single autothermal reactor (ATR) in vapour phase. Since ethanol and water are in liquid phase at room temperature. This process was done by heating the materials with heaters until 100 oC as the ethanol and water boiling point are 78.1 Results for Base Case Study The base case of this study was developed by introducing all the raw materials which were ethanol. 25 oC. 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.40 CHAPTER V RESULTS AND DISCUSSIONS 5.4 oC and 100 oC. these two materials need to be converted to gas phase first. .

H2 is also produced.2).4) are being given by: CH 3 CH 2 OH + 0. al. (2006).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. the main reactions (3. after total oxygen conversion. 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.1) and (3. 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. The basic reaction scheme. (3. The reaction is strongly endothermic and produces only H2 and CO2 if ethanol reacts in the most desirable way.5O2 → CH 3 CHO + H 2 O . However. Total oxidation of ethanol to H2 and acetaldehyde respectively.41 Figure 5.

acetaldehyde too reacts and produces CO and H2 (3. (3. (3. (3. CH4 and H2 (3.1) .7) or CO.15).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. ethanol dehydration to ethylene (3.10).42 Other reactions that can also occur are: ethanol dehydrogenation to acetaldehyde (3. 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 → 0.8).22) and (3.17).5O2 + 2 H 2 O → 6CO2 + 8CO + 23H 2 (5.16) and (3. All these 13 reactions are reacting in an autothermal reactor (ATR) in vapour phase.5O2 → CO + 2 H 2 CH 4 + O2 → CO2 + 2 H 2 Steam reforming of methane will give more production of hydrogen.5CO2 + 1. ethanol decomposition to CO2 and CH4 (3. C 2 H 4 O + H 2 O → 2CO + 3H 2 When O2 occur. Total reaction for all the reactions (5.1) are given as: 7CH 3CH 2 OH + 5. methane will react and turn out total oxidation. The reactions of the process.6).5CH 4 CH 3 CH 2 OH → CO + CH 4 + H 2 At low temperature in steam reforming conditions. CH 4 + 2O2 → CO2 + 2 H 2 O CH 4 + 0. and partial oxidation.5).

5783 69.57 kgmole/hr respectively. the flow rate for oxygen and water is 78. The flow rate of the ATR effluent is given in Table 5.2490 129.3220 0 0 0 0 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. Taking basis 100 kgmole/hr of reactant ethanol.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 3.1: Table 5. . This will make the air flow rate is 374.1597 kgmole/hr.2 simulation.4019 259.6610 43.43 From the total reaction.5714 kgmole/hr and 28.5:2 for ethanol over oxygen over water. the feed ratio that should be introduced into the reactor is 7:5.

3 Results for Heat Integration The feed stream was basically in a room temperature condition.3586 0 0 0 0 Simulated 0 0 0.2 show the diagram of the heater being attached. three heaters were installed to the feed stream.3708 0 0 0 0 0. ranging from 1. 25°C.2 is valid and can be used as a real plant for further analysis. The outlet temperature from ATR was above 700°C.1387 0.1626 0. Figure 5.0122 0 0 0 0 From Table 5. .2%7.0869 0.0544 0.3987 0.0734 0.3%. so we can apply the heat exchanger network. Since the errors are small. 5.44 Table 5.0239 0.3253 Error 0 0 0.1040 0. In order to achieve this target. we can conclude that the simulation model developed using Aspen HYSYS 3.0496 0. errors for all components are very small. The temperature required to enter the ATR reactor was 100°C.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 0.2.

25°C. HE2. The hot streams from ATR vapour out will cooling down by cold stream from stream ethanol. and out to 100°C.45 Figure 5.2: The heater attachment on the ATR reactor Heat exchanger network from three cold stream and hot stream was being applied. water and air.5 °C before entering WGS. and HE3 was replaced for heater-1. Heat exchanger HE1. heater-2 and heater-3. .3 shows the ATR reactor after heat integration.3 °C to 497. All these stream was entered the heat exchanger at room temperature. The temperature ATR vapour stream was cooled from 763. Figure 5.

This component was unprofitable and dangerous to environment.23) in which CO was converted to meet the specification. 5. This process was repeated until to LTS reactor.1 Water Gas Shift The ATR effluent was passed through ATR cooler to cool down its temperature to the desired HTS inlet temperature.3 shows the molar flow of the component out of all reactors involved.4 show the WGS reactor being attached after outlet ATR reactor. needs to be cleans up by using water gas shift reaction and preferential oxidation reactions. The HTS was performed the water gas shift reaction (3. From the water gas reaction. Figure 5.4.4 Results for CO Clean Up CO needs to be cleans up for the safety. the composition of CO decreased . Then the outlet from HTS was being cool to enter MTS reactor. The CO was produced in ATR. 5. The Table 5.46 Figure 5.3: The heaters at the feed streams were exchange with the heat exchanger.

1864 60.3257 109.2 Preferential Oxidation Effluent from the LTS was cooled down first to the required PROX inlet temperature.24) and (3.4.6961 112.8729 63.27% to 7.3846 112.6040 295.1596 60.5772 ATR HTS MTS LTS 5.3924 259. simultaneously.25) took place in PROX conversion reactor.6629 295. . Meanwhile the composition of hydrogen was increased from 32.20%.4: The WGS reactor Table 5. Figure 5. This extra air stream was needed in the optimization.6%.5390 0.4513 328.5390 0. (3. Preferential oxidation reactions.4781 328.47 from 16. Additional air was attached to the PROX reactor with zero molar flow as shown in Figure 5.5390 69. CO was oxidized to CO2 and the H2 was oxidized to H2O.5390 2.4114 295.3: Effluent molar flow after water gas shift reaction for each reactor Master Component Nitrogen Water Carbon monoxide Carbon dioxide Hydrogen 43.5.53% to 41.2453 129.2925 295.7628 325.

4114 5.5: The preferential oxidation reactor Table 5. 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. .5390 0. WGS optimization optimized the water molar flow rate and increase the water gas shift reaction in HTS..1596 60.4114 After PROX 295.4781 328.5 Plant Wide Optimization Plant wide optimization was set to optimize the hydrogen production while minimize the CO concentration with several constraints.5772 112.48 Figure 5.5390 0.1596 60.4: Effluent molar flow after partial oxidation reaction Master Component Nitrogen Water Carbon monoxide Carbon dioxide Hydrogen After LTS 295.4781 328.5772 112.

The results for case study one and case study two are presented in Figure 5. ATR out .Temperature C 800 600 400 200 0 100 350 600 850 1100 1350 air .5. With that air molar flow rate range. the hydrogen and CO molar flow rate was monitored. Then it began constant after 550 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. From Figure 5. Two case studies were developed in order to do this optimization. From figure 5. the temperature out of ATR is over 700 oC only after the molar flow rate of air greater or equal 350 kgmole/hr.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.7. This is because the heat from the stream can be used later for heat integration. The optimized air molar flow rate was taken at temperature of the ATR vapour stream is above 700 oC.Molar Flow kgmole/h Figure 5.6: Temperature of ATR vapour for varies air Feed molar flow .6 and Figure 5. 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.49 5.6. 1200 temperature 1000 .7. the flow rate of hydrogen produced by the ATR is decreasing when of air molar flow rate greater than 350 kgmole/hr.

8 shows the result of case study where the concentration of H2 and CO after ATR was monitored.9.50 270 Hydrogen Master Comp Molar Flow (Hydrogen) kgmole/h . 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. 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 760°C which is 370 kgmole/hr. one case study was developed to optimized value of feed water molar flow to reduce concentration of CO through water gas shift reaction.Molar Flow kgmole/h 250 240 230 220 210 Figure 5. 130 Master Comp Molar Flow (CO) kgmole/h 125 120 115 110 105 100 100 350 600 850 1100 1350 air . 260 CO 135 .322 kgmole/hr.5. 5.2 Water Gas Shift Optimization In WGS optimization. . At that slope. This is suitable flow rate because at this rate hydrogen molar flow rate begin to decrease. hydrogen is 259.

temperature was 250. 380 Comp Molar Flow (CO) kgmole/h 370 Hydrogen CO 360 350 340 330 320 30 70 110 150 190 230 270 water . 390 . the value of water molar flow rate that was chosen was 150 kgmole/hr.51 Water molar flow rate was optimized from 30 to 300 kgmole/hr.8. Comp Molar Flow (H2) kgmole/h Figure 5. So.9 show it. The optimum water molar flow rate was taken when H2 at its higher molar flow rate.8: Molar flow of CO and H2 effluent for varies water feed molar flow . As we can see from Figure 5. At this point.Molar Flow kgmole/h .1°C as a Figure 5. H2 produced the greatest flow rate and CO reduced the lowest flow rate. At that state. the H2 show an increasing slope and the increasing is a bit slower at 388 kgmole/hr.

2453 129.5390 69.02% and H2 was increased from 27.5: Molar flow of the effluent before optimization for ATR.Temperature C Figure 5. so the effluent of ATR did not change except for steam. Other reactors show the same similarity. From the ATR to LTS.3924 259. ATR out .5772 112.05% to 40. which were CO and steam being reduced and H2 and CO2 were increased.5390 2.3257 HTS 295. HTS.4114 .4781 328.1596 60.6629 43.52 500 450 400 350 300 250 200 150 100 50 30 70 110 150 190 230 270 air .8749 63. CO was reduced from 13.53% to 0.Molar Flow kgmole/h temperature .6961 MTS 295. HTS.3846 LTS 295. MTS and LTS.1864 60.5390 0.56%. Table 5. The increasing in water molar flow rate did not affect the reactions in ATR. Component Nitrogen Water CO CO2 Hydrogen ATR 295.6040 112.7628 325. MTS and LTS before and after WGS optimization being done.4513 328.5390 0.9: Temperature to HTS for varies water feed molar flow Table 5.2925 109.5 compares the effluent produced by ATR.

4577 377. Table 5.5703 388.6629 43. The concentration of CO in PROX was required under 10 ppm.3257 HTS 295.02% because H2 was reacted with O2 in PROX to produce H2O .5390 61.6743 129. After being optimized.5976 161.6992 5.4964 0.6: Molar flow of the effluent after optimization for ATR. MTS and LTS.5.4850 172.3 Preferential oxidation optimization Figure 5. The concentration of H2 was decreased from 42.3924 259.HTS. where the 10.6 C.5390 61.10 show the result of the concentration of CO in ppm after varying the air molar at PROX reactor.5390 72.7659 388. Component Nitrogen Water CO CO2 Hydrogen ATR 295.3910 MTS 295.31 % to 34.5390 190.6090 11.2894 172.3008 0.5036 LTS 295.055 ppm and the temperature at 112.7 compare the effluent of PROX reactor after optimization was achieved. air molar flow was setup at 550 kgmole/hr.53 Table 5.

9891 368.5390 61. CO molar flow .3008 0.7: Molar flow of the effluent before and after optimization for PROX Component Nitrogen Water CO CO2 Hydrogen PROX Before 295.Molar Flow kgmole/h Figure 5.9891 .50 81.6992 After 434.0109 199.10: CO Molar flow in PROX effluent for varies air feed molar flow Table 5.2894 172.7659 388.0109 0.ppm 120 CO 80 40 0 100 250 400 550 700 850 1000 1150 1300 1450 air .54 200 160 .

the temperature rises just a little and that same goes to LTS reactor.8 oC ). Then the temperature occurred at ATR will be used to heating the raw materials by heat integrations process. The temperature of effluents feed into the prox reactor were set to 70 oC. 1000 800 Temperature . the temperature raise to 240. The temperature rose up after flow out from ATR (955.6 Temperature Profile of Fuel Processor System Figure 5.6 oC. After flow out from MTS reactor.4 oC but then was set to cool at 100 oC before enter the MTS reactor. Finally the temperature of prox vapour is at 112.11 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. 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 .55 5. The temperature slowly cooled down to 100 oC during the heat integration process. At the first WGS reactor (HTS). The temperatures start up with 100 oC.

9891 kgmole/h.7 Component Profile of Fuel Processor System Figure 5. 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 O2.12 shows the profile of CO and H2 component through the whole plant.56 5.055 ppm of the PROX outlet and H2 molar flow was 368. it is important to monitor concentrations of H2 and CO. Therefore. 400 350 H2 300 250 Molar flow . The behaviour of the two component profile was very different after ATR.0109 kgmole/h which was 10.12: H2 and CO profile for the whole unit operation . 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. The molar flow of CO was 0. 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.

From the ATR reactor through the heat integration. H2. the main product. .8 Fuel Processor Efficiency From equation (3. was produced.6%. all the scope from earlier chapter had we did it. WGS reactor and finally reach PROX reactor. The result is based on the requirement in the scope. the fuel processor efficiency of plant was calculated.57 5. with the water optimization at 150 kgmole/hr and air optimization at 550 kgmole/hr. By optimize the water and air molar flow rate. we achieve to reduces the CO concentration and produces 34% H2. 5.26).9 Summary From this chapter. The simulation was successfully developed.. In this study. the calculated fuel processor system efficiency is about 83.

4114 kgmole/hr.58 CHAPTER VΙ CONCLUSIONS AND RECOMMENDATIONS 6. there were 13 reactions that add on this entire plant which are total oxidation (TOX).3257 kgmole/hr. From the validation of the stoichiometry . and cracking in this processes and three reactions occurred for the clean up of carbon monoxide at the WGS and PROX reactor. After the stream through three WGS reactor and being optimization by water molar flow rate the H2 molar flow rate was increased to 328.9891 kgmole/hr. water and air were the inlet stream that through in this plant. Ethanol. For the first reactor that is at the ATR reactor.1 Summary Ethanol was simulated and optimized to produce H2 for fuel cell application.2. By try to produce it from different material such as natural gas. partial oxidation (POX). Then. alcohol and nafta. the air optimization made once again the H2 molar flow rate increasing . steam reforming (SR). Using 100 kgmole/h of ethanol as basis. This case study is about using simulation to optimization the ethanol to get the highest selectivity yield H2 by using Aspenplus HYSYS 3. hydrogen that produced after the optimization was 259. the plant was achieved to produce the main product which is theH2 that produced about 368. Many researched been search a lot the usage of H2 for fuel cell application. for the last reactor that is PROX reactor. many result can be conclude.

3. are the following: 1. To get 100% yield of H2. 2. By optimizing the water and air on the WGS reactor and PROX reactor. The main contributions of this research to the simulation of hydrogen production plant for fuel cell applications. Purification of H2 By using water gas shift reaction and preferential oxidation. optimization is one of this case study scopes. The simulation of hydrogen production plant model using autothermal reforming of ethanol had been successfully developed using Aspen HYSYS 3. 6.5 respectively to produce 34% hydrogen and 10.59 For this plant.5 and 1.2 Recommendations In the future works.67. the CO been reduces to minimum concentration.055 ppm of CO. 83.2. other components need to . it is recommended to study and integrate the following aspect: 1. which also represent the view developments in this field.% of fuel processor efficiency was achieved 6. the component that can be reduced was only CO. the H2 was produced to highest flow rate. With optimum parameter above. The optimum A/F and S/F ratios are 5.2 Conclusions A number of important observations were noted based on the analysis of results as presented in the previous chapter. Meanwhile.

In order to get rid of them. a new reactor or new study case need to carry out. In order to do that. and H2O are the final component that flow out with H2 . exhaust pressure. this recovery depends on the factor as exhaust temperature. Waste process heat is utilized to generate the steam needed in the process. 3. Energy integration basis Economical factor was the solution to archive a high efficiency fuel processor. one of the objectives of the fuel processor system can maintain self-sufficiency with respect to water needs. Steam is required for the autothermal reformer. air feed rate and fuel processor efficiency.60 observe. 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. With all these. CO2. energy integration was the good choices. 2. . N2. 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.

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APPENDIX A Final result from Simulation Aspen HYSYS 3.2

66

67

68 .

69 .