Group 9 Chapters 1 - 6

DESIGN OF 30,000 TONS/YEAR METHANOL VIA CATALYTIC HYDROGENATION
OF FLARE GAS FROM CRUDE OIL WELLS
A FINAL YEAR DESIGN PROJECT
PRESENTED TO
THE DEPARTMENT OF CHEMICAL ENGINEERING
BY
GROUP 9
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE

BACHELOR OF ENGINEERING (B.Eng.) IN CHEMICAL ENGINEERING, COVENANT
UNIVERSITY, OTA
OCTOBER 2022
i
DESIGN TEAM
1. CHARLES DANIEL CHRIS 18CF023951
2. SHOWUNMI MOFEYIFOLUWA 18CF023999
3. OJOMO PETER 17CF022368
4. OKEGBENRO OLAMIDE 17CF022370
5. OKPARA UCHENNA 18CF023983
6. SHOROYE MODESOLA ESTHER 18CF023998
7. SHOWUNMI MOFEYIFOLUWA 18CF023999
ii
ABSTRACT
The utilization of captured carbon to synthesize valuable products such as methanol is just one of
many ways in abating the impact of greenhouse gases on the environment. In this report, a plant
with a production capacity of 30,000 tons per year of methanol at storage conditions of 25 ℃ is
designed. The feedstock used in this process is flare gas which is a major contributor to the
emission of carbon dioxide in Nigeria. The methanol production process can be divided into
several stages namely: the reforming process where flare gas is converted into carbon dioxide
and hydrogen which are the key reactants; the methanol synthesis process where the key
reactants under the right conditions are converted into methanol, and finally the methanol
purification process where methanol is separated from impurities. The methanol product
obtained was of a purity of 99.89 wt%. The methanol production process was simulated using
simulation software, Aspen Plus V11. The process conditions specified in this process were
based on existing literature.
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TABLE OF CONTENT
DESIGN TEAM ii
LIST OF TABLES vii
LIST OF FIGURES ix
CHAPTER 1 1
1.1 Background of Study 1
1.2 Statement of Problem 2
1.3 Aim and Objectives 3
1.4 Justification of Study 4
1.5 Scope of the Study 5
CHAPTER 2 6
2.1 Greenhouse Gas Emissions 6
2.1.1 Overview of Greenhouse Gases 6
2.1.2 Major Contributors to CO2 Emission in Nigeria 6
2.1.3 Effects of CO2 Emission 9
2.1.4 Strategies to Lower Co2 Emissions 11
2.2 Carbon Capture 12
2.2.1 Definition 12
2.2.2 Types of Carbon Capture 13
2.2.3 Carbon Capture Technologies 15
2.3 Gas Flaring 21
2.3.1 Overview of Flare Gas 21
2.3.2 Effects of Gas Flaring in Nigeria 22
2.3.3 Gas Flaring Process 23
iv
2.3.4 Composition of Flare Gas 24
2.4 Overview of Hydrogen 25
2.4.1 Description of Hydrogen 25
2.4.2 Industrial Preparation of Hydrogen 26
2.4.3 Industrial Applications of Hydrogen 29
2.5 Overview of Methanol 29
2.5.1 Brief Description of Methanol 29
2.5.2 Industrial Applications of Methanol 30
2.6 Production of Methanol From Co2 32
2.6.1 Heterogeneous Catalytic Hydrogenation of CO2 32
2.6.3 Electrochemical Reduction Of CO2 To Methanol 34
2.6.4 Photochemical Reduction of CO2 35
2.6.5 Photoelectrochemical Reduction Of CO2 To Methanol 36
2.7 Factors Affecting Yield of Methanol 37
2.7.1 Effect of a Catalyst 37
2.7.2 Effect of Temperature 38
2.7.3 The Effect of Pressure 38
2.7.4 Effect of Reactor Type and Reactor Design 38
2.8 Methanol Synthesis from Flare Gas Of Crude Oil Wells 39
2.8.1 Overview of the Process 39
2.8.2 Selection of Catalyst in Synthesis Reactor 40
2.8.3 Selection of Adsorbents 40
2.8.4 Operating Conditions of Methanol Synthesis 41
2.8.5 Storage of Products 41
2.8.6 Utilization of Byproducts 42
v
CHAPTER 3 44
3.1 Introduction 44
3.2 Aspen Simulation 44
3.3 Overall Material Balance for the Production Process 45
3.4 Reforming Process 46
3.4.1 Material Balance around PSA (A) 47
3.4.2 Material Balance around Heater (B) 50
3.4.3 Material Balance around Mixer 1 51
3.4.4 Material Balance around Heater (C) 54
3.4.5 Material Balance around Pre-reformer Reactor (D) 56
3.4.6 Material Balance around Heater (E) 58
3.4.7 Material Balance around Steam Reformer (F) 60
3.4.8 Material Balance around Cooler (G) 62
3.4.9 Material Balance around Water Gas Shift Reactor (W.G.S.) (H) 64
3.5 Methanol Synthesis Process 66
3.5.1 Material Balance around Compressor (I) 66
3.5.2 Material Balance around Cooler J 68
3.5.3 Material Balance around Synthesis Reactor (K) 70
3.5.4 Material Balance around Cooler (L) 72
3.5.6 Material Balance around Compressor (N) 75
3.5.7 Material Balance around Heater (O) 77
3.5.8 Material balance around Synthesis Reactor 2 (P) 79
3.5.9 Material Balance around Cooler (Q) 80
3.5.12 Material Balance around P.S.A(S) 86
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3.5.13 Material Balance around Compressor (T) 88
3.5.14 Material balance around Cooler (U) 89
3.5.16 Material balance around Expansion Valve (V) 95
3.5.17 Material balance around Flash Drum 3 (W) 96
3.6 Purification Process 98
3.6.1 Material balance around Distillation Column (X) 99
3.6.2 Material balance around Cooler (Y) 101
CHAPTER 4 103
4.1 Introduction 103
4.2 Overall Energy Balance 104
4.2.1 Energy Balance around PSA (A) 105
4.2.2 Energy Balance around Heater B 107
4.2.3 Energy Balance around Heater (C) 108
4.2.4 Energy Balance around Pre-Reformer reactor (D) 109
4.2.5 Energy Balance around Heater E 110
4.2.6 Energy Balance around Steam Reformer (F) 111
4.2.7 Energy Balance around Cooler (G) 113
4.2.8 Energy Balance around Water Gas Shift Reactor (W.G.S.) (H) 114
4.2.9 Energy Balance around Compressor (I) 116
4.2.10 Energy Balance around Cooler J 117
4.2.11 Energy Balance around Synthesis Reactor (K) 118
4.2.11 Energy Balance around Cooler (L) 121
4.2.12 Energy Balance around Flash Drum (M) 122
4.2.13 Energy Balance around Compressor (N) 123
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4.2.14 Energy Balance around Heater (O) 125
4.2.16 Energy Balance around Cooler (Q) 127
4.2.17 Energy Balance around Flash Drum (R) 129
4.2.18 Energy Balance around P.S.A(S) 130
4.2.19 Energy Balance around Compressor (T) 132
4.2.20 Energy balance around Cooler (U) 133
4.2.21 Energy balance around Expansion Valve (V) 134
4.2.22 Energy balance around Flash Drum 3 (W) 135
4.2.23 Energy balance around Distillation Column (X) 136
4.2.25 Energy balance around Cooler (Y) 138
CHAPTER 5 140
5.2 Process Design 140
5.3 Reforming Process 144
5.4 Methanol Synthesis Process 145
5.5 Methanol Purification 145
5.6 Chemical Engineering Design of Process Equipment 145
5.6.1 Chemical engineering design of Pressure swing adsorber (A, S) 145
5.6.2 Chemical Engineering Design of Heaters and Coolers 146
5.6.3 Chemical Engineering Design of Flash Drums (M, R and W) 154
5.6.4 Chemical Engineering Design of Compressors (I, N and T) 156
5.6.5 Chemical Engineering Design of Methanol Synthesis Reactors 157
5.6.6 Chemical Engineering Design of Pre-reformer (D) 159
5.6.7 Chemical engineering design of Steam Methane Reforming Reactor (F) 159
5.6.8 Chemical engineering design of Water Gas Shift Reactor (H) 160
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5.6.9 Chemical Engineering Design of Expansion Valve (V) 160
5.6.10 Chemical engineering design of Distillation Column (X) 161
5.6.11 Chemical engineering design of Storage vessels 161
CHAPTER 6 164
6.2 Mechanical Design Specifications of Process Equipment 166
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LIST OF TABLES
Table 2.1: Sources of emission of major greenhouse gases............................................................7
Table 2.2: Properties of Methanol.................................................................................................34
Table 3.4: Material balance around P.S.A (A)..............................................................................56
Table 3.5: Material balance around Mixer....................................................................................58
Table 2.1: Composition of Flare Gas.............................................................................................43

Table 2.2: Properties of Methanol.................................................................................................47
Table 3.1: Components Specifications Table................................................................................67
Table 3.2: Overall material balance for the production process....................................................68
Table 3.3: Overall material balance for reforming process...........................................................71
Table 3.4:Material Balance around PSA (A)................................................................................73
Table 3.5: Material Balance around Heater (B).............................................................................75
Table 3.6: Material Balance around Mixer....................................................................................76
Table 3.7: Material Balance around Heater(C).............................................................................78
Table 3.8: Material Balance around Pre-reformer Reactor (D).....................................................80
Table 3.9: Material Balance around Heater (E).............................................................................82
Table 3.10: Material Balance around Steam Reformer (F)...........................................................84
Table 3.11: Material Balance around Cooler (G)..........................................................................86
Table 3.12: Material Balance around W.G.S reactor (H)..............................................................88
Table 3.13: Overall Material balance around Methanol Synthesis Process..................................90
Table 3.14: Material Balance around Compressor (I)...................................................................91
Table 3.15: Material Balance around Cooler (J)...........................................................................93
Table 3.16: Material Balance around Synthesis Reactor (K)........................................................95
Table 3.17: Material Balance around Cooler (L)...........................................................................97
Table 3.18: Material Balance around Flash Drum (M).................................................................99
Table 3.19: Material Balance around Compressor (N)................................................................101
Table 3.20: Material Balance around Heater (O).....................................................................102
Table 3.21: Material Balance around Synthesis Reactor (P).......................................................104
Table 3.22: Material Balance around Cooler (Q)........................................................................106
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Table 3.23: Material Balance around Flash Drum (R)................................................................108
Table 3.24: Material Balance around Mixer 3.............................................................................110
Table 3.25: Material Balance around P.S.A (S)..........................................................................112
Table 3.26: Material Balance around Compressor (T)................................................................114
Table 3.27: Material balance around Cooler (U).........................................................................115
Table 3.28: Material Balance for Mixer 3...................................................................................117
Table 3.29: Material balance around Expansion Valve (V)........................................................120
Table 3.30: Material balance around Flash Drum 3 (W).............................................................122
Table 3.31: Overall Material Balance for Methanol Purification Process...................................124
Table 3.32: Material balance around Distillation column (X).....................................................126
Table 3.33: Material balance around Cooler (Y).........................................................................127
Table 4.1: Overall Energy balance for the production process...................................................131
Table 4.2: Energy Balance around PSA (A)................................................................................134
Table 4.3: Energy Balance around Heater (B).............................................................................135
Table 4.4: Energy Balance around Heater (C).............................................................................136
Table 4.5: Energy Balance around Pre-Reformer reactor(D)......................................................137
Table 4.6: Energy Balance around Heater (E).............................................................................139
Table 4.7: Energy Balance around Steam Reformer (F).............................................................140
Table 4.8: Energy Balance around Cooler (G)............................................................................142
Table 4.9: Energy Balance around W.G.S reactor (H)................................................................143
Table 4.10: Energy Balance around Compressor (I)...................................................................144
Table 4.11: Energy Balance around Cooler (J)...........................................................................145
Table 4.12: Energy Balance around Synthesis Reactor (K)........................................................147
Table 4.13: Energy Balance around Cooler (L)...........................................................................148
Table 4.14: Energy Balance around Flash Drum (M).................................................................150
Table 4.15: Energy Balance around Compressor (N)..................................................................151
Table 4.16: Energy Balance around Heater (O)..........................................................................152
Table 4.17: Energy Balance around Synthesis Reactor 2 (P)......................................................154
Table 4.18: Energy Balance around Cooler (Q)..........................................................................155
Table 4.19: Material Balance around Flash Drum (R)................................................................157
Table 4.20: Energy Balance around P.S.A (S)............................................................................158
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Table 4.21: Energy Balance around Compressor (T)..................................................................159
Table 4.22: Energy balance around Cooler (U)...........................................................................160
Table 4.23: Energy balance around Expansion Valve (V)..........................................................161
Table 4.24: Energy balance around Flash Drum 3 (W)...............................................................163
Table 4.25: Energy balance around Distillation column (X).......................................................164
Table 4.26: Energy balance around Cooler (Y)...........................................................................165
Table 5.1: Chemical Engineering specifications for Pressure swing absorber (A).....................171
Table 5.2: Chemical Engineering specifications for Pressure swing absorber (S)......................172
Table 5.3: Chemical Engineering design for Heater (B).............................................................174
Table 5.4: Chemical Engineering specifications for Heater (C)..................................................175
Table 5.5: Chemical Engineering specifications for Heater (E)..................................................175
Table 5.6: Chemical Engineering specifications for Heater (O).................................................176
Table 5.7: Chemical Engineering specifications for Cooler (G).................................................177
Table 5.8: Chemical Engineering specifications for Cooler (J)..................................................178
Table 5.9: Chemical Engineering specifications for Cooler (L)..................................................178
Table 5.10: Chemical Engineering specifications for Cooler (Q)...............................................179
Table 5.11: Chemical Engineering specifications for Cooler (U)...............................................180
Table 5.12: Chemical Engineering specifications for Cooler (Y)...............................................180
Table 5.13: Chemical Engineering specifications for Flash drum (M).......................................181
Table 5.14: Chemical Engineering specifications for Flash drum (R)........................................182
Table 5.15: Chemical Engineering specifications for Flash drum (W).......................................182
Table 5.16: Chemical Engineering specifications for Compressor (I)........................................183
Table 5.17: Chemical Engineering specifications for Compressor (N).......................................184
Table 5.18: Chemical Engineering specifications for Compressor (T).......................................184
Table 5.19: Chemical Engineering specifications for Synthesis Reactor (K).............................185
Table 5.20: Chemical Engineering specifications for Synthesis Reactor (P)..............................186
Table 5.21: Chemical Engineering specifications for Pre-reformer (D).....................................187
Table 5.22: Chemical Engineering specifications for Steam Methane Reformer (F).................187
Table 5.23: Chemical Engineering specifications for Water Gas Shift Reactor (H)...................188
Table 5.24: Chemical Engineering specifications for Expansion Valve (V)...............................189
Table 5.25: Chemical Engineering specifications for Distillation Column (X)..........................189
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Table 5.26: Chemical Engineering specifications for impure flare gas storage vessels (SV-01)190
Table 5.27: Chemical Engineering specifications for process water storage vessels..................191
Table 5.28: Chemical Engineering specifications for methanol storage vessels.........................191
Table 5.29: Chemical Engineering specifications for CO2 storage vessels.................................191
Table 5.30: Chemical Engineering specifications for hydrogen storage vessels.........................191
Table 6.1: Minimum wall thickness guide..................................................................................194
Table 6.2: Mechanical Engineering Design specifications for PSA (A).....................................196
Table 6.3: Mechanical Engineering Design specifications for Heater (B)..................................197
Table 6.4: Mechanical Engineering Design specifications for Heater (C)..................................198
Table 6.5: Mechanical Engineering Design specifications for Pre-Reformer Reactor (D).........198
Table 6.6: Mechanical Engineering Design specifications for Heater (E)..................................199
Table 6.7: Mechanical Engineering specifications for Steam Methane Reformer (F)................200
Table 6.8: Mechanical Engineering specifications for Cooler (G)..............................................200
Table 6.9: Mechanical Engineering specifications for W.G.S Reactor (H)................................201
Table 6.10: Mechanical Engineering specifications for Compressor (I).....................................202
Table 6.11: Mechanical Engineering specifications for Cooler (J).............................................203
Table 6.12: Mechanical Engineering specifications for Synthesis Reactor (K)..........................204
Table 6.13: Mechanical Engineering specifications for Cooler (L)............................................204
Table 6.14: Mechanical Engineering specifications for flash drum (M).....................................205
Table 6.15: Mechanical Engineering specifications for Compressor (N)...................................206
Table 6.16: Mechanical Engineering specifications for Heater (O)............................................206
Table 6.17: Mechanical Engineering specifications for Synthesis Reactor (P)...........................207
Table 6.18: Mechanical Engineering specifications for Cooler (Q)............................................207
Table 6.19: Mechanical Engineering specifications for Flash drum (R).....................................208
Table 6.20: Mechanical Engineering specifications for P.S.A (S)..............................................209
Table 6.21: Mechanical Engineering specifications for Compressor (T)....................................209
Table 6.22: Mechanical Engineering specifications for Cooler (U)............................................210
Table 6.23: Mechanical Engineering specifications for Expansion valve (V)............................211
Table 6.24: Mechanical Engineering specifications for Flash drum (W)....................................211
Table 6.25: Mechanical Engineering specifications for Distillation column (X)........................212
Table 6.26: Mechanical Engineering specifications for Cooler (Y)............................................213
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Table 6.27: Mechanical engineering design of flare gas storage vessel (SV-01)........................214
Table 6.28: Mechanical engineering design of process water storage vessels (SV-02)..............214
Table 6.29: Mechanical Engineering specifications for methanol storage vessels (SV-03).......215
Table 6.30: Mechanical Engineering specifications for CO2 storage vessels..............................215
Table 6.31: Mechanical Engineering specifications for hydrogen storage vessels.....................216
LIST OF FIGURES
Figure 2.1: Power sector emissions in Nigeria from 2000 to 2020 (in million metric tons of
carbon dioxide equivalent) 25
Figure 2.2: Trend in Carbon emissions 26
Figure 2.3: Generic process flow of post combustion carbon capture systems 31
Figure 2.4: Methods of Carbon Capture 32
Figure 2.5: Simplified process for the extraction of CO2 from flue gas by absorption 33
Figure 2.6: Simplified process flow for the extraction of CO2 from flue gas by adsorption 35
Figure 2.7: Process flow diagram for the CO2 capture from flue gas by membranes 36
Figure 2.8: The process flow diagram for packed bed low temperature CO2 separation 37
Figure 2.9: Process flow diagram for the CO2 capture from flue gas by low temperature process
38
Figure 2.10: Carbon dioxide emission generated by gas flaring 39
Figure 2.11: Hydrogen production by electrolysis of water 43
Figure 2.12: Methane pyrolysis 44
Figure 2.2.13:Process flow diagram of steam reforming process 45
Figure 2.14: Heterogeneous catalytic process for the conversion of CO2 to methanol using
Cu/ZrO/ZrO2 50
Figure 2.15: NHC-catalyzed CO2 conversion and the subsequent methanol hydrolytic 51
Figure 2.16: Schematic illustration of the photo reduction and photooxidation reactions in the
photochemical process. 52
photochemical process 53
Figure 2.18: A schematic diagram of the CAMERE process. 60
xiv
Figure 2.19: A comparison between the performance of conventional and CAMERE process in
methanol mole fraction during the length of methanol synthesis reactor. 60
Figure 2.20: A comparison between the performance of conventional and CAMERE process in
water mole fraction during the length of methanol synthesis reactor. 61
Figure 3.1: Overall Aspen flow diagram 64
Figure 3.2: Overall process flow diagram 65
Figure 3.3: Block diagram of overall process 66
Figure 3.4: Process Flow Diagram for Reforming Process 69
Figure 3.5: Process Flow Diagram for PSA (A) 71
Figure 3.6: Aspen Simulation Diagram for PSA (A) 72
Figure 3.3.7: Process flow diagram for Heater (B) 73
Figure 3.8 Aspen Simulation diagram for Heater (B) 73
Figure 3.9: Process flow diagram for Mixer 1 74
Figure 3.10: Aspen Simulation diagram for Mixer 1 75
Figure 3.11: Process flow diagram for Heater (C) 76
Figure 3.12: Aspen Simulation diagram for Heater (C) 76
Figure 3.13: Process Flow diagram for Pre-reformer Reactor (D) 78
Figure 3.14: Aspen Simulation diagram for Pre-reformer Reactor (D) 78
Figure 3.15: Process flow diagram for Heater (E) 80
Figure 3.16: Aspen Simulation diagram for Heater (E) 80
Figure 3.17:Process flow diagram for Steam Methane Reformer (F) 82
Figure 3.18: Aspen Simulation diagram for Steam Methane Reformer (F) 82
Figure 3.19: Process flow diagram for Cooler (G) 84
Figure 3.20: Aspen Simulation diagram for Cooler (G) 84
Figure 3.21: Process flow diagram for W.G.S Reactor (H) 86
Figure 3.22: Aspen Simulation diagram for W.G.S Reactor (H) 86
Figure 3.23: Process Flow Diagram for Synthesis Process 88
Figure 3.24: Process flow diagram for Compressor (I) 90
Figure 3.25: Aspen Simulation diagram for Compressor (I) 90
Figure 3.26: Process flow diagram for Cooler (J) 91
Figure 3.27: Aspen Simulation diagram for Cooler (J) 92
xv
Figure 3.28: Process Flow Diagram for Synthesis Reactor (K) 93
Figure 3.29: Aspen Simulation Diagram for Synthesis Reactor (K) 93
Figure 3.30: Process Flow Diagram for Cooler (L) 95
Figure 3.31: Aspen Simulation Diagram for Cooler (L) 95
Figure 3.32: Process Flow Diagram for Flash Drum (M) 97
Figure 3.33: Aspen Simulation Diagram for Flash Drum (M) 97
Figure 3.34: Process Flow Diagram for Compressor (N) 99
Figure 3.35: Aspen Simulation Diagram for Compressor (N) 99
Figure 3.36: Process Flow Diagram for Cooler (O) 101
Figure 3.37: Aspen Simulation Diagram for Heater (O) 101
Figure 3.38: Process flow diagram for Synthesis Reactor (P) 103
Figure 3.39: Aspen Simulation Diagram for Synthesis Reactor(P) 103
Figure 3.40: Process Flow Diagram for Cooler (Q) 104
Figure 3.41: Aspen Simulation Diagram for Cooler (Q) 105
Figure 3.42: Process Flow Diagram for Flash Drum (R) 106
Figure 3.43: Aspen Simulation Diagram for Flash Drum (R) 107
Figure 3.44: Process Flow Diagram for Mixer 3 108
Figure 3.45: Aspen Simulation Diagram for Mixer 3 108
Figure 3.46: Process Flow Diagram for P.S.A (S) 110
Figure 3.47: Aspen Simulation Diagram for P.S.A (S) 110
Figure 3.48: Process Flow Diagram for Compressor (T) 112
Figure 3.49: Aspen Simulation Diagram for Compressor (T) 112
Figure 3.50: Process flow Diagram for Cooler (U) 114
Figure 3.51: Aspen Simulation Diagram for Cooler (U) 114
Figure 3.52: Process Flow Diagram for Mixer 3 115
Figure 3.53: Aspen Simulation Diagram for Mixer 3 115
Figure 3.54: Process flow Diagram for Expansion valve (V) 118
Figure 3.55: Aspen Simulation Diagram Block for Expansion valve (V) 118
Figure 3.56: Process flow Diagram for Flash drum 3 (W). 120
Figure 3.57: Aspen Simulation Diagram Block for Flash Drum 3 (W) 121
Figure 3.58: Process Flow Diagram for Purification Process 122
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Figure 3.59: Process flow Diagram for Distillation column (X) 124
Figure 3.60: Aspen Simulation Diagram for Distillation column (X) 124
Figure 3.61: Process flow Diagram for Cooler (Y) 126
Figure 3.62: Aspen Simulation Diagram for Cooler (Y). 126
Figure 4.1: Process Flow Diagram for PSA (A) 132
Figure 4.2: Aspen Simulation Diagram for PSA (A) 132
Figure 4.3: Process flow diagram for Heater (B) 133
Figure 4.4: Aspen Simulation diagram for Heater (B) 134
Figure 4.5: Process flow diagram for Heater (C) 134
Figure 4.6: Aspen Simulation diagram for Heater (C) 135
Figure 4.7: Process Flow diagram for Pre-reformer Reactor (D) 136
Figure 4.8: Aspen Simulation diagram for Pre-reformer Reactor (D) 136
Figure 4.9: Process flow diagram for Heater (E) 137
Figure 4.10: Aspen Simulation diagram for Heater (E) 137
Figure 4.11: Process flow diagram for Steam Methane Reformer (F) 138
Figure 4.12: Aspen Simulation diagram for Steam Methane Reformer (F) 139
Figure 4.13: Process flow diagram for Cooler (G) 140
Figure 4.14: Aspen Simulation diagram for Cooler (G) 140
Figure 4.15: Process flow diagram for W.G.S Reactor (H) 141
Figure 4.16: Aspen Simulation diagram for W.G.S Reactor (H) 142
Figure 4.17: Process flow diagram for Compressor (I) 143
Figure 4.18: Aspen Simulation diagram for Compressor (I) 143
Figure 4.19: Process flow diagram for Cooler (J) 144
Figure 4.20: Aspen Simulation diagram for Cooler (J) 144
Figure 4.21: Process Flow Diagram for Synthesis Reactor (K) 145
Figure 4.22: Aspen Simulation Diagram for Synthesis Reactor (K) 145
Figure 4.23: Process Flow Diagram for Cooler (L) 147
Figure 4.24: Aspen Simulation Diagram for Cooler (L) 147
Figure 4.25: Process Flow Diagram for Flash Drum (M) 148
Figure 4.26: Aspen Simulation Diagram for Flash Drum (M) 148
Figure 4.4.27: Process Flow Diagram for Compressor (N) 149
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Figure 4.28: Aspen Simulation Diagram for Compressor (N) 150
Figure 4.29: Process Flow Diagram for Heater (O) 151
Figure 4.30: Aspen Simulation Diagram for Heater (O) 151
Figure 4.31: Process flow diagram for Synthesis Reactor 2 (P) 152
Figure 4.32: Aspen Simulation Diagram for Synthesis Reactor 2 (P) 152
Figure 4.33: Process Flow Diagram for Cooler (Q) 153
Figure 4.34: Aspen Simulation Diagram for Cooler (Q) 154
Figure 4.35: Process Flow Diagram for Flash Drum (R) 155
Figure 4.36: Aspen Simulation Diagram for Flash Drum (R) 155
Figure 4.37: Process Flow Diagram for P.S.A (S) 156
Figure 4.38: Aspen Simulation Diagram for P.S.A (S) 157
Figure 4.39: Process Flow Diagram for Compressor (T) 158
Figure 4.40: Aspen Simulation Diagram for Compressor (T) 158
Figure 4.41: Process flow Diagram for Cooler (U) 159
Figure 4.42: Aspen Simulation Diagram for Cooler (U) 159
Figure 4.43: Process flow Diagram for Expansion valve (V) 160
Figure 4.44: Aspen Simulation Diagram Block for Expansion valve (V) 160
Figure 4.45: Process flow Diagram for Flash drum 3 (W). 161
Figure 4.46: Aspen Simulation Diagram Block for Flash Drum 3 (W) 161
Figure 4.47: Process flow Diagram for Distillation column (X). 162
Figure 4.48: Aspen Simulation Diagram for Distillation column (X) 163
Figure 4.49: Process flow Diagram for Cooler (Y) 164
Figure 4.50: Aspen Simulation Diagram for Cooler (Y). 164
Figure 5.1: Process Flow Diagram 168
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CHAPTER 1
INTRODUCTION
1.1 Background of Study
Energy is a crucial resource for the sustenance and growth of any civilization. Among the
various energy sources in the world today, fossil fuels are the most predominant, generating
about 87% of energy consumed worldwide (Legemza et al., 2019). This is due to the host of
advantages they offer such as relatively high availability, low cost, and generation of useful
by-products. However, there is great concern regarding the finiteness of fossils. Oil experts
predict that with the continuous increase in population and hence, demand, fossil fuels will
eventually be depleted (White, 2012).
Moreover, fossil fuels have made a transition to renewable energy inevitable. There have
been numerous significant breakthroughs in the development of renewable energy, however,
the world still relies heavily on fossil fuels. As a result of this overdependence on fossil fuels,
massive amounts of greenhouse gases have been released. Oil companies in Nigeria, for
instance, contribute the most to greenhouse gas emissions in Nigeria by flaring gas during
extraction of oil from wells (Vincent & Ezaal, 2022). Nearly 17.2 billion m3 of natural gas is
flared as crude oil is explored in many parts of Niger delta.
Carbon dioxide, a constituent of flare gas, is the second most abundant greenhouse gas in the
atmosphere and is primarily a result of anthropogenic activities. Mankind is involved in
numerous activities that although are significant to the society, deal heavy damage to the
environment such as deforestation, mining, combustion of fossils, etc. For this reason, the
emissions of CO2 have increased between pre-industrial age (1970) and recent years by 90%
(Edenhofer et al, 2014). Having this greenhouse gas in such high concentrations in the
atmosphere has had adverse effects on our ecosystem such as climate change and ozone layer
depletion.
Hence, it is pertinent to reduce our Carbon footprint in as many ways as possible. As a result,
world governments have enacted laws that make it mandatory for all industries to implement
methods which will reduce the amount of CO2 in their effluents such as reconfiguring
production processes or employing carbon capture technologies to isolate carbon dioxide
from their effluent streams. Carbon capture can further be divided based on what is done with
19
the Carbon once it is captured. In carbon capture and storage (CCS), after the separation has
been completed, carbon (in its pure form or as a compound) is compressed and transported to
be stored in another location. This unsurprisingly raises questions on the amount of carbon
these facilities can take and the duration for which they can safely retain it. The possibility of
leakage is another great concern as carbon dioxide at such high concentrations is toxic and
can cause asphyxiation (Permentier, Vercammen, Soetaert, 2017).
Carbon capture and utilization (CCU) involves the processing of CO 2 into useful products
such as liquid fuels. The production of methanol from CO 2 is a prime example and has seen
wide adoption due to methanol’s high demand. Asides being a clean fuel, methanol also has
various uses in the chemical industry such as the production of biodiesel, aromatics, dimethyl
ether, etc. Methanol can also be blended with gasoline and used as a fuel. This would not
only serve to reduce the amount of CO 2 being allowed to escape into the atmosphere but also
as a source of renewable energy. In the long-term, this approach can help achieve the goal of
energy production with zero carbon emission.
The conventional method of methanol production from CO2 has been from the hydrogenation
of syngas. However, the direct conversion of CO2 to methanol has recently been gaining
headway due to the process advantages it entails. To begin with, syngas possesses many
constituents apart from carbon dioxide. Hence, crude methanol will contain more impurities
compared to a feed stream of only CO2 and as a result, more energy is expended in the
separation of these impurities. Moreover, tThe chemistry of the two processes is very similar
but still shares some differences. The major difference being that although conversion from
syngas and direct conversion from CO2 are both exothermic reactions, the heat released from
the latter is roughly half the amount released by the former. Hence, this reduces cost as there
is no need to spend on equipment suited to withstand high temperature.
This paper entails the design of a plant that recovers carbon dioxide from flare gas and
undergoes catalyzed hydrogenation to produce methanol. Hydrogen is synthesized by steam
methane reforming process.
1.2 Statement of Problem
The emergence of sustainable development goals (SDGs) emphasized the importance of

sound social and safe environment as critical for wellbeing. SDG 13 focuses on combating
climate change. In response to this, Nigeria, much like many other parts of the world, began
making conscious efforts to scale up renewable energy production processes. However, the
20
fact remains fossils are still a far cry from being replaced by green energy and whilst waiting
for this full transition, greenhouse gases are constantly being released into the atmosphere.
The constant emission of greenhouse gases today has led to numerous problems for our
ecosystem such as ozone layer depletion which allows harmful UV rays to penetrate into our
immediate environment. Greenhouse gases also increase the retention of heat in the Earth’s
atmosphere raising the overall temperature of the planet, otherwise known as global warming.
This effect was very prominent in 2015 which was recorded as the hottest year in global
history (Ogundipe, 2019).
Again, there is the low level of power supply in Nigeria. With a population of over 200
million, Nigeria has an estimated 12,522 Megawatts (MW) of electricity generating capacity,
5,000 MW of transmission capacity, and a range of 3,500MW to 4,200MW of distribution
capacity (Azeez, 2022). This means that more than half of the power generated is lost. As a
result, rural areas have little to no access to power supply. In an economy like the Nigerian
economy which relies solely on oil for majority of its revenue, but ironically consumes
almost as much as it generates, there is a dire need for an alternative source of energy, which
is affordable so that it can be made available to rural areas, and also accrue income.
Furthermore, rate at which GHGs are being released is at an alarming rate. The energy sector
is one of the major emitters of greenhouse gases in Nigeria, contributing 32.6 percent of
Nigeria’s total emission as of 2014 (Greenhouse Gas Emissions Factsheet: Nigeria, 2019).
The sector comprises of power plants which generate power chiefly through the combustion
of oil, natural and coal. The ever-increasing rate of consumption of fossil fuels carries grave
consequences. Continuous emission of GHGs which is inherent with the use of fossils have
caused higher temperatures facilitating the emergence of droughts and low water supplies.
This will invariably affect the yield of crops reducing food supply and causing the prices of
the available food resources to rise.
Finally, Nigeria is currently ranked among the top seven gas-flaring countries. This is not
only a waste of a potential energy source, but gas flaring also has adverse effects on the
health of the immediate environs. It has been found to cause neurological problems and even
inhibit the action of blood-clotting cells. Due to factors such as weak enforcement of existing
anti-flaring laws such as the Petroleum Industry Administration Bill, absence of
infrastructural support and lack of sufficient deterrent, gas flaring has yet to be ceased
21
(Olujobi et al., 2022). Hence, it is pertinent to find a means by which flare gas can be turned
into a more valuable and harmless product.
1.3 Aim and Objectives
The aim of this project is to design a plant that produces methanol from carbon dioxide
isolated from coal power plant flue gas.
The specific objectives are to:
 Establish a process philosophy and flowsheet to produce methanol from carbon

dioxide
 Simulate the production process and obtain both the material and energy balances of
the process.
 Establish the chemical and mechanical design of each equipment
 Select suitable materials of construction of the process equipment
 Design the process control systems
 Establish necessary safety measures
 Conduct the cost evaluation and feasibility study of the project
 Establish plant and site layout and waste disposal system.
1.4 Justification of Study
This research contributes to securing an adequate supply methanol, which is a renewable

source of energy. With an alternative energy source being available, prices of petroleum-
based fuel will become less expensive. Moreover, a low carbon-content fuel such as methanol
will reduce Carbon footprints, hence, impeding further development of climate change and
other adverse effects of greenhouse gas emissions. This coincides with the United Nations'
Sustainable Development Goals (SDGs), specifically Goal 7: Affordable and clean energy,
and Goal 13: Climate action.
Moreover, methanol is an important product due to its versatile nature. Asides being used as a
clean fuel; methanol has numerous other purposes. It can be used as a catalyst in the
production of biodiesel, as an antifreeze, as a raw material for synthesizing other useful
products such as dimethyl ether, acetic acid and formaldehyde, etc. Thus, methanol is
constantly in high demand.
22
As a matter of fact, the global methanol market was estimated at $20.5bn as of 2020 and is
projected to be worth $26.6bn by 2025. In Nigeria, there is a very high demand for methanol
by various industries. As a result, the cost of importing methanol increased from $237/ton in
2020 to $428/ton in the year 2021 (Ekbom et al, 2022). In the manufacturing industry for
instance, methanol is an essential feedstock in many processes such as in the manufacture of
foams by companies such as Vitafoam Limited; paints by companies such as Berger Paints,
etc. It is also needed in the transportation sector. As a fuel, methanol is cheaper than PMS
(Petrol), it is more friendly to the environment, has higher octane rating and enhances the
performance of vehicles.
1.5 Scope of the Study
The project design will cover all aspects of methanol production from CO 2. Beginning from
the reforming of flare gas to yield carbon dioxide and hydrogen (feedstock) to the catalyzed
hydrogenation process and finally the purification of the crude methanol removes impurities
(mostly water) to obtain pure methanol. Furthermore, after identifying and resolving as many
constraints as possible, and considering the material and energy balances, specifications and
materials of construction of the equipment cost and risk hazard, the best design will be
implemented.
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CHAPTER 2
LITERATURE REVIEW
2.1 Greenhouse Gas Emissions
2.1.1 Overview of Greenhouse Gases

Greenhouse gases (GHGs) refer to gases that absorb and release infrared light. Studies reveal
that the Earth's surface would be roughly 15℃ colder than it is today, making greenhouse
gases essential for maintaining a habitable temperature for the planet (Easterbrook, 2016).
Due to the greenhouse effect, higher temperatures are experienced in the troposphere. During
the day, solar energy warms the surface of the Earth, which then releases infrared radiation
(IR) into the atmosphere and this radiation is then absorbed by greenhouse gases. The
temperature of the atmosphere and the abundance of greenhouse gases in the atmosphere
have a significant impact on the greenhouse effect's intensity.
Water vapour, carbon dioxide, methane, nitrous oxide, and ozone are examples of common
greenhouse gases and make up majority of the greenhouse gases in the atmosphere. Global
warming and climate change are just a few of the effects of greenhouse gases on the
ecosystem. Researchers have noted that CO2 is the most abundant greenhouse gas present in
the atmosphere, second only to water vapour. (Berou, et al., 2009). As a result, various
methods to extract CO2 have been developed.
2.1.2 Major Contributors to CO2 Emission in Nigeria
Some of the major contributors to emission of carbon dioxide in Nigeria are discussed briefly
below.
2.1.2.1 Power Sector
Energy production is one of the major contributors to carbon dioxide (CO 2) emissions in
Nigeria. The energy sector in Nigeria is heavily dependent on fossil fuels, particularly crude
oil, which is the country's main source of energy. According to the International Energy
Agency, Nigeria is the largest oil producer in Africa and the 12th largest in the world. Oil
production and refining processes in Nigeria release significant amounts of CO 2 into the
atmosphere. The burning of crude oil to generate electricity is also a major contributor to
CO2 emissions in the country.
24
In addition, Nigeria also has a relatively large gas-to-power generation capacity, which is also
a significant source of CO2 emissions. Furthermore, Nigeria also has a significant energy
sector that relies on coal, which is another major source of CO2 emissions. The country has
several coal-fired power plants, and despite efforts to transition to more renewable energy
sources, coal remains a significant source of energy for Nigeria. As of 2020, carbon
emissions from the power sector in Nigeria reached around 11.7 million metric tons of carbon
dioxide equivalent. This kept stable from the previous year. Within the period reviewed
(2000 – 2020), the highest volume of emissions from electricity generation in the country was
achieved in 2014, when nearly 12.8 million metric tons of CO2 equivalent was registered.
Figure 2.1: Power sector emissions in Nigeria from 2000 to 2020 (in million metric tons of
carbon dioxide equivalent)
Source: Doris, 2022
2.1.2.2 Manufacturing Sector
The manufacturing industry is another significant source of CO2 emissions. This is because
manufacturing processes use large amounts of energy, much of which is generated from fossil
fuels. In addition, many manufacturing industries also release large amounts of CO2 as a
25
byproduct of their operations. The Nigerian manufacturing sector accounted for about 13% of
the country's GDP in 2020, with an average growth rate of 4.75% (Doris, 2022). However,
besides the sector’s contribution to economic growth, it also constituted about 12% of direct
CO2 emissions from the continuous utilization of fossil-based energy and 2% of electricity-
related emissions. In a study by Olivier et al. 2022, the trend of CO 2 emissions in the
Nigerian manufacturing sector from 2010 to 2020 was studied. The overall CO 2 emissions
increased from 7.3% in 2010 to 12.9% in 2020, equal to an increase of 1668.10 GJ between
2010 and 2020.
Figure 2.2: Trend in Carbon emissions
Source: Olivier et al. 2022

2.1.2.3 Transportation Sector
The transport sector is the backbone of any productive system; enabling the mobility of
people and goods means connecting people and nations and fostering economic and cultural
exchanges and social development. It is a major emitter of GHGs in Nigeria, and accounts for
nearly one-tenth of total Nigerian emissions (Eleri et al., 2013). However, by 2016 it
accounted for 31.9% of total emissions in Nigeria.
The link between CO2 emissions and transportation arises as a result of emissions by the
various modes of transportation which contribute to global warming and climate change.
According to IEA (2014). the global CO2 emissions from the transportation sector are
projected to increase by 140% from 2000 to 2050, with the biggest increase in developing
26
countries such as Nigeria. In the study by Effiong (2020), the road transport sector
contributes about 20.67% to total CO2 emissions caused by anthropogenic activities. In 2022,
26235 Gg of CO2 was emitted by road transport alone and by 2027 will emit an estimate of
416 Gg of CO2.
2.1.2.4 Agricultural Sector
The agriculture, forestry, and other land uses (AFOLU) is a major sector that has the most
significant contribution to climate change. Destructive land use practices such as
deforestation, uncontrolled use of fertilizers and poor livestock management contribute
significantly to the release of GHGs, particularly carbon-dioxide (CO 2), nitrous oxide (N2O)
and methane (CH4). According to Nigeria’s Third National Communication submitted to the
UNFCCC 2020, total GHG emissions from AFOLU stands at 366,734 Gg CO 2-eq,
representing about 60% of the total net GHG emissions for the country.
2.1.3 Effects of CO2 Emission
2.1.3.1 Climate Change

Changes in the abundance of greenhouse gases (GHG’s) in the atmosphere alter the energy
balance of the climate system. This change is referred to as climate change. Climate change is
the alteration in the usual weather found in our respective climates. Spanning from the
industrial revolution around 1950, human activities such as burning fossil fuels to power our
cars, homes, and industries, has led us into an era with the most amount of excess CO 2.
Average atmospheric carbon dioxide concentrations have increased from about 280 ppm in
1750 to 416 ppm in 2022, now increasing at an average rate of 2 ppm pr year (Garnaut,
2008).
When sun rays reach the earth, it should reflect out. Some of the heat from the rays gets
trapped in the greenhouse gases and stops it from escaping into space, which is also known as
the greenhouse effect. Greenhouse gases like CO2 and CH4 keeps heat from the sun in the
earth and so the earth retains a higher average temperature but, eliminating these gases would
cause the earth to freeze up. This shows these gases are required. However, when in excess in
the atmosphere, they trap the sun rays, and cause drastic changes within the earth.
When the earth gets hotter, oceans and sea levels expand, and the water levels rise. This heat
melts ice glaciers that increase the sea level further. The rapid change destabilizes the climate
and leads to flooding, extreme weather, storms leading to destruction. Global warming makes
27
heat waves and wildfires more frequent and extreme. Any extreme weather leads to drought
which kills crops and leads to starvation.
2.1.3.2 Global Warming

CO2 emissions act like a blanket in the air, trapping heat in the atmosphere, and warming up
the Earth. This layer prevents the Earth from cooling, and thus raises global temperatures.
Global warming would affect environmental conditions, food and water supplies, weather
pattern, and sea levels. Based on the National Oceanic and Atmospheric Administration
(NOAA) Global Climate Summary, it stated that combined land and ocean temperature since
1880 has increased with an average rate of 0.07 ◦C per decade. The temperature continues
rising since 1981, with an average rate of 0.18 ◦C, which is over twice as massive as previous
times (Ali et al., 2020). Higher temperatures can cause increased mortality, reduced
productivity and damage to infrastructure.
The most vulnerable members of the population, such as the elderly and infants, will be most
severely affected. Higher temperatures are also expected to cause a shift in the geographical
distribution of climate zones. These changes are altering the distribution and abundance of
many plant and animal species, which are already under pressure from habitat loss and
pollution. Temperature rises are also likely to influence phenology – the behaviour and
lifecycles of animal and plant species. This could in turn lead to increased numbers of pests
and invasive species, and a higher incidence of certain human diseases.
2.1.3.3 Droughts
A drought is an unusual and temporary deficit in water availability caused by the combination
of lack of precipitation and more evaporation (due to high temperatures). It differs from water
scarcity, which is the structural year-round lack of fresh water resulting from the over-
consumption of water. Due to the changing climate, regions around the world are facing more
frequent, severe, and longer lasting droughts. Higher temperatures increase the evaporation of
water, which – together with the lack of precipitation – increases the risks of severe droughts.
Droughts often have knock-on effects, for example on transport infrastructure, agriculture,
forestry, water and biodiversity. They reduce water levels in rivers and ground water, stunt
tree and crop growth, increase pest attacks and fuel wildfires.
With a global average temperature increase of 3°C, it is projected that droughts would happen
twice as often and absolute annual losses from droughts would increase to EUR 40 billion per
year, with the most severe impacts in the Mediterranean and Atlantic regions. More frequent
28
and severe droughts will increase the length and severity of the wildfire season, particularly
in the Mediterranean regions.
2.1.4 Strategies to Lower Co2 Emissions

The three strategies of lowering CO2 emissions to mitigate climate change are as follows.
2.1.4.1 Carbon Capture
Carbon dioxide is one of the GHGs that build up in our atmosphere, trapping heat from the
sun and stopping it from escaping into space. CO, CO2, and other greenhouse gases are
released when fossil fuels are burned, and these gases are released into the atmosphere.
Sustainable practices and ecological restoration methods can reduce the detrimental effects of
CO2 in the atmosphere. Carbon Sequestration is one of these ecological restoration projects.
Carbon sequestration is a process of transferring and storing atmospheric carbon and its
oxides into strata like oceans, abiotic and biotic, and geological zones, in a solid, liquid or gas
form, to reduce its net rate in the atmosphere. Some methods are naturally occurring, but
deliberate effort is needed to reduce the excess GHG’s and therefore, artificial methods are
also employed.
2.1.4.2 Reducing the global energy use:
There are a variety of ways global energy use can be reduced. Some of these include:
i. Implementing a carbon tax: Carbon taxes reduce emissions and improve the economy.
It encourages industries and power houses to depend less on fossil fuels which
reduces pollution and cuts government spending.
ii. Decreasing the number of cars and automobiles on the roads and providing
convenient public transport systems would reduce carbon emissions greatly.
iii. Replacing coal and other fossil fuel electric plants with natural gas-powered facilities.
iv. Solar electricity use should be encouraged. Many solar panels should be used to
produce hydrogen for fuel in cars.
v. Increase the production of alcohols from CO2 and other GHG’s by various conversion
mechanisms.
vi. The rate at which deforestation occurs should be balanced with at least one third of
the rate at which trees are planted.
29
2.1.4.3 Developing Zero or Low-Carbon Fuels
In comparison to traditional fuels, natural gas like methane and propane are low carbon fuels.
The emission factor of these is much lower than that of coal, diesel, and they have higher
carbon content, so they release more CO 2 when they are burnt. Depending on gases like
methane would go a long way in reducing the excess GHG’s in the ecosystem. Though it is a
potent GHG, it has a much shorter lifespan than CO2 and it also produces less carbon dioxide
for each unit of heat released.
Methanol is another good example of a low-carbon fuel. Not only is it relatively cheaper than
other alternative fuels, but it is also much safer as it is less flammable than other fuels.
2.2 Carbon Capture
2.2.1 Definition
Carbon capture refers to the process of capturing carbon dioxide (CO 2) from industrial
processes, power generation, or other sources and storing it safely to prevent it from being
released into the atmosphere. The aim of carbon capture is to reduce the amount of
greenhouse gases, such as CO2, in the atmosphere and mitigate the impacts of climate
change.
2.2.2 Types of Carbon Capture
2.2.2.1 Pre-Combustion Carbon Capture

Pre-combustion carbon capture is a process used in power generation that involves removing
carbon dioxide (CO2) from a fuel before it is burned. The process typically involves three
steps:
i. Gasification: The fuel (usually coal or natural gas) is gasified, which means it is
converted into a mixture of carbon monoxide (CO) and hydrogen (H2).
ii. Shift reaction: The mixture of CO and H2 is then subjected to a shift reaction, where
the CO is converted into CO2 and the H2 is converted into water (H2O). This reaction
is typically done with the use of a catalyst.
iii. Carbon capture: The CO2 generated in the shift reaction is then separated from the H2
and other gases. This CO2 can then be compressed and transported for use in various
applications, such as enhanced oil recovery,
30
The advantages of pre-combustion carbon capture technology include:
i. Compared to the post and oxy capture options, it has higher efficiency.
ii. It has comparatively easier carbon removal.
iii. The fuel it produces poses less harm to the environment.
iv. It is easy to adopt in every power plant.
The disadvantages of pre-combustion Carbon Capture Technology
i. The overall capital cost is high when considering the gasification process.
ii. Heat transfer challenges may occur.
iii. There may be decay issues with hydrogen rich fuel utilization.
2.2.2.2 Post Combustion Carbon Capture
The post combustion process is used to capture carbon after a fuel-air mixture has been
combusted. The flue gas- which is the by-product waste gases of the combustion process, is
removed through an exhaust valve. It is then cleaned of impurities like oxides of nitrogen and
sulphur. In a typical absorption process, the remaining flue gas is fed into an absorber where
a solvent absorbs CO2 from the O2 and N2 gases. The stream is then fed into a stripper where
the gas is stripped off the solvent. It is then fed into the condenser, condensed into a liquid,
and then pumped into the ground. Though challenging, this is the most straight forward
technology that can be applied in power plants, the industry, and many other facilities.
31
Figure 2.3: Generic process flow of post combustion carbon capture systems
Source: Alamo et al, 2015
The advantages of post combustion capture technology include:
i. It is a more advanced technology.

ii. It makes use of standard and recognized techniques and installation is done in new
and existing plants.
The disadvantages of post combustion capture technology include:
i. It has lower efficiency than the pre-combustion option and is more expensive.
ii. There may be low CO2 concentration in flue gas.
2.2.2.3 Oxyfuel Combustion
This type of capture is used in powerplants, cement production plants and, the iron and steel
industry. The air entering the boiler is purified of nitrogen and other impurities. The air
entering the boiler is mainly O2. It helps eliminate the other gases and compounds that may
be hard to separate from the CO2 gas. This makes it easier to get pure CO 2. A filter is used to
remove ash and other particulate matter and a flue gas desulphurization tank removes all the
sulphur oxides from the gas. After, the gas is compressed and pumped underground.
32
Figure 2.4: Methods of Carbon Capture
Source: Jordal et al, 2004
33
2.2.3 Carbon Capture Technologies
2.2.3.1 Absorption
Chemical absorption using aqueous alkanolamine solutions is believed to be the most feasible
solution for CO2 capture up until 2030. However, there are certain drawbacks to aqueous
alkanolamine solutions, such as a high rate of equipment degradation, high energy needs for
regeneration, and a high absorber volume required.
Figure 2.5: Simplified process for the extraction of CO2 from flue gas by absorption
Source: Cheng-Hsiu Yu et al, (2012)
 Physical Absorption
The basis for the operation of physical absorption is Henry's Law. CO 2 is absorbed at high
pressure and low temperature, while it is desorbed at low pressure and high temperature. This
technique has been widely applied in a variety of industrial operations, such as the creation of
natural gas, synthesis gas, and hydrogen with elevated CO 2 concentrations. There are many
commercially available techniques that are currently in use, including the Selexol Process,
Rectisol Process, Purisol Process, etc.
 Chemical Absorption
The absorbent is thermally regenerated in a stripper between the absorber and the absorbent
in a traditional chemical absorption process. During chemical absorption, the absorbent is fed
into a packed bed absorber from the top and makes countercurrent contact with the CO 2-
containing gas. The absorbent (now containing CO 2) is introduced into a stripper for heat
34
regeneration. After regeneration, the CO2-lean absorbent is re - injected to the absorber for
reuse. The high-purity CO2 that was released from the stripper was compressed for further
transit and storage.
Alkanolamines are the most often used absorbents for CO 2 capture. Examples of primary,
secondary, and tertiary amines with at least one hydroxyl and amine group are
monoethanolamine (MEA), diethanolamine (DEA), and N-methyldiethanolamine (MDEA).
Since different amines have different advantages and characteristics, mixed amines have been
proposed as a technique to increase CO2 collection effectiveness and decrease regeneration
costs.
The advantage of chemical absorption technology is that it is the most sophisticated and
widely used technique for capturing CO2, even if it has not been applied to remove CO 2 from
power plants. Another advantage is that this technology can be retrofitted into current power
facilities. Despite this, there are certain drawbacks to the technology, including some of the
following:
i. Limited capacity to load CO2

ii. Corrosion of equipment is a common occurrence.
iii. Amine is degraded by SO2, NO2, and O2 in flue gases, leading to a high absorbent
makeup rate.
iv. High power usage when regenerating highly heat-absorbing materials
v. Size of industrial equipment (Resnik, 2004 and Haszeldine, 2009)..
vi.
vii.
2.2.3.2 Adsorption
Aqueous amine absorption techniques may be replaced by solid adsorption techniques since
they have fewer disadvantages such as small gas-liquid contact surfaces, limited CO2 loading,
and considerable absorbent degradation. Although the rate-limiting step for aqueous amine
absorption is the CO2 mass transfer across the gas-liquid interface, it is about three orders of
magnitude higher than that for adsorption, which is the spread of CO 2 from flue gas to the
inner pore of a mesoporous adsorbent (Khatri et al., 2005), some current problems, such as
poor CO2 loading capacities at low pressures and influences from water vapor prevent the
effective use of adsorption to extract CO 2. Carbonaceous adsorbents like activated carbon
have been widely used for CO2 collection because of their vast availability, low cost,
35
outstanding thermal stability, and reduced sensitivity to moisture (Plaza et al., 2010),
although their use is restricted to highly pressurized operations.
Figure 2.6: Simplified process flow for the extraction of CO2 from flue gas by adsorption
process
Source: Cheng-Hsiu Yu, et al 2012
2.2.3.3 Membranes
Membrane contactor technology involves the use of tubular reactors with both chemical
reaction and product separation equipment. This kind of technology is widely employed in
industry because of its lower initial investment costs and ability to assist the intended reaction
in reaching its completion. These reactors are employed in most dehydrogenation reactions.
Since H2 molecules can traverse the membrane, conversion is increased, and the process is
more productive economically. Due to its application in CO2 collecting, membrane contactor
technology has recently gained a lot of popularity. The two most common types of membrane
contactors are catalytic (made of a catalyst material to aid in the reaction and inert (the
membrane responds as a barrier).
36
Figure 2.7: Process flow diagram for the CO2 capture from flue gas by membranes
Source: Tuinier et al, 2011
Membrane-based CO2 removal systems have demonstrated to be significantly more

successful than conventional ones. One main benefit of using membrane technology is that
the reaction and detaching units of the process are combined into one unit. As a result,
additional separation units are no longer required, making the procedure more sustainable and
environmentally friendly. Supported liquid membranes, dense membrane gas permeation,
using a microporous membrane, and non-dispersive contact are the three fundamental
membrane systems that are frequently used for CO2 removal.
Non-dispersive membranes are often utilized in post-combustion collection systems.

Since the gas and liquid flow rates are independently controlled, and because the interfacial
area is changeable, it is simpler to predict how the membrane contactor will behave. The
system is both compact and energy-efficient, and linear scaleup is made possible by the
membrane contactors' simplicity. In addition, issues with floods, diverting, and retention are
prevented because the two phases travel in opposite directions.
2.2.3.4 Cryogenic-Based Technology
Cryogenic techniques extract CO2 from exhaust gases using low temperatures for the various
processes such as separation and purification. This yields CO2 of much higher purity
(99.99%) than earlier separation technologies. Cryogenic-based approaches are gaining
popularity despite the possibility of blockages from other elements (such water) and
escalating capture prices. There have been many cryogenic CO2 capture methods described
up to this point. Enhanced cryogenic separation technologies that eliminate obstructions
37
through condensed water and improved thermal performance that lowers energy penalty and
energy loss are just two of the specific treatments that have been proposed. Tuinier et al.
proposed dynamic driven packed beds for cryogenic CO2 capture.
Figure 2.8: The process flow diagram for packed bed low temperature CO2 separation
Source: Baxter et al, 2018
The cold energy comes from liquefied natural gas, and the packed material is a steel
monolith. The advantage of this method is that water and carbon dioxide can be
simultaneously separated from flue gas due to the different dew and dissolution points of
water and carbon dioxide. Pressure decreases in the cryogenic packed bed, and clogging
issues can be avoided. The cryogenic packed-bed CO2 capture technology has higher
potential than MEA absorption and VPSA techniques, but several issues need to be resolved
before it can be applied commercially. For example, the cryogenic packed beds need to be
better insulated to be minimize heat losses.
The main problem now plaguing most CO2 collection techniques is how much energy they
use. Reduced energy consumption for cryogenic capture techniques can be achieved by
recycling excess cold energy from industrial effluents (such as LNG) via units such as
evaporative cooling loops. A hybrid cryogenic system for carbon recovery that utilizes an
external cooling loop is shown in Figure 2.9.
38
Figure 2.9: Process flow diagram for the CO2 capture from flue gas by low temperature
process
Source: Baxter et al, 2018
The CO2 is retained in the liquid phase, allowing a stream that is concentrated in N2 to be
discharged. This capacity controls the power losses of CO 2 removal by using a reserved
refrigerant to power the process when demand is high, delivering the reduced parasitic load to
the grid to help meet needs, and renewing the refrigerant when demand is low. The
CCCECL's fast load changes also make it simpler to pair conventional power generation
systems with sporadic renewable energy sources. The CCCECL approach uses less energy
overall than other conventional techniques.
2.3 Gas Flaring
2.3.1 Overview of Flare Gas

Flare gas is one of the major by-products of many industrial activities, some of which include
effluent water treatment, landfill gas production, oil and gas exploration, and petrochemical
processing. Making use of flare gas to generate heat and electricity on a large scale can work
successfully but may negate attempts at energy recycling. Gas flaring is a common but
contentious method of getting rid of excess gas.
In oil and gas exploration, flaring is a controlled process of burning unwanted natural gas
during operations releasing up to 400 million tonnes of CO2 into the earth’s atmosphere each
year. When crude oil is pumped from oil producing regions, flaring is used in some
39
infrastructures to remove the associated gas, as many companies consider it more economic
to burn the natural gas and pay a fine as opposed to re-injecting into oil wells.
Gas flaring in Nigeria in 2020 released about 1.06 million tonnes of carbon dioxide (CO2)
into the atmosphere. The total volume of CO2 released in 2020 fell from that released in
2019. The effect of COVID-19 affected the production, demand, and supply of petroleum
products, resulting in a decrease in the volume of CO2 emitted from 1.3 million tonnes in
2019 to 1.06 million tonnes in 2020. From 2012 to 2020, approximately 12.85 million tonnes
of CO2 have been released into the atmosphere from gas flaring alone.
Figure 2.10: Carbon dioxide emission generated by gas flaring
Source: Doris, 2022
2.3.2 Effects of Gas Flaring in Nigeria
i. Climate change.
Gas flaring from fossil fuels like coal and oil, contributes to climate change by releasing large
of amounts of greenhouse gases such as CO2 and methane into the atmosphere.
40
ii. Decrease in Vegetation
Flaring gives room for atmospheric contaminants to exist in more concentrated forms. Oxides
of nitrogen, sulphur and carbon, hydrocarbons and ash, particulate matter, hydrogen sulphide,
photochemical oxidants and other pollutants make the soil acidic and deplete its nutrients,
which lowers the crops' nutritional value. they harbour. It leads to stunted growth scotched
plants and other fertility related issues.
iii. Health effects.
The gas flaring process releases hazardous air pollutants that impact breathing, and leads to
cancer, neurological problems, reproductive and developmental issues, and skin related
disorders The hydrocarbons present can also cause negative changes in haematological
parameters which have the tendency to affect blood and blood forming cells. It can cause
anaemia, pancytopenia, and leukaemia (Okedere et al., 2021).
iv. Economic loss.
In Nigeria and many parts of the world today, billions of dollars’ worth of gas is flared up
into the atmosphere. Redirecting this gas instead of flaring, can be used to measure up to the
electricity demand of the nation and other domestic purposes. Despite Nigeria’s dependence
on fossil fuels for energy generation, gas flaring operations result in annual losses of around
$2.5 billion. (Ajugwo, 2013).
2.3.3 Gas Flaring Process

Gases are normally burned with an evident flame at the upmost part of the stack throughout
the majority of flaring operations. The height of the flame is characterized by the degree to
which gas is emancipated, while its color and brightness are determined by the type of gas.
Systems for gas flaring are used in port facilities, onshore and offshore platforms, storage
tank farms, transport vessels, producing fields, and storage and distribution pipes. A complete
flare system, as depicted in Figure 2.15, includes pipes that gathers the gases to be flared as
well as the flare stack or boom. The flare tip is constructed to attract air inside the flare and
improve burn efficiency. It is located at the end of the stack or boom.
Any liquid present in the gas that is being directed to the flare is collected and stored in a
vessel at the bottom of the stack, and seals installed inside the stack prevent the flame from
41
flashing back. Depending on the design, a process location can need just one flare or several.
A flare often produces heat, noise, and is visible. The main byproducts of the gas used in
flaring are water vapor and CO 2. Low pressure pipe flares are not meant to operate liquids,
and when hydrocarbon liquids are added to the flare system, they do not function effectively.
Efficient combustion in the flame requires both the absence of liquids and a proper mixing of
the fuel gas and air (or steam) (Gzar & Kseer, 2009).
Figure 2.11: Overall flare stack system

Source: Barati et al., 2019
The operations involved in gas flaring can be divided into three categories: production
flaring, process flaring, and emergency flaring. A fire, a valve breaking procedure, or
compressor issues can all result in emergency flaring. As a result, a substantial amount of gas
moving at a fast speed is wasted in a short length of time. Process flaring often occurs at a
lesser rate; for instance, during the petrochemical process, specific unwanted gases are
withdrawn from the production stream and flared. During such operations, the volume of
flared gas might vary from a few m 3 per hour to hundreds of m3 per hour, depending on the
plant's functionality and defects. Production flaring is carried out by the oil and gas industry's
exploration and production division. During the gas-oil proposed test assessment, a sizable
volume of gas is consumed to ascertain the well's capacity for production.
42
2.3.4 Composition of Flare Gas
The table below is the composition of flare gas at a typical downstream plant.
Table 2.1: Composition of Flare Gas
Component Mass
fraction
Methane 60
Ethane 7.7
Propane 13.5
N-butane 10.8
N-pentane 4.8
Carbon dioxide 0.33
Nitrogen 1.3
Source: Bahadori, 2014
2.4 Overview of Hydrogen
2.4.1 Description of Hydrogen

Hydrogen is one of the most abundant elements on earth, second only to Carbon. But it is
believed that hydrogen might be more abundant than carbon as most of the carbon found
come in form of hydrocarbons which means they are made up of hydrogen and carbon. It is
the first element on the periodic table with a relative atomic number of 1 as other element are
measured against it. With a valence range between 1 and 2, hydrogen can take place in
numerous oxidation and reduction reactions. Because of this ability to react with numerous
elements while releasing or accepting electrons, hydrogen is broadly used in many reactions.
This property also makes it hard for hydrogen to be found on its own in nature. Rather, it is
majorly found bonded with oxygen to form water. In its standard form, it has the formula
(H2), and it is a colorless, odorless, tasteless, nontoxic gas while being highly combustible.
The hydrogen system is too small to observe so various models have been developed to do
this including the Bohr’s model and the quantum model, yet it is the only atomic system that
can be solved exactly. Atomic hydrogen also has the simplest line spectrum.
43
2.4.2 Industrial Preparation of Hydrogen
2.4.2.1 Water Electrolysis
Water can be decomposed into its constituent elements by passing an electric current is sent
through it. Oxygen and hydrogen gases are deposited at the anode and cathode respectively.
When creating hydrogen for storage, the cathode is often constructed of platinum or another
inert metal. If the gas is to be burned on-site, oxygen is preferred to aid combustion, thus both
electrodes would be composed of inert metals. (For example, iron would oxidize, reducing
the amount of oxygen released.) The equation of the reaction is given below:
2 H2O(l) → 2 H2(g) + O2(g) (2.1)
Figure 2.11: Hydrogen production by electrolysis of water

Source: Naimi, Antar, 2018
2.4.2.2 Methane Pyrolysis
The production of hydrogen by pyrolysis of methane is a process does not emit any
greenhouse gas. Increasing volume production using this technology is critical to enabling
faster carbon reduction through the use of hydrogen in industrial processes, fuel cell electric
heavy truck transportation, and gas turbine electric power generation. To execute methane
pyrolysis, methane is bubbled up through a molten metal catalyst containing dissolved nickel
at 1,340 K (1,070 °C). As a result, the methane degrades into hydrogen gas and solid carbon,
with no other byproducts (Upham et al, 2017). Methane pyrolysis is being researched and is
thought to be appropriate for commercial bulk hydrogen production.
44
CH4(g) → C(s) + 2 H2(g) (2.2)
Figure 2.12: Methane pyrolysis

Source: Ruland, et al, 2020
2.4.2.3 Steam-Methane Reforming
Steam methane reforming (SMR) is a method of producing syngas (hydrogen and carbon
monoxide) through the interaction of hydrocarbons with steam. The majority of the world's
hydrogen is produced by steam reforming natural gas. Water is heated in a furnace at about
800℃ to generate the steam used in the process. Natural gas is commonly used as the other
required feedstock due to the high partial pressure of methane. The primary goal of this
technology is to produce hydrogen (Lui Ke et al, 2009). The reaction occurs in the presence
of a nickel catalyst to obtain 80% methane conversion and a syngas with hydrogen to carbon
monoxide ratio of 4.9 (Mary et al, 2022). The equation is given below.
CH4 + H2O → CO + 3 H2 (2.3)
At the end of the reaction, carbon monoxide, which is a toxic substance is produced. The
outlet stream is then fed into another reactor where it reacts with water still present to convert
carbon monoxide into carbon dioxide and in the process, yield even more hydrogen. This
reaction is known as the water gas shift reaction (W.G.S) and is given by the equation below:
CO + H2O → CO2 + H2 (2.4)
45
W.G.S process takes place in two reactors operating at high temperature and low temperature
known as high temperature shift reactor and low temperature shift reactor respectively.
Hydrogen is produced alongside impurities such as carbon dioxide, carbon monoxide, etc. A
pressure swing adsorption unit is the conventional purification step for isolating hydrogen
due its cost effectiveness and high purity.
Figure 2.2.13:Process flow diagram of steam reforming process

Source: Shiraski, Yasuda, 2013
There are other less used industrial methods of producing hydrogen such as: metal-acid,
thermochemical and serpentinization reaction.
2.4.3 Industrial Applications of Hydrogen

i. Hydrogen can be used to synthesize methanol by hydrogenating carbon dioxide in the
presence of a catalyst.
ii. In the petrochemical industry for upgrading fossil fuels. Majorly in reactions known
as hydrogenolysis (this is the cleavage of bonds to carbon). A good example is the
separation of Sulphur from fossil fuel.
R2S + 2H2 → H2S + 2RH (2.5)
iii. Hydrogen is used in the production of ammonia, which is then converted into nitric
acid and nitrogenous fertilizers.
iv. It is used to reduce heavy metal oxides to metals in metallurgical processes.
46
v. Hydrogen is used to generate electric energy through fuel cells. This form of energy
has numerous benefits over conventional fossil fuels and other forms of energy. It
does not release any harmful substances into the environment causing air pollution. It
produces greater energy per unit mass of fuel as compared to gasoline and other fuels.
2.5 Overview of Methanol
2.5.1 Brief Description of Methanol

Methanol, also referred to as methyl alcohol is the most basic alcohol. Methanol, unlike
ethanol, cannot be consumed because doing so could cause blindness, neurological damage,
and nervous system damage. Methanol is a chemical molecule with the formula CH 3OH that
is also known as methyl alcohol, carbinol, wood alcohol, wood naphtha, or wood spirits
(often abbreviated MeOH).
Methanol is naturally formed in the anaerobic metabolism of many different types of bacteria.
As a result, a trace amount of methanol vapor exists in the atmosphere. Over the course of
several days, oxygen oxidizes air methanol to carbon dioxide and water with the help of
sunlight. It is a polar liquid at room temperature and is used as an antifreeze, solvent, fuel,
and ethyl alcohol denaturant. It is also utilized in the transesterification procedure to produce
biodiesel.
Methanol burns in air forming carbon dioxide and water. A methanol flame is almost
colorless, causing an additional safety hazard around open methanol flames.
Table 2.2: Properties of Methanol
Formula CH3OH or CH4O

Molecular Weight / Molar Mass 32.04 g/mol
Density 792 Kg/m3
Boiling Point 64.7 0C
Melting Point -97.6 0C
Vapor Pressure 13.02 Kpa (at 20 0c)
Acidity(pKa ) 15.5
Conjugate Acid Methyloxonium
Conjugate Base Methanolate
Refractive Index (nD) 1.33141
Viscosity 0.545 mPa.s ( at 25 0c)
47
Solubility in water Miscible
Odor Sweet and pungent
Appearance Colorless liquid
2.5.2 Industrial Applications of Methanol

In 2010, global methanol demand achieved 49 million tons and, according to the IHS Markit
World Analysis—Methanol 2017. By 2021, the demand will surpass 95 million tons, with
China playing the role of leader in this market, with around 54% of world capacity and 46%
of global production. It is estimated that, by 2021, nearly one in five tons of global methanol
production will be useful for the methanol-to-olefins process and to satisfy the Chinese
chemical demand.
2.5.2.1 Lower Emission Transportation Fuel
Methanol has long been used as a car fuel. Even though it hasn't been utilized as much as
ethanol, there appear to have been additional research projects conducted while employing
methanol. Methanol is frequently used to make ethers that are combined with gasoline. Both
conventional and reformulated gasoline use methyl tertiary butyl ether (MTBE), which is
made from roughly 40% methanol and 60% of a C 4-olefin. Since MTBE has a high-octane
number, one of its uses as an addition is to raise the octane rating of gasoline.
With M85 and M100 fuels, methanol can cut hydrocarbon emissions by 30 to 40% and up to
80%, respectively. Methanol also offers significant benefits in terms of emissions when
compared to fuel. When methanol is utilized in a fuel cell vehicle—automobiles that
transform a fuel's chemical energy into electricity and heat without combustion—emissions
are significantly reduced.
Today, natural gas and coal are used most frequently to generate methanol on a large scale.
Methanol can support society's decarbonization objectives because it can also be produced
from renewable sources such municipal garbage, biomass, and recycled carbon dioxide. Due
to its effective combustion, simplicity of delivery, and widespread availability worldwide,
methanol is employed as an economical alternative liquid transportation fuel. Around the
world, methanol is utilized in gasoline blends at large volume percentages (50-100%), mid-
range (15-30%), and low percentages (3-5%).
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2.5.2.2 Raw Material for Other Valuable Products
Several chemical processes use more than half of the methanol produced worldwide. Acetic
acid and formaldehyde, which are utilized in items including adhesives, foams, plywood
subfloors, solvents, and windshield washer fluid, are produced using methanol as a feedstock.
2.5.2.3 Generation of Hydrogen
Hydrogen is currently seen as a clean energy source, playing a relevant role in refining,
chemical, and electronic industry. However, hydrogen presents some drawbacks in terms of
the difficulties in its storing and transportation, negatively affecting its wider utilization.
Consequently, hydrogen generation from an easily transported liquid source may represent a
valid option. Methanol is considered an excellent candidate as a hydrogen carrier, showing
low toxicity and easy handling. Methods of production include the following:
i. Methanol decomposition reaction

ii. Methanol–Water solution electrolysis
iii. Methanol steam reforming reaction for hydrogen generation
2.5.2.4 Other Uses of Methanol
 A lot of methanol is used to make formaldehyde and acetic acid.

 Methanol is frequently used as a denaturant when ethanol is added to prevent it from
being consumed for recreational purposes.
 In many pipes, this substance is also employed as antifreeze, which lowers the
freezing point of a liquid.
 Because it provides denitrifying bacteria with a carbon-based food source, it is also
employed in sewage treatment facilities.
 Methanol is used in the Polyacrylamide Gel Electrophoresis (PAGE) procedure as a
destaining agent.
 In order to boost power, high-performance engines use a mixture of water and
methanol.
 Additionally, it is employed in the creation of methylamines and methyl esters.
49
2.6 Production of Methanol from CO2
Several research and technological approaches are being used to enable CO 2 to be effectively
converted to value-added chemicals. Researchers have discovered that CO2 can be converted
into methanol, an industrial commodity with high efficiency.
2.6.1 Heterogeneous Catalytic Hydrogenation of CO2
Heterogeneous catalysis occurs when a substance in a different phase from that of the
reactant phase (usually a solid material) increases the rate of a chemical reaction without
being incorporated into the overall stoichiometric equation. A major advantage of
heterogeneous catalysis is ease of separating liquid from solid catalyst, simplicity of handling
in different reactor types, and the ability to regenerate catalysts after they have been used.
Several studies have focused on developing effective and stable heterogeneous catalysts for
reducing carbon dioxide in the production of methanol.
However, numerous studies have shown that Cu-based catalysts with ZrO 2 or ZrO3 additives
are more stable and more active. As a result of the kinetic limitations (15–25%), conventional
CO2 hydrogenation into methanol is carried out at low temperatures (230–270 °C). The high
deactivation of conventional Cu–ZnO catalysts makes them less efficient with syngas
because carbon dioxide is a very stable molecule. In a study published by Arena et al. 2008,
the solid-state interactions, functionality, and adsorption sites of Cu-ZnO/ZrO 2 catalysts and
their ability to convert CO2 into methanol were evaluated. Using the results of the
characterization studies, it was established that the strong interaction between Cu and ZnO
effectively promotes the dispersion of the metal copper in oxygen, which is in accordance
with the results of the characterization studies.
As a result, the reactivity of the material increases. The Cu-ZnO/ZrO 2 catalysts result in the
hydrogenation of CO2 into methanol at the metal/oxide interface. Figure 2.15 illustrates the
dual-site reaction path that explains why the CO 2 conversion rate is not affected by the form
of the catalyst over Cu–ZnO/ZrO2.
50
Figure 2.14: Heterogeneous catalytic process for the conversion of CO2 to methanol using
Cu/ZrO/ZrO2
Source: Arena et al, 2008
2.6.2 Homogenous Catalytic Hydrogenation Of CO2
Homogeneous catalysis occurs as a result of the catalyst and reactants being in the same
phase at the same time during the catalysis process. As reported by Tominaga et al. 2011,
homogeneous catalysts were capable of directly converting CO2 into methanol.
Hydrogenating CO2 with Ru3(CO)12 catalyst precursors and KI additives produces methane,
methanol, and carbon dioxide. Additionally, Ru3(CO)12–KI outperformed W(CO)6, Fe2(CO)9,
Ir4(CO)12, Mo(CO)6, CO2(CO)8, and Rh4(CO).
Huff and Sanford proposed that CO2 is hydrogenated into formic acid, esterified into formate
esters, and then hydrogenated again into methanol. CO2 can also be homogeneously
chemically reduced to methanol by silanes and hydrides, with N-heterocyclic carbenes
(NHCs) acting as catalysts. The high cost of silanes did not prevent Zhang et al. NHC
catalysts can convert CO2 into methoxides at ambient temperatures.
51
Figure 2.15: NHC-catalyzed CO2 conversion and the subsequent methanol hydrolytic
Source: Riduan, Zang, Yin, 2009
2.6.3 Electrochemical Reduction Of CO2 To Methanol

In recent years, electrochemical reductions of carbon dioxide have been extensively
researched. As carbon dioxide is reduced at metal electrodes in aqueous solutions, formate
and carbon monoxide are generated. Copper electrodes can produce methane and ethylene
under the right electrolysis conditions. In spite of the fact that carbon dioxide can be reduced
thermodynamically to methanol, a well-established method does not appear to exist for
achieving this reaction with extremely high current efficiency close to 100%, despite the fact
that ruthenium, gallium arsenide, and RuO2, TiO2 cathodes have been used to produce
methanol using aqueous solutions.
It is more important to select the catalysts and conditions for the reaction than to be able to
control a variety of reduced products. When CO 2 electrocatalysts use H2O as an electrolyte,
the hydrogen evolution reaction (HER) plays an important role. This results in relatively high
HER overpotentials in metals that are useful as electrocatalysts for CO 2 reduction. A great
deal of work will be required to find the best electrode for CO 2 electrochemical reduction that
will reduce CO2 selectivity while maintaining high rates and low overpotentials without
reducing water.
When CO2 is converted directly into methanol, a useful product can be produced that is
useful for many energy-consuming devices. A process like this can be used to recycle CO 2
and produce methanol, which can replace fossil fuels in energy-consuming devices. As a
result of this electroreduction process, it is possible to reduce CO 2 directly in the electrolysis
cell back to methanol in one step by reducing it back to CO2 by electroreduction.
52
2.6.4 Photochemical Reduction of CO2
Photochemical reduction involves chemical reduction caused by the photoexcitation of

another molecule, called a photosensitizer. The photocatalytic method is used to convert CO 2
directly to methanol, despite its low selectivity for methanol. Photocatalytic CO2 conversion
involves a complex combination of photophysical and photochemical. Therefore, this method
is processes similar to electrocatalytic CO2 reduction, a process that also relies on molecular
catalysts to reduce CO2. Sacrificial hydride sources limit the reduction rate during
photocatalytic CO2 reduction. The electrocatalytic reduction of CO2 uses ascorbic acid,
amine, and 1-benzyl-1,4-dihydro-nicotinamide as sacrificial hydride sources. Researchers
have tested the ability of semiconductors and metal oxides to convert CO2 to methanol.
As shown in Figure 2.17, the photochemical process involves two competitive reactions,
photo-oxidation and photo-reduction. The photo-oxidation rate (Ko) will be slower than the
photoreduction rate (Kr) when the reaction begins because of the low concentration of
produced methanol. CO2 conversion into methanol was found to have a maximum molar
concentration of 1.25 mmol/l and a photonic efficiency of 1.95%.
photochemical process.
Source: Li et al, 2012
53
2.6.5 Photoelectrochemical Reduction Of CO2 To Methanol
The photoelectrocatalytic CO2 reduction technique combines photocatalysis and

electrocatalysis. It has been attempted to identify the best semiconductor for use as a
photoelectrode in a PEC (photoelectrochemical) cell; however, no tested semiconductor has
been found to meet the requirements for stability and efficiency. In order to reduce CO 2 by
photoelectrochemical means, 1.5 eV of thermodynamic energy is required. PEC cells require
more energy input because of band bending losses, overvoltage potentials, and resistance
losses.
Methanol is reduced by photoelectrochemical (PEC) processes to produce hydrogen ions and

electrons. Light illuminates semiconductors (e.g., SiC, GaP) as sources of energy higher than
their band gap. A cathode counter electrode is connected to an external connection, which
results in electrons being transferred from the valance band to the conduction band. The
semiconductor also separates electrons from holes at or near the interface to produce the
electrochemical reduction and oxidation reactions.
photochemical process
Source: Zhao et al., 2014
54
2.7 Factors Affecting the Yield of Methanol
2.7.1 Effect of a Catalyst

A catalyst is a substance that alters the rate of a process. With very few exceptions, H 2 is inert
toward organic molecules in the absence of metal catalysts. Once the unsaturated substrate
has chemisorbed there, the majority of the catalyst's sites are covered by it. Hydrogen creates
surface hydrides (M-H) on heterogeneous catalysts, from which hydrogens can be transported
to the chemisorbed substrate.
The choice of catalyst is important, as different catalysts can have varying levels of activity
and selectivity for the methanol synthesis reaction. For example, copper-based catalysts are
commonly used for methanol synthesis due to their high activity and selectivity, but
alternative catalysts such as zinc oxide or iron oxide can also be used (Baltes et al, 2008).
2.7.2 Effect of Temperature

As with other chemical reactions, raising the temperature speeds up hydrogenation.
Researchers showed the effect of reaction temperature on the time-dependent patterns of CO 2
conversion. Since CO yield rose with temperature, conversion only slightly increased with
longer reaction times, and this is not surprising since CO is formed via the RWGS reaction,
which is a reversible endothermic reaction; therefore, finding a technique to prevent this
thermal conflict between these reactions seems to be crucial.
2.7.3 The Effect of Pressure

The pressure of the reaction can have a significant effect on the yield of methanol produced.
In general, increasing the pressure of the reaction can increase the reaction rate and overall
methanol yield. This is due to the higher concentration of reactants in the reaction mixture,
which leads to an increased rate of reaction.
However, the relationship between pressure and methanol yield is not always straightforward
and can be influenced by other process conditions, such as temperature and catalyst type. For
example, while increasing the pressure can increase the reaction rate, it can also increase the
rate of side reactions and decreased catalyst activity. In addition, high pressure can increase
the cost of the process, making it less economically viable. However, being that most
methanol processes employ Cu-based catalyst, high pressure favours conversion as it
increases the methanol selectivity of the catalyst (Etim et al., 2020).
55
2.7.4 Effect of Reactor Type and Reactor Design
The type of reactor used for methanol synthesis can have a significant effect on the yield of
methanol produced. There are several different types of reactors that can be used for
methanol synthesis, including fixed-bed reactors, fluidized-bed reactors, and slurry reactors.
The choice of reactor can impact various factors such as temperature, pressure, and mixing
conditions, which can in turn impact the reaction kinetics and methanol yield.
For example, fixed-bed reactors provide a well-defined environment for the reaction, but they
can be less flexible in terms of temperature control and pressure regulation. On the other
hand, fluidized-bed reactors offer improved mixing and heat transfer, which can improve
reaction kinetics and overall methanol yield.
Slurry reactors can be particularly useful for the synthesis of methanol from coal or natural
gas, as they can effectively handle the solid feedstocks and provide good mixing and heat
transfer.
In general, the choice of reactor will depend on various factors, including the feedstock being
used, the desired production rate, and the overall economic feasibility of the process. The
most appropriate reactor for a particular application will depend on a careful balance of these
factors and the trade-off between the desired methanol yield and the cost of the reactor
(Samrand et al., 2014).
2.8 Methanol Synthesis from by Hydrogenation Flare Gas from Crude Oil Wells
Having defined important concepts and processes related to this study, this section describes
the process designed in this project. A brief overview of the process, the rationale behind
adsorbents, catalysts selected, and operating conditions used in the process are discussed.
Furthermore, the utilization of the byproducts and their storage conditions until sale are
highlighted.
2.8.1 Overview of the Process

For economic and safety reasons, natural gas generated during crude oil exploration is burnt
in flare systems to yield a substantial amount of carbon dioxide. Although, the emission of
methane has been avoided, carbon dioxide is still a potent greenhouse gas.
In this process, pre-combustion carbon capture is employed i.e. associated gas is sent to
methanol production plant before it is combusted, as this is a far more economical approach.
A pressure swing adsorber (P.S.A) is first used to remove inherent hydrogen sulphide to
56
protect downstream equipment from fouling and corrosion. The H2S-free gas is then mixed
with steam before being sent to a pre-reformer to convert higher hydrocarbons into methane
and prevent accumulation of soot, and then finally to the SMR reactor where methane
(principal constituent) is converted into syngas. The outlet stream (syngas) undergoes a high
temperature water gas shift reaction to give required stoichiometric ratio of carbon dioxide
and hydrogen alongside impurities such as carbon monoxide. The reaction is given by
equations 2.6, 2.7 and 2.8.
In the presence of a Cu/ZnO/ZrO2 catalyst, carbon dioxide is hydrogenated to yield methanol,

water and unused reactants. The following reactions occur in this reactor:
CO2 + 3H2 CH3OH + H2O (2.6)
CO + 2H2 CH3OH (2.7)
CO2 + H2 CO + H2O (2.8)
The outlet stream is separated into distinct phases of liquid and gas by a flash drum. The
gaseous components are sent to another reactor for further processing whereas the liquid
stream composed of methanol, water and traces of gaseous substances is further purified by a
flash drum before being fed to a distillation column which ultimately yield a high-purity
methanol stream (99 wt%).
2.8.2 Selection of Catalyst in Synthesis Reactor

The conventional catalyst, Cu/ZnO/Al2O3 suffers from a series of technical problems when
converting CO2 to methanol directly, which include low single-pass conversion, low
methanol selectivity, requiring high pressure and fast deactivation by the reverse water gas
shift reaction. The catalyst chosen for this process is Cu/ZnO/ZrO 2. It was chosen for the
following reasons:
i. Increases the hydrophobic properties of catalyst thus making it less prone to

deactivation and increasing the lifespan.
ii. Higher thermal stability.
iii. Improved surface area, thus allowing better conversion.
2.8.3 Selection of Adsorbents

2.8.3.1 Adsorbent for Removal of H2S
57
The adsorbent selected for the capture of hydrogen sulphide is Cu-ZnO-SBA-15 and was
chosen for the following reasons:
i. Easily regeneratable
ii. High selectivity
iii. High capacity
2.8.3.2 Adsorbent for Removal of Hydrogen (H2)
The adsorbent selected for the capture of hydrogen is Zeolite 5A and was chosen for the
following reasons:
i. High capacity
ii. Well-defined porous structure
iii. High selectivity
2.8.4 Operating Conditions of Methanol Synthesis

The hydrogenation of CO2 is a parallel reaction. Under different conditions, different
products are formed. The hydrogenation of carbon dioxide (CO 2) to carbon monoxide (CO)
occurs at very high temperatures. On the other hand, methanol production is favoured at
lower temperatures and higher pressures.
Hence, the process is carried out at 58 bars and 200℃ in order to favour the formation of
methanol. To attain these conditions, the mixture of the outlet stream from the W.G.S is first
compressed and cooled prior to entry into the synthesis reactor.
2.8.5 Storage of Products
2.8.5.1 Storage of Methanol

Stainless steel containers are used to store methanol. Although, they possess a higher capital
cost than carbon steel, they offer the advantage of lower life cycle maintenance cost, and
reduced likelihood of methanol contamination. Furthermore, due to methanol
being extremely flammable, static electricity needs to be under control. Metal cans or drums
are typically the ideal containers because they can be grounded (Cade, 2021).
The container is also able to store at least 110% of the capacity at the moment in order to
protect against potential thermal expansion or else there would be a leak in the container. The
lids of these containers can be repeatedly resealed after opening. Methanol is stored at a
temperature of 25℃.
58
2.8.5.2 Storage of Hydrogen
Hydrogen is mainly stored either as a compressed gas or liquid under cryogenic conditions.
In this process, hydrogen is compressed to 700 bars and cooled to a suitable temperature of
25℃ and stored in its gaseous form. Storing hydrogen as a gas has several advantages over
storing it as a liquid:
i. Safety: Storing hydrogen as a gas eliminates the risk of leaks or spills that can occur
when storing hydrogen as a liquid, especially if the storage container is damaged.
Hydrogen gas is also less likely to ignite or explode than liquid hydrogen.
ii. Cost: Storing hydrogen as a liquid requires specialized equipment, such as cryogenic
tanks, which can be expensive. Storing hydrogen as a gas requires simpler and less
costly equipment, such as high-pressure gas tanks.
iii. Convenience: Storing hydrogen as a gas is more convenient than storing it as a liquid,
as it can be stored and transported in smaller, lighter containers.
iv. Energy efficiency: Storing hydrogen as a liquid requires a significant amount of

energy to keep it at its boiling point of -253°C (-423°F). On the other hand, storing
hydrogen as a gas requires less energy, as it can be stored at ambient temperature and
pressure.
2.8.5.3 Storage of CO2
Carbon dioxide is another byproduct from the process and is stored under temperatures of
25°C and 30 bars which is considered to be a low-pressure storage of CO 2. The storage tanks
are made of Aluminium. Aluminum is a lightweight and corrosion-resistant material that is
often used for low-pressure CO2 storage tanks. Aluminum tanks are typically lined with a
barrier material, such as polyethylene, to prevent contamination from the stored CO2.
2.8.6 Utilization of Byproducts

The products of this process and the uses to which they are put are listed below.
i. The overhead product of the distillation column consisted of methanol and is the main
product of this process. It is stored and sold to potential buyers such as manufacturing
companies for use as a feedstock or fuel.
ii. The stream of water obtained at the bottom of the final distillation column can be
passed to chillers and then re-used as cooling medium e.g. in condensers.
59
iii. The byproducts which are hydrogen and carbon dioxide and stored and subsequently
sold to potential buyers such as beverage and metallurgical industries that require
carbon dioxide and hydrogen respectively.
2.9 Review of Past Reports
The production of methanol from carbon dioxide is a project that has been studied and put to
practice. From past reports, it is indeed possible to produce methanol from carbon dioxide via
hydrogenation in particular. These are a few past research which involved the production of
methanol from carbon dioxide including challenges faced, limitations, method of production
and so on.
Review Number One
(Samimi, Karimipourfard, Rahimpour, 2018) carried out research producing methanol

from carbon dioxide through the reverse water gas shift reaction otherwise known as the
CAMERE (carbon dioxide hydrogenation to form methanol via a reverse-water- gas-shift
reaction) process.
Although direct conversion from CO2 has been found to be more effective than conventional
conversion from syngas in terms of lower heat profile and less impurities, the process is still
plagued by the amount of water formed during the reaction which results in deactivation of
the copper-based catalysts and thus, lower conversion. Hence, the CAMERE process was
brought forward and was studied in this paper. Furthermore, the research compared the
results of the process against that of the conventional process (conversion from syngas).
The feed which was a mixture of carbon dioxide and hydrogen in the molar ratio 1:3 was split
into streams. The majority was sent to the RWGS reactor while the remainder was kept to
correct (if necessary) the composition of the outlet stream. Water is formed in this reactor but
is eliminated by a condenser. This serves to prolong the lifespan of the catalyst, which in this
case was Ni/Al12O19. Furthermore, their research featured water-selective membrane coating
in the second reactor (methanol synthesis reactor) to remove even more amounts water of
water, facilitating more conversion to methanol.
60
Figure 2.18: A schematic diagram of the CAMERE process.
Source: Samimi, Karimipourfard, Rahimpour, 2018
Parameters affecting the performance of the RWGS reactor, particularly the inlet temperature
and pressure were investigated. To do this, a kinetic model was developed based on the
recent work of Kaiser et al. (2013) who investigated the RWGS kinetics over Ni/Al 12O19
catalyst at temperatures up to 1200 degrees centigrade, against pre-existing literature that
only considered up to 500.
Figure 2.19: A comparison between the performance of conventional and CAMERE process
in methanol mole fraction during the length of methanol synthesis reactor.
61
Figure 2.20: A comparison between the performance of conventional and CAMERE process
in water mole fraction during the length of methanol synthesis reactor.
Source: Samimi, Karimipourfard, Rahimpour, 2018
The reason for this being that at temperatures higher than 700, there is little to zero formation
of methane. The model then was validated when compared to plant data. Having investigated
the aforementioned parameters, optimized conditions were then determined including
optimized feed fraction. Finally, at these optimized conditions, the process was then
compared with conventional synthesis from syngas.
The comparison was in terms of H 2, CO2, H2O, CO and methanol mole fraction. Figure 2.32
is the comparison between the two processes in terms of methanol fraction during the length
of the synthesis reactor. Clearly, the CAMERE process resulted in higher conversion.
However, the water produced even with the presence of the membrane was more than
the conventional process.
Review Number Two
(Nieminen, Laari, Koiranen, 2019) investigated a novel route in methanol production. With
large-scale commercialization of methanol still not achieved, novel methods to improve
economic feasibility are needed. In this research, alcoholic solvents were used to catalyze the
process. The solvents employed were 2-butanol or 1-butanol. Methanol synthesis in the
62
presence of alcohol happens through an altered reaction mechanism that uses the alcohol's
formate ester to enable lower reaction temperatures, thereby reducing processing costs.
The lower temperature also permits a larger equilibrium conversion for the synthesis of
methanol. To accurately determine the economic feasibility of this liquid-phase process, the
alcohol-promoted process was compared to the conventional gas-phase process by means of
process flowsheet simulation and subsequent economic analysis.
The process was able to achieve higher equilibrium conversion of carbon dioxide to
methanol. This was shown to reduce operating and capital costs, albeit very slight. However,
due to the high solvent content of the reactor effluent, a costly and time-consuming
separation stage was necessary, requiring two distillation columns as opposed to one in the
gas-phase process. Azeotropes that developed between the alcohols and the water byproduct
hindered the separation process and caused solvent losses. Hence, with an increased energy
consumption and cost of solvent make-up, even when coupled with heat integration, the gas-
phase process still proved to be more cost-effective than the liquid-phase process.
63
CHAPTER 3
MATERIAL BALANCE
3.1 Introduction
For the study of physical systems, mass or material balance is based on the law of
conservation of matter. This The law asserts that mass cannot be created or destroyed by
physical or chemical methods in an ideal system, and that mass remains constant. Theis
equation for material balance equation calculates determines the number of reactants and
products needed required for a process, and, as well as their quantities that can be obtained in
the appropriate amounts. Hence, Mmaterial balances are is fundamental to the control of
processingprocess control, particularly in the control of yields of the products.
The general material balance equation for a system is given below;
Mass Input + Mass Generation – Mass Output - Mass Consumption = Mass Accumulation
(3.1)
Where:
i. Mass Input: Enters Matter entering through the system boundaries
ii. Mass Generation: Matter pProduced within the system
iii. Mass Output: Matter lLeavinges through system boundaries
iv. Mass Consumption: Matter cConsumed within the system
v. Mass Accumulation: MatterMass built dup within the system
3.2 Aspen PlusAspen Simulation
The simulation of this process was carried out using the process simulation software, Aspen
Plus (V11). The process was simulated to achieve the design intent of producing 30,000 tons
of pure methanol per year using flare gas from crude oil wells as a feedstock.The Aspen Plus
simulation flowsheet and overall block diagram for the process is shown in Figures 3.1 and
3.2
64
Figure 3.21: Overall Aspen flow diagram
65
Figure 3.22: Overall process flow diagram
66
Table 3.3: Components Specifications Table
COMPONENT TYPE COMPONENT NAME CHEMICAL

ID FORMULA
CO2 Conventional CARBON DIOXIDE CO2
H2O Conventional WATER H2O
CO Conventional CARBON MONOXIDE CO
H2 Conventional HYDROGEN H2
CH3OH Conventional METHANOL METHANOL
CH4 Conventional METHANE CH4
C3H8 Conventional PROPANNE C3H8
C2H6 Conventional ETHANE C2H6
N-BUTANE Conventional N-BUTANE C4H10
N-PENTANE Conventional N-PENTANE C5H12
ISO-BUTANE Conventional ISO-BUTANE HC(CH3)3
ISO-PENTANE Conventional ISO-PENTANE CH3CH2CH(CH3)2
N-HEXANE Conventional N-HEXANE C6H14
N-HEPTANE Conventional N-HEPTANE C7H16
H2S Conventional HYDROGEN SULPHIDE H2S
3.3 Overall Material Balance for the Production Process
The material balance calculations performed around the various unit operations and
equipment in the green hydrogen productionmethanol production process can be grouped into
the following:
i. Material balance around the reforming process

ii. Material balance around the synthesis process
iii. Material balance around the purification process
The overall material balance of the system is shown in Table 3.2
Figure 3.23: Block diagram of overall process
67
Table 3.4: Overall material balance for the production process
68
FEED PRODUCT
COMPONENT 1 4 3 31 34 37 38
S (Impure (Water) (Clean (CO2) (H2) (H2O) (MeOH)
flare gas) Mass flow flare gas) Mass flow Mass flow Mass flow Mass flow
Mass flow rate (kg/hr) Mass flow rate (kg/hr) rate (kg/hr) rate (kg/hr) rate (kg/hr)
rate (kg/hr) rate (kg/hr)
METHANE 1393.07691 91.9192174 1.27405E- 0.00303461
5 0 0 7 0 59 9
From ETHANE 0.10819852 9.93823E- Table 3.2
above, 307.215498 0 0 2 0 55 2.8278E-05 the
following deduction
is made: PROPANE 220.023996 2.79242E- 1.94717E- 8.99226E-
2 0 0 05 0 56 09
BUTANE 60.8900738
4 0 0 6.2839E-09 0 0 0
N-PENTANE 21.0390216
5 0 0 0 0 0 0
N-HEXANE 19.5449798
9 0 0 0 0 0 0
N-HEPTANE 10.8220363
2 0 0 0 0 0 0
CO2 123.864701 1426.15299 5.60181E-
9 0 0 9 0 45 3.68091214
H2S 0.0368084
0.03680843 0 3 0 0 0 0
WATER 5.05869062 5836.9507 7.33918616 2969.75149 0.00061955
4 2 0 6 0 3 8
69
METHANOL 6.83092314 3116.81283
0 0 0 54.3862047 0 5 5
Total feed mass flowrate = 2235.31952 + 5836.95072 = 8072.27024 kg/hr
Total product mass flowrate = 0.03680843 + 1593.780496 + 381.3728921 + 2976.582416 + 3120.497641 = 8072.27024 kg/hr.
Since the total feed mass flowrate and product mass flowrate are equal, this implies that there is no accumulation in the system. Hence, it is
balanced.
70
3.4 Reforming Process
Figure 3.24: Process Flow Diagram for Reforming Process
71
72
Table 3.5: Overall material balance for reforming process
FEED PRODUCT
Components 1 4 3 12
(CO2 + H2O)
(IMPURE (WATER) (CLEAN
Mass flow rate
FLARE GAS) Mass flow rate FLARE GAS)
(kg/hr)
Mass flow rate (kg/hr) Mass flow rate
(kg/hr) (kg/hr)
METHANE 1393.076915 0 0 91.92225209
ETHANE 307.215498 0 0 0.1082268
PROPANE 220.0239962 0 0 2.79331E-05
BUTANE 60.89007384 0 0 6.28554E-09
N-PENTANE 21.03902165 0 0 0
N-HEXANE 19.54497989 0 0 0
N-HEPTANE 10.82203632 0 0 0
CO2 123.8647019 0 0 5527.055638
H2S 0.03680843 0 0.03680843 0
WATER 5.058690624 5836.95072 0 1299.905837
METHANOL 0 0 0 0
H2 0 0 0 968.9284606
CO 0 0 0 184.3129951
ISO-BUT 49.59088488 0 0 4.29727E-09
ISO-PENT 24.15591374 0 0 0
Total (kg/hr) 1393.076915 5836.95072 0.03680843 8072.233437
73
From table 3.3 above,
Total feed mass flowrate = 1393.076915 + 5836.95072 = 8072.233432 kg/hr
Total product mass flowrate = 0.03680843 + 8072.233437 = 8072.233432 kg/hr
Since the total feed mass flowrate and product mass flowrate are equal, this implies that there
is no accumulation in the system. Hence, it is balanced.
3.4.1 Material Balance around PSA (A)

This is a desulfurizer that is used to separate H2S from the feed gas to protect downstream
equipment from corrosion and fouling.
Assumptions
1. High selectivity of hydrogen sulphide (H2S)
Figure 3.25: Process Flow Diagram for PSA (A)
74
CL-FLGAS
FLGAS PSA-01
H2S
Figure 3.26: Aspen Simulation Diagram for PSA (A)
Table 3.6:Material Balance around PSA (A)
STREAMS INPUT OUTPUT
COMPO- 1 2 3
NENTS Clean flare gas H2S
Impure flare gas
Mass flow Composition Mass flow Composition Mass flow Compositi

on
(kg/hr) (kg/hr)
(kg/hr)
METHANE 1393.07691 0.6232218 0 0

1393.07691 0.623211537
ETHANE 307.215498 0.137439214 0 0
307.215498 0.13743695
PROPANE 220.023996 0.09843229 0 0
220.023996 0.098430669
BUTANE 60.8900738 0.027240435 0 0
60.8900738 0.027239987
N-PENTANE 21.0390216 0.009412242 0 0
21.0390216 0.009412087
N-HEXANE 19.5449798 0.008743851 0 0
19.5449798 0.008743707
N-HEPTANE 10.8220363 0.004841462 0 0
10.8220363 0.004841382
CO2 123.864701 0.055413439 0 0
123.864701 0.055412526
H2S 0 0 0.03680843 1.00000
0.03680843 1.64667E-05
H2O 5.05869062 0.00226311 0 0
5.05869062 0.002263073
75
ISO-BUT 49.5908848 0 0 0
49.5908848 0
ISO-PENT 24.1559137 0 0 0
24.1559137 0
TOTAL 2235.31952 1.00000000 2235.28271 1.00000000 0.03680843 1.000000
From Table 3.4 above, the following deduction is made:

Total feed mass flowrate = 2235.31952 kg/hr
Total product mass flowrate = 2235.28271 +0.03680843 = 2235.31952 kg/hr
Since the total feed mass flowrate and product mass flowrate of the pre-treatment section are
equal, this implies that there is no accumulation of mass in this section. Hence the
pretreatment section operates at steady state.
3.4.2 Material Balance around Heater (B)

This is used to heat feed water and thus, generate steam which is needed in subsequent
reactions.
Assumptions
1. Operates isothermally at 100℃
Figure 3.3.27: Process flow diagram for Heater (B)
HEATR-01
WATER STEAM
Figure 3.28 Aspen Simulation diagram for Heater (B)
76
Table 3.7: Material Balance around Heater (B)
COMPONENTS 4 5
Water Steam
Mass flow Composition Mass flow Composition
(kg/hr) (kg/hr)
H2O 5836.95072 1.00000000 5836.95072 1.00000000
TOTAL 5836.95072 1.00000000 5836.95072 1.00000000

Total product mass flowrate = 5836.95072 kg/hr
equal, this implies that there is no accumulation of mass in this section. Hence the pre-
treatment section operates at steady state.
3.4.3 Material Balance around Mixer 1
Figure 3.29: Process flow diagram for Mixer 1
77
STEAM
H2OCH4-1
MIX-01
CL-FLGAS
Figure 3.30: Aspen Simulation diagram for Mixer 1
Table 3.8: Material Balance around Mixer

COMPO- 2 5 6
NENTS
Clean Flare Gas Steam Steam + Methane
Mass flow Mass flow Mass flow

Composition Composition Composition
(kg/hr) (kg/hr) (kg/hr)
METHANE 1393.076915 0.6232218 0 0 1393.076915 0.172576391

ETHANE 307.215498 0.137439214 0 0 307.215498 0.038058302
PROPANE 220.0239962 0.09843229 0 0 220.0239962 0.027256892

BUTANE 60.89007384 0.027240435 0 0 60.89007384 0.007543151
N-
PENTANE 21.03902165 0.009412242 0 0 21.03902165 0.002606345
N-
HEXANE 19.54497989 0.008743851 0 0 19.54497989 0.00242126
N-
HEPTANE 10.82203632 0.004841462 0 0 10.82203632 0.00134065
CO2 123.8647019 0.055413439 0 0 123.8647019 0.015344539
H2O 5.058690624 0.00226311 5836.95072 1.00000000 5842.009411 0.72371661
ISO-BUT 49.59088488 0 0 0 49.59088488 0.006143391
ISO-PENT 24.15591374 0 0 0 24.15591374 0.00299247
TOTAL 2235.282712 1.00000000 5836.95072 1.00000000 8072.233432 1.00000000
78
Total feed mass flowrate = (2235.282712+ 5836.95072) kg/hr = 8072.233432 kg/hr
3.4.4 Material Balance around Heater (C)

This heater raises the temperature of the steam and flare gas (methane) mixture to the
necessary temperature required for the pre-reforming reaction i.e breakdown of
hydrocarbons.
Assumptions
Figure 3.31: Process flow diagram for Heater (C)
H2OCH4-2
H2OCH4-1
HEATR-02
Figure 3.32: Aspen Simulation diagram for Heater (C)
79
Table 3.9: Material Balance around Heater(C)
COMPONENTS 6 7
Steam + Methane Pre-Reformer Feed

(kg/hr) (kg/hr)
METHANE 1393.076915 0.172576391 1393.076915 0.172576391

ETHANE 307.215498 0.038058302 307.215498 0.038058302
PROPANE 220.0239962 0.027256892 220.0239962 0.027256892
BUTANE 60.89007384 0.007543151 60.89007384 0.007543151
N-PENTANE 21.03902165 0.002606345 21.03902165 0.002606345

N-HEXANE 19.54497989 0.00242126 19.54497989 0.00242126
N-HEPTANE 10.82203632 0.00134065 10.82203632 0.00134065
CO2 123.8647019 0.015344539 123.8647019 0.015344539
H2O 5842.009411 0.72371661 5842.009411 0.72371661
ISO-BUT 49.59088488 0.006143391 49.59088488 0.006143391
ISO-PENT 24.15591374 0.00299247 24.15591374 0.00299247
TOTAL 8072.233432 1.00000000 8072.233432 1.00000000

80
3.4.5 Material Balance around Pre-reformer Reactor (D)
In this reactor, steam reacts with the higher hydrocarbons present in flare gas such as ethane,
propane, isobutane, etc to yield methane. The decomposition of these components will also
serve to reduce the amount of soot generated.
Assumption
1. 99% conversion of hydrocarbons into methane.
Figure 3.33: Process Flow diagram for Pre-reformer Reactor (D)
H2OCH4-3
H2OCH4-2
PRE-REF
Figure 3.34: Aspen Simulation diagram for Pre-reformer Reactor (D)
81
Table 3.10: Material Balance around Pre-reformer Reactor (D)
COMPONEN 7 8
TS
Pre-Reformer Feed Pre-Reformer Outlet

(kg/hr) (kg/hr)
METHANE 1393.076915 0.172576391 1838.445042 0.227749241

ETHANE 307.215498 0.038058302 0.1082268 1.34073E-05
PROPANE 220.0239962 0.027256892 2.79331E-05 3.4604E-09
BUTANE 60.89007384 0.007543151 6.28554E-09 7.78661E-13
N-PENTANE 21.03902165 0.002606345 1.17289E-12 1.453E-16

N-HEXANE 19.54497989 0.00242126 1.8339E-16 2.27186E-20
N-HEPTANE 10.82203632 0.00134065 3.02687E-20 3.74973E-24
CO2 123.8647019 0.015344539 990.1197326 0.12265747
H2O 5842.009411 0.72371661 5118.351568 0.634068825
H2 0 0 102.7261869 0.012725869
CO 0 0 22.482653 0.002785184
ISO-BUT 49.59088488 0.006143391 4.29727E-09 5.32352E-13
ISO-PENT 24.15591374 0.00299247 1.76971E-12 2.19234E-16
TOTAL 8072.233432 1.00000000 8072.233437 1.00000000

82
3.4.6 Material Balance around Heater (E)

Here, the temperature of the reactor feed (methane and steam) is raised to the necessary
temperature which is 8000C
Assumptions
Figure 3.35: Process flow diagram for Heater (E)
HEATR-03
H2OCH4-3 H2OCH4-4
Figure 3.36: Aspen Simulation diagram for Heater (E)
83
Table 3.11: Material Balance around Heater (E)
COMPONEN 8 9
TS
Pre-Reformer Outlet Reformer Feed

(kg/hr) (kg/hr)
METHANE 1838.445042 0.227749241 1838.445042 0.227749241

ETHANE 0.1082268 1.34073E-05 0.1082268 1.34073E-05
PROPANE 2.79331E-05 3.4604E-09 2.79331E-05 3.4604E-09
BUTANE 6.28554E-09 7.78661E-13 6.28554E-09 7.78661E-13
N-PENTANE 1.17289E-12 1.453E-16 1.17289E-12 1.453E-16

N-HEXANE 1.8339E-16 2.27186E-20 1.8339E-16 2.27186E-20
N-HEPTANE 3.02687E-20 3.74973E-24 3.02687E-20 3.74973E-24
CO2 990.1197326 0.12265747 990.1197326 0.12265747
H2O 5118.351568 0.634068825 5118.351568 0.634068825
H2 102.7261869 0.012725869 102.7261869 0.012725869
CO 22.482653 0.002785184 22.482653 0.002785184
ISO-BUT 4.29727E-09 5.32352E-13 4.29727E-09 5.32352E-13
ISO-PENT 1.76971E-12 2.19234E-16 1.76971E-12 2.19234E-16
TOTAL 8072.233437 1.00000000 8072.233437 1.00000000

84
equal, this implies that there is no accumulation of mass in this section. Hence the pre-
treatment section operates at steady state.
3.4.7 Material Balance around Steam Reformer (F)

In this reactor, methane present in the flare gas reacts with steam to produce carbon
monoxide and hydrogen at a pressure of 25 bars and 800ºC.
Assumptions
1. It operates isothermally at 800ºC and 25 bars.
2. There is 95% conversion of methane

[add BFD].
Figure 3.37:Process flow diagram for Steam Methane Reformer (F)
85
H2OCH4-4
REFORMER
CO-H2-1
Figure 3.38: Aspen Simulation diagram for Steam Methane Reformer (F)
Table 3.12: Material Balance around Steam Reformer (F)
FEED PRODUCT
Components 98 Composition 109 Composition

(REFORMER (REFORMER
FEED) OUTLET)
Mass flow rate Mass flow rate
(kg/hr) (kg/hr)
METHANE 1838.445042 0.227749241 91.92225209 0.011387462
ETHANE 0.1082268 1.34073E-05 0.1082268 1.34073E-05
PROPANE 2.79331E-05 3.4604E-09 2.79331E-05 3.4604E-09
BUTANE 6.28554E-09 7.78661E-13 6.28554E-09 7.78661E-13
N-PENTANE 1.17289E-12 1.453E-16 0 0
N-HEXANE 1.8339E-16 2.27186E-20 0 0
N-HEPTANE 3.02687E-20 3.74973E-24 0 0
CO2 990.1197326 0.12265747 990.1197326 0.12265747
H2S 0 0 0 0
WATER 5118.351568 0.634068825 3157.08698 0.39110452
METHANOL 0 0 0 0
H2 102.7261869 0.012725869 761.112966 0.094287779
CO 22.482653 0.002785184 3071.883252 0.380549358
ISO-BUT 4.29727E-09 5.32352E-13 4.29727E-09 5.32352E-13
86
ISO-PENT 1.76971E-12 2.19234E-16 0 0
Total (kg/hr) 8072.233437 1 8072.233437 1
From Table 3.10 above,
The tTotal feed mass flowrate = 8072.233437 kg/hr
And the tTotal product mass flowrate = 8072.233437 kg/hr
The total feed mass flowrate and product mass flowrate are equal, therefore there is no
accumulation of mass in the system. The unit is balanced.
3.4.8 Material Balance around Cooler (G)

In the cooler, the temperature of the hot stream outlet of the Steam Methane Reformer (F) to
the required temperature for the Water Gas Shift reaction (H) at 430℃.
Assumptions
Figure 3.39: Process flow diagram for Cooler (G)
87
CO-H2-1
COOL-01
CO-H2-2
Figure 3.40: Aspen Simulation diagram for Cooler (G)
88
Table 3.13: Material Balance around Cooler (G)
FEED PRODUCT
Components 10 Mass 11 Mass

(REFORMER Fraction (SYNGAS) Fraction
OUTLET) Mass flow
Mass flow rate (kg/hr)
rate (kg/hr)
METHANE 91.92225209 0.011387462 91.92225209 0.011387462
ETHANE 0.1082268 1.34073E-05 0.1082268 1.34073E-05
PROPANE 2.79331E-05 3.4604E-09 2.79331E-05 3.4604E-09
BUTANE 6.28554E-09 7.78661E-13 6.28554E-09 7.78661E-13
N-PENTANE 0 0 0 0
N-HEXANE 0 0 0 0
N-HEPTANE 0 0 0 0
CO2 990.1197326 0.12265747 990.1197326 0.12265747
H2S 0 0 0 0
WATER 3157.08698 0.39110452 3157.08698 0.39110452
METHANOL 0 0 0 0
H2 761.112966 0.094287779 761.112966 0.094287779
CO 3071.883252 0.380549358 3071.883252 0.380549358
ISO-BUT 4.29727E-09 5.32352E-13 4.29727E-09 5.32352E-13
ISO-PENT 0 0 0 0
Total (kg/hr) 8072.233437 1 8072.233437 1
89
3.4.9 Material Balance around Water Gas Shift Reactor (W.G.S.) (H)
In the W.G.S reactor, carbon monoxide reacts with steam to yield carbon dioxide and more
hydrogen.
Assumptions
1. 1. Adiabatic operation.
2. 2. 95% conversion of carbon monoxide.
Figure 3.41: Process flow diagram for W.G.S Reactor (H)
CO-H2-2
HT-WGS
CO2-H2-1
Figure 3.42: Aspen Simulation diagram for W.G.S Reactor (H)
90
Table 3.14: Material Balance around W.G.S reactor (H)
FEED PRODUCT

(SYNGAS) Fraction (CO2 + H2O) Fraction
Mass flow Mass flow
rate (kg/hr) rate (kg/hr)
METHANE 91.92225209 0.011387462 91.92225209 0.011387462
ETHANE 0.1082268 1.34073E-05 0.1082268 1.34073E-05
PROPANE 2.79331E-05 3.4604E-09 2.79331E-05 3.4604E-09
BUTANE 6.28554E-09 7.78661E-13 6.28554E-09 7.78661E-13
N-PENTANE 0 0 0 0
N-HEXANE 0 0 0 0
N-HEPTANE 0 0 0 0
CO2 990.1197326 0.12265747 990.1197326 0.12265747
H2S 0 0 0 0
WATER 3157.08698 0.39110452 3157.08698 0.39110452
METHANOL 0 0 0 0
H2 761.112966 0.094287779 761.112966 0.094287779
CO 3071.883252 0.380549358 3071.883252 0.380549358
ISO-BUT 4.29727E-09 5.32352E-13 4.29727E-09 5.32352E-13
ISO-PENT 0 0 0 0
Total (kg/hr) 8072.233437 1 8072.233437 1
3.5 Methanol Synthesis Process
91
Figure 3.43: Process Flow Diagram for Synthesis Process
92
Table 3.15: Overall Material balance around Methanol Synthesis Process
FEED PRODUCT
Components 12 31 34 35
(CO2 + H2O) (CO2 FOR (H2 FOR (MeOH, H2O)
Mass flow rate (kg/hr) STORAGE) STORAGE) Mass flow rate
Mass flow (kg/hr)
Mass flow
rate (kg/hr)
rate (kg/hr)
METHANE 91.92225209 91.85176137 0 0.00303461938

ETHANE 0.1082268 0.107889555 0 0.00002827802
PROPANE 2.79331E-05 2.77437E-05 0 0.00000000899
BUTANE 6.28554E-09 6.21414E-09 0 1.64121E-12
N-PENTANE 0 0 0 0
N-HEXANE 0 0 0 0
N-HEPTANE 0 0 0 0
CO2 5527.055638 1417.499065 0 3.68091214
H2S 0 0 0 0
WATER 1299.905837 0.593376554 0 2969.752112
METHANOL 0 12.16510419 0 3123.643758
H2 968.9284606 0 381.3728921 0.00019649958
CO 184.3129951 13.87264025 0 0.00001419294
ISO-BUT 4.29727E-09 4.27054E-09 0 2.87403E-13
ISO-PENT 0 0 0 0
Total (kg/hr) 8072.233437 1536.089865 381.3728921 6097.080056
Total product mass flowrate = 1536.089865 + 381.3728921 + 6097.080056 = 8072.233437
93
3.5.1 Material Balance around Compressor (I)
This unit raises the pressure of the W.G.S reaction from (H) to the required pressure of 58
bars.
Assumptions
1. It operates isentropically with a discharge pressure of 58 bar.

2. Isentropic efficiency is 75%
Figure 3.44: Process flow diagram for Compressor (I)
CO2-H2-2
CO2-H2-1
COMP-01
Figure 3.45: Aspen Simulation diagram for Compressor (I)
Table 3.16: Material Balance around Compressor (I)
FEED PRODUCT

(CO2 + H2O) Fraction (COMPRESSE Fraction
Mass flow D CO2 + H2O)
rate (kg/hr) Mass flow rate
(kg/hr)
METHANE 91.92225209 0.011387462 91.92225209 0.011387462
ETHANE 0.1082268 1.34073E-05 0.1082268 1.34073E-05
PROPANE 2.79331E-05 3.4604E-09 2.79331E-05 3.4604E-09
94
BUTANE 6.28554E-09 7.78661E-13 6.28554E-09 7.78661E-13
N-PENTANE 0 0 0 0
N-HEXANE 0 0 0 0
N-HEPTANE 0 0 0 0
CO2 990.1197326 0.12265747 990.1197326 0.12265747
H2S 0 0 0 0
WATER 3157.08698 0.39110452 3157.08698 0.39110452
METHANOL 0 0 0 0
H2 761.112966 0.094287779 761.112966 0.094287779
CO 3071.883252 0.380549358 3071.883252 0.380549358
ISO-BUT 4.29727E-09 5.32352E-13 4.29727E-09 5.32352E-13
ISO-PENT 0 0 0 0
Total (kg/hr) 8072.233437 1 8072.233437 1
3.5.2 Material Balance around Cooler J

This unit reduces the temperature of the compressor (I) outlet to the required inlet
temperature for the synthesis reactor (K) at 184ºC as higher temperatures (250℃ and above)
would reduce reactant conversion.
Assumptions
1. 1. Operates isothermally at 184ºC

2. It is capable of handling liquid and vapour.
Figure 3.46: Process flow diagram for Cooler (J)
95
COOL-02
CO2-H2-3
CO2-H2-2
Figure 3.47: Aspen Simulation diagram for Cooler (J)
Table 3.17: Material Balance around Cooler (J)
FEED PRODUCT
Components 139 Mass 14 Mass Fraction

(COMPRESSED CO2 Fraction (MeOH SYNTHESIS
+ H2O) REACTOR 1 FEED)
Mass flow rate (kg/hr) Mass flow rate (kg/hr)
METHANE 91.92225209 0.011387462 91.92225209 0.011387462
ETHANE 0.1082268 1.34073E-05 0.1082268 1.34073E-05
PROPANE 2.79331E-05 3.4604E-09 2.79331E-05 3.4604E-09
BUTANE 6.28554E-09 7.78661E-13 6.28554E-09 7.78661E-13
N-PENTANE 0 0 0 0
N-HEXANE 0 0 0 0
N-HEPTANE 0 0 0 0
CO2 990.1197326 0.12265747 990.1197326 0.12265747
H2S 0 0 0 0
WATER 3157.08698 0.39110452 3157.08698 0.39110452
METHANOL 0 0 0 0
H2 761.112966 0.094287779 761.112966 0.094287779
CO 3071.883252 0.380549358 3071.883252 0.380549358
ISO-BUT 4.29727E-09 5.32352E-13 4.29727E-09 5.32352E-13
ISO-PENT 0 0 0 0
Total (kg/hr) 8072.233437 1 8072.233437 1
96
3.5.3 Material Balance around Synthesis Reactor (K)

The hydrogenation of carbon dioxide to yield methanol takes place in this reactor. There is
conversion of over 20%.
Assumption
1. 30% conversion of carbon dioxide
Figure 3.48: Process Flow Diagram for Synthesis Reactor (K)
CRDMEOH1
CO2-H2-3
SYNRCTR1
MEOHH2O1
Figure 3.49: Aspen Simulation Diagram for Synthesis Reactor (K)
97
Table 3.18: Material Balance around Synthesis Reactor (K)
INPUT OUTPUT
STREAMS 14 15 016
COMPONENT MeOH Synthesis Reactor 1 MeOH, H2O – R1 CO, CO2, H2 - R1
Feed
Mass flow Composition Mass flow Composition Mass flow Composition
METHANE 91.9222520 0.011387462 0.01374762 4.05314E-05 91.9085044 0.011885157
9 8 7
ETHANE 0.1082268 1.34073E-05 2.70182E-05 7.96564E-08 0.10819978 1.39919E-05
2
PROPANE 2.79331E-05 3.4604E-09 5.40167E-09 1.59255E-11 2.79277E-05 3.61148E-09
BUTANE 6.28554E-09 7.78661E-13 8.71024E-13 2.568E-15 6.28467E-09 8.12702E-13
N-PENTANE 0 0 0 0 0 0
N-HEXANE 0 0 0 0 0 0
N-HEPTANE 0 0 0 0 0 0
CO2 5527.05563 0.684699678 1.11225170 0.003279196 3189.50997 0.41245179
8 8 1
H2S 0 0 0 0 0 0
WATER 1299.90583 0.161034223 275.811191 0.813160309 1980.50667 0.256109412
7 3 7
METHANOL 0 0 62.2244186 0.183453134 1827.04470 0.236264463
8 6
H2 968.928460 0.120032265 0.02191243 6.46033E-05 624.165082 0.080713968
6 4 7
CO 184.312995 0.022832961 0.00072796 2.14622E-06 19.8059965 0.002561214
1 4 7
ISO-BUT 4.29727E-09 5.32352E-13 3.92505E-13 1.1572E-15 4.29688E-09 5.55651E-13
ISO-PENT 0 0 0 0 0 0
TOTAL 8072.23343 1 339.184276 1 7733.04916 1
7 8 5
98
Since the total feed mass flowrate and product mass flowrate of the section are equal, this
implies that there is no accumulation of mass in this section. Hence the section operates at
steady state.
3.5.4 Material Balance around Cooler (L)

This is done to condense water vapour to aid the removal of water
Assumption
Figure 3.50: Process Flow Diagram for Cooler (L)
COOL-03
CRDMEOH2
CRDMEOH1
Figure 3.51: Aspen Simulation Diagram for Cooler (L)
99
Table 3.19: Material Balance around Cooler (L)
INPUT OUTPUT
STREAMS 16 17
COMPONENT CO, CO2, H2 - R1 CO, CO2, H2 - R1
(kg/hr) (kg/hr)
METHANE 91.90850447 0.01188515 91.90850447 0.01188515
7 7
ETHANE 0.108199782 1.39919E-05 0.108199782 1.39919E-05
PROPANE 2.79277E-05 3.61148E-09 2.79277E-05 3.61148E-09
BUTANE 6.28467E-09 8.12702E-13 6.28467E-09 8.12702E-13
N-PENTANE 0 0 0 0
N-HEXANE 0 0 0 0
N-HEPTANE 0 0 0 0
CO2 3189.509971 0.41245179 3189.509971 0.41245179
H2S 0 0 0 0
WATER 1980.506677 0.25610941 1980.506677 0.25610941
2 2
METHANOL 1827.044706 0.23626446 1827.044706 0.23626446
3 3
H2 624.1650827 0.08071396 624.1650827 0.08071396
8 8
CO 19.80599657 0.00256121 19.80599657 0.00256121
4 4
ISO-BUT 4.29688E-09 5.55651E-13 4.29688E-09 5.55651E-13
ISO-PENT 0 0 0 0
TOTAL 7733.049165 1 7733.049165 1

100
steady state.
3.5.5 Material Balance around Flash Drum (M)

This is used to remove unreacted gases from the mixture of water and methanol which is sent
downstream for purification of methanol.
Assumptions
1. Operates isothermally at 65ºC

2. High vapour-liquid separation efficiency
Figure 3.52: Process Flow Diagram for Flash Drum (M)
CO2-H2-4
CRDMEOH2
FLDRM1
MEOHH2O2
Figure 3.53: Aspen Simulation Diagram for Flash Drum (M)
101
Table 3.20: Material Balance around Flash Drum (M)
INPUT OUTPUT
STREAMS 17 18 19
COMPONEN CO, CO2, H2 - R1 CO, CO2, H2 – FLDRUM MeOH, H2O – FLDRUM
T 1 1
Mass flow Compositio Mass flow Compositio Mass flow Composition
(kg/hr) n (kg/hr) n (kg/hr)
METHANE 91.9085044 0.01188515 91.8030697 0.02245758 0.10543473 2.89242E-05
7 7 3 2 4
ETHANE 0.10819978 1.39919E- 0.10789588 2.63943E- 0.00030389 8.33681E-08
2 05 8 05 4
PROPANE 2.79277E- 3.61148E- 2.78578E- 6.81478E- 6.99771E- 1.92E-11
05 09 05 09 08
BUTANE 6.28467E- 8.12702E- 6.27322E- 1.5346E-12 1.14449E- 3.13971E-15
09 13 09 11
N-PENTANE 0 0 0 0 0 0
N-HEXANE 0 0 0 0 0 0
N-HEPTANE 0 0 0 0 0 0
CO2 3189.50997 0.41245179 3166.13183 0.77452382 23.3781340 0.006413392
1 7 3 6
H2S 0 0 0 0 0 0
WATER 1980.50667 0.25610941 32.4098528 0.00792835 1948.09682 0.534427072
7 2 1 4
METHANOL 1827.04470 0.23626446 153.508902 0.03755254 1673.53580 0.459105948
6 3 8 3 3
H2 624.165082 0.08071396 624.07916 0.15266710 0.08592274 2.35714E-05
7 8 3 8
CO 19.8059965 0.00256121 19.8023191 0.00484419 0.00367745 1.00885E-06
7 4 2 7 2
ISO-BUT 4.29688E- 5.55651E- 4.29278E- 1.05013E- 4.09512E- 1.12343E-15
09 13 09 12 12
ISO-PENT 0 0 0 0 0 0
TOTAL 7733.04916 1 4087.84306 1 3645.2061 1
102
5 5
steady state.
3.5.6 Material Balance around Compressor (N)

This compressor serves to raise the temperature of the unreacted gases back to the required
pressure for the synthesis reaction i.e., 58 bars.
Assumptions
1. Operates isentropically with a discharge pressure of 58 bar.

Figure 3.54: Process Flow Diagram for Compressor (N)
103
CO2-H2-5
COMP-02
CO2-H2-4
Figure 3.55: Aspen Simulation Diagram for Compressor (N)
104
Table 3.21: Material Balance around Compressor (N)
INPUT OUTPUT
STREAMS 18 20
COMPONENT CO, CO2, H2 – FLDRUM 1 Compressed CO2 + H2O
(kg/hr) (kg/hr)
METHANE 91.80306973 0.02245758 91.80306973 0.022457582
2
ETHANE 0.107895888 2.63943E-05 0.107895888 2.63943E-05
PROPANE 2.78578E-05 6.81478E-09 2.78578E-05 6.81478E-09
BUTANE 6.27322E-09 1.5346E-12 6.27322E-09 1.5346E-12
N-PENTANE 0 0 0 0
N-HEXANE 0 0 0 0
N-HEPTANE 0 0 0 0
CO2 3166.131837 0.77452382 3166.131837 0.774523823
3
H2S 0 0 0 0
WATER 32.4098528 0.00792835 32.4098528 0.007928351
1
METHANOL 153.5089028 0.03755254 153.5089028 0.037552543
3
H2 624.07916 0.15266710 624.07916 0.152667103
3
CO 19.80231912 0.00484419 19.80231912 0.004844197
7
ISO-BUT 4.29278E-09 1.05013E-12 4.29278E-09 1.05013E-12
ISO-PENT 0 0 0 0
TOTAL 4087.843065 1 4087.843065 1
105
steady state.
3.5.7 Material Balance around Heater (O)

Although, there is an increase in temperature of the feed due to compression, the temperature
is still inadequate. Thus, a heater is used to increase the feed temperature to desired level of
184℃
Assumptions
A. Operates isothermally at 184ºC.
Figure 3.56: Process Flow Diagram for Cooler (O)
HEATR-04
CO2-H2-6
CO2-H2-5
Figure 3.57: Aspen Simulation Diagram for Heater (O)
Table 3.22: Material Balance around Heater (O)
INPUT OUTPUT
STREAMS 20 21
COMPONENT Compressed CO2 + H2O MeOH Synthesis Reactor 2 Feed
Mass flow (kg/hr) Composition Mass flow (kg/hr) Composition
METHANE 91.80306973 0.022457582 91.80306973 0.022457582
106
ETHANE 0.107895888 2.63943E-05 0.107895888 2.63943E-05
PROPANE 2.78578E-05 6.81478E-09 2.78578E-05 6.81478E-09
BUTANE 6.27322E-09 1.5346E-12 6.27322E-09 1.5346E-12
N-PENTANE 0 0 0 0
N-HEXANE 0 0 0 0
N-HEPTANE 0 0 0 0
CO2 3166.131837 0.774523823 3166.131837 0.774523823
H2S 0 0 0 0
WATER 32.4098528 0.007928351 32.4098528 0.007928351
METHANOL 153.5089028 0.037552543 153.5089028 0.037552543
H2 624.07916 0.152667103 624.07916 0.152667103
CO 19.80231912 0.004844197 19.80231912 0.004844197
ISO-BUT 4.29278E-09 1.05013E-12 4.29278E-09 1.05013E-12
ISO-PENT 0 0 0 0
TOTAL 4087.843065 1 4087.843065 1

steady state.
3.5.8 Material balance around Synthesis Reactor (P)

Synthesis reactor (P) is another packed bed reactor that converts more reactants into
methanol.
Assumptions
1. 30% conversion of carbon dioxide
107
Figure 3.58: Process flow diagram for Synthesis Reactor (P)
CRDMEOH3
CO2-H2-6
SYNRCTR 2
MEOH H2O3
Figure 3.59: Aspen Simulation Diagram for Synthesis Reactor(P)
Table 3.23: Material Balance around Synthesis Reactor (P)
INPUT OUTPUT
STREAMS 21 22 23
(CO, CO2, H2 – R2)
(MeOH Synthesis Reactor 2 (MeOH, H2O – R2)
Feed)
COMPONENTS Mass Flow Mass Mass Flow Mass Mass Flow Mass
(kg/hr) Fraction Fraction (kg/hr) Fraction
(kg/hr)
METHANE 91.80306973 0.022457582 0 0 91.80306973 0.022457582
ETHANE 0.107895888 2.63943E-05 0 0 0.107895888 2.63943E-05
PROPANE 2.78578E-05 6.81478E-09 0 0 2.78578E-05 6.81478E-09
108
BUTANE 6.27322E-09 1.5346E-12 0 0 6.27322E-09 1.5346E-12
CO2 3166.131837 0.774523823 0 0 1405.343525 0.343786075
WATER 32.4098528 0.007928351 0 0 753.1832827 0.184249559
METHANOL 153.5089028 0.037552543 0 0 1442.269742 0.352819254
H2 624.07916 0.152667103 0 0 381.2652535 0.093268075
CO 19.80231912 0.004844197 0 0 13.87027089 0.003393054
ISO-BUT 4.29278E-09 1.05013E-12 0 0 4.29278E-09 1.05013E-12
TOTAL 4087.843 1 0 0 4087.843 1

The mass accumulation is calculated thus;
Mass accumulation = Mass input - Mass output
Mass accumulation (0+4087.843) - (4087.843) = 0 kg/hr
Mass accumulation= 0 kg/hr
Since mass accumulation is zero the system is balanced
3.5.9 Material Balance around Cooler (Q)
This is done to condense water vapour to aid the removal of water.
Assumptions
1. Operates isothermally at 30ºC.
2. Capable of handling liquid and vapour phase
Figure 3.60: Process Flow Diagram for Cooler (Q)
109
COOL-05
CRDMEOH3
CRDMEOH4
Figure 3.61: Aspen Simulation Diagram for Cooler (Q)
Table 3.24: Material Balance around Cooler (Q)
INPUT OUTPUT
STREAM 23 24
(CO, CO2, H2 – R2 ) (CO, CO2, H2 – R2)
COMPONENT Mass Flow Mass Mass Flow Mass
(kg/hr) Fraction (kg/hr) Fraction
METHANE 91.80306973 0.022457582 91.80306973 0.022457582
ETHANE 0.107895888 2.63943E-05 0.107895888 2.63943E-05
PROPANE 2.78578E-05 6.81478E-09 2.78578E-05 6.81478E-09
BUTANE 6.27322E-09 1.5346E-12 6.27322E-09 1.5346E-12
CO2 1405.343525 0.343786075 1405.343525 0.343786075
WATER 753.1832827 0.184249559 753.1832827 0.184249559
METHANOL 1442.269742 0.352819254 1442.269742 0.352819254
H2 381.2652535 0.093268075 381.2652535 0.093268075
CO 13.87027089 0.003393054 13.87027089 0.003393054
ISO-BUT 4.29278E-09 1.05013E-12 4.29278E-09 1.05013E-12
TOTAL 4087.843 1 4087.843 1

Mass accumulation= Mass input - Mass output
Mass accumulation (0+4087.843) - ( 4087.843) = 0 kg/hr
110
3.5.10 Material Balance around Flash Drum (R)

This is used to remove unreacted gases from the mixture of water and methanol which is sent
downstream for purification of methanol. Unreacted gases are sent to P.S.A (S)
Assumptions:

2. High vapour-liquid separation efficiency.
Figure 3.62: Process Flow Diagram for Flash Drum (R)
111
C RD MEOH4
C O2-H2-7
FLDRM2
MEOH H2O4
Figure 3.63: Aspen Simulation Diagram for Flash Drum (R)
Table 3.25: Material Balance around Flash Drum (R)
INPUT OUTPUT
STREAMS 24 25 26
(CO, CO2, H2) (CO, CO2, H2) (MeOH, H2O)
COMPONENTS Mass Flow Mass Mass Flow Mass Mass Flow Mass
(kg/hr) Fraction (kg/hr) Fraction (kg/hr) Fraction
91.8030697 0.02245758 91.6781164 0.04798762
METHANE 3 2 4 9 0.12495329 1
0.10789588 2.63943E- 0.10738868 5.62111E- 0.00050720
ETHANE 8 05 6 05 1 2.3294E-07
2.78578E- 6.81478E- 2.76767E- 1.81095E- 8.31707E-
PROPANE 05 09 05 1.4487E-08 07 11
6.27322E- 6.23073E- 3.26139E- 4.24881E- 1.95133E-
BUTANE 09 1.5346E-12 09 12 11 14
1405.34352 0.34378607 1385.60944 0.72527790 0.00906318
CO2 5 5 4 9 19.7340812 2
753.183282 0.18424955 3.59038763 0.00187933 0.34426212
WATER 7 9 9 8 749.592895 7
1442.26974 0.35281925 34.3763621 0.01799382 0.64659680
METHANOL 2 4 3 7 1407.89338 3
381.265253 0.09326807 381.223909 0.19954633 0.04134373 1.89877E-
H2 5 5 7 1 5 05
13.8702708 0.00339305 13.8674832 0.00278763 1.28027E-
CO 9 4 5 0.00725874 9 06
4.29278E- 1.05013E- 4.27849E- 2.23952E- 1.42865E- 6.56129E-
ISO-BUT 09 12 09 12 11 15
TOTAL 4087.843 1 1910.453 1 2177.39 1
112
The mass accumulation is calculated thus:
Mass accumulation= Mass input - Mass ouput
Mass accumulation = (4087.843) - (1910.453+2177.39) = 0 kg/hr
Figure 3.64: Process Flow Diagram for Mixer 3
113
MIX-03
CO2-H2-7
CO2-H2-9
CO2-H2-8
Figure 3.65: Aspen Simulation Diagram for Mixer 3

COMPO- 25 29 30
NENTS
(CO, CO2, H2) (CO, CO2, H2) (CO2, H2)
Mass flow Composition Mass flow Composition Mass flow Composition

METHANE 91.67811644 0.047987629 0.241101033 0.00372643 91.91921747 0.046537762

ETHANE 0.107388686 5.62111E-05 0.000809835 1.25167E-05 0.108198522 5.47798E-05
PROPANE 2.76767E-05 1.4487E-08 2.47482E-07 3.82505E-09 2.79242E-05 1.41377E-08

BUTANE 6.23073E-09 3.26139E-12 5.31628E-11 8.21678E-13 6.2839E-09 3.18147E-12
CO2 1385.609444 0.725277909 1426.152999 40.54355483 0.626636579 0.722046707

WATER 3.590387639 0.001879338 3.748798527 0.057941004 7.339186166 0.003715755
METHANO
L 34.37636213 0.017993827 20.00984257 0.309269855 54.3862047 0.02753518
H2 381.2239097 0.199546331 0.148982417 0.002302655 381.3728921 0.193085203
CO 13.86748325 0.00725874 0.007178863 0.000110956 13.87466211 0.0070246
ISO-BUT 4.27849E-09 2.23952E-12 1.84867E-11 2.85728E-13 4.29698E-09 2.17552E-12
TOTAL 1910.453 1 64.70026832 1 1975.153 1
114
Table 3.26: Material Balance around Mixer 3

Mass accumulation = Mass input-Mass output
Mass accumulation (1910.453+64.70026832) - (1975.153) = 0 kg/hr
3.5.12 Material Balance around P.S.A (S)
Here, hydrogen is separated from the effluent stream and stored leaving behind a stream of
90% carbon dioxide.
Assumptions
1. High hydrogen (H2) selectivity
Figure 3.66: Process Flow Diagram for P.S.A (S)
115
PSA-02
CO2-H2-9 CO2
H2
Figure 3.67: Aspen Simulation Diagram for P.S.A (S)
116
Table 3.27: Material Balance around P.S.A (S)
INPUT OUTPUT
STREAMS 30 31 32
(CO2)
(CO2, H2) (CO2)
COMPONENTS Mass Flow Mass Mass Flow Mass Fraction Mass Flow Mass
(kg/hr) Fraction (kg/hr) (kg/hr) Fraction
91.9192174
METHANE 91.91921747 0.046537762 7 0.0576737 0 0
0.10819852
ETHANE 0.108198522 5.47798E-05 2 6.7888E-05 0 0
PROPANE 2.79242E-05 1.41377E-08 2.79242E-05 1.75207E-08 0 0
BUTANE 6.2839E-09 3.18147E-12 6.2839E-09 3.94276E-12 0 0
N-PENTANE 0 0 0 0 0 0
N-HEXANE 0 0 0 0 0 0
N-HEPTANE 0 0 0 0 0 0
1426.15299
CO2 1426.152999 0.722046707 9 0.894823975 0 0
H2S 0 0 0 0 0 0
7.33918616
WATER 7.339186166 0.003715755 6 0.004604891 0 0
METHANOL 54.3862047 0.02753518 54.3862047 0.034124025 0 0
H2 381.3728921 0.193085203 0 0 381.3728921 1
13.8746621
CO 13.87466211 0.0070246 1 0.008705504 0 0
ISO-BUT 4.29698E-09 2.17552E-12 4.29698E-09 2.69609E-12 0 0
ISO-PENT 0 0 0 0 0 0
TOTAL 1975.153 1 1593.78 1 381.373 1

Mass accumulation = Mass input-Mass output
117
Mass accumulation = (1975.153) - (1593.78+381.373) = 0 kg/hr
3.5.13 Material Balance around Compressor (T)
In order to store hydrogen as a gas, it has to be compressed to high pressures. Here, it is
compressed to a pressure of 700 bars.
Assumptions:
1. Operates isentropically with a discharge pressure of 700 bar.

Figure 3.68: Process Flow Diagram for Compressor (T)
COMP-H2
H2
COMP-03
Figure 3.69: Aspen Simulation Diagram for Compressor (T)
118
Table 3.28: Material Balance around Compressor (T)
INPUT OUTPUT
STREAM 32 33
(H2) (Compressed H2)
COMPONENT Mass Flow Mass Mass Flow Mass
(kg/hr) Fraction (kg/hr) Fraction
METHANE 0 0 0 0
ETHANE 0 0 0 0
PROPANE 0 0 0 0
BUTANE 0 0 0 0
N-PENTANE 0 0 0 0
N-HEXANE 0 0 0 0
N-HEPTANE 0 0 0 0
CO2 0 0 0 0
H2S 0 0 0 0
WATER 0 0 0 0
METHANOL 0 0 0 0
H2 381.3728921 1 381.3728921 1
CO 0 0 0 0
ISO-BUT 0 0 0 0
ISO-PENT 0 0 0 0
TOTAL 381.373 1 381.373 1

Mass accumulation= Mass input-Mass output
Mass accumulation (381.373) - (381.373) = 0 kg/hr
3.5.14 Material balance around Cooler (U)

This reduces the temperature to a suitable temperature for storage.
Assumptions
119
1. Operates isothermally at 25℃.
Figure 3.70: Process flow Diagram for Cooler (U)
Figure 3.71: Aspen Simulation Diagram for Cooler (U)
Table 3.29: Material balance around Cooler (U)
FEED PRODUCT
Components 33 34
(Compressed H2) (H2 for Storage)
Mass flow Mass Mass flow Mass
rate (kg/hr) Fraction rate (kg/hr) Fraction
METHANE 0 0 0 0
ETHANE 0 0 0 0
PROPANE 0 0 0 0
BUTANE 0 0 0 0
N-PENTANE 0 0 0 0
N-HEXANE 0 0 0 0
N-HEPTANE 0 0 0 0
CO2 0 0 0 0
H2S 0 0 0 0
WATER 0 0 0 0
METHANOL 0 0 0 0
H2 381.3728921 1 381.3728921 1
CO 0 0 0 0
ISO-BUT 0 0 0 0
120
ISO-PENT 0 0 0 0
Total (kg/hr) 381.3728921 1 381.3728921 1

is no accumulation of mass in the system. Hence, the system is balanced.
Figure 3.72: Process Flow Diagram for Mixer 3
121
MEOHH2O3
MEOHH2O4
MEOHH2O2
MEOHH2O5
MIX-02
MEOHH2O1
Figure 3.73: Aspen Simulation Diagram for Mixer 3
122
Table 3.30: Material Balance for Mixer 3
FEED PRODUCT
Component 15 19 22 26 27
MeOH, H2O – R1 MeOH, H2O – FLDRUM 1 MeOH, H2O – MeOH, H2O – FLDRUM 2 (MeOH, H2O)
R2
Mass flow Mass Mass flow Mass Mass Mass Mass flow Mass Mass flow Mass
rate Fraction rate fraction flow fracti rate Fraction rate fraction
(kg/hr) (kg/hr) rate on (kg/hr) (kg/hr)
(kg/hr)
METHA 0.0137476 4.05314E-05 0.105434734 2.89242E-05
-01 0 0 0.12495329 1 0.244135653 3.9621E-05
ETHAN 2.70182E-05 7.96564E-08 0.000303894 8.33681E-08
-01 0 0 0.000507201 2.3294E-07 0.000838113 1.36018E-07
PROPA 5.40167E-09 1.59255E-11 6.99771E-08 1.92E-11
-01 0 0 1.81095E-07 8.31707E-11 2.56474E-07 4.16233E-11
N-BUT 8.71024E-13 2.568E-15 1.14449E-11 3.13971E-15
-01 0 0 4.24881E-11 1.95133E-14 5.4804E-11 8.89419E-15
N-PEN 0 0 0 0
-01 0 0 0 0 0 0
N-HEX 0 0 0 0
-01 0 0 0 0 0 0
N-HEP 0 0 0 0
-01 0 0 0 0 0 0
CO2 1.112251708 0.003279196 23.37813406 0.006413392 0 0 19.7340812 0.009063182 44.22446697 0.007177222
H2S 0 0 0 0 0 0 0 0 0 0
WATER 275.8111913 0.813160309 1948.096824 0.534427072 0 0 749.592895 0.344262127 2973.500911 0.482571717
METH 62.22441868 0.183453134 1673.535803 0.459105948
ANOL 0 0 1407.89338 0.646596803 3143.653601 0.510185926
H2 0.021912434 6.46033E-05 0.085922748 2.35714E-05 0 0 0.041343735 1.89877E-05 0.149178917 2.42104E-05
123
CO 0.000727964 2.14622E-06 0.003677452 1.00885E-06 0 0 0.002787639 1.28027E-06 0.007193056 1.16737E-06
ISO-BUT 3.92505E-13 1.1572E-15 4.09512E-12 1.12343E-15 0 0 1.42865E-11 6.56129E-15 1.87741E-11 3.04686E-15
ISO-PENT 0 0 0 0 0 0 0 0 0 0
TOTAL (kg/hr) 339.1842768 1 3645.2061 1 0 0 2177.39 1 6161.780325 1
124
3.5.16 Material balance around Expansion Valve (V)

This is used to increase the pressure of crude methanol stream before sending to flash drum
(W)
Assumption
1. Operates at a discharge pressure of 4 bars.
Figure 3.74Figure 753.6: Block Process flow Diagram for Expansion valve (V)
Figure 3.76: Aspen Simulation Diagram Block for Expansion valve (V)
125
Table 3.31: Material balance around Expansion Valve (V)
FEED PRODUCT
Component 27 28
(MeOH, H2O) (Low Pressure MeOH, H2O)
rate (kg/hr) fraction rate (kg/hr) fraction
METHANE 0.24413565 0.24413565
3 3.9621E-05 3 3.9621E-05
ETHANE 0.00083811 0.00083811
3 1.36018E-07 3 1.36018E-07
PROPANE 2.56474E-07 4.16233E-11 2.56474E-07 4.16233E-11
BUTANE 5.4804E-11 8.89419E-15 5.4804E-11 8.89419E-15
N-PENTANE 0 0 0 0
N-HEXANE 0 0 0 0
N-HEPTANE 0 0 0 0
CO2 44.2244669 44.2244669
7 0.007177222 7 0.007177222
H2S 0 0 0 0
WATER 2973.50091 2973.50091
1 0.482571717 1 0.482571717
METHANOL 3143.65360 3143.65360
1 0.510185926 1 0.510185926
H2 0.14917891 0.14917891
7 2.42104E-05 7 2.42104E-05
CO 0.00719305 0.00719305
6 1.16737E-06 6 1.16737E-06
ISO-BUT 1.87741E-11 3.04686E-15 1.87741E-11 3.04686E-15
ISO-PENT 0 0 0 0
TOTAL (kg/hr) 6161.78032 6161.78032
5 1 5 1

126
127
3.5.17 Material balance around Flash Drum 3 (W)
Here, there is further separation of gases from the liquid phase (water and methanol)
Assumptions

2. High vapour-liquid separation efficiency.
Figure 3.77: Process flow Diagram for Flash drum 3 (W).
Block
128
Figure 3.78: Aspen Simulation Diagram Block for Flash Drum 3 (W)
Table 3.32: Material balance around Flash Drum 3 (W)
FEED PRODUCT
Component 28 29 35
(Low Pressure MeOH, H2O) (CO, CO2, H2) (MeOH, H2O)
Mass flow Mass fraction Mass flow Mass fraction Mass flow Mass fraction
rate (kg/hr) rate (kg/hr) rate (kg/hr
METHANE 0.244135653 3.9621E-05 0.241101033 0.00372643 0.003034619 4.97717E-07
ETHANE 0.000838113 1.36018E-07 0.000809835 1.25167E-05 2.8278E-05 4.63796E-09
PROPANE 2.56474E-07 4.16233E-11 2.47482E-07 3.82505E-09 8.99226E-09 1.47485E-12
BUTANE 5.4804E-11 8.89419E-15 5.31628E-11 8.21678E-13 1.64121E-12 2.6918E-16
N-PENTANE 0 0 0 0 0 0
N-HEXANE 0 0 0 0 0 0
N-HEPTANE 0 0 0 0 0 0
CO2 44.22446697 0.007177222 40.54355483 0.626636579 3.68091214 0.000603717
H2S 0 0 0 0 0 0
WATER 2973.500911 0.482571717 3.748798527 0.057941004 2969.752112 0.487077763
METHANOL 3143.653601 0.510185926 20.00984257 0.309269855 3123.643758 0.512317983
H2 0.149178917 2.42104E-05 0.148982417 0.002302655 0.0001965 3.22285E-08
CO 0.007193056 1.16737E-06 0.007178863 0.000110956 1.41929E-05 2.32783E-09
ISO-BUT 1.87741E-11 3.04686E-15 1.84867E-11 2.85728E-13 2.87403E-13 4.71378E-17
129
ISO-PENT 0 0 0 0 0 0
Total (kg/hr) 6161.780325 1 64.70026832 1 6097.080056 1

Total product mass flowrate = 64.70026832 kg/hr + 6097.080056 kg/hr = 6161.780325 kg/hr
3.6 Purification Process
Figure 3.79: Process Flow Diagram for Purification Process
130
Table 3.33: Overall Material Balance for Methanol Purification Process
FEED PRODUCT
Component 35 37 38
(MeOH, H2O) (WATER) (MeOH FOR
Mass flow rate Mass flow rate STORAGE)
(kg/hr) (kg/hr) Mass flow rate
(kg/hr)
METHANE 0.00303461938 1.27405E-59 0.003034619
ETHANE 0.00002827802 9.93823E-55 2.8278E-05
PROPANE 0.00000000899 1.94717E-56 8.99226E-09
BUTANE 1.64121E-12 0 0
N-PENTANE 0 0 0
N-HEXANE 0 0 0
N-HEPTANE 0 0 0
CO2 3.68091214 5.60181E-45 3.68091214
H2S 0 0 0
WATER 2969.752112 2969.751493 0.000619558
METHANOL 3123.643758 6.830923145 3116.812835
H2 0.00019649958 1.33101E-75 0.0001965
CO 0.00001419294 1.9241E-73 1.41929E-05
ISO-BUT 2.87403E-13 0 0
ISO-PENT 0 0 0
Total (kg/hr) 6097.080056 2976.582416 3120.497641
Total product mass flowrate = 2976.582416 + 3120.497641 = 6097.080056 kg/hr
131
3.6.1 Material balance around Distillation Column (X)
This separates water from methanol using 58 stages and a reflux ratio of 5.
Assumptions
1. Operates with 58 stages at reflux of 5.

2. Partial condenser is used.
Figure 3.80: Process flow Diagram for Distillation column (X)
Figure 3.81: Aspen Simulation Diagram for Distillation column (X)
132
Table 3.34: Material balance around Distillation column (X)
FEED PRODUCT
Component 35 36 37
(MeOH, H2O) (MeOH – Distillate) (Water – Bottoms)
Mass flow rate Mass fraction Mass flow Mass fraction Mass flow Mass fraction
(kg/hr) rate (kg/hr) rate (kg/hr)
METHANE 0.00303461
0.003034619 4.97717E-07 9 9.72479E-07 1.27405E-59 4.28024E-63
ETHANE 2.8278E-05 4.63796E-09 2.8278E-05 9.06202E-09 9.93823E-55 3.3388E-58
PROPANE 8.99226E-
8.99226E-09 1.47485E-12 09 2.88168E-12 1.94717E-56 6.54164E-60
BUTANE 1.64121E-12 2.6918E-16 0 0 0 0
N-PENTANE 0 0 0 0 0 0
N-HEXANE 0 0 0 0 0 0
N-HEPTANE 0 0 0 0 0 0
CO2 3.68091214 0.000603717 3.68091214 0.001179591 5.60181E-45 1.88196E-48
H2S 0 0 0 0 0 0
WATER 0.00061955
2969.752112 0.487077763 8 1.98544E-07 2969.751493 0.997705112
METHANOL 3116.81283
3123.643758 0.512317983 5 0.998819161 6.830923145 0.002294888
H2 0.0001965 3.22285E-08 0.0001965 6.29706E-08 1.33101E-75 4.47159E-79
CO 1.41929E-
1.41929E-05 2.32783E-09 05 4.54829E-09 1.9241E-73 6.46412E-77
ISO-BUT 2.87403E-13 4.71378E-17 0 0 0 0
ISO-PENT 0 0 0 0 0 0
Total (kg/hr) 3120.49764
6097.080056 1 1 1 2976.582416 1

Total product mass flowrate = 3120.497641kg/hr + 2976.582416Kg/hr = 6097.080056 kg/hr
3.6.2 Material balance around Cooler (Y)

This reduces the temperature of the pure methanol stream to a suitable temperature (25℃) for
storage.
Assumptions.
133
Figure 3.82: Process flow Diagram for Cooler (Y)
Figure 3.83: Aspen Simulation Diagram for Cooler (Y).
Table 3.35: Material balance around Cooler (Y).

FEED PRODUCT
Component 36 38
(MeOH – Distillate) (MeOH for Storage)
rate (kg/hr) fraction rate (kg/hr) fraction
METHANE 0.003034619 9.72479E-07 0.003034619 9.72479E-07
ETHANE 2.8278E-05 9.06202E-09 2.8278E-05 9.06202E-09
PROPANE 8.99226E-09 2.88168E-12 8.99226E-09 2.88168E-12
BUTANE 0 0 0 0
N-PENTANE 0 0 0 0
N-HEXANE 0 0 0 0
N-HEPTANE 0 0 0 0
CO2 0.00117959
3.68091214 1 3.68091214 0.001179591
H2S 0 0 0 0
WATER 0.000619558 1.98544E-07 0.000619558 1.98544E-07
METHANOL 0.99881916
3116.812835 1 3116.812835 0.998819161
H2 0.0001965 6.29706E-08 0.0001965 6.29706E-08
CO 1.41929E-05 4.54829E-09 1.41929E-05 4.54829E-09
ISO-BUT 0 0 0 0
ISO-PENT 0 0 0 0
134
Total (Kg/hr) 3120.497641 1 3120.497641 1
3.7 Conclusion to Material Balance
From the material balances, it is deduced that 2235.31952 kg/hr of impure flare gas at 25℃
and 25 bars and 5836.95072 kg/hr of water at 25℃ and 1 atm are required to produce
3120.497641 kg/hr (30,000 tons) of methanol at the storage conditions of 25℃ and 1 atm.
The purity of the methanol produced is 99.89 wt%. Furthermore, at the current rate of
processing (2235.31952 kg/hr of impure flare gas and 5836.95072 kg/hr of water),
381.3728921 kg/hr of pure hydrogen is obtained as a byproduct.
135
CHAPTER 4
ENERGY BALANCE
4.1 Introduction
The application of theWhen the rule of conservation of energy is applied to the study of
physical systems in a processis, this is known as energy balance. All processes, excluding
nuclear operations, can conserve energy individually. Except for nuclear operations, all
processes can conserve energy individually. Energy can be created or expended in a chemical
reaction, which and this distinguishes energy conservation from mass conservation.
Energy may be created or consumed in a chemical reaction, which distinguishes it from mass
conservation. When the mass of a system is in mass balanced, the amount of material that
goes in must equal the amount of material that comes out. Furthermore, this is true for energy
but not for stream enthalpy. If energy is created or utilisedutilized during the a process;, for
example, as a result of the heat of reaction, the total enthalpy of the exit streams will be less
than the enthalpy of the entrance stream. Energy is expensive, and as such, a chemical
engineer must learn how to effectively utilize the resource the effective use of energy is an
important task for a chemical engineer (Harding, 2018).
Similar to the mass balance equation, the eEnergy balance equation is s are similar to mass
balance equations and are given below:
Energy in – Energy out = generation – consumption + accumulation
At steady state, this equation can be written as follows:
(Internal energy + Kinetic Energy + Potential energy + Work + Heat) into the system =
(Internal energy + Kinetic Energy + Potential energy + Work + Heat) out of the system. (4.1)
It can also be written as:
𝛥𝐻 ̇ + 𝛥𝐸𝑘 + 𝛥𝐸𝑝̇ = ̇- ̇ (4.2)
Where,
𝛥𝐻̇ = is Enthalpy,
𝛥𝐸𝑘̇ is = Kinetic Energy,
𝛥𝐸̇𝑝 is = Potential Energy,
136
𝑄 is = Heat and,
𝑊 is = Work.
Due to the following assumptionsAssuming the following, equation 4.2 is reduced into
another form as shown in equation 4.3:
i. No change in the velocity of the process fluids.
ii. Negligible elevation difference between the streams of the unit equipment.
Equation 4.2 is reduced into another form as shown in equation 4.3 below:The reduced
form is shown below:
(4.3)
4.2 Overall Energy Balance
The difference between the enthalpy of streams into (feed) and out of (product) of the system
boundary is considered and compared with the energy in transit (heat and work) in the system
to account for the energy balance across the system.
Table 4.1 below shows the streams and equipment considered in the energy balance of the
entire system.
137
Table 4.36: Overall Energy balance for the production process
Enthalpy change Enthalpy in transit
Feed Enthalpy Product Enthalpy Heat duty Work Duty

Equipment Equipment
stream H1 (kJ/s) stream H2 (kJ/s) (kJ/s) (kJ/s)
-0.004280021
kJ/s
1 3
Compressor
(Impure -2638.813004 (Clean flare -0.010851126 Heater (B) 4416.5287 1795.43166
(I)
flare gas) gas)
4 31 Compressor
-25896.72479 -3826.885603 Heater (C) 2041.25279 113.692773
(Water) (CO2) (N)
Pre-
34 Compressor
34.39130599 Reformer 510.819682 1013.867112
(H2) (T)
reactor(D)
37
-12903.76908 Heater (E) 1863.81402
(H2O)
Steam
38
-6529.182452 Methane 6843.79442
(MeOH)
Reformer (F)
Cooler (G) -2413.32104
Cooler (J) -4471.54116
Synthetic
-1219.86194
Reactor (K)
Cooler (L) -2412.63087
Flash Drum
13.8305701
(M)
Heater (O) 310.547165
Synthesis -668.872799
138
Reactor 2 (P)
Cooler(Q) -1434.36741
Flash drum
6.971053
(R)
P.S.A(S) -21.9037651
Cooler (U) -992.930777
Distillation
1158.91381
column (X)
Flash drum
-9.90033
(W)
Cooler (Y) -1134.04722
TOTAL -28535.537794 -23225.45668 2387.094899 2922.991545
From Table 4.1, the following deduction is made:
Change in enthalpy, ΔH = H2 – H1 = 5310.081 kJ/s
Energy in transit, Q + W = 5310.081 kJ/s
Since the overall enthalpy change of the streams is equal to the energy in transit across the process boundary, this implies that there is no energy
accumulation in the process.
139
4.2.1 Energy Balance around PSA (A)
Figure 4.84: Process Flow Diagram for PSA (A)
CL-FLGAS
FLGAS PSA-01
H2S
Figure 4.85: Aspen Simulation Diagram for PSA (A)
140
Table 4.37: Energy Balance around PSA (A)
INPUT OUTPUT
STREAMS 1 2 3
Impure flare Clean flare gas H2S
gas
PARAMETER UNITS
S
Temperature o
C 25 25 25
Pressure bar 25 25 25
Enthalpy flow kJ/sec -2638.813004 -2638.806433 -0.010851126
Heat duty kJ/sec 0
The enthalpy flow is calculated thus:
Enthalpy change across equipment = Enthalpy out – Enthalpy in
ΔH = ΔHout – ΔHin = (-2638.806433 + -0.010851126) - ( -2638.813004) kJ/sec = -

0.004280021 kJ/sec.
Heat duty (Q) = -0.004280021 kJ/sec.
Since heat duty equals enthalpy change, therefore the energy of the system is balanced.
4.2.2 Energy Balance around Heater B
Figure 4.86: Process flow diagram for Heater (B)
141
HEATR-01
WATER STEAM
Figure 4.87: Aspen Simulation diagram for Heater (B)
Table 4.38: Energy Balance around Heater (B)
INPUT OUTPUT
4 5
STREAMS
Water Steam
PARAMETERS UNITS
Temperature o
C 25 120
Pressure bar 1.01325 1.01325
Enthalpy flow kJ/sec -25896.72479 -21480.19609
Heat duty kJ/sec 4416.5287

ΔH = ΔHout – ΔHin = (-21480.19609) - ( -25896.72479) kJ/sec= 4416.5287 kJ/sec.
Heat duty (Q) = 4416.5287 kJ/sec.
4.2.3 Energy Balance around Heater (C)
Figure 4.88: Process flow diagram for Heater (C)
142
H2OCH4-2
H2OCH4-1
HEATR-02
Figure 4.89: Aspen Simulation diagram for Heater (C)
Table 4.39: Energy Balance around Heater (C)
INPUT OUTPUT
STREAMS 6 7
Steam + Methane Pre-Reformer
Feed
PARAMETERS UNITS
Temperature o
C 205.6349692 500
Pressure bar 25 25

ΔH =ΔHout – ΔHin = (-22077.74973) - ( -24119.00253) kJ/sec= 2041.25279 kJ/sec.
Heat duty (Q) = 2041.25279 kJ/sec
143
4.2.4 Energy Balance around Pre-Reformer reactor (D)
Figure 4.90: Process Flow diagram for Pre-reformer Reactor (D)
H2OCH4-3
H2OCH4-2
PRE-REF
Figure 4.91: Aspen Simulation diagram for Pre-reformer Reactor (D)
Table 4.40: Energy Balance around Pre-Reformer reactor(D)
INPUT OUTPUT
STREAMS 7 8
Pre-Reformer Feed Pre-Reformer Outlet
PARAMETERS UNITS
Temperature o
C 500 500
Pressure bar 25 25
144
Enthalpy change across equipment =
Enthalpy out – Enthalpy in ΔH =
ΔHout – ΔHin = (-21566.93005) - ( -22077.74973) kJ/sec= 510.819682 kJ/sec.
4.2.5 Energy Balance around Heater E
Figure 4.92: Process flow diagram for Heater (E)
HEATR-03
H2OCH4-3 H2OCH4-4
Figure 4.93: Aspen Simulation diagram for Heater (E)
145
Table 4.41: Energy Balance around Heater (E)
INPUT OUTPUT
STREAMS 8 9
Pre-Reformer Reformer Feed
Outlet
PARAMETERS UNITS
Temperature o
C 500 800
Pressure bar 25 25

ΔHout – ΔHin = (-19703.11603) -( -21566.93005) kJ/sec= 1863.81402 kJ/sec.
4.2.6 Energy Balance around Steam Reformer (F)
Figure 4.94: Process flow diagram for Steam Methane Reformer (F)
146
H2OCH4-4
REFORMER
CO-H2-1
Figure 4.95: Aspen Simulation diagram for Steam Methane Reformer (F)
Table 4.42: Energy Balance around Steam Reformer (F)
INPUT OUTPUT
STREAMS 98 109
(REFORMER
(SMR REACTOR
OUTLET)
FEED)
PARAMETERS UNITS
Temperature o
C 800 800
Pressure bar 25 25
The enthalpy flow is calculated as,
Enthalpy change across equipment = Enthalpy out – enthalpy in
ΔH = ΔHout – ΔHin
ΔH = -12859.32161- (-19703.11603) = 6843.79442 kJ/sec
Heat Duty (Q) = 6843.79442 kJ/sec
The heat duty equals enthalpy change; therefore, the energy of the system is balanced.
147
4.2.7 Energy Balance around Cooler (G)
Figure 4.96: Process flow diagram for Cooler (G)
CO-H2-1
COOL-01
CO-H2-2
Figure 4.97: Aspen Simulation diagram for Cooler (G)
148
Table 4.43: Energy Balance around Cooler (G)
INPUT OUTPUT
STREAMS 109 11
(REFORMER
(SYNGAS)
OUTLET)
PARAMETERS UNITS
Temperature o
C 430 430
Pressure bar 25 25
Heat duty kJ/sec -2413.32104
ΔH = -15272.64266 – (-12859.32161) = -2413.32104 kJ/sec

Heat Duty (Q) = -2413.32104 kJ/sec
4.2.8 Energy Balance around Water Gas Shift Reactor (H)
Figure 4.98: Process flow diagram for W.G.S Reactor (H)
149
CO-H2-2
HT-WGS
CO2-H2-1
Figure 4.99: Aspen Simulation diagram for W.G.S Reactor (H)
Table 4.44: Energy Balance around W.G.S reactor (H)
INPUT OUTPUT
11 129
STREAMS
(SYNGAS) (CO2 + H2O)
PARAMETERS UNITS
Temperature o
C 430 591.266415
Pressure bar 25 25
Heat duty kJ/sec 0
ΔH = ΔHout – ΔHin = -15272.64266 – (-15272.64266) = 0 kJ/sec
The unit is assumed to be adiabatic therefore there is no change in energy within.
150
4.2.9 Energy Balance around Compressor (I)
Figure 4.100: Process flow diagram for Compressor (I)
CO2-H2-2
CO2-H2-1
COMP-01
Figure 4.101: Aspen Simulation diagram for Compressor (I)
Table 4.45: Energy Balance around Compressor (I)
INPUT OUTPUT
13
129
STREAMS (COMPRESSED
(CO2 + H2O)
CO2 + H2O)
PARAMETERS UNITS
Temperature o
C 0 848.993381
Pressure bar 58 58
Work done kJ/sec 1795.43166
151
ΔH = ΔHout – ΔHin = -13477.211– (-15272.64266) = 1795.43166 kJ/sec
Work done = 1795.43166 kJ/sec

The work duty equals enthalpy change; therefore, the energy of the system is balanced.
4.2.10 Energy Balance around Cooler J
Figure 4.102: Process flow diagram for Cooler (J)
COOL-02
CO2-H2-3
CO2-H2-2
Figure 4.103: Aspen Simulation diagram for Cooler (J)
Table 4.46: Energy Balance around Cooler (J)
INPUT OUTPUT
13 14
(COMPRESSED CO2
(MeOH SYNTHESIS
+ H2O)
REACTOR 1 FEED)
PARAMETERS UNITS
Temperature o
C 184 184
Pressure bar 58 58
152
ΔH = ΔHout – ΔHin = -17948.752154323 – (-13477.211) = -4471.54116 kJ/sec
4.2.11 Energy Balance around Synthesis Reactor (K)
Figure 4.104: Process Flow Diagram for Synthesis Reactor (K)
CRDMEOH1
CO2-H2-3
SYNRCTR1
MEOHH2O1
Figure 4.105: Aspen Simulation Diagram for Synthesis Reactor (K)
153
Table 4.47: Energy Balance around Synthesis Reactor (K)
INPUT OUTPUT
14
15 16
STREAMS MeOH Synthesis
MeOH, H2O – R1 CO, CO2, H2 - R1
Reactor 1 Feed
PARAMETERS UNITS
Temperature 0
C 184 184 184
ΔH = ΔHout – ΔHin = (-1286.875054+17881.73904) - (17948.75215) kJ/sec= -1219.86194

kJ/sec.
Heat duty (Q) = -1219.86194 kJ/sec
154
4.2.11 Energy Balance around Cooler (L)
Figure 4.106: Process Flow Diagram for Cooler (L)
COOL-03
CRDMEOH2
CRDMEOH1
Figure 4.107: Aspen Simulation Diagram for Cooler (L)
Table 4.48: Energy Balance around Cooler (L)
INPUT OUTPUT
STREAMS (16) (17)

CO, CO2, H2 - R1 CO, CO2, H2 - R1
PARAMETERS UNITS
Temperature 0
C 184 65
Pressure bar 58 58

ΔH = ΔHout – ΔHin = (-20294.36992) - (-17881.73904) kJ/secv= -2412.63087 kJ/sec.
155
4.2.12 Energy Balance around Flash Drum (M)
Figure 4.108: Process Flow Diagram for Flash Drum (M)
CO2-H2-4
CRDMEOH2
FLDRM1
MEOHH2O2
Figure 4.109: Aspen Simulation Diagram for Flash Drum (M)
156
Table 4.49: Energy Balance around Flash Drum (M)
INPUT OUTPUT
18 19
17
STREAMS CO, CO2, H2 - MeOH, H2O -
CO, CO2, H2 - R1
FLDRUM 1 FLDRUM 1
PARAMETER
UNITS
S
Temperature 0
C 65 65 65
ΔH = ΔHout – ΔHin = (-12012.80182 + -8267.737528) - (-20294.36992) kJ/sec =

13.8305701kJ/sec.
4.2.13 Energy Balance around Compressor (N)
Figure 4.4.110: Process Flow Diagram for Compressor (N)
157
CO2-H2-5
COMP-02
CO2-H2-4
Figure 4.111: Aspen Simulation Diagram for Compressor (N)
Table 4.50: Energy Balance around Compressor (N)

N INPUT OUTPUT
STREAMS 18 20
CO, CO2, H2 – FLDRUM 1 Compressed CO2 + H2O
PARAMETERS UNITS
Temperature 0
C 65 97.68721266
Pressure bar 45 58
ΔH = ΔHout – ΔHin = (-8154.044755) - (-8267.737528) kJ/sec= 113.692773 kJ/sec.
158
4.2.14 Energy Balance around Heater (O)
Figure 4.112: Process Flow Diagram for Heater (O)
HEATR-04
CO2-H2-6
CO2-H2-5
Figure 4.113: Aspen Simulation Diagram for Heater (O)
Table 4.51: Energy Balance around Heater (O)
O INPUT OUTPUT
STREAMS (20) Compressed CO2 + H2O (21) MeOH Synthesis Reactor

2 Feed
PARAMETER UNITS
S
Temperature 0
C 97.68721266 184
Pressure bar 58 58

Enthalpy out – Enthalpy in
ΔH = ΔHout – ΔHin = (-7843.497589) - (-8154.044755) kJ/sec= 310.547165 kJ/sec.
159
4.2.15 Energy balance around Synthesis Reactor 2 (P)
Figure 4.114: Process flow diagram for Synthesis Reactor 2 (P)
CRDMEOH3
CO2-H2-6
SYNRCTR 2
MEOH H2O3
Figure 4.115: Aspen Simulation Diagram for Synthesis Reactor 2 (P)
160
Table 4.52: Energy Balance around Synthesis Reactor 2 (P)
INPUT OUTPUT
STREAMS 21 22 23
MeOH MeOH, H2O. CO, CO2, H2
PARAMETERS UNITS
Temperature o
C 184 0 184
Enthalpy flow kJ/sec -7843.497589 0 -8512.370388

ΔHout – ΔHin = (-8512.370388) -( -7843.497589) kJ/sec= -668.872799 kJ/sec.
4.2.16 Energy Balance around Cooler (Q)
Figure 4.116: Process Flow Diagram for Cooler (Q)
161
COOL-05
CRDMEOH3
CRDMEOH4
Figure 4.117: Aspen Simulation Diagram for Cooler (Q)
Table 4.53: Energy Balance around Cooler (Q)
INPUT OUTPUT
STREAMS 23 24
(CO, CO2, H2 ) (CO, CO2, H2)
PARAMETERS UNITS
Temperature o
C 184 30
Pressure bar 58 58
Enthalpy flow kJ/sec
-8512.370388 -9946.737806

ΔH = ΔHout – ΔHin = (-8512.370388) - ( -9946.737806) kJ/sec= 1434.367418 kJ/s
Heat duty (Q) = 1434.367418 kJ/s
162
4.2.17 Energy Balance around Flash Drum (R)
Figure 4.118: Process Flow Diagram for Flash Drum (R)
C RD MEOH4
C O2-H2-7
FLDRM2
MEOH H2O4
Figure 4.119: Aspen Simulation Diagram for Flash Drum (R)
163
Table 4.54: Material Balance around Flash Drum (R)
INPUT OUTPUT
STREAMS 24 25 26
CO, CO2, H2 CO, CO2, H2 MeOH, H2O
PARAMETERS UNITS
Temperature o
C 30 30 30
Enthalpy flow kJ/sec -
-9946.737806 3642.314239 -6297.453514

ΔHout – ΔHin = (-9946.737806) -( -3642.314239-6297.453514) kJ/sec= -6.971053 kJ/s
Heat duty (Q) = -6.971053 kJ/s
Since heat duty equals enthalpy change, therefore the energy of the system is balanced
4.2.18 Energy Balance around P.S.A(S)
Figure 4.120: Process Flow Diagram for P.S.A (S)
164
PSA-02
CO2-H2-9 CO2
H2
Figure 4.121: Aspen Simulation Diagram for P.S.A (S)
Table 4.55: Energy Balance around P.S.A (S)
INPUT OUTPUT
STREAMS 30 31 32
CO2, H2 CO2 H2
PARAMETERS UNITS
Temperature o
C 33.22977841 33.22977841 33.22977841
Enthalpy flow kJ/sec -3756.388756 -3687.193995 13.45497086
ΔH = ΔHout – ΔHin = (-3756.388756) - ( -3687.193995+13.45497086) kJ/sec =

21.90376514 kJ/s
165
4.2.19 Energy Balance around Compressor (T)
Figure 4.122: Process Flow Diagram for Compressor (T)
COMP-H2
H2
COMP-03
Figure 4.123: Aspen Simulation Diagram for Compressor (T)
Table 4.56: Energy Balance around Compressor (T)

INPUT OUTPUT
STREAMS 32 33
(H2 ) (Compressed H2)
PARAMETERS UNITS
Temperature o
C 33.22977841 654.7308786
Pressure bar 30 700
Enthalpy flow kJ/sec 13.45497086 1027.322083

ΔH = ΔHout – ΔHin = (13.45497086) - ( 1027.322083) kJ/sec= -1013.867112 kJ/s
Heat duty (Q) = -1013.867112 kJ/s
166
4.2.20 Energy balance around Cooler (U)
Figure 4.124: Process flow Diagram for Cooler (U)


Figure 4.125: Aspen Simulation Diagram for Cooler (U)
Table 4.57: Energy balance around Cooler (U)
INPUT OUTPUT
STREAM 33 34
(Compressed H2) (H2 for Storage)
Parameter Unit
Temperature o
C 654.7308786 25
Pressure bar 700 700
Enthalpy kJ/sec 1027.322083 34.39130599
flow

= (34.39130599) –1027.322083) = -992.930777 kJ/sec
167
4.2.21 Energy balance around Expansion Valve (V)
Figure 4.126Figure 1273.6: Block Process flow Diagram for Expansion valve (V)
Figure 4.128: Aspen Simulation Diagram Block for Expansion valve (V)
Table 4.58: Energy balance around Expansion Valve (V)
INPUT OUTPUT
STREAM 27 28
(MeOH, H2O) (Low Pressure
MeOH, H2O)
Parameter Unit
Temperature o
C 60.46468661 60.92899253
Pressure Bar 30 4
Enthalpy -19597.13039 -19597.13039
flow kJ/sec
Heat duty kJ/sec 0

= (-19597.13039) – (-19597.13039) = 0 kJ/sec
Heat Duty (Q) = 0 kJ/sec
168
4.2.22 Energy balance around Flash Drum 3 (W)
Figure 4.129: Process flow Diagram for Flash drum 3 (W).
Block
Figure 4.130: Aspen Simulation Diagram Block for Flash Drum 3 (W)
169
Table 4.59: Energy balance around Flash Drum 3 (W).
INPUT OUTPUT
STREAM 28 29 35
(Low Pressure (CO, CO2, H2) (MeOH,
MeOH, H2O) H2O)
Parameter Unit
Temperature o
C 60.92899253 58.4596 58.4596
Pressure Bar 4 1.1 1.1
Enthalpy
flow kJ/sec -19597.13039 -149.21262 -19457.8181

= (-149.21262 +-19457.8181) – (-19597.13039) = -9.90033KJ/sec
Heat Duty (Q) = -9.90033KJ/sec
4.2.23 Energy balance around Distillation Column (X)
Figure 4.131: Process flow Diagram for Distillation column (X).
170
Figure 4.132: Aspen Simulation Diagram for Distillation column (X)
Table 4.60: Energy balance around Distillation column (X)

INPUT OUTPUT
STREAM 35 36 37
(MeOH, H2O) (MeOH - (Water –
Distillate) Bottoms)
Parameter Unit
Temperatur o
C 58.4596 63.7020724 101.1710289
e
Pressure Bar 1.1 1 1
Enthalpy
flow kJ/sec -19457.81813 -5395.135236 -12903.76908
Heat duty KJ/sec 1158.91381

= ((-5395.135236)+ (-12903.76908)) – (-19457.81813) = 1158.91381 kJ/sec
Heat Duty (Q) = 1158.91381 kJ/sec
171
4.2.25 Energy balance around Cooler (Y)
Figure 4.133: Process flow Diagram for Cooler (Y)
Figure 4.134: Aspen Simulation Diagram for Cooler (Y).
Table 4.61: Energy balance around Cooler (Y).

INPUT OUTPUT
STREAM 36 38
(MeOH – Distillate) (MeOH for Storage)
Parameter Unit
Temperature o
C 63.7020724 25
Pressure Bar 1 1
Enthalpy
flow kJ/sec -5395.135236 -6529.182452

= (-6529.182452) – (– 5395.135236) = 1158.91381KJ/sec
172
CHAPTER 5
CHEMICAL ENGINEERING DESIGN
5.1 Introduction
‘Design’ in Chemical Engineering is concerned with achieving a balance between real-world

applications and the theoretical aspects of process and plant design. Chemical engineering
design involves the determination of the operating conditions of equipment included in
different unit processes. Furthermore, fluid flow in packed columns, reactor kinetics, cooling
tower height estimation, process control system installation, and other issues are considered
in chemical engineering design (Yargeau, 2005).
5.2 Process Design
The choices made in the process of design are represented on flow sheets, making it possible
to interpret the overall production process to other engineers and personnel involved. Also,
the flow sheets serve as important documents required when certain chemical engineering
projects are being carried out. These projects may include modifications and additions to
existing plants, development, and implementation of novel processes, etc.
The process design can be divided into three different processes:
i. Reforming process
ii. Methanol synthesis process
iii. Methanol purification process
A process flow diagram (simply referred to as a PFD), shows the manner in which the
process equipment and their associated accessories are setup, the connection of each process
stream, and other important information required by a design engineer. (Shah, Baral, &
Manandhar, 2016).
In this process, the reforming section converts the feedstock (impure flare gas) into carbon
dioxide and hydrogen, the required reactants for the methanol synthesis process. The
equipment involved in this section are:
A. P.S.A: used as a desulfurizer used to separate H2S from the feed gas to prevent
corrosion and fouling in downstream equipment.
173
B. Heater: generates steam used to heat feed water, also used in subsequent reactions.
C. Heater: used to raise the temperature of the steam and flare gas (methane) mixture to
the required temperature for the pre-reforming reaction i.e., the breakdown of
hydrocarbons to yield methane which is 500℃.
D. Pre-Reformer: a reactor where steam is combined with the higher hydrocarbons (such
as ethane, propane, isobutane, etc.) present in flare gas to yield methane. The
decomposition of these components will also serve to reduce the amount of soot
generated.
E. Heater: used to raise the temperature of the reactor feed (methane and steam) to the
required temperature, 800℃.
F. Steam Methane Reforming (SMR) Reactor: This reactor uses steam to convert the
methane present in flare gas into carbon monoxide and hydrogen. It operates at
800℃.
G. Cooler: used to reduce the temperature of the SMR reactor outlet to a temperature of
430℃, suitable for the water gas shift reaction.
H. W.G.S Reactor: used to convert carbon monoxide into carbon dioxide, also producing
more hydrogen as a result. It operates adiabatically at a temperature of 430℃
In the methanol synthesis section, carbon dioxide and hydrogen are converted into methanol.
This is achieved using the following equipment:
I. Compressor: used to increase the pressure of the synthesis reactor feed stream to the
required pressure, 58 bar.
J. Cooler: used to reduce the temperature of the synthesis reactor to 200℃ favoring
methanol production, as a high temperature favours the production of carbon
monoxide.
K. Synthesis Reactor: used to hydrogenate carbon dioxide to yield methanol, where there
is a conversion of about 20%.
L. Condenser: used to condense water vapour to aid further removal of water
M. Flash drum: used to remove unreacted gases from the mixture of water and methanol,
after which methanol is sent downstream for purification.
174
N. Compressor: used to raise the pressure of the unreacted gases to the required pressure
for the synthesis reaction, 58 bar.
O. Heater: Although, there is an increase in temperature of the feed due to compression,

the temperature is still inadequate. This heater is used to increase the feed temperature
to desired level, 200℃
P. Synthesis Reactor: used to convert more of the reactants into methanol.
Q. Condenser: used to condense water vapour for easy removal of water
R. Flash drum: used to remove unreacted gases from the mixture of water. Methanol is
then sent downstream for purification. Unreacted gases are sent to P.S.A (S)
S. P.S.A: used to separate hydrogen from the effluent stream, accumulating a stream of
90% carbon dioxide.
T. Compressor: In order to store hydrogen as a gas, it has to be compressed to high

pressures. This unit compressed hydrogen to a pressure of 700 bar.
U. Cooler: used to reduce the temperature to a suitable range for storage.
V. Valve: used to increase the pressure of crude methanol stream before being sent to the
flash drum (W)
W. Flash Drum: used to further separate gaseous components from the liquid components
(water and methanol)
The methanol purification step is used to separate methanol from impurities such as water
and unreacted gases. The equipment employed in this section are:
Y. Distillation column: used to separate water from methanol using 58 stages with a
reflux ratio of 5.
Z. Cooler: used to reduce the temperature of the pure methanol stream to a suitable
temperature (25℃) for storage.
175
Figure 5.135: Process Flow Diagram
176
5.3 Reforming Process
This section serves to convert methane in natural gas to syngas via steam methane reforming.
PSA (A) was used to remove hydrogen sulphide as it poisons equipment downstream and the
catalysts used in this process. The methane content of natural gas is increased using a pre-
reformer then methane is converted to syngas with a steam methane reformer. The pre-
reformer was modelled using a REquil reactor in Aspen because more than one reaction
involved are equilibrium reaction. The steam methane reformer was modelled using the
RStoic reactor in Aspen Plus since there is sufficient information about the reactions taking
place and the fractional conversions are known.
In the pre-reformer, the heavy hydrocarbons in the natural gas reacts with steam to produce
methane. The reaction is carried out at 500℃ and 25 bar. Equation 5.1-5.3 of reaction for
pre-reforming process is given as:
y (5.1)
CnHy +n H2O → nCO + ( +n )H2
2
(5.2)
CO + H2O → CO2 + H2
(5.3)
CO + H2→ CH4 + H2O
In the steam reformer, the methane in the syngas stream was reacted with steam to produce
hydrogen and carbon monoxide. This reaction was carried out at 800℃ and 25 bar
(isothermal conditions).
177
5.4 Methanol Synthesis Process
Carbon dioxide and hydrogen are converted into methanol in two synthesis reactors K and P. The
liquid phase (methanol and water) is separated from unreacted gases first using flash drums and
then sent to distillation column (X) to obtain pure methanol.
5.5 Methanol Purification
In the methanol purification process, methanol is separated from water using a distillation
column of 30 equilibrium stages and a reflux ratio of 5.
5.6 Chemical Engineering Design of Process Equipment
The chemical engineering specifications of each process equipment is explained under the
following subsections.
5.6.1 Chemical engineering design of Pressure swing adsorber (A, S)

Pressure-swing adsorption (PSA) is potentially the separation technology of choice for
separation of gas mixtures at moderate throughputs with high purity requirements (Ruthven et
al., 1994). Each Pressure swing adsorber consists of two vessels carrying out the same operation
(adsorption and degeneration) to obtain a continuous process.
Chemical Engineering design for Pressure swing absorber (A)

P.S.A (A) is used to separate H 2S from the feed gas (impure flare gas) to protect downstream
equipment from corrosion and fouling. The chemical engineering specifications of the PSA (A)
as adopted from Zhou (2004) is summarized in Table 5.1 below.
Table 5.62: Chemical Engineering specifications for Pressure swing absorber (A)
Parameters Values
Operating temperature (ºC) 25
Operating pressure (bar) 25
Valid phases Vapour
Adsorbent Silica gel coated with N-
methyl-2-pyrrolidone (NMP)
Number of vessels 2
Particle size (m) 0.00028
178
Bulk density (g-1) 335
Pore volume (cm3 g-1) 0.85
Average pore size (nm) 8
Adsorption capacity (mg H2S/g 76
adsorbent)
Contact time (s) 240
Inlet flow rate (m3/s) 0.02715
Capacity of each vessel (m3) 6.516
Chemical Engineering design for Pressure swing absorber (S)

P.S.A (S) was used to recover hydrogen from the effluent stream stored leaving behind a stream
of 90% carbon dioxide. The chemical engineering specifications of the PSA (S) as adopted from
Pan (2017) is summarized in Table 5.2 below.
Table 5.63: Chemical Engineering specifications for Pressure swing absorber (S)
Parameters Values
Valid phases Vapour
Adsorbent Zeolite 5A
Adsorbent shape Spherical
Pore volume (ml/g) 0.77
Median pore size (nm) 0.5
Contact time (s) 240

179
5.6.2 Chemical Engineering Design of Heaters and Coolers
Using the available temperature differences, the main goal in the design of heaters, coolers, and
in general, heat exchangers; is to determine the surface area needed for the stated duty (rate of
heat transfer).
The general heat transfer across a surface is given as:
Q = UA∆Tm (5.1)
Where;
Q = heat transferred per unit time (Watt),
U = overall heat transfer coefficient (W/m2 oC),
ΔTm = mean temperature difference (oC) or log mean temperature difference (Log mean
temperature difference) for heat exchangers.
For electrically-heated heaters, the mean temperature difference was taken as the difference in
the temperature of the electrically heated surface and the inlet temperature of the process fluid.
For heat exchangers, the log mean temperature difference (LMTD) is calculated as:
(T 1−t 2 )(T 2 −t 1 )
For counter-current flow, Log mean temperature difference (∆Tm) =
ln (T 1−t 2)(T 2−t 1)
(5.2)
Where;
T1 = inlet tube side fluid temperature
T2 = outlet tube side fluid temperature
t1 = inlet shell side fluid temperature
t2 = outlet shell side fluid temperature
The following factors were used in choosing the fluid for both tube and shell sides of the shell
and tube heat exchangers:
180
I. Fluid pressure: High-pressure fluid is forced through the tube's side. This is because the
smaller-diameter tubes would need less thickness to sustain the same pressure than the
shell, lowering the heat exchanger's price.
II. Fluids' tendency to corrode: When choosing materials for equipment, corrosion's impact
must be considered. However, even with consideration, after a few years of continuous
use, the equipment may start to experience the effects using condensed liquid to
accumulate in the heat exchanger, fluids that could condense are run via the shell side.
III. Fluids' propensity to foul: The fluid that is most likely to foul the tube is run through the
tube side. This is because a heat exchanger's tube side has an easier cleaning procedure.
Chemical engineering design of Heater B

Heater (B) was used to generate steam used to heat feed water, also employed in subsequent
reactions. The temperature was raised from 25 ºC to 120 ºC. Table 5.3 below, gives a summary
of the chemical engineering specifications for heater (B)
Table 5.64: Chemical Engineering design for Heater (B)
Parameters Values
Operating Pressure (atm) 1
Heat duty (kJ/s) 4416.5287
Overall heat transfer coefficient (W/m2ºC) 400
Surface area required (m2) 39.43
Type of Heater Immersion Heater
Heat Source Electrical coil
Valid phases Vapour and liquid
Temperature of heating coil (ºC) 400
Mean temperature difference (ºC) 280
Heating period (s) 120
181
Chemical engineering design of Heater C
This heater is used to raise the temperature of the steam and flare gas (methane) mixture to the
necessary temperature, 500℃, for the pre-reforming reaction i.e, the breakdown of hydrocarbons
to yield syngas. Table 5.4 below gives a summary of the chemical engineering specifications for
heater (C).
Table 5.65: Chemical Engineering specifications for Heater (C)
Parameters Values
Operating Pressure (bar) 25
Overall heat transfer coefficient (W/ m2ºC) 400
Type Immersion Heater
Heat Element Electrical coil
Heating period (s) 120
Capacity (m3) 18.996
Chemical engineering design of Heater E

This heater is used to raise the temperature of the steam and flare gas (methane) mixture to the
necessary temperature, 800℃, for the reforming reaction i.e, conversion of of methane into
syngas. Table 5.5 below gives a summary of the chemical engineering specifications for heater
(E)
Table 5.66: Chemical Engineering specifications for Heater (E)
Parameters Values
182
Heating element Electric coil
Valid phases Vapour
Residence time (s) 120
Capacity (m3) 40.23
Chemical engineering design of Heater (O)

Although, there is an increase in temperature of the feed due to compression, the temperature is
still inadequate. Thus, heater (O) is used to increase the feed temperature to desired level of
184℃. Table 5.6 below gives a summary of the chemical engineering specifications for heater
(O)
Table 5.67: Chemical Engineering specifications for Heater (O)
Parameters Values
Overall heat transfer coefficient (W/ m2ºC) 400
Heating element Electric coil
Valid phases Vapour
183
Capacity (m3) 7.08

Chemical engineering design of Cooler G
Cooler G was used to reduce the temperature of the steam reformer outlet to a temperature of
430℃ which is suitable for the water gas shift reaction. Table 5.7 below gives a summary of the
chemical engineering specifications for cooler G.
Table 5.68: Chemical Engineering specifications for Cooler (G)
Parameters Values
Shell side operating temperature (ºC) 25
Shell side operating pressure (atm) 1
Tube side operating temperature (ºC) 800
Tube side operating pressure (bar) 25
Type Shell and tube heat exchanger
Shell side fluid Ambient water at 20ºC
Tube side fluid Syngas
Flow pattern Counter current
Log mean temperature difference (ºC) 573.26313
Maximum temperature change in utility (ºC) 5
Cooling duty (kJ/s) 2413.32104
Flowrate of ambient water required (kg/s) 114.92
Chemical engineering design of Cooler (J)
184
Cooler (J) is used to reduce the temperature of the synthesis reactor to 184℃ to favour
production of methanol as high temperature favours production of carbon monoxide. Table 5.8
below gives a summary of the chemical engineering specifications for cooler (J).
185
Table 5.69: Chemical Engineering specifications for Cooler (J)
Parameters Values
Tube side operating temperature (ºC) 848.99338
Tube side fluid Carbon dioxide and hydrogen
Chemical engineering design of Cooler (L)

Cooler (L) is used to condense water vapour to aid the removal of water. Table 5.9 below gives a
summary of the chemical engineering specifications for cooler (L).
Table 5.70: Chemical Engineering specifications for Cooler (L)
Parameters Values
Tube side fluid Crude Methanol
186
Chemical engineering design of Cooler (Q)

Cooler (Q) is used to condense water vapour to aid the removal of water. Table 5.10 below gives
a summary of the chemical engineering specifications for cooler (Q).
Table 5.71: Chemical Engineering specifications for Cooler (Q)
Parameters Values
Tube side fluid Crude Methanol
187
Chemical engineering design of Cooler (U)
Cooler (U) is used to reduce the temperature of the pure hydrogen stream to a suitable
temperature (25℃) for storage. Table 5.11 below gives a summary of the chemical engineering
specifications for cooler (U).
Table 5.72: Chemical Engineering specifications for Cooler (U)
Parameters Values
Tube side fluid Pure Hydrogen
Chemical engineering design of Cooler (Y)

Cooler (Y) reduces the temperature of the pure methanol stream to a suitable temperature (25℃)
for storage. Table 5.12 below gives a summary of the chemical engineering specifications for
cooler (Y).
Table 5.73: Chemical Engineering specifications for Cooler (Y)
Parameters Values
188
Tube side operating pressure (atm) 1
Tube side fluid Methanol
Flowrate of ambient water required (kg/s) 27
5.6.3 Chemical Engineering Design of Flash Drums (M, R and W)

Flash drums were used in this process to separate a multi-phase stream into distinct phases of
liquid and vapour. All flash drums separated unreacted gases from methanol and water.
Chemical Engineering design for Flash Drum (M)

Flash Drum (M) is used to remove unreacted gases from the mixture of water and methanol
which is sent downstream for purification of methanol. Table 5.13 below gives a summary of the
chemical engineering specifications for flash drum (M).
Table 5.74: Chemical Engineering specifications for Flash drum (M)
Parameters Values
Operating Temperature (ºC) 65
Capacity (m3) 16.44
189
Orientation Vertical
Vapour fraction 0.71
Mode of operation Gravity settling
Chemical Engineering design for Flash Drum (R)

Flash Drum (R) is used to remove unreacted gases from the mixture of water and methanol
chemical engineering specifications for flash drum (R).
Table 5.75: Chemical Engineering specifications for Flash drum (R)
Parameters Values
Chemical Engineering design for Flash Drum (W)

Flash Drum (W) is used to further separate gaseous components from the liquid components
chemical engineering specifications for flash drum (W).
Table 5.76: Chemical Engineering specifications for Flash drum (W)
Parameters Values
190
Operating Pressure (bar) 1.1
Capacity (m3) 7.05
5.6.4 Chemical Engineering Design of Compressors (I, N and T)

A compressor is used to increase the pressure of a gas so that it meets the requirement by the
downstream equipment. However, when a gas is compressed, its temperature is increased in the
process, as compression increases the internal energy of the gas. Hence, whenever the
temperature is to be maintained between a certain range, a cooler follows such compressor.
Tables 5.16, 5.17 and 5.18 below give the summary of the chemical engineering specifications of
compressors I, N and T respectively.
Chemical Engineering design for Compressor (I)

Compressor (I) is used to increase the pressure of the synthesis reactor feed stream to the
required pressure of 58 bar. This increase in pressure results in a corresponding increase in
temperature. Table 5.16 below gives a summary of the chemical engineering specifications for
compressor (I).
Table 5.77: Chemical Engineering specifications for Compressor (I)
Parameters Values
Discharge pressure (bar) 58
Inlet pressure (bar) 25
Type Reciprocating
Isentropic efficiency 0.72
Work duty (kW) 1795.43166
Driver type Motor
Inlet temperature (ºC) 591.3
191
Calculated outlet temperature (ºC) 848.99
Inlet volumetric flow rate (m3/s) 0.5546
Outlet volumetric flow rate (m3/s) 0.311185
Chemical Engineering design for Compressor (N)
Compressor (N) increases the pressure of the synthesis reactor feed stream to the required
pressure of 58 bar. This increase in pressure results in a corresponding increase in temperature.
Table 5.17 below gives a summary of the chemical engineering specifications for compressor
(N)
Table 5.78: Chemical Engineering specifications for Compressor (N)
Parameters Values
Type Reciprocating
Driver type Motor
Inlet temperature (ºC) 65
Chemical Engineering design for Compressor (T)
Compressor (T) increases the pressure of the synthesis reactor feed stream to the required
pressure of 58 bar. This increase in pressure causes an increase in temperature as well. Table
5.18 below gives a summary of the chemical engineering specifications for compressor (T)
192
Table 5.79: Chemical Engineering specifications for Compressor (T)
Parameters Values
Driver type Motor
5.6.5 Chemical Engineering Design of Methanol Synthesis Reactors

The following reactions occur in the methanol synthesis reactors.
CO2 + 3H2 CH3OH + H2O (5.6)
CO + 2H2 CH3OH (5.7)
CO2 + H2 CO + H2O (5.8)
The CO2 hydrogenation equation could be a linear combination of the other two reactions,
indicating that these reactions are not necessarily independent. Due to the endothermic nature of
the reverse water-gas shift reaction, the increase in temperature has a positive impact on
equilibrium. However, because equations 5.6 and 5.7 (the hydrogenation of CO and CO2) are
exothermic, the temperature increase has a detrimental impact on equilibrium. As a result, more
methanol yield is realized at higher pressures and lower temperatures (Jamshidi et al., 2023). The
chemical engineering specifications of the Synthesis Reactor (K) as adopted from Samimi (2018)
as summarized in Tables 5.19 and 5.20 below.
Chemical Engineering design for Synthesis Reactor (K)
193
Table 5.19 below gives a summary of the chemical engineering specifications for synthesis
reactor (K). below.
Table 5.80: Chemical Engineering specifications for Synthesis Reactor (K)
Parameters Values
Type of reactor Plug flow
Valid Phases Vapour and Liquid
Capacity (m3) 11.62
Contact time (s) 90
Catalyst Cu/ZnO/ZrO2
Catalyst geometry Spherical
Composition of catalyst (Cu:ZnO:ZrO2) 60:30:10
Size of catalyst particle (nm) 5.47
Bed void fraction 0.4
Density of catalyst bed (kg/ m3) 1140
Chemical Engineering design for Synthesis Reactor (P)

Synthesis reactor (P) is used to convert more reactants into methanol. Table 5.20 below gives a
summary of the chemical engineering specifications for synthesis reactor (P)
Table 5.81: Chemical Engineering specifications for Synthesis Reactor (P)
Parameters Values
Operating Temperature (C) 184
Valid Phases Vapour and Liquid
Capacity (m3) 8.4
194
Contact time (s) 90
Catalyst Cu/ZnO/ZrO2
Composition of catalyst (Cu:ZnO:ZrO2) 60:30:10
Diameter of catalyst particle (mm) 5.47
Bed void fraction 0.4
Density of catalyst bed (kg/ m3) 1140
5.6.6 Chemical Engineering Design of Pre-reformer (D)

In this reactor, steam reacts with the higher hydrocarbons present in flare gas such as ethane,
propane, isobutane, etc. to yield methane. The decomposition of these components reduces the
amount of soot generated in the operation. Table 5.21 below gives a summary of the chemical
engineering specifications for pre-reformer (D).
Table 5.82: Chemical Engineering specifications for Pre-reformer (D)
Parameters Values
Process type Isothermal
Valid phases Vapor
Mean residence time (s) 50
Capacity (m3) 15.2
Catalyst used Nickel oxide
Size of catalyst (nm) 11
5.6.7 Chemical engineering design of Steam Methane Reforming Reactor (F)

The steam reformer (S) was used to convert the methane present in flare gas using steam into
carbon monoxide and hydrogen. It operates at 800℃. The reaction is given below:
CH4 + H2O <=> CO + 3H2 (5.6)
195
The reaction is strongly endothermic (ΔHSR = 206 kJ/mol).
Table 5.22 below gives a summary of the chemical engineering specifications for S.M.R reactor
(F).
Table 5.83: Chemical Engineering specifications for Steam Methane Reformer (F)
Parameters Values
Valid phases Vapor
Type of operation Isothermal
Contact time (seconds) 50
Capacity (m3) 23.46
Catalyst Ni/ZnO/Al2O3
Catalyst nature Porous
Size of catalyst particles (mm) 0.1
5.6.8 Chemical engineering design of Water Gas Shift Reactor (H)

To maximize the conversion of CO (output from Cooler G), the water gas shift reaction is
conducted in an adiabatic reactor. The catalyst used in the HTS reaction is iron-chrome oxide
because it has better activity at temperatures between 583 and 723K (A. Iulianelli, 2015). Table
5.23 below gives a summary of the chemical engineering specifications for water gas shift
reactor (H).
Table 5.84: Chemical Engineering specifications for Water Gas Shift Reactor (H)
Parameters Values
Operating Mode Adiabatic
Type Plug flow
196
Valid Phases Vapour
Capacity (m3) 22.53
Contact time (s) 50
Catalyst Chromium-promoted iron oxide
Composition 74.2% Fe2O3, 10.0% Cr2O3, 0.2% MgO
(remaining percentage attributed to volatile
components)
Catalyst nature Porous
Size of catalyst particles (mm) 0.5
Particle density (kg/ m3) 2018.33
5.6.9 Chemical Engineering Design of Expansion Valve (V)

An expansion valve is a device used to regulate the flow of a fluid by restricting the flow through
a fixed orifice. In the context of crude methanol, the expansion valve is used to reduce the
pressure of the stream by reducing the flow rate through the valve. Table 5.24 below gives a
summary of the chemical engineering specifications for expansion valve (V).
Table 5.85: Chemical Engineering specifications for Expansion Valve (V)
Parameters Values
Flow coefficient, Cv 1.3
Pressure drop (bar) 26
Type Globe valve
Flow velocity (m/s) 2
5.6.10 Chemical engineering design of Distillation Column (X)

Distillation Column (X) separates water from methanol using 30 stages, with a reflux ratio of 5.
Table 5.25 below gives a summary of the chemical engineering specifications for flash drum
(W).
Table 5.86: Chemical Engineering specifications for Distillation Column (X)
197
Parameters Values
Number of stages 30
Operating pressure (atm) 1
Type of Condenser Partial-Vapor
Type of Reboiler Kettle
Valid phase Vapor-Liquid
Reflux Ratio 5
Internal components Plates
Tray type Sieve
Tray spacing (m)
Feed Stage 16
Feed entry temperature (ºC) 58.5
Feed entry pressure (bar) 1.1
Condenser cooling duty (kJ/s) -5076.76405
Condenser utility flowrate (kg/sec) 241.75
Condenser utility Cooling water at 20ºC
Condenser pressure (atm) 1
Reboiler operating temperature (ºC) 184
Reboiler operating pressure (atm) 1
Reboiler heat duty (kW) 6235.67786
Required reboiler area (m2) 158.05
Reflux pump efficiency 0.7
Distillate rate (kmol/hr) 97.36
Boilup rate (kmol/hr) 530.44
Bottoms rate (kmol/hr) 165.06
198
5.6.11 Chemical engineering design of Storage vessels
 The storage vessel for the feedstock (impure flare gas), is designed to have a holding
capacity that can run the process for two weeks.
 The water holding vessels are designed to hold water required to run the process for five
days, as water will be gotten from underground bodies such as boreholes.
 The methanol, carbon dioxide and hydrogen storage vessels are designed to hold the
product for five days.
 The hydrogen sulphide storage tanks are designed to hold the product for a week.
The storage capacity of each vessel is estimated as the product of the stream volume flow (m3
/day) and the specified number of days of storage.
Table 5.87: Chemical Engineering specifications for impure flare gas storage vessels (SV-01)
Parameters Values
Storage temperature (ºC) 25
Storage pressure (bar) 25
Required capacity (m3) 32956.5
Number of storage vessels prescribed 7
Capacity per storage vessel (m3) 4708.07159
Table 5.88: Chemical Engineering specifications for process water storage vessels
Parameters Values
Storage pressure (bar) 1.01325
Table 5.89: Chemical Engineering specifications for methanol storage vessels
199
Parameters Values
Storage pressure (bar) 1.01325
Required capacity (m3) 490
Number of storage vessels 5
Capacity per storage vessel (m3) 98
Table 5.90: Chemical Engineering specifications for CO2 storage vessels
Parameters Values
Table 5.91: Chemical Engineering specifications for hydrogen storage vessels
Parameters Values
200
CHAPTER 6
MECHANICAL ENGINEERING DESIGN
6.1 Introduction
Mechanical engineering design places a premium on defining the physical properties of

equipment used in the manufacturing process. It is concerned with the physical configuration of
process equipment such as tanks, pumps, filters, and heat exchangers, among other things. The
mechanical engineer is in charge of the machinery. Fabrication of equipment according to the
chemical engineer's standards. The process conditions, such as temperature and pressure, are the
focus of mechanical design rather than the procedure itself. It aids in the identification of design
restrictions and costs, both of which influence the final cost and also design feasibility.
It's critical because design flaws can disrupt the entire process and jeopardize the safety of plant
personnel. There are two types of equipment used in the chemical process industries: proprietary
and non-proprietary. Non-proprietary equipment is rigorously constructed based on customer
specifications, whereas proprietary equipment is often designed and manufactured by specialised
firms. Pumps, filters, dryers, and other proprietary equipment are examples of proprietary
equipment, whereas absorption and adsorption columns, heat exchangers, reactors, separators,
and other non-proprietary equipment are examples of non-proprietary equipment.
The general mechanical engineering design specifications as related to this report are explained
below:
1. Design pressure: In this report, the design pressure (sometimes called maximum allowable
working pressure or MAWP) was determined as the sum of the operating pressure, 20 % of the
operating pressure (includes required margin and hydrostatic head) and 1 atm (accounts for the
possibility of the vessel to be subjected to a vacuum). This can be simplified into the equation
below simplifies to the equation below:
Design pressure (atm) = 1.20 × operating pressure (atm) + 1 (6.1)
This is done to ensure safety of the equipment and its continued performance.
201
2. Design temperature: In this design work, for equipment operating at ambient conditions, the
design temperature is taken as 40ºC, while a margin of 20% is used for non-ambient equipment.
3. Design stress: The design stress which is a function of the design temperature, material of
construction and factor of safety for the equipment in the report were obtained from the British
Standard Public Document, PD 5500. For the material of construction of each equipment, see
chapter eight.
4. Corrosion allowance: For this project, a corrosion allowance of 2 mm is used since the
material of construction is usually a carbon or low-carbon alloy steel. Corrosion allowance is the
extra thickness of metal provided to compensate for material loss due to corrosion and erosion,
also known as scaling. Most design codes and standards specify a minimum allowance of 1.0
mm (Towler & Sinnot, 2021).
5. Wall thickness: There is a minimum wall thickness required to ensure that any vessel is
sufficiently rigid to withstand its own weight and any incidental loads. As a general guide the
wall thickness of any vessel should not be less than the values given below; the values include a
corrosion allowance of 2 mm:
Table 6.92: Minimum wall thickness guide
Vessel diameter Minimum wall thickness (mm)

(m)
1 5
1 to 2 7
2 to 2.5 9
2.5 to 3.0 10
3.0 to 3.5 12
6. Choice of head and closure: The choice of head in this report was based on the following
criteria provided by Coulson & Richardson (2004):
i. Flange-only heads are the cheapest type of formed head to manufacture, but their use is
limited to low-pressure and small-diameter vessels.
202
ii. Standard torispherical heads (dished ends) are the most commonly used end closure for
vessels up to operating pressures of 15 bar. They can be used for higher pressures, but
above 10 bar their cost should be compared with that of an equivalent ellipsoidal head.
iii. Above 15 bar an ellipsoidal head will usually prove to be the most economical closure to
use. A hemispherical head is the strongest shape; capable of resisting about twice the
pressure of a torispherical head of the same thickness.
8. Slenderness ratio: this is the ratio of the length – to – diameter of a column. It gives as
indication of buckling failure to occur in a column due to instability. The more the
slenderness ratio, the more likely the column will fail by column. A slenderness ratio
of 4-6 is maintained where possible in the design of the equipment in this report.
9. Thickness and volume: In this report, the thickness and volumes of vessels were
derived in the following manner:
For a cylindrical shell, the minimum thickness (e) required to resist internal pressure as obtained
from the British standard PD 5500 is given below:
Pi D i
e= (6.2)
2 f −P i
where Pi is the internal pressure
Di is the internal diameter of the vessel
f is the design stress
For an ellipsoidal head, the thickness (e) required to resist internal pressure as obtained from the
British standard PD 5500 is given below:
Pi D i
e= (6.3)
2 f −0.2 Pi
203
For a hemispherical head, the thickness (e) required to resist internal pressure as obtained from
the British standard PD 5500 is given below:
Pi D i
e= (6.4)
4 f −0.4 Pi
For vessels that er cylindrical in shape, the volume is calculated by the formula below:
π D2
V= (6.5)
4
where v is the volume of the vessel in m3
Di is the diameter of the vessel in m
6.2 Mechanical Design Specifications of Process Equipment
The Mechanical engineering specifications of all process equipment in this report are given in
the following as determined using the laid down principles in section 6.1 above.
Table 6.93: Mechanical Engineering Design specifications for PSA (A)
Operating Temperature (0C) 25
Design Temperature (0C) 40
Design Pressure (bar) 31
Height (m) 6.38
Design Stress (bar) 1750
Diameter of each vessel (m) 1.28
204
Slenderness ratio 5
Head Type Ellipsoidal
Diameter of head (m) 1.28
Wall Thickness of vessel (mm) 11.44
Thickness of head (mm) 11.36
Joint efficiency 1
Table 6.94: Mechanical Engineering Design specifications for Heater (B)
Heater type Immersion heater
Operating temperature (0C) 120
Design temperature (0C) 144
Operating pressure (atm) 1
Design pressure (atm) 2.2
Vessel Head Type Formed flat end
Heating Element Cylindrical rod
Vessel orientation Vertical
Heat source Electrical coil
Vessel diameter (m) 1.59
205
Vessel height (m) 9.6
Wall thickness of vessel (mm) 1.46
Capacity (m3) 19.26
Table 6.95: Mechanical Engineering Design specifications for Heater (C)
Design pressure (bar) 31
Vessel Head Type Ellipsoidal
Table 6.96: Mechanical Engineering Design specifications for Pre-Reformer Reactor (D)
206
Length of vessel (m) 9.55
Diameter of vessel (m) 1.59
Capacity (m3) 19
Valid phases Vapour
Slenderness ratio 6
Orientation Horizontal
Table 6.97: Mechanical Engineering Design specifications for Heater (E)
207
Table 6.98: Mechanical Engineering specifications for Steam Methane Reformer (F)

Length (m) 9.77
Design stress (bar) 800
Operating temperature (°C) 800
Design temperature (°C) 960
Slenderness ratio 5
Table 6.99: Mechanical Engineering specifications for Cooler (G)
208
Type Shell and tube
Operating temperature of tube 800
side fluid (°C)
Operating temperature of shell 25
side fluid (°C)
Operating pressure of tube side 25
fluid (bar)
Operating pressure of shell side 1
fluid (atm)
Design temperature of tube side 960
fluid (°C)
Design temperature of shell side 40
fluid (°C)
Design pressure of tube side fluid 31
(bar)
Design pressure of shell side fluid 2.22
(atm)
Shell head type Formed flat end
Tube head type Ellipsoidal
Shell TEMA symbol E
Number of tube passes 1
Number of shell passes 1
Diameter of tube (mm) 35.4
Length of tube (m) 3.66
TEMA symbol Front end – B

Shell – E
Rear end – M
Table 6.100: Mechanical Engineering specifications for W.G.S Reactor (H)
209
Head type Ellipsoidal

Inlet Operating temperature (°C) 430
Outlet Operating temperature (°C) 591.2
Design temperature (°C) 709.4
Slenderness ratio 5
Table 6.101: Mechanical Engineering specifications for Compressor (I)
Operating inlet temperature (ºC) 591.2

Operating discharge temperature
(ºC) 849
Operating inlet pressure (bar) 25
Operating discharge pressure (bar) 58
Design temperature Inlet (ºC) 709.44
Design temperature Outlet (ºC) 1018.8
Design pressure Inlet (bar) 55
Design pressure Outlet (bar) 70.6
Thickness of case (mm) 108
210
Type Reciprocating
Driver type Motor

Isentropic efficiency (%) 72
Power required (kW) 1795.43166
Design power requirement (kW) 2250
Table 6.102: Mechanical Engineering specifications for Cooler (J)

Operating temperature of tube 592
side fluid (°C)
Operating temperature of shell 25
side fluid (°C)
Operating pressure of tube side 25
fluid (bar)
Operating pressure of shell side 58
fluid (bar)
Design temperature of tube side 711.4
fluid (°C)
Design temperature of shell side 40
fluid (°C)
Design pressure of tube side fluid 30
(bar)
Design pressure of shell side fluid 69.6
(bar)
Tube head type Hemispherical
Shell TEMA symbol E
211
Diameter of tube (mm) 21

Shell – E
Rear end – M
Table 6.103: Mechanical Engineering specifications for Synthesis Reactor (K)


Head type Hemispherical
Design temperature (°C) 220.8
Design pressure (bar) 70.6
Slenderness ratio 6
Table 6.104: Mechanical Engineering specifications for Cooler (L)
Tube side maximum working temperature 65

(oC)
Tube side maximum working pressure (Bar) 58
Shell side maximum working temperature 25
(oC)
212
Shell side maximum working pressure (Bar) 1.01325
Tube side design temperature (oC) 78
Tube side design pressure (Bar) 70.6
Shell side design temperature (oC) 40
Shell side design pressure (Bar) 2.22
Orientation of equipment Horizontal
Shell TEMA symbol E

Shell – E
Rear end – M
Table 6.105: Mechanical Engineering specifications for flash drum (M)
Height (m) 8.68

Operating temperature (oC) 65
Operating pressure (Bar) 45
Design temperature (oC) 78
Design pressure (Bar) 55
Capacity (m3) 20.55
213
Slenderness ratio 5
Table 6.106: Mechanical Engineering specifications for Compressor (N)
Operating inlet temperature (ºC) 65

Operating discharge temperature
(ºC) 97.69
Operating outlet pressure (bar) 45
Outlet operating discharge pressure
(bar) 58
Design temperature (ºC) 117.228
Design pressure Outlet (bar) 70.6
Type Reciprocating
Design power requirement (kW) 142.11
Table 6.107: Mechanical Engineering specifications for Heater (O)
Type of heater Electrical

214
Design stress (N/mm2 ) 110
Type of heating element Cylindrical rod
Table 6.108: Mechanical Engineering specifications for Synthesis Reactor (P)

Design temperature (°C) 960
Table 6.109: Mechanical Engineering specifications for Cooler (Q)

Shell side operating pressure (bar) 1.01325
Shell side design temperature (ºC) 30
Shell side design pressure (bar) 2.2
215
Tube side design temperature (ºC) 220.8
Tube side design pressure (bar) 70.6
Tube shell type Hemispherical
Shell TEMA symbol E

Shell – E
Rear end – M
Table 6.110: Mechanical Engineering specifications for Flash drum (R)
Height (m) 7.43

Operating temperature (oC) 30
Operating pressure (Bar) 30
Design temperature (oC) 36
216
Capacity (m3) 12.86
Slenderness ratio 5
Table 6.111: Mechanical Engineering specifications for P.S.A (S)
Operating Temperature (0C) 25
Height (m) 8.31
Capacity of each vessel (m3) 18
Slenderness ratio 5
Head Type Ellipsoidal
Wall Thickness of vessel (mm) 17.74
Table 6.112: Mechanical Engineering specifications for Compressor (T)
Operating inlet temperature (ºC) 33

Operating discharge temperature 655
217
(ºC)
Operating inlet pressure (bar) 30
Operating discharge pressure (bar) 700
Design temperature Inlet (ºC) 39.6
Design temperature Outlet (ºC) 786
Design pressure Inlet (bar) 37
Design pressure Outlet (bar) 841
Type Reciprocating
Design power requirement (kW) 1215
Table 6.113: Mechanical Engineering specifications for Cooler (U)
Type Shell and tube
Tube side fluid Hydrogen gas
Shell side fluid Ambient water at 25 oC
Tube side maximum working 655

temperature (oC)
Tube side maximum working 700

pressure (bar)
Shell side maximum working 90

temperature (oC)
218
Shell side maximum working 4
pressure (Bar)
Tube side design pressure (Bar) 840
Shell TEMA symbol E

Shell – E
Rear end – M
Table 6.114: Mechanical Engineering specifications for Expansion valve (V)

Outlet temperature (ºC) 60.92
Outlet pressure (bar) 4
Pressure drop (bar) 26
219
Valve diameter (cm) 3.6
Table 6.115: Mechanical Engineering specifications for Flash drum (W)
Height (m) 6.55

Head type Torispherical
Inlet Operating temperature (oC) 61
Inlet Operating pressure (Bar) 4
Outlet Operating temperature (oC) 58
Outlet Operating pressure (Bar) 1.1
Design temperature (oC) 73.2
Design pressure (Bar) 5.8
Capacity (m3) 8.81
Slenderness ratio 5
Table 6.116: Mechanical Engineering specifications for Distillation column (X)
Joint efficiency 1
Number of stages 30
Condenser operating pressure (atm) 1
Condenser Design pressure (Bar) 2.22
Reboiler operating temperature (oC) 120
220
Reboiler operating pressure (Bar) 1.01325
Reboiler Design temperature (oC) 2.22
Reboiler Design pressure (Bar) 1.32
Column height (m) 11.73
Column diameter (m) 1.95

Tray spacing (m) 0.32

Slenderness ratio 6
Reboiler head type Ellipsoidal
Tube pitch symbol Triangular
Table 6.117: Mechanical Engineering specifications for Cooler (Y)
Tube side maximum working temperature 65

(oC)
Tube side maximum working pressure (Bar) 1.01325
Shell side maximum working temperature 25

(oC)
Shell side maximum working pressure (Bar) 1.01325
Tube side design pressure (Bar) 2.2
221

Tube head type Formed flat end
Shell TEMA symbol E

Shell – E
Rear end – M
Table 6.118: Mechanical engineering design of flare gas storage vessel (SV-01)

Required capacity (m3) 65,913
Design temperature (ºC) 40
Diameter of each vessel (m) 10
Height of each vessel (m) 59.98
Joint efficiency 1
Slenderness ratio 6
222
Table 6.119: Mechanical engineering design of process water storage vessels (SV-02)

Storage pressure (atm) 1
Head type Formed flat end
Joint efficiency 1
Table 6.120: Mechanical Engineering specifications for methanol storage vessels (SV-03)

Storage pressure (atm) 1
Capacity per storage vessel (m3) 98
Design pressure (atm) 2.2
Head type Formed flat end
223
Joint efficiency 1
Table 6.121: Mechanical Engineering specifications for CO2 storage vessels

prescribed
Wall thickness (mm) 56
Joint efficiency 1
Table 6.122: Mechanical Engineering specifications for hydrogen storage vessels

prescribed
224
Wall thickness (mm) 164
Joint efficiency 1
225
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DESIGN OF 30,000 TONS/YEAR METHANOL VIA CATALYTIC HYDROGENATION

OF FLARE GAS FROM CRUDE OIL WELLS

A FINAL YEAR DESIGN PROJECT

THE DEPARTMENT OF CHEMICAL ENGINEERING

IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE

1. CHARLES DANIEL CHRIS 18CF023951

2. SHOWUNMI MOFEYIFOLUWA 18CF023999

3. OJOMO PETER 17CF022368

4. OKEGBENRO OLAMIDE 17CF022370

5. OKPARA UCHENNA 18CF023983

6. SHOROYE MODESOLA ESTHER 18CF023998

7. SHOWUNMI MOFEYIFOLUWA 18CF023999

LIST OF TABLES vii

1.1 Background of Study 1

1.2 Statement of Problem 2

1.3 Aim and Objectives 3

1.4 Justification of Study 4

1.5 Scope of the Study 5

2.1 Greenhouse Gas Emissions 6

2.1.1 Overview of Greenhouse Gases 6

2.1.2 Major Contributors to CO2 Emission in Nigeria 6

2.1.3 Effects of CO2 Emission 9

2.1.4 Strategies to Lower Co2 Emissions 11

2.2 Carbon Capture 12

2.2.2 Types of Carbon Capture 13

2.2.3 Carbon Capture Technologies 15

2.3 Gas Flaring 21

2.3.1 Overview of Flare Gas 21

2.3.2 Effects of Gas Flaring in Nigeria 22

2.3.3 Gas Flaring Process 23

2.4 Overview of Hydrogen 25

2.4.1 Description of Hydrogen 25

2.4.2 Industrial Preparation of Hydrogen 26

2.4.3 Industrial Applications of Hydrogen 29

2.5 Overview of Methanol 29

2.5.1 Brief Description of Methanol 29

2.5.2 Industrial Applications of Methanol 30

2.6 Production of Methanol From Co2 32

2.6.1 Heterogeneous Catalytic Hydrogenation of CO2 32

2.6.3 Electrochemical Reduction Of CO2 To Methanol 34

2.6.4 Photochemical Reduction of CO2 35

2.6.5 Photoelectrochemical Reduction Of CO2 To Methanol 36

2.7 Factors Affecting Yield of Methanol 37

2.7.1 Effect of a Catalyst 37

2.7.2 Effect of Temperature 38

2.7.3 The Effect of Pressure 38

2.7.4 Effect of Reactor Type and Reactor Design 38

2.8 Methanol Synthesis from Flare Gas Of Crude Oil Wells 39

2.8.1 Overview of the Process 39

2.8.2 Selection of Catalyst in Synthesis Reactor 40

2.8.3 Selection of Adsorbents 40

2.8.4 Operating Conditions of Methanol Synthesis 41

2.8.5 Storage of Products 41

2.8.6 Utilization of Byproducts 42

3.2 Aspen Simulation 44

3.3 Overall Material Balance for the Production Process 45

3.4 Reforming Process 46

3.4.1 Material Balance around PSA (A) 47

3.4.2 Material Balance around Heater (B) 50

3.4.3 Material Balance around Mixer 1 51

3.4.4 Material Balance around Heater (C) 54

3.4.5 Material Balance around Pre-reformer Reactor (D) 56