TEAM 03 - Full Report PDF

SMJC 4824 CHEMICAL PROCESS DESIGN
PRODUCTION OF
22, 000 METRIC TONNES PER YEAR OF
METHANOL FROM BIOGAS
TEAM 03
No. Team Members Matric No.
1 Gan Cheng Ling A18MJ0035
2 Amir Hamdi Bin Aznil A18MJ3012
3 Muhammad Fitri Bin Rozmi A18MJ0086
4 Nur Qamarina Binti Hazian A18MJ0120
5 Rashmeera Siva Vijian A18MJ0196
SUPERVISOR: DR ROSHAFIMA RASIT ALI &
DR NURFATEHAH WAHYUNY CHE JUSOH

ABSTRACT
Methanol is used as a feedstock in various chemical applications. In this

chemical design project, methanol with purity of 99.85% is produced at 22,000 metric
tonnes per year by using biogas as the raw material. The methanol production plant
will be located at Taman Sri Kluang, Johor which will operate for 330 days per year.
The biogas which consists of 60% of methane and 40% of carbon dioxide (CO₂) is
supplied at a rate of 1,500 kg/hr to the plant. Steam reforming reaction is selected as
the best reaction route to produce methanol. The biogas will be separated into methane
and carbon dioxide by using membrane separator. The methane is then entered the
steam reforming reactor to react with steam to produce syngas. The water in the syngas
will be removed by flash separators and the top product will be mixed with carbon
dioxide before entering the methanol synthesis reactor. The methanol-water mixture
will be separated from the unreacted gaseous mixture using the second flash column.
The gaseous mixture will recycle back to the mixer again to improve the yield of
product. The methanol-water mixture is finally separated by distillation column to
obtain the high purity methanol. The mass and energy balance for the entire process
are calculated and simulated using AVEVA PRO/II simulator. All the effluents from
the chemical process will undergo treatment by using different technologies as
described in Chapter 3. Energy integration is carried out to maximize the heat recovery
in the process and reduce the energy usage. A total of 54.05% of heat is saved for hot
utility whereas the cold utility achieves 51.74% of heat saving. Process safety is
described in detail in Chapter 5 including HAZOP analysis, CHRA analysis and plant
layout is attached. Based on the profitability analysis, the methanol production plant
is estimated to have a ROI of 140% with 7 years of payback period. Therefore, the
methanol production is worth for investment.
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TABLE OF CONTENTS
TITLE PAGE
ABSTRACT iii
TABLE OF CONTENTS iv
LIST OF TABLES xii
LIST OF FIGURES xx
LIST OF APPENDICES xxiv
CHAPTER 1 INTRODUCTION 1
1.1 Company Background 1
1.2 Chemical Background 2
1.2.1 Background of Methanol 2
1.2.2 Physical and Chemical Properties of Methanol 3
1.2.3 Application of Methanol 4
1.2.4 Background of Biogas 6
1.2.5 Physical Properties of Biogas 8
1.2.6 Safety Information of Methanol and Biogas 9
1.3 Sustainable Justification 11
1.3.1 Pros and Cons of Biogas 11
1.3.1.1 Benefits of Biogas to Environment 12
1.3.1.2 Benefits of Biogas In Term of
Economics 13
1.3.1.3 Negative Impact of Biogas
Economically 14
1.3.2 Pros and Cons of Methanol 15
1.3.2.1 Benefits of Methanol in
Pharmaceutical 15
1.3.2.2 Methanol Usage as Fuels 16
1.3.2.3 Benefits of Methanol to the
Environment 16
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1.3.2.4 Disadvantages of Methanol 17
1.3.3 Circular Economy and Carbon Footprint 18
1.4 Market Survey of Methanol 18
1.4.1 Global Demand and Supply of Methanol 18
1.4.2 Covid-19 Impact on Methanol Demand and
Supply 21
1.4.3 Methanol Market in Malaysia 21
1.4.4 Market Price of Methanol 23
1.5 General Site Consideration 24
1.5.1 Comparisons Between Potential Locations 26
CHAPTER 2 PROCESS SYNTHESIS 1 35

2.1 Process Route 1: Catalytic Partial Oxidation of
Methane 35
2.1.1 Process Description 35
2.1.2 Chemical Reaction of Process Route 1 37
2.1.3 Gross Profit Margin Calculation for Process
Route 1 37
2.2 Process Route 2: Dry Reforming of Methane 38
Route 2 40
2.3 Process Route 3: Steam Reforming of Methane 41
Route 3 42
2.4 Process Route Selection 43
2.4.1 Technology Comparison 43
2.4.2 Sustainability Justification 46
2.5 Process Block Diagram 48
2.6 Overall Process 51
2.6.1 Raw Material 51
v
2.6.2 Main Product and By-products 52
2.6.3 Overview of Process Flow Diagram 53
2.7 Equipment Basis 56
2.7.1 Methane Steam Reforming Reactor (R-101) 56
2.7.2 Methanol Synthesis Reactor (R-102) 58
2.7.3 Distillation Column (T-101) 60
2.7.4 Flash Separator 66
2.7.4.1 Flash Separator (F-102) 70
2.7.5 Membrane Separator 72
2.7.6 Mixer (M-101) 73
2.7.7 Auxiliary 73
2.7.7.1 Compressor 74
2.7.7.2 Intercooler 75
2.7.7.3 Heater 75
2.7.7.4 Condenser 76
2.7.7.5 Pump 76
2.7.7.6 Cooler 76
Manual Calculation for Mass and Energy Balance
(MEB) 77
2.8 77
2.8.1 Mass Balance 77
2.8.1.1 Steam Reforming Reactor (R-101) 79
2.8.1.2 Methanol Synthesis Reactor (R-102) 80
2.8.1.3 Membrane Separator (F-101) 81
2.8.1.4 Flash Column (F-102) 82
2.8.1.5 Flash Column (F-103) 83
2.8.1.6 Distillation Column (T-101) 84
2.8.1.7 Compressor (C-101) 85
2.8.1.8 Compressor (C-102) 86
2.8.1.9 Compressor (C-103) 87
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2.8.1.10 Compressor (C-104) 88
2.8.1.11 Compressor (C-105) 89
2.8.1.12 Compressor (C-106) 90
2.8.1.13 Compressor (C-107) 91
2.8.1.14 Intercooler (E-101) 91
2.8.1.15 Intercooler (E-103) 93
2.8.1.16 Heater (E-104) 94
2.8.1.17 Heater (E-105) 95
2.8.1.18 Heater (E-106) 96
2.8.1.19 Heater (E-108) 97
2.8.1.20 Heater (E-109) 98
2.8.1.21 Pump (P-101) 99
2.8.1.22 Cooler (E-102) 100
2.8.1.23 Cooler (E-107) 101
2.8.1.24 Cooler (E-109) 102
2.8.1.25 Mixer (M-101) 103
2.8.1.26 Condenser (E-109) 104
2.8.1.27 Splitter (S-101) 105
2.8.1.28 Throttling Valve (V-101) 106
2.8.1.29 Throttling Valve (V-102) 107
2.8.2 Mass Balance Comparison 108
2.8.3 Energy Balance 110
2.8.3.1 Manual calculation of Energy
Balance 115
2.8.4 Energy Balance Comparison 116
CHAPTER 3 EFFLUENT AND WASTE MANAGEMENT 119

3.1 Introduction 119
3.1.1 Waste Management Practices 120
3.1.2 Legalization in Malaysia 121
3.1.3 Sustainable Development Goals 122
vii
3.1.4 Effluent and Waste Generated from Methanol
Production Plant 126
3.2 Solid Waste 127
3.2.1 Solid Catalyst 127
3.2.2 Management of Solid Waste 128
3.2.3 Comparison Solid Waste Management
Methods 131
3.3 Liquid Waste 132
3.3.1 Wastewater 132
3.3.1.1 Management of Wastewater
Treatment 133
3.3.2 Comparison of Wastewater Treatment Methods
135
3.4 Gas Waste 136
3.4.1 Membrane Separation of Gas Wastes 136
3.4.2 Flaring Method of Gas Wastes 137
3.4.3 Electrostatic Precipitator 138
3.4.4 Comparison of Gas Waste Management
Method 141
CHAPTER 4 ENERGY INTEGRATION 143

4.2 Stream Identification 144
4.3 Composite Curves 148
4.4 Problem Table Algorithm 153
4.5 Heat Exchanger Network for Maximum Energy
Recovery 157
4.5.1 Above Pinch Design 159
4.5.2 Below Pinch Design 159
4.6 Comparison Between Utilities Consumption Before
and After HEN 161
4.6.1 Total Utilities Consumption Before and After
HEN 161
4.6.2 Comparison of Before and After Heat
Integration 162
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CHAPTER 5 PROCESS CONTROL 167
5.2 Process Control System 168
5.2.1 Process Control Objectives 168
5.2.2 Process Control Variables 170
5.2.3 Process Control Configuration 171
5.2.3.1 Feedback Control 172
5.2.3.2 Feedforward Control 173
5.2.3.3 Ratio Control 174
5.2.3.4 Cascade Control 175
5.2.4 Process Control Instrumentation 176
5.3 Control System for Individual Equipment 179
5.3.1 Catalytic Fixed Bed Reactor 179
5.3.2 Flash Separators 185
5.3.4 Membrane Separator (F-101) 197
5.3.5 Throttling valve 201
5.3.6 Splitter 204
5.3.7 Compressor 207
5.3.8 Condenser 215
5.3.9 Heater 219
5.3.10 Cooler 225
5.3.11 Pump 230
CHAPTER 6 PROCESS SAFETY 239

6.2 Plant Safety 240
6.2.1 Plant Location 240
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6.2.2 Chemical Storage and Process Vessel 241
6.2.3 Transportation 242
6.3 Labor Safety 243
6.3.1 General Personnel Safety 244
6.3.2 Personal Protective Equipment (PPE) 245
6.4 Fire Hazards 248
6.4.1 Fire Safety Policy 248
6.4.2 Fire Detection and Alarm System 250
6.5 Emergency Response 253
6.6 HAZOP Study 255
6.6.1 Catalytic Fixed Bed Reactor (R-101, R-102) 258
6.6.2 Flash Separators (F-102, F-103) 266
6.6.4 Membrane Separator (F-101) 288
6.6.5 Heaters (E-105, E-108, E-110, E-113, E-114) 297
6.6.6 Cooler (E-101, E-102, E-103, E-111) 300
6.6.7 Condensers (E-116. E-117, E-118) 303
6.6.8 Throttling Valve (V-101, V-102) 306
6.6.9 Compressors (C-101 to C-107) 309
6.6.10 Pump (P-101) 315
6.7 Chemical Health Risk Assessment (CHRA) 321
6.8 Plant Start-Up and Shut-Down Procedure 331
6.8.1 Plant Start-Up Procedure 331
6.8.2 Error Elimination Test for Plant Startup 333
6.8.3 Plant Shut-Down Procedure 334
6.8.3.1 Scheduled Shut Down 334
6.8.3.2 Unexpected Shut Down 335
6.8.3.3 Emergency Shut Down 335
6.9 Plant Layout 336
6.9.1 Process Area 338
6.9.2 Non-Process Area 340
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CHAPTER 7 PROFITABILITY ANALYSIS 342
7.2 Bare-Module Equipment Cost 345
7.2.1 Catalytic Fixed Bed Reactor 345
7.2.2 Flash Separator 353
7.2.3 Distillation Column 360
7.2.4 Membrane Separator 366
7.2.5 Mixer (M-101) 369
7.2.6 Compressors 374
7.2.7 Pump 385
7.2.8 Heaters 388
7.2.9 Condenser 397
7.2.10 Coolers 404
7.2.11 Heat Exchangers 412
7.2.12 Total Bare-Module Cost 422
7.3 Total Capital Investment 424
7.4 Total Depreciable Capital 428
7.5 Direct Wages and Benefits 430
7.6 Total Annual Production Cost 432
7.7 Annual Net Profit and Return on Investment (ROI) 435
7.8 Cash Flow Analysis 437
7.9 Conclusion 446
REFERENCES 447
xi
LIST OF TABLES
TABLE NO. TITLE PAGE
Table 1.1 Properties of Methanol 3

Table 1.2 Comparison of Biogas and Natural Gas 7
Table 1.3 Properties of Methane 8
Table 1.4 Properties of Carbon Dioxide 9
Table 1.5 NFPA Diamond Rating for Methanol and Biogas
Components 10
Table 1.6 Methanol Derivatives and The End-User Industry (Mordor
Intelligence, 2020). 19
Table 1.7 Geography Demand of Methanol (Mordor Intelligence,
2020). 20
Table 1.8 Comparison Between Three Different Sites 27
Table 2.1 Advantages and Disadvantages for Process Route 1 36
Table 2.2 Chemical Reaction for Process Route 1 37
Table 2.3 Side Reactions for Process Route 2 37
Table 2.4 Gross Profit Margin for Process Route 1 37
Table 2.6 Chemical Reaction for Process Route 2 39
Table 2.7 Side Reactions for Process Route 2 39
Table 2.10 Chemical Reaction of Process Route 3 42
Table 2.11 Side Reactions of Process Route 3 42
Table 2.13 Technology Comparison for Three Process Routes 43
Table 2.14 Sustainability Justification for Process Routes 46
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Table 2.15 By-Product in Methanol Synthesis Plant 52
Table 2.16 Operating Condition of R-101 57
Table 2.17 Operating Condition of R-102 60
Table 2.18 Operating Condition for Distillation Column 62
Table 2.19 Components boiling points at standard temperature (1 bar) 67
Table 2.20 Operating Conditions of Flash Separator (F-102) 71
Table 2.21 Operating Conditions of Flash Separator (F-103) 71
Table 2.22 Operating Conditions of Membrane Separator (F-101) 72
Table 2.23 Operating Conditions of Mixer (M-101) 73
Table 2.24 Operating Conditions for Compressors 74
Table 2.25 Operating Conditions for Intercooler 75
Table 2.26 Operating Conditions for Heater 75
Table 2.27 Operating Conditions for Condenser 76
Table 2.28 Operating Conditions for Pump 76
Table 2.29 Operating Conditions for Cooler 77
Table 2.30 Steam Reforming Reactor (R-101) 79
Table 2.31 Methanol Synthesis Reactor (R-102) 80
Table 2.32 Mass Balance on Membrane Separator (F-101) 81
Table 2.33 Mass Balance on Flash Column (F-102) 82
Table 2.34 Mass Balance on Flash Column (F-103) 83
Table 2.35 Mass Balance on Distillation Column (T-101) 84
Table 2.36 Mass Balance on Compressor (C-101) 85
Table 2.43 Mass Balance on Intercooler (E-101) 91
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Table 2.45 Mass Balance on Heater (E-104) 94
Table 2.46 Mass Balance on Heater (E-105) 95
Table 2.50 Mass Balance on Pump (P-101) 99
Table 2.51 Mass Balance on Cooler (E-102) 100
Table 2.54 Mass Balance on Mixer (M-101) 103
Table 2.55 Mass Balance on Condenser (E-109) 104
Table 2.56 Mass Balance on Splitter (S-101) 105
Table 2.57 Mass Balance on Throttling Valve (V-101) 106
Table 2.58 Mass Balance on Throttling Valve (V-102) 107
Table 2.59 Comparison of Mass Balance Between Manual Calculation
and AVEVA PRO/II Simulation in Mass Flow Rate 108
Table 2.60 Reference State for Each Component 111
Table 2.61 State of Component at Reactor Temperature and Pressure 112
Table 2.62 Manual Calculation of Energy Balance for Each Equipment
115
Table 2.63 Comparison of Energy Balance Between Manual
Calculation and AVEVA PRO/II Simulation 116
Table 3.1 Classification of Effluent and Waste Produced by the Plant 126
Table 3.2 Mechanism of Catalyst Deactivation. 127
Table 3.3 Comparison Between Spent Catalyst Management Methods
131
Table 3.4 DOE Acceptable Standard Industrial Effluent Discharge
Conditions 133
Table 3.5 Comparison between trickling filtration and membrane
filtration treatment method 135
xiv
Table 3.6 The Comparison Between Absorption and Membrane
Separation of Carbon Dioxide Treatment Methods 141
Table 4.1 Summary of the hot and cold stream available for heat
integration analysis. 147
Table 4.2 Data for hot composite curve 149
Table 4.3 Data for cold composite curve 150
Table 4.4 Shifted Temperature for ΔTmin = 10℃ 154

Table 4.5 Problem Table Algorithm 155
Table 4.6 Consumption of hot and cold utilities before implementing
hen 161
Table 4.7 Consumption of hot and cold utilities after implementing
hen 162
Table 4.8 Comparison of the utility consumption before and after
HEN 163
Table 5.1 Type of Control System 170
Table 5.2 Process control instruments and their functions 177
Table 5.3 Basic symbols of process control 178
Table 5.4 Operating conditions of R-101 181
Table 5.5 Control system for steam reforming reactor (R-101) 182
Table 5.6 Operating conditions of R-102 183
Table 5.7 Control system for methanol synthesis reactor (R-102) 184
Table 5.8 Operating conditions of F-102 186
Table 5.9 Control system for flash separator (F-102) 187
Table 5.11 Control system for flash separator (F-103) 190
Table 5.12 Operating conditions of T-101 194
Table 5.13 Control system for distillation column (T-101) 194
Table 5.15 Control system for membrane separator (F-101) 200
Table 5.16 Control system for throttling valve (V-101) 202
Table 5.17 Control system for throttling valve (V-102) 203
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Table 5.18 Control system for splitter (S-101) 205
Table 5.19 Control system for splitter (S-102) 206
Table 5.20 Control system for compressor (C-101) 208
Table 5.27 Control system for condenser (E-116) 216
Table 5.30 Control system for heater (E-105) 220
Table 5.35 Control system for cooler (E-101) 226
Table 5.39 Control system for pump (P-101) 231
Table 6.1 Personal Protective Equipment (PPE) 245
Table 6.2 Terminologies in HAZOP study 255
Table 6.3 Guide word for HAZOP 257
Table 6.4 HAZOP for catalytic fixed bed reactor 259
Table 6.5 HAZOP for flash separators 267
Table 6.6 HAZOP for distillation column 278
Table 6.7 HAZOP for membrane separator 289
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Table 6.8 HAZOP for heater 298
Table 6.9 HAZOP for cooler 301
Table 6.10 HAZOP for condensers 304
Table 6.11 HAZOP for throttling valve 307
Table 6.12 HAZOP for compressors 310
Table 6.13 HAZOP for pump 316
Table 6.14 Chemicals used in work unit (Form B1) 325
Table 6.15 Chemicals released by the processes or work activities
(Table B2) 326
Table 6.16 Inhalation exposure assessment (form c1) 327
Table 6.17 Dermal Assessment (Form C2) 329
Table 7.1 Chemical Engineering Plant Cost Index (CEPCI) (Seider et
al., 2017; Jenkins, 2020) 344
Table 7.2 Equipment specification sheet of steam reforming reactor
(R-101) 350
Table 7.3 Equipment specification sheet of methanol synthesis
reactor (R-102) 352
Table 7.4 Equipment specification sheet of flash column (F-102) 357
Table 7.5 Equipment specification sheet of flash column (F-103) 359
Table 7.6 Equipment specification sheet for distillation column (T-
101) 364
Table 7.7 Equipment specification sheet for membrane separator (F-
101) 368
Table 7.8 Equipment specification sheet of mixer (M-101) 372
Table 7.9 Equipment specification sheet of compressor (C-101) 378
Table 7.16 Equipment specification sheet for pump (P-101) 386
xvii
Table 7.17 Overall heat transfer coefficient values in heat exchangers 388
Table 7.18 Tube length factor 390
Table 7.19 Equipment specification sheet for heater (E-105) 392
Table 7.26 Equipment specification sheet for condenser (E-116) 401
Table 7.31 Equipment specification sheet of cooler (E-101) 408
Table 7.37 Equipment specification sheet of heat exchanger (E-104) 416
Table 7.43 Total bare-module cost 422
Table 7.44 Allocated capital investment costs for utility 425
Table 7.45 Detail calculation of the allocated cost, 𝐶𝑎𝑙𝑙𝑜𝑐 426
xviii
Table 7.46 Calculation of total capital investment, 𝐶𝑇𝐶𝐼 427
Table 7.47 Calculation of total depreciable capital, CTCI 429

Table 7.48 Estimated Number of Required Operators 430
Table 7.49 Annual Cost Summary 432
Table 7.50 Total Annual Sale 435
Table 7.51 Cash flow analysis (in million ringgit) for 0% interest rate 439
Table 7.52 Cash flow analysis for different interest rate 443
Table 7.53 Summary of profitability analysis 446
xix
LIST OF FIGURES
FIGURE NO. TITLE PAGE
Figure 1.1 Company Organizational Chart 1

Figure 1.2 Chemical Structure of Methanol 2
Figure 1.3 Uses of Methanol (Data for 2015, from IHS Markit, 2015) 5
Figure 1.4 Anaerobic Digestion Process 12
Figure 1.5 The Production and Application of Biogas (Bilal
Abderezzak, 2017). 14
Figure 1.6 The overall application of Methanol (Rajesh, 2021). 17
Figure 1.7 The Global Methanol Supply and Demand Chart (Methanol
Institute, 2021). 19
Figure 1.8 The Methanol Market for Derivatives in the Year 2020
(Mordor Intelligence, 2020). 21
Figure 1.9 Sarawak Petchem's Methanol Project Located at Bintulu
(Robert, 2021). 23
Figure 1.10 Global Methanol demand by Region (Methanol Market
Share, 2018). 24
Figure 2.1 Process Block Diagram 48
Figure 2.2 Schematic Diagram of Packed Bed Reactor (Hafeez et al.,
2019). 56
Figure 2.3 Sketch of a catalytic packed bed multi-tube reactor
(Eigenberger and Ruppel, 2000) 59
Figure 2.4 Individual Parts of Distillation Column (SRS Engineering
Corporation, 2016). 61
Figure 2.5 Symbol of Steam Reforming Reactor (R-101) in PFD 79
Figure 2.6 Symbol of Methanol Synthesis Reactor (R-102) in PFD 80
Figure 2.7 Symbol of Membrane Separator (F-101) in PFD 81
Figure 2.8 Symbol of Flash Column (F-102) in PFD 82
Figure 2.9 Symbol of Flash Column (F-103) in PFD 83
xx
Figure 2.10 Symbol of Distillation Column (T-101) in PFD 84
Figure 2.11 Symbol of compressor (C-101) in PFD 85
Figure 2.18 Symbol of Intercooler (E-101) in PFD 91
Figure 2.19 Symbol of Intercooler (E-103) in PFD 93
Figure 2.20 Symbol of Heater (E-104) in PFD 94
Figure 2.25 Symbol of Pump (P-101) in PFD 99
Figure 2.26 Symbol of Cooler (E-102) in PFD 100
Figure 2.29 Symbol of Mixer (M-101) in PFD 103
Figure 2.30 Symbol of Condenser (E-109) in PFD 104
Figure 2.31 Symbol of Splitter (S-101) in PFD 105
Figure 2.32 Mass Balance on Throttling Valve (V-101) 106
Figure 2.33 Mass Balance on Throttling Valve (V-102) 107
Figure 3.1 The SDG Governance Structure in Malaysia (EPU, 2021). 123
Figure 3.2 Methods for Handling the Spent Catalyst (ECMA, 2018) 130
Figure 3.3 Membrane Filtration Process in Wastewater Treatment
(Singh, 2014) 134
Figure 3.4 A Generalized Schematic Diagram of an Activated Sludge
Process. (Salam Al-Dawery., 2013) 134
xxi
Figure 3.5 The Principle of Membrane Separation (Green, 2015). 137
Figure 3.6 Flaring Process in An Oil Refinery Plant (Karthikayen,
2020). 138
Figure 4.1 Example of heat exchanger network (Dunn & El-Halwagi,
2003) 143
Figure 4.2 Hot and Cold Equipment in Methanol Production Plant 145
Figure 4.3 Hot and Cold Equipment in Methanol Production Plant
(Continued) 146
Figure 4.4 Hot composite curve 149
Figure 4.5 Cold composite curve 150
Figure 4.6 Combined hot and cold composite curves at ∆𝑇 = ∆𝑇𝑚𝑖𝑛 =

10℃ 151
Figure 4.7 Grid diagram for Heat Exchanger Network 158
Figure 5.1 Block diagram of a feedback control system (Woolf, 2022).
172
Figure 5.2 Block diagram of a feedforward control system (Mokhatab,
2012) 173
Figure 5.3 Configuration of a ratio control system (Fraley, 2022) 174
Figure 5.4 Configuration of cascade control system (Bolton, 2021). 175
Figure 5.5 P&ID for steam reforming reactor (R-101) 181
Figure 5.6 P&ID for methanol synthesis reactor (R-102) 183
Figure 5.7 P&ID for flash separator (F-102) 186
Figure 5.8 P&ID for flash separator (F-103) 189
Figure 5.9 P&ID for distillation column (T-101) 194
Figure 5.10 P&ID for membrane separator (F-101) 198
Figure 5.11 P&ID for throttling valve (V-101) 202
Figure 5.12 P&ID for throttling valve (V-102) 203
Figure 5.13 P&ID for splitter (S-101) 205
Figure 5.14 P&ID for splitter (S-102) 206
Figure 5.15 P&ID for compressor (C-101) 208
xxii
Figure 5.22 P&ID for condenser (E-116) 216
Figure 5.25 P&ID for heater (E-105) 220
Figure 5.30 P&ID for cooler (E-101) 226
Figure 5.34 P&ID for pump (P-101) 231
Figure 6.1 Combustion triangle that represents the three essential
components for fire ignition (Fogler, 2022). 249
Figure 6.2 Smoke detector 250
Figure 6.3 Basic components in a fire alarm system 252
Figure 6.4 Plant layout design for methanol production plant 337
Figure 7.1 Cumulative cash flow for 0% interest rate 441
Figure 7.2 Cumulative cash flow analysis for different interest rate 445
xxiii
LIST OF APPENDICES
APPENDIX TITLE PAGE
Appendix A Material Safety Data Sheet (MSDS) 459
xxiv
CHAPTER 1
INTRODUCTION
1.1 Company Background
Vermonix Technology Consultancy was established in 2017 by a group of

chemical engineers, and will propose a chemical processing plant design to produce
methanol from biogas. The organizational chart of the company is shown in Figure
1.1.
Figure 1.1 Company Organizational Chart
1
1.2 Chemical Background
1.2.1 Background of Methanol
Methanol, commonly known as methyl alcohol, is a chemical that has the

formula CH3OH and is the simplest alcohol. It's a flammable, light, volatile, colorless
liquid with a pronounced alcoholic odor comparable to ethanol. Approximately 85%
of methanol produced is used in the chemical industry as a starting material or solvent
for synthesis (J. Ott et al., 2000).
Figure 1.2 Chemical Structure of Methanol
Previously, it was originally mostly manufactured by the destructive

distillation of wood, earning it the moniker of wood alcohol. However, the earliest
known usage of methanol was its use in the embalming process by ancient Egyptians
(Cheng et al., 1994). It would be mixed into a mixture containing itself, formaldehyde,
and glutaraldehyde. The purpose of the methanol was to hold the formaldehyde in
solution. The ancient Egyptians would gain methanol through the pyrolysis, earning it
the moniker of wood alcohol (Odasaboglu et al., 2005).
Methanol was later heralded as the future transportation fuel in the 1980s.
Major corporations have positioned themselves to profit from the next wave. Ford
collaborated with the California Department of Transportation's Alternative and
Renewable Fuel and Vehicle program to operate methanol-powered vehicles in a 15-
year experiment. ARCO developed the Los Angeles fueling stations. Then, additional
oil firms added more fueling stations, resulting in the formation of a methanol corridor.
Other automakers followed suit, producing flex fuel vehicles that could run on either
2
methanol or gasoline. Eventually, 5,000 automobiles were using clean motor fuel in
that route. From a technical sense, the demonstration was a success (Bechtold et al.,
2007).
However, commercially, it stagnated. Methanol costs were almost the same as

gasoline prices at the time. There was no incentive for motorists to switch fuels, and
there was little campaigning to persuade them. So, after failing to become the preferred
oxygenate for vehicle fuels, methanol gave way to its lower octane relative, ethanol.
Due to the recent push for renewable energy however, methanol-based fuel is making
a resurgence, particularly in China and Israel.
1.2.2 Physical and Chemical Properties of Methanol
Methanol, CH3-OH, is a colorless, somewhat volatile liquid with a mildly

sweet pungent odor that is comparable to, but slightly milder and sweeter than, ethanol.
Because of the relationship between a methyl (–CH3) group and a hydroxyl group (–
OH) in its chemical structure, it is also known as MeOH, where Me stands for Methyl
(Biology Dictionary, 2017).
Table 1.1 Properties of Methanol
Properties Values
Chemical Formula CH OH
3
Molar Mass 32.04 g/mol
Melting Point - 97.6 °C
Boiling Point - 64.7 °C
Thermal Conductivity 0.202 W/m °C
Heat of Formation - 6398 kJ/kg
Heat of Evaporation 1165 kJ/kg
Density (gas) at 0.17 bar 0.220 kg/m3
3
Density (liquid) 786.3 kg/m3
Refractive Index 1.328 at 20 °C
Critical Pressure 82.2 bar (81.1 atm)
Critical Temperature 240.2 °C
Magnetic Susceptibility 5.3×10−7 cm3·g−1
Dielectric Constant 32.70
Flashpoint 11 °C
Autoignition Point 464 °C
The Lower Limit of Flammability 6% by volume of air
1.2.3 Application of Methanol
In terms of applications, Methanol is fairly versatile. Because of its efficiency

as an energy carrier, it is increasingly being employed as a fuel in industrial and power
generation. Methanol has enormous promise as an ecologically friendly fuel source,
and global demand for it as a promising resource for a new era of clean energy is
developing.
Methanol is a kind of alcohol that is mostly derived from biogas. Methanol

may be used as an intermediate material to make literally hundreds of methanol and
methanol derivative products that are used in practically every aspect of our lives by
mixing it with these substances (Dalena et al., 2018). It is a component of acetic acid
and formaldehyde and both are utilized as vital ingredients in the construction industry.
Certain pharmaceuticals have also made use of methanol as a chemical agent.
Methanol has grown prevalent in our lives and across society as a result of its diverse
applications.
4
Figure 1.3 Uses of Methanol (Data for 2015, from IHS Markit, 2015)
Methanol as a fuel is a promising alternative to traditional vehicle fuel (Schultz

et al., 2001). Methanol burns cleaner and more effectively than gasoline, creating less
carbon monoxide and NOx. It is not necessary to drill for it. It can be created from
biomass and, until that is accessible in sufficient quantities, from abundant coal and
natural gas. On the other hand, because of its low energy density, it takes more
methanol to travel the same distance as a gallon of gasoline. In addition, infrastructure
for gasoline delivery and pumps would need to be built.
In relation to the prevention of the Covid-19 pandemic, the use of methanol as

a chemical feedstock cannot be overlooked. Methanol is a base material in the
formation of formalin, otherwise known as formaldehyde. Although formaldehyde is
best recognised for its use in creating a wide range of value-added goods, it is also
well-known for its preservative and antibacterial qualities (Ong et al., 2010).
Formaldehyde has a long history of having been used in the production of viral and
bacterial vaccinations. It is used to inactivate viruses so that they do not cause disease
(for example, the polio virus used in polio vaccination) and to detoxify bacterial toxins
(for example, the toxin used in diphtheria vaccine). With the outbreak of the Covid-19
virus, the demand for formalin has risen, and in turn the demand for methanol.
5
1.2.4 Background of Biogas
Biogas is an environmentally friendly, clean, renewable energy source. It is

formed when bacteria decompose organic materials like food or animal dung in the
absence of oxygen, a process known as anaerobic digestion. To do this, the waste must
be confined in an oxygen-free environment. It can happen naturally or as part of an
industrial process to create biogas for use as a fuel (Weiland, 2010). Agricultural
waste, municipal trash, plant debris, sewage, and food or crop waste are all sources of
biogas.
Biogas is produced as a result of anaerobic decomposition of biomass, which

happens when anaerobic bacteria eat and digest biomass. Anaerobic bacteria are found
in soils, bodies of water such as swamps and lakes, as well as human and animal
digestive systems. Municipal solid waste dumps and animal manure holding ponds can
be used to generate biogas. Anaerobic digesters, which are specialized tanks, may also
create biogas under regulated circumstances. Digestate is the byproduct of anaerobic
digestion; it is high in nutrients and may be utilized as fertilizer.
Municipal solid waste landfills are a source of biogas (Manna et al., 1999).
Landfill gas is generated naturally by anaerobic microorganisms in municipal solid
waste dumps. Because methane is combustible, landfill gas with a high methane
concentration can be hazardous to humans and the environment. Methane is a potent
greenhouse gas as well. In low quantities, biogas includes hydrogen sulfide, an
unpleasant and possibly poisonous chemical.
The composition of biogas is determined by a variety of factors, including the

process design and the type of the substrate processed. The presence of nitrogen in
landfill gas is a distinguishing trait. Biogas in itself is mostly composed of methane
(CH4) and carbon dioxide (CO2). Biogas can also contain trace amounts of other
gases, but it can otherwise be used directly or be treated to remove them. Treated
biogas can alternatively be referred to as renewable natural gas or biomethane.
6
Table 1.2 Comparison of Biogas and Natural Gas
Biogas Natural Gas
Definition A gas that arises A naturally occurring gas

spontaneously as a result of formed by the decomposition of
the decomposition of raw fossils.
organic material.
Sources There are natural biogas Natural gas cannot be

sources. manufactured, it has a restricted
number of natural sources.
Sustainability Biogas is a renewable energy Natural gas is a nonrenewable

source. energy source.
Raw Sources of raw organic Natural gas comes from layers of

Material material, such as agricultural, organic material decomposed
municipal, and biowaste. under the earth, making it a
fossil fuel.
Formation Anaerobic digestion of organic Natural gas is generated by

materials produces biogas. geological processes that break
down biological substances.
Composition Biogas is mostly composed of Methane and basic alkanes make

methane and carbon dioxide. up natural gas. Trace amounts of
Trace levels of hydrogen carbon dioxide, nitrogen,
sulfide, nitrogen, and carbon hydrogen, and sulfide can also
monoxide are present. be found in its composition.
In the scope of sustainability, natural gas is limited due to its dependence on a

finite resource. As the population grows, the consumption of energy will keep
increasing. This limitation is not shared by biogas, as biogas is formed from the
breakdown of natural organic waste. Biogas can even be produced from the waste of
said growing population, contributing to its cheaper price in the long-term as fossil
fuels run out. By using material that already exists and would otherwise go to waste,
landfills and digesters supply a similar fuel without the environmental impact of
fracking.
7
1.2.5 Physical Properties of Biogas
Methane and carbon dioxide are the most common components of biogas.
Methane, the main component of natural gas, is used as a feedstock in the chemical
industry. Methane (CH4) is a colorless and odorless gas. The vapors have a lower
density than air. Methane burns quickly. If containers are subjected to fire or severe
heat for a lengthy period of time, they may break violently and rocket.
Table 1.3 Properties of Methane
Properties Values
Chemical Formula CH₄
Melting Point -182.5 °C
Boiling Point -161.50 °C
Thermal Conductivity 0.0339 W/m°C
Heat of Evaporation 511 kJ/kg
Density (gas) 0.657 kg/m3
Density (liquid), at - 162°C 422.6 kg/m3
Refractive Index 1.000444
Critical Pressure 45.99 bar (45.39 atm)
Critical Temperature - 82.59 °C
Magnetic Susceptibility −17.4×10 cm /mol

−6 3
Dielectric Constant 1.68 ε at −182 °C
Flashpoint - 188 °C
Autoignition Point 537 °C
The Lower Limit of Flammability 4.4% by volume of air
8
Carbon dioxide, or CO2, is a colorless and odorless gas. It is harmless and
noncombustible, although it is heavier than air and may cause asphyxiation due to air
displacement. Mild carbonic acid is generated when CO2 is dissolved with water. Dry
ice is solidified CO2 that has been cooled.
Table 1.4 Properties of Carbon Dioxide
Properties Values
Chemical Formula CO₂
Melting Point - 56.65 °C
Boiling Point (Sublimation Point) - 78.464 °C
Thermal Conductivity 0.01663
Heat of Evaporation, at 15 °C 379.5 kJ/kg
Density 1.795 kg/m3
Refractive Index 1.000449 at 589.3 nm and 0 °C
Critical Pressure 73.8 Bar (72.8 atm)
Critical Temperature 30.98 °C
Magnetic Susceptibility N/A
Dielectric Constant 1.45 ε at 22 °C
1.2.6 Safety Information of Methanol and Biogas
We place a high priority on safety procedures when handling both our product
and raw materials. We have presented the information below in the interest of safety
to safeguard the safety and health of our staff while working in the facility.
9
Table 1.5 NFPA Diamond Rating for Methanol and Biogas Components
Hazard Rating Description
NFPA Health Hazard: 1 - Can cause significant irritation.
NFPA Flammability Hazard: 3 - Can be ignited under almost all

ambient temperature conditions.
Methanol
NFPA Instability Hazard: 0 - Normally stable, even under fire
conditions.
NFPA Health: 2 - Can cause temporary incapacitation or residual

injury.
NFPA Flammability: 4 - Ignites with ease. At atmospheric

Methane pressure and typical ambient temperature, it vaporizes quickly or
entirely.
NFPA Instability: 0 - Normally stable, even under fire

conditions.
NFPA Health Hazard: 2
NFPA Flammability Hazard: 0
Carbon NFPA Instability Hazard: 0

Dioxide
NFPA Special - Asphyxiant (reduces oxygen available for
breathing).
As for methane, it is recommended for the methane containers to be isolated

from any material that would set it aflame. Not only is it easily ignited but the
prolonged exposure to fire or intense heat could cause the methane to rupture violently
and cause an explosion. It should also be isolated from powerful oxidizers such as
iodine because they can cause it to violently react and explode. Workers must be
forbidden from smoking while handling or nearby any methane. Areas used for storing
the raw material (such as a livestock manure pile) should be properly ventilated as high
concentrations can cause asphyxiation. If the area is somehow closed off, safety gear
such as goggles and a breathing mask are required to enter it safely. In the event of an
emergency leak, the area should be immediately evacuated and isolated. Fires should
be put out with CO2 if they are small and water sprays if they are big. Unaffected
containers in the area can be moved as long as it poses no risk.
10
Carbon dioxide might usually be present around us, but it is best to ensure
sufficient ventilation as a CO2 leak in a closed-off area could potentially asphyxiate
the people inside. To that end, it is best to ensure there is no leak in the first place and
that the cylinder valve is closed. The escape of lingering CO2 gas can be prevented by
fully closing the cylinder valve before disconnecting any hoses. Failure to properly
ventilate the area can cause suffocation and even death as the CO2 reduces the oxygen
available to breathe. Transportation of the CO2 tanks should use carts specifically
designed to handle them, and the tanks should always be kept upright. Containers
should be stored in a well-ventilated area, away from sources of high heat as well as
anything electrical. They should be properly secured at all times. In the event of an
emergency, do not enter the exposed area especially if it contains extremely
concentrated levels of CO2. If there are any individuals trapped in the enclosed area,
do not attempt to recover them and wait for emergency responders to do so instead.
1.3 Sustainable Justification
The positive and negative impact of biogas and methanol in terms of safety
factor, environment and economy is revised and discussed in this section.
1.3.1 Pros and Cons of Biogas
Biogas is used as the feedstock for the production of methanol. Biogas is

produced from biomass through anaerobic digestion, where the process is mainly
composed of methane and carbon dioxide (Deublein & Steinhauser, 2008).
11
Figure 1.4 Anaerobic Digestion Process
Food wastes, animal manure, wastewater, and crop residue are some of the
organic materials used for biogas. Methane and carbon dioxide are released during the
decomposition of organic matter. Biogas contains about 50% to 70% methane, 30% to
40% carbon dioxide, and other gases (Lima et al., 2017). Based on Figure 1.4, biogas
can be used to produce heat and electricity for engines, microturbines and fuel.
1.3.1.1 Benefits of Biogas to Environment
Biogas has some of its own benefits mainly to the environment. Recently, an
increase in global warming has become a worrying issue all around the world. Fuel
prices have also increased and therefore the development of sustainable energy is much
needed these days. Today, renewable resources are more demanded compared to fossil
fuels due to lower greenhouse gas emission (Paepatung et al., 2009). The carbon
dioxide concentration during the pre-industrial era was around 280ppm. Currently, the
concentration of carbon dioxide in the atmosphere is higher by over 100 ppm (Saeidi
et al., 2014; Abdelaziz et al., 2017). Kyoto Protocol imposed the European Union and
some other 37 industrial nations to decrease their emissions on average to a level of
5.2% in order to decrease global warming (Helm, 2014; Abdelaziz et al., 2017). Thus,
this explains why the demand for biogas is high.
12
Biogas is a renewable fuel and does not cause global warming unlike fossil
fuel. The greenhouse gas emission is lower too (IEA Bioenergy, 2020). Stored biogas
limits the amount of methane released into the atmosphere and reduces dependence on
fossil fuels. Compressed natural gas derived from biogas reduces greenhouse gas
emissions by up to 91 percent relative to petroleum gasoline (Environmental and
Energy Study Institute, 2017).
The release of landfill gas (LFG) to the environment can also be reduced
through the usage of biogas. Anaerobic digestion requires bacteria from landfills to
produce biogas. Instead of allowing LFG to escape into the atmosphere, it can be
collected and used as energy to produce biogas. During these times, the United States
produces roughly 17 billion KW/hr of electricity. They provide about 98 billion cubic
feet of LFG to the pipelines of natural gas or directly to the end-user industry
(Environmental and Energy Study Institute, 2017).
1.3.1.2 Benefits of Biogas In Term of Economics
The technology used to produce biogas is reasonably cheap, easy to set up and
operate, and requires lesser investment of work and time. We can produce biogas from
houses itself, using kitchen waste and animal manure. Then, the gas obtained can be
used directly for cooking and electricity (HomeBiogas, 2020). Farms can obtain biogas
by their livestock and they can also convert the biogas to supply electricity and heat to
their farm. The manure of one cow can be used to light a lightbulb for an entire day.
Biogas can be compressed to produce good quality natural gas and to be used to power
automobiles. As mentioned earlier, biogas plants require low investment and are
environmentally friendly. For example, in India, many jobs involving the collection of
waste and converting it to biogas is done each year mostly in rural areas (Energypedia,
2021).
13
Figure 1.5 The Production and Application of Biogas (Bilal Abderezzak, 2017).
1.3.1.3 Negative Impact of Biogas Economically
Biogas also has its disadvantages. In today's time, there is not complete
advancement in the production of biogas. There are no new technologies yet that can
make the production of biogas more abundant and affordable. This is why biogas
cannot be supplied in a large population (Home Biogas,2020). Additional research is
needed to develop new technology and make the production more efficient.
Governments provide more support on established energy sources such as solar,
geothermal, wind, and hydropower instead of biogas. Most governments are not ready
to invest their time and money into biogas production (Energypedia, 2021).
The main disadvantage of biogas plants is that they are temperature sensitive.
Anaerobic digestion requires bacteria that can only function in a specific temperature.
Anaerobic bacteria can only perform fermentation at an optimum temperature of 37℃.
Therefore, during cold weather conditions, external heat supply is needed for the
digester to continue production (Linquip, 2020). This is why certain cold countries do
not have biogas plants.
14
The production of biogas contains impurities at the final stage of digestion. At
the final stage, the gases are refined and compressed but still contain a certain amount
of impurities. These impurities make biogas an inappropriate option for powering the
vehicles because they can ruin or corrode certain parts of the engine. This corrosion
would lead to increased maintenance costs. Therefore, this biofuel is mainly a suitable
source of energy for stoves and lamps (Linquip, 2020).
1.3.2 Pros and Cons of Methanol
Methanol (CH3OH), also known as methyl alcohol or wood alcohol, consists

of methyl group (CH3), linked with hydroxyl group (OH). Methanol is produced from
syngas, a mixture of hydrogen and carbon dioxide derived from biomass (Britannica,
2019). Methanol is an important and primary chemical used in chemical synthesis. It
is used as solvent and as feedstock for the production of a vast number of chemicals
(Chen et al., 2011). It can be used as synthetic dyestuffs, resins, pharmaceuticals, and
perfumes.
1.3.2.1 Benefits of Methanol in Pharmaceutical
Methanol plays an important role in the pharmaceutical industry. It is used as

a solvent in the manufacture of cholesterol, streptomycin, vitamins, hormones, and
other pharmaceuticals. Methanol is the feed in most chemical industries which is used
to produce various chemical products and materials such as, formaldehyde, methyl
tert-butyl ether and acetic acid. It is also a starting material for chloromethanes,
methylamines, methyl methacrylate and dimethyl terephthalate (Olah et al., 2009).
15
1.3.2.2 Methanol Usage as Fuels
Recently, methanol is primarily used as an alternative fuel in automobiles. It is

combined with dimethyl ether to produce high quality fuel (Hoseiny et al., 2016).
Methanol is a clear-burning alternative source of energy. It is a carbon-neutral free
fuel. Thus, methanol can only be produced from renewable sources such as biomass,
wind along with carbon captured from power plants or taken directly from air (Nils
Linstrad, 2019). There are no greenhouse gas emissions, mainly nitrogen oxide into
the atmosphere. Methanol can function independently as a fuel for automobiles or even
mixed directly into gasoline to produce a high-octane, efficient fuel which is
environmentally friendly. China widely uses vehicles that operate using methanol and
this is also introduced in other countries (Methanex, 2020).
Methanol is an emerging fuel for electricity generation. During hot days,

electricity demand is high, where turbine engines are often used as peak generators to
increase the electric grid’s capacity (Britannica, 2019). Methanol is used as a fuel for
these generators and it is highly preferred due to its environmentally friendly
performance. Minimum modifications and development are only needed to adapt
existing power plants and associated infrastructure to accommodate the use of
methanol as a fuel for power (Methanol Institute, 2016). Methanol’s low heating value,
low lubricity, and low flash point make it an efficient turbine fuel compared to fossil
fuels (Methanex, 2020).
1.3.2.3 Benefits of Methanol to the Environment
Methanol is biodegradable in both aerobic and anaerobic environments, with a

shorter half-life compared to benzene which takes a few hundreds of days. A report
prepared by the environmental consulting firm Malcolm Pirnie made a conclusion
saying that compared to gasoline and diesel fuel, methanol is safer for the environment
(Methanol fuels, 2017).
16
Methanol is also used to produce olefins. This process is known as the MTO
process. The olefins can be reacted to produce polyolefins, which are used to make
many plastic materials from natural gas. In recent years, methanol and olefins have
increased in demand. The methanol-to-olefin process has high cost competition
compared to the use of naphtha. The demand for MTO is said to be increasing in
upcoming years in China. (Methanex, 2020).
Figure 1.6 The overall application of Methanol (Rajesh, 2021).
1.3.2.4 Disadvantages of Methanol
Methanol also has its disadvantages mostly to human health. Methanol is a

toxic and highly flammable alcohol. Methanol is extremely toxic to humans if ingested
or if vapors are inhaled. Products that contain methanol include windshield washer
fluid, gas line antifreeze, carburetor cleaner, copy machine fluid, perfumes, food
warming fuel, and other types of fuels. Most of them are household products and thus
must be properly stored and only be handled by trained people (Methanol Institute,
2016). Direct exposure to methanol should be avoided, as methanol can be harmful if
swallowed, absorbed through the skin, or inhaled. Even if methanol is ingested into
our body in a small amount, it can affect the nervous system. Methanol is poisonous
and can damage the optic nerve and the central nervous system (CNS). Methanol can
17
also degrease the skin, which may cause dermatitis. Continuous methanol exposure
can cause headache, body weakness, dizziness, nausea and breathing difficulties. It
can also cause death to certain people. Patients may improve and then get worse again
up to 30 hours later (Ashurst, 2021).
1.3.3 Circular Economy and Carbon Footprint
Based on the benefits of biogas, we know that it is a renewable source of energy

that can reduce the carbon footprint in the environment. Carbon footprint is the total
amount of greenhouse gases released into the atmosphere from a plant. Since biogas
is a form of natural gas, it is absolutely environmentally friendly. Based on research
done, we can strongly prove that biogas is safer and sustainably effective than fossil
fuels. It releases zero net carbon to the atmosphere and becomes a high demand among
other countries due to its low emissions.
Carbon dioxide and carbon monoxide are produced in the methanol synthesis
but then they are recycled back to the reactor instead of releasing it to the atmosphere.
Thus, the circular economy is achieved by recycling the carbon dioxide and carbon
monoxide which creates a closed - loop system which can minimize resource input,
pollution and carbon emission.
1.4 Market Survey of Methanol
1.4.1 Global Demand and Supply of Methanol
Methanol industry is vastly growing around the world, mainly in Asia, North
and South America, Europe, Africa and the Middle East. Currently, methanol has been
a focus of development primarily in the Asia-Pacific Region. China happens to lead
the world in both methanol production as well as consumption (Yang et al., 2012).
There are over 90 methanol plants worldwide, with a combined production capacity of
18
about 110 million metric tons. Global methanol demand reached 75 million metric tons
in 2015. Each day, nearly 200,000 tons of methanol is used as a chemical feedstock or
as a transportation fuel. That’s enough methanol every day to fill nearly 7,500 tanker
trucks stretching end-to-end for 63 miles or 100 kilometers. Figure 1.7 below shows
the supply and demand of methanol from 2016 to 2021, but the data for 2021 has not
been finalized yet (Methanol Institute, 2021).
Figure 1.7 The Global Methanol Supply and Demand Chart (Methanol Institute,
2021).
Table 1.6 Methanol Derivatives and The End-User Industry (Mordor

Intelligence, 2020).
Derivatives End-user Industry
Formaldehyde Direct end-user Indirect end-user

Methanol-to-olefins (MTO)/Methanol-to- Automotive Construction
Propylene (MTP)
Methyl Tert-butyl Ether (MTBE)/Tertiary Paints and Packaging

Amyl Methyl Ether (TAME) Coatings
19
Dimethyl Terephthalate (DMT) Pharmaceuticals Electrical and
Electronics
Acetic Acid Agriculture others
Table 1.7 Geography Demand of Methanol (Mordor Intelligence, 2020).
Geography
Asia-Pacific North America Europe South America Middle-East

Africa
China United States Germany Brazil Saudi Arabia
India Canada United Argentina South Africa

Kingdom
Japan Mexico Italy Rest of South Rest of middle-

America east Africa
South Korea Rest of North France

America
Rest of Asia- Rest of

Pacific Europe
Based on Table 1.6 and Table 1.7, the demand of methanol is categorised
based on derivatives, end-user industry, and geography. The main factor that impacts
the rise of methanol demand is due to methanol-based fuel. Methanol is more preferred
as an alternative fuel compared to gasoline because it reduces carbon monoxide,
nitrogen oxides, and hydrocarbon emissions. This is why methanol is used as an
alternative in major economic countries of North America and Europe (Mordor
Formaldehyde is the highest demand of derivatives from methanol. Its

application is used in urea, phenol, melamine-formaldehyde resins (UF, PF, and MF
resins), polyacetal resins, pentaerythritol, methylenebis(4-phenyl isocyanate) (MDI),
1,4-butanediol (BDO), and hexamethylenetetramine (HMTA).
20
Figure 1.8 The Methanol Market for Derivatives in the Year 2020 (Mordor
1.4.2 Covid-19 Impact on Methanol Demand and Supply
Suppliers such as Celanese Corporation (Texas), BASF SE (Germany),

Methanex Corporation (Canada), SABIC (Saudi Arabia), PETRONAS (Malaysia),
Mitsubishi Gas Chemical Company (Japan), and Mitsui & Co., Ltd. (Japan) faced a
downtime during the pandemic. These suppliers manufacture methanol in various
countries such as Asia Pacific, Europe, North America, South America and Middle
East and Africa. During the pandemic, these suppliers undergo lower production rates
due to the lowered demand and supply chain bottlenecks. Some even had to shut down
their factories for the sake of their employees' safety. As a result, there is a decline in
the demand for methanol in the supply chain (Methanol Market, 2020).
1.4.3 Methanol Market in Malaysia
In Malaysia, methanol industry production consists only 3 percent of the

overall production of the Asia- Pacific region. The demand is expected to increase in
21
the coming years due to a healthy demand from the formaldehyde-based resin and
automobile fuel sector. The growth in demand for methanol in Malaysia is expected to
be at the rate of five percent during the forecast period, and the majority of domestic
demand would be fulfilled by imports (Methanol Industry In Malaysia, 2021).
Malaysia Methanol market demand stood at 966 thousand tonnes in 2020 and is
forecast to reach 1664.13 thousand tonnes by 2030, growing at a healthy CAGR of
5.09% until 2030 (Malaysia Methanol Market Analysis, 2021). Basically, the
formaldehyde sector was mainly having a demand on Malaysia’s methanol market.
The methanol market in Malaysia is highly consolidated, with only one player,
PETRONAS (Methanol Industry In Malaysia, 2021). Petronas accounted for 100% of
the installed capacity in the region during 2011. The domestic demand was fulfilled
by in-house production, and the majority of in-house production was exported to Japan
and China (Methanol Industry In Malaysia, 2021). However, Sarawak Petchem Sdn.
Bhd. A company of oil and gas firm that was owned by Malaysia’s Sarawak state
government has let a contract to a division of Air Liquide SA to license process
technology for a grassroots methanol plant which is still under development and
located at Bintulu, Sarawak. As part of the June 7 contract, Air Liquide Engineering
& Construction will deliver licensing of its proprietary Lurgi Mega Methanol
technology for the planned 5,000-tonne/day (1.7-million tonne/year) methanol plant,
Air Liquide said (Robert, 2021).
22
Figure 1.9 Sarawak Petchem's Methanol Project Located at Bintulu (Robert,
2021).
This company is most probably based on derivation of natural gas. However,

the exact details were still to be disclosed. Thus, our company, on the other hand, can
have a good competition with them. It is because our feedstock is renewable energy
which can be sustained for a long-term.
1.4.4 Market Price of Methanol
The global methanol market size was estimated to be USD 38.9 billion in 2018
and is forecasted to grow at a CAGR of 9.8 % from 2019 to 2026. (Methanol Market
Share, 2018). Based on the chart on figure 2, it can be seen that the global methanol
capacity in the market witnessing moderate growth that owing to increasing
application, technological advancements and growing demand for this methanol in The
Asia Pacific mostly and other such as North America, Europe, CSA and Middle East
Asia (MEA).
23
Figure 1.10 Global Methanol demand by Region (Methanol Market Share, 2018).
1.5 General Site Consideration
Properly in considering site selection is one of the major factors for the
effectiveness of one chemical. There are actually lots of criteria to be considered before
choosing a proper site. Based on study by (Sinnott, n.d,), the criteria example can be
categorized as a marketing area, raw material supply, transport facilities, availability
of labour, availability of utilities such as water, fuel and power, availability of suitable
land, environmental effect including effluent disposal, local community
considerations, climate and also political and strategic considerations.
First and foremost, the location chosen must be easily accessed in terms of
marketing. If the plant produces high-volume and low-cost products, such as cement
and fertilizer, it may be better to situate the plant closer to the primary market since
transportation cost is a large fraction of the sales price (Ellen, 2016). However, if the
product is different from that, the benefits of being closer to the primary market may
not be there. The raw material supply is also a major consideration before choosing
the plant site since the facilities that produce chemicals in bulk need to be near to the
source of the raw material.
24
Next, we also need to consider the transport facility. At least two major
transport facilities need to be near to the site such as transport by road or transport by
railway. This can make the raw material easily transported to the site. Availability of
labour is also important to be considered. Imagine having a good plant design but lack
of technical labour at the site. That is why there should be a local pool of unskilled
labor that can be trained to operate the plant, and of skilled craft workers to maintain
the process units (Ellen, 2016). We should also consider the local labour laws, trade
union customs and restrictive practices for recruitment and training.
Another consideration is of course the utilities supplied. In order to operate a

plant, it requires a vast amount of electricity and also fuel and power. Water is also
important for cooling or maybe for cleaning any materials used. Other than that is the
availability of the suitable land. considerations have to be made if the land is reclaimed
land near the ocean in earthquake zones (Ellen, 2016). Since property taxes vary area
to area, it is also a factor when choosing a site. Also avoid building a plant near the
residential area as it can affect the life of people living nearby by the sound of the
machine and also the chemicals released from the plant.
Finally, consider the environment and also the climate at the site since some
climate may affect the process itself and also the cost. The location also sometimes
becomes difficult in terms of waste disposing and high cost. Last but not least are the
political and strategic considerations. Sometimes, the government will provide the
plant with capital grants, tax concessions and other incentives to encourage the plant
to be built in certain areas. Physical assistance such as roads, water, and other public
infrastructure are more popular than financial assistance (Ellen, 2016). With
preferential tariff agreements, the company can also globalize and take advantage of
areas. Basically, these are some of the considerations before considering any site for
our designated chemical plant.
25
1.5.1 Comparisons Between Potential Locations
Plant location is considered based on the industrial area located in Malaysia.

The area that was chosen has been compared with each in terms of some important
factors. The locations are as below:
(a) Megah Industrial Park, Tawau, Sabah
(b) Taman Sri Kluang, Johor
(c) Kawasan Perindustrian Semambu, Kuantan, Pahang
The factors are rated from 0 to 2, which indicates least favourable (0),
favourable (1) and most favourable (2).
26
Table 1.8 Comparison Between Three Different Sites
Megah Industrial Park, Tawau, Kawasan Perindustrian

Location Taman Sri Kluang, Johor
Sabah Semambu,Kuantan, Pahang
Kalabakan Palm Oil Mill, Tawau, Felda Kahang Palm Oil Mill, Kilang Bukit Sagu, Kuantan,
Raw Material Availability Sabah- 91.8 km Kluang, Johor- 41.6 km Pahang- 33.4 km
1 2 2
• Jangdah Garment
Industries Sdn Bhd
• Asta Chemical Sdn Bhd
• Pioneer Osb Sdn Bhd
• Asta Chemical Sdn Bhd • TS Maritime Sdn Bhd
• Nippon Paint Sdn Bhd
Market Target • TS Maritime Sdn Bhd • Songsang Plywood (M)
• Jotun Paints Malaysia Sdn.
Sdn Bhd
Bhd.
1 2 2
27
Tenaga Nasional Berhad (TNB) Tenaga Nasional Berhad (TNB) Tenaga Nasional Berhad (TNB)
Peak Period: 33.70 sen/kWh Peak Period: 33.70 sen/kWh Peak Period: 33.70 sen/kWh
Electric Supply Off-peak period: 20.20 sen/kWh Off-peak period: 20.20 sen/kWh Off-peak period:20.20 sen/kWh
2 2 2
Syarikat Air Pahang Berhad
Syarikat Air Johor (50 Km)
Jabatan Air Tawau (6.5Km) (13.6 Km)
0m3 – 35m3: RM 2.80
0m3-70m3: RM1.60 0m3-20m3: RM0.57
Water Supply >35m3: Rm3.00
>70m3: RM 2.00 21m3-35m3: RM1.03
>35m3: RM 2.00
2 0 1
• Road: Jalan Air Putih

• Highway: Jalan Tiku,
• Mersing Road,Kluang, (2.8 Km) (5 min)
Tawau, Sabah (10.3 Km)
Johor (7.4 Km)(10 min) • Seaway: Pelabuhan
(14 min)
• KTM Mengkibol, Kluang, Kuantan (25.4km) (26
• Seaway: Pelabuhan Tawau,
Transport Facility Johor (7.5 Km) (10 min) min)
Sabah (11 Km) (16 min)
• Airway: Kluang Airstrip • Airway: Sultan Ahmad
• Airway: Tawau Airport,
(4.8 Km) (9 min) Shah Airport (20 Km)
Sabah (31.9 km) (38 min)
(21min)
0 2 1
28
Labour Availability
The labour is available because The labour is available because The labour is available because
near to the industrial area. near to the industrial area. near to the industrial area.
2 2 2
• Average temperature
• Average temperature 23˚C • Average temperature 23˚C 21˚C -33˚C (November)
- 31˚C -32˚C (November) • Max wind speed
Climate (November) • Max wind speed (6km/h) (3km/h)
• Max wind speed (7km/h) • 195.11 mm rainfall • 378.70 mm rainfall
• 2276 mm rainfall annually annually annually
1 2 2
Government Support • Green Investment Tax Allowance (GITA)
• Green Income Tax Exemption (GITE)
• Incentives for Waste Eco Parks (WEP)
• Import Duty Exemption
2
Total Score 13 14 15
29
We have considered three potential location areas to build the chemical plant.
Some factors were rated based on how it can fulfil the criteria to benefit the plant. All
information has been tabulated as well as rated based on the suitable criteria between
the range of 0 to 2. The bad one will be 0 and the good one will be 2. The final total
number with the highest number will be chosen as the final decision on where to build
the plant. Several choices were listed based on the suitability of location of the
petrochemical industry in Malaysia. The three choices listed are located at Megah
Industrial Park, Tawau, Sabah, Taman Sri Kluang, Johor and also Kawasan
Perindustrian Semambu, Kuantan, Pahang.
The raw material availability, market target, land availability and price,
transport facilities, utilities, labour availability and climate are the factors that need to
be considered as to do comparison on where the chemical plant should be built. Based
on the listed criteria in the table, it can be said that the raw materials were the most
important criteria to decide the plant location but of course other criterias are important
as well. The availability of the feedstock is important because if the product cannot be
manufactured there will be no point in building the plant site. The Biogas plant is
located within a palm oil plantation, and the biogas is produced by the process of
anaerobic digestion using palm oil mill effluent as the raw material. The location that
is nearest to the site location is Kawasan Perindustrian Semambu, Kuantan, Pahang
following with Taman Sri Kluang, Johor and lastly Megah Industrial Park, Tawau,
Sabah. That is how the 2, 2 and 1 come from based on the distance that needs to be
considered.
As for the market target, the location is not the main criteria that we consider
since methanol demand is not that high in Malaysia. However, to have a better
domestic market, we consider companies which really need methanol to manufacture
their products in Malaysia since based on our research, the demand of methanol in
Malaysia and worldwide will increase annually. So, the company that we target can be
said to have a huge need of methanol as their raw materials such as Asta Chemical
Sdn. Bhd., TS Maritime Sdn. Bhd., Jangdah Garment Industries Sdn. Bhd., Pioneer
Osb Sdn. Bhd., Nippon Paint Sdn. Bhd., Jotun Paints Malaysia Sdn. Bhd. and
Songsang Plywood (M) Sdn. Bhd.
30
The land availability on each location was obtained from the latest price and
sources on the market for all the three sites. The size of the land is enough to build the
plant, and there is space available for any expansion in future. For utilities which are
the electric and water supply, the rating is given based on the current price of each of
the utilities with their respective locations. Example, for the electric. Since we only
have one major electric resource in Malaysia which is Tenaga Nasional Berhad (TNB),
we will have to use its services to operate our plant in the manufacturing process.
Based on the current table, the current rate for their services is 33.70 sen per kilowatts
at the peak period and 20.20 sen per kilowatts at the Off- peak period. As for the water
supply, the rate was calculated based on the location of each power plant. For example,
Megah Industrial Park, Tawau, Sabah we have Jabatan Air Tawau with a water supply
rate of 0 m3 until 70 m3 that will cost us RM1.60 and more than 70 m³ will cost Rm
2.00. For Taman Sri Kluang, Johor, the water supply rate will be from Jabatan Air
Johor which will cost us RM 2.80 for 0 m³ until 35 m³ and RM 3.00 for more than 35
m³. Lastly, for Kawasan Perindustrian Semambu, Kuantan, Pahang, the rate of water
supply will come from Syarikat Air Pahang Berhad that will cost us RM 0.57 for 0 m³
until 20 m³, RM 1.03 for 21 m³ until 35 m³ and RM 2.00 for more than 35 m³. Based
on the overall utilities of electricity and water, we would say that everything can be
suited well in our plant operation although the prices may differ a bit. These were the
reasons why we could consider the rate as 2 for each respective plant site for utilities
of electricity. However, for the utilities of water supply, only Megah Industrial Park,
Tawau, Sabah and Kawasan Perindustrian Semambu,Kuantan, Pahang we rate as 2
while for Taman Sri Kluang, Johor we rate as 1 due to the distance from the water
supply to our plant site.
Meanwhile, in terms of transport facilities, all the places were rated based on
the accomodations and the distance and time needed from the palm oil to the plant site
as stated in the table. Kawasan Perindustrian Semambu,Kuantan, Pahang have the
nearest location to their respective raw materials place compared to Megah Industrial
Park, Tawau, Sabah and Taman Sri Kluang, Johor. Although in Kluang we got to have
the nearest accommodation for the distance and time needed for the worker to come to
the plant site or importing our products to the targeted market, we still consider on
Kawasan Perindustrian Semambu,Kuantan, Pahang because the distance is not that
31
much different from Taman Sri Kluang, Johor and what is the most important is the
distance between the raw materials and the plant site is the nearest compared to other
two plant site that we proposed. As for the labour availability, all three are available
since all of them are near to the industrial area. The availability that will be discussed
refers to potential meet to the man power required for the operation of the methanol
manufacturing plant. Due to the pandemic that hit the country, the number of
unemployed persons in Malaysia increased from 768,700 in June to 777,200 in July.
It increased about 1.2% between June and July, though the unemployment rate stayed
at 4.8%. This can be compared with July 2020 where the unemployment rate saw an
uptick of 0.1 percentage point from 4.7% based on the data provided by Department
of Statistics Malaysia (DOSM) (Mung, 2021). We believe that each state in Malaysia
was deeply impacted with the current scenario that we’ve been through so far. This
means that it is actually a good opportunity given that may help us to gather as much
manpower as we could for our plant construction as well as helping those unemployed
workers to be employed.
The next factor that needs to be considered is climate change. It is important

because Malaysia is a country that in one year will at least encounter humid and hot
weather as well as rain. In this part, we have considered several important parts such
as the minimum and maximum temperature with respect to each location we choose.
Also, the wind speed and the annual rainfall for each location. In order to manufacture
our raw material which is biogas to produce methanol, it is important to apply the
suitable temperature and pressure. The environment temperature plays their part as
well. So, it is important to study well on the location chosen to avoid the sudden change
in surrounding temperature that may affect the production of our product in general
and also can help us make any backup plan if the original plan went demolished. The
wind speed and the annual rainfall were solely to predict the probability of natural
disasters that may occur to our site such as tornadoes or maybe heavy floods. However,
based on the data collected, there is not much difference in the three of the locations
except for the annual rainfall at Tawau is the highest compared to at Kluang and
Kuantan. So, that is why we rate Tawau as 1 and other 2 as 2.
32
Last but not least is the government's support. As for this part, before building
our plant and operation, we will need a government permission by the governmental
policies of Malaysia if we use government land and not private land. The incentives
that will be covered by the government were based on the table. Government gave
investor lot of benefits such as Green Investment Tax Allowance (GITA) & Green
Income Tax Exemption (GITE) where from this incentive, government encourage on
investors that providing green technology services by 100% of qualifying capital
expenditure incurred on green technology project for 3 years from the date of first
qualifying capital expenditure (CAPEX) incurred (MIDA, 2021) and Green Income
Tax Exemption of 70% on statutory income for qualifying green service for the period
of 3 years. Meanwhile, for the waste management incentives, investor will get Pioneer
Status (PS) where investor will get exemption of 70% of the statutory income for a
period of 5 years and Investment Tax Allowance (ITA) where investors will get 60%
on the qualifying capital expenditure incurred within a period of 5 years to be offset
70% of the statutory income (MIDA, 2021). Apart from that, the government also
introduced the incentive of Waste Eco Park (WEP) to promote waste management in
a more integrated manner and investors can get an income tax exemption of 70%. For
import duty exemption, based on Malaysian Investment Development Authority
(MIDA), Companies in the selected industries which manufacture finished products
not subjected to sales tax can also benefit from tax exemption on imported or locally
sourced raw materials and components. Based on these overall criteria, our product
manufacturing really fulfilled the conditions needed to get these government support
based on the location as well as our manufacturing process.
In conclusion, the location which has the highest score among the three sites is
Kawasan Perindustrian Semambu,Kuantan, Pahang. Therefore, Kawasan
Perindustrian Semambu,Kuantan, Pahang is chosen to be the plant site to produce
methanol from biogas.
33
CHAPTER 2
PROCESS SYNTHESIS 1
2.1 Process Route 1: Catalytic Partial Oxidation of Methane
2.1.1 Process Description
Catalytic partial oxidation of methane involves the reaction of transforming

methane in biogas into synthesis gas (syngas) in a one-step reaction. The process can
be conducted at the atmospheric pressure and temperature of 400°C to 1000°C, using
oxygen as an oxidising agent. The product molar ratio of H₂/CO equals to 2 of the
catalytic partial oxidation process enables its direct utilization for methanol or Fisher-
Tropsch process without additional adjustment.
Catalytic partial oxidation is mildly exothermic, with heat of reaction of -36

kJ/mol. For methane partial oxidation to syngas, York, Xiao & Green (2003) suggests
a high temperature is advantageous for high methane conversion and selectivity to CO
and H₂. However, increasing the pressure in the reactor is unfavorable for CH₄
conversion and CO and H₂ selectivity. Apparently, under 1 bar at 800°C, theoretical
CH₄ conversion should be up to 80%, and selectivities to CO and H₂ are 97%. In
catalytic partial oxidation reaction, the noble metal (platinum, rhodium, iridium,
palladium) and non-noble metal (nickel, cobalt) catalyst plays an important role due
to the excessive temperature gradients at high conversion rate, the exothermic nature
of the reaction and fast deactivation due to carbon deposition on the catalyst's surface
(Galvan et al., 2019). According to a review from York et al. (2003), study from
Lunsford and colleagues shows that a nickel supported on alumina partial oxidation
system, with a temperature ranging from 447°C to 900°C, has a CO selectivity
approaching 95% and at 700°C could achieved a complete conversion of methane.
However, the amount of oxygen should be higher than the stoichiometric requirements
to achieve a sustainable stable operation. Therefore, nickel is selected because it is
35
readily available, inexpensive, and has a high initial catalytic activity. Nevertheless,
carbon deposition was likely to occur when involving synthesis gas.
The syngas produced from catalytic partial oxidation is then converted to

methanol via Fisher-Tropsch process or CO hydrogenation. The syngas-to-methanol
reaction is conventionally performed in a fixed-bed tubular reactor operating at 60 bar
to 100 bar and 250°C to 280°Cover a Cu/ZnO/Al₂O₃ catalyst (Giuliano, Freda &
Catizzone, 2020). The selectivity of methanol can achieve up to 99%. However, the
deactivation phenomenon is a typical problem for methanol synthesis catalysts.
Table 2.1 Advantages and Disadvantages for Process Route 1
Advantages Disadvantages
• External Heat or Heat • Operate at a very high

Exchange was not required in temperature
this process • Need to remove excessive heat
• Desulfurization of feedstock is • The exothermic nature of the
not necessary. reaction creates intense hot areas
• The process temperature can be with increased temperatures,
significantly lower with the which ignite a variety of CH4/O2
presence of a catalyst and mixtures.
enhance product selectivity. • There is a limitation of
• Can achieve high methane catalysts/oxygen carriers that are
conversion with excellent both efficient and stable while
hydrogen selectivity at being economically feasible.
relatively high space velocities. • Over oxidation may occur that
results in a local temperature rise
at the catalyst surface leading to
catalyst deactivation along with
small reduction in CO selectivity,
owing to its sintering and carbon
formation.
36
2.1.2 Chemical Reaction of Process Route 1
Table 2.2 Chemical Reaction for Process Route 1
1
1 Catalytic Partial Oxidation of Methane 𝐶𝐻4 + 𝑂2 ↔ 𝐶𝑂 + 2𝐻2
2
2 Fisher-Tropsch process 𝐶𝑂 + 2𝐻2 → 𝐶𝐻3 𝑂𝐻
1
3 Overall process 𝐶𝐻4 + 𝑂2 → 𝐶𝐻3 𝑂𝐻
2
Table 2.3 Side Reactions for Process Route 2
1 Total Oxidation of Methane 𝐶𝐻4 + 2𝑂2 ↔ 𝐶𝑂2 + 2𝐻2 𝑂
2 Partial Oxidation of Methane 𝐶𝐻4 + 𝑂2 → 𝐶𝑂2 + 2𝐻2
3 Water Gas Shift Reaction 𝐶𝑂 + 𝐻2 𝑂 ↔ 𝐶𝑂2 + 𝐻2
2.1.3 Gross Profit Margin Calculation for Process Route 1
Table 2.4 Gross Profit Margin for Process Route 1
Reactants Products
Chemicals
CH₄ O₂ CH₃OH
Stoichiometric ratio 1 1/2 1
Molecular weight
(kg/kmol) 16.04 16 32.04
37
Mass (kg) 16.04 8 32.04
kg/kg of Methanol 0.5006 0.2497 1
Price (RM/kg) 0.17 0.02 1.96
(1.96)(1) - [(0.5006)(0.17) + (0.02)(0.2497)]

Gross Profit
= RM 1.87/kg CH₃OH
2.2 Process Route 2: Dry Reforming of Methane
Dry reforming of methane (DRM) process uses two components in biogas

which are carbon dioxide and methane to produce synthesis gas (syngas) with a H₂/CO
ratio of 1.0. The syngas is then subsequently converted to methanol via the Fisher-
Tropsch process, which is similar to the partial oxidation reaction in process route 1.
Typically, DRM process is performed in temperature range of 600°C to 1000°C and
at 1 bar to 20 bar. DRM is an extremely endothermic reaction, with heat of reaction
equals to 247.3 kJ/mol. Therefore, to achieve the equilibrium conversion of syngas, a
reverse water gas shift reaction with heat of reaction of is required.
According to Jang et al. (2013), to achieve higher conversion, DRM should be

operated at a high temperature above 850℃ and low pressure. Therefore, it totally
depends on the type of catalyst used in this process. Several types of catalysts for the
DRM process have been documented, such as noble metals, spinels, perovskites,
hydrotalcite, pyrochlore, and supported base metals. Supported nickel is the most
suited catalyst for the DRM process from an industrial standpoint due to its availability
and inexpensive cost, although Ni-based catalysts are more sensitive to deactivation
for high temperature reactions than noble metal catalysts. The syngas produced from
dry reforming process will then converted to meth
38
• Environmentally friendly • High energy requirement (no
because of utilizing two largely reduced steam content is
greenhouse gases into methanol needed)
• The dry reforming of methane is • High susceptibility to coke
the most endothermically formation (solid carbon)
reaction that causes the CO2 • Large number of side reactions
oxidizing agent to be the most to produce undesired product
stable. • Low H₂/CO ratio which results
in low quality syngas
Table 2.6 Chemical Reaction for Process Route 2
1 Dry Reforming 𝐶𝐻4 + 𝐶𝑂2 ↔ 2𝐶𝑂 + 2𝐻2
2 Reverse Water Gas Shift 𝐶𝑂2 + 𝐻2 ↔ 𝐶𝑂 + 𝐻2 𝑂
3 Fisher-Tropsch process 𝐶𝑂 + 2𝐻2 → 𝐶𝐻3 𝑂𝐻
4 Overall process 𝐶𝐻4 + 2𝐶𝑂2 + 𝐻2 → 𝐶𝐻3 𝑂𝐻 + 2𝐶𝑂 + 𝐻2 𝑂
Table 2.7 Side Reactions for Process Route 2
1 Methane Cracking 𝐶𝐻4 ↔ 𝐶 + 2𝐻2
2 Boudouard Reaction 2𝐶𝑂 ↔ 𝐶 + 𝐶𝑂2
3 Coke Reforming 𝐶 + 𝐻2 𝑂 → 𝐶𝑂 + 𝐻2
39
4 Coke Oxidation 𝐶 + 𝑂2 → 𝐶𝑂2
5 Methanation 𝐶𝑂2 + 4𝐻2 → 𝐶𝐻4 + 2𝐻2 𝑂
Reactants Products
Chemicals
CH₄ CO₂ H₂ CH₃OH CO H₂O
Stoichiometric
ratio 1 2 1 1 2 1
Molecular weight
(kg/kmol) 16.04 44.01 1.01 32.04 28.01 18.02
Mass (kg) 16.04 88.02 1.01 32.04 56.02 18.02
kg/kg of
Methanol 0.5006 2.7472 0.0315 1 1.7484 0.5624
Price (RM/kg) 0.17 - 0.008 1.96 - 0.0028
[(1.96)(1) + (0.0028)(0.5624)] - [(0.5006)(0.17) +

Gross Profit
(0.008)(0.0315)] = RM 1.88/kg CH₃OH
40
2.3 Process Route 3: Steam Reforming of Methane
Steam reforming is used to convert methane in the biogas into synthesis gas
(syngas) through the reaction with water. The methane is contacted with steam over a
heated catalyst at high pressure and temperature to produce hydrogen rich syngas. with
a H₂/CO ratio of 3:1. The syngas is then converted to methanol through catalytic
hydrogenation of carbon dioxide and carbon monoxide.
The steam reforming process is highly endothermic, with a heat of reaction of

206 kJ/mol, requires operating temperature higher than 700°C. A steam-to-methane
ratio of 2.5 to 3.0 is required to reduce coke formation. The process typically occurs
at 900°C and 15 bar to achieve higher selectivity and yield (Ghosh et al., 2019).
According to a study done by Ali et al. (2016), by using Ni/SiO₂Al₂O₃ as catalyst, the
conversion of CH₄ in steam reforming can achieve 96% at the operating temperature
of 650°C to 900°C with the ratio of CH₄/H₂O equals to 1. The CO, CO₂ and H₂
produced from the steam reforming is then entering the methanol synthesis reactor to
produce methanol by Fisher-Tropsch process, which is same as process route 1 and 2.
• Produces highest yield of • Continuous supply of heat is
hydrogen which will be used in needed due to the large
the Fisher-Tropsch process endothermic reaction
• Good availability of steam • Higher carbon dioxide emission
• Oxygen is not required • High technical complexity for
• Commercially available the facilities because of the heat
transfer
41
Table 2.10 Chemical Reaction of Process Route 3
1 Steam Reforming 𝐶𝐻4 + 𝐻2 𝑂 ↔ 𝐶𝑂 + 3𝐻2
2 Fisher-Tropsch Process 𝐶𝑂 + 2𝐻2 → 𝐶𝐻3 𝑂𝐻
3 Overall process 𝐶𝐻4 + 𝐻2 𝑂 + 𝐻2 → 𝐶𝐻3 𝑂𝐻
Table 2.11 Side Reactions of Process Route 3
1 Water Gas Shift Reaction 𝐶𝑂 + 𝐻2 𝑂 ↔ 𝐶𝑂2 + 𝐻2
2 Reverse Water Gas Shift Reaction 𝐶𝑂2 + 𝐻2 ↔ 𝐶𝑂 + 𝐻2 𝑂
3 Hydrogenation of Carbon Dioxide 𝐶𝑂2 + 3𝐻2 → 𝐶𝐻3 𝑂𝐻 + 𝐻2 𝑂
Reactants Products
Chemicals
CH₄ H₂O H₂ CH₃OH
Stoichiometric
ratio 1 1 1 1
Molecular
weight 1.01
16.04 18.02 32.04
(kg/kmol)
Mass (kg) 16.04 18.02 1.01 32.04
42
kg/kg of
Methanol 0.5006 0.5624 0.0315 1
Price (RM/kg) 0.17 0.0028 0.008 1.96
(1.96)(1) - [(0.5006)(0.17) + (0.0028)(0.5624) + (0.008)(0.0315)]

Gross Profit
= RM 1.87/kg CH₃OH
2.4 Process Route Selection
2.4.1 Technology Comparison
Since the three process routes has similar reaction to convert syngas into
methanol by Fisher-Tropsch process, the technology comparison will mainly focus on
the production of syngas from biogas.
0 – Least favourable ; 1 – Favourable ; 2 – Most favourable
Table 2.13 Technology Comparison for Three Process Routes
Partial Dry Steam

Factors Composition
Oxidation Reforming Reforming
2 reaction 3 reaction 2 reaction

Reaction step 5% steps steps steps
2 1 2
CH₄ 80% 99% 96%

20%
Conversion 0 2 2
2:1 1:1 3:1

H₂/CO Ratio 20%
1 0 2
43
Operating 800°C 850°C 900°C
10%
Temperature 1 1 1
Operating 1 bar 14 bar 15 bar

10%
Pressure 2 1 1
Ni/Al₂O₃ Ni/Al₂O₃ Ni/SiO₂Al₂O₃

Catalyst 10%
2 2 2
C, CH₄, H₂,
H₂, CO₂, CO, H₂, CO₂, CO,
CO₂, CO,
By-product 10% H₂O H₂O
H₂O
2 0 2
RM 1.87/kg RM 1.88/kg RM 1.87/kg

Gross Profit 15%
2 2 2
Total Score 100% 65% 60% 90%
In order to produce methanol from biogas, comparisons were drawn and

detailed between three process route options. These were Catalytic Partial Oxidation,
Dry Reforming, and Steam Reforming. In order to select the most fitting process, the
process route was chosen based on the main criteria of economic viability as well as
environmental consciousness.
In terms of reaction steps, Dry Reforming is less ideal as it requires 3 reaction

steps compared to the other routes. Both Partial Oxidation and Steam reforming only
require 2 reaction steps in contrast. As for the conversion rate of methane, Partial
Oxidation is 80%, Dry Reforming at 99%, and Steam Reforming at 96%. The methane
in the Steam Reforming Route is contacted with steam over a heated catalyst at high
pressure and temperature to produce hydrogen rich syngas with the preferred H₂/CO
ratio of 3:1, which allows for high quality syngas. The operating conditions for
temperature and pressure are comparable, along with choice of catalyst for each route.
Dry Reforming possesses the disadvantage of having a large number of side reactions
to produce undesired product.
44
To conclude, Process Route 3, Steam Reforming of Methane which
produces the highest yield among the three process routes is selected as the best route
to produce methanol from biogas.
45
2.4.2 Sustainability Justification
Table 2.14 Sustainability Justification for Process Routes
Factors Dry Reforming Steam Reforming Partial Oxidation
Environment • Mainly used nickel-based

catalyst which is much
• Has highest air emission of CO₂ which
more affordable.
significantly contributes to health
• Use of two greenhouse gases, • The use of free radical
problems such as lung cancer, respiratory
carbon dioxide and methane as catalysts will greatly
infection and heart disease.
the feedstock which has high contribute to the depletion
• However, all the greenhouse gases
availability in some gas fields. of ozone layers, which
produced will be recycled back to the
• Reduce landfills waste creates a hole along with
feed stream of methanol synthesis reactor
overexposure of harmful
for full utilization within the plant.
UV radiations to the
human.
Economic • The methane and carbon dioxide in the

• It is obvious that DRM results
biogas is separated first before entering • Higher operation cost.
in reduced manufacturing costs
the steam reforming reactor in order to • To achieve high purity
as compared to commercial
decrease the size of reformer used and undiluted syngas, oxygen
SRM. This is mostly due to the
reduce the energy needed for is preferable to air as an
reduced capital cost of the
reforming. Also, prevent the happening oxidant which requires
DRM process, which is related
of dry reforming reaction which has additional costs for gas
to the lack of an auto reforming
lower conversion compared to steam separation.
unit.
reforming.
46
Safety • Instead of releasing the • Over exposure to steam methane • Present problems due to
greenhouse gases, CO₂ to the reformer gas can cause severe acute carbon formation, which is
atmosphere, DRM able to respiratory problem as it is high in undesirable because it
consume it with almost 100% toxicity. Furthermore, if exceeds the leads to catalyst
of conversion (CO₂). exposure limits, burns and frostbite was deactivation and increases
likely to occur. the reactor pressure, which
may lead to explosion
47
2.5 Process Block Diagram
H₂
CO
CO₂
Figure 2.1 Process Block Diagram
48
The feedstock, biogas which contains 60% of 𝐶𝐻4 and 40% of 𝐶𝑂2 is
compressed in a two-stage compressor at 25˚C and 1 bar before entering the membrane
separator. 𝐶𝐻4 and 𝐶𝑂2 will enter the membrane separator at 30˚C and 5 bar. The
membrane separator functions as a molecular sieve that purifies methane, in other
words, it separates methane and carbon dioxide. The membrane used in the separator
is polyimide 6FDA-m-DDS. This polyimide membrane has superior flux at low
temperature for carbon dioxide and other condensable gases. Thus, carbon dioxide can
easily be roved. The top stream from the membrane separator which contains methane
is heated to 900˚C using a heater before entering the steam methane reforming reactor
whereas the bottom stream that contains carbon dioxide (𝐶𝑂2 ) is sent to the methanol
synthesis reactor. The 𝐶𝑂2 is compressed in a two-stage compressor before entering
the methanol synthesis reactor.
The methane reforming is a process in which methane reacts with steam at

900˚C and 15 bar in the presence of catalyst to produce hydrogen (𝐻2 ), carbon
monoxide (CO) and a relatively small amount of (𝐶𝑂2 ). This process is endothermic
thus heat must be supplied to the process for the reaction to proceed. There are two
reactions that occur in the methane reforming reactor, which is the steam reforming of
methane and water gas shift reaction as shown in Equation 2.1 and 2.2 respectively.
In the water-gas shift reaction, CO and steam are reacted using Ni/SiO₂Al₂O₃ catalyst
to produce 𝐶𝑂2 and 𝐻2 . The catalyst is used to increase the selectivity and yield of 𝐻2
from the methane reaction.
𝐶𝐻4 + 𝐻2 𝑂 ↔ 𝐶𝑂 + 3𝐻2 (2.1)

𝐶𝑂 + 𝐻2 𝑂 ↔ 𝐶𝑂2 + 𝐻2 (2.2)
Once steam reforming is done, gases such as CO, 𝐶𝑂2, 𝐻2 and unreacted
methane will be produced from the reforming reactor, alongside water. These effluents
are cooled down using a cooler before being fed to the first flash column. The flash
column operating at 82.3˚C and 14 bar removes water from the gases mixture. The
wastewater undergoes treatment before being discharged to the environment. The
gases from the top stream of flash column are heated using a heater before being fed
into the methanol synthesis reactor. The methanol synthesis reactor is a catalytic multi-
49
tubular reactor that operates at 250˚C and 50 bar that uses the commercial
𝐶𝑢/𝑍𝑛𝑂/𝐴𝑙2 𝑂3 catalyst. Methanol synthesis reactor is highly exothermic that uses
carbon monoxide, hydrogen and carbon dioxide gases to produce methanol. Water is
the by-product from this reaction. The reactions happening in the methanol synthesis
reactor is stated as below:
𝐶𝑂 + 2𝐻2 → 𝐶𝐻3 𝑂𝐻 (2.3)

𝐶𝑂2 + 3𝐻2 ↔ 𝐶𝐻3 𝑂𝐻 + 𝐻2 𝑂 (2.4)
𝐶𝑂 + 𝐻2 𝑂 ↔ 𝐶𝑂2 + 𝐻2 (2.5)
Mixture of unreacted gases containing CO, 𝐶𝑂2, 𝐻2 , 𝐶𝐻4 , methanol and water
is produced from the methanol synthesis reactor. These products enter the second flash
column at 75˚C and 30 bar where unreacted gaseous mixtures are separated from the
methanol and water. The unreacted gaseous mixture from the flash column is recycled
back into the methanol synthesis reactor but a certain amount of these gaseous are
purged to restrict the build-up in concentration of the components when recycled back
to the reactor. Before being recycled back to the methanol synthesis reactor, the gas
are sent to the compressor to compress the gaseous mixture back up to meet the
standard of synthesis reactor pressure conditions.
The methanol and water from the flash separator is fed into a distillation
column to separate methanol from water. The distillation column operates at 75 ˚C and
2 bar, where the top stream contains the desired product which is the methanol whereas
the bottom stream contains the by-product which is the water. Lastly, 99.85% purity
of methanol is recovered in the top stream but the remaining methanol is mixed
together with water at the bottom stream. This wastewater will undergo wastewater
treatment to remove impurities before being discharged to the environment.
50
2.6 Overall Process
The chemical plant is designed to utilize biogas as the feedstock to produce

methanol as the main product, at the same time producing some by-products. The
overall process of the plant is illustrated by the process flow diagram (PFD).
2.6.1 Raw Material
For the production of methanol, the main raw material used is biogas. Unlike
fossil fuels, biogas is naturally renewable since it is produced from biomass, and
effectively can be a new solar energy through the use of the photosynthesis process.
Anaerobic digestion (AD) from biogas will not only improve a country's source of
energy but will also significantly contribute to the natural resource in conservation and
environmental protection. Biogenic substances are what made the biogas. Naturally,
biogas spreads into the environment and its principal component, methane, has a
significant negative impact on global warming. In other words, methane contributes to
the higher emission rate of the main greenhouse gases (GHG). Over the last several
decades, methane has been used as an essential fossil fuel activity and was converted
to provide electricity, transportation, and heating. Nowadays, natural gas accounts for
the majority of methane consumption and usage. In this project, the biogas feedstock
which consists of 60% methane (CH4) and 40% carbon dioxide (CO2) is supplied at
1500 kg/hour to the plant.
Currently, natural gas resources account for most of the methane consumption
and usage, while bio-methane generation from waste recovery technologies has grown
significantly. Over the last nine years, its manufacturing capacity has increased by 4%.
(From 2010 to 2018). Nowadays, around 3.5 Mtoe of biomethane is generated
globally, with a potential for biomethane production of over 700 Mtoe. However, the
drawback for methane conversion was not practical to use from all natural resources.
In other words, biogas infrastructure is heavily reliant on specialised equipment.
51
2.6.2 Main Product and By-products
The main product of the chemical processing plant is pure methanol (CH3 OH).
It is an important building block of chemical industry for a vast range of chemicals
from plastics to antifreeze solutions and solvent. In this chemical plant, methanol is
produced at 2283 kg/hour or annual production of 150 000 tonnes with 99.9% purity.
While methanol is produced as the main products, there are some by-products of the
process which include water, carbon dioxide, carbon monoxide, hydrogen and catalyst.
The by-products generated throughout the process are summarized in Table 2.15 with
their respective sources and streams.
Table 2.15 By-Product in Methanol Synthesis Plant
By Products Source Stream

Water, H2 O Flash Column, F-102 S19
Distillation Column, T-101 S36
Membrane Separator, F-101 S7
Carbon Dioxide, CO2
Flash Column, F-103 S32
Methane CH4 Steam Reforming Reactor, R-101 S16
Zn-CuO/Al₂O₃ Methanol Synthesis Reactor, R-102
Ni/SiO2 Al2 O3 Steam Reforming Reactor, R-101
The major by-product of the process is carbon dioxide which is originally

present in the biogas feedstock and is produced by Membrane Separator. Other by-
products are water from Distillation Column (T-101), The management of these by
products are discussed in Chapter 3.
52
2.6.3 Overview of Process Flow Diagram
Using biogas as the feed stock, the plant is designed to produce methanol as
the desired product. Biogas is compressed (C-101) before entering a cooler (E-101).
The stream is the compressed again (C-102) before entering a cooler (E-102). The
stream then enters a membrane separator, separating into two streams comprised of
Methane (CH4) and Carbon Dioxide (CO₂) respectively. The streams are both
compressed (C-103, C-105). The CO₂ stream is cooled down (E-103) before being
compressed once again. Both streams then enter a heater (E-104, E-105) each.
The CH₄ stream then enters the steam reforming reactor (R-101). Steam is
pumped into a heater (E-106) in order to reform CH₄ into syngas for steam reforming
is used to convert methane in the biogas into synthesis gas (syngas) through the
reaction with water. The methane is contacted with steam over a heated catalyst at high
pressure and temperature to produce hydrogen rich syngas. As the stream exits the
reactor it is cooled (E-107) and enters into a flash column (F-102) in order to separate
H2O from the stream. The stream, now comprised of H₂, CO, CO₂, is then compressed
(C-106) before being heated (E-108) to prepare for entering the mixer (M-101).
Meanwhile, the CO₂ stream has left the heater (E-105) and reunites with the
other stream inside the mixer (M-101). The mixed stream then enters the methanol
synthesis reactor (R-102). The mixed stream is expanded (EX-101) prior to being
separated in the flash column (F-102). The mixed stream is separated into two streams,
the product stream containing methanol (CH₃OH) and H₂O, and the side stream
containing H₂, CO, CO₂. The side stream is sent into a splitter (S-101) where the stream
is further purged of uwanted content. The side stream gets compressed (C-107) before
being fed back into the mixer (M-101)
The product stream passes through a throttling valve (V-101) and is condensed
(E-109) before entering a distillation column (T-101). From here, the H₂O is separated
from the product stream to deliver us our product, methanol.
53
54
55
2.7 Equipment Basis
To produce methanol from biogas, there were 2 reactors and 4 separators which
were among the 5 major unit operation involved. There was 1 catalytic packed bed
reactor and 1 catalytic plug flow reactor namely Steam Reforming reactor (SR) and
Methanol Synthesis reactor (MS). The separators include Flash column, Membrane
separator and Distillation column. Auxiliary equipment such as compressors,
intercoolers and throttling valves are also discussed in this section.
2.7.1 Methane Steam Reforming Reactor (R-101)
A catalytic packed bed reactors is used in the production plant, namely Steam
Reforming Reactor (R-101). Figure 2.2 shows the schematic diagram of a fixed bed
reactor.
Figure 2.2 Schematic Diagram of Packed Bed Reactor (Hafeez et al., 2019).
Methane Steam reforming is a chemical reaction in which methane interacts

with steam at 900°C and 15 bar pressure in the presence of a catalyst to create hydrogen
(H2 ), carbon monoxide (CO), and a tiny quantity of carbon dioxide (CO2 ). This process
56
is endothermic; therefore, heat must be provided to it in order to progress. The steam
reforming of methane and the water gas shift reaction are the two processes that occur
in the methane steam reforming reactor, as indicated in equations (1) and (2),
respectively. CO and steam are reacted with a Ni/SiO2 Al2 O3 catalyst to form CO2 and
H2 in the water-gas shift process. The catalyst is used to improve the methane
reaction's selectivity and yield of H2 .
In this project, the CH4 from the top stream of membrane separator enters the
steam methane reforming reactor (SMR) where nickel, Ni catalyst and steam, H2 O is
added in this reactor. Hydrogen gas, (H2), carbon monoxide, (CO), CO2 , H2 O and CH4
produced from SMR enters the flash separator to remove H2 O at the bottom stream.
The top stream that contains H2 , CO, CO2 , and CH4 enters the methanol synthesis
reactor.
kJ
CH4 + H2 O ←→ CO + 3H2 , ∆H298K = 206 mol (2.6)
kJ
CO + H2 O ←→ CO2 + H2 , ∆H298K = −41 (2.7)
mol
kJ
CH4 + 2H2 ←→ CO2 + 4H2 , ∆H298K = 165 mol (2.8)
Gases such as CO, CO2 , H2 and unreacted methane, as well as water, will be
generated from the reforming reactor after steam reforming is completed. Before being
supplied to the first flash column, these effluents are cooled with a cooler. Water is
removed from the gas mixture using a flash column running at 82.3°C and 14 pressure.
Before being released into the environment, the wastewater is treated. The operating
condition of the feed, distillate and bottom product were listed in the table below.
Table 2.16 Operating Condition of R-101
Aspect Description
Type of reactor Catalytic Packed Bed Reactor
Temperature 900°C
Pressure 15 bar
57
Reactant Carbon dioxide (CO₂), Water (H₂O),
Methane (CH₄)
Product Methane (CH₄) and Carbon monoxide
(CO),
Ratio of H₂O: CH₄ 1:1
Overall conversion of CO 10%
Conversion of CH₄ 80%
Catalyst Ni/SiO2 Al2 O3
2.7.2 Methanol Synthesis Reactor (R-102)
Methanol synthesis from synthetic gas (syngas) is carried out in a catalytic

fixed bed tubular reactor (R-102) to convert carbon monoxide (CO), carbon dioxide
(CO₂) and hydrogen (H₂) to methanol (CH₃OH) and water (H₂O). Catalytic fixed-bed
reactors are the most important type of reactor for the synthesis of largescale basic
chemicals and intermediates. A packed bed reactor (PBR) consists of a compact,
immobile stack of catalyst pellets within a generally vertical vessel. There are three
commonly used PBR, which are single-bed unit, multi-bed unit and multi-tube unit.
The multi-tube reactor is more common because heterogeneous catalytic processes
require effective heat transfer between the mobile fluid, catalyst bed and
heating/cooling media (Jakobsen, 2008). A tubular flow reactor is normally used to
describe chemical reactions in continuous, flowing systems in cylindrical pipe that is
usually operated at steady state condition (Vapored, 2021). Figure 2.3 shows the sketch
of a catalytic packed bed multi-tube reactor.
58
Figure 2.3 Sketch of a catalytic packed bed multi-tube reactor (Eigenberger and
Ruppel, 2000)
In the methanol synthesis reactor, zinc oxide and aluminium oxide supported
copper-based catalyst Cu-ZnO/Al₂O₃ is used as the catalyst to facilitate the reaction
and achieve 99% selectivity of methanol (da Silva, 2016). In the reactor, both the
carbon monoxide and carbon dioxide react with hydrogen gas to produce methanol
and water whereas the methane gas reacts with carbon dioxide in the side reaction to
produce more carbon monoxide and hydrogen to increase the yield of methanol.
Main reactions in the methanol synthesis reactor (R-102) are the hydrogenation
of carbon monoxide and carbon dioxide as shown in Equation 2.9 and Equation 2.10.
CO + 2H2 → CH3 OH (2.9)

CO2 + 3H2 → CH3 OH + H2 O (2.10)
Side reaction in R-102 is the reaction of methane with carbon dioxide as shown
in Equation 2.11.
CH4 + CO2 → 2CO + 2H2 (2.11)
Since the reaction is highly exothermic, the reactor should be operated at low
temperature, which is between 250°C to 280°C (da Silva, 2016). Therefore, the
reaction is operated at 280°C and 50 bar to achieve higher conversion of carbon
59
monoxide and carbon dioxide to methanol. The overall conversion of the main
reactions which is carbon monoxide and carbon dioxide to methanol is 70% (Luyben,
2010). On the other hand, the conversion of methane in side reaction is 96% (Hawk et
al., 1932). The outlet stream of R-102 contains methanol, water as well as unreacted
carbon monoxide, carbon dioxide, hydrogen and methane. The operating conditions
and equipment basis for the reactor R-102 are summarized in Table 2.17.
Table 2.17 Operating Condition of R-102
Aspect Description
Type of reactor Catalytic Packed Bed Multi-Tubular
Reactor
Temperature 280°C
Pressure 50 bar
Reactant Carbon monoxide (CO), Carbon dioxide
(CO₂), Hydrogen (H₂), Methane (CH₄)
Product Methanol (CH₃OH) and Water (H₂O)
Overall conversion of CO and CO₂ 70%
Conversion of CH₄ 96%
Catalyst Cu-ZnO/Al₂O₃
2.7.3 Distillation Column (T-101)
Distillation is commonly known as one of the most widely used method of

separating fluid mixtures into its component parts, or fractions, according to the
volatilities. It is by far the most common separation process in practice, separating
based on vapor-liquid equilibrium. Thus, a distillation column was a major refinery
process and an essential equipment especially in the oil and chemical industries.
Distillation column consists of a reboiler at the bottom and a condenser at the top. A
single liquid distillate stream can be produced if the total condenser was used.
Meanwhile, a partial condenser will generate a liquid distillate stream and a gaseous
60
overhead stream. Several components inside the distillation column are one of the key
factors for the process efficiency which is used to transfer heat energy or enhance
material transfer. A conventional distillation column consists of several major parts
which is:
(a) A vertical shell in which the components are separated

(b) Column internals (trays, plates, or packings) that improve the
separation of the component.
(c) A reboiler to produce the vaporisation required for the distillation
process
(d) A condenser to cool and condense the vapour exiting the columns top
(e) A reflux drum to collect condensed vapour from the top column
product so that liquid (reflux) may be recycled back into the column.
Figure 2.4 Individual Parts of Distillation Column (SRS Engineering Corporation,

2016).
The feed tray which is located at the middle of the column is where the
feedstock of liquid mixture is fed as an input. The feed tray separates the column into
61
two sections: top section (enriching, rectification) and bottom section (stripping). The
reboiler at the bottom collected the feed flow down into the column and a vapour was
generated from the heat supplied. The vapor flowing upwards the column and exit at
the top of the unit in which it is cooled by a condenser. A holding vessel known as
reflux drum kept the condensed liquid in which some of it were recycled back to the
top of the column. Distillate or top products was known as the condensed liquid that
is removed from the system (Speight.2020). The outlet stream of T-101 contains
Carbon dioxide (CO₂), Water (H₂O) and Methanol (CH₃OH) in which top products
was Methanol (CH₃OH) as distillate and the bottom product was Water (H₂O).
The feed has a concentration of 𝑥𝐹 (mole fraction) of the more volatile

component, and a distillate having a concentration of 𝑥𝐷 of the more volatile
component. Meanwhile, the bottom having a concentration of 𝑥𝐵 is desired.
Component with lower volatility can be known as light key (LK) whereas less volatile
component was called as heavy key (HK). In this project, the distillation column was
used to separate a mixture of methanol and water in which both were light key and
heavy key, respectively. The operating condition of the feed, distillate and bottom
product were listed in the table below:
Table 2.18 Operating Condition for Distillation Column
Aspect Description
Type of reactor Distillation Column
Temperature Inlet: 75℃
Distillate Outlet: 82.95℃
Bottom Outlet: 118.42℃
Pressure 2 bar
Reactant Carbon dioxide (CO₂), Water (H₂O) and
Methanol (CH₃OH)
Product Distillate: Methanol (CH₃OH) and
Carbon dioxide (CO₂)
Bottom: Water (H₂O)
62
In order to perform the mass and energy balance, the vapor pressure of each
component in the distillation column was calculated using Equation 2.12 (Yaw, 1999)
𝐶2
ln 𝑃° 𝑘 = 𝐶1 + + 𝐶3 ln 𝑇 + 𝐶4𝑇 𝐶5 (2.12)
𝑇
where,
𝑃° = saturated vapor pressure (Pa),
T = Temperature (K)
C1, C2, C3, C4, C5 = Vapor pressure constant
By assuming the system is ideal, Raoult’s law was used to determine the
relative volatility, αk/n, of component with Equation 2.13 (Geankoplis, 2003).
𝑃°𝑘 𝑃𝑖
𝛼𝑘/𝑛 = = (2.13)
𝑃°𝑛 𝑃𝑘
where:
𝛼𝑘/𝑛 = relative volatility of the component i
𝑃°𝑘 = vapour pressure of component
𝑃°𝑛 = vapour pressure of the heavy key component
The split fraction was then determined by Frenske-Underwood-Gillian shortcut

method. The split fraction, ξk, of each component in the stream was calculated using
Equation 2.14.
𝛼𝑖/𝑘 (𝜉𝑛 )
𝜉𝑘 = (2.14)
1+(𝛼𝑖/𝑘 −1)(𝜉𝑛 )
where:
𝜉k = relative volatility of the component
𝜉𝑛 = split fraction of the key component
63
The molar flowrate of each component at the distillate stream was calculated
using the formula as below:
𝜈𝑘 = 𝜉𝑘 × 𝑛(1.7) (2.15)
where:
𝜈𝑘 = molar flowrate of each component at the distillate stream (kmol/h)
𝑛 = inlet molar flow rate of component (kmol/h)
The mole fraction, 𝑦𝑘 of each distillate component was calculated using the
formula as below:
𝜈𝑘
𝑦𝑘 = (2.16)
𝑇𝑜𝑡𝑎𝑙 𝜈𝑘 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡
where:
𝑦𝑘 = mole fraction of component in distillate stream
The molar flowrate of the bottom product was 𝑙𝑘 was calculated using the
formula as below:
𝑙𝑘 = 𝑛 − 𝜈𝑘 (2.17)
The mole fraction, 𝑥𝑘 of each bottom component was calculated using the
formula as below:
𝑙𝑘
𝑥𝑘 = (2.18)
𝑇𝑜𝑡𝑎𝑙 𝑙𝑘 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡
The minimum number of stages, 𝑁𝑚 can be calculated by using Fenske’s

formula:
𝑦 𝑥
𝑙𝑜𝑔( 𝐿𝐾 ) ( 𝐿𝐾 )
𝑦𝐻𝐾 𝑑𝑖𝑠𝑡𝑖𝑙𝑙𝑎𝑡𝑒 𝑥𝐻𝐾 𝑏𝑜𝑡𝑡𝑜𝑚
𝑁𝑚 = (2.19)
𝑙𝑜𝑔(𝛼𝐿𝐾 )
where:
𝑥𝐿𝐾 = mole fraction of the light key in bottom stream
𝑥𝐻𝐾 = mole fraction of the heavy key in bottom stream
𝑦𝐿𝐾 = mole fraction of the light key in distillate stream
𝑦𝐻𝐾 = mole fraction of the heavy key in distillate stream
64
𝛼𝐿𝐾 = relative volatility of light key
The minimum reflux ratio, 𝑅𝑚 can be calculated using the Underwood’s

equation as below:
𝛼𝑥
𝑅𝑚 + 1 = ∑ 𝛼𝑖 −𝜃
𝑖,𝑑
(2.20)
𝑖
Where:
𝜃 is the Underwood Constant and can be calculated as the root of the following
equation:
𝛼𝑥
1 − 𝑞 = ∑ 𝛼𝑖 −𝜃
𝑖,𝑓
(2.21)
𝑖
where; 1 < 𝜃 < 𝛼𝐿𝐾
The optimal reflux ratio, R was then obtained by multiplying minimum reflux
ratio, Rm by 1.2 as shown in equation below:
R = 1.2R m (2.22)
where R = Optimal reflux ratio
The actual number of stages, N of distillation column was calculated using

Equation 2.23 and 2.24.
𝑁−𝑁𝑚 1+5.54𝑋 𝑋−1

𝑌= = 1 − exp [(11+117.2𝑋) ( 𝑋 0.5 )] (2.23)
𝑁+1
𝑅−𝑅𝑚
𝑋= (2.24)
𝑅 +1
To determine the estimated feed plate location, Equation 2.25 was used to
calculate the number of theoretical stages above and below the feed plate
2
𝑁𝑒 𝑥𝐻𝐾,𝑓 𝐵 𝑥𝐿𝐾,𝐵
log 𝑁 = 0.206 𝑙𝑜𝑔 [( 𝑥 )( )( ) ] (2.25)
𝑠 𝐿𝐾,𝑓 𝐷 𝑥 𝐻𝐾,𝐷
where:
𝑁𝑒 = number of theoretical stages above the feed plate
𝑁𝑠 = number of theoretical stages below the feed plate.
65
In order to determine the top temperature and bottom temperature of distillation
column, Raoult’s law and Dalton's law were combined to give the vapor-liquid
equilibrium constant, Ki as Equation 2.26 (Seader et al., 1998)
𝑦 𝑃𝑖 °
𝐾𝑖 = 𝑥𝑖 = (2.25)
𝑖 𝑃
where,
K i = vapor-liquid equilibrium constant for component i
yi = mole fraction of component i in vapor
xi = mole fraction of component i in liquid
Pi ° = vapor pressure of pure component i
P = total pressure
Bubble point and dew point can be calculated by using the formula below by
trial and error.
For the bubble point (bottom temperature),
∑𝑁𝐶 𝑁𝐶
𝑖=1 𝑦𝑖 = ∑𝑖=1 𝐾𝑖 𝑥𝑖 = 1.0 (2.26)
For the dew point (top temperature),
𝑦
∑𝑁𝐶 𝑁𝐶 𝑖
𝑖=1 𝑥𝑖 = ∑𝑖=1 𝐾 = 1.0 (2.27)
𝑖
2.7.4 Flash Separator
A separator is a device that separates a product into fractions with different

characteristics. There are various type of separators out there such as gas-liquid
separator, gas-gas separator and liquid-liquid separator. These separators are used
widely out there to help on handling various of human’s activities such as mining,
medicine, processing food and also agriculture.
66
Gas-liquid separator is a type of separator that widely used in many
applications such as nuclear energy and petroleum energy. It is most frequently
employed in oil, gas, and petrochemical (OGP) industries with one or a combination
of gravity settling, impingement, and centrifugation principles. The process is
significantly simple. By using a certain pressure and temperature, the liquid in the
liquid stream that contain several components will partially vaporised in a flash drum
resulting in two different phases which is liquid and gas.
In this process, flash separator is used to separate water from gases especially
methane which will be need to synthesis our final product which is methanol. By
inducing phase change of the multicomponent stream. Separating volatile components
(light key components) from less volatile components (heavy key components) is one
of the simplest isolation processes used in the industry. Using a certain temperature
and pressure, a fluid that flow through the separator that consist of several components
will partly vaporized by an external heat exchanger. The light key components will
flow through the top stream in a vapor form while the heavy key components will be
flow through the bottom stream in a liquid form.
Two flash separators (F-102 and F-103) are used in this process to separate
components by the difference of their boiling points. Based on the boiling points of
each component and the operating temperature of the flash separator, the light key and
heavy key components can be identified. The boiling points of components in the
product streams at 1 bar are summarized in Table 2.19.
Table 2.19 Components boiling points at standard temperature (1 bar)
Components Boiling Point (˚C)

Hydrogen (H2 ) -252.9
Carbon Monoxide (CO) -191.5
Carbon Dioxide (CO2 ) -78.46
Water (H2 O) 100
Methane (CH4 ) -161.6
Methanol (CH3 OH) 64.7
67
The heavy key component and the light key component are identified based on
the boiling points and the desired recovery fraction of the key components. By
definition, the light key actually has a lower boiling point than the heavy key. Another
feature for light key is actually the light key products will be release through the upper
column while the heavy key will be release through the bottom column. Based on the
boiling points of the components above, components with boiling point higher than
the operating temperature of flash separator indicates that the components are the
heavy components which is less volatile. Meanwhile, components with boiling lower
boiling point indicates that it is a light key component which is more volatile.
The method to perform the mass balance in flash separator are shown as below.
By assuming the multicomponent system is ideal, Raolt’s law is given by Equation
2.28 while Dalton’s law is given by Equation 2.29. Combination of the two questions
gives the vapor-liquid equilibrium constant, K 𝑖 as Equation 2.30 (Seader & Henley,
1998).
𝑃𝑖 = 𝑥𝑖 𝑃𝑖° (2.28)
𝑃𝑖 = 𝑦𝑖 𝑃 (2.29)
𝑥 𝑃𝑖°
𝐾𝑖 = 𝑦𝑖 = (2.30)
𝐼 𝑃
where,
𝐾𝑖 = vapor-liquid equilibrium constant for component i
𝑥𝑖 = mole fraction of component i in liquid
𝑦𝑖 = mole fraction of component i in vapor
𝑃𝑖 = partial pressure of component i (bar)
𝑃𝑖° = vapor pressure of pure component i (bar)
𝑃 = total pressure (bar)
To vapor pressure of each component in the flash separator based on the

operating temperature (T) using the Antoine Equation 2.31 below:
68
Vapour Pressure, P°k (pa) = exp [ C1+C2/T] + C3 x ln(T) + C4 + TC5 (2.31)
where:
P°k = Vapour pressure of the component
C1, C2, C3, C4, and C5 = Constants obtained from the Perry’s Hand Book
T = Temperature of the flash drum (K)
The relative volatility α is calculated based on Raoult’s law ideal system using
equation as below and the result of the calculation were tabulate in Table 2.5:
αk/n = P°k / Pc (2.32)
where:
α = relative volatility
P°k = vapour pressure of the component;
Pc = vapour pressure of heavy key component
The split fraction was then determined by Frenske-Underwood-Gillian shortcut

method. The split fraction, ξk, of each component in the stream was calculated using
Equation 2.25.
𝛼𝑘/𝑛 𝜀𝑛
𝜀𝑘 = (2.33)
1+(𝛼𝑘 −1)𝜀𝑛
𝑛
where,
𝜀𝑘 = split fraction of component
𝜀𝑛 = split fraction of key component
The molar flow rate of each component in the top stream product of the flash
separator was calculated using Equation 2.34.
𝑉𝑘 = 𝜀𝑘 × 𝑛 (2.34)
where,
𝑉𝑘 = molar flow rate of component in top stream (kmol/hr)
69
𝑛 = inlet molar flow rate of component (kmol/hr)
The mole fraction, 𝑦𝑘 , of each component in the top product stream was then
calculated using Equation 2.35.
𝑣𝑘
𝑦𝑘 = (2.35)
𝑇𝑜𝑡𝑎𝑙 𝑣𝑘
where,
𝑦𝑘 = mole fraction of component in top stream
For the bottom product of the flash separator, the molar flow rate, 𝐼𝑘 , of each
component was calculated using Equation 2.36.
𝐼𝑘 = 𝑛 − 𝑉𝑘 (2.36)
where,
𝐼𝑘 = molar flow rate of component in bottom stream (kmol/hr)
The mole fraction, 𝑥𝑘 , of each component in the bottom product stream was then
calculated using Equation 2.37.
𝐼𝑘
𝑥𝑘 = (2.37)
𝑇𝑜𝑡𝑎𝑙 𝐼𝑘
where,
𝑥𝑘 = mole fraction of component in bottom stream
2.7.4.1 Flash Separator (F-102)
Flash separator 1 (F-102) is designed to remove all the water from the gas
stream before entering next unit operation. The gas stream entering F-102 contains
water (H2 O), carbon monoxide (CO), carbon dioxide (CO2 ), hydrogen (H2 ) and
methane (CH4 ). Since H₂O can be condensed easily below 100℃ at atmospheric
pressure while keeping other components in vapor phase, the pressure and temperature
70
of F-102 are kept at 14 bar and 82.3 ℃ respectively. The operating for the flash
separator F-102 are summarized in Table 2.20.
Table 2.20 Operating Conditions of Flash Separator (F-102)
Phase Mixed
Pressure (bar) 14
Temperature (°C) 82.30
Inlet Components H2 O, CO, CO₂, H₂ and CH4
Top Stream Product CO, CO₂, H₂ and CH4
Bottom Stream Product H2 O
Separation Efficiency 99%
Flash separator 1 (F-102) is designed to remove all the water from the gas
stream before entering next unit operation. The gas stream entering F-103 contains
water (𝐻2 𝑂), carbon monoxide (CO), carbon dioxide (C𝑂2), hydrogen (𝐻2 ), methanol
(C𝐻3 𝑂𝐻) and methane (C𝐻4 ). The pressure used is 30 bar and the temperature use is
75 °C. During this separation process, the bottom stream will be used for our synthesis
of the final product to get almost pure methanol (C𝐻3 𝑂𝐻). Other components that are
transport to the top stream will be recycle back to the pipeline before entering the
methanol synthesis reactor. The operating conditions s for the flash separator F-103
are summarized in Table 2.21.
Table 2.21 Operating Conditions of Flash Separator (F-103)
Phase Mixed
Pressure 30
Temperature 75
Inlet H2O,
Top CO,
71
Bottom CH₃OH
2.7.5 Membrane Separator
A membrane is defined as a thin sheet, film, or layer, which works as a selective

barrier between two phases that can be liquid, gas, or vapor and it is an interface
between two adjacent phases acting as a selective barrier, regulating the transport of
species between the two compartments (Ulbricht, 2006). Membrane separation is a
separation based on the presence of semi permeable membranes. The principle is quite
simple: the membrane acts as a very specific filter that will let water flow through,
while it catches suspended solids and other substances.
Membrane separator (F-101) is designed to separate in between the

composition of biogas which consist of 60% of methane (CH4 ) and 40% of carbon
dioxide (CO2 ).The reason on doing the membrane separation is to retrieve as much
pure methane (CH4 ) gas from biogas as we can before react in in the steam reforming
reactor. The carbon dioxide retrieved will be directed to methanol synthesis reactor.
The membrane separation will be done at pressure of 5 bar and temperature of 30 °C.
The operating conditions s for the membrane separator (F-101) are summarized in
Table 2.22 with the efficiency of separation is assumed to be 0.99.
Table 2.22 Operating Conditions of Membrane Separator (F-101)
Phase Vapor
Pressure (bar) 5
Temperature (°C) 30
Inlet Components CO₂ and CH4
Permeate CH4
Retentate CO₂
72
2.7.6 Mixer (M-101)
Mixer as the name suggested is use to mix or allow heat or mass transfer
between one or more streams, the components used or phases. Industrial mixers are
used in processing adhesives, chemicals, cosmetics, food and beverages, coatings,
paper and pulp, plastics, pharmaceuticals, and waste/water treatments and improper
mixing may affect cost, profit, overtime and the amount of substandard or scrapped
products (materials that do not cure, air voids on surface, sticky surface, soft spots,
softening at elevated temperatures, changes in chemical or electrical resistance,
craters, fish eyes, cracking or weakening of the product) and many other undesirable
side effects (Adams, 2011). In this plant design, mixer (M-101) is use to mix the
components release from flash separator (F-102) with carbon dioxide before react the
total mixture in the methanol synthesis reactor. The purpose of doing a mixing is to
properly mix in between the gas compounds to achieve the best yield of the final
product. The operating condition of mixer (M-101) are summarized in Table 2.23.
Table 2.23 Operating Conditions of Mixer (M-101)
Phase Vapor
Pressure (bar) 50
Temperature (°C) 280
Inlet Streams SSS, S22 and S31
Outlet Streams S23
2.7.7 Auxiliary
In addition to major unit operations, auxiliary equipment such as condensers,

compressor and throttling valve are also used to provide enhanced properties and
processing of the production line.
73
2.7.7.1 Compressor
There are seven compressors used to increase the pressure of the gas streams.
After compressing the gas stream in a compressor, the exit temperature is higher than
the entering temperature. Based on heuristic 35, the discharge temperature of each
compressor was determined using Equation 2.28. The operating conditions for each
compressor are summarized in Table 2.24.
P a
T2 = T1 (P2 ) (2.28)
1
where,
T1 = Suction temperature
T2 = Discharge temperature
P1 = Suction pressure
P2= Discharge pressure
a = (k − 1)/k
k = gas-specific heat ratio
Table 2.24 Operating Conditions for Compressors
Suction Discharge Suction Discharge

Tag
Description Pressure Pressure Temperature Temperature
No.
(bar) (bar) (°C) (°C)
Compressor 1 C-101 1 2.236 25 85.23
Compressor 2 C-102 2.236 5 25 85.24
Compressor 3 C-103 5 15.81 30 121.3
Compressor 4 C-104 15.81 50 30 121.3
Compressor 5 C-105 5 15 30 116.57
Compressor 6 C-106 14 50 82.3 235.37
Compressor 7 C-107 30 50 75 129.87
74
2.7.7.2 Intercooler
There are two intercoolers which are used to reduce the fuel consumption while
increasing the engine power and efficiency. In addition, the intercooler able to reduce
the temperature of the inlet gas, therefore, optimize the combustion. The operating
conditions for each intercooler are summarized in Table 2.25.
Table 2.25 Operating Conditions for Intercooler

Tag
No.
(bar) (bar) (°C) (°C)
Throttling Valve 1 V-101 50 30 280 280
Throttling Valve 2 V-102 30 2 75 75
2.7.7.3 Heater
There are five heaters which are used to supply all heat required by the process
in one form or another in which that it can utilize gaseous or liquid fuels in which it
often produced as a by-product.
Table 2.26 Operating Conditions for Heater
Suction Suction Discharge

Descriptio Tag Discharge
Pressure Temperatur Temperatur
n No. Pressure (bar)
(bar) e (°C) e (°C)
Heater 1 E-104 50 50 121.3 280

Heater 2 E-105 15 15 116.57 900
Heater 3 E-106 15 15 25 900
Heater 4 E-108 50 50 235.37 280
Heater 5 E-110 50 50 129.87 280
75
2.7.7.4 Condenser
Condensers are employed in power plants to condense exhaust steam from

turbines and in refrigeration plants to condense refrigerant vapours, such as ammonia
and fluorinated hydrocarbons. In this plant design, condenser (E-101) is used after
separation process using flash column (F-103).
Table 2.27 Operating Conditions for Condenser

Tag
No.
(bar) (bar) (°C) (°C)
Condenser 1 E-109 30 30 280 75
2.7.7.5 Pump
There is only one pump used in the process to increase the pressure of water
before entering the steam reforming reactor.
Table 2.28 Operating Conditions for Pump
Discharge Suction Discharge

Tag Suction Pressure
Description Pressure Temperature Temperature
No. (bar)
(bar) (°C) (°C)
Pump 1 P-101 1 50 25 25
2.7.7.6 Cooler
The cooling system operates by eliminating the excess heat from the engine,
keeps the engine operating temperature where it is most efficient and brings the engine
up to the satisfactory operational temperature as rapidly as possible.
76
Table 2.29 Operating Conditions for Cooler
Discharge Suction Discharge

Suction
Description Tag No. Pressure Temperature Temperature
Pressure (bar)
(bar) (°C) (°C)
Cooler 1 E-102 5 5 85.24 30
Cooler 2 E-107 15 14 900 82.3
2.8 Manual Calculation for Mass and Energy Balance (MEB)
According to the law of conservation of mass, the mass of an isolated system

is neither created nor destroyed by chemical reactions or any physical transformations.
In other words, the mass of a products in a chemical reaction is equal to the mass of
the reactants. The application of these conservation rules in chemical and other
processes results in material (mass) and energy balances. In engineering practices,
material and energy balances is a key factor to developing any design equations
especially for designing a process plants, operational condition of a plant design and
evaluation of process units. The general material balance equation for a system is
represented by:
𝐼𝑛𝑝𝑢𝑡 + 𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 − 𝐶𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛 − 𝑂𝑢𝑡𝑝𝑢𝑡 = 𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛
2.8.1 Mass Balance
In designing the chemical plant for the methanol production from biogas,
several equipment such as Steam Reforming reactor, Methanol Synthesis reactor, flash
column, distillation columns and other auxiliary equipment have been selected to
perform their functions. All the equipment has their own operating conditions to carry
out their functions such as reactions, gas-liquid separation, liquid-liquid separation,
condensation, vaporization and gas compression. In order to perform the mass balance,
each unit operation and the auxiliary equipment has its specific calculation method.
All the formulas and equations required for manual calculation of the equipment have
77
been explained in detailed in the previous section (Section 2.6: Equipment Basis). The
results of the manual calculations of mass balance for all equipment and all streams
(enters through system boundaries) (produced within system) (leaves through system
boundaries) (consumed within system) (build up within system) () are presented in this
section. Several assumptions were made prior to performing the mass balance:
(a) Biogas containing 60% CH4 and 40% CO2 is used as the raw material
and is fed at the rate of 1500 kg/hr.
(b) The process is continuous and operating at steady state, thus there is
no accumulation in all equipment.
(c) The behaviour of all components in the system is in ideal condition.
(d) There is no pressure drop across the reactors, flash separators,
absorber, distillation columns and heat exchangers.
(e) At all auxiliary equipment such as condenser and compressors, there
is no side reaction occurs, thus making the mass balance of the inlet
stream to be same as the outlet stream.
(f) There is no leakage in the piping system and the joint connection
between equipment.
(g) The component with mass flow rate below 0.001wt% of the stream is
assumed to be in trace amount and is negligible.
78
2.8.1.1 Steam Reforming Reactor (R-101)
Figure 2.5 shows the symbol of Steam Reforming Reactor (R-101) in process
flow diagram (PFD). The results of mass balance on R-101 obtained by manual
calculation are summarized in Table 2.30:
S12
S16
S15
Figure 2.5 Symbol of Steam Reforming Reactor (R-101) in PFD
Table 2.30 Steam Reforming Reactor (R-101)
Inlet Outlet
Stream S12 S15 S16
Phase Vapor Vapor Vapor
Pressure (bar) 15 15 15
Temperature (°C) 900 900 900
Component Mass Flow Rate (kg/hr)
Water, H₂O 0 891 3.3223
Methane, CH₄ 891 0 178.200
Carbon Dioxide, CO₂ 6 0 219.1369
Carbon Monoxide, CO 0 0 1108.870
Hydrogen, H₂ 0 0 278.4708
Methanol, CH₃OH 0 0 0
897 891 1788
Total
1788 1788
79
2.8.1.2 Methanol Synthesis Reactor (R-102)
Figure 2.6 shows the symbol of Methanol Synthesis Reactor (R-102)in process
flow diagram (PFD). The results of mass balance on R-101 obtained by manual
calculation are summarized in Table 2.31:
S23 S24
Figure 2.6 Symbol of Methanol Synthesis Reactor (R-102) in PFD
Table 2.31 Methanol Synthesis Reactor (R-102)
Inlet Outlet
Stream S23 S24
Phase Mixed Mixed
Pressure ((bar) 50 50
Temperature (°C) 250 250
Water, H₂O 0.3088 116.3891
Methane, CH₄ 194.5945 7.7838
Carbon Dioxide, CO₂ 1137.2022 341.1606
Carbon Monoxide, CO 1979.8992 916.8728
Hydrogen, H₂ 1025.9104 786.9796
Methanol, CH₃OH 20.8005 2189.5297
Total 4358.7156 4358.7156
80
2.8.1.3 Membrane Separator (F-101)
Figure 2.7 shows the symbol of Membrane Separator (F-101) in process flow
diagram (PFD). The results of mass balance on F-101 obtained by manual calculation
are summarized in Table 2.32:
S6
S5
F-101
E-52
S7
Figure 2.7 Symbol of Membrane Separator (F-101) in PFD
Table 2.32 Mass Balance on Membrane Separator (F-101)
Inlet Outlet
Stream S5 S6 S7
Pressure ((bar) 5 5 5
Water, H₂O 0 0 0
Methane, CH₄ 900 891 9
Carbon Dioxide, CO₂ 600 6 594
Carbon Monoxide, CO 0 0 0
Hydrogen, H₂ 0 0 0
Methanol, CH₃OH 0 0 0
Total 1500 1500
81
2.8.1.4 Flash Column (F-102)
Figure 2.8 shows the symbol of Flash Column (F-102) in process flow diagram
(PFD). The results of mass balance on F-102 obtained by manual calculation are
summarized in Table 2.33:
S18
S17
S19
Figure 2.8 Symbol of Flash Column (F-102) in PFD
Table 2.33 Mass Balance on Flash Column (F-102)
Inlet Outlet
Stream S17 S18 S19
Phase Mixed Vapor Vapor
Water, H₂O 3.32 0.00 3.32
Methane, CH₄ 178.20 178.20 0.00
Carbon Dioxide, CO₂ 219.14 219.14 0.00
Carbon Monoxide, CO 1108.87 1108.87 0.00
Hydrogen, H₂ 278.47 278.47 0.00
Methanol, CH₃OH 0.00 0.00 0.00
1788.00 1784.68 3.32
Total
1788.00 1788.00
82
2.8.1.5 Flash Column (F-103)
Figure 2.9 shows the symbol of Flash Column (F-103) in process flow diagram
(PFD). The results of mass balance on F-103 obtained by manual calculation are
S27
S26
S32
Figure 2.9 Symbol of Flash Column (F-103) in PFD
Table 2.34 Mass Balance on Flash Column (F-103)
Inlet Outlet
Stream S26 S27 S32
Phase Liquid Vapor Liquid
Temperature (°C) 89.60 89.60 89.6
Water, H₂O 116.3891 0.3216 116.0675
Methane, CH₄ 7.7838 7.7837 0.0001
Hydrogen, H₂ 786.9796 786.9796 0.0000
Methanol, CH₃OH 2189.5297 21.8953 2167.6344
4358.7 2075.0 2283.7407
Total
4358.7 4358.7
83
2.8.1.6 Distillation Column (T-101)
Figure 2.10 shows the symbol of Distillation Column (T-101) in process flow
diagram (PFD). The results of mass balance on T-101 obtained by manual calculation
S35
S34
S36
Figure 2.10 Symbol of Distillation Column (T-101) in PFD
Table 2.35 Mass Balance on Distillation Column (T-101)
Inlet Outlet
Stream S34 S35 S36
Phase Liquid Liquid Liquid
Temperature (°C) 75.00 82.95 118.42
Water, H₂O 115.9594 1.1596 114.7998
Methane, CH₄ 0 0 0
Carbon Dioxide, CO₂ 0.1078 0.1077 0
Carbon Monoxide, CO 0 0 0
Hydrogen, H₂ 0 0 0
Methanol, CH₃OH 2167.344 2162.0494 5.5849
Total 2283.7015 2283.7015
84
2.8.1.7 Compressor (C-101)
Figure 2.11 shows the symbol of Compressor (C-101) in process flow diagram
(PFD). The results of mass balance on C-101 obtained by manual calculation are
S1
S2
Figure 2.11 Symbol of compressor (C-101) in PFD
Table 2.36 Mass Balance on Compressor (C-101)
Inlet Outlet
Stream S1 S2
Phase Vapor Vapor
Pressure ((bar) 1 2.236
Temperature (°C) 25.00 85.23
Water, H₂O 0.00 0.00
Methane, CH₄ 900.00 900.00
Hydrogen, H₂ 0.00 0.00
Methanol, CH₃OH 0.00 0.00
Total 1500.0 1500.0
85
S3
S4
Inlet Outlet
Stream S3 S4
Phase Vapor Vapor
Pressure ((bar) 2.236 5
Water, H₂O 0.00 0.00
Methane, CH₄ 900.00 900.00
Total 1500.0 1500.0
86
S7
S8
Inlet Outlet
Stream S7 S8
Phase Vapor Vapor
Pressure ((bar) 5 15.81
Water, H₂O 0.00 0.00
Methane, CH₄ 9.00 9.00
Total 603.0 603.0
87
S9
S10
Inlet Outlet
Stream S9 S10
Phase Vapor Vapor
Pressure ((bar) 15.81 50
Water, H₂O 0.00 0.00
Total 603.0 603.0
88
S6
S11
Inlet Outlet
Stream S6 S11
Phase Vapor Vapor
Temperature (°C) 30 116.57
Water, H₂O 0.00 0.00
Methane, CH₄ 891.00 891.00
Total 897.0 897.0
89
S18
S21
Inlet Outlet
Stream S18 S21
Phase Vapor Mixed
Water, H₂O 0.0033 0.0033
Methane, CH₄ 178.1996 178.20
Hydrogen, H₂ 278.4708 278.4708
Total 1784.68047 1784.6804
90
summarized in Table 2.42.
S28
S30
Inlet Outlet
Stream S28 S30
Phase Vapor Mixed
Pressure (bar) 30 50
Temperature (°C) 90 147
Water, H₂O 0.31 0.31
Hydrogen, H₂ 747.63 747.63
Total 1971.23 1971.23
91
2.8.1.14 Intercooler (E-101)
Figure 2.18 shows the symbol of Intercooler (E-101) in process flow diagram
(PFD). The results of mass balance on E-101 obtained by manual calculation are
S2 S3
Figure 2.18 Symbol of Intercooler (E-101) in PFD
Table 2.43 Mass Balance on Intercooler (E-101)
Inlet Outlet
Stream S2 S3
Phase Vapor Vapor
Pressure (bar) 2.236 2.236
Water, H₂O 0.0000 0.0000
Methane, CH₄ 900.0 900.0
Hydrogen, H₂ 0.0000 0.0000
Total 1500.0 1500.0
92
2.8.1.15 Intercooler (E-103)
Figure 2.19 shows the symbol of Intercooler (E-103) in process flow diagram
S8 S9
Figure 2.19 Symbol of Intercooler (E-103) in PFD
Inlet Outlet
Stream S8 S9
Phase Vapor Vapor
Pressure ((bar) 15.81 15.81
Water, H₂O 0.0000 0.0000
Hydrogen, H₂ 0.0000 0.0000
Total 603.0 603.0
93
2.8.1.16 Heater (E-104)
Figure 2.20 shows the symbol of Heater (E-104) in process flow diagram
S10 S20
Figure 2.20 Symbol of Heater (E-104) in PFD
Table 2.45 Mass Balance on Heater (E-104)
Inlet Outlet
Stream S10 S20
Phase Vapor Vapor
Water, H₂O 0.0000 0.0000
Methane, CH₄ 9.0000 9.0000
Hydrogen, H₂ 0.0000 0.0000
Total 603.0 603.0
94
2.8.1.17 Heater (E-105)
S11 S12
Table 2.46 Mass Balance on Heater (E-105)
Inlet Outlet
Stream S11 S12
Phase Vapor Vapor
Water, H₂O 0.0000 0.0000
Methane, CH₄ 891 891
Hydrogen, H₂ 0.0000 0.0000
Total 897 897
95
2.8.1.18 Heater (E-106)
S14 S15
Inlet Outlet
Stream S14 S15
Phase Liquid Vapor
Pressure (bar) 15 15
Water, H₂O 891 891
Methane, CH₄ 0 0
Carbon Dioxide, CO₂ 0 0
Carbon Monoxide, CO 0 0
Hydrogen, H₂ 0 0
Methanol, CH₃OH 0 0
Total 891 891
96
2.8.1.19 Heater (E-108)
S21 S22
Inlet Outlet
Stream S21 S22
Phase Mixed
Mixed
Pressure ((bar) 50
50
Temperature (°C) 280.00
235.37
Water, H₂O 0.0033 0.0033
Methane, CH₄ 178.200 178.200
Hydrogen, H₂ 278.4708 278.4708
Total 1784.6804 1784.6804
97
2.8.1.20 Heater (E-109)
S30 S31
Inlet Outlet
Stream S30 S31
Phase Mixed Mixed
Water, H₂O 0.3055 0.3055
Methane, CH₄ 7.3945 7.3945
Hydrogen, H₂ 747.6306 747.6306
Methanol, CH₃OH 20.8005 20.8005
Total 1971.2 1971.2
98
2.8.1.21 Pump (P-101)
Figure 2.25 shows the symbol of Pump (P-101) in process flow diagram (PFD).
The results of mass balance on P-101 obtained by manual calculation are summarized
in Table 2.50:
S14
S13
Figure 2.25 Symbol of Pump (P-101) in PFD
Table 2.50 Mass Balance on Pump (P-101)
Inlet Outlet
Stream S13 S14
Phase Liquid Liquid
Water, H₂O 891.0 891.0
Total 891.0 891.0
99
2.8.1.22 Cooler (E-102)
Figure 2.26 shows the symbol of Cooler (E-102) in process flow diagram
S14 S15
Figure 2.26 Symbol of Cooler (E-102) in PFD
Table 2.51 Mass Balance on Cooler (E-102)
Inlet Outlet
Stream S4 S5
Phase Vapor Vapor
Pressure ((bar) 5 5
Water, H₂O 0 0
Methane, CH₄ 900 900
Carbon Dioxide, CO₂ 600 600
Carbon Monoxide, CO 0 0
Hydrogen, H₂ 0 0
Total 1500 1500
100
2.8.1.23 Cooler (E-107)
S16 S17
Inlet Outlet
Stream S16 S17
Phase Vapor Mixed
Water, H₂O 3.3223 3.3223
Methane, CH₄ 178.2000 178.2000
Hydrogen, H₂ 278.4708 278.4708
Total 1788.0 1788.0
101
2.8.1.24 Cooler (E-109)
S16 S17
Inlet Outlet
Stream S25 S26
Phase Mixed Vapor
Water, H₂O 116.3891 116.3891
Methane, CH₄ 7.7838 7.7838
Hydrogen, H₂ 786.9796 786.9796
Methanol, CH₃OH 2189.5297 2189.5297
Total 4358.7 4358.7
102
2.8.1.25 Mixer (M-101)
Figure 2.29 shows the symbol of Mixer (M-101) in process flow diagram
(PFD). The results of mass balance on M-101 obtained by manual calculation are
S20
S23
S22
S31
M-101
Figure 2.29 Symbol of Mixer (M-101) in PFD
Table 2.54 Mass Balance on Mixer (M-101)
Inlet Outlet
Stream S20 S22 S31 S23
Phase Vapor Vapor Vapor Mixed
Pressure (bar) 50 50 50 50
Temperature (°C) 250 250 250 250
Water, H₂O 0.00 0.0033 0.31 0.31
Methane, CH₄ 9.00 178.20 7.39 194.59
Carbon Dioxide, CO₂ 594.00 219.14 324.07 1137.20
Carbon Monoxide, CO 0.00 1108.87 871.03 1979.90
Hydrogen, H₂ 0.00 278.47 747.44 1025.91
Methanol, CH₃OH 0.00 0.00 20.80 20.80
603.00 1784.68 1971.04
Total
4358.72 4358.72
103
2.8.1.26 Condenser (E-109)
Figure 2.30 shows the symbol of Condenser (E-109) in process flow diagram
S33 S34
Figure 2.30 Symbol of Condenser (E-109) in PFD
Table 2.55 Mass Balance on Condenser (E-109)
Inlet Outlet
Stream S33 S34
Phase Vapor Liquid
Pressure ((bar) 2 2
Water, H₂O 116.0675 116.0675
Methane, CH₄ 0.0001 0.0001
Hydrogen, H₂ 0.0000 0.0000
Methanol, CH₃OH 2167.6344 2167.6344
Total 2283.7 2283.7
104
2.8.1.27 Splitter (S-101)
Figure 2.31 shows the symbol of Splitter (S-101) in process flow diagram
(PFD). The results of mass balance on S-101 obtained by manual calculation are
S28
S27
S29
Figure 2.31 Symbol of Splitter (S-101) in PFD
Table 2.56 Mass Balance on Splitter (S-101)
Inlet Outlet
Stream S27 S28 S29
Temperature (°C) 89.60 89.60 89.6
Water, H₂O 0.3216 0.3055 0.0161
Methane, CH₄ 7.7837 7.3945 0.3892
Hydrogen, H₂ 786.9796 747.6306 39.3490
Methanol, CH₃OH 21.8953 20.8005 1.0948
2075.0 1971.2 103.7487
Total
2075.0 2075.0
105
2.8.1.28 Throttling Valve (V-101)
Figure 2.32 shows the symbol of Throttling Valve (V-101) in process flow
diagram (PFD). The results of mass balance on V-101 obtained by manual calculation
S24 S25
Figure 2.32 Mass Balance on Throttling Valve (V-101)
Table 2.57 Mass Balance on Throttling Valve (V-101)
Inlet Outlet
Stream S24 S25
Phase Vapor Vapor
Water, H₂O 116.3891 116.3891
Methane, CH₄ 7.7838 7.7838
Hydrogen, H₂ 786.9796 786.9796
Methanol, CH₃OH 2189.5297 2189.5297
Total 4358.7 4358.7
106
2.8.1.29 Throttling Valve (V-102)
Figure 2.33 shows the symbol of Throttling Valve (V-102) in process flow
diagram (PFD). The results of mass balance on V-102 obtained by manual calculation
S32 S33
Figure 2.33 Mass Balance on Throttling Valve (V-102)
Table 2.58 Mass Balance on Throttling Valve (V-102)
Inlet Outlet
Stream S32 S33
Phase Liquid Vapor
Water, H₂O 116.0675 116.0675
Methane, CH₄ 0.0001 0.0001
Hydrogen, H₂ 0.0000 0.0000
Methanol, CH₃OH 2167.6344 2167.6344
Total 2283.7 2283.7
107
2.8.2 Mass Balance Comparison
The comparison between the mass balance obtained by manual calculation and
by AVEVA PRO/II simulation were carried out by determining the percentage
deviation of the mass flow rates. Table 2.59 summarized the mass flow rates of all the
35 streams in the process based on manual calculation and simulation with respect to
their percentage deviation. The formula of percentage deviation calculation is given
below:
𝑀𝑎𝑛𝑢𝑎𝑙 − 𝑆𝑖𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛
𝑃𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝐷𝑒𝑣𝑖𝑎𝑡𝑖𝑜𝑛 = × 100%
𝑆𝑖𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛
Table 2.59 Comparison of Mass Balance Between Manual Calculation and

AVEVA PRO/II Simulation in Mass Flow Rate
Mass Flow Rate (kg/hr) Percentage

Stream
Manual Calculation Simulation Deviation (%)
S1 1500 1499.983251 0.00

S2 1500 1499.983251 0.00
S3 1500 1499.983251 0.00
S4 1500 1499.983251 0.00
S5 1500 1499.983251 0.00
S6 897 896.9829919 0.00
S7 603 896.9829919 32.77
S8 603 896.9829919 32.77
S9 603 896.9829919 32.77
S10 603 896.9829919 32.77
S11 897 896.9829919 0.00
S12 603 896.9829919 32.77
S13 603 2672.991914 77.44
S14 603 2672.991914 77.44
S15 891 2672.991914 66.67
S16 1788 3569.974907 49.92
108
S17 1788 3569.974907 49.92
S18 1784.68 3352.894835 46.77
S19 3.32 217.0800716 98.47
S20 603 896.9829919 32.77
S21 1784.68 3352.894835 46.77
S22 1784.68 3352.894835 46.77
S23 4358.72 10974.35982 60.28
S24 4358.72 10974.35982 60.28
S25 4358.72 10974.35982 60.28
S26 2074.96 10974.35982 81.09
S27 2074.96 8474.772604 75.52
S28 1971.21 6724.481987 70.69
S29 103.75 1750.441427 94.07
S30 1971.21 6724.481987 70.69
S31 1971.21 6724.481987 70.69
S32 2283.75 2499.587213 8.63
S33 2283.75 2499.587213 8.63
S34 2163.24 1202.881675 79.84
S35 120.51 1296.705538 90.71
According to Table 2.59, the deviation of mass flow rate for simulation and
manual calculation shows a big difference. This might be due to the calculation method
and data bank for the simulator is different from the manual calculation. The manual
calculation only uses Chemical Properties Handbook to obtain the constants and
formulas. However, the AVEVA PRO/II simulator might be using other method of
calculation such as American Society of Mechanical Engineers (ASME) standards.
Besides, the deviation might also due to different assumptions made in the simulator
and manual calculation. Less information is inserting into the simulator which is a
reason why the condition and flow rates generated by simulator is different from
manual calculation.
109
2.8.3 Energy Balance
Energy balance is defined as the state achieved when the energy intake equals
energy expenditure. The Law of Conservation of Energy states that energy can neither
be created nor destroyed, only converted from one form of energy to another. By
referring to the Yaw`s Chemical Properties Handbook 1999, specific heat capacity,
specific enthalpy, enthalpy flow rate and enthalpy change of each component can be
calculated.
The specific enthalpy of component can be calculated using Equation 2.38.
̂𝐣 = 𝐇
𝐇 ̂𝐟 + 𝐂𝐩 𝐝𝐓 (2.38)
where,
Hj = specific enthalpy of components j (J/mol)
Hf = specific heat of formation of the component j (J/mol)
Cp = specific heat capacity at constant pressure for component j (J/mol.K)
T = Temperature at reference state and desired temperature (K)
Equations 1.5 and 1.6 show the specific heat capacity of component in ideal
gas state and the integration of specific heat capacity (Yaws, 1999):
𝐓
∫ 𝐂𝐩𝐯 𝐝𝐓 = ∫𝐓𝐫𝐞𝐟(𝐀 + 𝐁𝐓 + 𝐂𝐓 𝟐 + 𝐃𝐓 𝟑 + 𝐄𝐓 𝟒 )𝐝𝐓 (2.39)
𝐓
𝐁𝐓 𝟐 𝐂𝐓 𝟑 𝐃𝐓 𝟒 𝐄𝐓 𝟓
𝐂𝐩𝐯 𝐝𝐓 = [𝐀𝐓 + + + + ] (2.40)
𝟐 𝟑 𝟒 𝟓 𝐓𝐫𝐞𝐟
where,
Cpv = specific heat capacity of component in ideal gas phase (J/mol.K)
Tref = reference temperature at boiling point (K)
T = reactor operating temperature (K)
A, B, C, D are the constants that can be obtained from Yaw’s Chemical Engineering
Handbook (1999).
110
To calculate specific enthalpy of component in liquid phase, Equations 2.41
and 2.42 are used (Yaws, 1999):
𝐓
∫ 𝐂𝐩𝐋 𝐝𝐓 = ∫𝐓𝐫𝐞𝐟(𝐀 + 𝐁𝐓 + 𝐂𝐓 𝟐 + 𝐃𝐓 𝟑 )𝐝𝐓 (2.41)
𝐓
𝐁𝐓 𝟐 𝐂𝐓 𝟑 𝐃𝐓 𝟒
𝐂𝐩𝐋 𝐝𝐓 = [𝐀𝐓 + + + ] (2.42)
𝟐 𝟑 𝟒 𝐓𝐫𝐞𝐟
where,
Cpv = specific heat capacity of component in ideal gas phase (J/mol.K)
Tref = reference temperature (K)
A, B, C, D are the constants that can be obtained from Yaw’s Chemical Engineering
Handbook (1999).
The heat of formation for component at specific temperature can be calculated

using Equation 2.43 (Yaws, 1999).
(∆𝐇𝐟° )𝐢 = 𝐀 + 𝐁𝐓 + 𝐂𝐓 𝟐 (2.43)
where,
(∆Hf° )i = heat of formation of component i (kJ/mol)
T = reactor operating temperature
A, B and C are the constants that can be obtained from Yaw’s Chemical Engineering
Handbook (1999).
Table 2.60 Reference State for Each Component
Component Temperature (K) Pressure (bar) Phase

Hydrogen, H₂ 298.15 1 Vapor
Carbon Monoxide, CO 298.15 1 Vapor
Methane, CH₄ 298.15 1 Vapor
Carbon Dioxide, CO₂ 298.15 1 Vapor
Methanol, CH₃OH 298.15 1 Liquid
111
Water, H₂O 298.15 1 Liquid
The state of the component at reference state which is 25°C and 1 bar is
compared with the state at reactor temperature and pressure. The boiling point of the
component at specific pressure is calculated using Equation 2.44 (Yaws, 1999).
𝐁
𝐥𝐨𝐠 𝟏𝟎 𝐏 = 𝐀 + 𝐓 + 𝐂𝐥𝐨𝐠 𝟏𝟎 𝐓 + 𝐃𝐓 + 𝐄𝐓 𝟐 (2.44)
where,
P = reactor operating pressure (mmHg)
A, B, C, D and E are the constants that can be obtained from Yaw’s Chemical
Engineering Handbook (1999).
The pressure is set at 50 bar and the boiling point of each component is obtained
using the “Goal Seek” function in Microsoft Excel. Table 2.61 shows the boiling point
and state of component at 50 bar and 250°C.
Table 2.61 State of Component at Reactor Temperature and Pressure
Component P (mmHg) P (bar) T (K) T (°C) Phase at 250°C

Hydrogen, H₂ 37503 50 44.40931 -228.741 Vapor
Carbon Monoxide, CO 37503 50 140.4031 -132.747 Vapor
Methane, CH₄ 37503 50 193.4309 -79.7191 Vapor
Carbon Dioxide, CO₂ 37503 50 287.3081 14.15809 Vapor
Methanol, CH₃OH 37503 50 484.5605 211.4105 Vapor
Water, H₂O 37503 50 537.12 263.97 Liquid
By comparing Table 2.60 and Table 2.61, we can observe that methanol
undergoes phase change from liquid state to vapor state in the reactor.
112
The energy balance calculation should include heat of vaporization when there
is a phase change for the component. The formula of heat of vaporization is shown in
Equation 2.45 (Yaws, 1999).
𝐓
∆𝐇𝐯𝐚𝐩 = 𝐀(𝟏 − 𝐓𝐁 )𝐧 (2.45)
𝐂
where,
∆Hvap = heat of vaporization of the component (J/kmol)
A, TC and n = Regression coefficient of the chemical compound
TB = Boiling point of the component at reactor pressure (K)
Therefore, specific enthalpy of the component without phase change is

calculated by adding the integration of specific heat capacity with heat of formation as
shown in Equation 2.46.
𝐓
𝐇𝐢 = (∆𝐇𝐟° )𝐢 + ∫𝐓 𝐂𝐩 𝐝𝐓 (2.46)
𝐫𝐞𝐟
where,
(∆Hf° )i = heat of formation of component i (J/kmol)
Cp = specific heat capacity of component (J/mol.K)
Whereas, specific enthalpy of component with phase change is calculated by

adding the integration of specific heat capacity, heat of formation and heat of
vaporization as shown in Equation 2.47.
𝐓 𝐓
𝐇𝐢 = (∆𝐇𝐟° )𝐢 + ∫𝐓 𝐂𝐩𝐕 𝐝𝐓 + ∫𝐓 𝐁 𝐂𝐩𝐋 𝐝𝐓 + ∆𝐇𝐯𝐚𝐩 (2.47)
𝐁 𝐫𝐞𝐟
where,
(∆Hf° )i = heat of formation of component i (J/kmol)
CpV = specific heat capacity of component in ideal gas state (J/mol.K)
113
CpL = specific heat capacity of component in liquid phase (J/mol.K)
∆Hvap = heat of vaporization of the component (J/kmol)
TB = Boiling point of the component at reactor pressure (K)
The enthalpy flow rate of each component is calculated by using Equation 2.48.
𝐇̇𝐢 = 𝐧𝐢 × 𝐇𝐢 (2.48)
where,
Ḣi = enthalpy flow rate of component i (J/hr)
ni = molar flow rate of component i (kmol/hr)
The enthalpy change across the reactor is then calculated using Equation 2.49.
∆𝐇̇ = ∑ 𝐇̇𝐨𝐮𝐭 − ∑ 𝐇̇𝐢𝐧 (2.49)
where,
∆Ḣ = enthalpy change (J/hr)
∑ Ḣout = Total enthalpy flow rate for outlet stream (J/hr)
∑ Ḣin = Total enthalpy flow rate for inlet stream (J/hr)
For an open system at steady state with negligible kinetic and potential energy
changes from inlet to outlet, and no energy transfer as shaft work, the energy balance
is shown in Equation 2.50.
𝐐̇ = ∆𝐇̇ (2.50)
where,
Q̇ = heat duty of the fixed bed reactor (J/hr)
114
2.8.3.1 Manual calculation of Energy Balance
The results on manual calculation of energy balance for each equipment in the
process are summarized in Table 2.62.
Table 2.62 Manual Calculation of Energy Balance for Each Equipment
Enthalpy Change (J/hr)

Equipment
Inlet Stream Outlet Stream
Compressor (C-101) 281755363.04
Intercooler (E-101) 159232741.09 0.00
Compressor (C-102) 281779098.15
Cooler (E-102) 159246340.57 12843291.08
Membrane Separator
0.00
(F-101)
Compressor (C-103) 85308709.82
Intercooler (E-103) 53924954.60 2700188.46
Compressor (C-104) 85308709.816689
Heater (E-104) 53924954.60 151043073.96
Compressor (C-105) 312939680.65
Heater (E-105) 195081222.44 2877122332.86
Pump (P-101) 1251365.06
Heater (E-106) 0.00 3708663091.48
Steam Reforming Reactor
6585785423.34 -995416993.19
(R-101)
Cooler (E-107) -995416993.19 330646224.91
Flash Column (F-102) 0.00
Compressor (C-106) -627704748.29
Heater (E-108) 1230614676.51 1498319558.09
Mixer (M-101) 0.00
Methanol Synthesis
4722773133.71 2776338822.65
Reactor (R-102)
115
Throttling Valve (V-101) -1344316236.67
Condenser (E-109) 6805101482.16 1209995662.97
Flash Column (F-103) 0.00
Splitter (S-101) 0.00
Compressor (C-107) 299846902.266352
Heater (E-110) 4323690810.64 3082550237.80
Throttling Valve (V-102) -8032907.843
Distillation Column
302792774.29 552792667.60
(T-101)
2.8.4 Energy Balance Comparison
The comparison between the mass balance obtained by manual calculation and
by AVEVA PRO/II simulation were carried out by determining the percentage
deviation of the energy flow rates. Table 2.63 summarized the energy flow rates of all
the 35 streams in the process based on manual calculation and simulation with respect
to their percentage deviation.
Table 2.63 Comparison of Energy Balance Between Manual Calculation and

AVEVA PRO/II Simulation
Energy Flow Rate (J/hr)

Percentage
Equipment Manual
Simulation Deviation (%)
Calculation
Compressor (C-101) 281755363 184379650.38 52.81
Intercooler (E-101) -159232741.09 184379650.38 186.36
Compressor (C-102) 281779098.2 185496403.68 51.91
Cooler (E-102) -146403049.48 193370299.49 175.71
Membrane Separator
0 0.00 -
(F-101)
Compressor (C-103) 85308709.82 278283039.16 69.34
Intercooler (E-103) -51224766.13 278283039.16 118.41
116
Compressor (C-104) 85308709.82 286685245.80 70.24
Heater (E-104) 97118119.37 496832766.12 80.45
Compressor (C-105) 312939680.6 264669627.06 18.24
Heater (E-105) 2682041109.41 2462852637.36 8.90
Pump (P-101) 1251365.059 4029901.55 68.95
Heater (E-106) 3708663091.48 10187604957.60 63.60
Steam Reforming
-7581202417 198280019.20 3923.48
Reactor (R-101)
Cooler (E-107) 1326063218 11980386457.20 88.93
Flash Column (F-
0 0.00 -
102)
Compressor (C-106) -627704748.3 116460575.86 638.98
Heater (E-108) 267704881.6 184686855.52 44.95
Mixer (M-101) 0 0.00 -
Methanol Synthesis
-1946434311 313816521.13 720.25
Reactor (R-102)
Throttling Valve (V-
-1344316237 0.00 -
101)
Condenser (E-109) -5595105819 11967976411.20 146.75
Flash Column (F-
0 0.00 -
103)
Splitter (S-101) 0 0.00 -
Compressor (C-107) 299846902.3 1003977164.52 70.13
Heater (E-110) -1241140573 3766326339.60 132.95
Throttling Valve (V-
-8032907.843 0.00 -
102)
Distillation Column
249999893.3 2899529111.16 91.38
(T-101)
According to Table 2.63, the percentage deviation between manual calculation

by Microsoft Excel and AVEVA PRO/II simulation are hugely different. There are six
equipment with enthalpy change difference larger than 100%. The largest difference
is found in the steam reforming reactor, which is more than 1000% deviation. The
possible reason to explain the difference is the simulator has different assumption on
the conversion of reactants. Besides, the other streams which has large different with
manual calculation might be due to different reference state used in simulator and
117
manual calculation. Therefore, the manual calculation should be verified by using
different simulator to check the validity of the result.
118
CHAPTER 3
EFFLUENT AND WASTE MANAGEMENT
3.1 Introduction
Regardless of the type of industry, whether it is the chemical industry or a

corporation, waste is unavoidable in every sector. Solid trash, liquid waste, and even
hazardous waste may be among the wastes. These wastes may not only be damaging
to the environment, but they may also pose a health risk to humans if not managed
appropriately. As a result, it is critical that waste management and disposal be carefully
examined. As a result, while selecting a location, it is critical to find one that has a
disposal system in place to effectively handle waste and effluent disposal.
Toxic, ignitable, corrosive, reactive, or radioactive waste are all examples of

hazardous waste. Wastes are substances that are disposed of, are intended to be
disposed of, or are required to be disposed of by national legislation, according to the
Basel agreement. While the United Nations Statistics Division (UNSD) defines waste
as resources that have no further value in terms of their production, transformation, or
consumption and that the user desires to dispose of. The raw materials from a plant
come in a range of compositions; those that aren't required for the final product will
be separated, leaving just the required goods.
It would be advantageous if the location had a proper waste disposal system.

There would be no waste problems as a result of this. Not only that, but everyone in
the facility should be trained in waste and effluent disposal so that the trash is not
exposed carelessly. Everyone in the facility should be aware of the rules and
regulations. Furthermore, relevant authorities should be engaged in order to better
understand and ensure that the plant waste and effluent disposal fulfils waste
management standards.
119
The undesired composition or trash is disposed of in a variety of methods.
There are rules for processing trash; the approach is such that garbage is collected,
stored, disposed of, or reused, as well as waste control. All types of trash, including
gaseous, liquid, and solid waste, must be treated. The method of waste management
might differ from firm to company. To protect the community's health and safety,
appropriate waste management is necessary to avoid any contamination in our society.
3.1.1 Waste Management Practices
Factories produce a lot of waste, most of which can pollute the air we breathe,
the water we drink, and the land we live on if improperly managed. As a result, we
must not only manage this garbage, but also devise plans for long-term waste
management. There have been several forms of sustainable waste management
proposed and utilised over the years.
Sustainable waste management entails collecting, sorting, processing, and

recycling garbage, as well as being a source of energy and resources when
appropriately enabled. As a result, it creates jobs, improves waste management
systems, and reduces the environmental effect of human activities, consequently
improving air and water quality. It also decreases food waste, lowers environmental
expenses, and avoids various human health disorders, therefore improving human life
in general.
There are criteria for waste treatment; the technique involved is waste
collection, storage, disposal, or reuse, as well as waste control. All types of garbage
must be managed, including gaseous, liquid, and solid waste. The approach to waste
management might differ from one firm to the next. To protect the community's health
and safety, appropriate waste management is necessary to avoid any contamination to
our society. This is due to the fact that the plant will be built in Malaysia in accordance
with the standards established by the Department of Environment (DOE). The DOE is
responsible for ensuring that all chemical facilities have constructed a waste treatment
unit to process waste in accordance with requirements.
120
3.1.2 Legalization in Malaysia
In Malaysia, the government has taken steps to address the potential problems
caused by the mismanagement of industrial waste disposal. In general, Malaysia's
industrial growth has changed dramatically since the 1970s. Part of it was Malaysia's
rapid rise in small and medium-sized industries (SMIS) throughout the 1990s (Harun
et al., 1992). However, it is worth noting that anytime industries or factories produce
items, they usually produce garbage/industrial waste. In reality, the overall amount of
garbage in this country has always risen as a result of industrial expansion, population
growth, and urbanisation (Abd Malek et al., 1996).
In Malaysia, the Department of Environment (DOE) is responsible for

overseeing the regulation of industrial waste, having passed the Environmental Quality
Act of 1984 with the intent of protecting the quality of the human environment, as well
as pollution prevention, abatement, and control, environmental enhancement, and
related purposes. As a result, the DOE has already enacted over twenty laws and
subsidiary legislations to safeguard the environment, as well as a variety of incentives
to encourage businesses to invest in cleaner technology rather than end-of-pipe
pollution treatment (Maidin, 2005). The Environmental Quality Act 1974 (Act 127)
and Regulations (EQA1974), Environmental Quality (Sewage and Industrial
Effluents) Regulations 1979, Environmental Quality (Prescribed Premises) (Schedule
waste treatment and disposal facilities) Order 1989, and Environmental Quality
(Scheduled Wastes) Regulations 1 are among the statutes and subsidiary legislations
introduced by the DOE in the area of industrial waste management control in Malaysia
(Awang et al., 1990).
The Environmental Act of 1974 contains Sections 25, 27, and 29 in relation to
the disposal of wastewater. Section 25 prohibits the pollution of inland waters, that no
person shall, unless licensed, dispose of any environmentally hazardous substances
into any inland waters. Section 27 expands on that, with the prohibition of discharge
of oil into Malaysian Waters. Similarly, Section 29 prohibits the discharge of wastes
into Malaysian waters in general, and any person to do so shall be guilty of an offence
and liable to a fine or imprisonment. These laws were instituted with the intent of
121
preventing major damage to the natural ecosystem and to force factories to keep proper
waste disposal in mind. It's important to note that most end-of-pipe treatment or
disposal options shift the problem elsewhere, resulting in higher costs for waste
treatment, handling, and disposal, as well as on-site waste control and monitoring, all
of which can amount to a significant financial investment on the company's part.
Furthermore, on-site waste storage is necessary, which is highly costly and may be
better used for productive operations. It's worth mentioning that end-of-pipe control is
typically expensive to build and execute, thus it doesn't always deliver the intended
effects. As a result, end-of-pipe management usually involves significant non-
production capital investments as well as continuing operational costs.
3.1.3 Sustainable Development Goals
Malaysia began its road toward sustainable development in the 1970s, when
the New Economic Policy (NEP) was implemented to eradicate poverty and reorganise
socioeconomic inequalities. All subsequent five-year national development plans have
emphasised the elements of sustainable development, which include sustainable
economic growth, growth that is distributed equitably to all segments of society,
balanced development, access to basic infrastructure and utilities, access to education
and healthcare services, and mainstreaming of environmental conservation.
In September 2015, the United Nations (UN) organized a call to action for its
constituent countries, including Malaysia, to adopt a set of policies meant to combat
several global issues at once. These were the Sustainable Development Goals (SDGs),
also known as the Global Goals, and were approved in 2015 by all United Nations
Member States as a global call to action to eradicate poverty, safeguard the
environment, and guarantee that all people live in peace and prosperity by 2030.
Malaysia's involvement in the international development of the SDGs began in late
2014, with the Economic Planning Unit (EPU) participating in the negotiation process
between United Nations country members (Inter-Governmental Meetings) held from
January to July 2015 to finalize the Post-2015 Development Agenda (P2015DA).
Discussions among United Nations nation members included the P2015DA
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declarations, Sustainable Development Goals and Targets, Means of Implementation,
and follow-up and evaluation.
In order to fulfil their commitment to the SDGs, Malaysia has established a

National Governance Council for SDGs, chaired by the Prime Minister of Malaysia.
As displayed below by Figure 3.1, the Council is supported by a National Steering
Committee (NSC) led by the Director General of the EPU. The High-level Political
Forum reports to the UN on the National SDG Council. The NSC is made up of five
SDG Cluster Working Committees (CWCs), each of which is made up of Task Forces
for each of the Goals. The figure also depicts the five CWCs and their related SDGs.
The CWCs are in charge of establishing indicators for each SDG, planning and
executing program, and reporting progress to the NSC.
Figure 3.1 The SDG Governance Structure in Malaysia (EPU, 2021).
There are 17 SDGs in total, each one interconnected with each other, which
means that actions in one area influence outcomes in others, and that development
must balance social, economic, and environmental sustainability. The 17 SDG targets
are critical in shaping the world, especially in the chemical industry in which several
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SDGs may be applied. The chemical industry's production of methanol generates
waste, which must be treated before it may be discharged into the environment. This
waste may be treated in accordance with regular waste disposal regulations as well as
the SDGs.
Among the SDGs applicable to the chemical industry include the 1st, 3rd, 6th,
12th, 13th, 14th, and 15th. The 1st SDG is "No Poverty," which entails focusing on
helping the most vulnerable people, expanding basic resources and services, and
assisting communities affected by conflict and climate-related disasters. Employers in
the chemical industry have a responsibility to pay livable salaries and give benefits to
their employees, as well as fulfil their supply chain duties. Progress made in terms of
financial growth should assist in promoting economic growth in poorer countries.
The 3rd SDG is “Good Health and Well-Being”. The 2030 Agenda recognises
the importance of good health in achieving sustainable development, and it reflects the
complexity and interconnection of the two. It considers growing economic and social
inequality, increased urbanization, climatic and environmental risks, the ongoing
burden of HIV and other infectious illnesses, and new issues such as
noncommunicable diseases. Universal health coverage will be integral to achieving
SDG 3, ending poverty and reducing inequalities. Emerging global health priorities
not explicitly included in the SDGs, including antimicrobial resistance, also demand
action. This means that the chemical industry should prioritize human health and safety
foremost among its employees.
Water shortages are becoming increasingly prevalent in more nations, and

rising drought and desertification are exacerbating the problem. It is predicted that by
2050, at least one in every four individuals would face periodic water shortages. It is
the aim of the 6th SDG, “Clean Water and Sanitation”, to address this issue. Access to
safe drinking water and sanitation is a global issue that must be addressed at the local
level, and chemistry plays a critical role. Innovative pipe solutions help to decrease
water loss in operations and supply chains while also aiding in the transformation of
water distribution networks. Water quality is enhanced as a result of developments in
the chemical industry's water management, which decreases pollution, eliminates
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improper disposal and minimizes the discharge of toxic chemicals and materials,
reduces the volume of untreated wastewater, and improves recycling and safe reuse.
That aside, to achieve economic growth and long-term development, we must

immediately shrink our ecological footprint by altering how we create and use
commodities and resources. Agriculture is the world's largest water user, and irrigation
currently accounts for about 70% of all freshwater used for human use. To this end,
SDG 12 is about ‘Responsible Consumption and Production”. The chemical industry
distributes goods that enhance the quality and efficiency of manufacturing processes
in a variety of sectors. Chemists have helped businesses in a variety of industries and
regions improve their water stewardship and energy efficiency. From food packaging
and additives to decrease food loss and waste to waste management system
improvements, the chemical industry is assisting in the transformation of production
and lowering the life cycle impacts of consumption.
Finally, SDG 13, 14, and 15 all seek to prevent and stymie the negative effects
that improper waste disposal can have on the environment. Plastic pollution has proven
disastrous for the planet and its passengers, both present and future. Three-quarters of
the world's largest open landfills are on the coast, seeping toxic pollutants into our
seas. There is unlikely to be a single beach on the planet that does not have the remains
of plastic fishing nets, cigarette butts, and plastic straws. Large sea creatures are
showing up dead on the beach, their stomachs so full with trash that they have starved.
People could put their trash on the ground and it would decompose only two
generations ago, before the advent of throwaway plastic. Not anymore, with plastic
blocking drains and being consumed by cattle.
Chemicals leak into groundwater, streams, and rivers from massive amounts
of discarded garbage. Land-based life can only be healthy if waste is appropriately
handled. Supporting vulnerable regions will have a direct impact not just on Goal 13,
but also on the other SDGs. These steps must be carried out in tandem with attempts
to include catastrophe risk reduction measures, sustainable natural resource
management, and human security into national development strategies. The chemical
industry has begun working together to address the issue of climate change through a
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number of efforts such as energy efficiency, lowering carbon footprints, and
developing new ways to reduce downstream emissions. Furthermore, chemical
businesses are collaborating to increase the sector's and its supply chain's resilience
and adaptive ability in response to the effects of climate change. The industry also
plays an important role in the development of solutions that will allow other sectors to
improve their resilience to climate-related threats.
3.1.4 Effluent and Waste Generated from Methanol Production Plant
In the case of the Methanol Production Plant, the by-products can be divided
into three categories, that is Solid, Liquid and Gas Waste. Table 3.1 below displays the
overall amount of each waste that is generated by the plant along with the source. Each
by-product is sorted into their respective classification.
Table 3.1 Classification of Effluent and Waste Produced by the Plant
Type of Source Stream

Waste Generated
Waste
Ni/SiO2Al2O3 Steam Methane Reforming

S16
Catalyst Reactor (R-101)
Solid
Cu/ZnO/Al2O3 Methanol Synthesis Reactor (R-
S23
Catalyst 102)
First Flash Column and

S19 &
Liquid Wastewater Distillation Column
S34
(F-102 &T-101)
Carbon Dioxide
Carbon Monoxide
Gas Flash Flash Column (F-103) S27
Methane
Hydrogen
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3.2 Solid Waste
In the production of methanol from the biogas process, solid waste is

generated from the catalyst used in the steam methane reforming reactor (SMR) and
also the methanol synthesis reactor. The SMR reactor is used to produce syngas, a
mixture of carbon monoxide and hydrogen from methane obtained from biogas.
3.2.1 Solid Catalyst
A catalyst helps to increase the rate of chemical reaction by lowering the

activation energy of the reaction itself, to produce a different end product (Solanki et
al., 2021). However, in a well-controlled process, the loss of catalytic activity or
selectivity happens over time. This occurrence is known as catalyst deactivation
(Bartholomew et al., 2001). In certain chemical plants, it costs billions of dollars per
year for catalysts replacement and process shutdown. The lifetime for catalysts varies
considerably. Some have a mortality of a few seconds whereas some catalysts take
years for deactivation. However, it is inevitable that all catalysts will decay. There are
certain mechanisms that cause catalyst deactivation which are listed in Table 3.2
(Morris et al., 2015).
Table 3.2 Mechanism of Catalyst Deactivation.
Mechanism Type Description
Strong chemisorption of species on

Poisoning Chemical catalytic sites which block sites for
catalytic reaction
Reaction of gas with catalyst phase to

Vapor formation Chemical
produce volatile compound
Vapor–solid and Reaction of vapor, support, or

solid–solid Chemical promoter with catalytic phase to
reactions produce inactive phase
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Physical deposition of species from
Fouling Mechanical fluid phase onto the catalytic surface
and in catalyst pores
Thermal Thermally induced loss of catalytic

Thermal
degradation and surface area, support area, and active
Thermal/chemical
sintering phase-support reactions
There are two types of catalyst used in the plant operation. The first catalyst
used is in the SMR reactor, which is the Ni/SiO2Al2O3 catalyst. This is to increase
the selectivity and yield of hydrogen produced from methane. The second catalyst used
is in the methanol synthesis reactor, which is the Cu/ZnO/Al2O3 catalyst. This is to
increase the conversion of methane and the selectivity of methanol.
3.2.2 Management of Solid Waste
In recent times, spent catalysts discarded as solid wastes by chemical plants are
increasing drastically. Spent catalysts are labelled as hazardous waste due to their toxic
nature. Environmental authorities are very strict about handling and managing this
hazardous waste safely (Marafi et al., 2003). Spent catalyst can be managed by
scheduled waste, regeneration of spent catalyst, and recovery of metal components
from spent catalyst.
Regeneration is the process of restoring the catalytic activity of a spent catalyst.

Thermal treat is used to remove surface coatings and/or absorbed species.
Regeneration is typically the environmentally and economically favored choice for
dealing with spent catalysts. It is technically feasible, as it enables extended catalyst
use, minimizes the use of new raw materials, and eliminates the need for ultimate
recovery or disposal (Morris et al., 2015).
The composition and physical properties of the regenerated catalyst can be

different from fresh catalyst and additional contaminants might be present. It is also
difficult to recover the function of a permanently deactivated catalyst with normal
128
regeneration procedures. Fortunately, the deactivation of the catalyst due to coke
deposition is normally reversible, and oxidation with aluminum will easily remove the
coke (Guisnet and Magnoux 1994). One of the most frequent methods of catalyst
regeneration is through air or oxygen via an oxidation phase. High exothermicity,
however, can easily cause overheating, leading to de-lighting, metal sintering, and
degradation of the catalyst (Zhou, Zhao et al. 2020).
In metal recovery from the spent catalyst method, large constituents dependent
on metals can be extracted by various treatments. Some of the process examples are
pyrometallurgy, hydrometallurgy, and biometallurgy (Micelli et al., 2021). Metal
recovery not only decreases the quantity of waste disposed but also conserves the
environment.
Another method for catalyst management is through scheduled waste.

Scheduled waste is defined as any waste falling within the categories of waste listed
in the First Schedule of the Environmental Quality (Scheduled Wastes) Regulations
2005. Based on the Environmental Quality (Scheduled Wastes) Regulations 2005,
within 30 days of the date of generation of scheduled wastes, each waste generator
must notify the Director General of the new types and quantities of scheduled wastes
generated. There are in total 77 types of schedule wastes listed in the regulations and
it is divided into 5 groups. Based on DOE, the catalysts waste from our plant will be
categorized as SW 2 which means the waste contains inorganic constituents which
may contain metals and organic materials. The catalyst waste is labelled as SW 202
under SW 2 code. As the waste generator, we will need to strictly follow the
regulations stated within the Environmental Quality (Schedule Wastes) Regulations
2005 to manage the solid wastes and also to avoid any pollution problem that can
occur. As an example, the waste can only be treated and disposed of at prescribed
premises only and the wastes may be stored for not more than 180 days and the
quantity must not exceed 20 tones.
129
Figure 3.2 Methods for Handling the Spent Catalyst (ECMA, 2018)
130
3.2.3 Comparison Solid Waste Management Methods
Table 3.3 Comparison Between Spent Catalyst Management Methods
Regeneration of Recovery of metal

Parameters Scheduled waste
spent catalyst components
High cost High initial None

Cost investment
(0) (0) (2)
Space Yes Yes None

requirement (0) (0) (2)
Save cost from Yes, metal recovered

None
buying new can be sold to scrap
Profitable catalysts dealers
(0)
(1) (2)
Requires labou\r
Requires labor load Easy operation and
load
Operation and monitoring no need manpower
and monitoring
(0) (2)
(0)
• Reduces the Disposal is Does not harm the

need for environmentally environment as long
disposal if friendly because as all the regulation
ultimate metal constituents from DOE are
Environmental
recovery are removed followed
effect
• Reduce accordingly
hazardous
waste
(2) (2) (2)
Total rating 3 4 8
Based on the comparison between the three methods, our company has decided
scheduled waste as our solid waste management method. This method is easier and
also cost effective. This method also does not require any space in our plant as
131
compared to the other two methods. Scheduled waste will not cause any harm to the
environment if Environmental Quality (Scheduled Wastes) Regulations 2005 is
followed accordingly. Regeneration method is not conducive for our company because
the regenerated catalyst may not have the same efficiency and activity level as the new
catalyst. The composition and the physical properties of the regenerated catalyst might
vary after the process. There will also be a certain amount of additional contamination
in the regeneration method. The catalyst cannot be used for many cycles as the catalyst
activity will decrease in each cycle. The recovery of metal components from the
catalyst method might be giving us profit but this process requires high cost and
maintenance also needs to be done from time to time. We also require more labor force
there which nullifies the profit gain from production of metals.
3.3 Liquid Waste
Wastewater is released from the first flash column and distillation column. In
the first flash column, the wastewater contains impurities in the form of carbon dioxide
since carbon dioxide is soluble in water. Wastewater from the distillation column will
have impurities such as methanol. The standard shall meet as that is set from the
Department of Environment (DOE) in Malaysia.
3.3.1 Wastewater
A wastewater treatment plant removes impurities from industrial wastewater

through physical, chemical and biological processes (Anjum et al., 2016). An effective
and well-designed treatment system will handle process fluctuations in contamination
and flow, variations in water chemistry needs and needed chemical volume
modifications, as well as any changes in water effluent requirements (SAMCO, 2016).
Industrial effluent is known as the used water from manufacturing and chemical
processes in a plant.
From our plant, the wastewater produced from the flash column and distillation
column will contain impurities such as carbon dioxide and methanol. Thus, it is
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necessary for the wastewater to be treated before being discharged to the environment.
Based on the Department of Environmental (DOE), the acceptable standard industrial
effluent discharge conditions under fifth schedule are listed in table below.
Table 3.4 DOE Acceptable Standard Industrial Effluent Discharge Conditions
Standard
Parameter
A B
Temperature (℃) 40 40
pH value 6.0-9.0 5.5-9.0
Biochemical Oxygen Demand (BOD) at 20℃ (mg/L) 20 50

Note: Standard A is only implemented for any inlands water areas attached to the third
schedule, while standard B is to any other inlands water including Malaysian waters.
3.3.1.1 Management of Wastewater Treatment
Wastewater treatment has three levels: primary, secondary and tertiary

treatment. In the primary treatment, 60% of total suspended solids (TSS) and 35% of
BOD is removed, but dissolved impurities are not removed here. It is usually done in
the secondary treatment and also 85% of both TSS and BOD is removed from
secondary treatment. Tertiary treatment is only done when more than 85% of total
solids and BOD is needed to be removed (Nathanson., 2021). The wastewater
treatment steps are screening and pumping, grit removal, primary settling, aeration,
secondary settling, filtration, disinfection and oxygen uptake. Methanol plants produce
large volume of wastewater containing less than 10% methanol (Dawery et al., 2007).
There are a few treatment technologies that can be used to treat wastewater.
For our company, we have compared membrane filtration and trickling filters.
Recently, membrane technology had a high demand compared to other treatment
methods (Haan et al., 2017). In the wastewater treatment, wastewater is pumped
through the membrane module and then returned to the bioreactor. Membrane
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bioreactor can remove particles as small as 1nm which makes this a very highly
efficient technology. Pre-treatment is required to avoid solids in the waste stream from
entering the membrane tank and damaging the membrane (Mukhtar et al., 2020).
Figure 3.3 Membrane Filtration Process in Wastewater Treatment (Singh, 2014)
Activated sludge process on the other hand is a wastewater treatment process

that uses microorganisms as a method to remove nutrients from the water. This process
has a multi-chamber reactor unit that uses oxygen to regulate aerobic conditions and
to suspend the sludge. This process begins with oxygen interacting with unsettled
sewage. The solid particles are broken down and air bubbles formed due to the sewage.
The sewage is discharged into an activated sludge chamber. Living bacteria settles to
the bottom of the tank and dead bacteria floats at the surface. Clean water is then
discharged. When wastewater that contains methanol undergoes activated sludge
treatment process, methanol concentrations will drop and will be consumed quickly
by the bacteria of the activated sludge as it enters to the sludge vessel. The bacteria
within the sludge solution can adapt to an organic source such as methanol (Al-Dawery
et al., 2015).
Figure 3.4 A Generalized Schematic Diagram of an Activated Sludge Process.

(Salam Al-Dawery., 2013)
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3.3.2 Comparison of Wastewater Treatment Methods
Table 3.5 Comparison between trickling filtration and membrane filtration

treatment method
Parameters Activated sludge Membrane Filtration
COD/BOD 61% >95%

elimination (0) (2)
Skilled operational staff

Only need monitoring for
required to check returned
Monitoring membrane fouling
sludge
(1)
(0)
Low installation cost but Equipment and membrane

high operating cost costing is high
Costing (RM22,000) Membrane: RM858
(12-18 months lifeline)
(1) (0)
Energy
0.30-0.65 0.03 to 0.2
requirement
(0) (2)
(kWh/𝑚3 )
Not very flexible Flexible

(changes in type or volume (can be used in the separation,
of sewage can affect effluent concentration and purification
Flexibility
quality) of a huge variety of materials
across a wide range industries)
(0) (2)
Total Rating 1 7
Based on the comparison done in the table above, the ratings for membrane
filtration method are higher than activated sludge. It is indeed true that the costing of
membrane filtration is more expensive, due to renewing membrane frequently and the
maintenance of membrane filter (Nguyen et al., 2020). But this disadvantage can be
overlooked due to other advantages such as its effluent quality and efficiency which is
more than 95%. Compared to activated sludge, membrane filtration is more flexible
and can function efficiently even in low temperatures. Thus, we have decided that
membrane filtration is the best method to treat our wastewater.
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3.4 Gas Waste
The production of methanol from biogas has generated a few gas wastes
namely carbon dioxide, carbon monoxide, methane, and hydrogen. These gases are
removed via the first and second flash columns. In the first flash column, a certain
amount of carbon monoxide, methane, and hydrogen gas is released as gas waste.
Carbon dioxide is not found here because this gas is soluble in water, therefore it is
removed in the wastewater. In the second flash column, certain amounts of gases such
as carbon dioxide, carbon monoxide, methane, and hydrogen are purged to restrict the
build up in concentration of the components when recycled back to the reactor. These
purged gases are also considered as gas waste from our plant. In our company, we have
compared using three methods such as, membrane filtration, electrostatic precipitator
and absorption process.
3.4.1 Membrane Separation of Gas Wastes
Membrane technology has evolved into a respectable separation technology

over the millennia. Membrane technology's key advantage is that it operates without
the use of chemicals, uses very little energy, and has simple and well-organized
process conductions. The most appealing feature of membrane separation is its
simplicity. One or more components of the gas mixture preferentially permeate
through the membrane, retaining the rest of the gaseous stream in the retentate.
Compressing the feed gas or utilizing a vacuum on the permeate side provide the
necessary driving force to promote permeation. To manufacture high purity gases, a
one-stage procedure is usually insufficient. To this end, multi-stage gas separation and
membrane-hybrid techniques have been devised (Brunetti et al., 2015). Membranes
are extremely appealing in situations where product demand is not consistent when
compared to classic technologies such as absorption, adsorption, and cryogenics
because of their operating simplicity and adaptability.
136
Figure 3.5 The Principle of Membrane Separation (Green, 2015).
The permeability and selectivity of the gas to be separated are key factors in
membrane gas separation. Selectivity is defined as the ratio of desired gas
permeabilities to all other gases passing through the membrane at the same time (Ji &
Zhao, 2017). The benefits of this method is that it has low energy demands, simple
maintenance (Shankar et al., 2019), environmentally friendly, low cost of the
polymeric membranes and has many manufacturers (Yan et al., 2019). The
disadvantages of this method are low permeability and selectivity, poor stability,
ageing, swelling and sensitivity to the content of impurities and water (Wang et al.,
2019).
3.4.2 Flaring Method of Gas Wastes
Many industrial processes, such as oil-gas extraction, refineries, chemical

plants, coal industries, and landfills, use gas flaring to burn related, undesirable, or
excess gases and liquids generated during normal or abnormal over-pressuring
operations (Emam., 2015). Gas flaring is not an environmentally friendly method of
recovering gases from the industry because it is a significant source of greenhouse
gases emissions. It also produces noise and heat, as well as rendering enormous areas
uninhabitable. According to the World Bank, between 150 and 170 billion 𝑚 of gases
are flared or vented each year, equating to $ 30.6 3 billion (Anderson et al., 2012).
Thus, the gas flaring method is not really an advisable method for gas recovery.
137
Therefore, there is a pressing need to measure flared gas by knowing its composition,
distribution and volume, additionally, applying the suitable flare gas recovery system
or disposal.
Figure 3.6 Flaring Process in An Oil Refinery Plant (Karthikayen, 2020).
3.4.3 Electrostatic Precipitator
An electrostatic precipitator (ESP), also known as an electrostatic air cleaner,

is a device that removes particles from a gas stream by charging particles positively or
negatively with electrical energy. The charged particles are then drawn to collecting
plates that are charged in the opposite direction. The collected particles can be taken
from the collection plates as dry material (dry ESPs) or washed away with water (wet
ESPs). ESPs can achieve collection efficiency of more than 99 percent.
A single transformer-rectifier (T-R) set power supply powers the discharge

electrodes. The activated electrodes generate ions, which collision with the particles
in the incoming gas stream and add an electrical charge to them. The charged
138
particulate matter is collected on the surfaces of the collecting plates or pipes. The
rapping system is in charge of eliminating particle debris from the collection surfaces.
Dry ESPs (the most often utilised) and wet ESPs are the two types of ESPs.
The fundamental distinction between the two categories is how the collection plates
are cleaned. The collecting plates of dry ESPs are cleaned by delivering mechanical
impulses or vibration to the plates, knocking free the accumulated particulate matter
(referred to as rapping). The collecting plates in wet ESPs are cleaned by rinsing with
water. When gas streams contain sticky particles with low resistivity, wet ESPs are
frequently used.
Particle resistivity can have an impact on ESP performance. Particle resistivity

is a characteristic that effects particle deposition and removal from collecting plates.
The ideal scenario is to have particles that carry away some of their charge once they
reach the plate, so that the deposition of subsequent particles is not hampered but retain
enough charge to hold them gently to the plate (Parker et al., 1997). The property is
known as mild resistivity. If the particles have a high resistivity, they take a long time
to conduct their charge away, causing a negative charge to accumulate on the plates,
preventing other particles from depositing. If the particles have a very low resistivity,
they rapidly lose their charge as they approach the plate and pick up the plate's charge,
causing them to be repelled back into the gas stream and negatively recharged.
The power supplies for the ESP convert the industrial AC voltage (220- 480
V) to pulsating DC voltage in the range of 20,000-100,000 V as needed. The supply
consists of a step-up transformer, high-voltage rectifiers, and sometimes filter
capacitors. The unit may supply either half-wave or fullwave rectified DC voltage.
There are auxiliary components and controls to allow the voltage to be adjusted to the
highest level possible without excessive sparking and to protect the supply and
electrodes in the event a heavy arc or short-circuit occurs (Kim et al., 1999). The
voltage applied to the electrodes causes the gas between the electrodes to break down
electrically, an action known as a "corona." The electrodes usually are given a negative
polarity because a negative corona supports a higher voltage than a positive corona
139
before sparking occurs. The ions generated in the corona follow electric field lines
from the wires to the collecting plates.
As a result, each wire establishes a charge zone across which particles must
pass. Particles travelling through the charging zone intercept some of the ions that get
bonded. Small aerosol particles (diameter 1 𝜇m) can absorb tens of ions before their
accumulated charge becomes significant enough to reject future ions, but giant
particles (diameter >10 𝜇m) can absorb tens of thousands. As a result, the electrical
forces on big particles are significantly greater (Turner et al., 1988).
As the particles pass each successive wire, they are driven closer and closer to
the collecting walls. The turbulence in the gas, however, tends to keep them uniformly
mixed with the gas. The collection process is therefore a competition between the
electrical and dispersive forces (Turner et al., 1988). Eventually, the particles approach
close eough to the walls so that the turbulence drops to low levels and the particles are
collected. If the collected particles could be dislodged into the hopper without losses,
the ESP would be extremely efficient. The rapping that dislodges the accumulated
layer also projects some of the particles (typically 12 percent for coal fly ash) back
into the gas stream. These reentrained particles are then processed again by later
sections, but the particles reentrained in the last section of the ESP have no chance to
be recaptured and so escape the unit.
ESPs are common installations on coal-fired power plants to remove over 99%
of ash particles from million ft3 per minute of fumes. They stand tens of meters tall.
These precipitators are built of high-alloy stainless steels and generally cost between
$90 and $120 per square foot. (Turner et al., 1988)
140
3.4.4 Comparison of Gas Waste Management Method
0 – Least favourable; 1 – Favourable; 2 – Most favourable
Table 3.6 The Comparison Between Absorption and Membrane Separation of

Carbon Dioxide Treatment Methods
Membrane Electrostatic
Parameters Flaring
Separation Precipitator
RM 200- RM395 -
RM 10,000-RM12,000
Cost RM400/ton RM526.68/ton
(0)
(2) (1)
100% 60-80% 95.7%–99.9%

Recovery
(2) (0) (1)
High greenhouse gas Conserves Conserves

Environmental
emission environment environment
Effects
(0) (2) (2)
Operating Moderate High Low

flexibility (0) (2) (0)
High Moderate Low

Maintenance
(0) (1) (2)
Total Rating 2 7 6
Based on the comparison done in table above, membrane separation has the
highest rating therefore this method is chosen for gas waste treatment in our plant.
When compared to the flaring method, membrane separation is cheaper and has easy
maintenance. Unfortunately, membrane separation is not 100% efficient in removing
gas wastes as compared to flaring but this is disregarded because flaring produces
greenhouse gases such as sulphur dioxide, carbon dioxide and NOx gases to the
environment. Flaring method is also expensive and has high maintenance. This method
causes high nuisance in the form of sound, smelled, warmth and light-production.
The electrostatic precipitator method does offer another viable solution to the
gas waste management. The efficiency of an electrostatic precipitator is determined by
a variety of elements such as particle resistivity, corona power ratio, and so on. Under
141
typical conditions, their effectiveness for particle removal is quite good, with up to
99% removal of dust particles. Over a wide range of particle sizes (0.05-5m),
electrostatic precipitators have reasonably good collection efficiency (99-100%).
Electrostatic precipitators have minimal operating costs and are economically viable
in the long term.
However, the high initial capital cost of electrostatic precipitators renders them
prohibitively expensive for small-scale companies. They are costly to buy and install.
They are not only expensive, but they also take up a lot of area to put up. Again, the
value proposition for small-scale enterprises is decreased since they are expensive and
require a lot of room to set up. Electrostatic precipitators lack operational flexibility.
It is impossible to adjust the capacity of the ESP or relocate it once it has been installed.
As a result, careful planning for the capacity, kind, and location of the ESP is required.
Due to these factors, the membrane separation is much more fitting for what we have
in mind in regard to this plant.
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CHAPTER 4
ENERGY INTEGRATION
4.1 Introduction
Process integration (PI) is defined as “a holistic approach to design and operation that
emphasises the unity of the process” and it has been used primarily to improve the efficiency
of process plants, thereby improving profitability while reducing resource consumption and
waste generation (Foo, El-Halwagi, & Tan, 2017). PI is a powerful tool for designing and
optimising processes in terms of efficiency in the use of energy, water and other resources, and
also sustainability and it has been widely extended, and has become both a part of the curricula
of most good engineering degree courses, as well as a routine tool for advanced design
and optimisation in various industries (Klemeš, 2013). It is indeed a good strategy to sustain
the energy produce and reused it back for the design and operation of chemical plant.
The research of PI has started since early 1980s with an emphasis on energy efficiency
(Babaei, et al., n.d). Systematic methods for the design of heat exchanger networks is actually
the first and main focus of process integration. Later on, the techniques and ideas was
developed to solve the heat exchanger network problem provided the basis for the extension of
the methodology into new areas. It is included on the network of the chemical plant.
Figure 4.1 Example of heat exchanger network (Dunn & El-Halwagi, 2003)
143
In the past, for waste reduction tasks, the industrial goal was to identify a recovery
system that would effectively allow the recycle and reuse of certain wastes and due to that, this
goal was generally accomplished by postulating a variety of process system configurations and
operating conditions and then individually screening these alternatives to evaluate their overall
economic impact to the company such as capital investment, operating cost and equipment cost
(Dunn & El-Halwagi, 2003)
In our plant, in order to produce methanol from biogas, there will be several operations
that will need to be consider such as separation and reaction inside the methanol synthesis
reactor. When the operations vary across the network of chemical plant, the unit operations that
will need to be used also need to be consider. In order to achieve desired temperature and
pressure, additional unit operations will need to be used such as cooler, intercooler and heat
exchanger. This unit operations can be costly for a plant site. So, in order to use it at maximum,
the heat or cold energy will be used back and recycle throughout the overall plant. This is why
understanding process integration and do heat integration will help in preventing any wastage
of energy.
4.2 Stream Identification
All of the hot and cold streams from the process flow diagram illustrated in Figure 4.2
are recognized before developing the heat exchanger network. Table 4.1 summarizes the hot
and cold streams from the process that may be employed to maximize energy recovery for the
process design.
144
Biogas Water
S14
S13
S1 S6
E-106
P-101
S15
C-101
C-105
S2 S5
F-101
E-101 E-102
To F-102
S11 S12 S16
S3 S4 Sheet 2 of 3
S7
E-105 E-107
R-101
C-102 C-103 S8 S9
E-103
C-104 To M-101
S10
Sheet 2 of 3
E-104
Figure 4.2 Hot and Cold Equipment in Methanol Production Plant
145
S28
E-110 C-107
S29 Purge
C-106
S31 S30 S-101
S18 S21 S27
E-111
E-109
E-108
S22 S23 S24 S25 S26 F-103
V-101
From E-107
S17
Sheet 1 of 3 F-102
M-101
S34
R-102 Methanol
T-101
S32
S19
S33
Water
(l) V-102 E-112
S35
Carbon dioxide
From E-104
S20 Water
Sheet 1 of 3
Figure 4.3 Hot and Cold Equipment in Methanol Production Plant (Continued)
146
The relevant values, such as supply temperature (Ts), target temperature (Tt), heat
capacity flow rate (CP), and change of enthalpy (H), are retrieved from the energy balance
calculations in Chapter 2. Heat capacity flow rate, CP is defined as the product of specific heat
capacity and mass flow rate of the related stream as shown in Equation 4.1.
𝐶𝑃 = 𝑚̇ × 𝐶𝑝 (4.1)
where,
CP = Heat capacity flow rate (kW/°C)
𝑚̇ = Mass flow rate (kg/s)
Cp = Specific heat capacity (J/kg.°C)
As indicated in Table 4.1, there are a total of 10 heat exchangers available for heat
integration analysis: five hot streams and five cold streams.
Table 4.1 Summary of the hot and cold stream available for heat integration analysis.
Enthalpy
Inlet Outlet Stream
Equipment Ts (°C) Tt (°C) change Cp (kW/°C)
Stream Stream Type
(kW)
E-101 S2 S3 Hot 85.23 25 44.2313 -0.7344
E-102 S4 S5 Hot 85.24 30 40.6675 -0.7362
E-103 S8 S9 Hot 121.3 30 14.2291 -0.1559
E-104 S10 S20 Hot 900 82.3 368.3509 0.4505
E-105 S11 S12 Hot 280 75 1956.1397 -9.5421
E-106 S14 S15 Cold 121.3 280 26.9773 0.1700
E-107 S16 S17 Cold 116.57 900 745.0114 0.9510
E-108 S21 S22 Cold 25 900 1030.1842 1.1774
E-109 S25 S26 Cold 235.37 280 74.3639 1.6662
E-110 S30 S31 Cold 129.87 280 509.5174 3.3938
147
4.3 Composite Curves
Composite curves are used to illustrate hot streams, cold streams, and the heat transfer
potential between them, on the same graph. It's a graphical method of calculating the heat
cascade. The total heat power for the hot and cold streams are calculated independently for
each temperature period. Then, for both hot and cold streams, the graph (T, H) is plotted. The
Composite Curves (T-H diagram) are created by dividing the temperature axis into intervals
based on the process streams' supply (𝑇𝑠 ) and target (𝑇𝑡 ) temperatures, and then adding the
enthalpy contributions (hot streams) and requirements (cold streams) in each temperature
interval. There are several key steps needed to be followed in order to obtain a correct graph:
1. 𝑇𝑚𝑖𝑛 , also known as the Heat Recovery Approximation Temperature (HRAT), is set to
10℃.
2. Before merging the hot and cold composite curves, they are drawn seperately.
3. The hot composite curve is fixed when combining the composite curves of hot and cold
streams, while the cold composite curve is presented in such a way that the difference
in minimum temperature or displacement between the two curves is equal to 𝑇𝑚𝑖𝑛 .
4. The hot composite curve is higher than the cold composite curve in the combined
composite curves.
5. The pinch point is the temperature at ∆𝑇 = ∆𝑇𝑚𝑖𝑛 .
Table 4.2 and Table 4.3 below show the data that is used to design the hot and cold
composite curves respectively. The hot composite curve is presented in the Figure 4.3 while
the cold composite curve is shown in the Figure 4.4 below. The combined hot and cold
composite curves which illustrate the energy integration are then presented in Figure 4.5.
148
Table 4.2 Data for hot composite curve
Total heat
T ∆𝑇 Total CP Cumulative
H1 H2 H3 H4 H5 duty,
(℃) (℃) (kW/℃) ∆𝐻 (kW)
∆𝐻 (kW)
900 2423.6185
620 0.4505 279.2926
280 2144.3259
158.7 9.9926 1585.8283
121.3 558.4976
36.06 10.1485 365.9537
85.24 192.5439
0.01 10.8847 0.1088
85.23 192.4351
2.93 11.6190 34.0438
82.3 158.3913
7.3 11.1686 81.5305
75 76.8608
45 1.6264 73.1889
30 3.6719
5 0.7344 3.6719
25 0
Hot Composite Curve

1000
900
800
Temperature (°C)
700
600
500
400
300
200
100
0
0 500 1000 1500 2000 2500 3000
Enthalpy (kW)
Figure 4.4 Hot composite curve
149
Table 4.3 Data for cold composite curve
Total heat
T ∆𝑇 Total CP Cumulative
H1 H2 H3 H4 H5 duty,
(℃) (℃) (kW/℃) ∆𝐻 (kW)
∆𝐻 (kW)
900 3537.4646
620 2.1283 1319.5549
280 2217.9097
44.63 7.3583 328.4044
235.37 1889.5053
105.5 5.6921 600.5213
129.87 1288.9840
8.57 2.2983 19.6965
121.3 1269.2875
4.73 2.1283 10.0669
116.57 1259.2206
91.57 1.1774 107.8102
25 1151.4104
Cold Composite Curve

1000
900
800
Temperature (°C)
700
600
500
400
300
200
100
0
0 500 1000 1500 2000 2500 3000 3500 4000
Enthalpy (kW)
Figure 4.5 Cold composite curve
150
∆𝑇𝑚𝑖𝑛 = 10℃
Pinch
𝑄𝐶𝑚𝑖𝑛 𝑀𝐸𝑅 = 1272.21𝑘𝑊 𝑄𝐻𝑚𝑖𝑛

= 1151.41𝑘𝑊 = 1113.85𝑘𝑊
Figure 4.6 Combined hot and cold composite curves at ∆𝑇 = ∆𝑇𝑚𝑖𝑛 = 10℃
151
Based on Figure 4.6, the results obtained from the combined composite curves
are summarized below:
1. Hot pinch temperature = 280℃
2. Cold pinch temperature = 270℃
3. Minimum heating requirement, 𝑄𝐻,𝑚𝑖𝑛 = 1113.87𝑘𝑊
4. Minimum cooling requirement, 𝑄𝐶,𝑚𝑖𝑛 = 1151.41𝑘𝑊
5. Maximum energy recovery, MER = 1272.21 kW
Figure 4.5 above shows the combined composite curves of hot and cold
streams. The cold stream has been shifted horizontally to the right in order to get the
minimum temperature difference of 10℃ between the two composite curves. The
minimum difference happen only at one point and this is known as pinch. The hot and
cold pinch temperatures calculated are 280℃ and 270℃ respectively. The overlap of
hot and cold composite curves (yellow shaded area) can provide a target for recovery
of heat. The maximum energy recovery (MER) of the overall process of methanol
production plant is calculated using the difference between 2423.62 (hot cascade) and
1151.41𝑘𝑊 (𝑄𝐶,𝑚𝑖𝑛 ) and determined as 1272.21 kW.
The displacement between the curves for hot at the top and cold at the bottom
can provide the hot and cold utility requirements. The minimum heating requirement
is found to be 1113.87𝑘𝑊 whereas the minimum cooling requirement obtained is
1151.41𝑘𝑊. These values will be used to satisfy the target temperatures. When
designing heat exchanger network, the minimum utility requirements can be used to
compare any design of exchanger network to check for any other further improvement
to get the highest energy efficiency.
The target or possible energy saving of heating and cooling requirement

through the energy integration are 53.32% and 31.74% respectively. The composite
curves of both hot and cold streams may provide some information that can be used to
improve the efficiency of the plant in terms of heat exchanger network.
152
4.4 Problem Table Algorithm
The Problem Table Algorithm (PTA) was an algebraic tool for pinch analysis
which contributes to generating the grand composite curve (GCC) that can determines
the surplus and deficit of heat duty in each temperature interval as well as the overall
external utility need. PTA was known to be the most significant step in achieving the
bare minimum of external utility requirements in a heat recovery network. In order to
obtain a PTA, several steps as stated below was taken into account:
1. Determine the shifted temperature intervals, T* from the actual supply and
target temperature. The shifting rule is applied to both the hot and cold streams
whereby the hot stream is shifted down in temperature by ΔTmin/2 and the
cold stream is shifted up to ΔTmin/2.
2. A vertical temperature scale is used to the stream population and as for the
temperature intervals, they are set to ΔTmin/2 below and above for hot and
cold stream temperature, respectively.
i. For hot streams,
TS *(shifted) = TS - (ΔTmin/2) and TT * (shifted) = TT - (ΔTmin/2)
ii. For cold streams,
TS * (shifted) = TS + (ΔTmin/2) and TT * (shifted) = TT + (ΔTmin/2)
3. The shifted temperatures are then arranged in descending order. The heat
capacity flow rates of all the hot streams that exist in that temperature interval
are added together and they are the deducted from the sum of cold stream heat
capacity flow rates to obtain the total CP.
4. To determine the total heat duty, total CP is multiplied with the temperature
interval.
5. A heat cascade (cumulative heat passing through at a given shifted
temperature) is obtained by adding on the total heat duty in each temperature
interval down the table.
6. The cascade obtained usually has negative heat flows which is not feasible
thermodynamically. Therefore, the largest negative value is taken and added to
the first interval in the cascade. This will increase all the net heat flows and
leaving the minimum value to be a zero instead of a negative value.
153
7. The hot utility target, QH,min is the heat added to the first interval and the cold
utility target, QC,min is the heat removed from the final interval. In the cascade,
the interval with zero net heat flow is the pinch point (Coker, 2014).
The shifted temperature for all the hot and cold streams at ΔTmin = 10℃ is
summarized in Table 4.4 while the problem table algorithm (PTA) is presented in
Table 4.5.
Table 4.4 Shifted Temperature for ΔTmin = 10℃
Actual Temperature Shifted Temperature
Equipment Stream Type Ts (°C) Tt (°C) Ts*(°C) Tt*(°C)
E-101 1 Hot 85.23 25 70.23 10

E-102 2 Hot 85.24 30 70.24 15
E-103 3 Hot 121.3 30 106.3 15
E-107 4 Hot 900 82.3 885 67.3
E-109 5 Hot 280 75 265 60
E-104 6 Cold 121.3 280 136.3 295
E-105 7 Cold 116.57 900 131.57 915
E-106 8 Cold 25 900 40 915
E-108 9 Cold 235.37 280 250.37 295
E-110 10 Cold 129.87 280 144.87 295
154
Table 4.5 Problem Table Algorithm
H1 H2 H3 H4 H5 C1 C2 C3 C4 C5 Total
ΔT Total Cp Initial Feasible
T* (℃) Cp=0.73 Cp=0.73 Cp=0.15 Cp=0.4 Cp=9.54 Cp=0.1 Cp=0.9 Cp=1.1 Cp=1.6 Cp=3.39 Duty,
(℃) (kW/°C) Cascade Cascade
43(kW/° 61(kW/° 58(kW/° 504(kW 2(kW/°C 699(k 509(kW 773(kW 66(kW/ 3(kW/°C ΔH(kW)
905 0 1113.85 Qhmin
10 -2.1283 -21.2831
895 -21.283 1092.56
610 -1.6778 -1023.48
285 -1044.8 69.0791
10 -6.9079 -69.0791
275 -1113.8 0
34.63 2.63424 91.2237
240.37 -1022.6 91.2237
105.5 4.30047 453.7
134.87 -568.92 544.923
8.57 7.69431 65.9403
126.3 -502.98 610.864
4.73 7.8643 37.1981
121.57 -465.78 648.062
5.27 8.81526 46.4564
116.3 -419.33 694.518
36.06 8.97111 323.498
80.24 -95.829 1018.02
0.01 9.70731 0.09707
80.23 -95.732 1018.11
2.93 10.4417 30.5941
77.3 -65.138 1048.71
7.3 9.99121 72.9358
70 7.79761 1121.64
40 0.44907 17.9627
30 25.7603 1139.61
5 1.62642 8.1321
25 33.8924 1147.74
5 0.73437 3.67187
20 37.5643 1151.41 Qcmin
155
Based on Table 4.5, the results obtained from the problem table algorithm are
summarized below:
1. Pinch temperature = 275°C

2. Hot pinch temperature = 280°C
3. Cold pinch temperature = 270°C
4. Minimum heating requirement, QH,min = 1113.8 kW
5. Minimum cooling requirement, QC,min = 1151.410 W
6. Maximum energy recovery, MER = 1272.21 kW
Table 4.5 shows 5 hot streams (H1, H2, H3, H4, H5) and 5 cold streams (C1,
C2, C3, C4, C5). Based on these streams in each temperature interval, the total Cp was
calculated. As for the total heat duty for each interval, it was obtained by multiplying
the total Cp and the change in temperature in each interval. The initial cascade value
was 0 and to obtain the next value, the value of total heat duty from the first interval,
-21.283kW was added to the 0. This same technique was repeated till the last
temperature interval. Since the largest negative value in the initial cascade was -
1113.8kW, it was used as the first value for the feasible cascade.
From the feasible cascade, a 0 value was attained at the shifted temperature of
275°C. Therefore, it is the pinch temperature. The hot pinch temperature and the cold
pinch temperature were attained via T = T*(shifted) + (ΔTmin/2) for hot pinch and T
= T*(shifted) - (ΔTmin/2) for cold pinch. Hence, the hot pinch temperature and the
cold pinch temperature are 280°C and 270°C respectively. As for the minimum heating
and cooling requirement, they were obtained from the first and last temperature of the
feasible cascade column. Therefore, the maximum energy recovery (MER) of the
overall process of the methanol production plant is 1272.21 kW. The results based on
the numerical method are in accordance with the results obtained from the graphical
method.
156
4.5 Heat Exchanger Network for Maximum Energy Recovery
Heat exchanger network (HEN) is designed to achieve the maximum energy

recovery obtained in Problem Table Algorithm. HEN design utilizes pinch design
method and is represented using grid diagram to display the heat transfer between hot
and cold streams. The pinch design method is divided into two parts, which is above
pinch design and below pinch design. The first heat exchanger is positioned at the
pinch, where the temperature difference is equal to the ∆𝑇𝑚𝑖𝑛 . Then moving outwards,
the heat exchangers are located at the right (above pinch) or left (below pinch). Lastly,
the hot and cold utilities are positioned accordingly.
The heat duty of heat exchanger is calculated using Equation 4.2 whereas the
outlet temperature leaving the heat changer is determined using Equation 4.3.
𝑄 = 𝐶𝑃 × |𝑇2 − 𝑇1 | (4.2)
𝑄
𝑇2 = 𝐶𝑃 + 𝑇1 (4.3)
where,
Q = Heat duty (kW)
CP = Heat capacity flow rate of the stream(kW/°C)
𝑇2 = Target temperature leaving the heat exchanger (°C)
𝑇1 = Supply temperature entering the heat exchanger (°C)
By setting the hot pinch temperature as 280°C and the cold pinch temperature
as 270°C, the heat exchanger network is presented in the grid diagram as shown in
Figure 4.6.
157
CP (kW/°C) H (kW)
25.28 kW
25°C 59.43 °C 85.23°C
C 1 0.7344 44.2313
40.67 kW
30°C 85.24°C 0.7362 40.6675
C 2
14.23 kW
30°C 121.3°C
C 3 0.1559 14.23
PINCH
89.06 kW
82.3°C 280°C 900°C
C 4 0.4505 368.35
850.64 kW 268.90 °C
75°C 105.23 °C 280°C
5 9.5421 1956.14
C
117.56 kW 139.87 °C
C
20.29 kW 126.57 °C
C
1.70 kW
6 121.3°C 270°C H 0.1700 26.98
18.95 kW 319.82 kW
116.57°C 270°C 563.7 °C 900°C 0.9510 745.01
7 H
145.91 kW 741.46 kW 279.31 kW
25°C 270°C H 900°C

8 1.1774 1030.18
288.46 kW 16.66 kW
235.37°C 270°C 280°C
9 H 1.6662 74.36
57.70 kW
33.94 kW
129.87°C 270°C 280°C
10 H 3.3938 509.52
Figure 4.7 Grid diagram for Heat Exchanger Network
158
4.5.1 Above Pinch Design
For above pinch design, the following rules must be fulfilled:
a) The temperature difference between hot and cold streams must greater than
∆𝑇𝑚𝑖𝑛 = 10°𝐶.
b) Cooler is prohibited in the above pinch design, only heater can be used.
c) The streams can only be paired when the heat capacity flow rate, CP for cold
streams is greater than hot streams (𝐶𝑃𝑐 ≥ 𝐶𝑃𝐻 ).
d) Ensure the temperature profile for the stream is matching with no crossing
occurring.
For the above pinch design, there is only one hot stream (S4) exceeds pinch
temperature and available for heat exchange. According to the CP, every cold stream
can pair with S4 since their CP are higher. However, the heat of S9 and S10 is not
enough to supply S4. Therefore, cold stream S7 is heated up from 270°C to 563.7°C
to cool the hot stream S4 from 900°C to 280°C. Then an additional heater is equipped
to heat up the S7 to 900°C. For the rest of the streams, heater is needed heat up the
stream to their respective target temperatures.
4.5.2 Below Pinch Design
For below pinch design, the following rules must be fulfilled:
a) The temperature difference between hot and cold streams must greater than
∆𝑇𝑚𝑖𝑛 = 10°𝐶.
b) Heater is prohibited in the above pinch design, only cooler can be used.
c) The streams can only be paired when the heat capacity flow rate, CP for hot
streams is greater than cold streams (𝐶𝑃𝐻 ≥ 𝐶𝑃𝐶 ).
d) Ensure the temperature profile for the stream is matching with no crossing
occurring.
159
For the below pinch design, heat can be exchanged from the hot streams (S1
and S5) and cold streams (S6 to S10). S1 is paired with S6 due to the higher CP value.
H1 is cooled from 85.23°C to 59.43°C to heat up S6 from 121.3°C to 270°C. A cooler
is installed in S1 to further cool down the temperature to 25°C. Then, S5 with CP value
9.5421 can fully supply the heat to the rest of the streams. First, S5 is cooled from
105.23°C to 25°C to fulfill the heat for S8 (288.46 kW). This is because only S8 has
supply temperature (25°C) lower than target temperature (75°C) of S5. The other
streams with supply temperatures higher than 75°C will cause the heat exchange to be
infeasible.
An alternative to solve this problem is to split the stream S5 to another two

streams. Starting from the heat recovery from S8, the first splitting stream with
temperature cooled from 280°C to 126.57°C (10°C higher than the supply temperature
of S7) is installed to fulfill 145.91 kW of S7. Secondly, 475.57 kW from S10 is
satisfied by cooling another splitting stream from 280°C to 139.87°C, which the outlet
temperature is also 10°C higher than the supply temperature. The CP of the last stream
is calculated by the original value (9.5421 kW/°C) deducting the first two splitting
stream. The stream is cooled from 280°C to 268.90°C to supply 57.70 kW of heat to
S9. Lastly, three coolers are positioned to cool down all the splitting streams to
105.23°C. The extra two streams will need two more cold utilities to supply the
remaining heat which will directly increase the utility cost. However, this is the bargain
between heat recovery and cost. The added cold utilities will need less energy since
some of the energy is recovered. This will eventually reduce the cost.
Therefore, the actual cooling requirement, 𝑄𝑐 is 1151.40 kW whereas the

actual heating requirement, 𝑄𝐻 is 1113.58 kW. The actual heat recovery from the HEN
design is 1272.23 kW, which is 100% of the maximum heat recovery (1272.21 kW).
160
4.6 Comparison Between Utilities Consumption Before and After HEN
This section presented the comparison of the total utility consumption for the
plant before and after implementing heat exchanger network.
4.6.1 Total Utilities Consumption Before and After HEN
Table 4.6 summarizes the consumption of hot and cold utilities before
implementing HEN and Table 4.7 presents the consumption of hot and cold utilities
after implementing HEN.
Table 4.6 Consumption of hot and cold utilities before implementing hen
Hot Utility Cold Utility

Equipment Tag Stream Type
(kW) (kW)
E-101 1 Hot 0.00 44.23

E-102 2 Hot 0.00 40.67
E-103 3 Hot 0.00 14.23
E-107 4 Hot 0.00 368.35
E-109 5 Hot 0.00 1956.14
E-104 6 Cold 26.98 0.00
E-105 7 Cold 745.01 0.00
E-106 8 Cold 1030.18 0.00
E-108 9 Cold 74.36 0.00
E-110 10 Cold 509.52 0.00
Total 2386.05 2423.62
161
Table 4.7 Consumption of hot and cold utilities after implementing hen
Cold Utility
Equipment Tag Stream Type Hot Utility (kW)
(kW)
E-101 1 Hot 0.00 18.95

E-102 2 Hot 0.00 40.67
E-103 3 Hot 0.00 14.23
E-107 4 Hot 0.00 89.06
E-109 5 Hot 0.00 988.49
E-104 6 Cold 1.70 0.00
E-105 7 Cold 319.82 0.00
E-106 8 Cold 741.46 0.00
E-108 9 Cold 16.66 0.00
E-110 10 Cold 33.94 0.00
Total 1113.58 1151.40
Based on Table 4.6, a minimum heating requirement of 2386.05 kW and a

minimum cooling requirement of 2423.62 kW are required before implementing HEN.
After implementing HEN, 1272.47 kW is reduced from both heating and cooling
requirements, which results in the heating requirement to be 1113.58 kW and the
cooling requirement to be 1151.40 kW, according to Table 4.7.
4.6.2 Comparison of Before and After Heat Integration
Table 4.8 shows the comparison of energy required before and after heat
integration and the percentage of energy saving.
162
Table 4.8 Comparison of the utility consumption before and after HEN
Utility Before HEN After HEN Energy Saving (%)

Hot 2386.05 1113.58 54.05
Cold 2423.62 1151.40 51.74
According to Table 4.3, a total of energy saving of 54.05% and 51.74% are
achieved for hot and cold utilities. This shows that unnecessary energy is recovered in
the methanol production plant after implementing the heat integration. The completed
process flow diagram is after energy integration is presented in the next page.
163
164
165
166
CHAPTER 5
PROCESS CONTROL
5.1 Introduction
The engineering details of the equipment, piping, instruments, valves, fittings,

and their arrangement can be known as the piping and instrument diagram (P&I
diagram or PID). In this chapter, we will discuss on the preliminary P&I diagrams at
the process design stage of the project. It is potentially hazardous in order to produce
a high quality of methanol, especially in a biogas processing plant. Subtle
improvements in a process will have a big impact on the outcome. Within the specified
limits, several factors should be consistently controlled such as temperature, pressure,
flow, and composition. This is to ensure the quality and safety of the process plant. A
well-designed, well-maintained, and leveraged control system will boost operating
profit, reduce start-up time, avoid forced shutdowns, keep operating and maintenance
costs as low as possible, aid in environmental compliance management, and support
plant safety and security needs without negatively impacting construction costs.
In recent years, the specifications for process plant efficiency have become
more necessary to attain, due to increased sustainability and safety regulations, as well
as increased competition among manufacturers. Fields of technology that are more
difficult to manage as a result of today's highly integrated plants with limited charge
resources between the different process units exacerbate the problem. The P&ID of
every unit operation used was prepared separately and usually used for service and
maintenance after construction for several years. The industrial facility operators used
the P&ID for troubleshooting, training and other related to maintaining the facilities.
As mandated by OSHA, it is very crucial for the plant to perform process hazard
assessments to prevent any serious incidents.
167
5.2 Process Control System
A plant process can be controlled and conduct subsequent emergency actions

by the existence of process controls. An unusual process occurrence cannot be
monitored, eliminated nor controlled if there are not enough functional process
controls. A simple manual action to computer logic controllers is one of the key
functions of process control along with several additional instrumentation of the
feedback systems. The design of the process control system is to reduce the activation
of backup safety devices. Therefore, this system is very crucial in keeping the
operating condition of methanol production plant at optimum conditions. Several
variables were taken into consideration in designing the process control for each of the
equipment used. Process principles, acceptable margins, reliability, and process
control methods are all inherent safety mechanisms that will influence the risk level at
a facility. This section presents the process control objectives, variables, configuration,
and instrumentation.
5.2.1 Process Control Objectives
Process control objectives can be viewed as a preliminary conditions or

constraints that needed to follow to stay within the parameters of the specified
conditions. The primary objectives when specifying instrumentation and control
schemes in designing the methanol production plant are:
1. Safe Plant Operation
It is very highly recommended for the power plant owners and industry to
further improved the safety of the employee. A safe working environment is to achieve
when designing a power plant for everyone’s best interest to minimize the possible
incident that might occur such as explosions. Therefore, the process variable such as
temperature, pressure and other parameter should be kept within a known safe
operating limit. For example, an interlocks and alarms should be provided to prevent
any dangerous operating procedures.
168
2. Production Rate
The design product output should be achieved according to the plant’s initial
design. The process control in this project was designed to help the plant to produce
22,000 metric tonnes of methanol per year.
3. Product Quality
The product composition that was obtained in this project was needed to
maintain following the specified quality standards. To meet performance targets in the
power industry, a capital project must fulfil its intended purpose, be executed safely,
and adhere to budget and schedule constraints. If quality standards are not met, the
project will fail.
4. Costing
Process controls are often used to operate the plant at the lowest production
cost. The extra raw resources and utilities can be reduced whereas the quality of the
products is at predetermined levels. As a result, the plant could save several
expenditure and economic capital while still generating a higher-margin income.
5. Stability
The control loop system was created to ensure that the condition of every
machinery inside the power plant stay within the equipment’s operation range. The
reason is that the automatic plant operation can be operated with minimal operator
intervention. For example, the amounts of product used inside the vessel or columns
should not be exceeded as this will overflow the system and results in leakage or
backflow.
169
5.2.2 Process Control Variables
Depending on what we want to monitor, specific control systems in a

production facility will serve a variety of functions. The variables that are most often
controlled are temperature, pressure, flow, and level. The maintenance of the plant's
targeted output state depends on these four factors. It may be visualised as indicated
below in Table 5.1.
Table 5.1 Type of Control System
Control System Description

Pressure Control Pressure controller systems are often employed in systems
involving vapour or gas phases since liquid and solid
materials are rarely compressed. In order to tackle the
problem of the flow from high to low pressure by raising
the pressure, the pressure control system typically uses a
pump and a compressor.
On the other hand, compression would cause a progressive

increase in temperature as pressure increased. To
guarantee that the temperature stays within the regulated
range, it is crucial to include a temperature controller after
equipment like the pump and compressor.
Level Control To specifically manage the fluid level in tanks, a

technology called as a "liquid level control system" was
developed. The main objective of these systems is to
control the rate at which the fluid is pumped into the tank
so that it can accumulate to the proper level inside the tank.
Temperature Control In every circumstance where maintaining a specific

temperature is necessary, temperature controls are
required. This can occur when an object has to be heated,
cooled, or both, and it must maintain the desired
temperature (setpoint) despite changes in its surroundings.
Open loop and closed loop controls are the two basic
methods of temperature control. The simplest type of loop
is an open loop, which continuously administers heating
and cooling without taking into account the temperature
output.
170
Flow Control A mechanism known as flow control controls the flow or
pressure of liquid. Flow control valves are utilised to
handle flow control effectively. Liquid flow is controlled
because these substances react to signals sent by separate
apparatuses like flow metres and temperature gauges.
5.2.3 Process Control Configuration
The ability to monitor and change a process to produce a desired output is

known as process control. It's utilized in the manufacturing business to preserve quality
and boost productivity. An unexpected process phenomenon cannot be observed,
regulated, or eliminated without adequate and trustworthy process controls (Nolan,
2011). A control system is required to perform either one or both task:
a) Maintain the process at the operational conditions and set points;

b) Transition the process from one operational condition to another.
The control model is a set of equations that may be used to forecast a system's
behavior and predict how it will respond to change. The state variable (x) is a
measurable variable that reflects the state of the system, such as temperature (energy
balance), volume (mass balance), or concentration (component balance). A defined
variable, such as flow rates, is called an input variable (u). A modified, disrupted, or
unmonitored variable can be used as a control input. Parameters (p) are frequently a
physical constraint and a standard for the system, such as the vessel volume or the
material viscosity. The output (y) metric is used to determine the system's behavior
(Bolton, 1998). Control systems consists of feedforward controller, feedback
controller, ratio controller and cascade controller. The details for each controller are
briefly discussed below.
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5.2.3.1 Feedback Control
A feedback control system consists of five basic components: (1) input, (2)
process being controlled, (3) output, (4) sensing elements, and (5) controller and
actuating devices. In a feedback control, the variable being controlled is measured and
compared to a target value. The error is the difference between the actual and desired
value. To reduce this inaccuracy, feedback control manipulates a system input. A basic
feedback control loop is represented in Figure 5.1 (Rahim et al., 2015). Desired Output
would be the system's error. The feedback control system reacts to the system and
attempts to reduce the error. A user interface is used to enter the required output into
the system. The system's output is measured (with a flow meter, thermometer, or other
equipment) and the difference is computed. This difference is utilized to control
system inputs in order to reduce system error (Woolf et al., 2022).
Figure 5.1 Block diagram of a feedback control system (Woolf, 2022).
Negative and positive feedback control are the two types of feedback control.
Negative feedback is the most helpful control type since it assists a system in achieving
equilibrium. Positive feedback, on the other hand, can move a system away from
equilibrium, making it unstable and sometimes yielding unanticipated results.
Negative feedback is most typically referred to when the term "feedback control" is
used.
172
The benefits of feedback control is that data is obtained at the process output.
As a result, the control account for unanticipated disturbances such as frictional and
pressure losses. The feedback control design ensures that the required performance is
achieved by promptly changing the inputs when deviations are detected, regardless of
what caused the disturbance. Another benefit of feedback control is that by examining
a system's output, unstable processes can be stabilized. Feedback controls do not
necessitate in-depth understanding of the system, nor do they necessitate a
mathematical model of the process. Controls for feedback can be readily copied from
one system to another. Time lag in a system causes the main disadvantage of feedback
control (Hahn et al, 2003).
5.2.3.2 Feedforward Control
Feedforward control differs from feedback control because it measures the load
or primary disturbance and adjusts the manipulated variable so that deviations from
the setpoint are minimized. Disturbances can then be rejected by the controller before
they have an impact on the regulated variable. For appropriate feedforward control,
models that relate the effect of the manipulated and disturbance variables on the
controlled variable should be based on steady-state or dynamic analysis. Feedforward
control should always be used in conjunction with feedback control because the model
is an approximation and not all disturbances are measured. Compensation for
measurable and unmeasured disturbances, as well as model mismatch, will be possible
with this combination (Mokhatab et al., 2012). Figure 5.2 shows the feedforward
system.
Figure 5.2 Block diagram of a feedforward control system (Mokhatab, 2012)
173
The control variable adjustment in a feed-forward system is not error-based.
Instead, it is based on process knowledge in the form of a mathematical model of the
process, as well as knowledge about, or measurements of, process disturbances. The
difficulty with feed-forward control is that the effects of the disturbances on the system
must be accurately predicted, and there must not be any unmeasured disturbances
(Haugen, 2009).
5.2.3.3 Ratio Control
Ratio control is a technique for maintaining the same ratio between two or more
process variables, such as material flows, even if their values change. The most typical
application of ratio control designs is to combine two feed streams to create a mixed
flow with a specified composition or physical feature downstream. As long as there is
one controllable feed stream, the ratio controller can theoretically control an endless
number of streams. The ratio control architecture is feedforward in this way. In the
field of chemical engineering, ratio controls are used in a variety of ways. They are
commonly employed to regulate the flow of chemicals in reactors. In these
circumstances, they maintain the right proportions of reactants entering a reaction
vessel in order to maintain optimal reaction conditions. They are also typically
employed for dilutions on a huge scale (Fraley et al., 2022). The configuration of ratio
control system is presented in Figure 5.3.
Figure 5.3 Configuration of a ratio control system (Fraley, 2022)
174
5.2.3.4 Cascade Control
Cascade control entails the employment of two controllers, with the first
controller's output serving as the set point for the second, and the feedback loop for
one controller nestled inside the feedback loop for the other, as shown in Figure 5.4
(Bolton et al., 2021). A system like this can provide a better response to disruptions.
Figure 5.4 Configuration of cascade control system (Bolton, 2021).
A generic cascade control system with two controllers, two sensors, and one
actuator acting on two processes in series is shown in the figure 5.2.3.4. A primary or
master controller generates a control effort that a secondary or slave controller uses as
a setpoint. The actuator, in turn, is used by the controller to direct its control effort to
the secondary process. The secondary process then produces a secondary process
variable that serves as the original process's control effort. This block diagram's
geometry defines an inner loop with the secondary controller and an outer loop with
the primary controller. The inner loop is similar to a standard feedback control system
in that it has a setpoint, a process variable, and a controller that acts on a process via
an actuator. The outer loop works in the same way as the inner loop, only it uses the
entire inner loop as an actuator (Vandoren, 2014).
Cascade control is generally advised for slow processes that are regulated by a
relatively quick process. Cascade control works well when there are disturbances that
have a demonstrable impact on the process output. As a result, cascade control
increases control performance for steam pressure disturbances, but has no effect on
feed rate or temperature. The increased complexity of cascade control, as well as the
additional measurement instrument and controller, are its drawbacks. When the inner
175
loop is at least three times quicker than the outer loop, the improved performance
justifies the investment (Dimian, 2014).
5.2.4 Process Control Instrumentation
Process control instrumentation focuses on employing hardware and software

to measure and control process variables in an industrial context. Mathematical models
of industrial processes and systems are used to create control systems. All industrial
and manufacturing activities rely on instrumentation and process control. Every
process in a manufacturing facility must be properly monitored and managed to ensure
that it runs in a predictable and safe manner. Temperature monitoring and control
systems, for example, prevent temperatures from reaching critical levels and causing
an explosion at petrochemical plants. There could be human lives lost and investments
destroyed if electric process heater control panels are not installed. Virtually every
industry that specializes in repeatable production requires industrial process
instrumentation and process control equipment. Some industries include:
1. Oil & Gas

2. Petrochemical
3. Wastewater Treatment
4. Food &Beverage
5. Manufacturing
Table 5.2 shows the list of process control instruments and their functions
whereas table 5.3 describes the basic symbols of each instrument.
176
Table 5.2 Process control instruments and their functions
Symbol Description Function

Temperature Control Instruments
TT Temperature Transforms the temperature sensor's small
Transmitter electrical signal into a more readable signal for
the processing unit
TIC Temperature Indicator Finalizes a decision by adjusting the valve's
Controller opening or closing based on the temperature
supplied.
TAH Temperature Alarm High temperature in the equipment is detected.
High As an example, when the temperature exceeds
the setpoint, it sends a signal to the TIC.
TAL Temperature Alarm Low temperature in the equipment is detected.
Low As an example, when the temperature is below
the setpoint, it sends a signal to the TIC
Pressure Control Instruments
PT Pressure Transmitter Detects variations in the equipment's pressure.
PIC Pressure Indicator Finalizes a decision by adjusting the valve's
Controller opening or closing based on the pressure
supplied.
PAH Pressure Alarm High High pressure in the equipment is detected. As
an example, when the pressure exceeds the
setpoint, it sends a signal to the PIC.
PAL Pressure Alarm Low Low pressure in the equipment is detected. As
an example, when the pressure is below the
setpoint, it sends a signal to the PIC.
ASC Anti-Surge Controller When the process compression stage is about to
surge, it detects it and takes action to keep the
flow at a minimum during extreme situations.
Flow Control Instruments
FT Flow Transmitter Detects variations in the equipment's flow.
177
FIC Flow Indicator Finalizes a decision by adjusting the valve's
Controller opening or closing based on the flow supplied
to system.
FFC Flow Fraction (Ratio) Finalized decision-making by adjusting the
Controller valve's opening or closing to maintain a
consistent ratio of two flows.
Liquid Level Control Instruments
LT Level Transmitter Detects variations in the equipment's liquid
level.
LIC Level Indicator Finalizes a decision by adjusting the valve's
Controller opening or closing based on the liquid level
supplied to system.
LAH Level Alarm High High liquid level in the equipment is detected.
As an example, when the liquid level exceeds
the setpoint, it sends a signal to the LIC.
LAL Level Alarm Low Low liquid level in the equipment is detected.
As an example, when the liquid level is below
the setpoint, it sends a signal to the LIC.
Table 5.3 Basic symbols of process control
Instruments Symbols Description

TT Temperature Transmitter
Transmitter
PT Pressure Transmitter
FT Flow Transmitter
LT Level Transmitter
TIC Temperature Controller
Controller PIC Pressure Controller
FIC Flow Controller
LIC Level Controller
FFC Flow Fraction (Ratio) Controller
ASC Anti-Surge Controller
178
Alarm TAH/TAL Temperature Alarm High/Low
PAH/PAL Pressure Alarm High/Low
LAH/LAL Level Alarm High/Low
Transmission Lines Pneumatic Signal
Electric Transmission Line
Data Link
Valve Diaphragm Valve
5.3 Control System for Individual Equipment
In the methanol production plant, there are 6 major equipment, which are steam
reforming reactor, methanol synthesis reactor, membrane separator, distillation
column and two flash columns. The auxiliary equipment including heat exchangers,
compressors, heaters, coolers, pump, throttling valves, splitter, condenser and mixer
are also available in the production plant to improve the process. The control system
is vital to achieve the desired operating conditions. The control system design for each
equipment and Piping and Instrumentation Diagram (P&ID) are presented in this
section.
5.3.1 Catalytic Fixed Bed Reactor
Steam reforming reactor and methanol synthesis reactor are the catalytic fixed
bed reactor in the methanol production plant. Steam reforming reactor converts
methane and steam into syngas (carbon dioxide, carbon monoxide and hydrogen)
whereas methanol synthesis reactor converts syngas into methanol and water. The
following controls are important in control system of catalytic fixed bed reactor:
1. Temperature control: Steam reforming reactor involves endothermic reaction

whereas methanol synthesis reactor involves exothermic reaction. The
179
temperature control is crucial in reactor to ensure the reaction rate and product
quality. The temperature control is adjusted by controlling the flow rate of inlet
cooling water stream entering the cooling jacket of the column by valve
adjustment.
2. Pressure control: The pressure control is important for reactor since the reactors
operate at high pressure. The pressure control plays a crucial role in safety
aspect to prevent the exploding of reactor as well as maintaining the conversion
of reactants. The pressure of the column is controlled by the flow rate of top
stream of reactor by valve adjustment.
3. Flow control: The flow control is to ensure the entering stream meet the
operating condition of column. The flow control can affect the other operating
conditions of stream, including temperature and pressure. The flow rate is
maintained by adjusting the flow control valve at the inlet stream.
The objectives of control system for catalytic fixed bed reactor are listed as
follows:
a) To control the temperature of the reactor by manipulating the flow rate of

cooling medium entering the reactor.
b) To control the pressure of the reactor by adjusting the flow rate of the outlet
stream for the reactor.
c) To control the flow rate of the inlet stream entering the reactor by valve
adjustment.
180
The operating conditions of steam reforming reactor is shown in Table 5.4 and
the control system of R-101 is presented in P&ID as shown in Figure 5.5. The
controlled variable, manipulated variable, disturbance, type of control and setpoint for
control system of R-101 is discussed in detail in Table 5.5.
Table 5.4 Operating conditions of R-101
Temperature 900 °C
Pressure 15 bar
Catalyst Ni/SiO2 Al2 O3
Figure 5.5 P&ID for steam reforming reactor (R-101)
181
Table 5.5 Control system for steam reforming reactor (R-101)
Controlled Manipulated Type of

Disturbance Setpoint
Variable Variable Controller
• Inconsistent
flow rate of
T = 900°C
cooling water
Flow rate of The alarm will
in cooling
cooling be activated
Temperature jacket
water in Feedback when the
of reactor • Changes in
cooling temperature
the
jacket reaches beyond
temperature
±10°C
of cooling
water source
• Changes in
P = 50 bar
the pressure
Flow rate of The alarm will
of inlet
Pressure of outlet stream be activated
stream (S23) Feedback
reactor (S16) exiting when the
• Inconsistent
the reactor pressure reaches
flow rate of
beyond ±5%
outlet stream
Flow ratio • Flow rate of

of inlet Steam flow outlet streams
Ratio of steam
stream rate (S15) from
(S15) and inlet
(S23) and before membrane Cascade
stream (S20) =
steam (S15) entering the separator (F-
1:1 ±5%
entering the reactor 101) and
reactor water utility
182
The operating conditions of steam reforming reactor is shown in Table 5.6 and
the control system of R-102 is presented in P&ID as shown in Figure 5.6. The
control system of R-101 is discussed in detail in Table 5.7.
Table 5.6 Operating conditions of R-102
Temperature 280 °C
Pressure 50 bar
Figure 5.6 P&ID for methanol synthesis reactor (R-102)
183
Table 5.7 Control system for methanol synthesis reactor (R-102)

• Inconsistent
flow rate of
cooling T = 280°C
Flow rate of water in The alarm will
cooling cooling be activated
Temperature of
water in jacket Feedback when the
reactor
cooling • Changes in temperature
jacket the reaches beyond
temperature ±10°C
of cooling
water source
• Changes in
P = 50 bar
Flow rate of the pressure
The alarm will
outlet of inlet
Pressure of be activated
stream (S24) stream (S23) Feedback
reactor when the
exiting the • Inconsistent
pressure reaches
reactor flow rate of
beyond ±5%
outlet stream
Inlet stream
flow rate =
Flow rate of Flow rate of • Inconsistent 4358.7 kg/h.
inlet stream inlet streams flow rate of The alarm will
Feedback
(S23) entering entering the inlet stream be activated
the reactor reactor (S23) when the flow
rate reaches
beyond ±5%
184
5.3.2 Flash Separators
There are two flash separators in methanol production plant, which are F-102
and F-103. F-102 is used to separate water from the syngas mixture whereas F-103 is
used to separate methanol and water from the gaseous mixture containing syngas and
remaining methane. The following control is crucial in flash separators:
1. Temperature Control: The temperature control is crucial in vapor-liquid

separation to ensure the separation efficiency and product quality since the feed
is separated by volatility. The temperature control is adjusted by controlling
the flow rate of inlet stream entering the column by valve adjustment.
2. Pressure Control: The pressure control is important for column involving

gaseous compounds and to maintain the operating condition of column. The
pressure of the column is controlled by the flow rate of top stream of column
by valve adjustment.
3. Flow Control: The flow control is to ensure the entering stream meet the
operating condition of column. The flow rate is maintained by adjusting the
flow control valve at the inlet stream.
4. Level Control: The level control is used in the column control system to
prevent the liquid in the column from drying up or overflowing. The level of
liquid in the column is controlled by the flow rate of bottom stream of column
The objectives of flash column control system are listed as below:
a) To control the temperature of the flash column by manipulating the flow rate
of stream entering the column.
b) To control the pressure of the flash column by adjusting the flow rate of the
outlet gaseous stream for the column.
185
c) To control the flow rate of the inlet stream entering the flash column by valve
adjustment.
d) To control the level of liquid in the flash column by adjusting the flow rate of
the outlet liquid stream for the column
The operating conditions of first flash column (F-102) is shown in Table 5.8
and the control system of F-102 is presented in P&ID as shown in Figure 5.7. The
control system of F-102 is discussed in detail in Table 5.9.
Table 5.8 Operating conditions of F-102
Temperature 82.3 °C
Pressure 14 bar
Figure 5.7 P&ID for flash separator (F-102)
186
Table 5.9 Control system for flash separator (F-102)

• Inconsistent T = 82.30°C
flow rate of The alarm will
Flow rate of
Temperature stream be activated
stream
of flash • Changes in Cascade when the
entering the
column the temperature
column
temperature reaches beyond
of stream ±10°C.
• Changes in
P = 14 bar
The alarm will
outlet of inlet
flash column when the
pressure reaches
column flow rate of
beyond ±5%.
outlet stream
Inlet stream
Flow rate of
Flow rate of flow rate = 1788
inlet streams • Inconsistent
inlet stream kg/h. The alarm
entering the flow rate of
(S17) entering Feedback will be activated
flash inlet stream
the flash when the flow
column (S17)
column rate reaches
(S17)
beyond ±5%.
187
The liquid level
will keep at the
range of 5%
Flow rate of (minimum) to
outlet 50%
• Inconsistent
Level of liquid streams (maximum) to
flow rate of
in flash leaving the Feedback avoid dying up
inlet stream
column flash or overflow. The
(S17)
column alarm will be
(S19) activated when
the flow rate
reaches beyond
±5%.
188
The operating conditions of first flash column (F-103) is shown in Table 5.10
and the control system of F-103 is presented in P&ID as shown in Figure 5.8. The
control system of F-103 is discussed in detail in Table 5.11.
Temperature 75 °C
Pressure 30 bar
Figure 5.8 P&ID for flash separator (F-103)
189
Table 5.11 Control system for flash separator (F-103)

• Inconsistent T = 75°C
Flow rate of
stream be activated
Temperature of stream
• Changes in Cascade when the
flash column entering the
the temperature
column
of stream ±10°C
• Changes in
P = 30 bar
The alarm will
outlet of inlet
flash column when the
pressure reaches
column flow rate of
beyond ±5%
outlet stream
Inlet stream
Flow rate of • Inconsistent
inlet streams flow rate of
entering the inlet stream
the flash when the flow
column (S26)
column rate reaches
beyond ±5%
190
The liquid level
will keep at the
range of 5%
outlet 50%
• Inconsistent
flow rate of
in flash leaving the Feedback avoid dying up
inlet stream
column flash or overflow. The
(S26)
column alarm will be
(S1932) activated when
the flow rate
reaches beyond
±5%.
191
Distillation column in utilized in methanol production plant as last separation

technique to separate methanol and water. Failure in control system may affect the
products from the separation process inside the distillation column. These are some of
the more important factors that can cause poor distillation column performance. Other
factors include changing operating conditions and throughputs, brought about by
changes in upstream conditions and changes in the demand for the products. All these
factors, including the associated control system, should be considered at the design
stages because once a column is built and installed, nothing much can be done to
rectify the situation without incurring significant costs. In this design project, the final
product distribution for the production of methanol from biogas will be 99.85% purity
of methanol, which is recovered in the top stream but the remaining methanol is mixed
together with water at the bottom stream. To achieve these values, the control loops
used in the operation of distillation column are
1. Temperature Control: Temperature control is perhaps the most popular way of

controlling product compositions. In this case, the control temperature is used
as a substitute to product composition analysis. Overheating will cause the
liquid to vaporize more than what is desired while under heating will cause the
efficiency of distillation column to drop.
2. Pressure Control: Vapor and gas plays a major role in distillation column. Thus,
failure to maintain the pressure control with these two properties will affect the
efficiency of pump or compressor and results in overhead, known as vapor flow
rate.
3. Level Control: One column has many trays. Thus, level controller are used to
maintain the level in the accumulator, reboiler, and also the intermediate
accumulator of a stacked column. A single distillation column will require two
level controller both installed in the two separate columns. The first level
controller system is the liquid level control system in the reflux drum.
Condenser plays a vital role in regulating the amount of liquid remaining in the
192
reflux drum. The higher the coolant flow rate, the higher the level in the reflux
drum. In other words, changes from vapour into liquid by condenser will be
faster. Next, the second level controller is at the base of the distillation column.
This is to avoid the distillation column from being flooded, dry up and also off-
specification product inside the column.
4. Flow Control: Flow control system will control the material balance on the feed
streams and measure the important for a flow of process mixture via ratio.
The control system for a distillation column is designed to achieve the

following objectives:
a) To control the flow rate of the inlet stream according the desired values by
adjusting the flow valve.
b) To control the temperature at the top of distillation column at the desired
temperature by regulating the inlet flow rate of the cooling water into the
condenser.
c) To control the temperature at the bottom of the distillation columns at the
desired temperature by manipulating the inlet flowrate of the steam into the
reboiler.
d) To control the liquid level at the desired level by manipulating the outlet
flowrate of bottom outlet stream.
e) To control the liquid level in the reflux drum at the desired level by
manipulating the flow rate of the overhead stream.
f) To control in the column at an optimum level by manipulating the flowrate of
the overhead vapor stream.
g) To maintain the reflux ratio of the overhead product stream and the reflux
stream by controlling the flowrate of reflux stream recycled into distillation
columns.
The operating conditions of distillation column (T-101) is shown in Table 5.12

and the control system of T-101 is presented in P&ID as shown in Figure 5.9. The
193
control system of T-101 is discussed in detail in Table 5.13.
Table 5.12 Operating conditions of T-101
Temperature 75 °C
Pressure 2 bar
Figure 5.9 P&ID for distillation column (T-101)
Table 5.13 Control system for distillation column (T-101)

Operating • Inconsistent
Flow rate of T = 82.95°C
temperature at flow rate of
refrigerant The alarm will
the top of refrigerant Feedback
entering the be activated
distillation • Changes in
condenser when the
column the
194
temperature temperature
of refrigerant reaches beyond
±10°C
T = 118.42°C
Operating The alarm will
Flow rate of • Accumulation
temperature at be activated
steam of
the bottom of Feedback when the
entering the temperature
distillation temperature
reboiler from reboiler
column reaches beyond
±10°C
• Changes in
Flow rate of P = 2 bar
the pressure
outlet The alarm will
Pressure of of inlet
stream be activated
distillation stream (S33) Feedback
(S34) when the
column • Inconsistent
exiting the pressure reaches
flow rate of
column beyond ±5%
outlet stream
Inlet stream
flow rate =
Flow rate of Flow rate of
• Inconsistent 2283.75 kg/h.
inlet stream inlet streams
(S33) entering entering the Feedback
inlet stream be activated
the distillation distillation
(S33) when the flow
column column
rate reaches
beyond ±5%
195
The liquid level
will keep at the
range of 5%
(minimum) to
50%
Flow rate of • Inconsistent
Level of (maximum) to
refrigerant flowrate of
condensate in Feedback avoid dying up
entering the the overhead
reflux drum or overflow.
condenser vapor stream
The alarm will
be activated
when the flow
rate reaches
beyond ±5%.
The liquid level
will keep at the
range of 5%
outlet 50%
• Inconsistent
flow rate of
in distillation leaving the Feedback avoid dying up
inlet stream
column flash or overflow.
(S33)
column The alarm will
(S35) be activated
when the flow
rate reaches
beyond ±5%.
Flowrate of
recycle inlet
• Flowrate of
Reflux ratio of stream Ratio Reflux ratio =
overhead
condensate entering the Control 0.4239
stream
distillation
column
196
5.3.4 Membrane Separator (F-101)
Membrane separation is a separation based on the presence of semi permeable

membranes. The principle is quite simple: the membrane acts as a very specific filter
that will let water flow through, while it catches suspended solids and other substances.
Membrane separator (F-101) is designed to separate in between the composition of
biogas which consist of 60% of methane (CH₄) and 40% of carbon dioxide (CO₂). The
reason on doing the membrane separation is to retrieve as much pure methane (CH₄)
gas from biogas as we can before reacting in in the steam reforming reactor. The
carbon dioxide retrieved will be directed to methanol synthesis reactor. The control
used in the control system of membrane separator is listed as below:
1. Temperature Control: F-101 has its own operating temperature which is 30°C.
Thus, controlling temperature of F-101 from exceeding or falling below the set
point is crucial. Temperature control must be implemented to prevent
disruption during process.
2. Flow Control: In order to maintain a steady and consistent production rate, the
flow control of the process stream is necessary. Maintaining the flow rate at
the required values helps to keep other variables at consistent values, thus
leading to a stable operation. The flow control also works together with the
temperature control to control the flow rate of the cooling or heating medium
in the reactor.
3. Pressure Control: Pressure control is crucial for most systems that involve
vapor or gas components. As F-101 contains vapor components and has a
pressure set point of 5 bar, the pressure control is required to maintain the
pressure at the optimum operating condition to ensure maximum conversion of
the feed into the desired products. Pressure control is also necessary to prevent
rupture of vessel, overpressure of reactor and explosion.
The objectives of flash column control system are listed as below:
197
a) To control the temperature of the membrane separator by manipulating the
flow rate of stream entering the column.
b) To control the pressure of the membrane separator by adjusting the flow rate
of the outlet gaseous stream for the column.
c) To control the flow rate of the inlet stream entering the membrane separator
The operating conditions of membrane separator (F-101) is shown in Table

5.14 and the control system of F-101 is presented in P&ID as shown in Figure 5.10.
The controlled variable, manipulated variable, disturbance, type of control and setpoint
for control system of F-101 is discussed in detail in Table 5.15.
Temperature 30 °C
Pressure 5 bar
Figure 5.10 P&ID for membrane separator (F-101)
198
F-101 is equipped with control valves which are represented by a gate valve.
In between control valve and the upstream block valve is often a drain valve. This
drain valve is sufficient to drain the piping segment if the control valve is of the "Fail
Open" kind. An additional drain valve is needed between the control valve and
downstream block valve if the control valve is of the "Fail Close" or "Fail in Position"
type, as illustrated in Figure 5.10.
As per project guidelines, control valves should include a bypass or hand-wheel

to enable vessel operation during control valve repair. Globe valve is selected as the
bypass valve on the control valve as it allows better control with opening. A flow
transmitter (FT) is installed at the inlet stream of F-101, to detect changes in flow
inputs. The electrical output from FT is received by the flow indicator controller (FIC),
which is installed at the gate valve. The FIC will finalize the opening and closing of
gate valve when the flow varies from set point.
Similar concept is applied for temperature and pressure variables. A

temperature transmitter (TT) and pressure transmitter (PT) is installed at F-101 to
detect changes in both these variables from the input and put stream. Temperature
indicator controller (TIC) and pressure indicator controller (PIC) is installed at F-101,
to finalize the decision of opening or closing the gate valves according to the variables’
set point.
199
Table 5.15 Control system for membrane separator (F-101)

• Inconsistent T = 30°C
Flow rate of flow rate of The alarm will
Temperature stream stream be activated
of membrane entering the • Changes in Cascade when the
separator membrane the temperature
separator temperature reaches beyond
of stream ±10°C.
• Changes in
Flow rate of P = 5 bar
the pressure
outlet The alarm will
Pressure of of inlet
stream (S6) be activated
membrane stream (S5) Feedback
exiting the when the
separator • Inconsistent
membrane pressure reaches
flow rate of
separator beyond ±5%.
outlet stream
Inlet stream
Flow rate of
inlet streams • Inconsistent
entering the flow rate of
membrane inlet stream
the membrane when the flow
separator (S5)
separator rate reaches
(S5)
beyond ±5%.
200
5.3.5 Throttling valve
Throttling valve is used to release the pressure of the stream within the process
of the plant by controlling the fluid flow. There are two throttling valves used in this
plant, V-101 and V-102. The effluent stream, S24, from the methanol synthesis
reactor, R-102, is at 50 bar and the inlet stream, S25, entering the condenser, E-109
will be at 30 bar. Thus, the first valve, V101, is used to decrease the stream pressure
from 50 bar to 30 bar to fit the desired pressure condition of E-109.
The second valve is, V-102, is used to reduce the outlet pressure of flash
column, F-103, from 30 bar (S32) to 2 bar (S33). This is to make sure that the inlet
stream, S33, meets the desired condition of distillation column, T-101. Pressure
controller is installed at each of the valve to make sure the pressure outlet of the valve
is not higher or lower than ±2 of the desired pressure that has been set. Figure 5.11 and
Figure 5.12 are the P&ID of control system for each throttling valve used in the plant
process while Table 5.16 and 5.17 shows the controlled variable, manipulated variable,
disturbance, type of control and setpoint of each of the valve control system,
respectively.
201
Figure 5.11 P&ID for throttling valve (V-101)
Table 5.16 Control system for throttling valve (V-101)

P = 30 bar
The transmitter
• Changes in (PT) will
Pressure at Valve V- the pressure transmit impulse
Feedback
stream S25 101 of inlet to controller
stream (S24) (PIC) when the
pressure reaches
beyond ±5%.
202
Figure 5.12 P&ID for throttling valve (V-102)
Table 5.17 Control system for throttling valve (V-102)

P = 2 bar
The transmitter
• Changes in (PT) will
Pressure at Valve V- the pressure transmit impulse
Feedback
stream S33 102 of inlet to controller
stream (S32) (PIC) when the
pressure reaches
beyond ±5%.
203
5.3.6 Splitter
There are two splitters in the methanol production plant. Splitter 1 (S-101) is
located at the top outlet flow of the flash column (F-103). As the name suggested, this
splitter separate in between two streamlines which were stream S29 and stream S28.
Split-range control is used when a single controller is employed to control two final-
control (Staff, 2022). For this case, ratio control will go in demand. Ratio control is
used to ensure that two or more process variables such as material flows are kept at the
same ratio even if they are changing in value (Holland, 2003). The purpose it is used
and ratio control is implemented was because to avoid accumulation to happen in the
stream line before entering the compressor that will end up in the reactor. 5% of the
top product from the flash separator will be direct to the purge and the remaining 95%
will be send directly to the compressor.
The second splitter (S-102) is located after the throttling valve (V-102). The
function of this splitter is to split the stream for heat integration purpose. Similar to S-
101, ratio control is used to adjust the ratio of the splitted streams. Figure 5.13 and
Figure 5.14 are the P&ID of control system for each splitter used in the plant process
while Table 5.18 and 5.19 shows the controlled variable, manipulated variable,
disturbance, type of control and setpoint of each of the splitter control system,
respectively.
204
Figure 5.13 P&ID for splitter (S-101)
Table 5.18 Control system for splitter (S-101)

• Flow rate of
outlet
Flow ratio of Flow rate of
streams Ratio of stream
outlet streams outlet
(S27) from Cascade S29 to stream
S27 and S28 stream (S28)
flash S28 = 5:95 ±5%
from splitter of splitter
separator (F-
103)
205
Figure 5.14 P&ID for splitter (S-102)
Table 5.19 Control system for splitter (S-102)

• Flow rate of
Flow rate of
Flow ratio of outlet
outlet Ratio of stream
outlet streams streams
streams S25c to S25a
S25a, S25b (S25) from Cascade
S25b and and S25b =
and and S25c throttling
S15c of 1:3.57:5.47±5%
from splitter valve (V-
splitter
101)
206
5.3.7 Compressor
A total of 7 compressors were used in this process power plant. Compressor C-

101 and C-102, known as a two-stage compressor were used to increase the pressure
of stream 2 and 4 up to 5 bar, following the desired value of the standard operation
condition of membrane separator (F-101) which is to separate the biogas into methane
and carbon dioxide. The membrane separator was used to purifies methane.
Meanwhile, compressor C-103 and C-104 was used to increase the pressure from the
membrane separator (F-101) which is at 5 bar up until 50 bar before entering the mixer
(M-101). The operating condition for mixer (M-101) was set to operate at a pressure
of 50 bar. The use of these two compressors was also to increase the temperature of
the inlet stream prior before entering the mixer (M-101).
The pressure of the inlet stream of the steam reforming reactor (R-101) was
increase beforehand with the help of compressor C-105, from 5 bar to 15 bar. As for
compressor C-106, it was used to raise the pressure from 14 bar to 50 bar of the outlet
stream of flash column (F-102) before entering the Mixer (M-101). As mentioned
earlier, the operating pressure for mixer was set to be at 50 bar. Compressor C-107
operated by increased the pressure from 30 bar to 50 bar of the outlet stream of the
splitter (S-101) from the second flash column (F-103). All 7 compressors are equipped
with an anti-surge controller valve, which directs the compressor's discharge flow
through the valve to maintain the outlet pressure set point while the process is carried
out in an optimal and safe condition. The anti-surge controller and control valve will
keep the flow through the compressor to a minimum while handling surges.
The compressors' inlets have temperature, flow, and pressure sensors, while
the outlets have pressure and temperature sensors. The anti-surge controller will
continuously calculate the distance between the compressor's set point and its surge
limit line, providing protection for the compressor. Pressure controller is installed at
each of the compressor to make sure the pressure outlet of the compressor is not higher
or lower than ±2 of the desired pressure that has been set. Figure 5.15 to Figure 5.21
are the P&ID of control system for each compressor used in the plant process while
Table 5.20 to Table 5.26 shows the controlled variable, manipulated variable,
207
disturbance, type of control and setpoint of each of the compressor control system,
respectively.
Figure 5.15 P&ID for compressor (C-101)
Table 5.20 Control system for compressor (C-101)

P = 2.236 bar
The anti-surge
• Pressure at
controller will
The anti- stream S1
open when the
Pressure at surge • Additional
Feedback pressure reaches
stream S2 control build up
beyond ±2%
(ASC) valve pressure in
while remain
compressor
closed for the
rest of the time.
208

P = 5 bar
The anti-surge
• Pressure at
controller will
The anti- stream S3
open when the
beyond ±2%
while remain
compressor
closed for the
rest of the time.
209

P = 15.81 bar
The anti-surge
• Pressure at
controller will
The anti- stream S7
open when the
beyond ±2%
while remain
compressor
closed for the
rest of the time.
210

P = 50 bar
The anti-surge
• Pressure at
controller will
The anti- stream S9
open when the
beyond ±2%
while remain
compressor
closed for the
rest of the time.
211

P = 15 bar
The anti-surge
• Pressure at
controller will
The anti- stream S6
open when the
beyond ±2%
while remain
compressor
closed for the
rest of the time.
212

P = 50 bar
The anti-surge
• Pressure at
controller will
The anti- stream S18
open when the
beyond ±2%
while remain
compressor
closed for the
rest of the time.
213

P = 50 bar
The anti-surge
• Pressure at
controller will
The anti- stream S28
open when the
beyond ±2%
while remain
compressor
closed for the
rest of the time.
214
5.3.8 Condenser
There are three condensers in the system to change the gaseous stream into
liquid-gas mixed steam before entering the flash column (F-103). The refrigerant is
used to cool down the different stream temperature to 105.23°C. The control system
is put in place to make sure the condenser's output temperature, which will be the flash
column's incoming stream, is at the proper temperature. The system will protect the
liquid from overcooling, which might cause it to freeze, as well as from temperatures
that are too high and could disrupt the plant's operations. Temperature control is used
to monitor and control the stream temperature to the desired conditions by adjusting
the flow rate of refrigerant entering the condenser by utilizing control valve. Figure
5.22 to Figure 5.24 show the P&ID for control system of condenser and Table 5.27 to
Table 5.29 present the controlled variable, manipulated variable, disturbance, type of
control and setpoint of each of the condenser control system.
215
Figure 5.22 P&ID for condenser (E-116)
Table 5.27 Control system for condenser (E-116)

• Temperature
T = 105.23°C
at stream
The transmitter
S25d
(TT) will
Inlet flow of • Inconsistent
transmit impulse
Temperature at refrigerant flow rate of
Feedback to controller
stream S25g entering the stream S25d
(TIC) when the
condenser • Changes in
temperature
the
reaches beyond
temperature
±5%.
of refrigerant
216

• Temperature
T = 105.23°C
at stream
The transmitter
S25e
(TT) will
transmit impulse
stream S25h entering the stream S25e
(TIC) when the
temperature
the
reaches beyond
temperature
±5%.
of refrigerant
217

• Temperature
T = 105.23°C
at stream
The transmitter
S25f
(TT) will
transmit impulse
stream S25i entering the stream S25f
(TIC) when the
temperature
the
reaches beyond
temperature
±5%.
of refrigerant
218
5.3.9 Heater
Heaters were placed along several streams in order to heat up the contents
passing through it. In every circumstance where maintaining a specific temperature is
necessary, temperature controls are required. This can occur when an object has to be
heated, cooled, or both, and it must maintain the desired temperature (setpoint) despite
changes in its surroundings. Using the control system that is installed depending on
the necessary parameters, the flow of the stream that enters the heater is adjusted to
obtain the appropriate temperature. In order to guarantee that the required result is
obtained, and the components are not combined, a properly operating control system
is extremely important. Prior to entering mixer M-101, streams S10a, S21a and S30a
are heated up to 280°C using heater E-105, E-113 and E-114. Before entering the
reactor R-101, two distinct streams, stream S11b and stream S14a, are individually
heated by heaters E-108 and E-110 to a setpoint of 900°C. High-pressure steam is used
as the heating utility to heat up the stream. Figure 5.25 to Figure 5.29 show the P&ID
for control system of heater and Table 5.30 to Table 5.34 present the controlled
variable, manipulated variable, disturbance, type of control and setpoint of each of the
heater control system.
219
Figure 5.25 P&ID for heater (E-105)
Table 5.30 Control system for heater (E-105)

• Temperature
at stream
T = 280°C
S10a
The transmitter
(TT) will
high flow rate of
transmit impulse
Temperature at pressure stream S10a
stream S20 steam (HPS) • Changes in
(TIC) when the
entering the the
temperature
heater temperature
reaches beyond
of high-
±5%.
pressure
steam (HPS)
220

• Temperature
at stream
T = 900°C
S11b
The transmitter
(TT) will
high- flow rate of
transmit impulse
Temperature at pressure stream S11b
(TIC) when the
entering the the
temperature
heater temperature
reaches beyond
of high-
±5%.
pressure
steam (HPS)
221

• Temperature
at stream
T = 900°C
S14a
The transmitter
(TT) will
high- flow rate of
transmit impulse
(TIC) when the
entering the the
temperature
heater temperature
reaches beyond
of high-
±5%.
pressure
steam (HPS)
222

• Temperature
at stream
T = 280°C
S21a
The transmitter
(TT) will
high- flow rate of
transmit impulse
(TIC) when the
entering the the
temperature
heater temperature
reaches beyond
of high-
±5%.
pressure
steam (HPS)
223

• Temperature
at stream
T = 280°C
S30a
The transmitter
(TT) will
high- flow rate of
transmit impulse
(TIC) when the
entering the the
temperature
heater temperature
reaches beyond
of high-
±5%.
pressure
steam (HPS)
224
5.3.10 Cooler
The temperature of the liquid and gases is lowered to the appropriate level
using a cooler. An intercooler will be used to cool down the temperature of the air
before entering the next stage of compression. The higher density of cool air makes it
easier to compress than hot air. There are two intercoolers used in the production plant,
which are E-101 and E-103. Another two coolers, E-102 and E-111 are used to reduce
the temperature of stream to meet the operating requirement of the subsequent
equipment.
Before entering the compressor C-102, Stream S3's temperature is lowered

from 85.23°C to 25°C using Cooler E-101. The stream enters Cooler E-102 after
leaving the compressor to cool it from 85.24°C to 30°C before it reaches the Flash
Separator F-101. The stream is split into a gas stream and a liquid stream, respectively,
using F-101. After Stream 7 passes through Compressor C-103, the Stream S8 is
cooled from 121.30°C to 30°C. Cooler E-111 is used to bring down the temperature
of stream S16a from 280°C to 82.3°C before entering the flash column (F-102).
Cooling water is used as the cooling medium to lower down the temperature of
stream. Temperature control is installed to the cooler to maintain the outlet temperature
at desired condition by controlling the flow rate of cooling water flowing into the
cooler. Figure 5.30 to Figure 5.33 show the P&ID for control system of cooler and
Table 5.35 to Table 5.38 present the controlled variable, manipulated variable,
disturbance, type of control and setpoint of each of the cooler control system.
225
Figure 5.30 P&ID for cooler (E-101)
Table 5.35 Control system for cooler (E-101)

• Temperature
T = 25°C
at stream S2a
The transmitter
• Inconsistent
Inlet flow of (TT) will
flow rate of
cooling transmit impulse
Temperature at stream S2a
water (CW) Feedback to controller
stream S3 • Changes in
entering the (TIC) when the
the
cooler temperature
temperature
reaches beyond
of cooling
±5%.
water (CW)
226

• Temperature
T = 30°C
at stream S4
The transmitter
• Inconsistent
flow rate of
Temperature at stream S4
the
cooler temperature
temperature
reaches beyond
of cooling
±5%.
water (CW)
227

• Temperature
T = 30°C
at stream S8
The transmitter
• Inconsistent
flow rate of
Temperature at stream S8
the
cooler temperature
temperature
reaches beyond
of cooling
±5%.
water (CW)
228

• Temperature
at stream T = 82.3°C
S16a The transmitter
Inlet flow of • Inconsistent (TT) will
cooling flow rate of transmit impulse
Temperature at
water (CW) stream S16a Feedback to controller
stream S17
entering the • Changes in (TIC) when the
cooler the temperature
of cooling ±5%.
water (CW)
229
5.3.11 Pump
Pump is used to increase the pressure of the liquid by using rotating blades to
increase the velocity of a liquid and then reduce the velocity of the liquid in the volute.
In the methanol production plant, pump (P-101) is used to increase the pressure of
water from 1 bar to 50 bar prior entering the steam reforming reactor (R-101) to react
with methane for the production of syngas. Therefore, pressure control is important in
pump control system to ensure the operating condition of stream achieves the desired
setpoint. Pressure of the pump control system is maintained by adjusting the flow rate
of stream using control valve.
Besides, flow control is also vital to the pump control system to reach the
minimum flow of inlet stream entering the pump for safety purpose. Minimum flow
the lowest continuous flow at which the pump was permitted to operate. The minimum
flow values is necessary for continuous operation, for intermittent operation and for
permissible temperature rise. A minimum flow controller is installed in the pump
control system to prevent the pump from overheating and keep away the pump from
pump surging when there is insufficient water for pumping to happen. Recycle stream
is needed for water to recycle back to the source when the amount of fluid is not
reaching the minimum flow. Figure 5.34 is presented the P&ID for pump control
system whereas Table 5.39 shows the controlled variable, manipulated variable,
disturbance, type of control and setpoint of each of the pump control system.
230
PIC
PT
P-101
S14
S13
FT
FC
Figure 5.34 P&ID for pump (P-101)
Table 5.39 Control system for pump (P-101)

P = 50 bar
• Changes in
The transmitter
(PT) will
stream of inlet
Pressure at transmit impulse
exiting the stream (S13) Feedback
stream S14 to controller
pump (P- • Rotation of
(PIC) when the
101) pump (P-
pressure reaches
101)
beyond ±5%.
Outlet stream
• Inconsistent flow rate = 891
Flow rate of flow rate of kg/hr. The
stream inlet stream stream will be
Flow rate of
exiting the (S13) Feedback recycled back to
stream S14
pump (P- • Rotation of the source when
101) pump (P- the flow rate
101) reaches less than
30% of setpoint.
231
232
233
234
235
236
237
238
CHAPTER 6
PROCESS SAFETY
6.1 Introduction
Process safety management is a risk-based method of hazard control that

prevents the unintended release of hazardous materials and other physical agents.
Process safety is concerned with preventing fires, explosions, and chemical accidents
at chemical processing facilities and other places, such refineries and oil and gas
production plants, that deal with potentially harmful compounds. Process safety
systems put a lot of focus on the engineering and design of the facility, equipment
maintenance, efficient alarms, appropriate control points, procedures, and training.
Process safety may be seen as the product or effect of several management,
organizational, and technology abilities working together in such a coordinated
fashion.
Applying sound design, engineering, and operational concepts, process safety

management is created to control the integrity of operational systems and processes
handling hazardous chemicals. Process safety management is crucial for managing
both basic and complicated chemical activities that include hazardous materials. Focus
is placed on Technology, Facilities, and Personnel by process safety management’s
components. The most important things to remember are that regardless of whether
the site is subject to regulatory requirements or not, all sites must exercise due
diligence to ensure that their facility is safe to operate, that equipment is maintained
properly, and that proper operating procedures are in place.
239
6.2 Plant Safety
Processes and plants in the chemical industry are generally subject to the
possibility of hazards for men and environment (Oberhoff & König, 2017). As a result,
every potential danger must be properly analyzed, and hazard potentials must be
decreased as much as is practical. Since the consequences on the entire plant system
might be higher from a tiny detail, each piece of equipment must implement security
measures but should not be labelled as significant equipment. Safety audits are
developed via methodical safety conversations for both new installations and existing
plants. By adopting low-risk process stages, chemicals, and appropriate instruments,
the risk potential may be minimized. Safety duties must be defined for any lingering
risks. Normally, they are managed by separate, redundant protective measures. Special
technical criteria are required if automated control systems are employed. The
following are a few different safety factors that must be taken into account while
evaluating the factory's safety. To guarantee adequate plant safety, the most important
thing to do is to prevent any undesired conditions. Even if a piece of equipment isn't
classified as important, safety precautions still need to be taken. The entire plant
system may be greatly impacted by these minute features. According to Sanjoy (2002),
by taking into account the plant's safe operation, the following variables must all be
taken into account for safety.
6.2.1 Plant Location
Many factors are to be considered before setting up any chemical plant’s

location. The early theories of industrial sites analyse a fundamental structure in which
the location and special diversification were determined by adjusting the features of
input and output weight distance. The raw material supply, location with respect to
market, transport facilities, availability of labour, availability of utilities, availability
of suitable land, environmental impacts, local community considerations, climate and
political and strategic considerations are a few of the elements to be taken into account.
Each chemical factory should be located as far away from residential areas as feasible
to reduce the possibility of injury to the general population.
240
6.2.2 Chemical Storage and Process Vessel
Most regulatory bodies, such as the Occupational Safety and Health

Administration (OSHA) along with the Control of Substances Hazardous to Health
Regulations (COSHH) law, mandate that chemicals should be stored properly at all
times. When chemicals are stored appropriately, the product is adequately maintained.
Despite the fact that most chemicals have a lengthy shelf life, spoilt chemicals can
result in unneeded environmental waste, a drop in potency that affects the quality of
the chemical, the production of dangerous goods, and significant financial losses.
Consider your household food. Chemicals are no different. Improper storage might
result in major health and safety risks.
Hazardous chemicals are substances that can harm people, property and the
environment, which including common industrial, commercial, pharmaceutical,
agricultural and domestic chemicals. Hazardous chemicals must be treated as a risk in
the workplace. Storing, handling and managing hazardous chemicals correctly is
important to avoid harm to workers, members of the public, property and the
environment. For storage, chemicals must be kept at the proper temperature and
humidity level. This can be particularly challenging in hot, muggy climates. Chemicals
shouldn't typically be kept close to heat sources like steam pipes or lab ovens.
Additionally, direct sunlight shouldn't be used to store chemicals. Chemical storage is
essential because chemicals pose a serious threat to both people who handle them and
those around (Torok et al., 2011). People typically overlook the different direct and
indirect dangers that have an impact on their health. Chemical exposure can result in
both short-term and long-term health issues, including burns, lifelong breathing issues,
and other biological reactions that can cause minor to deadly damage.
Accidents can still occur even though we have policies and procedures in place
for how our chemicals are stored. Contamination happens frequently when chemicals
enter the environment. It is quite challenging to eliminate chemicals after they have
been introduced to the environment. The most typical instance of this is when polluted
soil gradually mixes with human drinking water as well as that of flora and fauna.
241
6.2.3 Transportation
One of the key factors in determine the site selection is the transport of supplies
and products to and from the plant. If possible, a location near at least two main modes
of transportation was chosen such as road, rail, waterway (canal or river), or a harbor.
Movements of raw materials to, from, and within the site are commonly by road
because of the flexibility and convenience of road vehicle operation. Rail transport is
often less expensive for long-distance transfer of bulk chemicals. Industrial gases and
some bulk fuels usually use pipelines as a method of transportation. The transportation
network for the movement of supplies, personnel, and emergency traffic into, out of,
and around the site is an important concern that needs be considered. This is because
a good road network optimizes these movements by considering material types, traffic
volumes, site operations, economics, and safety.
According to the UK HSE guidance, the following requirements should be

taken account by the designers when planning the workplace traffic routes:
• It must be suitable for the people and vehicles using them and organized so
that they can both move around safely
• Enough separation (segregation) between the pedestrians and vehicles where
they share a traffic route
• Pedestrians or vehicles must be able to use a traffic route without causing
danger to the health or safety of people working near it
• Vehicle routes must be far enough away from doors or gates that pedestrians
use, or from pedestrian routes that lead on to them, such that the safety of
pedestrians is not threatened
• Every traffic route must have a well-drained surface that is suitable for its
purpose and must not be so uneven, potholed, sloped, or slippery that it might
expose anyone to a risk to their health or safety
• They must, so far as is reasonably practicable, be kept free from obstructions
and anything that may cause anyone to slip, trip, or fall
• They must have appropriate markings and signs where necessary for health or
safety reasons.
242
6.3 Labor Safety
Labor will be required for the plant's development and operation. Skilled
construction employees are frequently brought in from outside the site region, but there
should be a sufficient pool of unskilled labour and manpower suitable for training to
operate the plant accessible locally. Plant maintenance will necessitate the use of
skilled craft personnel such as electricians, welders, and pipe fitters. According to the
Bureau of Labor Statistics, dozens of workers have lost their lives in 2017 after inhale
a harmful chemicals substance. In every turn of chemical plants, it is filled with danger.
Thus, a proper management of worker safety is very important to make the workplace
more comfortable for employees. Every employee should have adequate instructions
before handling the heavy machinery or equipment other than wearing a protective
eyewear when using grinders and other equipment that may be hazardous to the eyes.
There are a few possible hazards for industry employees, including:
• Falls (from heights)

• Trench collapse
• Scaffold collapse
• Electric shock and arc flash/arc blast
• Failure to use proper personal protective equipment
• Repetitive motion injuries
243
6.3.1 General Personnel Safety
a) All workers should report any injuries and illnesses at workplace immediately.
b) Each employee should comply and know all the safety guidelines including
with warning signs and danger. The correct method on handling the fire
extinguishers, fire hoses, fire escapes, location of escapes routes must be
known by all of them.
c) An employee is responsible to inform the supervisors if there is any unsafe acts
or unsafe conditions
d) The use of seatbelts and safety helmet is compulsory for every worker
e) Firearms, explosives, and weapons are prohibited on company property
f) On Company Property or while "on duty," it is prohibited to use, possess, sell,
or be under the influence of illegal drugs, as well as to misuse prescription
drugs and/or alcohol.
g) Only authorised and trained employees are permitted to repair or adjust
machinery and equipment. Before removing any machine, guards or working
on powered machinery and equipment, Lock and Tag Out Procedures must be
followed. When the job is finished, replace all of the guards.
h) Trained and authorized employees are the only person who were permitted to
enter a posted confined space. A properly issued permit is required upon
entering.
i) Only authorised and trained employees are permitted to dispense or use
chemicals. It is their responsibility to know where to find SDS (Safety Data
Sheets) and to ensure that they are available for use and review.
j) Wear and use the Personal Protective Safety Equipment as instructed. This
includes foot protection, head protection, gloves, and other similar items.
k) Smoking is only allowed in designated "Smoking Areas."
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6.3.2 Personal Protective Equipment (PPE)
Personnel protective equipment (PPE) can be known as an equipment worn to

minimize the exposure to a serious workplace injuries and illnesses, such as from
chemical contact, physical, radiological, mechanical, electrical, or other workplace
hazards. The items which considered as PPE were shown as below, including with
descriptions.
Table 6.1 Personal Protective Equipment (PPE)
The use of safety helmet is crucial

and mandatory on almost all work
sites and manual working. The
purpose is to cover the head from
falling objects or any work which
requires force. The safety helmets
should be able to pass shock
absorption, resistance to penetrance
Safety Helmet and flame test. Components such as

shell, harness and headband are a
good protection to the head.
Goggles are the primary eye
protection devices designed to shield
the eyes from liquid or chemical
splashes, as well as irritating mists,
vapours, and fumes. They form a
protective seal around the eyes,
preventing objects or liquids from
entering through the goggles'
Safety Goggle openings. This is very crucial when

working with or near liquids that
could splash, spray, or mist.
245
Serious foot and leg injuries from
falling or rolling objects or slippery
surfaces can be prevented by
wearing safety boots. The sole
plates should be in a good condition
to prevent punctures. Safety boots
Safety Boots also comes with a slip-resistant soles
which protect against compression
and impact.
Example of respiratory protection
includes N95 masks, surgical mask
or gas mask. This equipment should
be worn when doing a task that can
cause inhalation of harmful
materials. This includes harmful
Respiratory Device chemical and gas, splatter that
contains viruses such as COVID-19
and large-particle droplets.
Hearing problems such as loss of
hearing can e prevented by wearing
earplugs or earmuffs. This can
happen when handling a heavy
machinery equipment which have
loud noise. A formable earplug
Earplugs
which fit on different sizes of ear
canal is recommended where it can
reduce the noise to an acceptable
level.
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Safety gloves should be used when
doing task that can cause hand and
skin burns, cuts, absorption of
harmful chemicals, amputations,
and fractures. It is always important
to replace the glove if it is already
worn-out or any presence of
contamination. To reduce the
Safety Gloves
electric shock, rubber gloves work
best.
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6.4 Fire Hazards
A hazard is something that poses danger, peril, risk, or difficulty. Fire hazards
are any acts, materials, or conditions that could raise the intensity or severity of a fire
or enable one to start. A flammable fuel or a heat source, such as a broken appliance,
could pose a threat. Fire, which can create explosions due to gases, vapors, mists, and
dusts that escape during the manufacturing, processing, transportation, and storage of
combustible materials, is the most significant threat to a chemical-based industry. Fire
risk management becomes extremely important and necessary in order to avoid any
casualties or property losses. Maintaining employee safety, preventing fires, and
responding effectively if a fire occurs are all critical parts of risk management. There
are procedures that can be taken to keep a fire from exploding and to keep the situation
under control without incurring any loss of life, property, or equipment.
6.4.1 Fire Safety Policy
Building fire safety rules apply both during construction and during the life of
the building. Local, subnational, and national governments establish building codes to
ensure features include proper fire escapes, signs, and construction details like fire
stops and fire-rated doors, windows, and walls. Electrical regulations also aim to avoid
overheating of wiring or equipment, as well as to protect against fires caused by
electrical failures. Portable fire extinguishers or permanent fire detection equipment
such as fire sprinkler system is required within a building (Purser, 2010).
Regular inspections for usable fire exits and proper escape signage, working
fire extinguishers of the correct type in accessible places, and the storage and handling
of hazardous products should be handled by local authorities concerned with fire
safety. A fire inspection may result in a notice of required action or the closure of a
structure until it can be brought into compliance with fire code requirements,
depending on local rules (Bhatia, 2021).
248
Additional fire policies may be implemented by building owners and
managers. An industrial facility, for example, may designate and train specific staff to
serve as fire fighters. Building managers must ensure that fire evacuation standards are
followed and that elements such as spray fireproofing are not destroyed. Fire rules may
be in place to mandate tenant and user training and awareness in order to avoid obvious
mistakes like propping open fire doors. Fire drills may be conducted at regular
intervals throughout the year in buildings, particularly institutions such as schools.
However, in order to have a safer plan, standard operating procedures that comply with
the Fire Services Act 1988 should be followed for the unpreventable ignition sources
in the factory, such as the presence of motors, boilers, and leakage.
In a chemical plant, fire or burning refers to the quick, exothermic oxidation of

the ignited fuel. Liquid and vapor fuels are more easily ignited. In order for a fire or
combustion explosion to occur, three conditions must be met:
a) Presence of fuel
b) Oxygen must be present to support the combustion reaction.
c) A source of ignition must be available.
Figure 6.1 Combustion triangle that represents the three essential components for
fire ignition (Fogler, 2022).
249
Thus, at a construction site, fire safety becomes everyone's responsibility.
Employers should educate employees about workplace fire hazards and what to do in
the event of a fire. In the case of a fire, this plan should include key personnel's
responsibilities as well as an evacuation plan for site workers. Prior to beginning any
deconstruction project in the construction sector, a "fire plan" should be established.
The following resources can help you recognize and evaluate hazards in the workplace,
as well as potential remedies (Schroll, 2002).
6.4.2 Fire Detection and Alarm System
Fire detection systems are meant to identify fires early in their course, when
there is still enough time for inhabitants to safely evacuate. Early detection is also
important for ensuring the safety of emergency response personnel. Early detection
can limit property loss and reduce downtime for the operation since control operations
can begin while the fire is still small. Most fire alarm systems offer emergency
responders with information on the location of the incident, which speeds up the
firefighting operation (Schroll, 2002).
Figure 6.2 Smoke detector
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Detectors must be used in conjunction with alarms to be effective. Alarm
systems normally send a signal to a staffed monitoring station, either on-site or off-
site, and offer warning to at least the building's residents. Alarms may be sent straight
to the fire department in some situations, however this is no longer the standard
procedure in most places. As previously said, these systems have various advantages.
The fact that they do nothing to contain or control the fire is a huge drawback. Fire
suppression systems, such as automatic sprinklers, are used to keep the fire under
control. They also provide notification that they are working, therefore if connected to
notification appliances throughout the building, they can serve as a heat detection-
based system. However, they will not react as quickly as a smoke detection system.
This is why, even if sprinklers are installed, facilities that require immediate
notification require detection and alarm systems.
A facility's fire detection and alarm system should be selected based on its fire
safety goals. These goals are derived from a risk analysis of the facilities and
operations. This method relies heavily on personal risk tolerance and how much money
one can afford to lose. Detectors come in a range of shapes and sizes. Heat, smoke,
and flame detectors are the three most common types. Several types of detectors are
utilised to activate suppression systems, such as flame detectors. The simplest basic
detection devices are heat detectors. They come in a variety of styles. These varieties
are separated into two groups: spot and line. Spot detectors are single units that are
placed throughout the protected area in discrete locations. Line detectors have a
continuous detector that covers the entire coverage area.
The fire alarm control panel can be connected to a variety of supervisory

equipment. Water control valves for automatic sprinkler systems, could have a tamper
switch. The tamper switch will send a supervisory signal to the control panel if this
valve is closed by an unauthorised individual, alerting your personnel to the problem.
For a wide range of applications, supervisory devices are available. There are two
types of systems: addressable and nonaddressable. All of the detectors on the system
have a unique digital identifier in addressable systems. Each device can communicate
with the fire alarm control panel separately. Detectors in non-addressable systems can
be classified into zones based on the fact that they all share the same pair of wires, but
251
the control panel cannot determine any information about a single detector (Bhatia,
2021).
Figure 6.3 Basic components in a fire alarm system
252
6.5 Emergency Response
Occupation Safety and Health Administration, is dedicated to maintaining high

standards for all types of employment conditions across the country. While it is vital
for all businesses to adhere to these safety and care standards, in some circumstances,
this is not enough: accidents can and do occur. Because of this constant threat, a
company's next step is to develop an effective emergency response plan in the case of
an accident or injury.
According to OSHA, any organisation with more than ten employees is

required to have an emergency plan in place. This plan should include actions for
everyone from management to employees, as well as what they should do in an
emergency. These plans should be evaluated on a regular basis with all employees at
the organisation. Not only does a company's workforce grow and change with time,
but so are the responsibilities of certain individuals; remaining informed and prepared
is critical because you never know when an emergency will strike.
Evacuation plans must be drawn out, as well as actions and rules for those in
charge of shutting down plant activities before departing. There should also be a
system in place to account for all employees present at the time, so that search and
rescue personnel don't waste time looking for someone who didn't show up for work
that day. Everyone should be aware of their various medical and rescue
responsibilities, and a structure should be in place to allow for emergency reporting in
the event that usual lines of communication are disrupted (U.S Department of
Homeland Security, 2022).
While it is easy to believe that a CEO or manager is in charge of everything, in

an emergency, multiple hands must be available to do critical tasks. It's critical to have
this chain of command figured out. It is essential to have an emergency coordinator so
that they are aware of the key persons to contact in the event of an emergency. They
must be taught about chemical risks, fire emergency response, and when to seek
outside assistance, among other things. These teams will also require training and
certification in areas like as first aid, CPR, fire extinguisher use, shutdown protocols,
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chemical spills, emergency response, hazardous materials response protocols, and so
on. Employees should understand and coordinate responsibilities, including knowing
who is responsible for:
a) Assessing the severity of the emergency

b) Creating specific procedures to address each situation
c) Emergency evacuation, and any other emergency activities
d) Notifying outside assistance and emergency response teams
e) Plant shut down operations and the delegation of other responsibilities
Employee training is a necessary in any workplace, but it is especially

important in industrial companies. All employees must be appropriately prepared to
handle their tasks and any equipment while on the job, and they must also be properly
trained in emergency response because other people's lives may depend on it. All
personnel (regardless of their job title) must be knowledgeable and prepared in the
event of an emergency. This includes understanding evacuation procedures, alarm
systems, shutdown procedures, and potential hazards posed by chemicals, equipment,
and flammable materials, among other things. OSHA mandates annual training for all
workplaces, ensuring that there is no excuse for being unprepared in the event of a
crisis.
Another important part of industrial plant preparation is medical response.

OSHA argues that first aid can be reached on site in less than four minutes (whether
it's a hospital or a clinic), and that if it can't, a qualified first-aid responder must be
present when workers arrive. First aid equipment, as well as the phone numbers for
any appropriate response teams, such as EMS, hospital emergency rooms, HAZMAT,
and so on, must always be on site.
254
6.6 HAZOP Study
HAZOP, or Hazard and Operability Study is a structured and systematic study

of a planned or current process or operation with the goal of identifying and evaluating
problems that may pose a risk to personnel or equipment or prohibit efficient operation.
HAZOP is usually carried out as a final check when the detailed design has been
completed. Since HAZOP is a complete identification of hazards from operational
upsets, operational procedures and equipment failures, it can prevent commissioning
and operational problem and thus, helps to improve the product quality.
A HAZOP should be held during a few occasions. Among the occasions

including the various stages of plant design. The HAZOP should be held at the
beginning of the project as a ‘safety and environmental specification’, as well as
towards the end of the process definition, which is when the process flow sheets are
available as a Safety and Environmental Review. Final design HAZOP should be held
when the Piping and Instrumentation Diagram (P&ID) are at “Approved for Design’
stage. Next, HAZOP study should be held during construction site inspection to ensure
the suggestions arising from the HAZOP or other safety and environmental reviews
are being implemented. Besides, HAZOP study is held together with a pre-
commissioning study to review the plant procedures and perform a conventional safety
audit. Lastly, once the plant is operating, HAZOP study is held at regular interval for
auditing plant and procedures to ensure ongoing safety awareness.
There are some specific terms or terminologies used in the HAZOP which
should be fully understand before constructing a HAZOP study. The terminologies
with their meanings are tabulated in Table 6.2.
Table 6.2 Terminologies in HAZOP study
Terminology Meaning
Section of equipment with definite
boundaries within which process
Study node
parameters are investigated for
deviation.
255
Definition of how the plant is expected
Design intent
to operate in the absence of deviations.
Simple words that are used to qualify the

design intention and to guide and
Guide words
stimulate for identifying process
hazards.
Physical or chemical property associated

with the process, including general terms
Process parameter such as reaction, mixing, concentration,
pH, specific items such as temperature,
pressure, phase and flow.
Departures from the design intent that

are discovered by systematically
Deviations
applying the guide words to process
parameters for each process section.
Reasons why deviation might occur.

These causes can be hardware failures,
Causes
human erros, unanticipated process
states, external disruption, etc.
Consequences Results of deviations.
Engineered systems or administrative

controls designed to prevent the causes
Safeguards
or mitigate the consequences of
deviations
Suggestion for design changes,

Actions procedural changes, or areas for further
study.
The steps to complete HAZOP analysis should begin with a detailed process
flow sheet. The flow sheet is broken into a number of process units, such as reactor or
storage tank. A unit is selected for the HAZOP study. Then, a study node should be
chosen from the unit, for example vessel, line or operating instruction. The design
intent of the study node selected is then described. For instance, vessel V-1 is designed
256
to store benzene feedstock and provide to the reactor. Next, a process parameter is
picked. The process parameters include flow, level, temperature, pressure,
concentration, pH, viscosity state, agitation, volume, reaction, sample, component
start, stop, stability, power, inert. Lastly, a guide word is applied to the process
parameter to suggest the possible deviations.
Guide word is used in HAZOP study to identify the deviations and explicitly
consider appropriate parameters which apply to the design intent. The guide word
chosen must be appropriate to the study node and neither too specific nor too general.
A set of guide words is provided as shown in Table 6.3.
Table 6.3 Guide word for HAZOP
Guide Word Meaning

No or not Complete negation of the design intent
More Quantitative increase
Less Quantitative decrease
Reverse Logical opposite of the design intent
Other than/ Instead Complete substitution
Early/ Late Relative to the clock time
Before/ After Relating to order or sequence
Faster/ Slower Relating to the wrong timing
Where else Applicable for flows, transfer, sources

and destinations
As well as Qualitative modification/increase
Part of Qualitative modification/decrease
After that, possible causes is determined once the deviation is applicable. Any
protective system should also be noted down in the HAZOP sheet before the
consequences of the deviation is evaluated. According to the consequences, action
should be recommended and described in detail. The previous steps should be repeated
until all the applicable guide words have been applied to the selected process
parameter. Next, the steps are repeated until all the applicable process parameters have
257
been considered for the given study node. Lastly, all the steps are repeated until all the
study nodes have been considered for the given section and proceed to the next section
on the flow sheet.
The HAZOP study is conducted for major and auxiliary equipment in methanol
production plant. The major equipment includes catalytic fixed bed reactors, flash
separators, distillation columns and membrane separator. The auxiliary equipment
includes compressors, condensers, coolers, heaters, pump and throttling valve.
6.6.1 Catalytic Fixed Bed Reactor (R-101, R-102)
The objectives of the HAZOP study on the catalytic fixed bed reactor are listed
as below:
a) To ensure the operating conditions, such as temperature and pressure are

maintained at optimum value to achieve higher production efficiency
b) To ensure the flow rate of the inlet stream entering the reactor is controlled at
desired value to maintain the reaction rate and quality of the product
c) To ensure the reactor is operated at safe conditions
Table 6.4 shows the HAZOP sheet for steam reforming reactor (R-101) and
methanol synthesis reactor (R-102). The HAZOP sheet consists of possible causes,
consequences, safeguards, and recommended action required for each deviation of
parameters.
258
Table 6.4 HAZOP for catalytic fixed bed reactor
HAZOP WORKSHEET
Project: Production of Methanol from Biogas Page: 1 of 7
Rev. No: 0000 Date: 4 July 2022
Node: Catalytic fixed bed reactor (R-101,
Design Intent: To produce methanol via methanol synthesis reaction
R-102)
Diagram: P&ID
No Parameter Guide Word Deviation Possible Causes Consequences Safeguards Action Required
1A Pressure Low Low ▪ Leakage in pipeline ▪ Low reaction rate and ▪ Install Pressure ▪ Monthly
pressure ▪ Failure of control low product yield Transmitter maintenance
valve at outlet ▪ Reactor will fail to (PT) and
stream operate ▪ Install Pressure monitoring
▪ Low temperature of ▪ Unreacted materials Indicator ▪ Regular check
inlet stream accumulate in reactor Controller on the
▪ High flow rate of ▪ Produce large amount (PIC) condition of
cooling water of side products ▪ Install Pressure the reactor
▪ Low flow rate of Alarm Low column
inlet stream (PAL)
259
HAZOP WORKSHEET
Node: Catalytic fixed bed reactor (R-101, R-
102)
Diagram: P&ID
Guide
No Parameter Deviation Possible Causes Consequences Safeguards Action Required
Word
1B Pressure High High ▪ Blockage in pipeline ▪ The pressure ▪ Install Pressure ▪ Monthly
Pressure ▪ Failure of control may build up in Transmitter maintenance
valve at outlet stream the reactor to (PT) and monitoring
▪ High temperature of cause ▪ Install Pressure ▪ Regular check
inlet stream overpressure Indicator on the
▪ Low flow rate of and explode Controller condition of the
cooling water ▪ Runaway (PIC) reactor column
▪ High flow rate of inlet reaction causes ▪ Install Pressure ▪ Prepare
stream low product Alarm High emergency
yield and low (PAH) shutdown
product quality procedure
260
HAZOP WORKSHEET
102)
Diagram: P&ID
Guide
Word
2A Temperature Low Low ▪ Low ▪ Low reaction rate, ▪ Install ▪ Monthly
Temperature temperature and low product yield Temperature maintenance
pressure of inlet and quality Transmitter (TT) and monitoring
stream ▪ Reactor will fail to ▪ Install ▪ Regular check
▪ Higher heat loss operate Temperature on the
rate in pipelines ▪ Unreacted materials Alarm Low condition of the
▪ Large amount accumulate in (TAL) reactor column
of cooling water reactor ▪ Install
entering reactor ▪ Produce large Temperature
amount of side Indicator
products Controller (TIC)
261
HAZOP WORKSHEET
102)
Diagram: P&ID
Guide
Word
2B Temperature High High ▪ High temperature ▪ Runaway ▪ Install ▪ Monthly
Temperature and pressure of reaction causes Temperature maintenance and
inlet stream low product Transmitter (TT) monitoring
▪ Less amount of yield ▪ Install ▪ Regular check on
cooling water ▪ Breakdown or Temperature the condition of
entering reactor explosion of Alarm High the reactor column
▪ Low temperature reactor due to (TAH) ▪ Prepare emergency
of cooling water overheating ▪ Install shutdown
Temperature procedure
Indicator
Controller (TIC)
262
HAZOP WORKSHEET
102)
Diagram: P&ID
Guide
Word
3A Flow No No flow ▪ Rupture of ▪ No reactant ▪ Install Flow ▪ Monthly
pipelines entering the Transmitter (FT) maintenance and
▪ Blockage of reactor ▪ Install Flow monitoring
pipelines ▪ No reaction Alarm Low ▪ Regular check on
▪ Malfunction of occurred in (FAL) the condition of the
control valve reactor ▪ Install Flow pipelines
▪ Failure of previous ▪ Breakdown of Indicator ▪ Prepare emergency
equipment reactor Controller (FIC) shutdown
▪ Install bypass procedure
line
263
HAZOP WORKSHEET
102)
Diagram: P&ID
3B Flow Less Less flow ▪ Rupture of pipelines ▪ Low reaction ▪ Install Flow ▪ Monthly
▪ Leakages of pipelines rate Transmitter maintenance and
▪ Malfunction of flow ▪ Low product (FT) monitoring
control valve yield ▪ Install Flow ▪ Regular check on
▪ Failure of previous ▪ Reactor will fail Alarm Low the condition of the
equipment to operate (FAL) pipelines
▪ Low product ▪ Install Flow
quality Indicator
Controller
(FIC)
▪ Install bypass
line
264
HAZOP WORKSHEET
102)
Diagram: Figure 1.8
3C Flow More More ▪ Failure of previous ▪ The pressure ▪ Install Flow ▪ Monthly
flow equipment may build up Transmitter maintenance and
▪ Malfunction of in the reactor (FT) monitoring
control valve to cause ▪ Install Flow ▪ Regular check on
overpressure Alarm High the condition of the
and explode (FAH) pipelines
▪ Produce large ▪ Install Flow ▪ Prepare emergency
amount of by- Indicator shutdown procedure
products Controller (FIC)
▪ Install bypass
line
265
6.6.2 Flash Separators (F-102, F-103)
The objectives of the HAZOP study on the flash separators are listed as below:
a) To ensure the operating parameters, such as temperature, level and pressure

are maintained at optimum value to achieve higher separation efficiency
b) To ensure the flow rate of the inlet stream entering the separator is controlled
at desired value to maintain the separation rate and quality of the product
c) To ensure the flash column is operated at safe conditions
Table 6.5 shows the HAZOP sheet for flash column F-101 and F-102. The
HAZOP sheet consists of possible causes, consequences, safeguards, and
recommended action required for each deviation of parameters.
266
Table 6.5 HAZOP for flash separators
HAZOP WORKSHEET
Node: Flash separators (F-102, F-103) Design Intent: To separate liquid mixtures based on volatility
Diagram: P&ID
1A Flow No No flow ▪ Malfunction of inlet ▪ No separation ▪ Install Flow ▪ Monthly
control valve process Transmitter maintenance and
▪ Pipe blockage happened (FT) monitoring
▪ Pipe rupture ▪ Loss of feed ▪ Install Flow ▪ Regular check on
Alarm Low the condition of the
(FAL) pipelines
▪ Install Flow ▪ Prepare emergency
Indicator shutdown procedure
Controller
(FIC)
▪ Install bypass
line
267
HAZOP WORKSHEET
Diagram: P&ID
1B Flow Less Less flow ▪ Malfunction of inlet ▪ Low liquid level ▪ Install Flow ▪ Monthly
control valve in column Transmitter maintenance and
▪ Pipeline leakage ▪ Column will dry (FT) monitoring
▪ Scaling in pipeline up easily ▪ Install Flow ▪ Regular check on
▪ Low separation Alarm Low the condition of the
efficiency (FAL) pipelines
quality Indicator
Controller
(FIC)
▪ Install bypass
line
268
HAZOP WORKSHEET
Diagram: P&ID
1C Flow More More ▪ Malfunction of inlet ▪ Flooding of ▪ Install Flow ▪ Monthly
flow control valve column Transmitter maintenance and
▪ Failure of previous ▪ Damage the (FT) monitoring
equipment column ▪ Install Flow ▪ Regular check on
Alarm High the condition of the
(FAH) pipelines
▪ Install Flow
Indicator
Controller
(FIC)
▪ Install bypass
line
269
HAZOP WORKSHEET
Diagram: P&ID
Guide
Word
1D Flow Reverse Reverse ▪ Malfunction of inlet ▪ Back flow of ▪ Install Flow ▪ Monthly
flow control valve vapor-liquid Transmitter (FT) maintenance and
▪ Low inlet pressure mixture ▪ Install Flow monitoring
▪ Damage the Alarm Low ▪ Regular check on
piping (FAL) the condition of the
system ▪ Install Flow pipelines
Alarm High
(FAH)
▪ Install Flow
Indicator
Controller (FIC)
▪ Install bypass line
270
HAZOP WORKSHEET
Diagram: P&ID
Guide
Word
2A Pressure Low Low pressure ▪ Leakage in ▪ Low ▪ Install Pressure ▪ Monthly
pipeline separation Transmitter (PT) maintenance
▪ Failure of control efficiency ▪ Install Pressure and monitoring
valve at outlet ▪ Low quality Indicator ▪ Regular check
stream product Controller (PIC) on the condition
▪ Low temperature ▪ Column ▪ Install Pressure of the column
of inlet stream rupture Alarm Low
▪ Low flow rate of (PAL)
inlet stream
271
HAZOP WORKSHEET
Diagram: P&ID
Guide
Word
2B Pressure High High pressure ▪ Blockage in ▪ Low ▪ Install Pressure ▪ Monthly
pipeline separation Transmitter (PT) maintenance
▪ Failure of control efficiency ▪ Install Pressure and monitoring
valve at outlet ▪ Flooding of Indicator ▪ Regular check
stream column Controller (PIC) on the condition
▪ High temperature ▪ Install Pressure of the column
of inlet stream Alarm High ▪ Prepare
▪ High flow rate of (PAH) emergency
inlet stream shutdown
procedure
272
HAZOP WORKSHEET
Diagram: P&ID
Guide
Word
3A Temperature Low Low ▪ Low ▪ Low separation ▪ Install ▪ Monthly
Temperature temperature and rate and Temperature maintenance
pressure of inlet efficiency Transmitter (TT) and monitoring
stream ▪ Low purity of ▪ Install ▪ Regular check
▪ Higher heat loss product Temperature on the condition
rate in pipelines Alarm Low of the reactor
▪ Large amount (TAL) column
of cooling water ▪ Install
entering reactor Temperature
(Failure of Indicator
cooling utility) Controller (TIC)
273
HAZOP WORKSHEET
Diagram: P&ID
Guide
Word
3B Temperature High High ▪ High temperature ▪ Low product ▪ Install ▪ Monthly
Temperature and pressure of inlet quality and Temperature maintenance and
stream efficiency (loss Transmitter (TT) monitoring
▪ Less amount of of desired ▪ Install ▪ Regular check on
cooling water product) Temperature the condition of
entering reactor ▪ Separation of Alarm High the column
▪ Low temperature of undesired (TAH) ▪ Prepare
cooling water product ▪ Install emergency
▪ Failure of occurred Temperature shutdown
temperature control ▪ Pressure of Indicator procedure
system column Controller (TIC)
increases
274
HAZOP WORKSHEET
Diagram: P&ID
Guide
Word
4A Level High High Level ▪ High flow rate of ▪ Low separation ▪ Install Level ▪ Monthly
inlet stream efficiency Transmitter maintenance and
▪ Malfunction of ▪ Flooding of (LT) monitoring
outlet flow control column ▪ Install Level ▪ Regular check on
valve Alarm High the condition of the
(LAH) column
▪ Install Level ▪ Prepare emergency
Indicator shutdown
Controller procedure
(LIC)
275
HAZOP WORKSHEET
Diagram: P&ID
Guide
Word
4B Level Low Low Level ▪ High flow rate of ▪ Low separation ▪ Install Level ▪ Monthly
▪ Malfunction of ▪ Low product (LT) monitoring
outlet flow control yield ▪ Install Level ▪ Regular check on
valve ▪ Column will Alarm Low the condition of the
▪ Leakage or dry up easily (LAL) column
blockage of ▪ Install Level
pipelines Indicator
Controller
(LIC)
276
The objectives of the HAZOP study on the distillation column are listed as
below:
a) To ensure the operating parameters, such as temperature, level, flow and

pressure are maintained at optimum value to achieve higher separation
efficiency
b) To ensure the final product exiting the distillation column reaches the desired
purity
c) To ensure the distillation column is operated at safe conditions
Table 6.6 shows the HAZOP sheet for distillation column T-101. The HAZOP
sheet consists of possible causes, consequences, safeguards, and recommended action
required for each deviation of parameters.
277
Table 6.6 HAZOP for distillation column
HAZOP WORKSHEET
Node: Distillation column (T-101) Design Intent: To separate liquid mixtures based on volatility
Diagram: P&ID
Guide
Word
1A Level Low Low Level ▪ Low flow rate of ▪ Low separation ▪ Install Level ▪ Monthly
▪ Malfunction of inlet ▪ Low product (LT) monitoring
flow control valve yield ▪ Install Level ▪ Regular check on
▪ Leakage or ▪ Distillation Alarm Low the condition of the
blockage of column will dry (LAL) column
pipelines up easily ▪ Install Level
Indicator
Controller
(LIC)
278
HAZOP WORKSHEET
Diagram: P&ID
Guide
Word
1B Level High High Level ▪ High flow rate of ▪ Low separation ▪ Install Level ▪ Monthly
▪ Malfunction of ▪ Flooding of (LT) monitoring
outlet flow control column ▪ Install Level ▪ Regular check on
valve Alarm High the condition of the
(LAH) column
▪ Install Level ▪ Prepare emergency
Indicator shutdown
Controller procedure
(LIC)
279
HAZOP WORKSHEET
Diagram: P&ID
Guide
Word
2A Temperature Low Low ▪ Low temperature ▪ Low ▪ Install ▪ Monthly
Temperature and pressure of separation Temperature maintenance and
inlet stream efficiency Transmitter (TT) monitoring
▪ Higher heat loss ▪ Low purity of ▪ Install ▪ Regular check on
rate in pipelines product Temperature the condition of
▪ Large amount of ▪ Low product Alarm Low the column
refrigerant yield (TAL)
entering reactor ▪ Install
▪ Less amount of Temperature
steam entering Indicator
reboiler Controller (TIC)
280
HAZOP WORKSHEET
Diagram: P&ID
Guide
Word
2B Temperature High High ▪ High temperature ▪ Low product ▪ Install ▪ Monthly
Temperature and pressure of inlet quality Temperature maintenance and
stream ▪ Loss of Transmitter (TT) monitoring
▪ Low flow rate of desired ▪ Install ▪ Regular check on
refrigerant entering product Temperature the condition of the
reactor ▪ Pressure of Alarm High column
▪ Large amount of column (TAH) ▪ Prepare emergency
steam entering increases ▪ Install shutdown
reboiler Temperature procedure
Indicator
Controller (TIC)
281
HAZOP WORKSHEET
Diagram: P&ID
Guide
Word
3A Pressure Low Low pressure ▪ Leakage in ▪ Low ▪ Install Pressure ▪ Monthly
pipeline separation Transmitter maintenance
▪ Failure of control efficiency (PT) and
valve at outlet ▪ Low product ▪ Install Pressure monitoring
stream yield Indicator ▪ Regular check
▪ Low temperature ▪ Distillation Controller on the
of inlet stream column fails (PIC) condition of
▪ Low flow rate of to operate ▪ Install Pressure the column
inlet stream Alarm Low
(PAL)
282
HAZOP WORKSHEET
Diagram: P&ID
Guide
Word
3B Pressure High High ▪ Blockage in pipeline ▪ Low purity ▪ Install Pressure ▪ Monthly
pressure ▪ Failure of control of product Transmitter maintenance and
valve at outlet stream ▪ Separation of (PT) monitoring
▪ High temperature of undesired ▪ Install Pressure ▪ Regular check on
inlet stream product Indicator the condition of
▪ High flow rate of inlet happened Controller the column
stream ▪ Overpressure (PIC) ▪ Prepare
of column ▪ Install Pressure emergency
Alarm Low shutdown
(PAL) procedure
283
HAZOP WORKSHEET
Diagram: P&ID
Guide
Word
4A Flow No No flow ▪ Malfunction of inlet ▪ Separation ▪ Install Flow ▪ Monthly
flow control valve process do not Transmitter maintenance and
▪ Pipe blockage occur (FT) monitoring
▪ Pipe rupture ▪ No product ▪ Install Flow ▪ Regular check on
▪ Scaling in pipeline ▪ Rupture of Alarm Low the condition of the
column (FAL) pipelines
▪ Loss of feed ▪ Install Flow
Indicator
Controller
(FIC)
▪ Install bypass
line
284
HAZOP WORKSHEET
Diagram: P&ID
Guide
Word
4B Flow Less Less flow ▪ Malfunction of inlet ▪ Low liquid level ▪ Install Flow ▪ Monthly
flow control valve in column Transmitter maintenance and
▪ Pipeline leakage ▪ Column will dry (FT) monitoring
▪ Scaling in pipeline up easily ▪ Install Flow ▪ Regular check on
▪ Low separation Alarm Low the condition of the
efficiency (FAL) pipelines
quality Indicator
Controller
(FIC)
▪ Install
bypass line
285
HAZOP WORKSHEET
Diagram: P&ID
Guide
Word
4C Flow More More flow ▪ Malfunction of inlet ▪ Flooding of ▪ Install Flow ▪ Monthly
flow control valve column Transmitter maintenance and
▪ Failure of previous ▪ Damage the (FT) monitoring
equipment column ▪ Install Flow ▪ Regular check on
Alarm High the condition of the
(FAH) pipelines
▪ Install Flow
Indicator
Controller
(FIC)
▪ Install bypass
line
286
HAZOP WORKSHEET

Diagram: P&ID
Guide
Word
4D Flow Reverse Reverse ▪ Malfunction of inlet ▪ Back flow of ▪ Install Flow ▪ Monthly
flow flow control valve vapor-liquid Transmitter maintenance and
▪ Low inlet pressure mixture (FT) monitoring
▪ Damage the ▪ Install Flow ▪ Regular check on
piping system Indicator the condition of the
Controller pipelines
(FIC)
▪ Install bypass
line
287
6.6.4 Membrane Separator (F-101)
The objectives of the HAZOP study on the membrane separator are listed as
below:
a) To ensure the operating parameters, such as temperature and pressure are

maintained at optimum value to achieve higher separation efficiency
b) To ensure the flow rate of the inlet stream entering the separator is controlled
at desired value to maintain the separation rate and quality of the product
c) To ensure the membrane separator is operated at safe conditions
Table 6.7 shows the HAZOP sheet for membrane separator F-101. The
HAZOP sheet consists of possible causes, consequences, safeguards, and
recommended action required for each deviation of parameters.
288
Table 6.7 HAZOP for membrane separator
HAZOP WORKSHEET
Node: Membrane Separator (F-101) Design Intent: To separate gas mixtures by using permeable membrane
Diagram: P&ID
1A Flow No No flow ▪ Closing of flow ▪ Separation ▪ Install Flow ▪ Monthly
control valve of inlet process does not Transmitter maintenance and
stream occur (FT) monitoring
▪ Pipe blockage ▪ Loss of feed ▪ Install Flow ▪ Regular check on
▪ Pipe rupture Alarm Low the condition of the
(FAL) pipelines
▪ Install Flow
Indicator
Controller
(FIC)
▪ Install bypass
line
289
HAZOP WORKSHEET
Diagram: P&ID
Guide
Word
1B Flow Less Less flow ▪ Malfunction of inlet ▪ Low separation ▪ Install Flow ▪ Monthly
control valve efficiency Transmitter maintenance and
▪ Pipeline leakage ▪ Low desired (FT) monitoring
▪ Scaling in pipeline product yield ▪ Install Flow ▪ Regular check on
Alarm Low the condition of the
(FAL) pipelines
▪ Install Flow
Indicator
Controller
(FIC)
▪ Install bypass
line
290
HAZOP WORKSHEET
Diagram: P&ID
Guide
Word
1C Flow More More flow ▪ Malfunction of inlet ▪ Membrane is ▪ Install Flow ▪ Monthly
control valve saturated and Transmitter maintenance and
▪ High flow rate of causing low (FT) monitoring
inlet stream entering separation ▪ Install Flow ▪ Regular check on
separator efficiency Alarm High the condition of the
▪ Damage (FAH) pipelines
pipeline system ▪ Install Flow
▪ Low product Indicator
purity Controller
(FIC)
▪ Install bypass
line
291
HAZOP WORKSHEET
Diagram: P&ID
Guide
Word
1D Flow Reverse Reverse ▪ Failure of flow ▪ Back mixing ▪ Install Flow ▪ Monthly
flow control valve might occur Transmitter (FT) maintenance and
▪ Pipe blockage ▪ Low product ▪ Install Flow Alarm monitoring
or leakage quality Low (FAL) ▪ Regular check on
▪ Low product ▪ Install Flow Alarm the condition of the
yield High (FAH) pipelines
▪ Damage of ▪ Install Flow
separator Indicator
Controller (FIC)
▪ Install bypass line
292
HAZOP WORKSHEET
Diagram: P&ID
Guide
Word
2A Pressure Low Low ▪ Low inlet flow rate ▪ Low ▪ Install Pressure ▪ Monthly
pressure of the membrane separation Transmitter (PT) maintenance
separator efficiency ▪ Install Pressure and monitoring
▪ Malfunction of ▪ Low product Indicator ▪ Regular check
pressure control quality Controller (PIC) on the condition
system ▪ Back mixing ▪ Install Pressure of the separator
▪ Failure of control might occur Alarm Low
valve at outlet (PAL)
stream
▪ Pipe leakage or
rupture
293
HAZOP WORKSHEET
Node: Membrane Separator (F-101) Design Intent: To separate liquid mixtures based on volatility
Diagram: P&ID
Guide
Word
2B Pressure High High pressure ▪ High inlet flow ▪ Pipeline ▪ Install Pressure ▪ Monthly
rate of the leakage Transmitter (PT) maintenance
membrane ▪ Separation of ▪ Install Pressure and monitoring
separator undesired Indicator ▪ Regular check
▪ Malfunction of product Controller (PIC) on the condition
pressure control occurred ▪ Install Pressure of the separator
system ▪ Damage the Alarm Low ▪ Prepare
▪ Failure of control separator (PAL) emergency
valve at outlet shutdown
stream procedure
294
HAZOP WORKSHEET
Diagram: P&ID
Guide
Word
3A Temperature Low Low ▪ High heat loss ▪ Low separation ▪ Install ▪ Monthly
Temperature rate in pipeline rate Temperature maintenance and
▪ Malfunction of ▪ Low purity of Transmitter (TT) monitoring
cooler (E-102) desired product ▪ Install ▪ Regular check on
Temperature the condition of
Alarm Low the separator
(TAL)
▪ Install
Temperature
Indicator
Controller (TIC)
295
HAZOP WORKSHEET
Diagram: P&ID
Guide
Word
3B Temperature High High ▪ Malfunction of ▪ Low product ▪ Install ▪ Monthly
Temperature cooler (E-102) quality Temperature maintenance and
▪ High flow rate of ▪ Separation of Transmitter (TT) monitoring
cooling water undesired ▪ Install ▪ Regular check on
entering cooler (E- product Temperature the condition of the
102) occurred Alarm High separator
▪ Damage the (TAH) ▪ Prepare emergency
separator ▪ Install shutdown
Temperature procedure
Indicator
Controller (TIC)
296
6.6.5 Heaters (E-105, E-108, E-110, E-113, E-114)
The objectives of the HAZOP study on the heater are listed as below:
a) To ensure the outlet temperature are maintained at optimum value to maintain

the product quality and production rate of the plant
b) To ensure the flow rate of the high-pressure steam entering the heater is
controlled at desired value to supply sufficient heat to the heater
c) To ensure the heater is operated at safe conditions
Table 6.8 shows the HAZOP sheet for heater. The HAZOP sheet consists of
possible causes, consequences, safeguards, and recommended action required for each
deviation of parameters.
297
Table 6.8 HAZOP for heater
HAZOP WORKSHEET
Node: Heaters (E-105, E-108, E-110, E-113, E- Design Intent: To increase the temperature of components in stream
114)
Diagram: P&ID
Guide
Word
1A Temperature Low Low ▪ Blockage at steam ▪ Failed to ▪ Install ▪ Monthly
Temperature pipelines achieve desired Temperature maintenance and
▪ Control valve temperature Transmitter monitoring
failure ▪ Affect the (TT) ▪ Regular check on
production rate ▪ Install the condition of
and efficiency Temperature the heater
of subsequent Indicator
processes Controller
(TIC)
298
HAZOP WORKSHEET
Node: Heaters (E-105, E-108, E-110, E-113, E- Design Intent: To increase the temperature of components in stream
114)
Diagram: P&ID
Guide
Word
1B Temperature High High ▪ Failure of the ▪ Explosion ▪ Install ▪ Monthly
Temperature steam utility might be Temperature maintenance and
service occurred Transmitter monitoring
▪ Control valve ▪ Increase the (TT) ▪ Regular check on
failure pressure of ▪ Install the condition of
stream Temperature the heater
▪ Affect the Indicator
production rate Controller
and efficiency (TIC)
of subsequent
processes
299
6.6.6 Cooler (E-101, E-102, E-103, E-111)
The objectives of the HAZOP study on the cooler are listed as below:

b) To ensure the flow rate of the cooling water entering the cooler is controlled
to cool down the stream to its desired value
c) To ensure the cooler is operated at safe conditions
Table 6.9 shows the HAZOP sheet for cooler. The HAZOP sheet consists of
300
Table 6.9 HAZOP for cooler
HAZOP WORKSHEET
Node: Coolers (E-101, E-102, E-103, E-111) Design Intent: To reduce the temperature of components in stream
Diagram: P&ID
Guide
Word
1A Temperature Low Low ▪ Failure of ▪ Failed to achieve ▪ Install ▪ Monthly
Temperature cooling water desired Temperature maintenance and
utility service temperature Transmitter monitoring
▪ Control valve ▪ Affect the (TT) ▪ Regular check on
failure production rate ▪ Install the condition of
▪ Blockage at and efficiency of Temperature the cooler
cooling water subsequent Indicator
pipelines processes Controller
▪ Damage of cooler (TIC)
equipment
301
HAZOP WORKSHEET
Node: Coolers (E-101, E-102, E-103, E-111) Design Intent: To reduce the temperature of components in stream
Diagram: P&ID
Guide
Word
1B Temperature High High ▪ Failure of cooling ▪ Failed to ▪ Install ▪ Monthly
Temperature water utility achieve desired Temperature maintenance and
service temperature Transmitter monitoring
▪ Leakage of the ▪ Affect the (TT) ▪ Regular check on
cooling water production rate ▪ Install the condition of
pipelines and efficiency Temperature the cooler
▪ Control valve of subsequent Indicator
failure processes Controller
▪ Damage of (TIC)
cooler
equipment
302
6.6.7 Condensers (E-116. E-117, E-118)
The objectives of the HAZOP study on the condenser are listed as below:

b) To ensure the flow rate of the refrigerant entering the condenser is controlled
to cool down the stream to its desired value
c) To ensure the phase change to occur to convert gaseous compound to liquid
d) To ensure the condenser is operated at safe conditions
Table 6.10 shows the HAZOP sheet for condenser. The HAZOP sheet consists
of possible causes, consequences, safeguards, and recommended action required for
each deviation of parameters.
303
Table 6.10 HAZOP for condensers
HAZOP WORKSHEET
Node: Condensers (E-116, E-117, E-118) Design Intent: To condense the stream into liquids
Diagram: P&ID
Guide
Word
1A Temperature Low Low ▪ Failure of ▪ Affect the production ▪ Install ▪ Monthly
Temperature refrigerant rate and efficiency of Temperature maintenance and
utility service subsequent processes Transmitter monitoring
▪ Malfunction ▪ May damage (TT) ▪ Regular check on
of refrigerant subsequent ▪ Install the condition of
inlet flow equipment Temperature the condenser
control valve ▪ Might freeze the Indicator
gaseous mixture in Controller
stream (TIC)
304
HAZOP WORKSHEET
Node: Condensers (E-116, E-117, E-118) Design Intent: To condense the stream into liquids
Diagram: P&ID
Guide
Word
1B Temperature High High ▪ Malfunction of ▪ Condensation ▪ Install ▪ Monthly
Temperature refrigerant inlet process failed to Temperature maintenance and
control valve occur Transmitter monitoring
▪ Leakage of the ▪ Affect the (TT) ▪ Regular check on
refrigerant tube production rate ▪ Install the condition of
▪ Failure of and efficiency of Temperature the condenser
refrigerant utility subsequent Indicator
service processes Controller
(temperature of ▪ May damage (TIC)
refrigerant too high) subsequent
equipment
305
6.6.8 Throttling Valve (V-101, V-102)
The objectives of the HAZOP study on the throttling valve are listed as below:
a) To ensure the outlet pressure are maintained at optimum value to maintain the
product quality and production rate of the plant
b) To ensure the condenser is operated at safe conditions
Table 6.11 shows the HAZOP sheet for valve. The HAZOP sheet consists of
306
Table 6.11 HAZOP for throttling valve
HAZOP WORKSHEET
Node: Throttling Valve (V-101, V-102) Design Intent: To reduce the pressure of stream
Diagram: P&ID
Guide
Word
1A Pressure Low Low pressure ▪ Leakage of ▪ Failed to achieve ▪ Install ▪ Monthly
the pipe desired Pressure maintenance and
stream temperature Transmitter monitoring
▪ Malfunction ▪ Affect the (PT) ▪ Regular check on
of valve production rate ▪ Install the condition of
▪ Pipe leakage and efficiency of Pressure the valve
or rupture subsequent Indicator
processes Controller
(PIC)
307
HAZOP WORKSHEET
Node: Throttling Valve (V-101, V-102) Design Intent: To reduce the pressure of stream
Diagram: P&ID
Guide
Word
1B Pressure High High pressure ▪ Malfunction ▪ Failed to achieve ▪ Install ▪ Monthly
of valve desired Pressure maintenance and
▪ High inlet temperature Transmitter monitoring
flow rate ▪ Affect the (PT) ▪ Regular check on
entering the production rate ▪ Install the condition of
valve and efficiency of Pressure the valve
▪ High subsequent Indicator
temperature processes Controller
of inlet (PIC)
stream
308
6.6.9 Compressors (C-101 to C-107)
The objectives of the HAZOP study on the compressor are listed as below:
b) To ensure the flow rate of inlet stream entering compressor is at desired value
to avoid rupture of compressor
c) To ensure the condenser is operated at safe conditions
Table 6.12 shows the HAZOP sheet for compressor. The HAZOP sheet
consists of possible causes, consequences, safeguards, and recommended action
required for each deviation of parameters.
309
Table 6.12 HAZOP for compressors
HAZOP WORKSHEET
Node: Compressors (C-101 to C-107) Design Intent: To increase the pressure of gas stream
Diagram: P&ID
Guide
Word
1A Pressure Low Low pressure ▪ Leakage or ▪ Reverse flow of ▪ Install ▪ Monthly
blockage of process streams Pressure maintenance and
the pipeline ▪ Failed to achieve Transmitter monitoring
▪ Failure of desired pressure (PT) ▪ Regular check on
compressor’s ▪ Install Anti- the condition of
motor Surge the compressor
Controller
(ASC)
310
HAZOP WORKSHEET
Diagram: P&ID
Guide
Word
1B Pressure High High pressure ▪ High inlet ▪ Damage the ▪ Install ▪ Monthly
flowrate compressor Pressure maintenance and
entering the ▪ Explosion might Transmitter monitoring
compressors be occurred (PT) ▪ Regular check on
▪ Failure of ▪ Additional ▪ Install Anti- the condition of
compressor’s pressure builds up Surge the compressor
motor in the pipe Controller
(ASC)
311
HAZOP WORKSHEET
Diagram: P&ID
Guide
Word
2A Flow No No flow ▪ Blockage or ▪ Reverse flow of ▪ Install Flow ▪ Monthly
leakage of process streams Transmitter maintenance and
pipelines ▪ Failed to achieve (FT) monitoring
▪ Failure of desired pressure ▪ Install Anti- ▪ Regular check on
previous ▪ Affect the Surge the condition of
equipment efficiency of Controller the compressor
subsequent (ASC)
processes
312
HAZOP WORKSHEET
Diagram: P&ID
Guide
Word
2B Flow Less Less flow ▪ Leakage or ▪ Reverse flow of ▪ Install Flow ▪ Monthly
blockage of process streams Transmitter maintenance and
the pipeline ▪ Failed to achieve (FT) monitoring
▪ Low flow rate desired pressure ▪ Install Anti- ▪ Regular check on
of inlet ▪ Affect the Surge the condition of
stream efficiency of Controller the compressor
▪ Failure of subsequent (ASC)
compressor’s processes
motor
313
HAZOP WORKSHEET
Diagram: P&ID
Guide
Word
2C Flow More More flow ▪ Failure of ▪ Damage the ▪ Install Flow ▪ Monthly
compressor’s compressor Transmitter maintenance and
motor ▪ Pressure builds up (FT) monitoring
▪ Failure of in the pipe ▪ Install Anti- ▪ Regular check on
previous ▪ Explosion might Surge the condition of
equipment be occurred Controller the compressor
▪ High flow (ASC)
rate of inlet
stream
314
6.6.10 Pump (P-101)
The objectives of the HAZOP study on the pump are listed as below:
b) To ensure the flow rate of inlet stream entering pump is at desired value to
avoid rupture of pump
c) To ensure the condenser is operated at safe conditions
Table 6.13 shows the HAZOP sheet for pump. The HAZOP sheet consists of
315
Table 6.13 HAZOP for pump
HAZOP WORKSHEET
Node: Pump (P-101) Design Intent: To increase the pressure of liquid stream
Diagram: P&ID
Guide
Word
1A Pressure Low Low pressure ▪ Leakage of ▪ Failed to achieve ▪ Install ▪ Monthly
the pipe desired pressure Pressure maintenance and
stream ▪ Affect the Transmitter monitoring
▪ Malfunction production rate (PT) ▪ Regular check on
of pump and efficiency of ▪ Install the condition of
▪ Pipe leakage subsequent Pressure the pump
or rupture processes Indicator
▪ Damage the pump Controller
(PIC)
316
HAZOP WORKSHEET
Diagram: P&ID
Guide
Word
1B Pressure High High pressure ▪ Malfunction ▪ Failed to achieve ▪ Install ▪ Monthly
of pump desired pressure Pressure maintenance and
▪ High inlet ▪ Affect the Transmitter monitoring
flow rate production rate (PT) ▪ Regular check on
entering the and efficiency of ▪ Install the condition of
pump subsequent Pressure the pump
▪ High processes Indicator
temperature ▪ Damage the pump Controller
of inlet (PIC)
stream
317
HAZOP WORKSHEET
Diagram: P&ID
Guide
Word
2A Flow No No flow ▪ Blockage in ▪ Damage the pump ▪ Install Flow ▪ Monthly
the pipeline ▪ Explosion might Transmitter maintenance and
▪ Leakage of occur (FT) monitoring
the pipeline ▪ Install ▪ Regular check on
Minimum the condition of
Flow the pump
Controller
▪ Install
bypass line
318
HAZOP WORKSHEET
Diagram: P&ID
Guide
Word
2B Flow Less Less flow ▪ Leakage of ▪ Damage the pump ▪ Install Flow ▪ Monthly
the pipeline ▪ Explosion might Transmitter maintenance and
stream occur (FT) monitoring
▪ Low flow rate ▪ Failed to achieve ▪ Install ▪ Regular check on
of inlet desired pressure Minimum the condition of
stream ▪ Affect the Flow the pump
▪ Failure of production rate Controller
pump’s motor and efficiency of ▪ Install
subsequent bypass line
processes
319
HAZOP WORKSHEET
Diagram: P&ID
Guide
Word
2C Flow More More flow ▪ Failure of ▪ Damage the pump ▪ Install Flow ▪ Monthly
pump’s motor ▪ Explosion might be Transmitter maintenance and
▪ High flow rate occurred (FT) monitoring
of inlet stream ▪ Pressure builds up in ▪ Install ▪ Regular check on
the pipe Minimum the condition of
▪ Failed to achieve Flow the pump
desired pressure Controller
▪ Affect the production ▪ Install
rate and efficiency of bypass line
subsequent processes
320
6.7 Chemical Health Risk Assessment (CHRA)
An employer’s duties were to protect it workers from the various effects of

chemicals according to the Occupational Safety and Health Act 1994. To fulfil this
obligation, an evaluation of all chemicals used in the workplace must be performed in
order to identify, evaluate, and regulate any health risk related with work activities that
involve the use of the chemicals. Employers are not authorized to carry out any
operation that employs any CHTH (Chemicals hazardous to health) unless the
evaluation has been completed under the USECHH (Occupational Safety and Health
(Use and Standard of Exposure of Chemicals Hazardous to Health) Regulations. As a
result, the employer is required to analyze the potential health hazards associated with
the use of CHTH at the workplace. The obligation applies to the manufacture,
processing, handling, storage, transportation, removal, disposal, or treatment of any
CHTH at the workplace.
An assessment of health risk is an examination of how CHTH are utilized at

work and the health risks involved. The appropriate step to restrict employees'
exposure will be determined by the degree of health risk posed by the usage of CHTH
in specific job activities. A thorough evaluation of health risk using a Chemical Health
Risk Assessment, or CHRA method was used, by following a step-by-step approach
and using specified approaches and structure. Other than that, the purpose of
conducting CHRA is to protect the workers and a safe working environment. The
objectives of the CHRA are:
a) Distinguish the hazards posed by each CHTH use in the workplace.

b) Assess the degree of exposure of workers to the CHTH, whether through
inhalation, dermal contact, or ingestion.
c) Evaluate the adequacy of existing control measures; and
d) Recommend additional appropriate control measures and prioritise actions to
be taken to prevent or reduce risks.
321
The purpose of conducting CHRA is to enable decisions to be made on:
a) Effective control measures.

b) Worker induction and training.
c) The need for an exposure monitoring programme; and
d) The need for a medical surveillance programme, as necessary to safeguard
the health of employees who may be exposed to CHTH at work.
In this methanol production plant, the CHRA will be performed for all crucial
chemicals that involve within the process of the plant. The chemicals are biogas
(mainly methane and carbon dioxide), oxygen, hydrogen, catalyst, carbon monoxide
and methanol. Each of the chemical is either from the feedstock or the product produce
from the plant operation. The objectives of CHRA in methanol production plant are
listed as belows:
a) To identify the risks and the hazards of the processes and of each chemical
used, stored, handled, or transported within the methanol synthesis reactor
operation area.
b) To monitor the workplace activities and evaluate the degree of exposure of
operators to the hazardous chemicals used, either through inhalation, skin
absorption, or ingestion.
c) To evaluate the sufficiency and effectiveness of current control measures
practiced by the operators.
d) To conclude on the significance of the health risk posed by the chemical
hazardous to health (CHH).
To recommend further appropriate control measures to prevent or reduce the

risks posed by chemical hazardous to health (CHH) in the methanol synthesis reactor
operation area.The CHRA forms for the chemicals are as shown below which are Form
B, list of chemicals hazardous to health assessed and Form C, work unit assessment.
Form B consists of two tables which are B1, chemical used in work unit and B2,
chemicals released by the processes or work activities. Meanwhile, for the Form C,
322
there are also two tables which showing the inhalation exposure assessment and dermal
assessment, which is C1 and C2, respectively.
The information of each of the chemical is obtained from the Material Safety
Data Sheet (MSDS) to be used as the guidelines to fill up any related form of CHRA
assessment. Form B and C stated below are fill up or evaluated based on the guideline
provided by OSHA (Malaysia, 2018). Form B listed all the chemicals hazardous to
health assessed, the classification of hazard and H-code were received from the
Material Safety Data Sheet (MSDS). The rating of the hazard (HR) was obtained based
on the hazard classification provided from the Safety Data Sheet. As for Work Unit
Assessment in Form C, the assessment is performed based on the task or job that
occurring in the workplace. The situation for the tasks for every chemical that is
involve in the process of the plant was from the feedstock loading to the products and
effluents management.
In table C1 in form C, the inhalation exposure assessment, the frequency

rating, duration rating and frequency duration rating are evaluated based on the tasks
involving the chemical. The frequency rating for all chemical is set to be at 5 where
the jobs is required the worker to be exposed one or more time per shift or per day and
as for the duration rating is varied from 2 to 4 where it depends on how long the
duration of the exposure. The permissible exposure limit (PEL) for each chemical is
gathered from OSHA either inside Malaysia or adapted from outside Malaysia. There
are no PEL of Catalyst and Hydrogen as stated in OSHA.
In terms of the degree of released or exposure, all the chemicals are stated to
be at high except for catalyst. The degree of the chemical inhaled is evaluated based
on how heavy the workload of the tasks involving each chemical. The low degree of
inhaled is due to the operators who will perform their which will not involve with
heavy task such as checking the pipelines or controlling using control panel.
Meanwhile, the moderate degree of inhaled will need the operators to frequently
monitor and control the pipeline for loading either into equipment or into storage tank.
The magnitude rating, MR is depending on the degree of released and degree of
inhaled. Lastly, the risk rating is rated depending on the exposure rating, ER and hazard
323
rating, HR. The risk will be high if the rating value is ranging from 15 to 25 whereas
less than 15 will be moderate and low risks.
Table C2 from Form C, which is the dermal assessment, the chemicals involve
in the process plant do not have any hazardous properties that related with the dermal
assessment according to the MSDS of each of the chemical except for Carbon
Monoxide, CO and methanol, CH₃OH. The dermal assessment is highly applicable to
the two of the chemicals. Carbon Monoxide, CO shows a moderate risk, M2 due to its
skin-absorption and other properties of hazardous properties evaluation. The dermal
contact area involve with the chemical will be small because the operators will need
to monitor the and controlling the pipeline loading of the effluent into storage tank for
selling purpose. The DEA shows high risk at H1 when expose to the chemical in terms
of dermal assessment. Form B1 and B2 are presented in Table 6.14 and Table 6.15
whereas Form C1 and C2 are displayed in Table 6.16 and Table 6.17. All the material
safety data sheets (MSDS) of the chemicals used in the ethylene production plant are
attached in Appendix A.
324
Table 6.14 Chemicals used in work unit (Form B1)
Form B: List of Chemicals Hazardous to Health Assessed

Work Unit: Maintenance Technician Date of Assessment: 16/06/2021
Table B1: Chemicals Used in Work Unit
Name of Physical Hazard Source of Dermal Ingestion

No. Hazardous Ingredient H-Code HR
Chemical Form Classification Information (Y/N) (Y/N)
Flammable Gas
H220 5
Methane and Category -1 Linde Safety
1 Biogas Gas Y N
Tetrahydrothiophene Gases Under Data Sheet
Pressure H280 3
325
Table 6.15 Chemicals released by the processes or work activities (Table B2)
Form B: List of Chemicals Hazardous to Health Assessed

Table B2: Chemicals Released by the Processes or Work Activities
Name of Hazardous Source of Dermal Ingestion

No. Physical Form Hazard Classification H-Code HR
Chemical Ingredient Information (Y/N) (Y/N)
Flammable Gas
Colourless H220 5
Category -1 Linde Safety
1 Methane Methane and odourless Y N
Data Sheet
gas Gases Under Pressure H280 3
Sigma-Aldrich
Carbon Carbon
2 Liquefied gas Gases Under Pressure H280 Safety Data 3 N N
Dioxide Dioxide
Sheet
Flammable Gas
H220 5
Category -1
Gases Under Pressure H280 3

Colourless Air Liquide
Carbon Carbon Acute toxicity
3 and odourless Safety Data Y Y
Monoxide Monoxide (Inhalation: gas) H331 3
gas Sheet
Category 3
Reproductive toxicity,
H360D 5
Category 1A
326
Specific target organ
toxicity - Repeated
H372 5
exposure,
Category 1
Flammable Gas
H220 5
Colourless and Category -1 BOC Safety
4 Hydrogen Hydrogen N N
Odourless gas Data Sheet
Gases Under Pressure H280 3
Chronic Aquatic Thermo Fisher

Ni/SiO₂Al₂O₃ H410 1
Toxicity - Category 1 Scientific
5 Catalyst Zn- Solid Pellets N Y
Acute Aquatic Safety Data
CuO/Al₂O₃ H410 1
Toxicity - Category 1 Sheet
Flammable Liquid
H225 4
Category -2
Acute toxicity (Oral, H301
dermal and inhalation) H331 3
Clear Category 3 H311 Sigma-Aldrich
6 Methanol Methanol Colourless Safety Data Y N
Liquid Sheet
Specific Target Organ
Toxicity - Single H370 5
Exposure, Category 1
Table 6.16 Inhalation exposure assessment (form c1)
Form C1: Work Unit Assessment
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Work Unit: Process Department Date of Assessment: 16/06/2021
Table C1: Inhalation Exposure Assessment
Degree
of
Degree of
Job or Task Name of Chemical FR DR FDR PEL Release MR ER HR RR
Chemical Inhaled
or
Exposure
Supply biogas Methane, CH4 and
through pipeline Carbon Dioxide, CO2 1000 25
5 4 5 High Moderate 4 5 5
ppm (High Risk)
Release to Carbon Dioxide, CO2

atmosphere
5000 20
through pipeline 5 4 5 High Low 3 4 5
ppm (High Risk)
Loading into Catalyst

Reactor 3
3 3 3 - Moderate Low 2 3 1
(Low Risk)
Storage Tank Methanol, CH3 OH

Handling 250 25
5 4 5 High High 5 5 5
ppm (High Risk)
Storage Tank Hydrogen, H2

Handling 20
5 3 4 - High Moderate 4 4 5
(High Risk)
328
Storage Tank Carbon Monoxide,
Handling CO3
50 20
5 3 4 High Moderate 4 4 5
ppm (High Risk)
Table 6.17 Dermal Assessment (Form C2)
Form C2: Dermal Assessment
329
Duration of Exposure
Extent of
Hazardous
Job or Task Name of Chemical Dermal Short Term Long Term Level or Risk
Properties
Contact (<15min/shift) (>15min/shift)
Methane, CH₄ and
Supply biogas through
Carbon Dioxide, - Small / -
pipeline
CO₂
Release to atmosphere Carbon Dioxide,
- Large / -
through pipeline CO₂
Loading into Reactor Catalyst - Small / -
Skin Irritation and H1
Storage Tank Handling Methanol, CH₃OH Large /
other properties (High Risk)
Storage Tank Handling Hydrogen - Small / -
Skin absorption
Carbon Monoxide, M2
Storage Tank Handling and other Small /
CO (Moderate Risk)
properties
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6.8 Plant Start-Up and Shut-Down Procedure
A chemical processing plant's start-up and shutdown are equally important,

mostly because of the dangers and difficulties that are likely to arise throughout both
processes. There are a variety of dangers and hazards in both methods. In order to
avoid harming both individuals and the environment, care must be taken when
performing these treatments.
6.8.1 Plant Start-Up Procedure
Process plants that have new facilities or even ones that are restarting after
significant modifications are responsible for starting up or commissioning a process
plant. In terms of administration and technicalities, there are a number of issues that
must be taken into account. No matter what size, kind, or even industry a plant is in,
every plant has a very distinct technique of starting up. Therefore, it's crucial to have
some expertise starting up a plant; else, you'll end up spending more and having a
longer start-up. The staff of the organisation should design the necessary operational
and safety procedures and get familiar with new tools, technologies, and procedures
(Promise Training and Consultancy, 2020). With that said, the start-up procedures are
stated as:
1. Before the manhole covers are mounted on the tower or vessel, a final
examination is conducted in the interiors for the conformance testing to fulfil
the requirement.
2. To ensure that everything has been finished and the related lines have been
correctly reassembled, a turnaround work list is necessary.
3. After the equipment has been put together, a hydrostatic test is conducted to
evaluate it.
4. Instrument control loops, control system and also the alarm system circuits
5. must be checked to make sure that they have been correctly located.
6. Verify that the level gauges' lenses are clear and that the operators can readily
record readings on them.
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7. Control valves must be examined to ascertain whether they are operable.
8. To ensure that orifice plates are placed correctly, check them.
9. Make sure that the power, steam, and cooling water supplies are working
properly.
10. Verify where the extinguishers, water hoses, nozzles, and steam hoses are
located and that they are available for use right away.
11. Make sure that all drains are disconnected, and that all equipment has had its
water drained.
12. Verify the tightness and quality of the gaskets on the flanges and man heads.
13. Verify that the blowdown, flare, and safety valve systems have been
successfully installed.
14. To ensure that air can be released with ease, all blinds must be examined for
tightness.
15. Make sure the steam tracings are operational by checking them.
16. The chemical supply on hand needs to be sufficient.
17. Check the gas blanketing.
18. As soon as the flow of reactants is started, the catalyst has to be turned on.
332
6.8.2 Error Elimination Test for Plant Startup
a) Dynamic Test
A closed-loop dynamic testing with the use of safe fluid entails operating
machinery or systems with air, water, or inert gas. Before using hazardous
chemicals, this approach allows for the testing of the equipment while also
thoroughly acquainting the personnel with the equipment. It provides the first
hint as to how the control loops function. Dynamic testing should never be
missed since it is risky and may result in costly delays. This is because
equipment can be repaired much more rapidly when it is just filled with air,
nitrogen, or water (Crowl & Louvar, 2001).
b) Dry Runs and Hot Test

These runs and tests are performed to make sure that the equipment's motors
are properly linked and turning in the appropriate direction, and that the shafts
and impellers can move freely and according to design. The person who
typically conducts the dry run testing of the running equipment is a
representative from the manufacturing business. It would be even better if the
test run was conducted with the operational representative there to assist with
running the apparatus and to enable the representative to instruct business
employees on how to properly use the apparatus and assess the suitability of
the tests (Crowl & Louvar, 2001).
c) Pressure Test
This test is often carried out by the construction team. For instance, it is
recommended to pull a vacuum during the final inspections of a vacuum system
using plant operating equipment before checking the rate of leakage on the
blocked system. The operating crew may, however, take part in some unique
or specialised tests. The operational team may do testing on equipment
conveying unpleasant or even lethal vapours, similar to how the construction
team would normally only test pipes, ducts, and equipment operating at or near
atmospheric pressure (Crowl & Louvar, 2001).
333
6.8.3 Plant Shut-Down Procedure
There are two basic types of plant shutdowns: scheduled shutdowns and
unexpected shutdowns. An unplanned shutdown can be partial or even entire and can
occur as a result of equipment failure or an unexpected power loss. A scheduled
shutdown often involves facility maintenance that only lasts a few hours. A thorough
assessment of the plant's condition must be done prior to any planned closure.
6.8.3.1 Scheduled Shut Down
Generally speaking, each facility will have a specific shutdown process for
situations like emergency, maintenance, etc. To guarantee that the plant can shut down
safely and without having an accident, the procedure must be designed in advance.
1. Unit Cooling and Depressurization - Prior to turning the power off

completely, it is imperative to gradually diminish the heat provided to each
device. Lowering the material's temperature will stop the vaporisation. The
side streams and overhead systems may be shut down because of the decrease
in vaporisation, which quickly makes them inoperable. Release of hydrocarbon
gases into a gas collection system can relieve pressure. If the unit tends to
become vacuumed up during cooling, the pressure of an inert gas should be
decreased to keep the pressure around atmospheric levels. An inert gas keeps
the apparatus from igniting or exploding. No air should be added to the unit
(Crowl & Louvar, 2001).
2. Unit Pumping - Each substance must be pumped into a certain location.

Centrifugal pumps need special attention because if they are allowed to run
dry, they might experience catastrophic damage. This is because they should
not lose suction before the facility is shut down. Reciprocal pumps are the
finest 302 pumps to use for pumping out if they are accessible since they offer
greater suction qualities and are less prone to breakage. In order to avoid any
334
fire dangers in the delivery tanks, the materials should be further cooled in the
heat exchanger as they are pumped out of the unit to a temperature that will not
cause water to flash in delivery lines or tanks and to a temperature below its
flash point.
3. Residue Removal - The residue should be expelled, and there are three main
ways to achieve this: displacement with inert gas, flooding with water until it
overflows, or a combination of these two techniques.
6.8.3.2 Unexpected Shut Down
Even though the facility will have a scheduled procedure for shutting down,
unplanned incidents can still occur. This shutdown often happens as a result of a power
outage, compressor malfunction, or process-related automatic shutdown mechanism.
A signal from the so-called voting system activates it in times of emergency. Each
possible general shutdown source is monitored by three instruments, and the system
only alerts to the presence of the relevant cause when it detects a failure. The shutdown
mechanism prompted an emergency shutdown, but the facility can resume operation
quickly and safely. To be dependable, secure, and economically advantageous for the
facility, the general shutdown system needs to be properly developed.
6.8.3.3 Emergency Shut Down
A mechanical malfunction in the equipment that precludes regular operations

or causes a major fire is an example of an emergency that often necessitates an
emergency shutdown. In addition, utility losses such those involving electrical power,
instrument air, steam, or cooling water will result in emergency shutdown. Therefore,
this emergency shutdown is essential to avoiding any major mishaps (Crowl & Louvar,
2001).
335
6.9 Plant Layout
The location of the new chemical plant must be one of the initial choices made
during design. The profitability of a project and the potential for future development
can be significantly impacted by the location of the plant. The following factors are
vital to consider when designing the ideal project, and they are listed below:
a) The best location for arrangement of the equipment and facilities.

b) Attention to the storage space and operating equipment
c) Consideration of the safe operational sequence inside the plant
d) Total cost of the construction and manufacturing activities
e) Convenience of operation
f) Convenience of maintenance
g) Future expansion
h) Modular construction which improved quality control, reduced construction
cost and less need for skilled labor on site
Therefore, the following list of important aspects must be taken into account
while designing an appropriate plant layout:
a) Prevent, limit and/or mitigate escalation of adjacent events (domino)

b) Ensure safety within on-site occupied buildings
c) Control access of unauthorized personnel d) Facilitate access for emergency
services
Process area and non-process area are the two main sections of the plant layout,
respectively. The risk of explosion and fire is present in the process area together with
all the equipment used in the process. Non-Process Areas are those locations with less
danger to the process units and employees and no production activity. Figure shows
the plant layout design for methanol production plant.
336
Figure 6.4 Plant layout design for methanol production plant
337
6.9.1 Process Area
All of the processing machinery is located in the process area. Since it deals
with chemicals used in the creation of hydrogen peroxide, this area is the most
dangerous. To prevent any mishaps, safe work procedures and a stop work policy must
be followed constantly. The following structures and units are located in this process
zone:
a) Plant Process Area

The production of methanol can be divided into six process units which are
membrane separation, steam reforming of methane, flash separation of water,
methanol synthesis reaction, flash separation for methanol and water and
finally distillation separation for desired product. All these processes are
located near to each other in order to minimize the piping distance between the
process.
b) Utilities area
The plant's process relies heavily on the utilities area. For instance,
refrigeration systems, compressed air, steam boilers, electricity generation, and
transformer stations are all necessary utilities. Because doing so can lower
costs and shorten the route provided, these utilities should be installed close to
the process area.
c) Waste Treatment Plant

Every factory needs a waste treatment unit to clean the waste water generated
by the process units before it is discharged into the environment. It is typically
located towards the end of the plant so that it can be quickly disposed of into
the sea following treatment.
d) Scheduled Waste Storage

There are some wastes, such as spent catalyst, that we would like a third party
manage in the future, thus it is necessary to keep all the scheduled waste in a
338
storage before the waste treatment plant process. Placement near the waste-
treatment facility is ideal.
e) Expansion Site
In the event that management decides to boost production rates or take other
important factors into account by installing or developing additional
equipment, the potential extension site is often positioned in the processing
area.
f) Feedstock, chemical and product storage farm

The plant's storage areas include feedstock, chemical, and product storage
areas. This storage is located close to the process area for ready operation of
the feedstocks, chemicals, and product rundowns but sufficiently removed
from the buildings occupied by site employees.
g) Shelter Building/ Staff Office

For engineers and technicians who must work in the plant's production area,
this facility is unique. The reason the shelter and administration buildings are
distinct is so that an engineer can have a modest office nearby that is safe and
easy to access.
h) Change House
The change house is a locker building for workers to wash or change their
clothes. The change house is generally located near to the toilet.
i) Assembly Area
In the event of a significant disaster, such as a fire, explosion, or other calamity,
all personnel, regardless of their roles, must assemble at the assembly point.
All personnel will congregate to the assembly location designated in the plant
layout as soon as the alarm sound can be heard. Two assembly points exist;
one in the plant's process area and the other one in the non-process area.
339
j) Electrical Sub-Station
Only the plant's production area has access to electrical substations. These
substations modify utility voltage levels before supplying the proper amounts
of power to a facility. As it requires different electricity to operate, the power
generation house for administrative buildings and other structures needs to be
kept apart from the plant's production area.
6.9.2 Non-Process Area
Non-process areas are those that take up a lesser portion of the total plant site
area and don't have any production going on in them. The facilities are often situated
in a secure region, away from the process zone and any unfavourable incidents or
accidents. The supporting structures and services needed on a site include:
a) Parking Area
Parking area facilities is provided near administrative office for both staff and
public users to park their vehicles before entering the plant site.
b) Guard House
The security office is located at the first entrance of the plant to ensure that
only authorized personnel can get access into the plant. Usually, there are 3
guard posts in the site which are:
• At the main entrance: To monitor the flow in and out of the workers
and the outsiders into the plant area.
• At the gate of loading and unloading process: Easy access for lorry or
container to go at loading bay.
• Process area: before entering the process area, the security will
monitor and do body check up on the workers or outsiders to make
sure no hazardous materials been brought into the process area such as
camera, mobile phone, and so on.
340
c) Workshop
All repairs and mending activities are done and placed in workshop area. It is
place in non-process area for easy access of maintenance staffs.
d) Administrative Building
The administrative office is built adjacent to the main entrance to allow the
administration workers to avoid hazardous area when entering the workplace.
In plant layout, the arrangement of admin building is placed in aligned with
the process area for the employee to be alert on any incidents happened at the
plant area.
e) Canteen
Canteen is built near administrative building as a facility for the employees to
minimize their time buying food at the shops outside. Also, it is located away
from process area to avoid contaminant in food and ensure the safety of the
workers.
f) Prayer Room
A place where all Muslims perform their prayers.
g) Fire Safety
Fire safety is needed in plant site to ensure the emergency team can give
quick response to any kind of incidents or accidents happened inside the
plant.
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CHAPTER 7
PROFITABILITY ANALYSIS
7.1 Introduction
A chemical plant design project's profitability is examined to gather

information from which operational and capital cost projections can be produced.
Chemical plants are designed to make a profit, therefore determining the capital
required is necessary to guarantee a project's viability (Sinnott, 2011). The
computations in this chapter are all precalculations for the discounted cash flow and
cash flow diagram. Economic analysis is therefore required, which entails calculating
fixed capital expenditure, total capital investment (TCI), total production cost, and
sales revenue.
For the methanol production plant, the capital estimates of the process design
are carried out using Preliminary Estimate based on the individual factor’s method of
Guthrie (1969, 1974). Guthrie approach recognizes the construction materials used for
machinery and whether the equipment is built to withstand high pressure, the base,
supporting building, and ladders, and even some electrical, insulation, and paint, would
cost the same. This method is best carried out after knowing the optimal process
design, complete mass and energy balance, equipment sizing and decision on materials
of construction, and also process control configuration developed as in P&ID.
Furthermore, preliminary estimate method shows that the foundation,

supporting structure and ladders, electrical insulations, and paint will have similar
costing despite the construction materials used or the ability of the equipment to
withstand high pressure. Guthrie method proposed Equation 7.1 and Equation 7.2 for
the calculation of total capital investment, 𝐶𝑇𝐶𝐼 .
342
𝐶𝑇𝐶𝐼 = 𝐶𝑇𝑃𝐼 + 𝐶𝑊𝐶 (7.1)
𝐶𝑇𝐶𝐼 = 1.18 (𝐶𝑇𝐵𝑀 + 𝐶𝑠𝑖𝑡𝑒 + 𝐶𝑏𝑢𝑖𝑙𝑑𝑖𝑛𝑔𝑠 +𝐶𝑜𝑓𝑓𝑠𝑖𝑡𝑒 𝑓𝑎𝑐𝑖𝑙𝑖𝑡𝑖𝑒𝑠 ) + 𝐶𝑊𝐶 (7.2)
where,
𝐶𝑇𝑃𝐼 = Total permanent investment
𝐶𝑊𝐶 = Working capital
𝐶𝑇𝐵𝑀 = Total bare-module investment
𝐶𝑠𝑖𝑡𝑒 = Site development cost
𝐶𝑏𝑢𝑖𝑙𝑑𝑖𝑛𝑔𝑠 = Building cost
𝐶𝑜𝑓𝑓𝑠𝑖𝑡𝑒 𝑓𝑎𝑐𝑖𝑙𝑖𝑡𝑖𝑒𝑠 = Offsite facility cost
The Guthrie method proceeds by steps as follows:
Step 1: Create a listing of the equipment based on the machine's configuration,

including the description, label, equipment size, the building materials, the design
temperature, and the design strength.
Step 2: Using the f.o.b. equipment procurement cost data from Phase 1, add
cost data, 𝐶𝑃𝑏 , and the associated cost index, 𝐼𝑏 , to the data sheet. The purchase cost
of the f.o.b. in the Guthrie process is the base price related to the closer construction
effect, the carbon steel as the construction material, and the main constructions.
Step 3: Update the financial information to represent the most recent cost table.
Until going to Step 4, determine the bare-module cost on each piece of equipment
using bare-module variables, 𝐹𝐵𝑀 , being cautious to specify whether the building
material is not carbon steel and/or the pressure is not near average, as seen in the
Equation 7.3. The bare-module cost accounts for transportation, insurance, taxation,
and direct matter.
𝐼
𝐶𝐵𝑀 = 𝐶𝑃𝑏 ( ) [𝐹𝐵𝑀 + (𝐹𝑑 𝐹𝑝 𝐹𝑚 − 1)] (7.3)
𝐼𝑏
where,
𝐶𝐵𝑀 = Bare-module cost
343
𝐶𝑃𝑏 = Base equipment purchase cost
I = Latest cost index
𝐼𝑏 = Base cost index
𝐹𝐵𝑀 = Bare-module factor
𝐹𝑑 = Equipment design
𝐹𝑝 = Pressure factor
𝐹𝑚 = Material factor
The value of 𝐹𝐵𝑀 is determined by the type of equipment such as pressure

vessel, furnace, heat exchanger and compressor. Once the 𝐶𝑃𝑏 is calculated, the most
recent Chemical Engineering Plant Cost Index (CEPCI) for the end of December 2019
is used and compared to CEPCI in 2013, which serves as the basis for overall costing.
As a result, the formula is used to measure inflation in equipment. Table 7.1 shows the
Chemical Engineering Plant Cost Index (CEPCI) for 2013 and 2022 which were used
in the calculation in this chapter.
Table 7.1 Chemical Engineering Plant Cost Index (CEPCI) (Seider et al., 2017;
Jenkins, 2020)
Year Chemical Engineering Plant Cost Index, I

2013 (basis) 567
2022 (latest) 797.6
Step 4: Add the bare-module costs of the process equipment to get the total
bare-module cost, 𝐶𝑇𝐵𝑀 .
Step 5: Estimate the total permanent investment (𝐶𝑇𝑃𝐼 ) and add an estimation
of working capital (𝐶𝑊𝐶 ) to this to get the total capital investment (𝐶𝑇𝐶𝐼 )
344
7.2 Bare-Module Equipment Cost
Bare-module cost, 𝐶𝐵𝑀 or installed is the sum of the direct and indirect costs
associated with equipment purchase and installation. The bare-module cost specifies
costs for a whole module that do not change by process or per unit of capacity or
energy consumed. The bare-module costs accounts for delivery, insurance, taxes,
direct materials and labor for installation.
In this section, bare-module cost for each equipment is presented. In methanol

production plant, there is a total of 36 equipment including catalytic fixed bed reactors,
flash separators, distillation column, membrane separator, heat exchangers, heater,
coolers, condensers, mixer and compressors.
7.2.1 Catalytic Fixed Bed Reactor
There are two catalytic fixed bed reactors used in the methanol production plant
to convert the methane to syngas and syngas to methanol and water. The reactors
involved are steam reforming reactor (R-101) and methanol synthesis reactor (R-102).
Both of the reactors are designed as vertical pressure vessel and are constructed from
stainless steel 309 and 304 to withstand the high operating temperature and pressure.
The reactor volume is obtained by multiplying the volumetric flow rate and
residence time.
𝑅𝑒𝑎𝑐𝑡𝑜𝑟 𝑉𝑜𝑙𝑢𝑚𝑒, 𝑉 = 𝑄 × 𝑡 (7.4)
By assuming the length to diameter ratio of the reactor is 3:1, the internal
diameter, 𝐷𝑖 can be calculated using Equation 7.5.
3 4𝑉
𝐼𝑛𝑡𝑒𝑟𝑛𝑎𝑙 𝑑𝑖𝑎𝑚𝑒𝑡𝑒𝑟, 𝐷𝑖 = √3𝜋 (7.5)
345
The design pressure establishes the highest acceptable pressure of a pressurized
system, and it is generally lower than or equal to the maximum allowable working
pressure (MAWP) of the system’s vessel. Generally, the design pressure incorporates
a margin of 10-25% above general operational pressures to allow for unexpected
surges. This additional buffer further reduces the risk of explosions failure. The design
pressure for catalytic fixed bed reactor is as shown in Equation 7.6.
2
𝐷𝑒𝑠𝑖𝑔𝑛 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒, 𝑃𝑑 = 𝑒 0.60608+0.91615[ln(𝑃𝑜 )]+0.0015655[ln(𝑃𝑜 )] (7.6)
where,
𝑃𝑜 = Operating pressure (psig)
𝑃𝑑 = Design pressure (psig)
Since the pressure for both of the reactors exceed 10 psig, which is considered
as high pressure vessel, internal pressure has the largest magnitude. The cylindrical
shell wall thickness is critical to withstand internal pressure of the reactor. The wall
thickness can be calculated from ASME pressure-vessel code formula as shown in
Equation 7.7.
𝑑 𝑖 𝑃 𝐷
𝑊𝑎𝑙𝑙 𝑡ℎ𝑖𝑐𝑘𝑛𝑒𝑠𝑠 𝑡𝑜 𝑤𝑖𝑡ℎ𝑠𝑡𝑎𝑛𝑑 𝑖𝑛𝑡𝑒𝑟𝑛𝑎𝑙 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒, 𝑡𝑝 = 2𝑆𝐸−1.2𝑃 (7.7)
𝑑
where,
𝐷𝑖 = Internal diameter (inch)
S = Maximum allowable stress (psi)
E = Welded joint efficiency
Besides, the effect of wind load or an earthquake on the vertical vessel have to
be taken into consideration. The thickness to withstand the wind load or earthquake at
the bottom of the reactor can be determined using Equation 7.8.
346
0.22(𝐷𝑜 +18)𝐿2
𝑇ℎ𝑖𝑐𝑘𝑛𝑒𝑠𝑠 𝑡𝑜 𝑤𝑖𝑡ℎ𝑠𝑡𝑎𝑛𝑑 𝑤𝑖𝑛𝑑 𝑙𝑜𝑎𝑑 𝑜𝑟 𝑒𝑎𝑟𝑡ℎ𝑞𝑢𝑎𝑘𝑒, 𝑡𝑤 = (7.8)
𝑆𝐷𝑜2
where,
𝐷𝑜 = Outer diameter (inch)
L = Tangent-to-tangent length (inch)
The average wall thickness of the reactor to withstand the internal pressure at
the top of the column and the wind load or earthquake at the bottom of the column is
computed in Equation 7.9 by using the average value of the thickness of the top (𝑡𝑝 )
and the bottom (𝑡𝑝 +𝑡𝑤 ).
𝑡𝑝 +(𝑡𝑝 +𝑡𝑤 )
𝐴𝑣𝑒𝑟𝑎𝑔𝑒 𝑤𝑎𝑙𝑙 𝑡ℎ𝑖𝑐𝑘𝑛𝑒𝑠𝑠, 𝑡𝑣 = (7.9)
2
where,
𝑡𝑝 = Wall thickness to withstand internal pressure at the top (inch)
𝑡𝑤 = Wall thickness to withstand wind load and earthquake at the bottom (inch)
Corrosion allowance refers to an extra measurement added to the thickness of

the wall to compensate the material loss due to corrosion and erosion throughout the
lifespan of the reactor. According to Ahmad (2006), the general practice is to allow
1/8 in, or 3.2 mm minimum corrosion allowance. Therefore, the final shell thickness
is determined by Equation 7.10.
𝑆ℎ𝑒𝑙𝑙 𝑡ℎ𝑖𝑐𝑘𝑛𝑒𝑠𝑠, 𝑡𝑠 = 𝑡𝑣 + 𝑡𝑐 (7.10)
The weight, W depends on the wall thicknesses of the vessel shell and the two
heads. Assuming the head thickness equal to the shell thickness, then, with 2:1
elliptical heads, the weight of the shell and the two heads is estimated using Equation
7.11.
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑊 = 𝜋(𝐷𝑖 + 𝑡𝑠 )(𝐿 + 0.8𝐷𝑖 )𝑡𝑠 𝜌 (7.11)
347
where,
𝑡𝑠 = Shell thickness (inch)
𝐿 = Tangent-to-tangent length (inch)
𝜌 = Density of the stainless steel (lb/inch³)
The added cost for platform and ladder depends on the vessel inside diameter,
𝐷𝑖 and the tangent-to-tangent length, L of the shell as shown in Equation 7.12. This
equation is applicable to vertical vessel for 3<𝐷𝑖 <21 ft and 12<L<40 ft.
𝑃𝑙𝑎𝑡𝑓𝑜𝑟𝑚 𝑎𝑛𝑑 𝑙𝑎𝑑𝑑𝑒𝑟 𝑐𝑜𝑠𝑡, 𝐶𝑃𝐿 = 410𝐷𝑖 0.73960 𝐿0.70684 (7.12)
where,
𝐷𝑖 = Internal diameter (ft)
𝐿 = Tangent-to-tangent length (ft)
The purchase cost for vertical empty vessel based on the weight of the shell
and the two heads, but including nozzles, manholes, and supports, is shown in
Equation 7.13.
𝑃𝑢𝑟𝑐ℎ𝑎𝑠𝑒 𝑐𝑜𝑠𝑡 𝑜𝑓 𝑒𝑚𝑝𝑡𝑦 𝑣𝑒𝑠𝑠𝑒𝑙, 𝐶𝑉

= exp[7.1390 + 0.18255[ln(W)] + 0.02297[ln(𝑊)]2 ] (7.13)
where,
W = Weight of shell (lb)
The purchased cost of an equipment is obtained from charts, equations or

quotes from vendors, and only valid for a certain period of time. The f.o.b purchase
cost commonly includes an allowance for platforms, ladders, and a nominal number
of nozzles, and manhole. However, due to the inflation, the purchase cost is estimated
to a later date using Chemical Engineering Plant Cost Index (CEPCI) as shown in
348
Equation 7.14. According to Seider et al. (2010), the materials-of-construction factor
for stainless steel 304 is 1.7.
𝐼2022
𝑃𝑢𝑟𝑐ℎ𝑎𝑠𝑒 𝑐𝑜𝑠𝑡, 𝐶𝑝 = (𝐹𝑀 𝐶𝑉 + 𝐶𝑃𝐿 ) × (𝐼 ) (7.14)
𝑏𝑎𝑠𝑒,2013
where,
𝐹𝑀 = Materials-of-construction factor = 1.7
𝐶𝑉 = Purchase cost of empty vessel (USD)
𝐶𝑃𝐿 = Purchase cost of platform and ladder (USD)
𝐼2022 = Cost index in January 2022 = 797.6 (Jenkins, 2022)
𝐼𝑏𝑎𝑠𝑒,2013 = Cost index in 2013 = 567 (Seider et al., 2010)
The bare-module cost is estimated using bare-module factor based on free-on-

board (f.o.b) purchase cost of equipment as shown in Equation 7.15. The bare module
factor for vertical pressure vessel can be obtained from Seider et al. (2010), which is
4.16.
𝐵𝑎𝑟𝑒 − 𝑚𝑜𝑑𝑢𝑙𝑒 𝑐𝑜𝑠𝑡, 𝐶𝐵𝑀 = 𝐹𝐵𝑀 × 𝐶𝑝 (7.15)
where,
𝐹𝐵𝑀 = Bare-module factor = 4.16
𝐶𝑝 = Purchase cost (USD)
In the steam reforming reactor, the methane separated from biogas reacts with
steam to produce syngas (carbon monoxide, carbon dioxide and hydrogen) at high
temperature (900°C) and high pressure (15 bar). The stainless steel 309 is used because
it is more suitable for high temperature use and gives greater resistance to oxidation at
349
a high temperature. The stainless steel 309 has high corrosion resistance and strength
as it is an alloy with high chromium content.
Table 7.2 Equipment specification sheet of steam reforming reactor (R-101)
Equipment Specification Sheet

Steam methane reforming reactor (R-
Equipment name
101)
Function To convert methane to syngas
Orientation Vertical
Material of construction Stainless steel 309
Operating Condition
Operating pressure, 𝑃𝑜 Operating
15 900
(bar) temperature, 𝑇𝑜 (℃)
217.6 1652
(psig) temperature, 𝑇𝑜 (℉)
Design pressure, 𝑃𝑜 Design temperature,
239.3 990
(psig) 𝑇𝑜 (℃)
Design pressure, 𝑃𝑜 Design temperature,
16.5 1814
(bar) 𝑇𝑜 (℉)
Flow rate, Q (L/min) 29.80
Catalyst 𝑁𝑖/𝑆𝑖𝑂2 𝐴𝑙2 𝑂3
Characteristics of Reactor
Maximum allowable
Vessel volume, V (L) 149778 22475
stress, S (psi)
Vessel volume, V (𝑓𝑡 3 ) 5289.36 Shell thickness, 𝑡𝑠
0.748
Inside diameter, 𝐷𝑖 (ft) 11.91 (in)
Corrosion allowance,
Inside diameter, 𝐷𝑖 (in) 142.91 0.0315
𝑡𝑐 (in)
Outside diameter, 𝐷𝑜 Bare-module factor,
149.13 4.16
(in) 𝐹𝐵𝑀
Tangent-to-tangent Material density, ρ
47.64 0.289
length, L (ft) (lb/𝑖𝑛3 )
Material factor, 𝐹𝑀 1.7 Weight (Ib) 1135210
Cost of empty vessel, 𝐶𝑉 (USD) 35,120
Cost of platforms and ladders, 𝐶𝑃𝐿 (USD) 39,293
Purchase cost, 𝐶𝑃 (USD) 98,998
350
Bare module cost, 𝐶𝐵𝑀 (USD) 411,831
Bare module cost, 𝐂𝐁𝐌 (RM) 1,812,059
Methanol synthesis reactor converts syngas to methanol and water at high

temperature of 280°C and high pressure of 50 bar. Stainless steel 304 grade is chosen
as the material of construction of the reactor. The carbon content is low enough for
351
heat treatment not to be normally needed with thin sections to prevent weld decay. The
stainless steel 304 has high tensile strength, toughness and hardness which makes it
very durable and ideal to make a chemical reactor.
Methanol synthesis reactor is designed as a vertical pressure vessel with

tangent-to-tangent length of 8.158 m and an internal diameter of 2.719 m. It requires
47.388 m³ volume with a total of 45 tubes of 32 mm of diameter is needed to fill with
catalyst to accelerate the reaction. The equipment specification sheet of methanol
synthesis reactor (R-102) is presented in Table 7.3.
Table 7.3 Equipment specification sheet of methanol synthesis reactor (R-102)

Methanol synthesis reactor (R-102)
Equipment name
Function To convert syngas to methanol and water

Operating Condition
Operating pressure, 𝑃𝑜 Operating temperature, 𝑇𝑜
50 280
(bar) (℃)
Operating pressure, 𝑃𝑜 Operating temperature, 𝑇𝑜
725.2 536
(psig) (℉)
Design pressure, 𝑃𝑜 Design temperature, 𝑇𝑜
803.5 307.8
(psig) (℃)
Design pressure, 𝑃𝑜 Design temperature, 𝑇𝑜
55.4 586
(bar) (℉)
Maximum allowable
Vessel volume, V (L) 47388 12683.55
stress, S (psi)
Vessel volume, V (𝑓𝑡 3 ) 1673.5 Fractional weld
1.0
Inside diameter, 𝐷𝑖 (ft) 8.92 efficiency, E
Inside diameter, 𝐷𝑖 (in) 107.1 Insulation material, ρi Mineral wool
352
Outside diameter, 𝐷𝑜 Insulation thickness, t i
9.53 3.937
(ft) (in)
Wall thickness to
Outside diameter, 𝐷𝑜
114.4 withstand internal 3.525
(in)
pressure, 𝑡𝑝 (in)
Wall thickness to
Tangent-to-tangent
26.77 withstand wind load, 𝑡𝑤 0.018
length, L (ft)
(in)
Tangent-to-tangent Average wall thickness, 𝑡𝑣
321.24 3.534
length, L (in) (in)
Material density, ρ Corrosion allowance, 𝑡𝑐
0.289 0.125
(lb/𝑖𝑛3 ) (in)
Material factor, 𝐹𝑀 1.7 Shell thickness, 𝑡𝑠 (in) 3.659
Bare-module factor,
4.16 Weight,W (Ib) 148099
𝐹𝐵𝑀
Cost of empty vessel, 𝐶𝑉 (USD) 287,287.48
Cost of platforms and ladders, 𝐶𝑃𝐿
21,126.07
(USD)
Purchase cost, 𝐶𝑃 (USD) 716,735.44
Bare module cost, 𝐶𝐵𝑀 (USD) 2981,619.43
Bare module cost, 𝑪𝑩𝑴 (RM) 13,089,309.29
7.2.2 Flash Separator
Flash separator is a separation unit to separate the components in a single-phase

mixture based on their boiling points. The more volatile components will leave the
column as top product whereas the less volatile components will remain in liquid form
and exit as bottom product. By operating at certain pressure and temperature, the liquid
in the liquid stream that contain several components will be partially vaporized in a
flash separator and resulting in two different phases which is liquid and gas. The first
flash column (F-102) is used to separate water from the syngas mixture exiting the
353
steam reforming reactor. The second flash separator (F-103) is operated to separate
methanol and water mixture from gaseous mixtures containing carbon monoxide,
carbon dioxide and methane. Stainless steel 304 is used as the material of construction
for both flash separators due to the high operating conditions.
The flash column volume is determined by multiplying the volumetric flow

rate and residence time as shown in Equation 7.16.
𝑉𝑜𝑙𝑢𝑚𝑒, 𝑉 = 𝑄 × 𝑡 (7.16)
The ratio of internal diameter to tangent-to-tangent length is set at 3:1. The

internal diameter can calculate using Equation 7.17.
3 4𝑉
When the operating pressure is between 10 psig to 1000 psig, according to

Seider, et al., (2016), the internal design gauge pressure (𝑃𝑑) can be determined based
on Equation 7.18.
𝑃𝑑 = 𝑒𝑥𝑝{0.60608 + 0.91615[ln(𝑃𝑜 )] + 0.0015655[ln(𝑃𝑜 )]2 } (7.18)
where,
Once the internal design gauge pressure was calculated, the cylindrical shell
wall thickness can be calculated from the ASME pressure-vessel code formula as
shown in Equation 7.19.
𝑃 𝐷
𝑑 𝑖
𝑡𝑝 = 2𝑆𝐸−1.2𝑃 (7.19)
𝑑
354
where,
𝑡𝑝 = Wall thickness (inch)
The thickness to withstand the wind load or earthquake at the bottom of the
reactor can be determined using Equation 7.20.
0.22(𝐷𝑜 +18)𝐿2
𝑡𝑤 = (7.20)
𝑆𝐷𝑜2
where,
𝑡𝑤 = Thickness to withstand wind load or earthquake (inch)
computed in Equation 7.21.
2
where,
The final shell thickness is determined by Equation 7.22.
355
The weight, W depends on the wall thicknesses of the vessel shell and the two
heads.Tthe weight of the shell and the two heads is estimated using Equation 7.23.
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑊 = 𝜋(𝐷𝑖 + 𝑡𝑠 )(𝐿 + 0.8𝐷𝑖 )𝑡𝑠 𝜌 (7.23)
where,
𝜌 = Density of the stainless steel (lb/inch³)
The added cost for platform and ladder depends on the vessel inside diameter,
𝐷𝑖 and the tangent-to-tangent length, L of the shell as shown in Equation 7.24. This
equation is applicable to vertical vessel for 3<𝐷𝑖 <21 ft and 12<L<40 ft.
𝑃𝑙𝑎𝑡𝑓𝑜𝑟𝑚 𝑎𝑛𝑑 𝑙𝑎𝑑𝑑𝑒𝑟 𝑐𝑜𝑠𝑡, 𝐶𝑃𝐿 = 410𝐷𝑖 0.73960 𝐿0.70684 (7.24)
where,
𝐿 = Tangent-to-tangent length (ft)
The purchase cost of the vertical tower can be calculated using Equation 7.25.
𝑃𝑢𝑟𝑐ℎ𝑎𝑠𝑒 𝑐𝑜𝑠𝑡 𝑜𝑓 𝑒𝑚𝑝𝑡𝑦 𝑣𝑒𝑠𝑠𝑒𝑙, 𝐶𝑉

= exp[7.1390 + 0.18255[ln(W)] + 0.02297[ln(𝑊)]2 ] (7.25)
where,
W = Total weight of skirt support vessel (lb)
The purchase cost is estimated to a later date using Chemical Engineering Plant
Cost Index (CEPCI) as shown in Equation 7.26. According to Seider et al. (2010), the
materials-of-construction factor for stainless steel 304 is 1.7.
356
𝐼2022
𝑃𝑢𝑟𝑐ℎ𝑎𝑠𝑒 𝑐𝑜𝑠𝑡, 𝐶𝑝 = (𝐹𝑀 𝐶𝑉 + 𝐶𝑃𝐿 ) × (𝐼 ) (7.26)
where,
𝐹𝑀 = Materials-of-construction factor = 1.7
𝐶𝑉 = Purchase cost of empty vessel (USD)
𝐶𝑃𝐿 = Purchase cost of platform and ladder (USD)
The bare-module cost is estimated using bare-module factor based on free-on-

board (f.o.b) purchase cost of equipment as shown in Equation 7.27. The bare module
factor for vertical pressure vessel can be obtained from Seider et al. (2010), which is
4.16.
where,
The flash separator F-102 is operated at 82.3°C and 14 bar to separate water
from the gaseous mixtures containing methane, carbon monoxide, carbon dioxide and
hydrogen. The equipment specification sheet for flash separator F-102 with bare-
module cost is shown in Table 7.4.
Table 7.4 Equipment specification sheet of flash column (F-102)
357
Equipment name Flash Column (F-102)
To separate between liquid-vapor
Function
mixture in stream, S17
Operating Condition
14 82.3
(bar) temperature, 𝑇𝑜 (℃)
203.053 180.14
(psig) temperature, 𝑇𝑜 (℉)
Design pressure, 𝑃𝑜 Design pressure, 𝑃𝑜
63.82 4.4
(psig) (bar)
Maximum allowable
Vessel volume, V (L) 9480 15,000
stress, S (psi)
Vessel volume, V (𝑓𝑡 3 ) 334.78 Minimum thickness
0.122
Inside diameter, 𝐷𝑖 (ft) 3.28 of cylinder, 𝑡𝑠 (in)
Corrosion allowance,
𝑡𝑐 (in)
Feed nozzle diameter, D Bare-module factor,
19.67 4.16
(in) 𝐹𝐵𝑀
6.792 8.116
Material factor, 𝐹𝑀 1.7 Weight (Ib) 8041.05
Cost of empty vessel, 𝐶𝑉 (USD) 47,883.70
Cost of platforms and ladders, 𝐶𝑃𝐿 (USD) 13,809.80
358
The flash separator F-103 is operated at 75°C and 30 bar to separate methanol
and water from gaseous mixtures containing methane, carbon monoxide, carbon
dioxide and hydrogen. The equipment specification sheet for flash separator F-102
with bare-module cost is shown in Table 7.5.
Table 7.5 Equipment specification sheet of flash column (F-103)

Equipment name Flash Column (F-103)
To separate water and methanol from the
Function
stream
Operating Condition
Operating pressure, 𝑃𝑜 Operating temperature,
30 75
(bar) 𝑇𝑜 (℃)
Operating pressure, 𝑃𝑜 Operating temperature,
435.113 167
(psig) 𝑇𝑜 (℉)
Design pressure, 𝑃𝑜 Design pressure, 𝑃𝑜
63.82 4.4
(psig) (bar)
Maximum allowable
Vessel volume, V (L) 110.96 15,000
stress, S (psi)
Vessel volume, V (𝑓𝑡 3 ) 391.852 Minimum thickness of
0.088
Inside diameter, 𝐷𝑖 (ft) 0.08 cylinder, 𝑡𝑠 (in)
Corrosion allowance, 𝑡𝑐
(in)
Feed nozzle diameter, D Bare-module factor,
0.823 4.16
(in) 𝐹𝐵𝑀
7.76 8.116
Material factor, 𝐹𝑀 1.7 Weight (Ib) 10,948.53
Cost of empty vessel, 𝐶𝑉 (USD)
22,154
359
Cost of platforms and ladders, 𝐶𝑃𝐿
12,56.65
(USD)
Bare module cost, 𝑪𝑩𝑴 (RM) 428,313.80
7.2.3 Distillation Column
Distillation column (T-101) is used in this project to separate methanol from

water. The distillation column operates at 75 ˚C and 2 bar, where the top stream
contains the desired product which is the methanol whereas the bottom stream contains
the by-product which is the water. 99.85% purity of methanol is recovered in the top
stream, but the remaining methanol is mixed together with water at the bottom stream.
The main constructions material of the column is carbon steel, with height of 13.745m
and 0.40 m diameter. Carbon steel is used as the material of construction due to the
higher durability and tensile strength.
360
The tower volume is determined by multiplying the volumetric flow rate and
residence time as shown in Equation 7.28.
𝑇𝑜𝑤𝑒𝑟 𝑉𝑜𝑙𝑢𝑚𝑒, 𝑉 = 𝑄 × 𝑡 (7.28)
The internal design gauge pressure (𝑃𝑑) can be determined based on Equation
7.29.
𝑃𝑑 = 𝑒𝑥𝑝{0.60608 + 0.91615[ln(𝑃𝑜 )] + 0.0015655[ln(𝑃𝑜 )]2 } (7.29)
where,
The ratio of internal diameter to tangent-to-tangent length is set at 3:1. The

internal diameter can calculate using Equation 7.30.
3 4𝑉
The cylindrical shell wall thickness can be calculated from the ASME pressure-
vessel code formula as shown in Equation 7.31.
𝑃 𝑑 𝐷𝑖
𝑡𝑝 = (7.31)
2𝑆𝐸−1.2𝑃𝑑
where,
𝑡𝑝 = Wall thickness (inch)
361
The thickness to withstand the wind load or earthquake at the bottom of the
reactor can be determined using Equation 7.32.
0.22(𝐷𝑜 +18)𝐿2
𝑡𝑤 = (7.32)
𝑆𝐷𝑜2
where,
𝑡𝑤 = Thickness to withstand wind load or earthquake (inch)
computed in Equation 7.33.
2
where,
The final shell thickness is determined by Equation 7.34.
The weight of the tower, W in the cost correlations for a pressure vessel or
tower depends on the wall thicknesses of the heads and may be required to be
somewhat thicker than the shell, particularly at high pressure, it is sufficient for cost-
estimation purposes to assume head thicknesses equal to the shell thicknesses, 𝑡𝑠 . Then
with 2:1 elliptical head, the weight of the shell and the two heads is approximately:
𝑊 = 𝜋(𝐷𝑖 + 𝑡𝑠 )(𝐿 + 0.8𝐷𝑖 )𝑡𝑠 𝜌 (7.35)
362
where,
𝜌 = Density of the carbon steel = 0.284 lb/inch³
The added cost, CPL , for platforms and ladders for towers depend on the tower
inside diameter, Di in feet and on the tangent-to-tangent of the shell, L, in feet, and is
given by:
CPL = 341(Di )0.63316 (L)0.80161 (7.36)
The base cost, CBT , is for sieve trays at a CE cost index of 567, where the inside
diameter of the tower is in feet and the equation is valid for 2 to 16 ft.
CBT = 468 exp(0.1482)Di (7.37)
Vertical towers for absorption, distillation, and stripping utilize trays (plates)
and/or packing. Thus, the cost for the installed trays, CT all with the downcomers is
given by:
CT = NT FNT FTT FTM CBT (7.38)
where:
NT = Number of Trays
FNT = Factor ( if NT > 20, FNT = 1 )
FTT = Factors for the type of tray, as for sieve tray, FTT = 1.0
FTM = factor which depends on the column diameter in feet, corrects for the material
of constructions, for carbon steel, FTM = 1.0
CBT = Base cost for Sieve Trays
The purchase cost, CP can be calculated using the equation below:
363
CP = FM CV + CPL (7.39)
where:
FM = Materials-of-Constructions factors (For carbon steel = 1.0)
CV = The f.o.b purchase cost-at a CE index 567 of the empty vessel.
CPL = The added cost
The total purchase cost, CTP can be calculate using the equation below:
CTP = CT + CP (7.40)
where:
CT = The cost for the installed trays
CP = purchase cost
The Bare-module cost or installed cost is estimated using bare-module factor

FBM based on free-on-board (f.o.b., exclude delivery costs) purchase cost of
equipment. below are the equation used:
CBM = FMB CTP (7.41)
where:
FMB = bare-module factor (For Vertical pressure vessels = 4.16
CTP = Total purchase cost
Table 7.6 shows the equipment specification sheet for distillation column (T-
101) with mechanical details and cost estimation.
Table 7.6 Equipment specification sheet for distillation column (T-101)

Equipment Name Distillation Column (T-101)
To separate methanol and water from
Function
product stream
364
Material of construction Carbon Steel
Length: Diameter ratio 8:1
Tray type Sieve Tray
Operating Conditions
Operating Pressure, PO Operating temperature at top
2 82.95
(bar) (℃)
Operating Pressure, PO Operating temperature at
29.01 118.42
(psi) bottom (℃)
Operating temperature at
Design Pressure, Pd (bar) 2.814 244.4
bottom (℉)
Design Pressure, Pd
40.81 Design Temperature, Td (℃) 120
(psig)
Flow rate, Q (L/min) 51.01 Design Temperature, Td (℉) 298
Characteristics of Distillation Column
Vessel volume, V (L) 765.2 Wall thickness to withstand
0.302
3
Vessel volume, V (ft ) 27.02 internal pressure, t p (in.)
Inside diameter, Di (ft) 1.63 Wall thickness to withstand

0.056
Inside diameter, Di (in.) 19.56 wind load, t 𝑤 (in.)
Average wall thickness, t v
Outside diameter, Di (in.) 22.69 0.10
(in.)
Tangent-to-tangent length,
13.01 Corrosion allowance, t c (in.) 0.13
L (ft)
Tangent-to-tangent length,
156.12 Shell thickness, t s (in.) 1.59
L (in.)
Material density, 𝜌 (ln/in3) 0.284 Weight, W (lb) 5140.2
Material factor, FM 1 Number of Trays, NT 22
Maximum allowable
12900 FNT 1.0
stress, S (psi)
Fractional Weld
0.85 FTT 1.0
Efficiency, E
Bare-module factor, FBM 4.16 FTM 1.0
Base cost for sieve trays, CBT (USD) 595.88
Cost for installed trays, CT (USD) 13109.29
Cost for empty vessel, CV (USD) 38384.06
Cost of platforms and ladders, CPL
3633.45
(USD)
365
Purchase cost, CP (USD) 55126.80
Bare module cost, CBM (USD) 283862.17
Bare module cost, CBM (RM) 1 251 832.15
7.2.4 Membrane Separator
Purchase costs of other chemical processing equipment in Product and Process

Design Principles: Synthesis, Analysis, and Evaluation (Seider et al., 2010) is used as
the basis of calculation for bare-module cost calculation for membrane separator. In
methanol production plant, membrane separator is used to separate methane and
carbon dioxide from biogas. The operating condition of membrane separator is 6 bar
and 30 °C. The purchase cost of membrane separation is calculated using Equation
7.42.
𝐼2022
𝐶𝑝 = 43𝐴 × (𝐼 ) (7.42)
366
where,
A = Membrane surface area (ft²)
A few assumptions are made in the calculation of membrane surface area in

order to ensure the cost can be reduced without having any disturbance on the
separation of the gaseous mixtures.
a) Length to diameter ratio = 3

b) Residence time = 5 minutes
c) Shape: Cylindrical
d) Material of construction: Stainless steel
The separator volume in ft³ is determined by multiplying the volumetric flow

rate and residence time as shown in Equation 7.43.
𝑇𝑜𝑤𝑒𝑟 𝑉𝑜𝑙𝑢𝑚𝑒, 𝑉 = 𝑄 × 𝑡 (7.43)
The volume and length to diameter ratio is then used to calculate the internal
diameter, 𝐷𝑖 using the volume calculated before.
3 4𝑉
The length, L is multiplied with the internal diameter, 𝐷𝑖 to obtain the

membrane surface area, 𝐴𝑚 as stated below.
𝐴𝑚 = 𝐿 × 𝐷𝑖 (7.45)
where,
𝐴𝑚 = Membrane surface area (ft²)
367
L = Length (ft)
The bare module factor for vertical pressure vessel can be obtained from Seider
et al. (2010), which is 4.16.
where,
Table 7.7 shows the equipment specification sheet for membrane separator (F-
101) with mechanical details and cost estimation.
Table 7.7 Equipment specification sheet for membrane separator (F-101)

Equipment name Membrane separator (F-101)
To separate methane and carbon dioxide from
Function
biogas
Type of membrane
Pervaporation
separation
Material of construction Stainless steel
Operating Pressure, 𝑃0 Operating
5.00 30.00
(bar) temperature, 𝑇0 (⁰C)
Operating pressure, 𝑃0 Operating
72.52 86.00
(psig) temperature, 𝑇0 (⁰F)
368
Design Pressure (psig) 95.53 Design Temperature, Td (⁰C) 57.78
Design Pressure (bar) 6.50 Design Temperature, Td (⁰F) 136.00
L/D ratio 3.00 Residence time (mins) 5.00
Flow rate, Q (kg/hr) 1500.00
Characteristics of membrane separator
139407. 4923.1
Volume, L Volume in ft³
78 4
Tangent to Tangent Length, L
Length, L (ft) 38.35 460.23
(inch)
Internal diameter, Di (ft) 12.78 Membrane area, Am (ft²) 490.32
Bare Module Factor, 𝐹𝐵𝑀 4.16
Purchase cost, 𝐶𝑝 (RM) 21,083.56
7.2.5 Mixer (M-101)
Mixer (M-101) in this plant is located on the streamline 24. The purpose of
mixer was to mix the ratio desired from three different streams which were stream
20,22 and 31. The mixing involved gases compound which in this methanol production
plant consist of Carbon dioxide (C𝑂2 ), Carbon monoxide (CO), Hydrogen (𝐻2 )
Methane (C𝐻4 ) and Methanol (𝐶𝐻3 𝑂𝐻). Some of the gases were actually recycled gas
that was produced at the top stream of the flash separator 1 (F-102) and flash separator
2 (F-103). Gas mixers provide the greatest degree of freedom for desired mixing ratios.
Thus, the mixture consists of a stream of distinct gases that have been dosed
individually. For the gas mixers to operate perfectly, the various gases must all have
the same intake pressure. In order to calculate the bare module cost of the mixer, the
369
purchase cost, 𝐶𝑃 of the mixer pressure vessel need to be calculated first by using the
following Equation 7.47.
𝐶𝑃 = 𝐹𝑀 𝐶𝑉 + 𝐶𝑃𝐿 (7.47)
where,
𝐹𝑀 = material factor
𝐶𝑉 = purchase cost of empty vessel but involve nozzles, manholes and supports
𝐶𝑃𝐿 = Additional cost for ladders and platforms
𝐹𝑀 = 1.00 was chosen as the material factor for mixer (M-101). Given that this
mixer is a vertical vessel, the required weight (W) must fall between 4,200 and
1,000,000 lb. Based on Seider et al., (2019), Equation 7.48 can be used to calculate the
purchase cost of empty vessel, CV .
𝐶𝑉 = 𝑒𝑥𝑝{7.3190 + 0.18255[𝑙𝑛(𝑊)] + 0.02297[𝑙𝑛(𝑊)]2 } (7.48)
where,
W = Weight of the mixer
Equation 7.49 can be used to calculate the weight of the mixer. Noted that the
weight of the mixer does depends on the wall thickness of the shell and the two heads.
W = 𝜋 (𝐷𝑖 + 𝑡𝑠 )(𝐿 + 0.8𝐷𝑖 )𝑡𝑠 𝜌 (7.49)
where,
𝐷𝑖 =vessel inside diameter (inch)
𝑡𝑠 = shell thickness (inch)
𝐿 = tangent to tangent length of shell (inch)
𝜌 = Density of carbon steel material (0.284 lb/𝑖𝑛3 )
370
If the internal pressure of a pressure vessel is larger than the exterior pressure,
consideration should be given to issues about the lack of corrosion, wind, and
earthquakes. Therefore, cylindrical shell wall thickness (𝑡𝑝 ) should be calculated using
equation 4 which is the ASME pressure-vessel code formula:
𝑃 𝑑 𝐷𝑖
𝑡𝑝 = (7.50)
2𝑆𝐸−1.2𝑃𝑑
where,
𝑡𝑝 = wall thickness (inch)
𝑃𝑑 = internal design gauge pressure (psig)
𝑆 = maximum allowable stress of the shell material (lb/𝑖𝑛3 )
𝐸 = fractional weld efficiency (0.85)
Operating pressure, 𝑃𝑜 can be used to calculate the internal pressure (, 𝑃𝑑 ) .

Operating pressure has to be between 10 psig and 1000 psig to use Equation 7.51.
Thus, Equation 7.51 will be used since the mixer (M-101) operates at a pressure of 50
bar, or 725.189 psig.
𝑃𝑑 = 𝑒𝑥𝑝 {0.60608 + 0.91615 [𝑙𝑛(𝑃𝑂 )] + 0.0015655[𝑙𝑛(𝑃𝑂 )]2 } (7.51)
Since the chosen material is carbon steel (SA-285, grade C) and the design
temperature used is 50 °𝐶 or 122 °F which ranges in between -20°F to 650°F, the
allowed stress value, S, is set at 15,000 psi. Additionally, 𝐶𝑃𝐿 requires on 𝐷𝑖 (ft),
whereas a vertical vessel depends on L (ft). Based on Warren D. Seider et al., (2019),
Equation 7.52 can be used to calculate the added cost, 𝐶𝑃𝐿 .
𝐶𝑃𝐿 = 410 (𝐷𝑖 )0.73960 (𝐿)0.70684 (7.52)
Vertical pressure vessels should fall within the following range:

Weight: 4200 to 1,000000 lbs.
Internal diameter: 3 to 21 feet.
Length: 12 to 40 feet.
371
Two assumptions are used, namely that the length to diameter ratio is 1:3 and
that the residence period is set to 5 minutes, in order to compute the internal diameter
and length within the acceptable range. Based on Warren D. Seider et al., (2019), the
gas mixer will likely be made of carbon steel and have a cylindrical form. For mixer
(M-101), the total flowrates through outlet stream will most likely be
4743579773.9328 J/hr. After several parameters have been calculated, with the bare-
module factor (𝐹𝐵𝑀 ) of the pressure vessel to be 4.16, the bare-module cost (𝐶𝐵𝑀 ) can
finally be calculated using Equation 7.53. Table 7.8 showed the summary design of
mixer (M-101).
𝐼
𝐶𝐵𝑀 = 𝐹𝐵𝑀 × 𝐶𝑝 (𝐼 ) (7.53)
2013
where,
Table 7.8 Equipment specification sheet of mixer (M-101)

Equipment No. Gas Mixer
To mix gases from three different streams (S31, S22 and
Function
S20)
Material of
Carbon steel
construction
Operating Condition
Operating Design
280 395.1
Temperature, (°𝐶) Temperature, (°𝐶)
Operating Design
553.15 668.25
Temperature, (K) Temperature, (K)
Operating Pressure, Design Pressure,
50 9.51
(bar) (bar)
372
Operating Pressure, Design Pressure,
725.189 113.181
(psig) (psig)
Feed Flowrate, (kg/hr) 4358.72
Feed Flowrate, (l/min) 9477.60
Residence Time, 𝑡𝑟
5
(min)
Characteristic of Mixer (M-101)
Maximum allowable
15 000 Weld efficiency, E 0.85
stress, S (psi)
Vessel volume, V
Vessel volume, V (L) 47390 1683.40
(f𝑡 3 )
Tangent to tangent
Length, L (ft) 36.9 442.65
length, L (inch)
Internal diameter, 𝐷𝑖 Outer diameter, 𝐷𝑂
12.30 12.48
(ft) (ft)
Thickness to
Thickness to withstand
0.02 withstand internal 4.9309
wind load, 𝑡𝑤 (inch)
pressure, 𝑡𝑝 (inch)
Bare-module factor,
4.16 Material factor, 𝐹𝑀 1.00
𝐹𝐵𝑀
Average wall Outside diameter,
4.9309 115.4
thickness, 𝑡𝑣 (inch) 𝐷𝑂 (inch)
Corrosion allowance, Internal diameter,
0.13 147.6
𝑡𝑐 (inch) 𝐷𝑖 (inch)
Shell thickness,
Material density, lb/i𝑛3 0.28 4.4888
𝑡𝑠 (inch)
Vessel volume, V
Weight, W (lb) 386124 2908915.2
(incℎ3 )
Purchase cost of empty
vessel but involve Platform and
590301.47 33607.12
nozzles, manholes and ladders, 𝐶𝑝 𝐿
supports, 𝐶𝑣
Purchase cost, 𝐶𝑝 (RM) 591207.72
Bare-module cost, 𝑪𝑩𝑴 (RM) 𝟐𝟔𝟑𝟓𝟎𝟗𝟕. 𝟐𝟖
373
7.2.6 Compressors
The production plant of methanol from biogas has a total of 7 compressors

which assist in regulating the pressure in the operation. Screw compressor was chosen
to be the type of compressor used in this power plant. Screw compressors have the
smallest pressure range, up to 400 psig, for flow rates from 800 to 20,000 ACFM, with
horsepower to 6,000 per machine (Seider et. al). The other optional compressors were
reciprocating compressor and centrifugal compressor. In terms of efficiency,
reciprocating compressors is more efficient than screw compressors with 80%-90%
and 75%-85%, respectively. However, it is more expensive than the screw compressor.
In addition, centrifugal compressor has the same application as screw compressor and
mostly known to be widely used in every power plant due to its smooth flow rate
delivery. However, it is less efficient (70%-75%) and more expensive than a screw
compressor. Besides, based on the calculation that have been made, the horsepower of
374
compressors that were used in this project were less than 750 Hp. Therefore, it is
reasonable to use screw compressors.
Cast iron was chosen to be as the material of the construction for all the
compressor used. The electric motor is chosen as the drive of the compressors due to
its high efficiency (95%). The equation below was used to calculate the brake
horsepower, PB of the compressor by assuming the ideal gas law and a constant specific
heat ratio:
k
k QI PI PO k-1
PB =0.00436 (k-1) [( ) -1] (7.54)
ηC PI
where,
PB = brake horsepower (bp)
k = specific heat ratio
QI = inlet volumetric flowrate (ft 3 /min )
PI = inlet pressure (psi)
PO = outlet pressure (psi)
ηC = compressor efficiency (0.90)
375
The power consumption of the compressor was calculated by using the
equation below where the electric motor was assumed to be at 95%
P
PC = η B (7.55)
M
where,
PC = horsepower (hp)
ηM =electric motor efficiency = 0.95
For screw compressor, the base purchase cost, 𝐶𝐵 is calculated using Equation
7.56 which is valid from 𝑃𝐶 = 10 to 750Hp.
CB = exp{8.2496 + 0.7243[ln PC ]} (7.56)
The f.o.b. purchase cost, 𝐶𝑃 of the compressor was calculated using equation
below. The drive factor 𝐹𝐷 = 1.0 for electric motor drive, and material factor 𝐹𝑀 = 1.0
for cast iron as material of construction.
I
CP = (FD FM CB ) × I (7.57)
b
where:
FD = drive factor
FM = material factor
CB = base cost
I = latest CE index in 2021 = 797.6
Ib = CE index in 2013 = 567
Therefore, the bare-module cost, CBM of the compressor can be obtained using
equation (). According to Seider et al. (2017), bare-module factor FBM of compressor
is 2.15.
376
CBM = CP × FBM (7.58)
where:
CBM = base-module cost of compressor
FBM = base-module factor
The equipment specification sheets of compressors C-101, C-102, C-103, C-

104, C-105, C-106, C-107 are presented in Table 7.9 to 7.15respectively together with
the results of all calculation and cost estimation.
377
Table 7.9 Equipment specification sheet of compressor (C-101)

Equipment Name Biogas Compressor (C-101)
Function To compress biogas from 1 bar to 2 bar
Type of compressor Reciprocating Compressor
Material of construction Cast Iron
Drive Electric Motor
Operating Condition
Pressure inlet, PI (psi) 14.50
Pressure outlet, PO (psi) 32.43
Pressure outlet, PO (bar) 2.236
Pressure inlet, PI (bar) 1
Pressure ratio, PO /PI 2.236
Inlet flow rate, Qi (ft 3 /min) 1017.38
Specific heat ratio, k 1.29
Compressor efficiency, ηC 0.9
Electric motor efficiency, ηM 0.9
Compressor power consumption, PC 70.17
Brake horsepower, Pb (Hp) 63.15
Drive Factor, FD 1.00
Material factor, FM 1.00
Bare module factor, FBM 2.15
Base Purchase Cost, CB 89776.80
Bare module cost, 𝐂𝐁𝐌 (RM) 1 062 897.45
378

Equipment Name Compressor (C-102)
Operating Condition
Pressure outlet, PO (bar) 5
Pressure inlet, PI (bar) 2.236
Inlet flow rate, Qi (ft 3 /min) 455
379

Operating Condition
Pressure outlet, PO (bar) 15.81
Bare module cost, 𝐂𝐁𝐌 (RM) 476 014.59
380

Operating Condition
Pressure inlet, PI (bar) 15.81
Bare module cost, 𝐂𝐁𝐌 (RM) 476 044.70
381

Operating Condition
Pressure ratio, PO /PI 3
382

Operating Condition
383

Operating Condition
384
7.2.7 Pump
The function of pump in methanol production plant is to increase the pressure

of water to 15 bar before entering the steam reforming reactor. Pump has identical
performance with compressor but has different phase involved. There are two costs
involved in the costing calculation of pump, which are pump cost and electric motor
cost. Pump head, brake horsepower, size factor, material factor and type factor are
important in the calculation of pump cost. Equation 7.59 is the formula to calculate
pump power consumption.
𝑃𝑇 𝑃 𝑄𝐻𝜌
𝑃𝑐 = 𝜂 = 𝜂 𝐵 = 33000𝜂 (7.59)
𝑃 𝜂𝑀 𝑀 𝑃 𝜂𝑀
where,
𝑃𝑐 = Power consumption
𝜂𝑀 = Electric motor efficiency (as function of brake horsepower)
𝜂𝑃 = Function of the volumetric flowrate
𝜌 = Liquid density (lb/gal)
Q = Volumetric flow rate (gal/min)
H = Pump head (ft)
The pressure difference between inlet and outlet of pump pressure is needed to
calculate the pump head. The purchase cost of pump is calculated using Equation 7.60.
𝐶𝑃 = 𝐹𝑇 𝐹𝑀 𝐶𝐵 (7.60)
where,
𝐹𝑇 = Type factor of pump
𝐹𝑀 = Material factor of pump
𝐶𝐵 = Base purchase cost of pump
385
Pump is a motor-driven equipment. The purchase cost of electric motor should
also be included in the bare-module cost calculation. Equation 7.61 shows the purchase
cost of electric motor.
𝐶𝑃 = 𝐹𝑇 𝐹𝑀 𝐶𝐵 (7.61)
where,
𝐹𝑇 = Type factor of electric motor
𝐶𝐵 = Base purchase cost of electric motor
Lastly, the bare-module cost can be found using Equation 7.62.
I
CBM = CP × FBM × I (7.62)
b
where:
CBM = base-module cost of compressor
FBM = base-module factor
I = latest CE index in 2021 = 797.6
Ib = CE index in 2013 = 567
The equipment specification sheet for pump (P-101) is presented in Table 7.16
with the summary of all information and cost estimation.
Table 7.16 Equipment specification sheet for pump (P-101)

Equipment Name Pump (P-101)
Function To increase pressure of water from 1 bar to 15 bar
Operating Condition
Pressure outlet, Po (psi) 217.56
386
Pressure outlet, Po (bar) 15
Pressure ratio, Po/PI 15
Inlet flow rate (kg/hr) 891
Inlet flow rate (m³/hr) 0.8937
Inlet flow rate (gpm) 5.2834
Compression ratio 15
Liquid density (lb/gal) 8.32
Characteristics of Pump
Pump head (ft) 275.60
Size factor, S 65.32
Type factor, Ft 1.00
Material factor, Fm 1.00
Base purchase cost, 𝐶𝐵 (USD) 7,235.39

Purchase cost, 𝐶𝑝 (USD) 7,235.39
Characteristics of Electric Motor
Brake horsepower, 𝑃𝐵 (BHp) 72.66
Efficiency of pump, 𝜂𝑝 0.0505
Efficiency of motor, 𝜂𝑀 0.9033
Power consumption, 𝑃𝐶 80.44
Motor type factor, 𝐹𝑡 1.7
Base purchase cost, 𝐶𝐵 (USD) 3,717.30
Purchase cost, 𝐶𝑝 (USD) 3,717.30
Total purchase cost, 𝐶𝑝 (USD) 6,319.41
Bare module factor, 𝐹𝐵𝑀 3.3
Bare module cost, 𝐂𝐁𝐌 (RM) 21,838.81
387
7.2.8 Heaters
There are a total of five heaters used in the methanol production plant. All the
heaters are used to increase the temperature of the stream to the required set point of
the upcoming process. Based on preliminary study, the most suitable heat exchanger
used in increasing the temperature of fluid either in liquid or gas form is by using the
shell and tube heat exchanger (Albrecht, 2004). High pressure steam is utilized as the
heating medium for the heater. The material of construction is assumed to be carbon
steel and stainless steel for shell and tubes respectively.
For the bare-module cost calculation of the heater, the equations shown below
are used to determine the parameters present in the equipment specification sheets.
The heat duty of heater, Q is obtained from heat integration chapter. The surface area,
A of the heater is calculated based on the Equation 7.63.
𝑄
𝐴 = 𝑈×∆𝑇 (7.63)
𝐿𝑀
where:
𝐴 = heat transfer surface area (𝑚2 )
𝑄 = heat duty of heater (W)
𝑈 = overall heat transfer coefficient for water to water (𝑊 ⁄𝑚2 . ℃)
∆𝑇𝐿𝑀 = log mean temperature difference (℃)
As for the U value, it is taken from Table 7.17, water to water fluid combination
(Gibson, 2021). Therefore, U=850 W⁄m². ℃ is assumed.
Table 7.17 Overall heat transfer coefficient values in heat exchangers
388
To calculate the log mean temperature difference, ∆𝑇𝑙𝑚 , Equation 7.64 is used.
(𝑇1 −𝑡2 )−(𝑇2 −𝑡1 )

∆𝑇𝑙𝑚 = (𝑇 −𝑡 ) (7.64)
𝑙𝑛 1 2
(𝑇2 −𝑡1)
where:
𝑇1 = inlet hot fluid temperature
𝑇2 = outlet hot fluid temperature
𝑡1 = inlet cold fluid temperature
𝑡2 = outlet cold fluid temperature
The base cost, 𝐶𝐵 of shell and tube heater is calculated using Equation 7.65
where A is surface area in square feet.
𝐶𝐵 = exp (11.5510 − 0.9186(𝑙𝑛𝐴) + 0.09790(𝑙𝑛𝐴)2 ) (7.65)
The pressure factor, 𝐹𝑃 is based on the shell side pressure P, in psig as shown
in Equation 7.66. For shell-and-tube heater, the pressure factor, 𝐹𝑃 = 1.0 for shell side
pressure lower than 100 psig.
When P = 100 to 2000 psig,
𝑃 𝑃
𝐹𝑃 = 0.9803 + 0.018 (100) + 0.0017(100)2 (7.66)
The material factor, 𝐹𝑀 of shell-and-tube heater is determined by Equation 7.67

as a function of the surface area, A in square feet. The constants a and b are based on
the combination of tube and shell material. For carbon steel shell and stainless-steel
tube, a = 1.75 while b = 0.13. The HPS stream pressure is assumed to be 75 psig
(Collins, 2022).
𝐴
𝐹𝑀 = 𝑎 + (100)𝑏 (7.67)
389
The tube length factor, 𝐹𝐿 of shell-and-tube heater is the tube-length correction.
It is determined by referring to Table 7.18. For 8 ft tube length, the value of 𝐹𝐿 is 1.25
and for 12ft tube length, the value of 𝐹𝐿 is 1.12.
Table 7.18 Tube length factor
Tube length (ft) 𝐅𝐋

8 1.25
12 1.12
16 1.05
20 1.00
To complete the calculation of the heater design, the purchase cost for heaters
are determined by using the equation below:
𝐼
𝐶𝑝 = (𝐹𝑃 𝐹𝑀 𝐹𝐿 𝐶𝐵 ) × 𝐼 (7.68)
𝑏
where:
𝐹𝑃 = pressure factor
𝐹𝐿 = tube length factor
𝐶𝐵 = base cost
𝐼 = latest CE index in 2019 = 797.6 (Jenkins, 2020)
𝐼𝑏 = CE index in 2013 = 567 (Seider et al., 2017)
Therefore, the bare-module cost, 𝐶𝐵𝑀 of the heater can be obtained using
Equation 7.69. According to Seider et al. (2017), bare-module factor 𝐹𝐵𝑀 of shell-and
tube heater is 3.17.
𝐶𝐵𝑀 = 𝐶𝑃 × 𝐹𝐵𝑀 (7.69)
where:
390
𝐶𝐵𝑀 = bare-module cost of heater
𝐹𝐵𝑀 = bare-module factor
The equipment specification sheet for the heaters (E-105, E-108, E-110, E-113,
E-114) are presented in Table 7.19 to Table 7.23 together with the results of all
calculation and cost estimation.
391
Table 7.19 Equipment specification sheet for heater (E-105)

Equipment name Heater (E-105)
Function To heat stream S10a from 270℃ to

280℃
Type of heat exchanger Shell and Tube
Flow configuration Countercurrent
Heating medium High pressure steam
Material of Construction
Shell Carbon steel
Tube Stainless steel
Shell side Heat duty (kW) 1.7
Heat transfer coefficient,
Inlet Temperature, 𝑇1 (℃) 320 850
U (W/𝑚2 . ℃)
Log mean temperature
Outlet Temperature, 𝑇2 (℃) 300 34.76
driving force, ∆𝑇𝑙𝑚 (℃)
Pressure (bar) 5.171 Surface area (𝑓𝑡 2 ) 2.587
Pressure (psig) 75 Tube length (ft) 8
Tube side Tube length factor, 𝐹𝐿 1.25
Inlet Temperature, 𝑡1 (℃) 270 Material factor, 𝐹𝑀 2.37
Outlet Temperature, 𝑡2 (℃) 280 Pressure factor, 𝐹𝑃 0.994
Pressure (bar) 50
Pressure (psig) 725.189
Base cost, 𝐶𝐵 (USD) 47,403.20
392

To heat stream S11b from 563.7℃ to
Function
900℃
Shell Carbon steel
Heat transfer coefficient,
Inlet Temperature, 𝑇1 (℃) 1190 850
U (W/𝑚2 . ℃)
Outlet Temperature, 𝑇2 Log mean temperature
640 160.05
(℃) driving force, ∆𝑇𝑙𝑚 (℃)
Inlet Temperature, 𝑡1 (℃) 563.7 Material factor, 𝐹𝑀 2.59
Outlet Temperature, 𝑡2
900 Pressure factor, 𝐹𝑃 0.995
(℃)
Pressure (bar) 15
393

Function To heat stream S14a from 270℃ to 900℃
Shell Carbon steel
Inlet Temperature, 𝑇1 Heat transfer coefficient,
1200 850
(℃) U (W/𝑚2 . ℃)
300 117.26
Inlet Temperature, 𝑡1
270 Material factor, 𝐹𝑀 2.72
(℃)
(℃)
Pressure (bar) 15
394

Shell Carbon steel
320 850
(℃) U (W/𝑚2 . ℃)
300 34.76
(℃)
(℃)
Pressure (bar) 50
395

Shell Carbon steel
Shell side Heat duty (btu/hr) 33.94
320 850
(℃) U (W/𝑚2 . ℃)
300 34.76
(℃)
(℃)
Pressure (bar) 50
396
7.2.9 Condenser
The condensers (E-116, E-117, E-118) in the methanol production plant is used
to cool the inlet process streams to the required set point. The type of condensers used
are shell and tube. The cooling medium for condensers are refrigerant. The material of
construction is assumed to be carbon steel and stainless steel for shell and tubes
respectively.
For the bare-module cost calculation of the condensers, the equations shown
below are used to determine the parameters present in the equipment specification
sheets. The surface area, A of the condenser is calculated based on the Equation 7.70.
𝑄
𝐴 = 𝑈×∆𝑇 (7.70)
𝐿𝑀
where:
𝑈 = overall heat transfer coefficient for water to water (𝑊 ⁄𝑚2 . ℃)
As for the U value, it is taken from Table 7.24, water to water fluid combination
(Gibson, 2021). Therefore, U=850 W⁄m². ℃ is assumed.
397
(𝑇1 −𝑡2 )−(𝑇2 −𝑡1 )
∆𝑇𝑙𝑚 = (𝑇 −𝑡 ) (7.71)
𝑙𝑛 1 2
(𝑇2 −𝑡1)
where:
The base cost, 𝐶𝐵 of shell and tube heater is calculated using Equation 7.72
𝐶𝐵 = exp (11.5510 − 0.9186(𝑙𝑛𝐴) + 0.09790(𝑙𝑛𝐴)2 ) (7.72)
in Equation 7.73. For shell-and-tube heater, the pressure factor, 𝐹𝑃 = 1.0 for shell side
𝑃 𝑃
𝐹𝑃 = 0.9803 + 0.018 (100) + 0.0017(100)2 (7.73)
The material factor, 𝐹𝑀 of shell-and-tube heater is determined by Equation 7.74

tube, a = 1.75 while b = 0.13. The HPS stream pressure is assumed to be 75 psig
(Collins, 2022).
𝐴
𝐹𝑀 = 𝑎 + (100)𝑏 (7.74)
398
and for 12ft tube length, the value of 𝐹𝐿 is 1.12.

8 1.25
12 1.12
16 1.05
20 1.00
To complete the calculation of the heater design, the purchase cost for heaters
𝐼
𝐶𝑝 = (𝐹𝑃 𝐹𝑀 𝐹𝐿 𝐶𝐵 ) × 𝐼 (7.75)
𝑏
where:
tube heater is 3.17.
𝐶𝐵𝑀 = 𝐶𝑃 × 𝐹𝐵𝑀 (7.76)
where:
399
The equipment specification sheet for the condensers (E-116, E-117, E-118)are
presented in Table 7.26 to Table 7.28 together with the results of all calculation and
cost estimation.
400
Table 7.26 Equipment specification sheet for condenser (E-116)

Equipment name Condenser (E-116)
To cool stream S25d from 139.87℃
Function
to 105.23℃
Heating medium Refrigerant
Shell Carbon steel
Heat transfer
Inlet Temperature, 𝑇1 (℃) 139.87 coefficient, U 3000
(𝑊 ⁄𝑚2 . ℃)
Log mean temperature
Outlet Temperature, 𝑇2 (℃) 105.23 driving force, 22.44
∆𝑇𝑙𝑚 (℃)
Pressure (bar) 30 Surface area (𝑓𝑡 2 ) 18.79
Pressure (psig) 435.113 Tube length (ft) 8
Inlet Temperature, 𝑡1 (℃) 80 Material factor, 𝐹𝑀 2.55
Outlet Temperature, 𝑡2 (℃) 120 Pressure factor, 𝐹𝑃 1.09
Pressure (bar) 1 Bare module factor,
3.17
Pressure (psig) 0 𝐹𝐵𝑀
Bare module cost, 𝐶𝐵𝑀 (USD) 253143.2497
401

To cool stream S25e from 268.9℃ to
Function
105.23℃
Shell Carbon steel
268.9 3000
(℃) U (𝑊 ⁄𝑚2 . ℃)
105.23 64.75
(℃)
(℃)
Pressure (bar) 1
Pressure (psig) 0
402

To cool stream S25f from 126.57℃ to
Function
105.23℃
Shell Carbon steel
Shell side Heat duty (Kw) 20.29
126.57 1000
(℃) U (𝑊 ⁄𝑚2 . ℃)
105.23 19.43
(℃)
(℃)
Pressure (bar) 1
Pressure (psig) 0
403
7.2.10 Coolers
Cooler is used to reduce the temperature of the stream to achieve the optimum
value. In methanol synthesis plant, there are 4 coolers which are E-101, E-102, E-103
and E-111. The cooling medium in cooler is cooling water at 1 bar. U-tube type shell
and tube is the type of cooler used in the plant. The material of construction for shell
and tube are assumed to be carbon steel and stainless steel respectively.
As for the 𝑈 value, it is taken from Table 7.29, finned tube heat exchanger
(water in tubes, air in cross flow) (Gibson, 2021). Therefore, 𝑈 = 40 𝑊 ⁄𝑚2 . ℃ is
assumed.
The surface area, A of the cooler is calculated based on the Equation 7.77.
𝑄
𝐴 = 𝑈×∆𝑇 (7.77)
𝐿𝑀
where:
𝑈 = overall heat transfer coefficient (𝑊 ⁄𝑚2 . ℃)
404
(𝑇1 −𝑡2 )−(𝑇2 −𝑡1 )

∆𝑇𝑙𝑚 = (𝑇 −𝑡 ) (7.78)
𝑙𝑛 1 2
(𝑇2 −𝑡1)
where:
The base cost, 𝐶𝐵 of shell and tube cooler is calculated using Equation 7.79
𝐶𝐵 = exp (11.5510 − 0.9186(𝑙𝑛𝐴) + 0.09790(𝑙𝑛𝐴)2 ) (7.79)
in Equation 7.80. For shell-and-tube cooler, the pressure factor, 𝐹𝑃 = 1.0 for shell side
𝑃 𝑃
𝐹𝑃 = 0.9803 + 0.018 (100) + 0.0017(100)2 (7.80)
The material factor, 𝐹𝑀 of shell-and-tube cooler is determined by Equation 7.81

tube, a = 1.75 while b = 0.13. The cooling water pressure is assumed to be 1 bar.
𝐴
𝐹𝑀 = 𝑎 + (100)𝑏 (7.81)
405
and for 12 ft tube length, the value of 𝐹𝐿 is 1.12.

8 1.25
12 1.12
16 1.05
20 1.00
To complete the calculation of the heater design, the purchase cost for coolers
𝐼
𝐶𝑝 = (𝐹𝑃 𝐹𝑀 𝐹𝐿 𝐶𝐵 ) × 𝐼 (7.82)
𝑏
where:
tube cooler is 3.17.
𝐶𝐵𝑀 = 𝐶𝑃 × 𝐹𝐵𝑀 (7.83)
where:
406
The equipment specification sheet for the coolers (E-101, E-102, E-103, E-
111) are presented in Table 7.31 to Table 7.34 together with the results of all
calculation and cost estimation.
407
Table 7.31 Equipment specification sheet of cooler (E-101)

Equipment name Cooler (E-101)
Function To cool stream S3 from 59.43℃ to 25℃
Heating medium Cooling water
Shell Carbon steel
59.43 40
(℃) U (𝑊 ⁄𝑚2 . ℃)
25 12.08
(℃)
(℃)
Pressure (bar) 1
Pressure (psig) 0
408

Shell Carbon steel
85.24 40
(℃) U (𝑊 ⁄𝑚2 . ℃)
30 12.44
(℃)
(℃)
Pressure (bar) 1
Pressure (psig) 0
409

Shell Carbon steel
121.30 40
(℃) U (𝑊 ⁄𝑚2 . ℃)
30 10.15
(℃)
(℃)
Pressure (bar) 1
Pressure (psig) 0
410

Function To cool stream S17 from 280℃ to 82.3℃
Shell Carbon steel
280 40
(℃) U (𝑊 ⁄𝑚2 . ℃)
82.30 11.11
(℃)
(℃)
Pressure (bar) 1
Pressure (psig) 0
411
7.2.11 Heat Exchangers
Heat exchanger is an equipment used for heat exchange between cold streams
and hot streams. There are six heat exchangers in the methanol production plant, which
are E-104, E-106, E-107, E-109, E-112 and E-115. The hot stream pipeline will be the
utility tube that will channel the heat to the cold stream in order to increase the
temperature of cold process stream to the desired set point. Shell-and-tube heat
exchanger is the type of heat exchanger used in the methanol synthesis plant due to the
ability to withstand a wide range of temperatures. The material of construction for shell
and tube are assumed to be carbon steel and stainless steel respectively.
As for the 𝑈 value, it is taken from Table 7.35, finned tube heat exchanger
(water in tubes, air in cross flow) (Gibson, 2021). Therefore, 𝑈 = 40 𝑊 ⁄𝑚2 . ℃ is
assumed.
The surface area, A of the cooler is calculated based on the Equation 7.84.
𝑄
𝐴 = 𝑈×∆𝑇 (7.84)
𝐿𝑀
where:
𝑈 = overall heat transfer coefficient (𝑊 ⁄𝑚2 . ℃)
412
(𝑇1 −𝑡2 )−(𝑇2 −𝑡1 )

∆𝑇𝑙𝑚 = (𝑇 −𝑡 ) (7.85)
𝑙𝑛 1 2
(𝑇2 −𝑡1)
where:
The base cost, 𝐶𝐵 of shell and tube cooler is calculated using Equation 7.86
𝐶𝐵 = exp (11.5510 − 0.9186(𝑙𝑛𝐴) + 0.09790(𝑙𝑛𝐴)2 ) (7.86)
in Equation 7.87. For shell-and-tube cooler, the pressure factor, 𝐹𝑃 = 1.0 for shell side
𝑃 𝑃
𝐹𝑃 = 0.9803 + 0.018 ( ) + 0.0017( )2 (7.87)
100 100
The material factor, 𝐹𝑀 of shell-and-tube cooler is determined by Equation 7.88

tube, a = 1.75 while b = 0.13. The cooling water pressure is assumed to be 1 bar.
𝐴
𝐹𝑀 = 𝑎 + (100)𝑏 (7.88)
413
and for 12 ft tube length, the value of 𝐹𝐿 is 1.12.

8 1.25
12 1.12
16 1.05
20 1.00
To complete the calculation of the heater design, the purchase cost for coolers
𝐼
𝐶𝑝 = (𝐹𝑃 𝐹𝑀 𝐹𝐿 𝐶𝐵 ) × 𝐼 (7.89)
𝑏
where:
tube cooler is 3.17.
𝐶𝐵𝑀 = 𝐶𝑃 × 𝐹𝐵𝑀 (7.90)
where:
414
The equipment specification sheet for the heat exchangers (E-104, E-106, E-
107, E-109, E-112 and E-115) are presented in Table 7.37 to Table 7.42 together with
the results of all calculation and cost estimation.
415
Table 7.37 Equipment specification sheet of heat exchanger (E-104)

Equipment name Heat Exchanger (E-104)
To exchange heat of hot stream (S10) with
Function
cold stream (S2)
Shell Carbon steel
121.3 40
(℃) U (𝑊 ⁄𝑚2 . ℃)
270 146.06
(℃)
(℃)
Pressure (bar) 50
416

Function
cold stream (S11a)
Shell Carbon steel
280 40
(℃) U (𝑊 ⁄𝑚2 . ℃)
126.57 14.43
(℃)
(℃)
Pressure (bar) 30
417

Function
cold stream (S11b)
Shell Carbon steel
900 40
(℃) U (𝑊 ⁄𝑚2 . ℃)
280 92.82
(℃)
563.7 Pressure factor, 𝐹𝑃 1.03
(℃)
Pressure (bar) 15
418

Function
cold stream (S14a)
Shell Carbon steel
105.23 40
(℃) U (𝑊 ⁄𝑚2 . ℃)
75 96.24
(℃)
(℃)
Pressure (bar) 15
419

To exchange heat of hot stream (S25h) with
Function
cold stream (S21)
Shell Carbon steel
280 40
(℃) U (𝑊 ⁄𝑚2 . ℃)
268.90 19.45
(℃)
(℃)
Pressure (bar) 50
420

To exchange heat of hot stream (S25g) with
Function
cold stream (S30)
Shell Carbon steel
280 40
(℃) U (𝑊 ⁄𝑚2 . ℃)
139.87 14.43
(℃)
(℃)
Pressure (bar) 50
421
7.2.12 Total Bare-Module Cost
The total bare-module cost including all the equipment are calculated and
summarized in Table 7.43. The total bare-module cost is RM
Table 7.43 Total bare-module cost
Equipment Name Equipment Label Bare-Module Cost (RM)

Steam reforming reactor R-101 1812,059.00
Methanol synthesis reactor R-102 13,089,309.29
Membrane separator F-101 93,972.44
Flash column 1 F-102 11,311,037.40
Flash column 2 F-103 428,313.80
Distillation column T-101 1,251,832.15
Mixer M-101 2,635,097.28
Pump P-101 21,838.81
Compressor C-101 1,062,897.45
Compressor C-102 1,021,146.41
Compressor C-103 4,766,014.59
Compressor C-104 476,044.70
Compressor C-105 1,274,766.27
Compressor C-106 4,209,300.80
Compressor C-107 3,384,527.51
Cooler E-101 237,623.32
Cooler E-102 238,842.42
Cooler E-103 268,729.88
Cooler E-111 245,666.90
Heater E-105 2,743,009.00
Heater E-108 936,363.00
Heater E-110 723,136.40
Heater E-113 1,625,425.80
Heater E-114 1,173,619.50
Condenser E-116 1,113,830.30
422
Condenser E-117 821,576.95
Condenser E-118 13,366,450.20
Heat Exchanger E-104 656,359.66
Total Bare-Module Cost RM 45,700,494.96
423
7.3 Total Capital Investment
Based on the Plant Capital Cost (n.d.), the total capital investment (CTCI ),
which includes the testing and troubleshooting phases prior to the commencement of
real production, is required to establish and operate a chemical plant. It excludes
maintenance and operational costs incurred during the production process. For this
chemical plant, the methanol producing facility requires a total capital investment
(CTCI ) to be ready for start-up. In addition to the working capital investment, some
process expenses also need to be calculated such equipment, site development,
buildings, and off-site amenities. Equation 7.91 illustrates how to determine the total
capital investment using the Guthrie technique.
CTCI = CTPI + CWC (7.91)
where:
CWC = =Working capital
CTPI = Total permanent investment which can calculated using Equation 7.92
CTPI = 1.18 (𝐶𝑇𝐵𝑀 + 𝐶𝑠𝑖𝑡𝑒 + 𝐶𝑏𝑢𝑖𝑙𝑑𝑖𝑛𝑔𝑠 + 𝐶𝑜𝑓𝑓𝑠𝑖𝑡𝑒 𝑓𝑎𝑐𝑖𝑙𝑖𝑡𝑖𝑒𝑠 ) (7.92)
where:
𝐶𝑇𝐵𝑀 = Total bare-module investment
𝐶𝑠𝑖𝑡𝑒 = Site development cost
𝐶𝑏𝑢𝑖𝑙𝑑𝑖𝑛𝑔𝑠 = Building cost
𝐶𝑜𝑓𝑓𝑠𝑖𝑡𝑒 𝑓𝑎𝑐𝑖𝑙𝑖𝑡𝑖𝑒𝑠 = Offsite facility cost
The total bare-module investment, or 𝐶𝑇𝐵𝑀 , is the sum of the bare-module costs
for all of the equipment, which has been total up to be RM 45,700,494.96. For the
grassroots methanol manufacturing plant's site development cost, 𝐶𝑠𝑖𝑡𝑒 , a value of 15%
of 𝐶𝑇𝐵𝑀 is allocated. The cost for buildings, 𝐶𝑏𝑢𝑖𝑙𝑑𝑖𝑛𝑔𝑠 , in the Guthrie approach may be
calculated as 20% of 𝐶𝑇𝐵𝑀 and includes both process buildings and non-process
buildings. Utility, waste-treatment, off-site tankage, receiving, and shipping facilities
424
are examples of off-site facilities. Calculating the allotted capital investment expenses
for the utility, 𝐶𝑎𝑙𝑙𝑜𝑐 , as well as an additional 5% of 𝐶𝑇𝐵𝑀 to cover other facilities, yields
the cost of off-site facilities, or𝐶𝑜𝑓𝑓𝑠𝑖𝑡𝑒 𝑓𝑎𝑐𝑖𝑙𝑖𝑡𝑖𝑒𝑠 . A contingency of 15% and a
contractor charge of 3% are included in factor 1.18 of Equation 7.93.
The allocated costs, 𝐶𝑎𝑙𝑙𝑜𝑐 , to purchase or upgrade the utilities including steam,
electricity, cooling water, process water and refrigeration is summarized in Table 7.44.
Upon calculation, the allocated costs, 𝐶𝑎𝑙𝑙𝑜𝑐 obtained is RM 85 614 481.78. The detail
calculation of the allocated cost is tabulated in Table 7.45. The calculation highly
depending on the size factor, S for each types of utility.
Table 7.44 Allocated capital investment costs for utility
Allocated cost Allocated cost

Utility Size Factor, S
(USD) (RM)
Steam 20000 lb/hr 2833461.037 12,495,563.17
Electricity 0.5 MW 16313348.03 71,941,864.80
Cooling water 1000 gpm 120612.6016 531,901.57
Process water 50 gpm 72687.56585 320,552.17
Refrigeration 10 tons 73605.45692 324,600.07
Allocated capital investment costs for utility, 𝐂𝐚𝐥𝐥𝐨𝐜 85,614,481.78
425
Table 7.45 Detail calculation of the allocated cost, 𝐶𝑎𝑙𝑙𝑜𝑐
Utility Calculation
Steam Calloc = 930 × S 0.81
= 930 × 20 0000.81
= $2833461.037
= RM 12,495,563.17
Electricity Calloc = 2 900 000 × S 0.83

= 2 900 000 × 0.50.81
= $16,313,348.03
= RM 71,941,864.80
Cooling water Calloc = 1100 × S 0.68
= 1100 × 1 0000.68
= $120612.6016
= RM 531,901.57
Process water Calloc = 1700 × S 0.96
= 1700 × 500.96
= $72687.56585
= RM 320,552.17
Refrigeration Calloc = 12 500 × S 0.77
= 12 500 × 100.77
= $73605.45692
= RM 324,600.07
The CTPI may be determined by adding together the CTBM , Csite , Cbuildings ,
Coffsite facilities , and Total Permanent Investment. The working capital is calculated at
17.6% of the total permanent investment, in line with the Lang-factor technique. The
cost of all significant technical components taken together and divided by the expected
overall cost of developing a process inside a facility is known as the Lang Factor. The
total capital investment, or CTCI , can be calculated as a result in Table 7.46 which also
provides a summary of the total capital investment calculation.
426
Table 7.46 Calculation of total capital investment, 𝐶𝑇𝐶𝐼
Cost Equation Total cost (RM)
Total bare-module investment, CTBM ∑ CTBM 45,700,494.96
Site development cost, Csite 15% of CTBM 6,855,074.24

Building cost, Cbuildings 20% of CTBM 91,40,098.99
Offsite facility cost, Coffsite facilities Calloc + 5% of CTBM 87,899,506.53
1.18 (CTBM + Csite +
Total permanent investment, CTPI Cbuildings + 176,522,306.20
Coffsite facilities )
Working capital, CWC 17.6% of CTPI 31,067,925.89
Total Capital Investment, 𝐂𝐓𝐂𝐈 𝐂𝐓𝐏𝐈 + 𝐂𝐖𝐂 207,590,232.10
According to Table 7.46, after adding up all the requirement cost needed to
calculate the total capital investment, CTCI , the methanol producing plant's total capital
investment, CTCI can be finalised to be is RM 207,590,232.10.
427
7.4 Total Depreciable Capital
Depreciation is the decline in the economic value of an asset over time.

Depreciated cost is the value of a fixed asset minus all of the accumulated depreciation
that has been recorded against it. As the company uses equipment for manufacturing
purposes, depreciation is crucial in order to minimize the taxes needed to pay. The
total depreciable capital, CTDC is determined using Equation 7.93.
CTDC = CDPI + Ccont (7.93)
where,
CDPI = Total direct permanent investment which can calculated using Equation 7.94
Ccont = Cost of contingencies and contractor's fee
CDPI = CTBM + Csite + Cserv + Calloc (7.94)
where,
CTBM = Total bare module investment
Csite = Site preparation cost
Cserv = Service facilities cost
Calloc = Allocated costs for utility plants and related facilities
The total cost for site preparation and service facilities are estimated as 30% of
the total bare-module investment. With the total bare-module investment calculated in
Table 7.43 and the allocated cost determined in Table 7.44, the total direct permanent
investment can thus be calculated.
The cost of contingencies is generally to set a7.side 15% of total direct

permanent investment and a 3% of total direct permanent investment is added as
contractor’s fee (Guthrie, 1969). Therefore, the Ccont is calculated as a total of 18% of
CDPI . The CDPI is then summed up with Ccont to obtain the total depreciable capital,
CTCI . The detail calculation for total depreciable capital is presented in Table 7.47.
428
Table 7.47 Calculation of total depreciable capital, CTCI
Cost Equation Total cost (RM)

Total bare-module
∑ CTBM 45,700,494.96
investment, CTBM
Site development cost and
service facilities cost, 30% of CTBM 13,710,148.49
Csite + Cserv
Allocated capital investment
From Table 7.44 85,614,481.78
costs for utility, Calloc
Total direct permanent
CTBM + Csite + Cserv + C𝑎𝑙𝑙𝑜𝑐 145,025,125.23
investment, CDPI
Cost of contingencies and
18% of CDPI 26,104,522.54
contractor's fee, C𝑐𝑜𝑛𝑡
Total Depreciable Capital,
𝐂𝐃𝐏𝐈 + 𝐂𝒄𝒐𝒏𝒕 171,129,647.77
𝐂𝐓𝐃𝐂
According to Table 7.47, after adding up all the requirement cost needed to
calculate the total depreciable capital, CTDC , the methanol producing plant's total
depreciable capital, CTDC can be finalised to be is RM 171,129,647.77.
429
7.5 Direct Wages and Benefits
Prior to determining the direct pay and benefits, the number of operators
needed for the ethylene manufacturing facility is determined for the labor-related
activities (O) (DW&B). Two operator per shift is assigned to each section since the
methanol manufacturing plant is an autonomously managed fluids processing unit that
runs continuously. The facility runs in two shifts each day for 360 days out of the year.
Each operator does one shift every day for a total of twelve hours (7am to 7pm). Each
operator is thought to be paid RM 2000 each month. Based on the equipment, the
number of operators each shift, and the number of shifts per day as given in Table 7.48,
an estimate of the necessary number of operators is made.
Table 7.48 Estimated Number of Required Operators
Operator per Number of Total

Equipment No. of Unit
Shift shifts per day Operator
Reactor 2 2 2 8
Flash Column 2 2 2 8
Membrane
1 2 2 4
Separator
Distillation
1 2 2 4
Column
Cooler 4 2 2 16
Heat
6 2 2 24
Exchanger
Heater 5 2 2 20
Condenser 3 2 2 12
Compressor 7 2 2 28
Wastewater
1 2 2 4
Treatment
Total Number of Operators 128
430
According to Table 7.48, 128 operators are needed to cover two shifts each
day. In order to determine the direct wages and benefits (DW&B), multiply the number
of operators by the yearly compensation according to the Equation 7.95.
2000
𝐷𝑖𝑟𝑒𝑐𝑡 𝑊𝑎𝑔𝑒𝑠 𝑎𝑛𝑑 𝐵𝑒𝑛𝑒𝑓𝑖𝑡𝑠 = 128 𝑂𝑝𝑒𝑟𝑎𝑡𝑜𝑟𝑠 𝑥 𝑅𝑀 𝑚𝑜𝑛𝑡ℎ 𝑥 12 𝑚𝑜𝑛𝑡ℎ𝑠 (7.95)
By using the above equation, we can determine that the direct wages and
benefits (DW&B) cost for methanol production plant would be equal to RM 3,072,000
per annum.
431
7.6 Total Annual Production Cost
The whole cost to maintain and run the production facility over the course of a
year is the total yearly production. The sum of all manufacturing costs (COM) and all
general expenses (GE) constitutes the total annual production cost. The cost of
manufacturing is determined by summing all expenses necessary to operate and
maintain the process, including those for the purchase of feedstock, utilities, labour,
maintenance, taxes, and insurances, as well as accounting for depreciation. Transfer,
research, and development (R&D), administrative, and management costs are among
the general expenses that must be incurred in order to maintain and operate the process
plant. The equation for total annual production cost is shown as below:
Total Annual Production Cost = COM + General Expenses (7.96)

where,
COM = Total cost of manufacturing
The annual cost is summarized in Table 7.49 which includes representative unit
costs and typical factors that are used to estimate each cost factor.
Table 7.49 Annual Cost Summary
Annual Cost Summary

Cost Factor Typical Factor Annual Cost (RM)
Feedstocks
Biogas RM167/tonne 2,194,380
Total Feedstock Cost 2,194,380
Utilities
Total Utilities Cost 85,614,482
Labor Operations Cost
Direct Wages and
- 3,072,000
Benefits (DW&B)
Direct Salaries and
15% of DW&B 439,200
Benefits
432
Operating Supplies and
6% of DW&B 175,680
Services
Technical Assistance to
- 738,000
Manufacturing
Control Laboratory - 799,500
Total Labor Cost 5,224,380
Maintenance
Maintenance Wages and
3.5% of CTDC 8,651,802
Benefits (MW&B)
Salaries and Benefits 25% of MW&B 2,162,950
Materials and Services 100% of MW&B 8,651,802
Maintenance Overhead 5% of MW&B 432,590
Total Maintenance Cost 19,899,144
Operating Overhead
Combined Salary, Wages, Benefits, for Maintenance
14,325,952
and Labor Costs, M&O-SW&B
General Plant Overhead 7.1% of M&O-SW&B 1,006,912
Mechanical Department
2.4% of M&O-SW&B 340,367
Services
Employee Relations
5.9% of M&O-SW&B 836,735
Department
Business Services 7.4% of M&O-SW&B 1,049,464
Total Operating Overhead 17,415,430
Property Taxes and Insurance
Property Taxes and
2% of CTDC 4,943,887
Insurance
Depreciation
8% of (CTDC –
Direct Plant 11,693,539
1.18Calloc )
Allocated Plant 6% of 1.18Calloc 5,136,869
Total Depreciation, D 16,830,408
Total Cost of Manufacture, COM 152,122,111
433
General Expenses
Selling or Transfer
3% of Sales 1,452,410
Expense
Direct Research 4.8% of Sales 2,323,856
Allocated Research 0.5% of Sales 242,068
Administrative Expense 2% of Sales 968,273
Management Incentive
1.25% of Sales 605,170
Compensation
Total General Expenses, GE 5,591,777
Total Production Cost COM + GE 157,713,888
According to Table 7.49, the total cost of manufacturing (COM) is RM

152,122,111 whereas the total general expenses (GE) is RM 5,591,777. Therefore, the
total annual production cost for methanol production plant is RM 157,713,888.
434
7.7 Annual Net Profit and Return on Investment (ROI)
The profit of the methanol production plant is generated from the product
revenue, which is methanol. The market price of methanol is RM 2662 per tonne.
According to the mass balance calculation, a total of 22000 tonne of methanol will be
produced annually. The production rate is then multiplied with the market price of
methanol to obtain the total annual sales as shown in Table 7.50. A total annual sales
of RM 48,413,673 per year is estimated to be generated from the methanol production
plant.
Table 7.50 Total Annual Sale
Annual Production Market Price Product Revenue

Product
Rate (tonne/year) (RM/tonne) (RM/year)
Methanol 22000 26040 572,880,000
Total Annual Sales 572,880,000
Profit margin is important for a chemical plant to determine whether the

production plant is profitable. The gross profit is calculated as the amount of net
income earned after deducting the annual production cost from the cost of production
revenue. Equation 7.97 shows the gross profit calculation.
Annual gross profit = Product revenue – Total production cost (7.97)

= RM 572,880,000 – RM 157,713,888
= RM 415,166,112
The net earning or the after-tax earnings is the reduction of income tax from
the gross earnings. According to the Lembaga Hasil Dalam Negeri (2021), the income
tax rate, t for the chargeable income exceeding RM 2,000,000 is 30%. Therefore, the
annual net earnings is calculated in Equation 7.98.
435
Annual net earnings = (1–t) x gross earnings (7.98)
= (1–0.3) x RM 415,166,112
= RM 290,616,278.40
Therefore, the annual net earning or profit of the methanol production plant is
RM 290,616,278.40. The return of investment (ROI) of the plant can be estimated
based on the annual net earnings.
Return on investment (ROI) or return on costs is a ratio between net income

and investment. Return on investment (ROI) is calculated by dividing the profit earned
on an investment by the cost of that investment. A high ROI means the investment's
gains compare favourably to its cost. The ROI can be calculated using Equation 7.99.
𝐴𝑛𝑛𝑢𝑎𝑙 𝑛𝑒𝑡 𝑒𝑎𝑟𝑛𝑖𝑛𝑔𝑠

𝑅𝑂𝐼 = 𝑇𝑜𝑡𝑎𝑙 𝑐𝑎𝑝𝑖𝑡𝑎𝑙 𝑖𝑛𝑣𝑒𝑠𝑡𝑚𝑒𝑛𝑡,𝐶 × 100% (7.99)
𝑇𝐶𝐼
𝑅𝑀 290,616,278.40
= × 100%
𝑅𝑀 207,590,232.10
= 140%
Hence, according to the calculation, the return on investment of the ethylene

production plant is 140%, which indicates that the project is profitable with high return
rate.
436
7.8 Cash Flow Analysis
Cash flow is a measure of how much cash a business brought in or spent in

total over a period of time. Cash flow is typically broken down into cash flow from
operating activities, investing activities, and financing activities on the statement of
cash flows, a common financial statement. A cash flow analysis determines a
company’s working capital — the amount of money available to run business
operations and complete transactions. For investment evaluation, investments are
considered a negative cash flow, whereas after-tax profits plus depreciation are
positive cash flows.
Cash flow analysis is important to determine the payback period (PBP), the
discounted breakeven period (DBEP), and net present value (NPV) of the methanol
production plant. The term payback period refers to the amount of time it takes to
recover the cost of an investment, whereas a discounted payback period gives the
number of years it takes to break even from undertaking the initial expenditure, by
discounting future cash flows and recognizing the time value of money. Net Present
Value (NPV) is the value of all future cash flows (positive and negative) over the entire
life of an investment discounted to the present.
The cash flow analysis diagram is plotted to visually represent the overall flow
of incomes and expenses with respect to a lifetime of the plant and obtain the payback
period of the methanol production plant. A series of calculation such as operating
expenses, revenue, cash flow before tax and after tax are required in order to plot a
cumulative cash flow diagram. The effective tax rate, Te is calculated using equation
7.110 by taking the federal rate as 25% (Inland Revenue Board of Malaysia, 2020) and
assuming local rate as 5%. There are a few assumptions have been made for the cash
flow analysis:
a) The lifetime of the methanol production plant is assumed to be 20 years.
437
b) No revenue will be generated in the first two years of operation and the plant
will not reach the maximum operation for the next three years. The revenue for
the plant will be 20%, 30% and 50% for the three years.
c) The construction period of the plant is assumed to be 2 years. Hence, the capital
investment is distributed as 50% for first year, 40% for second year and 10%
for the third year.
438
Table 7.51 Cash flow analysis (in million ringgit) for 0% interest rate
Annual Total Cash Flow Cash Flow

Operating
Capital Revenue, Before Depreciation, Taxable After Cumulative
Year expenses, Taxes, Te = 0.30
Investment R Taxes, D Income, TI Taxes, Cash Flow
OE
cost, 𝐶𝑇𝐶𝐼 CFBT CFAT
0 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

1 103.80 0.00 0.00 -103.80 0.00 0.00 0.00 -103.80 -103.80
2 83.04 0.00 0.00 -83.04 0.00 0.00 0.00 -83.04 -186.83
3 20.76 83.03 157.71 -95.44 16.83 -91.51 -21.96 -73.48 -260.31
4 124.55 157.71 -33.16 16.83 -49.99 -12.00 -21.17 -281.47
5 207.58 157.71 49.87 16.83 33.04 7.93 41.94 -239.53
6 415.17 157.71 257.45 16.83 240.62 57.75 199.70 -39.83
7 415.17 157.71 257.45 16.83 240.62 57.75 199.70 159.87
8 415.17 157.71 257.45 16.83 240.62 57.75 199.70 359.58
9 415.17 157.71 257.45 16.83 240.62 57.75 199.70 559.28
10 415.17 157.71 257.45 16.83 240.62 57.75 199.70 758.98
11 415.17 157.71 257.45 16.83 240.62 57.75 199.70 958.68
12 415.17 157.71 257.45 16.83 240.62 57.75 199.70 1158.39
439
13 415.17 157.71 257.45 16.83 240.62 57.75 199.70 1358.09
14 415.17 157.71 257.45 16.83 240.62 57.75 199.70 1557.79
15 415.17 157.71 257.45 16.83 240.62 57.75 199.70 1757.50
16 415.17 157.71 257.45 16.83 240.62 57.75 199.70 1957.20
17 415.17 157.71 257.45 16.83 240.62 57.75 199.70 2156.90
18 415.17 157.71 257.45 16.83 240.62 57.75 199.70 2356.61
19 415.17 157.71 257.45 16.83 240.62 57.75 199.70 2556.31
20 415.17 157.71 257.45 16.83 240.62 57.75 199.70 2756.01
440
Cumulative Cash Flow For 0% Interest Rate
$3,000
$2,500
Cumulative cash flow ( in million RM)
$2,000
$1,500
$1,000
$500
$0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
-$500
Years
Figure 7.1 Cumulative cash flow for 0% interest rate
441
According to Table 7.51 and Figure 7.1, the cumulative cash flow value shows
negative trend for the first four years due to the three years construction period of
methanol production plant. At the beginning of plant building period, an investment is
needed to provide funds for start-up. The cumulative cash flow starts to show an
increasing trend from the fourth year. This is because the revenue is started to generate
from the sales of methanol to the market. From Table 7.51, the negative value of
cumulative cash flow indicates the paying period of total capital investment. The total
investment cost is fully paid off after 6.2 years. After 6.2 years, the revenue generated
by the methanol production plant is able to cover the operating expenses and the
project is generating profit continuously towards the end of the project. However, the
rate of cash flow tends to fall off due to the increasing operating cost and reducing of
sales volume and price.
Therefore, different interest rates should be considered in the cash flow

analysis. Interest rates are a key quantitative representation of the time value of money.
The time value of money is the degree to which cash available today is worth more
than the identical sum at some point in the future, due to its potential for growth. The
time value of money is important to a chemical plant, as it will affect the cash flow
performance of the plant every year. Also, different payback period corresponds to
different interest rates will also be obtained from the cash flow analysis. This payback
periods are known as discounted payback period (DPP). Different values of interest
rates which are 5%, 10% and 15% are computed in the cash flow analysis by
calculating the present worth value as presented in Equation 7.100.
1
𝑃 = 𝐹 [(1+𝑖)𝑛] (7.100)
where,
P = Present worth
F = Future worth
n = Number of years
i = Interest rate
442
Table 7.52 Cash flow analysis for different interest rate
I=0% i=5% i=10% i=15%

Cash Flow Non-
Year After Tax, Present Discounted Present Discounted Present Discounted
discounted
CFAT Value, Cumulative Value, Cumulative Cash Value, Cumulative
cumulative
(PV) Cash Flow (PV) Flow (PV) Cash Flow
cash
0 0 0 0 0 0 0 0 0
1 -103.80 -103.80 -98.85 -98.85 -94.36 -94.36 -90.26 -90.26
2 -83.04 -186.83 -75.32 -174.17 -68.62 -162.98 -62.79 -153.04
3 -73.48 -260.31 -63.47 -237.64 -55.20 -218.19 -48.31 -201.36
4 -21.17 -281.47 -17.41 -255.05 -14.46 -232.64 -12.10 -213.46
5 41.94 -239.53 32.86 -222.19 26.04 -206.60 20.85 -192.61
6 199.70 -39.83 149.02 -73.17 112.73 -93.88 86.34 -106.27
7 199.70 159.87 141.93 68.75 102.48 8.60 75.08 -31.19
8 199.70 359.58 135.17 203.92 93.16 101.77 65.28 34.09
9 199.70 559.28 128.73 332.65 84.69 186.46 56.77 90.86
10 199.70 758.98 122.60 455.25 76.99 263.45 49.36 140.22
11 199.70 958.68 116.76 572.01 69.99 333.45 42.92 183.15
12 199.70 1158.39 111.20 683.22 63.63 397.08 37.33 220.47
443
13 199.70 1358.09 105.91 789.12 57.85 454.93 32.46 252.93
14 199.70 1557.79 100.86 889.99 52.59 507.51 28.22 281.15
15 199.70 1757.50 96.06 986.05 47.81 555.32 24.54 305.70
16 199.70 1957.20 91.49 1077.53 43.46 598.78 21.34 327.04
17 199.70 2156.90 87.13 1164.66 39.51 638.29 18.56 345.59
18 199.70 2356.61 82.98 1247.64 35.92 674.21 16.14 361.73
19 199.70 2556.31 79.03 1326.67 32.65 706.86 14.03 375.76
20 199.70 2756.01 75.27 1401.94 29.68 736.55 12.20 387.97
444
Cumulative Cash Flow for Interest Rate =0%, 5%, 10% and 15%
$3,000
$2,500
Cumulative cash flow (in million RM)
$2,000
$1,500
$1,000
i=0%
$500 i=5%
i=10%
$0 i=15%
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
-$500
Years
Figure 7.2 Cumulative cash flow analysis for different interest rate
445
Table 7.52 and Figure 7.2 shows the cumulative cash flow trend at discounted
value of 0% interest rate and discounted values at 5%, 10% and 15% interest rates.
The payback periods is shorter with increasing interest rate. The payback periods for
interest rates from 0% to 15% are approximately 7 to 8 years after two years of start-
up period. The undiscounted cash flow with interest rate of 0% has the shorted payback
period. This is due to the reduction of cash flow performance for methanol production
plant due to inflation, rising of operating cost and falling of sales. This analysis shows
that the methanol production plant is still able to obtain revenue even with the highest
interest rate of 15%. Therefore, the methanol production plant is profitable and worth
for investment.
7.9 Conclusion
The profitability analysis for methanol production plant is summarized in

Table 7.53 as shown in below:
Table 7.53 Summary of profitability analysis
Aspect Value
Total Bare Module Investment, 𝐶𝐵𝑀 RM 45,700,494.96
Total Capital Investment, 𝐶𝑇𝐶𝐼 RM 207,590,232.10
Total Depreciable Capital, 𝐶𝑇𝐷𝐶 RM 171,129,647.77
Direct Wages and Benefits (DW&B) RM 3,072,000
Total Annual Production Cost RM 157,713,888
Total Annual Revenue RM 572,880,000
Annual Net Earnings RM 290,616,278.40
Return on Investment 140%
Payback Period Around 7 years
In conclusion, methanol production plant can generate RM 290,616,278.40 of

annual net earnings with payback period of 7 years and 140% of ROI along 20 years
of operation. Therefore, this project is worth for investment.
446
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Appendix A Material Safety Data Sheet (MSDS)
The material safety data sheets for all chemicals involved in methanol
production plant are attached for the use of Chemical Health Risk Assessment (CHRA)
in Chapter 6.
459
SAFETY DATA SHEET
BIOGASS (CBG KOMPRIMERT GASS)
Issue Date: 07.10.2015 Version: 1.1 SDS No.: 000010027930
Last revised date: 21.01.2020 1/16
SECTION 1: Identification of the substance/mixture and of the company/undertaking
1.1 Product identifier

Product name: BIOGASS (CBG KOMPRIMERT GASS)
Trade name: Biogas, compressed
1.2 Relevant identified uses of the substance or mixture and uses advised against
Identified uses: Industrial and professional. Perform risk assessment prior to use.
Fuel gas
Consumer use.
Fuel gas
Uses advised against Uses other than those listed above are not supported. Contact supplier for
more information on uses.
1.3 Details of the supplier of the safety data sheet

Supplier
Linde Gas AS Telephone: +4723177200
Postboks 13 Nydalen
N-0409 Oslo Norway
E-mail: sds.ren@linde.com
1.4 Emergency telephone number: +47 22 59 13 00 (24h - Giftinformasjonssentralen)
SECTION 2: Hazards identification
2.1 Classification of the substance or mixture
Classification according to Regulation (EC) No 1272/2008 as amended.

Physical Hazards
Flammable gas Category 1 H220: Extremely flammable gas.
Gases under pressure Compressed gas H280: Contains gas under pressure; may explode if
heated.
2.2 Label Elements
Signal Words: Danger
SDS_NO - 000010027930
SAFETY DATA SHEET
Hazard Statement(s): H220: Extremely flammable gas.

H280: Contains gas under pressure; may explode if heated.
Precautionary Statements
Prevention: P210: Keep away from heat, hot surfaces, sparks, open flames and other
ignition sources. No smoking.
Response: P377: Leaking gas fire: Do not extinguish, unless leak can be stopped safely.
P381: In case of leakage, eliminate all ignition sources.
Storage: P403: Store in a well-ventilated place.
Disposal: None.
2.3 Other hazards: None.
SECTION 3: Composition/information on ingredients
3.2 Mixtures
Chemical name Chemical Concentration CAS-No. EC No. REACH Registration Notes

formula No.
Tetrahydrothiophene C4H8S 10PPM 110-01-0 203-728-9 01-2119489799-07
Methane CH4 99,9990% 74-82-8 200-812-7 01-2119474442-39
The concentrations of the components in the SDS header, product name on page one and in section 3.2 are in mol due to regulatory requirements.
All concentrations are nominal.
# # This substance has workplace exposure limit(s).
PBT: persistent, bioaccumulative and toxic substance.
vPvB: very persistent and very bioaccumulative substance.
Classification
Chemical name Classification Notes
Tetrahydrothiophene CLP: Acute Tox. 4;H332, Acute Tox. 4;H302, Eye Irrit. 2;H319, Skin
Irrit. 2;H315, Aquatic Chronic 3;H412, Flam. Liq. 2;H225,
Acute Tox. 4;H312
Methane CLP: , Flam. Gas 1;H220, Press. Gas Compr. Gas;H280 Note U
CLP: Regulation No. 1272/2008.
Note U: When put on the market gases have to be classified as 'Gases under pressure', in one of the groups compressed gas,
liquefied gas, refrigerated liquefied gas or dissolved gas. The group depends on the physical state in which the gas is packaged and
therefore has to be assigned case by case.
The full text for all H-statements is displayed in section 16.
SDS_NO - 000010027930
SAFETY DATA SHEET
SECTION 4: First aid measures
General: In high concentrations may cause asphyxiation. Symptoms may include loss of
mobility/consciousness. Victim may not be aware of asphyxiation. Remove victim
to uncontaminated area wearing self contained breathing apparatus. Keep victim
warm and rested. Call a doctor. Apply artificial respiration if breathing stopped.
4.1 Description of first aid measures

Inhalation: In high concentrations may cause asphyxiation. Symptoms may include loss of
Eye contact: Adverse effects not expected from this product.
Skin Contact: Adverse effects not expected from this product.
Ingestion: Ingestion is not considered a potential route of exposure.
4.2 Most important symptoms and Respiratory arrest.

effects, both acute and
delayed:
4.3 Indication of any immediate medical attention and special treatment needed
Hazards: None.
Treatment: None.
SECTION 5: Firefighting measures
General Fire Hazards: Heat may cause the containers to explode.
5.1 Extinguishing media

Suitable extinguishing media: Water. Dry powder. Foam.
Unsuitable extinguishing Carbon Dioxide.

media:
5.2 Special hazards arising from the Incomplete combustion may form carbon monoxide
substance or mixture:
5.3 Advice for firefighters

Special fire fighting In case of fire: Stop leak if safe to do so. Do not extinguish flames at leak because
procedures: possibility of uncontrolled explosive reignition exists. Continue water spray from
protected position until container stays cool. Use extinguishants to contain the
fire. Isolate the source of the fire or let it burn out.
SDS_NO - 000010027930
SAFETY DATA SHEET
Special protective equipment Firefighters must use standard protective equipment including flame retardant
for fire-fighters: coat, helmet with face shield, gloves, rubber boots, and in enclosed spaces, SCBA.
Guideline: EN 469 Protective clothing for firefighters. Performance requirements
for protective clothing for firefighting. EN 15090 Footwear for firefighters. EN 659
Protective gloves for firefighters. EN 443 Helmets for fire fighting in buildings and
other structures. EN 137 Respiratory protective devices - Self-contained open-
circuit compressed air breathing apparatus with full face mask - Requirements,
testing, marking.
SECTION 6: Accidental release measures
6.1 Personal precautions, Evacuate area. Provide adequate ventilation. Consider the risk of potentially
protective equipment and explosive atmospheres . In case of leakage, eliminate all ignition sources. Monitor
emergency procedures: the concentration of the released product. Prevent from entering sewers,
basements and workpits, or any place where its accumulation can be dangerous.
Wear self-contained breathing apparatus when entering area unless atmosphere
is proved to be safe. EN 137 Respiratory protective devices - Self-contained open-
testing, marking.
6.2 Environmental Precautions: Prevent further leakage or spillage if safe to do so.
6.3 Methods and material for Provide adequate ventilation. Eliminate sources of ignition.
containment and cleaning up:
6.4 Reference to other sections: Refer to sections 8 and 13.
SDS_NO - 000010027930
SAFETY DATA SHEET
SECTION 7: Handling and storage:
7.1 Precautions for safe handling: Only experienced and properly instructed persons should handle gases under
pressure. Use only properly specified equipment which is suitable for this product,
its supply pressure and temperature. Purge system with dry inert gas (e.g. helium
or nitrogen) before gas is introduced and when system is placed out of service.
Purge air from system before introducing gas. Containers, which contain or have
contained flammable or explosive substances, must not be inerted with liquid
carbon dioxide. Assess the risk of a potentially explosive atmosphere and the
need for suitable equipment i.e. explosion-proof. Take precautionary measures
against static discharges. Keep away from ignition sources (including static
discharges). Provide electrical earthing of equipment and electrical equipment
usable in explosive atmospheres. Use non-sparking tools. Refer to supplier's
handling instructions. The substance must be handled in accordance with good
industrial hygiene and safety procedures. Ensure the complete system has been
(or is regularly) checked for leaks before use. Protect containers from physical
damage; do not drag, roll, slide or drop. Do not remove or deface labels provided
by the supplier for the identification of the container contents. When moving
containers, even for short distances, use appropriate equipment eg. trolley, hand
truck, fork truck etc. Secure cylinders in an upright position at all times, close all
valves when not in use. Provide adequate ventilation. Suck back of water into the
container must be prevented. Do not allow backfeed into the container. Avoid
suckback of water, acid and alkalis. Keep container below 50°C in a well
ventilated place. Observe all regulations and local requirements regarding storage
of containers. When using do not eat, drink or smoke. Store in accordance with… .
Never use direct flame or electrical heating devices to raise the pressure of a
container. Leave valve protection caps in place until the container has been
secured against either a wall or bench or placed in a container stand and is ready
for use. Damaged valves should be reported immediately to the supplier Close
container valve after each use and when empty, even if still connected to
equipment. Never attempt to repair or modify container valves or safety relief
devices. Replace valve outlet caps or plugs and container caps where supplied as
soon as container is disconnected from equipment. Keep container valve outlets
clean and free from contaminates particularly oil and water. If user experiences
any difficulty operating container valve discontinue use and contact supplier.
Never attempt to transfer gases from one container to another. Container valve
guards or caps should be in place.
7.2 Conditions for safe storage, All electrical equipment in the storage areas should be compatible with the risk of
including any incompatibilities: a potentially explosive atmosphere. Segregate from oxidant gases and other
oxidants being stored. Containers should not be stored in conditions likely to
encourage corrosion. Stored containers should be periodically checked for general
conditions and leakage. Container valve guards or caps should be in place. Store
containers in location free from fire risk and away from sources of heat and
ignition. Keep away from combustible material.
7.3 Specific end use(s): None.
SDS_NO - 000010027930
SAFETY DATA SHEET
SECTION 8: Exposure controls/personal protection
8.1 Control Parameters

Occupational Exposure Limits
None of the components have assigned exposure limits.
DNEL-Values
Critical component Type Value Remarks
Tetrahydrothiophene Workers - Inhalation, Local, 180 mg/m3 respiratory tract irritation
long-term
Workers - Dermal, Systemic, 7,5 mg/kg Repeated dose toxicity
long-term bw/day
Workers - Inhalation, 180 mg/m3 Repeated dose toxicity
Systemic, long-term
Workers - Inhalation, Local, 180 mg/m3 respiratory tract irritation
short-term
Workers - Eyes, Local effect Low hazard (no threshold derived)
PNEC-Values
Critical component Type Value Remarks
Tetrahydrothiophene Aquatic (freshwater) 0,024 mg/l -
Aquatic (marine water) 0,002 mg/l -
Sewage treatment plant 31 mg/l -
8.2 Exposure controls

Appropriate engineering Consider a work permit system e.g. for maintenance activities. Ensure adequate
controls: air ventilation. Provide adequate general and local exhaust ventilation. Keep
concentrations well below lower explosion limits. Gas detectors should be used
when quantities of flammable gases or vapours may be released. Provide
adequate ventilation, including appropriate local extraction, to ensure that the
defined occupational exposure limit is not exceeded. Systems under pressure
should be regularly checked for leakages. Product to be handled in a closed
system. Only use permanent leak tight installations (e.g. welded pipes). Take
precautionary measures against static discharges.
Individual protection measures, such as personal protective equipment
General information: A risk assessment should be conducted and documented in each work area to
assess the risks related to the use of the product and to select the PPE that
matches the relevant risk. The following recommendations should be considered.
Keep self contained breathing apparatus readily available for emergency use.
Personal protective equipment for the body should be selected based on the task
being performed and the risks involved. Refer to local regulations for restriction of
emissions to the atmosphere. See section 13 for specific methods for waste gas
treatment. Do not eat, drink or smoke when using the product.
SDS_NO - 000010027930
SAFETY DATA SHEET
Eye/face protection: Wear eye protection to EN 166 when using gases.

Guideline: EN 166 Personal Eye Protection.
Skin protection
Hand Protection: Wear working gloves while handling containers
Guideline: EN 388 Protective gloves against mechanical risks.
Body protection: Wear fire resistant or flame retardant clothing.

Guideline: ISO/TR 2801:2007 Clothing for protection against heat and flame --
General recommendations for selection, care and use of protective clothing.
Other: Wear safety shoes while handling containers

Guideline: ISO 20345 Personal protective equipment - Safety footwear.
Respiratory Protection: Wear air supplied respiratory protection. When allowed by a risk assessment
Respiratory Protective Equipment (RPE) may be used The selection of the
Respiratory Protective Device (RPD) must be based on known or anticipated
exposure levels, the hazards of the product and the safe working limits of the
selected RPD.
Guideline: EN 136 Respiratory protective devices. Full face masks. Requirements,
testing, marking.
Guideline: EN 137 Respiratory protective devices - Self-contained open-circuit
compressed air breathing apparatus with full face mask - Requirements, testing,
marking.
Thermal hazards: No precautionary measures are necessary.
Hygiene measures: Specific risk management measures are not required beyond good industrial
hygiene and safety procedures. Do not eat, drink or smoke when using the
product.
Environmental exposure For waste disposal, see section 13 of the SDS.

controls:
SECTION 9: Physical and chemical properties
9.1 Information on basic physical and chemical properties

Appearance
Physical state: Gas
Form: Compressed gas
Color: CH4: Colorless
C4H8S: Colorless
Odor: CH4: Odorless
C4H8S: Pungent
Odor Threshold: Odor threshold is subjective and is inadequate to warn of over
exposure.
pH: Not applicable.
SDS_NO - 000010027930
SAFETY DATA SHEET
Melting Point: -182,47 °C Experimental result, Key study

Boiling Point: -161,48 °C
Sublimation Point: Not applicable.
Critical Temp. (°C): -82,0 °C
Flash Point: Not applicable to gases and gas mixtures.
Evaporation Rate: Not applicable to gases and gas mixtures.
Flammability (solid, gas): Flammable Gas
Flammability Limit - Upper (%): 17 %(V)
Flammability Limit - Lower (%): 4,4 %(V)
Vapor pressure: No reliable data available.
Vapor density (air=1): 0,56 (calculated) (15 °C)
Relative density: 0,42 (25 °C )
Solubility(ies)
Solubility in Water: 22 mg/l (25 °C)
Partition coefficient (n-octanol/water): 1,09
Autoignition Temperature: 537 °C Experimental result, Key study
Decomposition Temperature: Not known.
Viscosity
Kinematic viscosity: No data available.
Dynamic viscosity: 0,011 mPa.s (27 °C)
Explosive properties: Not applicable.
Oxidizing properties: Not applicable.
9.2 Other information: None.
SECTION 10: Stability and reactivity
10.1 Reactivity: No reactivity hazard other than the effects described in sub-section below.
10.2 Chemical Stability: Stable under normal conditions.
10.3 Possibility of hazardous Can form a potentially explosive atmosphere in air. May react violently with
reactions: oxidants.
10.4 Conditions to avoid: Keep away from heat, hot surfaces, sparks, open flames and other ignition
sources. No smoking.
10.5 Incompatible Materials: Air and oxidizers. For material compatibility see latest version of ISO-11114.
10.6 Hazardous Decomposition Under normal conditions of storage and use, hazardous decomposition products
Products: should not be produced.
SDS_NO - 000010027930
SAFETY DATA SHEET
SECTION 11: Toxicological information
General information: None.
11.1 Information on toxicological effects
Acute toxicity - Oral

Product Based on available data, the classification criteria are not met.
Component Information
Tetrahydrothiophene LD 50 (Rat): 1.850 mg/kg Remarks: Experimental result, Key study
Acute toxicity - Dermal

Tetrahydrothiophene LD 0 (Rabbit): > 2.000 mg/kg Remarks: Experimental result, Key study
Acute toxicity - Inhalation

Tetrahydrothiophene LOAEL (Rat, 4 h): 3090 ppm Remarks: Vapor Experimental result, Key study
LC 50 (Rat, 4 h): 6270 ppm Remarks: Vapor Experimental result, Key study
Methane LC 50 (Rat, 10 min): > 800000 ppm Remarks: Inhalation Experimental result, Key
study
Repeated dose toxicity

Tetrahydrothiophene NOAEL (Rat(Female, Male), Inhalation, 13 Weeks): 1.442 ppm(m) Inhalation
Experimental result, Key study
NOAEL (Rat(Male), Dermal, 14 d): 450 mg/kg Dermal Experimental result, Not
specified
Methane NOAEL (Rat(Female, Male), Inhalation, 13 Weeks): 10.000 ppm(m) Inhalation
Read-across based on grouping of substances (category approach), Key study
Skin Corrosion/Irritation
SDS_NO - 000010027930
SAFETY DATA SHEET
Tetrahydrothiophene in vivo (Rabbit): Category 2 Experimental result, Key study
Serious Eye Damage/Eye Irritation

Respiratory or Skin Sensitization

Germ Cell Mutagenicity

In vitro
Methane Chromosome aberration (OECD Guideline 473 (In Vitro Mammalian Chromosome
Aberration Test)): Negative.
In vivo
Methane Drosophila Sex-Linked Recessive Lethal Assay (SLRL) test: Negative.
Carcinogenicity
Reproductive toxicity
Reproductive toxicity (Fertility)

Methane Gestation: Rat Inhalation (OECD Guideline 422 (Combined Repeated Dose Toxicity
Study with the Reproduction / Developmental Toxicity Screening Test))
NOAEC: 9.000 ppm
Fertility: Rat Inhalation (OECD Guideline 422 (Combined Repeated Dose Toxicity
Study with the Reproduction / Developmental Toxicity Screening Test))
NOAEC: 3.000 ppm
Developmental toxicity (Teratogenicity)

Methane Rat Inhalation (OECD Guideline 422 (Combined Repeated Dose Toxicity Study
with the Reproduction / Developmental Toxicity Screening Test))
NOAEC: 9.000 ppm
SDS_NO - 000010027930
SAFETY DATA SHEET
Specific Target Organ Toxicity - Single Exposure

Specific Target Organ Toxicity - Repeated Exposure

Aspiration Hazard
Product Not applicable to gases and gas mixtures..
SECTION 12: Ecological information
12.1 Toxicity
Acute toxicity
Product No ecological damage caused by this product.
Acute toxicity - Fish

Tetrahydrothiophene NOAEL (Danio rerio, 96 h): > 24 mg/l (Static) Remarks: Experimental result, Key
study
Methane LC 50 (Various, 96 h): 49,9 mg/l (QSAR) Remarks: QSAR QSAR, Key study
Acute toxicity - Aquatic Invertebrates

Tetrahydrothiophene EC 50 (Daphnia magna, 24 h): 66 mg/l (Static) Remarks: Experimental result, Key
study
Methane LC 50 (Daphnia sp., 48 h): 69,43 mg/l Remarks: QSAR QSAR, Key study
Toxicity to microorganisms
Methane EC 50 (Alga, 96 h): 19,37 mg/l Not harmful to microorganisms
12.2 Persistence and Degradability

Biodegradation
Tetrahydrothiophene < 10 % (28 d) Detected in water. Experimental result, Key study
Methane 100 % (385,5 h) Detected in water. Experimental result, Key study
SDS_NO - 000010027930
SAFETY DATA SHEET
12.3 Bioaccumulative potential

Product The subject product is expected to biodegrade and is not expected to persist for
long periods in an aquatic environment.
12.4 Mobility in soil

Product Because of its high volatility, the product is unlikely to cause ground or water
pollution.
Methane Henry's Law Constant: 3.690 MPa (25 °C)
12.5 Results of PBT and vPvB

assessment
Product Not classified as PBT or vPvB.
12.6 Other adverse effects:
Global Warming Potential

Global warming potential: 25
Contains greenhouse gas(es). When discharged in large quantities may contribute
to the greenhouse effect.
Methane EU. Non-Fluorinated Substance GWPs (Annex IV), Regulation 517/2014/EU on
fluorinated greenhouse gases
- Global warming potential: 25
SECTION 13: Disposal considerations
13.1 Waste treatment methods
General information: Do not discharge into any place where its accumulation could be dangerous.
Consult supplier for specific recommendations. Do not discharge into areas where
there is a risk of forming an explosive mixture with air. Waste gas should be flared
through a suitable burner with flash back arrestor.
Disposal methods: Refer to the EIGA code of practice (Doc.30 "Disposal of Gases", downloadable at
http://www.eiga.org) for more guidance on suitable disposal methods. Dispose
of container via supplier only. Discharge, treatment, or disposal may be subject to
national, state, or local laws.
European Waste Codes

Container: 16 05 04*: Gases in pressure containers (including halons) containing
dangerous substances.
SDS_NO - 000010027930
SAFETY DATA SHEET
SECTION 14: Transport information
ADR
14.1 UN Number: UN 1971
14.2 UN Proper Shipping Name: NATURAL GAS, COMPRESSED
14.3 Transport Hazard Class(es)
Class: 2
Label(s): 2.1
Hazard No. (ADR): 23
Tunnel restriction code: (B/D)
14.4 Packing Group: –
14.5 Environmental hazards: Not applicable
14.6 Special precautions for user: –
RID

14.2 UN Proper Shipping Name NATURAL GAS, COMPRESSED
Class: 2
Label(s): 2.1
IMDG
14.2 UN Proper Shipping Name: NATURAL GAS, COMPRESSED
Class: 2.1
Label(s): 2.1
EmS No.: F-D, S-U
SDS_NO - 000010027930
SAFETY DATA SHEET
IATA

14.2 Proper Shipping Name: Natural gas, compressed
14.3 Transport Hazard Class(es):
Class: 2.1
Label(s): 2.1
Other information
Passenger and cargo aircraft: Forbidden.
Cargo aircraft only: Allowed.
14.7 Transport in bulk according to Annex II of MARPOL and the IBC Code: Not applicable
Additional identification: Avoid transport on vehicles where the load space is not separated from
the driver's compartment. Ensure vehicle driver is aware of the potential
hazards of the load and knows what to do in the event of an accident or
an emergency. Before transporting product containers ensure that they
are firmly secured. Ensure that the container valve is closed and not
leaking. Container valve guards or caps should be in place. Ensure
adequate air ventilation.
SECTION 15: Regulatory information
15.1 Safety, health and environmental regulations/legislation specific for the substance or mixture:
EU Regulations
Regulation (EC) No. 1907/2006 Annex XVII Substances subject to restriction on marketing and use:
Chemical name CAS-No. Concentration

Tetrahydrothiophene 110-01-0 - <0,1%
Methane 74-82-8 90 - 100%
EU. Directive 2012/18/EU (SEVESO III) on major accident hazards involving dangerous substances, as amended.:
Classification Lower-tier Upper-tier
Requirements Requirements
P2. Flammable gas 10 t 50 t
Directive 98/24/EC on the protection of workers from the risks related to chemical agents at work:
SDS_NO - 000010027930
SAFETY DATA SHEET

Methane 74-82-8 90 - 100%
Tetrahydrothiophene 110-01-0 0 - <0,1%
National Regulations
Council Directive 89/391/EEC on the introduction of measures to encourage

improvements in the safety and health of workers at work Directive 89/686/EEC on
personal protective equipment Directive 94/9/EC on equipment and protective
systems intended for use in potentially explosive atmospheres (ATEX) Only products
that comply with the food regulations (EC) No. 1333/2008 and (EU) No. 231/2012
and are labelled as such may be used as food additives.
This Safety Data Sheet has been produced to comply with Regulation (EU) 2015/830.
15.2 Chemical safety assessment: No Chemical Safety Assessment has been carried out.
SECTION 16: Other information
Revision Information: Not relevant.
Key literature references and Various sources of data have been used in the compilation of this SDS, they include
sources for data: but are not exclusive to:
Agency for Toxic Substances and Diseases Registry (ATSDR)
(http://www.atsdr.cdc.gov/).
European Chemical Agency: Guidance on the Compilation of Safety Data Sheets.
European Chemical Agency: Information on Registered Substances
http://apps.echa.europa.eu/registered/registered-sub.aspx#search
European Industrial Gases Association (EIGA) Doc. 169 Classification and Labelling
guide.
International Programme on Chemical Safety (http://www.inchem.org/)
ISO 10156:2010 Gases and gas mixtures - Determination of fire potential and
oxidizing ability for the selection of cylinder valve outlets.
Matheson Gas Data Book, 7th Edition.
National Institute for Standards and Technology (NIST) Standard Reference Database
Number 69.
The ESIS (European chemical Substances 5 Information System) platform of the
former European Chemicals Bureau (ECB) ESIS (http://ecb.jrc.ec.europa.eu/esis/).
The European Chemical Industry Council (CEFIC) ERICards.
United States of America’s National Library of Medicine’s toxicology data network
TOXNET (http://toxnet.nlm.nih.gov/index.html)
Threshold Limit Values (TLV) from the American Conference of Governmental
Industrial Hygienists (ACGIH).
Substance specific information from suppliers.
Details given in this document are believed to be correct at the time of publication.
Classification and procedure used to derive the classification for mixtures according to Regulation (EC) 1272/2008 [CLP]
SDS_NO - 000010027930
SAFETY DATA SHEET
Classification according to Regulation (EC) No Classification procedure

1272/2008 as amended.
Flammable gas, Category 1 On basis of test data
Gases under pressure, Compressed gas On basis of test data
Wording of the H-statements in section 2 and 3

H220 Extremely flammable gas.
H280 Contains gas under pressure; may explode if heated.

Flam. Gas 1, H220
Press. Gas Compr. Gas, H280
Other information: Before using this product in any new process or experiment, a thorough material
compatibility and safety study should be carried out. Ensure adequate air ventilation.
Ensure all national/local regulations are observed. Ensure equipment is adequately
earthed. Whilst proper care has been taken in the preparation of this document, no
liability for injury or damage resulting from its use can be accepted.
Last revised date: 21.01.2020

Disclaimer: This information is provided without warranty. The information is believed to be
correct. This information should be used to make an independent determination of
the methods to safeguard workers and the environment.
SDS_NO - 000010027930
SAFETY DATA SHEET Version 6.2
Revision Date 18.04.2021
Print Date 11.06.2022
SECTION 1: Identification of the hazardous chemical and of the supplier

1.1 Product identifiers
Product name : Carbon dioxide
Product Number : 295108

Brand : Aldrich
CAS-No. : 124-38-9
1.2 Other means of identification
No data available
Identified uses : For R&D use only. Not for pharmaceutical, household or other
uses.
Company : SIGMA-ALDRICH (M) SDN BHD
Level 3, Menara Sunway Annexe,
Jalan Lagoon Timur, Bandar Sunway,
46150 PETALING JAYA, SELANGOR
MALAYSIA
Telephone : +60 (603)03-563-53321
Fax : +60 (603)03-563-54116
1.5 Emergency telephone
Emergency Phone # : 1-800-815-308 (CHEMTREC) * + 62 0800
140 1253 (Customer Call Centre)
Section 2: Hazard identification

2.1 GHS Classification
Classification according to CLASS regulations 2013
Gases under pressure (Liquefied gas), H280
For the full text of the H-Statements mentioned in this Section, see Section 16.
2.2 GHS Label elements, including precautionary statements
Labelling according to CLASS regulations 2013
Pictogram
Signal word Warning

Hazard statement(s)
Aldrich- 295108 Page 1 of 8
The life science business of Merck operates as MilliporeSigma in

the US and Canada
Precautionary statement(s)
Storage
P410 + P403 Protect from sunlight. Store in a well-ventilated place.
2.3 Other hazards - none
SECTION 3: Composition and information of the ingredients of the hazardous chemical

Substance / Mixture : Substance
3.1 Substances
Formula : CO2
Molecular weight : 44.01 g/mol
CAS-No. : 124-38-9
EC-No. : 204-696-9
Hazardous ingredients
Component Classification Concentration
carbon dioxide
Press. Gas Liquefied gas; <= 100 %
H280

4.1 Description of first-aid measures
General advice
Consult a physician. Show this material safety data sheet to the doctor in attendance.
If inhaled
If breathed in, move person into fresh air. If not breathing, give artificial respiration.
Consult a physician.
In case of skin contact
Wash off with soap and plenty of water. Consult a physician.
In case of eye contact
Flush eyes with water as a precaution.
If swallowed
Never give anything by mouth to an unconscious person. Rinse mouth with water. Consult
a physician.
4.2 Most important symptoms and effects, both acute and delayed
The most important known symptoms and effects are described in the labelling (see section
2.2) and/or in section 11
No data available

Suitable extinguishing media
Use water spray, alcohol-resistant foam, dry chemical or carbon dioxide.

the US and Canada
5.2 Special hazards arising from the substance or mixture
Carbon oxides
Wear self-contained breathing apparatus for firefighting if necessary.
5.4 Further information
Use water spray to cool unopened containers.

6.1 Personal precautions, protective equipment and emergency procedures
Avoid breathing vapors, mist or gas. Ensure adequate ventilation. Evacuate personnel to
safe areas.
For personal protection see section 8.
6.2 Environmental precautions
Do not let product enter drains.
6.3 Methods and materials for containment and cleaning up
Clean up promptly by sweeping or vacuum.
6.4 Reference to other sections
For disposal see section 13.
SECTION 7: Handling and storage

7.1 Precautions for safe handling
For precautions see section 2.2.
7.2 Conditions for safe storage, including any incompatibilities
Storage conditions
Store in cool place. Keep container tightly closed in a dry and well-ventilated place.
Contents under pressure. Avoid heating above: 50°C
7.3 Specific end use(s)
Apart from the uses mentioned in section 1.2 no other specific uses are stipulated
SECTION 8: Exposure controls and personal protection

8.1 Control parameters
Ingredients with workplace control parameters
Component CAS-No. Value Control Basis
parameters
carbon dioxide 124-38-9 TWA 5,000 ppm Malaysia. Occupational Safety
9,000 mg/m3 and Health (Use and Standards
of Exposure of Chemicals
Hazardous to Health)
Regulations 2000.
Appropriate engineering controls
Handle in accordance with good industrial hygiene and safety practice. Wash hands
before breaks and at the end of workday.

the US and Canada
Personal protective equipment
Eye/face protection
Use equipment for eye protection tested and approved under appropriate
government standards such as NIOSH (US) or EN 166(EU).
Skin protection
Handle with gloves. Gloves must be inspected prior to use. Use proper glove
removal technique (without touching glove's outer surface) to avoid skin contact
with this product. Dispose of contaminated gloves after use in accordance with
applicable laws and good laboratory practices. Wash and dry hands.
The selected protective gloves have to satisfy the specifications of Regulation (EU)
2016/425 and the standard EN 374 derived from it.
Full contact
Material: butyl-rubber
Minimum layer thickness: 0.3 mm
Break through time: 480 min
Material tested:Butoject® (KCL 897 / Aldrich Z677647, Size M)
Splash contact
Material: Chloroprene
Material tested:Camapren® (KCL 722 / Aldrich Z677493, Size M)
data source: KCL GmbH, D-36124 Eichenzell, phone +49 (0)6659 87300, e-mail
sales@kcl.de, test method: EN374
If used in solution, or mixed with other substances, and under conditions which
differ from EN 374, contact the supplier of the EC approved gloves. This
recommendation is advisory only and must be evaluated by an industrial hygienist
and safety officer familiar with the specific situation of anticipated use by our
customers. It should not be construed as offering an approval for any specific use
scenario.
Body Protection
Impervious clothing, The type of protective equipment must be selected according
to the concentration and amount of the dangerous substance at the specific
workplace.
Respiratory protection
Where risk assessment shows air-purifying respirators are appropriate use a full-
face respirator with multi-purpose combination (US) or type AXBEK (EN 14387)
respirator cartridges as a backup to engineering controls. If the respirator is the sole
means of protection, use a full-face supplied air respirator. Use respirators and
components tested and approved under appropriate government standards such as
NIOSH (US) or CEN (EU).
Control of environmental exposure
Do not let product enter drains.

a) Appearance Form: Liquefied gas
b) Odor No data available

the US and Canada
c) Odor Threshold No data available
d) pH No data available
e) Melting Melting point/range: -78.5 °C - lit.
point/freezing point
f) Initial boiling point No data available
and boiling range
g) Flash point Not applicable
h) Evaporation rate No data available
i) Flammability (solid, No data available
gas)
j) Upper/lower No data available
flammability or
explosive limits
k) Vapor pressure 57,249 hPa at 20 °C
l) Vapor density 1.52 - (Air = 1.0)
m) Relative density No data available
n) Water solubility No data available
o) Partition coefficient: No data available
n-octanol/water
p) Autoignition No data available
temperature
q) Decomposition No data available
temperature
r) Viscosity Viscosity, kinematic: No data available
Viscosity, dynamic: No data available
s) Explosive properties No data available
t) Oxidizing properties No data available
9.2 Other safety information
Relative vapor 1.52 - (Air = 1.0)
density

10.1 Reactivity
No data available
10.2 Chemical stability
Stable under recommended storage conditions.
10.3 Possibility of hazardous reactions
No data available
10.4 Conditions to avoid
No data available
10.5 Incompatible materials
No data available

the US and Canada
10.6 Hazardous decomposition products
In the event of fire: see section 5

Acute toxicity
No data available
Skin corrosion/irritation
No data available
Serious eye damage/eye irritation
No data available
Respiratory or skin sensitization
No data available
Germ cell mutagenicity

No data available
Carcinogenicity
No data available
No data available
Specific target organ toxicity - single exposure

No data available
Specific target organ toxicity - repeated exposure
No data available
Aspiration hazard
No data available
11.2 Additional Information

RTECS: FF6400000
Nausea, Dizziness, Headache, Low to medium concentrations of carbon dioxide can:, affect
regulation of blood circulation, affect the acidity of body fluids, respiratory difficulties, At
high concentrations:, Breathing difficulties, Increased pulse rate, change in body acidity,
Very high concentrations can cause:, Unconsciousness, death
To the best of our knowledge, the chemical, physical, and toxicological properties have not
been thoroughly investigated.

12.1 Toxicity
No data available

the US and Canada
12.2 Persistence and degradability
No data available
No data available
No data available
12.5 Results of PBT and vPvB assessment
PBT/vPvB assessment not available as chemical safety assessment not required/not
conducted
12.6 Other adverse effects
No data available
SECTION 13: Disposal information

Product
Offer surplus and non-recyclable solutions to a licensed disposal company.
Contaminated packaging
Dispose of as unused product.
SECTION 14: Transportation information

14.1 UN number
ADR/RID: 1013 IMDG: 1013 IATA-DGR: 1013
14.2 UN proper shipping name
ADR/RID: CARBON DIOXIDE
IMDG: CARBON DIOXIDE
IATA-DGR: Carbon dioxide
14.3 Transport hazard class(es)
ADR/RID: 2.2 IMDG: 2.2 IATA-DGR: 2.2
14.4 Packaging group
ADR/RID: - IMDG: - IATA-DGR: -
14.5 Environmental hazards
ADR/RID: no IMDG Marine pollutant: no IATA-DGR: no
14.6 Special precautions for user
None
Other regulations
Hazchem Code : 2T

15.1 Safety, health and environmental regulations/legislation specific for the
substance or mixture
Notification status
AICS: On the inventory, or in compliance with the inventory

the US and Canada
DSL: All components of this product are on the Canadian DSL
ENCS: On the inventory, or in compliance with the inventory
ISHL: On the inventory, or in compliance with the inventory
KECI: On the inventory, or in compliance with the inventory
NZIoC: On the inventory, or in compliance with the inventory
PICCS: On the inventory, or in compliance with the inventory

Full text of H-Statements referred to under sections 2 and 3.
Further information
Copyright 2020 Sigma-Aldrich Co. LLC. License granted to make unlimited paper copies
for internal use only.
The above information is believed to be correct but does not purport to be all inclusive
and shall be used only as a guide. The information in this document is based on the
present state of our knowledge and is applicable to the product with regard to
appropriate safety precautions. It does not represent any guarantee of the properties of
the product. Sigma-Aldrich Corporation and its Affiliates shall not be held liable for any
damage resulting from handling or from contact with the above product. See
www.sigma-aldrich.com and/or the reverse side of invoice or packing slip for additional
terms and conditions of sale.
The branding on the header and/or footer of this document may temporarily not visually
match the product purchased as we transition our branding. However, all of the
information in the document regarding the product remains unchanged and matches the
product ordered. For further information please contact mlsbranding@sial.com.

the US and Canada
Page : 1/15
Revised edition no : 4.0
SAFETY DATA SHEET Revision date : 2021-06-22
Supersedes : 2020-07-15
NOAL_0019
Carbon monoxide Country : NO / Language : EN
1.1. Product identifier

Trade name : Carbon monoxide, Carbon monoxide N20, Kulilte, Carbon monoxide N47, Carbon monoxide
N23
SDS no : NOAL_0019
Chemical description : Carbon monoxide
CAS-No. : 630-08-0
EC-No. : 211-128-3
EC Index-No. : 006-001-00-2
Registration-No. : 01-2119480165-39
Chemical formula : CO
1.2. Relevant identified uses of the substance or mixture and uses advised against
Relevant identified uses : Industrial and professional uses. Perform risk assessment prior to use.
See the list of identified uses and exposure scenarios in the annex of the safety data sheet.
Contact supplier for more information on uses.
Uses advised against : Consumer use.
1.3. Details of the supplier of the safety data sheet

Company identification
AIR LIQUIDE NORWAY AS

Drammensveien 64 B
3050 Mjøndalen - NORWAY
T + 47 32 27 41 40
eunordic-sds@airliquide.com
E-Mail address (competent person) : eunordic-sds@airliquide.com
1.4. Emergency telephone number

Emergency telephone number : 112 / Giftinformasjon: + 47 22 59 13 00
Availability
(24 / 7)
2.1. Classification of the substance or mixture

Classification according to Regulation (EC) No. 1272/2008 [CLP]
Physical hazards Flammable gases, Category 1 H220
Gases under pressure : Compressed gas H280
Health hazards Acute toxicity (inhalation:gas) Category 3 H331
Reproductive toxicity, Category 1A H360D
Specific target organ toxicity — Repeated exposure, H372
Category 1
2.2. Label elements

Labelling according to Regulation (EC) No. 1272/2008 [CLP]
Hazard pictograms (CLP) :
SDS-Format HG2020002
GHS02 GHS04 GHS06 GHS08

Signal word (CLP) : Danger
Hazard statements (CLP) : H220 - Extremely flammable gas.
AIR LIQUIDE NORWAY AS Country : NORWAY (NO) Language : English (EN)

Drammensveien 64 B
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NOAL_0019
H280 - Contains gas under pressure; may explode if heated.

H331 - Toxic if inhaled.
H360D - May damage the unborn child.
H372 - Causes damage to organs through prolonged or repeated exposure.
Precautionary statements (CLP)

- Prevention : P202 - Do not handle until all safety precautions have been read and understood.
P260 - Do not breathe gas, vapours.
P210 - Keep away from heat, hot surfaces, sparks, open flames and other ignition sources. No
smoking.
- Response : P308+P313 - IF exposed or concerned: Get medical advice.
P304+P340+P315 - IF INHALED : Remove person to fresh air and keep comfortable for
breathing. Get immediate medical advice.
P377 - Leaking gas fire: Do not extinguish, unless leak can be stopped safely.
P381 - In case of leakage, eliminate all ignition sources.
- Storage : P405 - Store locked up.
P403 - Store in a well-ventilated place.
Supplemental information : Restricted to professional users.
2.3. Other hazards

: None.
3.1. Substances
Name Product identifier Composition [V-%]: Classification according to
Regulation (EC) No. 1272/2008 [CLP]
Carbon monoxide (CAS-No.) 630-08-0 100 Flam. Gas 1, H220
(EC-No.) 211-128-3 Press. Gas (Comp.), H280
(EC Index-No.) 006-001-00-2 Acute Tox. 3 (Inhalation:gas), H331
(Registration-No.) 01-2119480165-39 Repr. 1A, H360D
STOT RE 1, H372
Contains no other components or impurities which will influence the classification of the product.
3.2. Mixtures : Not applicable.
4.1. Description of first aid measures
- Inhalation : Remove victim to uncontaminated area wearing self contained breathing apparatus. Keep
victim warm and rested. Call a doctor. Perform cardiopulmonary resuscitation if breathing
stopped.
Provide oxygen.
- Skin contact : Adverse effects not expected from this product.
- Eye contact : Adverse effects not expected from this product.
- Ingestion : Ingestion is not considered a potential route of exposure.
4.2. Most important symptoms and effects, both acute and delayed
: Symptoms may include dizziness, headache, nausea and loss of co-ordination.
Delayed adverse effects possible.
Refer to section 11.
4.3. Indication of any immediate medical attention and special treatment needed
: Obtain medical assistance.

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NOAL_0019
5.1. Extinguishing media

- Suitable extinguishing media : Water spray or fog.
Dry powder.
- Unsuitable extinguishing media : Carbon dioxide.
Do not use water jet to extinguish.
5.2. Special hazards arising from the substance or mixture
Specific hazards : Exposure to fire may cause containers to rupture/explode.
Hazardous combustion products : None that are more hazardous than the product itself.
5.3. Advice for firefighters
Specific methods : Use fire control measures appropriate for the surrounding fire. Exposure to fire and heat
radiation may cause gas receptacles to rupture. Cool endangered receptacles with water spray
jet from a protected position. Prevent water used in emergency cases from entering sewers and
drainage systems.
If possible, stop flow of product.
Use water spray or fog to knock down fire fumes if possible.
Do not extinguish a leaking gas flame unless absolutely necessary. Spontaneous/explosive re-
ignition may occur. Extinguish any other fire.
Move containers away from the fire area if this can be done without risk.
Special protective equipment for fire fighters : Wear gas tight chemically protective clothing in combination with self contained breathing
apparatus.
Standard EN 943-2: Protective clothing against liquid and gaseous chemicals, aerosols and
solid particles. Gas-tight chemical protective suits for emergency teams.
Standard EN 137 - Self-contained open-circuit compressed air breathing apparatus with full
face mask.
6.1. Personal precautions, protective equipment and emergency procedures

: Try to stop release.
Evacuate area.
Monitor concentration of released product.
Consider the risk of potentially explosive atmospheres.
Wear self-contained breathing apparatus when entering area unless atmosphere is proved to
be safe.
Eliminate ignition sources.
Ensure adequate air ventilation.
Act in accordance with local emergency plan.
Stay upwind.
6.2. Environmental precautions
: Try to stop release.

6.3. Methods and material for containment and cleaning up
: Ventilate area.
6.4. Reference to other sections
: See also sections 8 and 13.
7.1. Precautions for safe handling

Safe use of the product : Do not breathe gas.

Drammensveien 64 B
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NOAL_0019
Avoid release of product into atmosphere.

The product must be handled in accordance with good industrial hygiene and safety
procedures.
Only experienced and properly instructed persons should handle gases under pressure.
Consider pressure relief device(s) in gas installations.
Ensure the complete gas system was (or is regularily) checked for leaks before use.
Do not smoke while handling product.
Avoid exposure, obtain special instructions before use.
Use only properly specified equipment which is suitable for this product, its supply pressure and
temperature. Contact your gas supplier if in doubt.
Installation of a cross purge assembly between the container and the regulator is
recommended.
Avoid suck back of water, acid and alkalis.
Assess the risk of potentially explosive atmospheres and the need for explosion-proof
equipment.
Purge air from system before introducing gas.
Take precautionary measures against static discharge.
Keep away from ignition sources (including static discharges).
Consider the use of only non-sparking tools.
Ensure equipment is adequately earthed.
Safe handling of the gas receptacle : Refer to supplier's container handling instructions.
Do not allow backfeed into the container.
Protect containers from physical damage; do not drag, roll, slide or drop.
When moving cylinders, even for short distances, use a cart (trolley, hand truck, etc.) designed
to transport cylinders.
Leave valve protection caps in place until the container has been secured against either a wall
or bench or placed in a container stand and is ready for use.
If user experiences any difficulty operating valve discontinue use and contact supplier.
Never attempt to repair or modify container valves or safety relief devices.
Damaged valves should be reported immediately to the supplier.
Keep container valve outlets clean and free from contaminants particularly oil and water.
Replace valve outlet caps or plugs and container caps where supplied as soon as container is
disconnected from equipment.
Close container valve after each use and when empty, even if still connected to equipment.
Never attempt to transfer gases from one cylinder/container to another.
Never use direct flame or electrical heating devices to raise the pressure of a container.
Do not remove or deface labels provided by the supplier for the identification of the content of
the container.
Suck back of water into the container must be prevented.
Open valve slowly to avoid pressure shock.
7.2. Conditions for safe storage, including any incompatibilities
: Observe all regulations and local requirements regarding storage of containers.
Containers should not be stored in conditions likely to encourage corrosion.
Container valve guards or caps should be in place.
Containers should be stored in the vertical position and properly secured to prevent them from
falling over.
Stored containers should be periodically checked for general condition and leakage.
Keep container below 50°C in a well ventilated place.
Store containers in location free from fire risk and away from sources of heat and ignition.
Keep away from combustible materials.
Segregate from oxidant gases and other oxidants in store.
All electrical equipment in the storage areas should be compatible with the risk of a potentially
explosive atmosphere.
7.3. Specific end use(s)
: None.

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NOAL_0019
SECTION 8: Exposure controls/personal protection
8.1. Control parameters
Carbon monoxide (630-08-0)

EU - Occupational Exposure Limits
Local name Carbon monoxide
IOELV TWA (mg/m³) 23 mg/m³
IOELV TWA (ppm) 20 ppm
IOELV STEL (mg/m³) 117 mg/m³
IOELV STEL (ppm) 100 ppm
Notes SCOEL Recommendations (1995)
Norway - Occupational Exposure Limits
Local name Karbonmonoksid
Grenseverdier (AN) (mg/m³) 29 mg/m³
Grenseverdier (AN) (ppm) 25 ppm
EU - Occupational Exposure Limits
Local name Carbon monoxide
IOELV TWA (mg/m³) 23 mg/m³
IOELV TWA (ppm) 20 ppm
IOELV STEL (mg/m³) 117 mg/m³
IOELV STEL (ppm) 100 ppm
Notes SCOEL Recommendations (1995)
Norway - Occupational Exposure Limits
Local name Karbonmonoksid
Grenseverdier (AN) (mg/m³) 29 mg/m³
Grenseverdier (AN) (ppm) 25 ppm

DNEL: Derived no effect level (Workers)
Acute - local effects, inhalation 100 ppm
Acute - systemic effects, inhalation 100 ppm
Long-term - local effects, inhalation 20 ppm
Long-term - systemic effects, inhalation 20 ppm
DNEL: Derived no effect level (Workers)
Acute - local effects, inhalation 100 ppm
Acute - systemic effects, inhalation 100 ppm
Long-term - local effects, inhalation 20 ppm
Long-term - systemic effects, inhalation 20 ppm
PNEC (Predicted No-Effect Concentration) : None established.
8.2. Exposure controls
8.2.1. Appropriate engineering controls

: Product to be handled in a closed system and under strictly controlled conditions.
Provide adequate general and local exhaust ventilation.
Preferably use permanent leak-tight installations (e.g. welded pipes).
Systems under pressure should be regularily checked for leakages.
Ensure exposure is below occupational exposure limits (where available).
Gas detectors should be used when toxic gases may be released.
Consider the use of a work permit system e.g. for maintenance activities.
8.2.2. Individual protection measures, e.g. personal protective equipment

: A risk assessment should be conducted and documented in each work area to assess the risks
related to the use of the product and to select the PPE that matches the relevant risk. The
following recommendations should be considered:
PPE compliant to the recommended EN/ISO standards should be selected.
• Eye/face protection : Wear safety glasses with side shields.

Standard EN 166 - Personal eye-protection - specifications.
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• Skin protection
- Hand protection : Wear working gloves when handling gas containers.
Standard EN 388 - Protective gloves against mechanical risk.
- Other : Consider the use of flame resistant anti-static safety clothing.
Standard EN ISO 14116 - Limited flame spread materials.
Standard EN 1149-5 - Protective clothing: Electrostatic properties.
Wear safety shoes while handling containers.
Standard EN ISO 20345 - Personal protective equipment - Safety footwear.
• Respiratory protection : Never use any kind of filtering respiratory protection equipment when working with this
substance due to it having poor or no warning properties.
Self contained breathing apparatus is recommended, where unknown exposure may be
expected, e.g. during maintenance activities on installation systems.
Standard EN 137 - Self-contained open-circuit compressed air breathing apparatus with full
face mask.
• Thermal hazards : None in addition to the above sections.
8.2.3. Environmental exposure controls

: Refer to local regulations for restriction of emissions to the atmosphere. See section 13 for
specific methods for waste gas treatment.
9.1. Information on basic physical and chemical properties

Appearance
 Physical state at 20°C / 101.3kPa : Gas
 Colour : Colourless.
Odour : Odourless.
Odour threshold : Odour threshold is subjective and inadequate to warn of overexposure.
pH : Not applicable for gases and gas mixtures.
Melting point / Freezing point : -205 °C
Boiling point : -192 °C
Flash point : Not applicable for gases and gas mixtures.
Evaporation rate : Not applicable for gases and gas mixtures.
Flammability (solid, gas) : Extremely flammable gas
Explosive limits : 10.9 - 76 vol %
Vapour pressure [20°C] : Not applicable.
Vapour pressure [50°C] : Not applicable.
Vapour density : Not applicable.
Relative density, liquid (water=1) : 0.79
Relative density, gas (air=1) : 1
Water solubility : 30 mg/l
Partition coefficient n-octanol/water (Log Kow) : 1.78
Auto-ignition temperature : 605 °C
Decomposition temperature : Not applicable.
Viscosity : No reliable data available.
Explosive properties : Not applicable.
Oxidising properties : Not applicable.
9.2. Other information

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Molar mass : 28 g/mol

Critical temperature [°C] : -140 °C
10.1. Reactivity
: No reactivity hazard other than the effects described in sub-sections below.
10.2. Chemical stability

: Stable under normal conditions.
10.3. Possibility of hazardous reactions

: Can form explosive mixture with air.
May react violently with oxidants.
10.4. Conditions to avoid

: Keep away from heat/sparks/open flames/hot surfaces. – No smoking.
Avoid moisture in installation systems.
10.5. Incompatible materials

: Air, Oxidisers.
For additional information on compatibility refer to ISO 11114.
See also 'EIGA Doc.95: Avoidance of Failure of CO and of CO/CO2 Mixtures Cylinders' at
www.eiga.eu.
10.6. Hazardous decomposition products

: Under normal conditions of storage and use, hazardous decomposition products should not be
produced.
11.1. Information on toxicological effects

Acute toxicity : Toxic if inhaled.
LC50 Inhalation - Rat [ppm] 3760 ppm/1h

1300 ppm/4h
LC50 Inhalation - Rat [ppm] 3760 ppm/1h
1300 ppm/4h
Skin corrosion/irritation : No known effects from this product.
Serious eye damage/irritation : No known effects from this product.
Respiratory or skin sensitisation : No known effects from this product.
Germ cell mutagenicity : No known effects from this product.
Carcinogenicity : No known effects from this product.
Reproductive toxicity :
Toxic for reproduction : Fertility : No known effects from this product.
Toxic for reproduction : unborn child : May damage the unborn child.
STOT-single exposure : Suppresses the oxygen uptake by red blood cells.
Target organ(s) : Blood.
STOT-repeated exposure : Causes damage to organs through prolonged or repeated exposure.
Target organ(s) : heart.
Aspiration hazard : Not applicable for gases and gas mixtures.

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12.1. Toxicity
Assessment : No ecological damage caused by this product.
EC50 48h - Daphnia magna [mg/l] : Study scientifically unjustified.

EC50 72h - Algae [mg/l] : Study scientifically unjustified.
LC50 96 h - Fish [mg/l] : Study scientifically unjustified.
EC50 48h - Daphnia magna [mg/l] Study scientifically unjustified.
EC50 72h - Algae [mg/l] Study scientifically unjustified.
LC50 96 h - Fish [mg/l] Study scientifically unjustified.
12.2. Persistence and degradability
Assessment : Will not undergo hydrolysis.

Not readily biodegradable.
12.3. Bioaccumulative potential
Assessment : Not expected to bioaccumulate due to the low log Kow (log Kow < 4).
Refer to section 9.
12.4. Mobility in soil
Assessment : Because of its high volatility, the product is unlikely to cause ground or water pollution.
Partition into soil is unlikely.
12.5. Results of PBT and vPvB assessment
Assessment : Not classified as PBT or vPvB.
12.6. Other adverse effects

Other adverse effects : No known effects from this product.
Effect on the ozone layer : None.
Effect on global warming : Contains greenhouse gas(es).
SECTION 13: Disposal considerations
13.1. Waste treatment methods

Contact supplier if guidance is required.
Do not discharge into areas where there is a risk of forming an explosive mixture with air.
Waste gas should be flared through a suitable burner with flash back arrestor.
Must not be discharged to atmosphere.
Ensure that the emission levels from local regulations or operating permits are not exceeded.
Refer to the EIGA code of practice Doc.30 "Disposal of Gases", downloadable at
http://www.eiga.org for more guidance on suitable disposal methods.
Return unused product in original container to supplier.
List of hazardous waste codes (from : 16 05 04 *: Gases in pressure containers (including halons) containing hazardous substances.
Commission Decision 2000/532/EC as
amended)
13.2. Additional information

: External treatment and disposal of waste should comply with applicable local and/or national
regulations.

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SECTION 14: Transport information
14.1. UN number
UN-No. : 1016
14.2. UN proper shipping name
Transport by road/rail (ADR/RID) : CARBON MONOXIDE, COMPRESSED
Transport by air (ICAO-TI / IATA-DGR) : Carbon monoxide, compressed
Transport by sea (IMDG) : CARBON MONOXIDE, COMPRESSED
14.3. Transport hazard class(es)

Labelling :
2.3 : Toxic gases.

2.1 : Flammable gases.
Transport by road/rail (ADR/RID)
Class : 2
Classification code : 1TF
Hazard identification number : 263
Tunnel Restriction : B/D - Tank carriage : Passage forbidden through tunnels of category B, C, D and E. Other
carriage : Passage forbidden through tunnels of category D and E
Transport by sea (IMDG)
Class / Div. (Sub. risk(s)) : 2.3 (2.1)
Emergency Schedule (EmS) - Fire : F-D
Emergency Schedule (EmS) - Spillage : S-U
14.4. Packing group

Transport by road/rail (ADR/RID) : Not established.
Transport by air (ICAO-TI / IATA-DGR) : Not established.
Transport by sea (IMDG) : Not established.
14.5. Environmental hazards

Transport by road/rail (ADR/RID) : None.
Transport by air (ICAO-TI / IATA-DGR) : None.
Transport by sea (IMDG) : None.
14.6. Special precautions for user

Packing Instruction(s)
Transport by road/rail (ADR/RID) : P200
Transport by air (ICAO-TI / IATA-DGR)
Passenger and Cargo Aircraft : Forbidden.
Cargo Aircraft only : Forbidden.
Transport by sea (IMDG) : P200

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Special transport precautions : Avoid transport on vehicles where the load space is not separated from the driver's
compartment.
Ensure vehicle driver is aware of the potential hazards of the load and knows what to do in the
event of an accident or an emergency.
Before transporting product containers:
- Ensure there is adequate ventilation.
- Ensure that containers are firmly secured.
- Ensure valve is closed and not leaking.
- Ensure valve outlet cap nut or plug (where provided) is correctly fitted.
- Ensure valve protection device (where provided) is correctly fitted.
14.7. Transport in bulk according to Annex II of Marpol and the IBC Code
: Not applicable.
15.1. Safety, health and environmental regulations/legislation specific for the substance or mixture
EU-Regulations
Restrictions on use : Restricted to professional users (Annex XVII REACH).

Seveso Directive : 2012/18/EU (Seveso III) : Covered.
National regulations
National legislation : Ensure all national/local regulations are observed.
15.2. Chemical safety assessment

: A CSA has been carried out.
Indication of changes : Revised safety data sheet in accordance with commission regulation (EU) No 453/2010.
Abbreviations and acronyms : ATE - Acute Toxicity Estimate

CLP - Classification Labelling Packaging Regulation; Regulation (EC) No 1272/2008
REACH - Registration, Evaluation, Authorisation and Restriction of Chemicals Regulation (EC)
No 1907/2006
EINECS - European Inventory of Existing Commercial Chemical Substances
CAS# - Chemical Abstract Service number
PPE - Personal Protection Equipment
LC50 - Lethal Concentration to 50 % of a test population
RMM - Risk Management Measures
PBT - Persistent, Bioaccumulative and Toxic
vPvB - Very Persistent and Very Bioaccumulative
STOT- SE : Specific Target Organ Toxicity - Single Exposure
CSA - Chemical Safety Assessment
EN - European Standard
UN - United Nations
ADR - International Agreement concerning the International Carriage of Dangerous Goods by
Road
IATA - International Air Transport Association
IMDG code - International Maritime Dangerous Goods
RID - Regulations concerning the International Carriage of Dangerous Goods by Rail
WGK - Water Hazard Class
STOT - RE : Specific Target Organ Toxicity - Repeated Exposure

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Training advice : Ensure operators understand the flammability hazard.

Users of breathing apparatus must be trained.
Ensure operators understand the toxicity hazard.
Full text of H- and EUH-statements

Acute Tox. 3 (Inhalation:gas) Acute toxicity (inhalation:gas) Category 3
Flam. Gas 1 Flammable gases, Category 1
Press. Gas (Comp.) Gases under pressure : Compressed gas
Repr. 1A Reproductive toxicity, Category 1A
STOT RE 1 Specific target organ toxicity — Repeated exposure, Category 1
H220 Extremely flammable gas
H280 Contains gas under pressure; may explode if heated
H331 Toxic if inhaled.
H360D May damage the unborn child.
H372 Causes damage to organs through prolonged or repeated exposure.
Full text of use descriptors

ERC2 Formulation of preparations
ERC6a Industrial use resulting in manufacture of another substance (use of intermediates)
ERC6b Industrial use of reactive processing aids
ERC8d Wide dispersive outdoor use of processing aids in open systems
PROC1 Use in closed process, no likelihood of exposure
PROC2 Use in closed, continuous process with occasional controlled exposure
PROC3 Use in closed batch process (synthesis or formulation)
PROC4 Use in batch and other process (synthesis) where opportunity for exposure arises
PROC8b Transfer of substance or preparation (charging/discharging) from/to vessels/large containers at
dedicated facilities
PROC9 Transfer of substance or mixture into small containers (dedicated filling line, including weighing)
SU14 Manufacture of basic metals, including alloys
SU15 Manufacture of fabricated metal products, except machinery and equipment
SU3 Industrial uses: Uses of substances as such or in preparations* at industrial sites
DISCLAIMER OF LIABILITY : Before using this product in any new process or experiment, a thorough material compatibility
and safety study should be carried out.
Details given in this document are believed to be correct at the time of going to press.
Whilst proper care has been taken in the preparation of this document, no liability for injury or
damage resulting from its use can be accepted.

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Annex to the safety data sheet
This Annex documents the Exposure Scenarios (ESs) related to the identified uses of the registered substance. The ESs detail
protective measures for workers and the environment in addition to those described in sections 7, 8, 11, 12 and 13 of the SDS that are
required to ensure that the potential exposure to workers and the environment remains within acceptable levels for each of the
identified uses.
Table of contents of the Annex
Identified Uses Es N° Short title Page
Formulation of mixtures in pressure receptacles EIGA01 Industrial uses, closed contained conditions 13
9-1
Metal treatment EIGA01 Industrial uses, closed contained conditions 13
9-1
Electronic component manufacture EIGA01 Industrial uses, closed contained conditions 13
9-1
Manufacture of pharmaceutical products EIGA01 Industrial uses, closed contained conditions 13
9-1
Intermediate (transported, on-site isolated) EIGA01 Industrial uses, closed contained conditions 13
9-1
Transfilling in pressure receptacles EIGA01 Industrial uses, closed contained conditions 13
9-1
Feedstock in chemical processes EIGA01 Industrial uses, closed contained conditions 13
9-1
Controlling agent in catalytic reaction EIGA01 Industrial uses, closed contained conditions 13
9-1
Monomer in polymer production EIGA01 Industrial uses, closed contained conditions 13
9-1
Calibration of analysis equipment EIGA01 Industrial uses, closed contained conditions 13
9-1

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MSAFE
1. EIGA019-1: Industrial uses, closed contained conditions

1.1. Title section
ES Ref.: EIGA019-1
Industrial uses, closed contained conditions
Revision date: 01/09/2016
Processes, tasks, activities covered Industrial uses, including product transfers and associated laboratory activities within
different closed or contained systems
Environment Use descriptors
CS1 ERC2, ERC6a, ERC6b, ERC8d
Worker Use descriptors
CS2 PROC1
CS3 PROC2, PROC3, PROC4
CS4 PROC8b, PROC9
Assessment method ECETOC TRA 2.0
1.2. Conditions of use affecting exposure

1.2.1. Control of environmental exposure: ERC2, ERC6a, ERC6b, ERC8d
ERC2 Formulation of preparations
ERC6a Industrial use resulting in manufacture of another substance (use of intermediates)
ERC6b Industrial use of reactive processing aids
ERC8d Wide dispersive outdoor use of processing aids in open systems
Product (article) characteristics

Physical form of product See section 9 of the SDS, No additional information
Concentration of substance in product <= 100 %
Amount used, frequency and duration of use (or from service life)
The actual tonnage handled per site is not considered
to influence the immissions as such for this scenario as
there is practically no release
Covers frequency up to: 5 days/week
Emission Days (days/year) 220
Technical and organisational conditions and measures

Wastewater emission controls are not applicable as there is no direct release to wastewater
Soil emission controls are not applicable as there is no direct release to soil
Ensure operatives are trained to minimise releases
Conditions and measures related to sewage treatment plant

Not applicable as there is no release to wastewater
Conditions and measures related to treatment of waste (including article waste)

External treatment and disposal of waste should
comply with applicable local and/or national regulations
See section 13 of the SDS
Other conditions affecting environmental exposure

No additional information
1.2.2. Control of worker exposure: PROC1

PROC1 Use in closed process, no likelihood of exposure

Amount used (or contained in articles), frequency and duration of use/exposure

The actual tonnage handled per shift is not considered
to influence the exposure as such for this scenario.
Instead, the combination of the scale of operation and
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level of containment/automation (as reflected in the

technical conditions) is the main determinant of the
process-intrinsic emission potential.
Exposure duration <= 8 h/day
Handle product within a closed system
Ensure operatives are trained to minimise exposure
Ensure supervision is in place to check that the RMMs are in place and are being used
correctly and that the OCs are being followed
Conditions and measures related to personal protection, hygiene and health evaluation
See section 8 of the SDS.
Other conditions affecting workers exposure

Indoor or outdoor use
1.2.3. Control of worker exposure: PROC2, PROC3, PROC4

PROC2 Use in closed, continuous process with occasional controlled exposure
PROC3 Use in closed batch process (synthesis or formulation)
PROC4 Use in batch and other process (synthesis) where opportunity for exposure arises


See section 8 of the SDS.

1.2.4. Control of worker exposure: PROC8b, PROC9

PROC8b Transfer of substance or preparation (charging/discharging) from/to vessels/large containers at dedicated facilities
PROC9 Transfer of substance or mixture into small containers (dedicated filling line, including weighing)


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1.3. Exposure estimation and reference to its source

1.3.1. Environmental release and exposure: ERC2, ERC6a, ERC6b, ERC8d
The exposure of aquatic, terrestrial, sediment and sewage treatment microorganisms is considered to be negligible because the substance
partitions primarily to air when released to the environment. ,The resulting environmental exposure is not expected to add significantly to already
present background levels of the gas in the environment
1.3.2. Worker exposure: PROC1
Route of exposure and type Exposure estimate Assessment conditions RCR

of effects
Inhalation - Long-term - 0.011 mg/m³ Indoor use , With LEV < 0.01
systemic effects
Inhalation - Acute - systemic 0.023 mg/m³ Indoor use , With LEV < 0.001
effects
1.3.3. Worker exposure: PROC2, PROC3, PROC4

of effects
Inhalation - Long-term - 11.7 mg/m³ Indoor use , With LEV 0.585
systemic effects 11.7 mg/m³ Indoor use , Without LEV 0.585
Inhalation - Acute - systemic 23.4 mg/m³ Indoor use , With LEV 0.234
effects 23.4 mg/m³ Indoor use , Without LEV 0.234
1.3.4. Worker exposure: PROC8b, PROC9

of effects
Inhalation - Long-term - 23.3 mg/m³ Indoor use , With LEV 1.165
systemic effects 23.3 mg/m³ Indoor use , Without LEV 1.165
Inhalation - Acute - systemic 46.7 mg/m³ Indoor use , With LEV 0.467
effects 46.7 mg/m³ Indoor use , Without LEV 0.467
1.4. Guidance to Downstream User to evaluate whether he works inside the boundaries set by the ES
1.4.1. Environment
Guidance - Environment Check that RMMs and OCs are as described above or of equivalent efficiency
1.4.2. Health
Guidance - Health Guidance is based on assumed operating conditions which may not be applicable to all sites; thus,
scaling may be necessary to define appropriate site-specific risk management measures. For scaling
see : http://www.ecetoc.org/tra

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End of document
SAFETY DATA SHEET
Hydrogen, compressed
Issue Date: 16.01.2013 Version: 1. 4 SDS No.: 000010021694
1.1 Product identifier

Product name: Hydrogen, compressed
Trade name: Hydrogen High Purity, Hydrogen CP Grade N5.0, Hydrogen Research Grade
N5.5, Hydrogen Zero Grade N4.5
Additional identification
Chemical name: hydrogen
Chemical formula: H2
INDEX No. 001-001-00-9
CAS-No. 1333-74-0
EC No. 215-605-7
REACH Registration No. Listed in Annex IV/V of Regulation (EC) No 1907/2006 (REACH), exempted
from registration.
Identified uses: Industrial and professional. Perform risk assessment prior to use.
Aerosol propellant. Balance gas for mixtures. Calibration gas. Carrier gas.
Chemical synthesis. Combustion, melting and cutting processes. Fuel cells.
Fuel gas for welding, cutting, heating, brazing and soldering applications.
Laboratory use. Laser gas. Process gas. Test gas.
Consumer use.
Fuel gas Propellant gas. Shielding gas in gas welding.
Uses advised against This gas is not intended to be filled into balloons for consumer use and
advertising purposes because of the danger of explosion. Do not inflate
commercial balloons.

Supplier
BOC Telephone: 0800 111 333
Priestley Road, Worsley
M28 2UT Manchester
E-mail: ReachSDS@boc.com
1.4 Emergency telephone number: 0800 111 333
SDS_GB - 000010021694
SAFETY DATA SHEET
2.1 Classification of the substance or mixture
Classification according to Directive 67/548/EEC or 1999/45/EC as amended.
F+; R12
The full text for all R-phrases is displayed in section 16.

Physical Hazards
Flammable gas Category 1 H220: Extremely flammable gas.
Gases under pressure Compressed gas H280: Contains gas under pressure; may explode if
heated.
2.2 Label Elements
Signal Words: Danger
Hazard Statement(s): H220: Extremely flammable gas.

H280: Contains gas under pressure; may explode if heated.
Precautionary Statement
Prevention: P210: Keep away from heat, hot surfaces, sparks, open flames and other
ignition sources. No smoking.
Response: P377: Leaking gas fire: Do not extinguish, unless leak can be stopped safely.
P381: Eliminate all ignition sources if safe to do so.
Storage: P403: Store in a well-ventilated place.
Disposal: None.
2.3 Other hazards: None.
SDS_GB - 000010021694
SAFETY DATA SHEET
3.1 Substances
Chemical name hydrogen

INDEX No.: 001-001-00-9
CAS-No.: 1333-74-0
EC No.: 215-605-7
REACH Registration No.: Listed in Annex IV/V of Regulation (EC) No 1907/2006 (REACH), exempted from
registration.
Purity: 100%
The purity of the substance in this section is used for classification only, and does
not represent the actual purity of the substance as supplied, for which other
documentation should be consulted.
Trade name: Hydrogen High Purity, Hydrogen CP Grade N5.0, Hydrogen Research Grade N5.5,
Hydrogen Zero Grade N4.5
SECTION 4: First Aid Measures
General: In high concentrations may cause asphyxiation. Symptoms may include loss of
4.1 Description of first aid measures

Inhalation: In high concentrations may cause asphyxiation. Symptoms may include loss of
Eye contact: Adverse effects not expected from this product.
Skin Contact: Adverse effects not expected from this product.
Ingestion: Ingestion is not considered a potential route of exposure.
4.2 Most important symptoms and Respiratory arrest.

effects, both acute and
delayed:
Hazards: None.
Treatment: None.
SDS_GB - 000010021694
SAFETY DATA SHEET
SECTION 5: Firefighting Measures
General Fire Hazards: Heat may cause the containers to explode.

Suitable extinguishing media: Water. Dry powder. Foam.
Unsuitable extinguishing Carbon dioxide.

media:
5.2 Special hazards arising from the None.

substance or mixture:
Hazardous Combustion Products: None.

Special fire fighting In case of fire: Stop leak if safe to do so. Do not extinguish flames at leak because
procedures: possibility of uncontrolled explosive re-ignition exists. Continue water spray from
protected position until container stays cool. Use extinguishants to contain the
fire. Isolate the source of the fire or let it burn out.
Special protective equipment Firefighters must use standard protective equipment including flame retardant
for firefighters: coat, helmet with face shield, gloves, rubber boots, and in enclosed spaces, SCBA.
Guideline: EN 469 Protective clothing for firefighters. Performance requirements
for protective clothing for firefighting. EN 15090 Footwear for firefighters. EN 659
Protective gloves for firefighters. EN 443 Helmets for fire fighting in buildings and
other structures. EN 137 Respiratory protective devices - Self-contained open-
testing, marking.
SECTION 6: Accidental Release Measures
6.1 Personal precautions, Evacuate area. Provide adequate ventilation. Consider the risk of potentially
protective equipment and explosive atmospheres . Eliminate all ignition sources if safe to do so. Monitor the
emergency procedures: concentration of the released product. Prevent from entering sewers, basements
and workpits, or any place where its accumulation can be dangerous. Wear self-
contained breathing apparatus when entering area unless atmosphere is proved
to be safe. EN 137 Respiratory protective devices - Self-contained open-circuit
compressed air breathing apparatus with full face mask - Requirements, testing,
marking.
6.2 Environmental Precautions: Prevent further leakage or spillage if safe to do so.
6.3 Methods and material for Provide adequate ventilation. Eliminate sources of ignition.
containment and cleaning up:
6.4 Reference to other sections: Refer to sections 8 and 13.
SDS_GB - 000010021694
SAFETY DATA SHEET
SECTION 7: Handling and Storage:
7.1 Precautions for safe handling: Only experienced and properly instructed persons should handle gases under
pressure. Use only properly specified equipment which is suitable for this product,
its supply pressure and temperature. Purge system with dry inert gas (e.g. helium
or nitrogen) before gas is introduced and when system is placed out of service.
Purge air from system before introducing gas. Containers, which contain or have
contained flammable or explosive substances, must not be inerted with liquid
carbon dioxide. Assess the risk of a potentially explosive atmosphere and the
need for suitable equipment i.e. explosion-proof. Take precautionary measures
against static discharges. Keep away from ignition sources (including static
discharges). Provide electrical earthing of equipment and electrical equipment
usable in explosive atmospheres. Use only non-sparking tools. Refer to supplier's
handling instructions. The substance must be handled in accordance with good
industrial hygiene and safety procedures. Ensure the complete system has been
(or is regularly) checked for leaks before use. Protect containers from physical
damage; do not drag, roll, slide or drop. Do not remove or deface labels provided
by the supplier for the identification of the container contents. When moving
containers, even for short distances, use appropriate equipment eg. trolley, hand
truck, fork truck etc. Secure cylinders in an upright position at all times, close all
valves when not in use. Provide adequate ventilation. Suck back of water into the
container must be prevented. Do not allow backfeed into the container. Avoid
suckback of water, acid and alkalis. Keep container below 50°C in a well
ventilated place. Observe all regulations and local requirements regarding storage
of containers. When using do not eat, drink or smoke. Store in accordance with
local/regional/national/international regulations. Never use direct flame or
electrical heating devices to raise the pressure of a container. Leave valve
protection caps in place until the container has been secured against either a wall
or bench or placed in a container stand and is ready for use. Damaged valves
should be reported immediately to the supplier Close container valve after each
use and when empty, even if still connected to equipment. Never attempt to
repair or modify container valves or safety relief devices. Replace valve outlet
caps or plugs and container caps where supplied as soon as container is
disconnected from equipment. Keep container valve outlets clean and free from
contaminates particularly oil and water. If user experiences any difficulty
operating container valve discontinue use and contact supplier. Never attempt to
transfer gases from one container to another. Container valve guards or caps
should be in place.
7.2 Conditions for safe storage, All electrical equipment in the storage areas should be compatible with the risk of
including any incompatibilities: a potentially explosive atmosphere. Segregate from oxidant gases and other
oxidants being stored. Containers should not be stored in conditions likely to
encourage corrosion. Stored containers should be periodically checked for general
conditions and leakage. Container valve guards or caps should be in place. Store
containers in location free from fire risk and away from sources of heat and
ignition. Keep away from combustible material.
7.3 Specific end use(s): None.
SDS_GB - 000010021694
SAFETY DATA SHEET
SECTION 8: Exposure Controls/Personal Protection
8.1 Control Parameters

Occupational Exposure Limits
None of the components have assigned exposure limits.

Appropriate engineering Consider a work permit system e.g. for maintenance activities. Ensure adequate
controls: air ventilation. Provide adequate general and local exhaust ventilation. Keep
concentrations well below lower explosion limits. Gas detectors should be used
when quantities of flammable gases or vapours may be released. Provide
adequate ventilation, including appropriate local extraction, to ensure that the
defined occupational exposure limit is not exceeded. Systems under pressure
should be regularly checked for leakages. Product to be handled in a closed
system. Use only permanent leak tight installations (e.g. welded pipes). Take
precautionary measures against static discharges.
Individual protection measures, such as personal protective equipment
General information: A risk assessment should be conducted and documented in each work area to
assess the risks related to the use of the product and to select the PPE that
matches the relevant risk. The following recommendations should be considered.
Personal protective equipment for the body should be selected based on the task
being performed and the risks involved. Refer to local regulations for restriction of
emissions to the atmosphere. See section 13 for specific methods for waste gas
treatment. Do not eat, drink or smoke when using the product.
Eye/face protection: Wear eye protection to EN 166 when using gases.

Guideline: EN 166 Personal Eye Protection.
Skin protection
Hand Protection: Wear working gloves while handling containers
Guideline: EN 388 Protective gloves against mechanical risks.
Body protection: Wear fire/flame resistant/retardant clothing.

Guideline: ISO/TR 2801:2007 Clothing for protection against heat and flame --
General recommendations for selection, care and use of protective clothing.
Other: Wear safety shoes while handling containers

Guideline: ISO 20345 Personal protective equipment - Safety footwear.
Respiratory Protection: Not required.
Thermal hazards: No precautionary measures are necessary.
Hygiene measures: Specific risk management measures are not required beyond good industrial
hygiene and safety procedures. Do not eat, drink or smoke when using the
product.
SDS_GB - 000010021694
SAFETY DATA SHEET
Environmental exposure For waste disposal, see section 13.

controls:
SECTION 9: Physical And Chemical Properties

Appearance
Physical state: Gas
Form: Compressed gas
Colour: Colorless
Odour: Odorless
Odour Threshold: Odour threshold is subjective and is inadequate to warn of over
exposure.
pH: not applicable.
Melting Point: -259.2 °C
Boiling Point: -253 °C
Sublimation Point: not applicable.
Critical Temp. (°C): -240.0 °C
Flash Point: Not applicable to gases and gas mixtures.
Evaporation Rate: Not applicable to gases and gas mixtures.
Flammability (solid, gas): Flammable Gas
Flammability limit - upper (%): 77 %(V)
Flammability limit - lower(%): 4 %(V)
Vapour pressure: No reliable data available.
Vapour density (air=1): 0.069
Relative density: 0.07
Solubility(ies)
Solubility in Water: 1.62 mg/l
Partition coefficient (n-octanol/water): Not known.
Autoignition Temperature: 560 °C
Decomposition Temperature: Not known.
Viscosity
Kinematic viscosity: No data available.
Dynamic viscosity: No data available.
Explosive properties: Not applicable.
Oxidising Properties: not applicable.
9.2 Other information: None.

Molecular weight: 2.02 g/mol (H2)
SECTION 10: Stability and Reactivity
10.1 Reactivity: No reactivity hazard other than the effects described in sub-section below.
SDS_GB - 000010021694
SAFETY DATA SHEET
10.2 Chemical Stability: Stable under normal conditions.
10.3 Possibility of Hazardous Can form a potentially explosive atmosphere in air. May react violently with
Reactions: oxidants.
10.4 Conditions to Avoid: Keep away from heat, hot surfaces, sparks, open flames and other ignition
sources. No smoking.
10.5 Incompatible Materials: Air and oxidisers. For material compatibility see latest version of ISO-11114.
10.6 Hazardous Decomposition Under normal conditions of storage and use, hazardous decomposition products
Products: should not be produced.
SECTION 11: Toxicological Information
General information: None.
Acute toxicity - Oral

Acute toxicity - Dermal

Acute toxicity - Inhalation

Skin Corrosion/Irritation
Serious Eye Damage/Eye Irritation

Respiratory or Skin Sensitisation

Germ Cell Mutagenicity

Carcinogenicity
Specific Target Organ Toxicity - Single Exposure

SDS_GB - 000010021694
SAFETY DATA SHEET
Specific Target Organ Toxicity - Repeated Exposure

Aspiration Hazard
SECTION 12: Ecological Information
12.1 Toxicity
Acute toxicity
Product No ecological damage caused by this product.
12.2 Persistence and Degradability

12.3 Bioaccumulative Potential

Product The product is expected to biodegrade and is not expected to persist for long
periods in an aquatic environment.
12.4 Mobility in Soil

Product Because of its high volatility, the product is unlikely to cause ground or water
pollution.
12.5 Results of PBT and vPvB

assessment
Product Not classified as PBT or vPvB.
12.6 Other Adverse Effects: No ecological damage caused by this product.
SECTION 13: Disposal Considerations
General information: Do not discharge into any place where its accumulation could be dangerous.
Consult supplier for specific recommendations. Do not discharge into areas where
there is a risk of forming an explosive mixture with air. Waste gas should be flared
through a suitable burner with flash back arrestor.
Disposal methods: Refer to the EIGA code of practice (Doc.30 "Disposal of Gases", downloadable at
http://www.eiga.org) for more guidance on suitable disposal methods. Dispose
of container via supplier only. Discharge, treatment, or disposal may be subject to
national, state, or local laws.
European Waste Codes

Container: 16 05 04*: gases in pressure containers (including halons) containing
dangerous substances
SDS_GB - 000010021694
SAFETY DATA SHEET
SECTION 14: Transport Information
ADR
14.2 UN Proper Shipping Name: HYDROGEN, COMPRESSED
Class: 2
Label(s): 2.1
Hazard No. (ADR): 23
Tunnel restriction code: (B/D)
Emergency Action Code: 2SE
14.5 Environmental hazards: not applicable
RID
14.2 UN Proper Shipping Name HYDROGEN, COMPRESSED
Class: 2
Label(s): 2.1
IMDG
14.2 UN Proper Shipping Name: HYDROGEN, COMPRESSED
Class: 2.1
Label(s): 2.1
EmS No.: F-D, S-U
IATA
14.2 Proper Shipping Name: Hydrogen, compressed
14.3 Transport Hazard Class(es):
Class: 2.1
Label(s): 2.1
Other information
Passenger and cargo aircraft: Forbidden.
Cargo aircraft only: Allowed.
14.7 Transport in bulk according to Annex II of MARPOL73/78 and the IBC Code: not applicable
SDS_GB - 000010021694
SAFETY DATA SHEET
Additional identification: Avoid transport on vehicles where the load space is not separated from
the driver's compartment. Ensure vehicle driver is aware of the potential
hazards of the load and knows what to do in the event of an accident or
an emergency. Before transporting product containers ensure that they
are firmly secured. Ensure that the container valve is closed and not
leaking. Container valve guards or caps should be in place. Ensure
adequate air ventilation.
15.1 Safety, health and environmental regulations/legislation specific for the substance or mixture:
EU Regulations
Regulation (EC) No. 1907/2006 Annex XVII Substances subject to restriction on marketing and use:

hydrogen 1333-74-0 100%
Directive 96/82/EC (Seveso II): on the control of major accident hazards involving dangerous substances:

hydrogen 1333-74-0 100%
Directive 98/24/EC on the protection of workers from the risks related to chemical agents at work:

hydrogen 1333-74-0 100%
National Regulations
Dangerous Substances and Explosive Atmospheres Regulations (DSEAR 2002 No.

2776). Management of Health and Safety at Work Regulations (1999 No. 3242). The
Regulatory Reform (Fire Safety) Order 2005 (2005 No. 1541). Control of Substances
Hazardous to Health Regulations (COSHH, 2002 No. 2677). Provision and Use of Work
Equipment Regulations (PUWER, 1998 No. 2306). Personal Protective Equipment
Regulations (1992 No. 2966). Control of Major Accident Hazards Regulations (COMAH,
2015 No. 483). Equipment and Protective Systems Intended for Use in Potentially
Explosive Atmospheres Regulations (EPS, 1996 No. 192). Pressure Systems Safety
Regulations (PSSR, 2000 No. 128). Only products that comply with the food
regulations (EC) No. 1333/2008 and (EU) No. 231/2012 and are labelled as such may
be used as food additives.
This Safety Data Sheet has been produced to comply with Regulation (EU) 453/2010.
15.2 Chemical safety assessment: No Chemical Safety Assessment has been carried out.
SDS_GB - 000010021694
SAFETY DATA SHEET
SECTION 16: Other Information
Revision Information: Not relevant.
Key literature references and Various sources of data have been used in the compilation of this SDS, they include
sources for data: but are not exclusive to:
Agency for Toxic Substances and Diseases Registry (ATSDR)
(http://www.atsdr.cdc.gov/).
European Chemical Agency: Guidance on the Compilation of Safety Data Sheets.
European Chemical Agency: Information on Registered Substances
http://apps.echa.europa.eu/registered/registered-sub.aspx#search
European Industrial Gases Association (EIGA) Doc. 169 Classification and Labelling
guide.
International Programme on Chemical Safety (http://www.inchem.org/)
ISO 10156:2010 Gases and gas mixtures - Determination of fire potential and
oxidizing ability for the selection of cylinder valve outlets.
Matheson Gas Data Book, 7th Edition.
National Institute for Standards and Technology (NIST) Standard Reference Database
Number 69.
The ESIS (European chemical Substances 5 Information System) platform of the
former European Chemicals Bureau (ECB) ESIS (http://ecb.jrc.ec.europa.eu/esis/).
The European Chemical Industry Council (CEFIC) ERICards.
United States of America’s National Library of Medicine’s toxicology data network
TOXNET (http://toxnet.nlm.nih.gov/index.html)
Threshold Limit Values (TLV) from the American Conference of Governmental
Industrial Hygienists (ACGIH).
Substance specific information from suppliers.
Details given in this document are believed to be correct at the time of publication.
EH40 (as amended) Workplace exposure limits.
Wording of the R-phrases and H-statements in sections 2 and 3

H220 Extremely flammable gas.
R12 Extremely flammable.
Training information: Users of breathing apparatus must be trained. Ensure operators understand the
flammability hazard.

Flam. Gas 1, H220
Press. Gas Compr. Gas, H280
SDS_GB - 000010021694
SAFETY DATA SHEET
Other information: Before using this product in any new process or experiment, a thorough material
compatibility and safety study should be carried out. Ensure adequate air ventilation.
Ensure all national/local regulations are observed. Ensure equipment is adequately
earthed. Whilst proper care has been taken in the preparation of this document, no
liability for injury or damage resulting from its use can be accepted. Note: When the
Product Name appears in the SDS header the decimal sign and its position comply
with rules for the structure and drafting of international standards, and is a comma
on the line. As an example 2,000 is two (to three decimal places) and not two
thousand, whilst 1.000 is one thousand and not one (to three decimal places).
Last revised date: 07.09.2016

Disclaimer: This information is provided without warranty. The information is believed to be
correct. This information should be used to make an independent determination of
the methods to safeguard workers and the environment.
SDS_GB - 000010021694
SAFETY DATA SHEET
Creation Date 24-Jan-2018 Revision Date 29-Feb-2020 Revision Number 2
1. Identification
Product Name Copper based low temperature water gas shift catalyst, HiFUEL®
W220
Cat No. : 45466

Synonyms No information available
Recommended Use Laboratory chemicals.

Uses advised against Food, drug, pesticide or biocidal product use.
Details of the supplier of the safety data sheet
Company
Alfa Aesar
Thermo Fisher Scientific Chemicals, Inc.
30 Bond Street
Ward Hill, MA 01835-8099
Tel: 800-343-0660
Fax: 800-322-4757
Email: tech@alfa.com
www.alfa.com
Emergency Telephone Number

During normal business hours (Monday-Friday, 8am-7pm EST), call (800) 343-0660.
After normal business hours, call Carechem 24 at (866) 928-0789.
2. Hazard(s) identification
Classification
Classification under 2012 OSHA Hazard Communication Standard (29 CFR 1910.1200)
Label Elements
None required
Hazards not otherwise classified (HNOC)

Very toxic to aquatic life with long lasting effects
______________________________________________________________________________________________
Page 1 / 7
Copper based low temperature water gas shift Revision Date 29-Feb-2020
catalyst, HiFUEL® W220
______________________________________________________________________________________________
3. Composition/Information on Ingredients
Component CAS-No Weight %
Copper oxide 1317-38-0 52
Zinc oxide 1314-13-2 30
Aluminum oxide 1344-28-1 17
Activated charcoal 7440-44-0 1
4. First-aid measures
General Advice If symptoms persist, call a physician.
Eye Contact Rinse immediately with plenty of water, also under the eyelids, for at least 15 minutes. Get
medical attention.
Skin Contact Wash off immediately with plenty of water for at least 15 minutes. If skin irritation persists,
call a physician.
Inhalation Remove to fresh air. If not breathing, give artificial respiration. Get medical attention if
symptoms occur.
Ingestion Clean mouth with water and drink afterwards plenty of water. Get medical attention if
symptoms occur.
Most important symptoms and None reasonably foreseeable.

effects
Notes to Physician Treat symptomatically
5. Fire-fighting measures
Unsuitable Extinguishing Media No information available
Flash Point Not applicable

Method - No information available
Autoignition Temperature No information available

Explosion Limits
Upper No data available
Lower No data available
Sensitivity to Mechanical Impact No information available
Sensitivity to Static Discharge No information available
Specific Hazards Arising from the Chemical

Do not allow run-off from fire-fighting to enter drains or water courses.
Hazardous Combustion Products

Copper oxides.
Protective Equipment and Precautions for Firefighters
As in any fire, wear self-contained breathing apparatus pressure-demand, MSHA/NIOSH (approved or equivalent) and full
protective gear.
NFPA
Health Flammability Instability Physical hazards
0 0 0 N/A
6. Accidental release measures
______________________________________________________________________________________________
Page 2 / 7
______________________________________________________________________________________________
Personal Precautions Ensure adequate ventilation. Use personal protective equipment as required. Avoid dust
formation.
Environmental Precautions Do not flush into surface water or sanitary sewer system. Do not allow material to
contaminate ground water system. Prevent product from entering drains. Local authorities
should be advised if significant spillages cannot be contained. Should not be released into
the environment.
Methods for Containment and Clean Sweep up and shovel into suitable containers for disposal. Keep in suitable, closed
Up containers for disposal.
7. Handling and storage

Handling Wear personal protective equipment/face protection. Ensure adequate ventilation. Do not
get in eyes, on skin, or on clothing. Avoid ingestion and inhalation. Avoid dust formation.
Storage Keep containers tightly closed in a dry, cool and well-ventilated place.
8. Exposure controls / personal protection

Exposure Guidelines
Component ACGIH TLV OSHA PEL NIOSH IDLH Mexico OEL (TWA)
Copper oxide TWA: 1 mg/m3 IDLH: 100 mg/m3
TWA: 0.1 mg/m3 TWA: 1
mg/m3
Zinc oxide TWA: 2 mg/m3 (Vacated) TWA: 5 mg/m3 IDLH: 500 mg/m3 TWA: 2 mg/m3
STEL: 10 mg/m3 (Vacated) TWA: 10 mg/m3 TWA: 5 mg/m3 STEL: 10 mg/m3
(Vacated) STEL: 10 mg/m3 STEL: 10 mg/m3
TWA: 5 mg/m3 Ceiling: 15 mg/m3
TWA: 15 mg/m3
Aluminum oxide TWA: 1 mg/m3 (Vacated) TWA: 10 mg/m3 TWA: 10 mg/m3 TWA: 1 ppm
(Vacated) TWA: 5 mg/m3
TWA: 15 mg/m3
TWA: 5 mg/m3
Activated charcoal TWA: 2 mg/m3
Legend
ACGIH - American Conference of Governmental Industrial Hygienists

OSHA - Occupational Safety and Health Administration
NIOSH IDLH: NIOSH - National Institute for Occupational Safety and Health
Engineering Measures Ensure adequate ventilation, especially in confined areas.
Personal Protective Equipment
Eye/face Protection Wear appropriate protective eyeglasses or chemical safety goggles as described by
OSHA's eye and face protection regulations in 29 CFR 1910.133 or European Standard
EN166.
Skin and body protection Wear appropriate protective gloves and clothing to prevent skin exposure.
Respiratory Protection Follow the OSHA respirator regulations found in 29 CFR 1910.134 or European Standard
EN 149. Use a NIOSH/MSHA or European Standard EN 149 approved respirator if
exposure limits are exceeded or if irritation or other symptoms are experienced.
Hygiene Measures Handle in accordance with good industrial hygiene and safety practice.
9. Physical and chemical properties
______________________________________________________________________________________________
Page 3 / 7
______________________________________________________________________________________________
Physical State Solid Pellets

Appearance No information available
Odor No information available
Odor Threshold No information available
pH Not applicable
Melting Point/Range No data available
Boiling Point/Range Not applicable
Flash Point Not applicable
Evaporation Rate Not applicable
Flammability (solid,gas) No information available
Flammability or explosive limits
Upper No data available
Lower No data available
Vapor Pressure No information available
Vapor Density Not applicable
Specific Gravity No information available
Solubility insoluble
Partition coefficient; n-octanol/water No data available
Autoignition Temperature No information available
Decomposition Temperature No information available
Viscosity Not applicable
10. Stability and reactivity

Reactive Hazard None known, based on information available
Stability Stable under normal conditions.
Conditions to Avoid Incompatible products.
Incompatible Materials
Hazardous Decomposition Products Copper oxides
Hazardous Polymerization Hazardous polymerization does not occur.
Hazardous Reactions None under normal processing.
11. Toxicological information

Acute Toxicity
Product Information
Oral LD50 Based on ATE data, the classification criteria are not met. ATE > 2000 mg/kg.
Dermal LD50 Based on ATE data, the classification criteria are not met. ATE > 2000 mg/kg.
Mist LC50 Based on ATE data, the classification criteria are not met. ATE > 5 mg/l.
Component LD50 Oral LD50 Dermal LC50 Inhalation
Zinc oxide LD50 > 5000 mg/kg ( Rat ) LD50 > 2000 mg/kg, 24h (Rat) LC50 > 5.7 mg/L, 4h (Rat)
Aluminum oxide > 5000 mg/kg ( Rat ) Not listed > 2.3 mg/l 4 h
(OECD Guideline 401) (OECD Guideline 403)
Activated charcoal LD50 > 10000 mg/kg ( Rat ) Not listed Not listed
Toxicologically Synergistic No information available

Products
Delayed and immediate effects as well as chronic effects from short and long-term exposure
Irritation No information available
______________________________________________________________________________________________
Page 4 / 7
______________________________________________________________________________________________
Sensitization No information available
Carcinogenicity The table below indicates whether each agency has listed any ingredient as a carcinogen.
Component CAS-No IARC NTP ACGIH OSHA Mexico

Copper oxide 1317-38-0 Not listed Not listed Not listed Not listed Not listed
Zinc oxide 1314-13-2 Not listed Not listed Not listed Not listed Not listed
Aluminum oxide 1344-28-1 Not listed Not listed Not listed Not listed Not listed
Activated charcoal 7440-44-0 Not listed Not listed Not listed Not listed Not listed
Mutagenic Effects No information available
Reproductive Effects No information available.
Developmental Effects No information available.
Teratogenicity No information available.
STOT - single exposure None known

STOT - repeated exposure None known
Aspiration hazard No information available
Symptoms / effects,both acute and No information available

delayed
Endocrine Disruptor Information No information available
Other Adverse Effects The toxicological properties have not been fully investigated.
12. Ecological information

Ecotoxicity
The product contains following substances which are hazardous for the environment. Very toxic to aquatic organisms, may cause
long-term adverse effects in the aquatic environment. May cause long-term adverse effects in the environment. Do not allow
material to contaminate ground water system.
Component Freshwater Algae Freshwater Fish Microtox Water Flea

Copper oxide Not listed Onchorhynchus mykiss: Not listed Daphnia: EC50: 0.04
LC50: 25 mg/L/48h mg/L/48h
Zinc oxide Not listed LC50: = 1.55 mg/L, 96h Not listed Not listed
static (Danio rerio)
Persistence and Degradability Insoluble in water May persist
Bioaccumulation/ Accumulation No information available.
Mobility Is not likely mobile in the environment due its low water solubility.
13. Disposal considerations

Waste Disposal Methods Chemical waste generators must determine whether a discarded chemical is classified as a
hazardous waste. Chemical waste generators must also consult local, regional, and
national hazardous waste regulations to ensure complete and accurate classification.
14. Transport information

DOT
UN-No UN3077
Proper Shipping Name Environmentally hazardous substances, solid, n.o.s.
Technical Name Copper oxide, Zinc oxide
Hazard Class 9
______________________________________________________________________________________________
Page 5 / 7
______________________________________________________________________________________________
Packing Group III

TDG
UN-No UN3077
Hazard Class 9
Packing Group III
IATA
UN-No UN3077
Hazard Class 9
Packing Group III
IMDG/IMO
UN-No UN3077
Hazard Class 9
Packing Group III
15. Regulatory information
United States of America Inventory
Component CAS-No TSCA TSCA Inventory notification - TSCA - EPA Regulatory

Active/Inactive Flags
Copper oxide 1317-38-0 X ACTIVE -
Zinc oxide 1314-13-2 X ACTIVE -
Aluminum oxide 1344-28-1 X ACTIVE -
Activated charcoal 7440-44-0 X ACTIVE -
Legend:
TSCA - Toxic Substances Control Act, (40 CFR Part 710)
X - Listed
'-' - Not Listed
TSCA 12(b) - Notices of Export Not applicable
International Inventories
Canada (DSL/NDSL), Europe (EINECS/ELINCS/NLP), Philippines (PICCS), Japan (ENCS), Australia (AICS), China (IECSC), Korea (ECL).
Component CAS-No DSL NDSL EINECS PICCS ENCS AICS IECSC KECL
Copper oxide 1317-38-0 X - 215-269-1 X X X X KE-08942
Zinc oxide 1314-13-2 X - 215-222-5 X X X X KE-35565
Aluminum oxide 1344-28-1 X - 215-691-6 X X X X KE-01012
Activated charcoal 7440-44-0 X - 231-153-3 X X X X KE-04671
U.S. Federal Regulations
SARA 313
Component CAS-No Weight % SARA 313 - Threshold
Values %
Copper oxide 1317-38-0 52 1.0
Zinc oxide 1314-13-2 30 1.0
Aluminum oxide 1344-28-1 17 1.0
SARA 311/312 Hazard Categories See section 2 for more information
CWA (Clean Water Act)

Component CWA - Hazardous CWA - Reportable CWA - Toxic Pollutants CWA - Priority Pollutants
Substances Quantities
Copper oxide - - X -
______________________________________________________________________________________________
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______________________________________________________________________________________________
Zinc oxide - - X -
Clean Air Act Not applicable
OSHA - Occupational Safety and Not applicable

Health Administration
CERCLA Not applicable
California Proposition 65 This product does not contain any Proposition 65 chemicals.
U.S. State Right-to-Know

Regulations
Component Massachusetts New Jersey Pennsylvania Illinois Rhode Island
Copper oxide - X X - -
Zinc oxide X X X - X
Aluminum oxide X X X - X
Activated charcoal - - - - X
U.S. Department of Transportation

Reportable Quantity (RQ): N
DOT Marine Pollutant N
DOT Severe Marine Pollutant N
U.S. Department of Homeland This product does not contain any DHS chemicals.
Security
Other International Regulations
Mexico - Grade No information available
16. Other information

Prepared By Health, Safety and Environmental Department
Email: tech@alfa.com
www.alfa.com
Creation Date 24-Jan-2018

Revision Date 29-Feb-2020
Print Date 29-Feb-2020
Revision Summary SDS authoring systems update, replaces ChemGes SDS No. 2,495. Initial Release.
Disclaimer
The information provided in this Safety Data Sheet is correct to the best of our knowledge, information and belief at the
date of its publication. The information given is designed only as a guidance for safe handling, use, processing, storage,
transportation, disposal and release and is not to be considered a warranty or quality specification. The information
relates only to the specific material designated and may not be valid for such material used in combination with any other
materials or in any process, unless specified in the text
End of SDS
______________________________________________________________________________________________
Page 7 / 7
SAFETY DATA SHEET Version 6.6
Revision Date 27.05.2021
Print Date 11.06.2022
SECTION 1: Identification of the hazardous chemical and of the supplier

1.1 Product identifiers
Product name : Methanol
Product Number : 322415

Brand : Sigma-Aldrich
CAS-No. : 67-56-1
1.2 Other means of identification
Methyl alcohol
Identified uses : For R&D use only. Not for pharmaceutical, household or other
uses.
Company : SIGMA-ALDRICH (M) SDN BHD
Level 3, Menara Sunway Annexe,
Jalan Lagoon Timur, Bandar Sunway,
46150 PETALING JAYA, SELANGOR
MALAYSIA
Telephone : +60 (603)03-563-53321
Fax : +60 (603)03-563-54116
1.5 Emergency telephone
Emergency Phone # : 1-800-815-308 (CHEMTREC) * + 62 0800
140 1253 (Customer Call Centre)
Section 2: Hazard identification

2.1 GHS Classification
Classification according to CLASS regulations 2013
Flammable liquids (Category 2), H225
Acute toxicity, Oral (Category 3), H301
Acute toxicity, Inhalation (Category 3), H331
Acute toxicity, Dermal (Category 3), H311
Specific target organ toxicity - single exposure (Category 1), Eyes, Central nervous system,
H370
2.2 GHS Label elements, including precautionary statements
Labelling according to CLASS regulations 2013
Pictogram
Signal word Danger

Sigma-Aldrich- 322415 Page 1 of 10

the US and Canada
Hazard statement(s)
H225 Highly flammable liquid and vapor.
H301 + H311 + H331 Toxic if swallowed, in contact with skin or if inhaled.
H370 Causes damage to organs (Eyes, Central nervous system).
Precautionary statement(s)
Prevention
P210 Keep away from heat/ sparks/ open flames/ hot surfaces. No
smoking.
P260 Do not breathe dust/ fume/ gas/ mist/ vapors/ spray.
P280 Wear protective gloves/ eye protection/ face protection.
Response
P301 + P310 + P330 IF SWALLOWED: Immediately call a POISON CENTER or doctor/
physician. Rinse mouth.
P307 + P311 IF exposed: Call a POISON CENTER or doctor/ physician.
P370 + P378 In case of fire: Use dry sand, dry chemical or alcohol-resistant
foam for extinction.
Storage
P403 + P233 Store in a well-ventilated place. Keep container tightly closed.
2.3 Other hazards - none
SECTION 3: Composition and information of the ingredients of the hazardous chemical

Substance / Mixture : Substance
3.1 Substances
Synonyms : Methyl alcohol
Formula : CH4O
Molecular weight : 32.04 g/mol
CAS-No. : 67-56-1
EC-No. : 200-659-6
Index-No. : 603-001-00-X
Hazardous ingredients
Component Classification Concentration
Methanol
Flam. Liq. 2; Acute Tox. 3; <= 100 %
STOT SE 1; H225, H301,
H331, H311, H370
Concentration limits:
>= 10 %: STOT SE 1,
H370; 3 - < 10 %: STOT
SE 2, H371;

4.1 Description of first-aid measures
No data available

the US and Canada
4.2 Most important symptoms and effects, both acute and delayed
The most important known symptoms and effects are described in the labelling (see section
2.2) and/or in section 11
No data available

No data available
5.2 Special hazards arising from the substance or mixture
Carbon oxides
Combustible.
No data available
5.4 Further information
No data available

6.1 Personal precautions, protective equipment and emergency procedures
For personal protection see section 8.
6.2 Environmental precautions
No data available
6.3 Methods and materials for containment and cleaning up
No data available
6.4 Reference to other sections
For disposal see section 13.

7.1 Precautions for safe handling
For precautions see section 2.2.
7.2 Conditions for safe storage, including any incompatibilities
No data available
7.3 Specific end use(s)
Apart from the uses mentioned in section 1.2 no other specific uses are stipulated
SECTION 8: Exposure controls and personal protection

8.1 Control parameters
Ingredients with workplace control parameters
Component CAS-No. Value Control Basis
parameters

the US and Canada
Methanol 67-56-1 TWA 200 ppm 262 Malaysia. Occupational Safety
mg/m3 and Health (Use and Standards
of Exposure of Chemicals
Hazardous to Health)
Regulations 2000.
Remarks Skin
Derived No Effect Level (DNEL)
Application Area Routes of Health effect Value
exposure
Workers Skin contact Long-term systemic effects 40mg/kg BW/d
Consumers Skin contact Long-term systemic effects 8mg/kg BW/d
Consumers Ingestion Long-term systemic effects 8mg/kg BW/d
Workers Skin contact Acute systemic effects 40mg/kg BW/d
Consumers Skin contact Acute systemic effects 8mg/kg BW/d
Consumers Ingestion Acute systemic effects 8mg/kg BW/d
Workers Inhalation Acute systemic effects 260 mg/m3
Workers Inhalation Acute local effects 260 mg/m3
Workers Inhalation Long-term systemic effects 260 mg/m3
Workers Inhalation Long-term local effects 260 mg/m3
Consumers Inhalation Acute systemic effects 50 mg/m3
Consumers Inhalation Acute local effects 50 mg/m3
Consumers Inhalation Long-term systemic effects 50 mg/m3
Consumers Inhalation Long-term local effects 50 mg/m3
Predicted No Effect Concentration (PNEC)
Compartment Value
Soil 23.5 mg/kg
Sea water 15.4 mg/l
Fresh water 154 mg/l
Fresh water sediment 570.4 mg/kg
Onsite sewage treatment plant 100 mg/kg
Personal protective equipment
Skin protection
This recommendation applies only to the product stated in the safety data sheet,
supplied by us and for the designated use. When dissolving in or mixing with other
substances and under conditions deviating from those stated in EN374 please
contact the supplier of CE-approved gloves (e.g. KCL GmbH, D-36124 Eichenzell,
Internet: www.kcl.de).
Full contact
Material: butyl-rubber
Material tested:Butoject® (KCL 898)
This recommendation applies only to the product stated in the safety data sheet,
supplied by us and for the designated use. When dissolving in or mixing with other
substances and under conditions deviating from those stated in EN374 please
contact the supplier of CE-approved gloves (e.g. KCL GmbH, D-36124 Eichenzell,
Internet: www.kcl.de).
Splash contact
Material: Viton®

the US and Canada
Material tested:Vitoject® (KCL 890 / Aldrich Z677698, Size M)
Control of environmental exposure

Prevent product from entering drains.

a) Appearance Form: liquid
Color: colorless
b) Odor characteristic
c) Odor Threshold 10 ppm
d) pH No data available
e) Melting Melting point/range: -98 °C
point/freezing point
f) Initial boiling point 64.7 °C
and boiling range
g) Flash point 9.7 °C - closed cup - Regulation (EC) No. 440/2008, Annex, A.9
h) Evaporation rate 6.3 - Diethyl ether1.9 - n-butyl acetate
i) Flammability (solid, No data available
gas)
j) Upper/lower Upper explosion limit: 44 %(V)
flammability or Lower explosion limit: 5.5 %(V)
explosive limits
k) Vapor pressure 169.27 hPa at 25 °C
l) Vapor density 1.11
m) Relative density 0.79 - 0.8 at 20 °C
n) Water solubility 1,000 g/l at 20 °C - completely miscibleat 20 °C soluble
o) Partition coefficient: log Pow: -0.77 - (Lit.), Bioaccumulation is not expected.
n-octanol/water
p) Autoignition 455.0 °C
temperature at 1,013 hPa - DIN 51794
q) Decomposition Distillable in an undecomposed state at normal pressure.
temperature
r) Viscosity Viscosity, kinematic: 0.54 - 0.59 mm2/s at 20 °C
Viscosity, dynamic: > 0.544 - < 0.59 mPa.s at 25 °C

s) Explosive properties No data available
t) Oxidizing properties No data available
9.2 Other safety information
Minimum ignition 0.14 mJ
energy

the US and Canada
Conductivity < 1 µS/cm
Relative vapor 1.11
density

10.1 Reactivity
No data available
10.2 Chemical stability
No data available
10.3 Possibility of hazardous reactions
Risk of explosion with:
Oxidizing agents
perchloric acid
perchlorates
salts of oxyhalogenic acids
chromium(VI) oxide
halogen oxides
nitrogen oxides
nonmetallic oxides
chromosulfuric acid
chlorates
hydrides
zinc diethyl
halogens
powdered magnesium
hydrogen peroxide
Nitric acid
sulfuric acid
permanganic acid
sodium hypochlorite
Exothermic reaction with:
acid halides
Acid anhydrides
Reducing agents
acids
Bromine
Chlorine
Chloroform
magnesium
tetrachloromethane
Risk of ignition or formation of inflammable gases or vapours with:
Fluorine
Oxides of phosphorus
Raney-nickel
Generates dangerous gases or fumes in contact with:
Alkaline earth metals
Alkali metals
10.4 Conditions to avoid

No data available

the US and Canada
various plastics, magnesium, zinc alloys
10.6 Hazardous decomposition products
In the event of fire: see section 5

Acute toxicity
Acute toxicity estimate Oral - 100.1 mg/kg
(Expert judgment)
Symptoms: Nausea, Vomiting
Acute toxicity estimate Inhalation - 4 h - 3.1 mg/l
(Expert judgment)
Symptoms: Irritation symptoms in the respiratory tract.
Acute toxicity estimate Dermal - 300.1 mg/kg
(Expert judgment)
Skin corrosion/irritation
Skin - Rabbit
Result: No skin irritation
Remarks: (ECHA)
Drying-out effect resulting in rough and chapped skin.
Serious eye damage/eye irritation
Eyes - Rabbit
Result: No eye irritation
Remarks: (ECHA)
Respiratory or skin sensitization
Sensitisation test: - Guinea pig
Result: negative
(OECD Test Guideline 406)
Germ cell mutagenicity
Based on available data the classification criteria are not met.
Test Type: Ames test
Test system: Salmonella typhimurium
Metabolic activation: with and without metabolic activation
Method: OECD Test Guideline 471
Result: negative
Test Type: In vitro mammalian cell gene mutation test
Test system: Chinese hamster lung cells
Metabolic activation: with and without metabolic activation
Result: negative
Test Type: Micronucleus test

Species: Mouse
Cell type: Bone marrow
Application Route: Intraperitoneal injection
Result: negative
Carcinogenicity
No data available

the US and Canada
Based on available data the classification criteria are not met.
Specific target organ toxicity - single exposure
Causes damage to organs. - Eyes, Central nervous system
Remarks: Classified according to Regulation (EU) 1272/2008, Annex VI (Table 3.1/3.2)
Specific target organ toxicity - repeated exposure
No data available
Aspiration hazard
No data available
11.2 Additional Information
RTECS: PC1400000
To the best of our knowledge, the chemical, physical, and toxicological properties have not
been thoroughly investigated.
Systemic effects:
acidosis
drop in blood pressure
agitation, spasms
inebriation
Dizziness
Drowsiness
Headache
Impairment of vision
Blindness
narcosis
Coma
Symptoms may be delayed.
Damage to:
Liver
Kidney
Cardiac
Irreversible damage of the optical nerve.
Other dangerous properties can not be excluded.
This substance should be handled with particular care.

12.1 Toxicity
Toxicity to fish flow-through test LC50 - Lepomis macrochirus (Bluegill) - 15,400.0
mg/l - 96 h
(US-EPA)
Toxicity to daphnia semi-static test EC50 - Daphnia magna (Water flea) - 18,260 mg/l -
and other aquatic 96 h
invertebrates (OECD Test Guideline 202)

the US and Canada
Toxicity to algae static test ErC50 - Pseudokirchneriella subcapitata (green algae) - ca.
22,000.0 mg/l - 96 h
Toxicity to bacteria static test IC50 - activated sludge - > 1,000 mg/l - 3 h
12.2 Persistence and degradability
Biodegradability Result: 99 % - Readily biodegradable.
(OECD Test Guideline 301D)
Biochemical Oxygen 600 - 1,120 mg/g
Demand (BOD) Remarks: (IUCLID)
Chemical Oxygen 1,420 mg/g
Demand (COD) Remarks: (IUCLID)
Theoretical oxygen 1,500 mg/g
demand Remarks: (Lit.)
Ratio BOD/ThBOD 76 %
Remarks: Closed Bottle test(IUCLID)
Bioaccumulation Cyprinus carpio (Carp) - 72 d
at 20 °C - 5 mg/l(Methanol)
Bioconcentration factor (BCF): 1.0

Will not adsorb on soil.
12.5 Results of PBT and vPvB assessment
PBT/vPvB assessment not available as chemical safety assessment not required/not
conducted
12.6 Other adverse effects
Additional ecological Avoid release to the environment.
information
Stability in water at 19 °C83 - 91 % - 72 h
Remarks: Hydrolyzes on contact with water.Hydrolyzes readily.
SECTION 13: Disposal information

No data available
SECTION 14: Transportation information

14.1 UN number
ADR/RID: 1230 IMDG: 1230 IATA-DGR: 1230
14.2 UN proper shipping name
ADR/RID: METHANOL
IMDG: METHANOL
IATA-DGR: Methanol

the US and Canada
14.3 Transport hazard class(es)
ADR/RID: 3 (6.1) IMDG: 3 (6.1) IATA-DGR: 3 (6.1)
14.4 Packaging group
ADR/RID: II IMDG: II IATA-DGR: II
14.5 Environmental hazards
ADR/RID: no IMDG Marine pollutant: no IATA-DGR: no
14.6 Special precautions for user
None
various plastics, magnesium, zinc alloys
Other regulations
Hazchem Code : •2WE

15.1 Safety, health and environmental regulations/legislation specific for the
substance or mixture
Notification status
DSL: All components of this product are on the Canadian DSL
ENCS: On the inventory, or in compliance with the inventory
ISHL: On the inventory, or in compliance with the inventory
KECI: On the inventory, or in compliance with the inventory
NZIoC: On the inventory, or in compliance with the inventory
PICCS: On the inventory, or in compliance with the inventory

Full text of H-Statements referred to under sections 2 and 3.
H225 Highly flammable liquid and vapor.
H301 Toxic if swallowed.
H311 Toxic in contact with skin.
H331 Toxic if inhaled.
H370 Causes damage to organs.
H371 May cause damage to organs.
The branding on the header and/or footer of this document may temporarily not visually
match the product purchased as we transition our branding. However, all of the
information in the document regarding the product remains unchanged and matches the
product ordered. For further information please contact mlsbranding@sial.com.

the US and Canada

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SMJC 4824 CHEMICAL PROCESS DESIGN

No. Team Members Matric No.

1 Gan Cheng Ling A18MJ0035

2 Amir Hamdi Bin Aznil A18MJ3012

3 Muhammad Fitri Bin Rozmi A18MJ0086

4 Nur Qamarina Binti Hazian A18MJ0120

5 Rashmeera Siva Vijian A18MJ0196

SUPERVISOR: DR ROSHAFIMA RASIT ALI &

DR NURFATEHAH WAHYUNY CHE JUSOH

Methanol is used as a feedstock in various chemical applications. In this

CHAPTER 2 PROCESS SYNTHESIS 1 35

CHAPTER 3 EFFLUENT AND WASTE MANAGEMENT 119

CHAPTER 4 ENERGY INTEGRATION 143

CHAPTER 6 PROCESS SAFETY 239

TABLE NO. TITLE PAGE

Table 1.1 Properties of Methanol 3

Table 4.4 Shifted Temperature for ΔTmin = 10℃ 154

Table 7.45 Detail calculation of the allocated cost, 𝐶𝑎𝑙𝑙𝑜𝑐 426

Table 7.47 Calculation of total depreciable capital, CTCI 429

FIGURE NO. TITLE PAGE

Figure 1.1 Company Organizational Chart 1

Figure 4.6 Combined hot and cold composite curves at ∆𝑇 = ∆𝑇𝑚𝑖𝑛 =

APPENDIX TITLE PAGE

Appendix A Material Safety Data Sheet (MSDS) 459

1.1 Company Background

Vermonix Technology Consultancy was established in 2017 by a group of

Figure 1.1 Company Organizational Chart

1.2.1 Background of Methanol

Methanol, commonly known as methyl alcohol, is a chemical that has the

Figure 1.2 Chemical Structure of Methanol

Previously, it was originally mostly manufactured by the destructive

However, commercially, it stagnated. Methanol costs were almost the same as

1.2.2 Physical and Chemical Properties of Methanol

Methanol, CH3-OH, is a colorless, somewhat volatile liquid with a mildly

Table 1.1 Properties of Methanol

Molar Mass 32.04 g/mol

Melting Point - 97.6 °C

Boiling Point - 64.7 °C

Thermal Conductivity 0.202 W/m °C

Heat of Formation - 6398 kJ/kg

Heat of Evaporation 1165 kJ/kg

Density (gas) at 0.17 bar 0.220 kg/m3

Refractive Index 1.328 at 20 °C

Critical Pressure 82.2 bar (81.1 atm)

Critical Temperature 240.2 °C

Magnetic Susceptibility 5.3×10−7 cm3·g−1

Dielectric Constant 32.70

Autoignition Point 464 °C

The Lower Limit of Flammability 6% by volume of air

1.2.3 Application of Methanol

In terms of applications, Methanol is fairly versatile. Because of its efficiency

Methanol is a kind of alcohol that is mostly derived from biogas. Methanol

Methanol as a fuel is a promising alternative to traditional vehicle fuel (Schultz

In relation to the prevention of the Covid-19 pandemic, the use of methanol as

Biogas is an environmentally friendly, clean, renewable energy source. It is

Biogas is produced as a result of anaerobic decomposition of biomass, which

The composition of biogas is determined by a variety of factors, including the

Biogas Natural Gas

Definition A gas that arises A naturally occurring gas

Sources There are natural biogas Natural gas cannot be

Sustainability Biogas is a renewable energy Natural gas is a nonrenewable

Raw Sources of raw organic Natural gas comes from layers of

Formation Anaerobic digestion of organic Natural gas is generated by