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Understand the pivotal role that the petrochemical industry will play in the energy transition by integrating renewable or low-carbon alternatives
Power into Chemicals and Fuels stresses the versatility of hydrogen as an enabler of the renewable energy system, an energy vector that can be transported and stored, and a fuel for the transportation sector, heating of buildings and providing heat and feedstock to industry. It can reduce both carbon and local emissions, increase energy security and strengthen the economy, as well as support the deployment of renewable power generation such as wind, solar, nuclear and hydro.
With a focus on power-to-X technologies, this book discusses the production of basic petrochemicals in such a way as to minimize the carbon footprint and develop procedures that save energy or use energy from renewable sources. Various different power-to-X system configurations are introduced with discussions on their performance, environmental impact, and cost. Technologies for sustainable hydrogen production are covered, focusing on water electrolysis using renewable energy as well as consideration of the remaining challenges for large scale production and integration with other technologies.
Power into Chemicals and Fuels readers will also find:
Power into Chemicals and Fuels is a valuable resource for scientists and engineers working in the petrochemicals and hydrocarbons industries, as well as for all industry professionals in these and related fields.
Martin Bajus, PhD is Professor of Chemical Technology at the Institute of Organic Chemistry, Catalysis, and Petrochemistry, Slovak University of Technology, Bratislava, Slovak Republic. He founded the Bratislava School of Pyrolysis at the Slovak University of Technology, and has published extensively on energy and petrochemical subjects.
About the Book xvii
Preface xix
Acknowledgments xxiii
General Literature xxv
Nomenclature xxxi
Abbreviations and Acronyms xxxiii
1 Power-to-Chemical Technology 1
1.1 Introduction 2
1.2 Power-to-Chemical Engineering 4
1.2.1 Carbon Dioxide Thermodynamics 4
1.2.2 Carbon Dioxide Aromatization Thermodynamics 12
1.2.3 Reaction Mechanism of Carbon Dioxide Methanation 14
1.2.4 Water Electrolysis Thermodynamics 18
1.2.5 Methane Pyrolysis Reaction Thermodynamic Consideration 20
1.2.5.1 The Carbon-Hydrogen System 20
1.2.6 Reaction Kinetics and Mechanism 27
1.2.7 Thermal Mechanism of Methane Pyrolysis into a Sustainable Hydrogen 28
1.2.8 Catalytic Mechanism Splitting of Methane into a Sustainable Hydrogen 30
1.2.9 Conversion of Methane over Metal Catalysts into a Sustainable Hydrogen 35
1.2.9.1 Nickel Catalysts 35
1.2.9.2 Iron Catalysts 37
1.2.9.3 Regeneration of Metal Catalysts 39
1.2.10 Conversion of Methane over Carbon Catalysts into Clean Hydrogen 40
1.2.10.1 Activity of Carbon Catalysts 40
1.2.10.2 Stability and Deactivation of Carbon Catalysts 42
1.2.10.3 Regeneration of Carbon Catalysts 43
1.2.10.4 Co-Feeding to Extend the Lifetime of Carbon Catalysts 44
1.2.11 Reactors 44
1.2.11.1 Conversion, Selectivity and Yields 44
1.2.11.2 Modelling Approach of the Structured Catalytic Reactors 45
1.2.11.3 Reactor Concept for Catalytic Carbon Dioxide Methanation 46
1.2.11.4 Monolithic Reactors 48
1.2.11.5 Mass Transfer in the Honeycomb and Slurry Bubble Column Reactor 49
1.2.11.6 Heat Transfer in Honeycomb and Slurry Bubble Column Reactors 50
1.2.11.7 Process Design 51
1.2.11.8 Comparison and Outlook 52
1.3 Potential Steps Towards Sustainable Hydrocarbon Technology: Vision and Trends 53
1.3.1 Technology Readiness Levels 54
1.3.2 A Vision for the Oil Refinery of 2030 59
1.3.3 The Transition from Fuels to Chemicals 60
1.3.3.1 Crude Oil to Chemicals Investments 66
1.3.3.2 Available Crude-to-Chemicals Routes 67
1.3.4 Business Trends: Petrochemicals 2025 67
1.3.4.1 Asia-Pacific 69
1.3.4.2 Middle East 70
1.3.4.3 United States 70
1.4 Digital Transformation 71
1.4.1 Benefits of Digital Transformation 71
1.4.2 A New Workforce and Workplace 72
1.4.3 Technology Investment 73
1.4.4 The Greening of the Downstream Industry 74
1.4.4.1 Sustainable Alkylation Technology 75
1.4.4.2 Ecofriendly Catalyst 75
1.5 RAM Modelling 76
1.5.1 RAM1 Site Model 77
1.5.2 RAM2 Plant Models 77
1.5.3 RAM3 Models 78
1.5.4 RAM Modelling Benefit 78
1.6 Conclusions 78
Further Reading 80
2 The Green Shift in Power-to-Chemical Technology and Power-to-Chemical Engineering: A Framework for a Sustainable Future 85
2.1 Introduction 86
2.2 Eco-Friendly Catalyst 87
2.2.1 Development of Catalysts Supported on Carbons for Carbon Dioxide Hydrogenation 88
2.2.2 Properties of Carbon Supports 89
2.3 Hydrogen 91
2.3.1 Different Colours and Costs of Hydrogen 92
2.3.1.1 Blue Hydrogen 92
2.3.1.2 Green Hydrogen 92
2.3.1.3 Grey Hydrogen 93
2.3.1.4 Pink Hydrogen 93
2.3.1.5 Yellow Hydrogen 93
2.3.1.6 Multi-Coloured Hydrogen 93
2.3.1.7 Hydrogen Cost 93
2.4 Alternative Feedstocks 95
2.4.1 Carbon Dioxide-Derived Chemicals 95
2.5 Alternative Power-to-X-Technology 97
2.5.1 Power-to-X-Technology to Produce Electrochemicals and Electrofuels 97
2.6 Partial Oxidation of Methane 99
2.7 Biorefining 99
2.8 Sustainable Production to Advance the Circular Economy 100
2.8.1 Introduction 100
2.8.2 Circular Economy 101
2.8.2.1 Sustainability 101
2.8.2.2 Scope 101
2.8.2.3 Background of the Circular Economy 102
2.8.2.3.1 Emergence of the Idea 102
2.8.2.3.2 Moving Away from the Linear Model 103
2.8.2.3.3 Towards the Circular Economy 103
2.8.3 Circular Business Models 103
2.8.4 Industries Adopting a Circular Economy 104
2.8.4.1 Minimizing Dependence on Fossil Fuels 104
2.8.4.2 Minimizing the Impact of Chemical Synthesis and Manufacturing 105
2.8.4.3 Future Research Needs in Developing a Circular Economy 106
2.9 New Chemical Technologies 106
2.9.1 Renewable Power 107
Further Reading 108
3 Storage Renewable Power-to-Chemicals 113
3.1 Introduction 113
3.2 Terminology 118
3.3 Energy Storage Systems 119
3.4 World Primary Energy Consumption 126
3.4.1 2019 Briefly 126
3.4.2 Energy in 2020 128
3.4.2.1 Not Just Green but Greening 128
3.4.2.2 For Energy, 2020 Was a Year Like No Other 129
3.4.2.3 Glasgow Climate Pact 129
3.4.2.4 Energy in 2020: What Happened and How Surprising Was It 131
3.4.2.5 How Should We Think About These Reductions 131
3.4.2.6 What Can We Learn from the COVID-induced Stress Test 133
3.4.2.7 Progress Since Paris – How Is the World Doing 134
3.5 Carbon Dioxide Emissions 135
3.5.1 Carbon Footprint 136
3.5.1.1 Climate-driven Warming 137
3.5.2 Carbon Emissions in 2020 138
3.6 Clean Fuels ‒ the Advancement to Zero Sulfur 139
3.7 Renewables in 2019 140
3.8 Hydroelectricity and Nuclear Energy 141
3.9 Conclusion 141
Further Reading 142
4 Carbon Capture, Utilization and Storage Technologies 145
4.1 Industrial Sources of Carbon Dioxide 145
4.2 Carbon Capture, Utilization and Storage Technologies 147
4.3 Carbon Dioxide Capture 147
4.4 Developing and Deploying CCUS Technology in the Oil and Gas Industry 155
4.5 Sustainable Steel/Chemicals Production: Capturing the Carbon in the Material Value Chain 158
4.5.1 Valorisation of Steel Mill Gases 158
4.5.2 Summary and Outlook 161
Further Reading 162
5 Integrated Refinery Petrochemical Complexes Including Power-to-X Technologies 165
5.1 Introduction 165
5.2 Synergies Between Refining and Petrochemical Assets 167
5.2.1 Reaching Maximum Added Value – Integrated Refining Schemes 168
5.2.1.1 Fluid Catalytic Cracking Alternates 168
5.2.1.2 Hydrocracking Alternates 170
5.2.2 Comparisons and Sensitivities to Product/Utility Pricing 172
5.2.3 Options for Further Increasing the Petrochemical Value Chain 174
5.3 Carbon Dioxide Emissions 175
5.3.1 Effect of a Carbon Dioxide Tax 176
5.3.2 Crude Oil Effects 179
5.4 Summary 180
5.5 Power- to-X Technology 181
5.6 The Role of Nuclear Power 185
5.6.1 Small Nuclear Power Reactors 187
5.6.2 Conclusion 187
Further Reading 188
6 Power-to-Hydrogen Technology 191
6.1 Introduction 192
6.2 Traditional and Developing Technologies for Hydrogen Production 193
6.3 Dry Reforming of Methane 195
6.4 Tri-reforming of Methane 197
6.5 Greenfield Technology Option → Low Carbon Emission Routes 198
6.5.1 Water Electrolysis 201
6.5.1.1 Alkaline Electrolysis 202
6.5.1.2 Polymer Electrolyte Membrane Electrolysis 203
6.5.1.3 Solid Oxide Electrolysis 204
6.5.2 Methane Pyrolysis 207
6.5.2.1 Process Concepts for Industrial Application 208
6.5.2.2 Perspectives of the Carbon Coproduct 211
6.5.3 Thermochemical Processes 213
6.5.4 Photocatalytic Processes 213
6.5.5 Biomass Electro-Reforming 214
6.5.6 Microorganisms 215
6.5.7 Hydrogen from Other Industrial Processes 215
6.5.8 Hydrogen Production Cost 215
6.5.9 Electrolysers 215
6.5.10 Carbon Footprint 216
6.6 Advances in Chemical Carriers for Hydrogen 216
6.6.1 Demand Drivers 217
6.6.2 Options for Hydrogen Deployment 218
6.6.3 Advances in Hydrogen Storage/Transport Technology 218
6.6.4 Global Supply Chain 220
6.6.5 Power-to-Gas Demo 220
6.6.5.1 Hydrogen Fuelling Stations 221
6.6.5.2 Pathway to Commercialization 221
6.6.5.3 Transportation Studies in North America 221
6.6.6 Future Applications 222
6.7 Ammonia Fuel Cells 223
6.7.1 Proton-Conducting Fuel Cells 223
6.7.2 Polymer Electrolyte Membrane Fuel Cells 224
6.7.3 Proton-conducting Solid Oxide Fuel Cells 224
6.7.4 Alkaline Fuel Cells 225
6.7.5 Direct Ammonia Solid Oxide Fuel Cell 226
6.7.6 Equilibrium Potential and Efficiency of the Ammonia-Fed SOFC 227
6.8 Conclusions 228
Further Reading 228
7 Power-to-Fuels 233
7.1 Introduction 234
7.2 Selection of Fuel Candidates 240
7.2.1 Fuel Production Processes 241
7.3 Power-to-Methane Technology 242
7.3.1 Carbon Dioxide Electrochemical Reduction 242
7.3.2 Carbon Dioxide Hydrogenation 244
7.4 Power-to-Methanol 248
7.5 Power-to-Dimethyl Ether 249
7.6 Chemical Conversion Efficiency 250
7.6.1 Exergy 250
7.6.2 Exergy Efficiency 251
7.6.3 Economic and Environmental Evaluation 251
7.6.4 Fuel Assessment 252
7.6.5 Performance of Fuel Production Processes 253
7.6.6 Process Chain Evaluation 254
7.6.7 Fuel Cost 255
7.7 Well-to-Wheel Greenhouse Gas Emissions 257
7.7.1 Environmental Impact 258
7.7.2 Infrastructure 258
7.7.3 Efficiency 259
7.7.4 Energy/Power Density 259
7.7.5 Pollutant Emissions 260
7.8 Gasoline Electrofuels 260
7.9 Diesel Electrofuels 261
7.10 Electrofuels and/or Electrochemicals 263
7.10.1 Physico-Chemical Properties 264
7.10.1.1 Density 264
7.10.1.2 Tribological Properties 264
7.10.1.3 Combustion Characteristics 265
7.10.1.4 Combustion and Emissions 267
7.10.2 Diesel Engine Efficiency 269
7.10.3 Potential of Diesel Electrofuels 269
7.11 Maturity, TRL, Production and Electrolysis Costs 271
7.11.1 Summary 273
7.12 Power-to-Liquid Technology 274
7.12.1 Power-to-Jet Fuel 275
7.12.2 Power-to-Diesel 276
7.13 Conclusion and Outlook 276
Further Reading 278
8 Power-to-Light Alkenes 283
8.1 Oxidative Dehydrogenation 283
8.1.1 Carbon Dioxide as a Soft Oxidant for Catalytic Dehydrogenation 283
8.1.2 Carbon Dioxide: Oxidative Coupling of Methane 285
8.1.3 From Carbon Dioxide to Lower Olefins 289
8.1.4 Low-Carbon Production of Ethylene and Propylene 291
8.1.4.1 Energy Demand per Unit of Ethylene/Propylene Production via Methanol 292
8.1.4.2 Carbon Dioxide Reduction per Unit of Ethylene/Propylene Production 292
8.1.4.3 Economics of Low-Carbon Ethylene and Propylene Production 293
8.2 Life Cycle Assessment 293
8.2.1 Small-Scale Production of Ethylene 293
8.3 Polymerization Reaction 294
8.3.1 Carbon Dioxide-Based Polymers 294
8.3.1.1 Perspective and Practical Applications 298
Further Reading 299
9 Power-to-BTX Aromatics 301
9.1 Low-Carbon Production of Aromatics 301
9.1.1 Methanol to Aromatics Process 303
9.1.1.1 ZSM-5 Catalyst 304
9.1.1.2 Process Variables 305
9.1.1.3 Kinetic Modelling 306
9.1.1.4 Aromatics via Hydrogen-Based Methanol (TRL7) 307
9.1.1.5 Energy Demand per Unit of Low-Carbon BTX Production 308
9.1.1.6 Carbon Dioxide Reduction 308
9.1.1.7 Economics of Low-Carbon BTX Production 308
9.2 Production of p-Xylene from 2,5-Dimethylfuran and Ethylene 308
9.3 Carbon Dioxide Dehydrogenation of Ethylbenzene to Styrene 309
Further Reading 310
10 Power-to-C 1 Chemicals 313
10.1 Introduction 314
10.2 Carbon Dioxide Utilization into Chemical Technology 317
10.3 Mechanism of Conversion of Carbon Dioxide 318
10.4 Hydrogenation of Carbon Dioxide 319
10.4.1 Heterogeneous Hydrogenation 319
10.4.2 Homogeneous Hydrogenation 323
10.5 Electrochemical Conversion of Carbon Dioxide into Valuable Chemicals 324
10.5.1 Technologies Available for Carbon Dioxide Reduction 325
10.6 Electrochemical Technologies 326
10.6.1 Roles of Ionic Liquids on Electrochemical Carbon Dioxide Reduction Promotion 328
10.6.2 Ionic Liquids as Absorbent for Carbon Dioxide Capture 328
10.6.3 Classification of the Electrode Material 328
10.6.4 High Hydrogen Evolution Overvoltage Metal 329
10.6.5 Low Hydrogen Evolution Overvoltage Metals 329
10.6.6 Copper Electrodes 329
10.6.7 Other Electrodes for Carbon Dioxide Reduction 330
10.7 Power-to-Methanol Technology 331
10.7.1 Carbon Dioxide Electrochemical Reduction 332
10.7.2 Direct Carbon Dioxide Hydrogenation into Methanol 334
10.7.3 Low-Carbon Methanol Production 336
10.7.4 Energy Demand 337
10.8 Power-to-Formic Acid Technology 337
10.8.1 Carbon Dioxide Electrochemical Reduction 338
10.8.2 Carbon Dioxide Hydrogenation 339
10.9 Power-to-Formaldehyde Technology 341
10.9.1 Carbon Dioxide Electrochemical Reduction 342
10.9.2 Carbon Dioxide Hydrogenation 342
10.10 Selective Hydrogenation of Carbon Dioxide to Light Olefins 343
10.10.1 Introduction 343
10.10.2 Carbon Dioxide via FTS to Lower Olefins 345
10.10.3 Methane via FTS to Lower Olefins 347
10.10.4 Carbon Dioxide via FTS to Liquid iso-C 5 -C 13 -Alkanes 349
10.10.4.1 Power-to-Liquids 352
10.10.4.2 Energy Demand per Unit of Synthetic Fuel Production 352
10.10.4.3 Carbon Dioxide Reduction per Unit of Synthetic Fuel Production 353
10.10.4.4 Economics 353
10.10.4.5 Comparison of the Hydrogen-Based Low-Carbon Synthesis Routes 353
10.11 Electrochemical Reduction of Carbon Dioxide to Oxalic Acid 354
10.11.1 Process Design and Modelling 355
10.11.2 Carbon Dioxide Absorption in Propylene Carbonate 356
Further Reading 356
11 Power-to-Green Chemicals 363
11.1 Introduction 364
11.2 Biomethanol Production 365
11.2.1 Biomethanol Production Process 365
11.2.2 Energy and Feedstock Demand per Unit of Biomethanol Production 366
11.2.3 Carbon Dioxide Reduction per Unit of Biomethanol Production 367
11.2.4 Economics of Biomethanol Production 367
11.3 Bioethanol Production 367
11.3.1 Bioethanol Production Process 368
11.3.2 Energy and Feedstock Demand per Unit of Bioethanol Production 369
11.3.3 Carbon Dioxide Reduction per Unit of Bioethanol Production 370
11.3.4 Carbon Dioxide Reduction for (Partially) Replacing Gasoline with Bioethanol 370
11.3.5 Economics of Bioethanol Production 370
11.4 Bioethylene Production 371
11.4.1 Bioethylene Production Process 371
11.4.2 Energy and Feedstock Demand per Unit of Bioethylene Production 371
11.4.3 Carbon Dioxide Reduction per Unit of Bioethylene Production 371
11.4.4 Economics of Bioethylene Production 372
11.5 Biopropylene Production 372
11.5.1 Biopropylene Production Processes 372
11.5.2 Energy and Feedstock Demand per Unit of Biopropylene Production 372
11.5.3 Carbon Dioxide Reduction per Unit of Biopropylene Production 373
11.6 BTX Production from Biomass 373
11.6.1 BTX Production Process 373
11.6.2 Energy and Feedstock Demand per Unit of BTX Production from Biomass 374
11.6.3 Carbon Dioxide Emissions per Unit of BTX Production from Biomass 374
11.7 Comparison of the Biomass-Based Synthesis Routes 374
11.8 Biofuels 376
11.8.1 Biodiesel Production 377
11.8.2 Purification of Glycerol 379
11.8.3 Conversion of Glycerol into Valuable Products 380
11.8.3.1 Solketal Synthesis Process 382
11.8.3.2 Reaction Mechanism 383
11.8.3.3 Kinetics of Reaction 384
11.8.3.4 Catalyst Design 385
11.8.3.5 Batch Process 387
11.8.3.6 Continuous Process 388
11.8.4 Current Issues and Challenges 389
11.8.5 Future Recommendation 391
11.8.6 Conclusion 391
11.9 Higher Alcohols and Ether Biofuels 392
11.9.1 Fuel Production Routes and Sustainability 393
11.9.2 Lignin 394
11.9.3 Fuel Properties 394
11.9.4 Concluding Remarks 396
11.10 Biofuels in the World: Biogasoline and Biodiesel 396
Further Reading 399
12 Industrial Small Reactors 405
12.1 Introduction 405
12.2 Thermochemical Water Splitting 406
12.3 Small Modular Reactors 407
12.4 Nuclear Process Heat for Industry 410
12.4.1 High-temperature Reactors for Process Heat 410
12.4.2 Recovery of Oil from Tar Sands 413
12.4.3 Oil Refining 414
12.4.4 Coal and Its Liquefaction 414
12.4.5 Biomass-Based Ethanol Production 415
12.4.6 District Heating 416
12.5 Microchannel Reduction Cell 416
12.6 Conversion of Carbon Dioxide to Graphene 417
12.7 The Ammonia Synthesis Reactor-Development of Small-scale Plants 419
Further Reading 421
13 Recycling of Waste Plastics → Plastics Circularity 423
13.1 Introduction 424
13.2 Mechanism Aspects of Waste Plastic Pyrolysis 426
13.2.1 Polyethylene and Polypropylene 428
13.2.2 Polyethylene Terephthalate 429
13.2.3 Polyvinyl Chloride 430
13.2.4 Polystyrene 431
13.2.5 Poly (Methyl Methacrylate) 432
13.3 Kinetics 433
13.4 Catalysts 434
13.4.1 Zeolites 434
13.4.2 Fluid Catalytic Cracking Catalysts 434
13.5 Parameters Affecting Pyrolysis 436
13.5.1 Type of Plastic Feed 436
13.5.2 Temperature and Residence Time 437
13.5.3 Pressure 438
13.6 Type of Reactors 438
13.6.1 Rotary Kiln Reactor 438
13.6.2 Screw Feed (Auger) Reactor 439
13.6.3 Fluid Catalytic Cracking Reactor 440
13.6.4 Stirred-Tank Reactor 440
13.6.5 Plasma Pyrolysis Reactor 441
13.6.6 Batch Reactor 442
13.6.7 Fixed Bed Reactor 442
13.6.8 Fluidized Bed Reactor 443
13.6.9 Conical Spouted Bed Reactor 443
13.6.10 Microwave Reactor 444
13.6.11 Pyrolysis in Supercritical Water 445
13.7 Applications of Pyrolysis Products 446
13.7.1 Pyrolysis Gases → Hydrogen and Methane 446
13.7.2 Pyrolysis Oil → Aromatics and Diesel Fuels 446
13.7.3 Pyrolysis Char → Nanotubes 449
Further Reading 450
Index 455
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