Preface xiii Part 1: Production 1 1 Energy Sources and Energy Supply 3 1.1 Introduction 3 1.2 Typical Energy Sources 8 1.2.1 Natural Gas and Natural Gas Hydrates 9 1.2.2 The Crude Oil Family 10 1.2.3 Extra Heavy Crude Oil and Tar Sand Bitumen 12 1.3 Other Energy Sources 15 1.3.1 Coal 16 1.3.2 Oil Shale 19 1.3.3 Biomass 21 1.3.4 Solid Waste 25 1.4 Energy Supply 28 1.4.1 Economic Factors 28 1.4.2 Geopolitical Factors 29 1.4.3 Physical Factors 29 1.4.4 Technological Factors 30 1.5 Energy Independence 31 References 36 2 Production of Synthesis Gas 41 2.1 Introduction 41 2.2 Synthesis Gas Generation 44 2.3 Feedstocks 46 2.3.1 Natural Gas 46 2.3.2 Crude Oil Resid, Heavy Crude Oil, Extra Heavy Crude Oil, and Tar Sand Bitumen 47 2.3.3 Refinery Coke 50 2.3.4 Coal 50 2.3.5 Biomass 52 2.3.6 Solid Waste 56 2.3.7 Black Liquor 59 2.3.8 Mixed Feedstocks 61 2.3.8.1 Biomass and Coal 62 2.3.8.2 Biomass and Municipal Solid Waste 62 2.4 Influence of Feedstock Quality 63 2.5 Gasification Processes 65 2.5.1 Feedstock Pretreatment 66 2.5.2 Feedstock Devolatilization 67 2.5.3 Char Gasification 68 2.5.4 General Chemistry 68 2.5.5 Stage-by-Stage Chemistry 72 2.5.5.1 Primary Gasification 72 2.5.5.2 Secondary Gasification 74 2.5.5.3 Water Gas Shift Reaction 76 2.5.5.4 Carbon Dioxide Gasification 77 2.5.5.5 Hydrogasification 78 2.5.5.6 Methanation 79 2.5.5.7 Catalytic Gasification 80 2.5.6 Physical Effects 80 2.6 Products 82 2.6.1 Gaseous Products 83 2.6.1.1 Low Btu Gas 84 2.6.1.2 Medium Btu Gas 85 2.6.1.3 High Btu Gas 86 2.6.1.4 Synthesis Gas 86 2.6.2 Liquid Products 87 2.6.3 Tar 88 References 89 3 Gasifier Types and Gasification Chemistry 95 3.1 Introduction 95 3.2 Gasifier Types 96 3.2.1 Fixed-Bed Gasifier 102 3.2.2 Fluid-Bed Gasifier 105 3.2.3 Entrained-Bed Gasifier 108 3.2.4 Molten Salt Gasifier 109 3.2.5 Plasma Gasifier 111 3.2.6 Other Types 113 3.2.7 Gasifier Selection 113 3.3 General Chemistry 115 3.3.1 Devolatilization 118 3.3.2 Products 118 3.4 Process Options 119 3.4.1 Effects of Process Parameters 120 3.4.2 Effect of Heat Release 121 3.4.3 Other Effects 121 References 122 4 Gasification of Coal 125 4.1 Introduction 125 4.2 Coal Types and Properties 128 4.3 Gas Products 130 4.3.1 Coal Devolatilization 131 4.3.2 Char Gasification 131 4.3.3 Gasification Chemistry 132 4.3.4 Other Process Options 133 4.3.4.1 Hydrogasification 133 4.3.4.2 Catalytic Gasification 134 4.3.4.3 Plasma Gasification 134 4.3.5 Process Optimization 135 4.4 Product Quality 136 4.4.1 Low Btu Gas 136 4.4.2 Medium Btu Gas 138 4.4.3 High Btu Gas 138 4.4.4 Methane 139 4.4.5 Hydrogen 139 4.4.6 Other Gases 140 4.5 Chemicals Production 140 4.5.1 Coal Tar Chemicals 140 4.5.2 Fischer-Tropsch Chemicals 143 4.5.2.1 Fischer-Tropsch Catalysts 143 4.5.2.2 Product Distribution 144 4.6 Advantages and Limitations 145 References 145 5 Gasification of Heavy Feedstocks 149 5.1 Introduction 149 5.2 Heavy Feedstocks 152 5.2.1 Crude Oil Residua 153 5.2.2 Heavy Crude Oil 155 5.2.3 Extra Heavy Crude Oil 155 5.2.4 Tar Sand Bitumen 155 5.2.5 Other Feedstocks 156 5.2.5.1 Crude Oil Coke 157 5.2.5.2 Solvent Deasphalter Bottoms 158 5.3 Synthesis Gas Production 159 5.3.1 Partial Oxidation Technology 160 5.3.1.1 Shell Gasification Process 162 5.3.1.2 Texaco Process 162 5.3.1.3 Phillips Process 163 5.3.2 Catalytic Partial Oxidation 163 5.4 Products 164 5.4.1 Gas Purification and Quality 165 5.4.2 Process Optimization 166 5.5 Advantages and Limitations 166 5.5.1 Other Uses of Residua 167 5.5.2 Gasification in the Future Refinery 167 References 169 6 Gasification of Biomass 173 6.1 Introduction 173 6.2 Gasification Chemistry 177 6.2.1 General Aspects 178 6.2.2 Reactions 181 6.2.2.1 Water Gas Shift Reaction 184 6.2.2.2 Carbon Dioxide Gasification 185 6.2.2.3 Hydrogasification 186 6.2.2.4 Methanation 186 6.3 Gasification Processes 187 6.3.1 Gasifiers 188 6.3.2 Fischer-Tropsch Synthesis 192 6.3.3 Feedstocks 193 6.3.3.1 Biomass 193 6.3.3.2 Gasification of Biomass with Coal 194 6.3.3.3 Gasification of Biomass with Other Feedstocks 198 6.4 Gas Production and Products 199 6.4.1 Gas Production 199 6.4.2 Gaseous Products 201 6.4.2.1 Synthesis Gas 201 6.4.2.2 Low-Btu Gas 203 6.4.2.3 Medium-Btu Gas 203 6.4.2.4 High-Btu Gas 204 6.4.3 Liquid Products 205 6.4.4 Solid Products 205 6.5 The Future 206 References 210 7 Gasification of Waste 217 7.1 Introduction 217 7.2 Waste Types 219 7.2.1 Solid Waste 220 7.2.2 Municipal Solid Waste 221 7.2.3 Industrial Solid Waste 221 7.2.4 Bio-Solids 222 7.2.5 Biomedical Waste 223 7.2.6 Sewage Sludge 223 7.3 Feedstock Properties 224 7.4 Fuel Production 224 7.4.1 Preprocessing 225 7.4.2 Process Design 227 7.5 Process Products 228 7.5.1 Synthesis Gas 228 7.5.2 Carbon Dioxide 228 7.5.3 Tar 229 7.5.4 Particulate Matter 231 7.5.5 Halogens/Acid Gases 231 7.5.6 Heavy Metals 232 7.5.7 Alkalis 233 7.5.8 Slag 233 7.6 Advantages and Limitations 234 References 235 8 Reforming Processes 239 8.1 Introduction 239 8.2 Processes Requiring Hydrogen 242 8.2.1 Hydrotreating 243 8.2.2 Hydrocracking 244 8.3 Feedstocks 245 8.4 Process Chemistry 246 8.5 Commercial Processes 248 8.5.1 Autothermal Reforming 249 8.5.2 Combined Reforming 249 8.5.3 Dry Reforming 250 8.5.4 Steam-Methane Reforming 251 8.5.5 Steam-Naphtha Reforming 253 8.6 Catalysts 254 8.6.1 Reforming Catalysts 254 8.6.2 Shift Conversion Catalysts 256 8.6.3 Methanation Catalysts 256 8.7 Hydrogen Purification 257 8.7.1 Wet Scrubbing 257 8.7.2 Pressure-Swing Adsorption Units 257 8.7.3 Membrane Systems 258 8.7.4 Cryogenic Separation 258 8.8 Hydrogen Management 259 References 260 9 Gas Conditioning and Cleaning 263 9.1 Introduction 263 9.2 Gas Streams 265 9.3 Synthesis Gas Cleaning 270 9.3.1 Composition 270 9.3.2 Process Types 272 9.4 Water Removal 274 9.4.1 Absorption 275 9.4.2 Adsorption 276 9.4.3 Cryogenics 278 9.5 Acid Gas Removal 278 9.5.1 Adsorption 279 9.5.2 Absorption 280 9.5.3 Chemisorption 281 9.5.4 Other Processes 285 9.6 Removal of Condensable Hydrocarbons 289 9.6.1 Extraction 291 9.6.2 Absorption 292 9.6.3 Fractionation 292 9.6.4 Enrichment 293 9.7 Tar Removal 294 9.7.1 Physical Methods 294 9.7.2 Thermal Methods 296 9.8 Other Contaminant Removal 296 9.8.1 Nitrogen Removal 296 9.8.2 Ammonia Removal 298 9.8.3 Particulate Matter Removal 298 9.8.4 Siloxane Removal 298 9.8.5 Alkali Metal Salt Removal 299 9.8.6 Biological Methods 299 9.8.6.1 Biofiltration 300 9.8.6.2 Bioscrubbing 302 9.8.6.3 Bio-Oxidation 303 9.9 Tail Gas Cleaning 303 9.9.1 Claus Process 304 9.9.2 SCOT Process 305 References 306 Part 2: Fuels and Chemicals from Synthesis Gas 311 10 The Fischer-Tropsch Process 313 10.1 Introduction 313 10.2 History and Development of the Process 317 10.3 Synthesis Gas 320 10.4 Production of Synthesis Gas 323 10.4.1 Feedstocks 323 10.4.2 Product Distribution 326 10.5 Process Parameters 327 10.6 Reactors and Catalysts 330 10.6.1 Reactors 330 10.6.2 Catalysts 332 10.7 Products and Product Quality 336 10.7.1 Products 336 10.7.2 Product Quality 337 10.8 Fischer-Tropsch Chemistry 339 10.8.1 Chemical Principles 340 10.8.2 Refining Fischer-Tropsch Products 344 References 346 11 Synthesis Gas in the Refinery 349 11.1 Introduction 349 11.2 Processes and Feedstocks 350 11.2.1 Gasification of Residua 353 11.2.2 Gasification of Residua with Coal 354 11.2.3 Gasification of Residua with Biomass 354 11.2.4 Gasification of Residua with Waste 356 11.3 Synthetic Fuel Production 358 11.3.1 Fischer-Tropsch Synthesis 359 11.3.2 Fischer-Tropsch Liquids 360 11.3.3 Upgrading Fischer-Tropsch Liquids 362 11.3.3.1 Gasoline Production 363 11.3.3.2 Diesel Production 365 11.4 Sabatier-Senderens Process 366 11.4.1 Methanol Production 367 11.4.2 Dimethyl Ether Production 368 11.5 The Future 369 References 373 12 Hydrogen Production 377 12.1 Introduction 377 12.2 Processes 381 12.2.1 Feedstocks 382 12.2.2 Commercial Processes 383 12.2.2.1 Hydrocarbon Gasification 384 12.2.2.2 Hypro Process 385 12.2.2.3 Hydrogen from Pyrolysis Processes 386 12.2.2.4 Hydrogen from Refinery Gas 387 12.2.2.5 Other Options 387 12.2.3 Process Chemistry 388 12.3 Hydrogen Purification 390 12.3.1 Wet Scrubbing 391 12.3.2 Pressure-Swing Adsorption 391 12.3.3 Membrane Systems 392 12.3.4 Cryogenic Separation 393 12.4 Hydrogen Management 394 References 395 13 Chemicals from Synthesis Gas 399 13.1 Introduction 399 13.2 Historical Aspects and Overview 410 13.3 The Petrochemical Industry 412 13.4 Petrochemicals 417 13.4.1 Primary Petrochemicals 417 13.4.2 Products and End Use 418 13.4.3 Production of Petrochemicals 419 13.4.4 Gaseous Fuels and Chemicals 425 13.4.4.1 Ammonia 425 13.4.4.2 Hydrogen 427 13.4.4.3 Synthetic Natural Gas 427 13.4.5 Liquid Fuels and Chemicals 428 13.4.5.1 Fischer-Tropsch Liquids 428 13.4.5.2 Methanol 428 13.4.5.3 Dimethyl Ether 429 13.4.5.4 Methanol-to-Gasoline and Olefins 429 13.4.5.5 Other Processes 429 13.5 The Future 430 References 437 14 Technology Integration 439 14.1 Introduction 439 14.2 Applications and Products 440 14.2.1 Chemicals and Fertilizers 441 14.2.2 Substitute Natural Gas 441 14.2.3 Hydrogen for Crude Oil Refining 442 14.2.4 Transportation Fuels 443 14.2.5 Transportation Fuels from Tar Sand Bitumen 445 14.2.6 Power Generation 445 14.2.7 Waste-to-Energy Gasification 446 14.2.8 Biomass Gasification 447 14.3 Environmental Benefits 449 14.3.1 Carbon Dioxide 450 14.3.2 Air Emissions 450 14.3.3 Solids Generation 450 14.3.4 Water Use 450 14.4 A Process for Now and the Future 451 14.4.1 The Process 451 14.4.2 Refinery of the Future 453 14.4.3 Economic Aspects 454 14.4.4 Market Outlook 455 14.5 Conclusions 455 References 457 Coversion Factors 459 Glossary 463 About the Author 489 Index 491

Written by one of the world's foremost petroleum engineers, this is the most comprehensive and up-to-date volume on synthesis gas, covering every aspect of the subject, including sources, production, feedstocks, gasification, and the environmental benefits. As a follow-up to the Handbook of Gasification Technology, also from Wiley-Scrivener, Synthesis Gas goes into more depth on how the products from this important technology can reduce our global carbon footprint and lead the United States, and other countries, toward energy independence. The environmental benefits are very high, and, along with carbon capture and renewable fuels, synthesis gas (or syngas) is a huge step toward environmental sustainability. Synthesis gas is one of the most important advancements that has ever occurred in energy production. Using this technology, for example, coal, biomass, waste products, or a combination of two or more of these can be gasified into a product that has roughly half the carbon footprint of coal alone. Used on a massive scale, just think of the potential for reducing carbon emissions! Synthesis Gas covers all aspects of the technology, from the chemistry, processes, and production, to the products, feedstocks, and even safety in the plant. Whether a veteran engineer or scientist using it as a reference or a professor using it as a textbook, this outstanding new volume is a must-have for any library. This groundbreaking new volume: Dovetailing with Handbook of Gasification Technology, also available from Wiley-Scrivener, continues to outline "greener" paths to environmental sustainability and energy independenceDescribes the environmental benefits and the need for synthesis gas across all areas of the energy sector and how this technology can reduce our carbon footprintOffers a thorough and comprehensive description of the basic science of synthesis gasThoroughly covers the equipment and processes of synthesis gas, including gasification, gasifier types, feedstocks, chemicals, and much moreIs a valuable reference for engineers and scientistsIs the perfect textbook for students studying petroleum, process, or chemical engineering