Synthesis Gas

James G. Speight, PhD, has more than 45 years of experience in energy, environmental science, and ethics. He is the author of more than 65 books in petroleum science, petroleum engineering, biomass and biofuels, and environmental sciences. Although he has always worked in private industry which focused on contract-based work, Dr. Speight has served as Adjunct Professor in the Department of Chemical and Fuels Engineering at the University of Utah and in the Departments of Chemistry and Chemical and Petroleum Engineering at the University of Wyoming. In addition, he was a Visiting Professor in the College of Science, University of Mosul, Iraq and has also been a Visiting Professor in Chemical Engineering at the University of Missouri-Columbia, the Technical University of Denmark, and the University of Trinidad and Tobago.

• Preface xiiiPart 1: Production 11 Energy Sources and Energy Supply 31.1 Introduction 31.2 Typical Energy Sources 81.2.1 Natural Gas and Natural Gas Hydrates 91.2.2 The Crude Oil Family 101.2.3 Extra Heavy Crude Oil and Tar Sand Bitumen 121.3 Other Energy Sources 151.3.1 Coal 161.3.2 Oil Shale 191.3.3 Biomass 211.3.4 Solid Waste 251.4 Energy Supply 281.4.1 Economic Factors 281.4.2 Geopolitical Factors 291.4.3 Physical Factors 291.4.4 Technological Factors 301.5 Energy Independence 31References 362 Production of Synthesis Gas 412.1 Introduction 412.2 Synthesis Gas Generation 442.3 Feedstocks 462.3.1 Natural Gas 462.3.2 Crude Oil Resid, Heavy Crude Oil, Extra Heavy Crude Oil, and Tar Sand Bitumen 472.3.3 Refinery Coke 502.3.4 Coal 502.3.5 Biomass 522.3.6 Solid Waste 562.3.7 Black Liquor 592.3.8 Mixed Feedstocks 612.3.8.1 Biomass and Coal 622.3.8.2 Biomass and Municipal Solid Waste 622.4 Influence of Feedstock Quality 632.5 Gasification Processes 652.5.1 Feedstock Pretreatment 662.5.2 Feedstock Devolatilization 672.5.3 Char Gasification 682.5.4 General Chemistry 682.5.5 Stage-by-Stage Chemistry 722.5.5.1 Primary Gasification 722.5.5.2 Secondary Gasification 742.5.5.3 Water Gas Shift Reaction 762.5.5.4 Carbon Dioxide Gasification 772.5.5.5 Hydrogasification 782.5.5.6 Methanation 792.5.5.7 Catalytic Gasification 802.5.6 Physical Effects 802.6 Products 822.6.1 Gaseous Products 832.6.1.1 Low Btu Gas 842.6.1.2 Medium Btu Gas 852.6.1.3 High Btu Gas 862.6.1.4 Synthesis Gas 862.6.2 Liquid Products 872.6.3 Tar 88References 893 Gasifier Types and Gasification Chemistry 953.1 Introduction 953.2 Gasifier Types 963.2.1 Fixed-Bed Gasifier 1023.2.2 Fluid-Bed Gasifier 1053.2.3 Entrained-Bed Gasifier 1083.2.4 Molten Salt Gasifier 1093.2.5 Plasma Gasifier 1113.2.6 Other Types 1133.2.7 Gasifier Selection 1133.3 General Chemistry 1153.3.1 Devolatilization 1183.3.2 Products 1183.4 Process Options 1193.4.1 Effects of Process Parameters 1203.4.2 Effect of Heat Release 1213.4.3 Other Effects 121References 1224 Gasification of Coal 1254.1 Introduction 1254.2 Coal Types and Properties 1284.3 Gas Products 1304.3.1 Coal Devolatilization 1314.3.2 Char Gasification 1314.3.3 Gasification Chemistry 1324.3.4 Other Process Options 1334.3.4.1 Hydrogasification 1334.3.4.2 Catalytic Gasification 1344.3.4.3 Plasma Gasification 1344.3.5 Process Optimization 1354.4 Product Quality 1364.4.1 Low Btu Gas 1364.4.2 Medium Btu Gas 1384.4.3 High Btu Gas 1384.4.4 Methane 1394.4.5 Hydrogen 1394.4.6 Other Gases 1404.5 Chemicals Production 1404.5.1 Coal Tar Chemicals 1404.5.2 Fischer-Tropsch Chemicals 1434.5.2.1 Fischer-Tropsch Catalysts 1434.5.2.2 Product Distribution 1444.6 Advantages and Limitations 145References 1455 Gasification of Heavy Feedstocks 1495.1 Introduction 1495.2 Heavy Feedstocks 1525.2.1 Crude Oil Residua 1535.2.2 Heavy Crude Oil 1555.2.3 Extra Heavy Crude Oil 1555.2.4 Tar Sand Bitumen 1555.2.5 Other Feedstocks 1565.2.5.1 Crude Oil Coke 1575.2.5.2 Solvent Deasphalter Bottoms 1585.3 Synthesis Gas Production 1595.3.1 Partial Oxidation Technology 1605.3.1.1 Shell Gasification Process 1625.3.1.2 Texaco Process 1625.3.1.3 Phillips Process 1635.3.2 Catalytic Partial Oxidation 1635.4 Products 1645.4.1 Gas Purification and Quality 1655.4.2 Process Optimization 1665.5 Advantages and Limitations 1665.5.1 Other Uses of Residua 1675.5.2 Gasification in the Future Refinery 167References 1696 Gasification of Biomass 1736.1 Introduction 1736.2 Gasification Chemistry 1776.2.1 General Aspects 1786.2.2 Reactions 1816.2.2.1 Water Gas Shift Reaction 1846.2.2.2 Carbon Dioxide Gasification 1856.2.2.3 Hydrogasification 1866.2.2.4 Methanation 1866.3 Gasification Processes 1876.3.1 Gasifiers 1886.3.2 Fischer-Tropsch Synthesis 1926.3.3 Feedstocks 1936.3.3.1 Biomass 1936.3.3.2 Gasification of Biomass with Coal 1946.3.3.3 Gasification of Biomass with Other Feedstocks 1986.4 Gas Production and Products 1996.4.1 Gas Production 1996.4.2 Gaseous Products 2016.4.2.1 Synthesis Gas 2016.4.2.2 Low-Btu Gas 2036.4.2.3 Medium-Btu Gas 2036.4.2.4 High-Btu Gas 2046.4.3 Liquid Products 2056.4.4 Solid Products 2056.5 The Future 206References 2107 Gasification of Waste 2177.1 Introduction 2177.2 Waste Types 2197.2.1 Solid Waste 2207.2.2 Municipal Solid Waste 2217.2.3 Industrial Solid Waste 2217.2.4 Bio-Solids 2227.2.5 Biomedical Waste 2237.2.6 Sewage Sludge 2237.3 Feedstock Properties 2247.4 Fuel Production 2247.4.1 Preprocessing 2257.4.2 Process Design 2277.5 Process Products 2287.5.1 Synthesis Gas 2287.5.2 Carbon Dioxide 2287.5.3 Tar 2297.5.4 Particulate Matter 2317.5.5 Halogens/Acid Gases 2317.5.6 Heavy Metals 2327.5.7 Alkalis 2337.5.8 Slag 2337.6 Advantages and Limitations 234References 2358 Reforming Processes 2398.1 Introduction 2398.2 Processes Requiring Hydrogen 2428.2.1 Hydrotreating 2438.2.2 Hydrocracking 2448.3 Feedstocks 2458.4 Process Chemistry 2468.5 Commercial Processes 2488.5.1 Autothermal Reforming 2498.5.2 Combined Reforming 2498.5.3 Dry Reforming 2508.5.4 Steam-Methane Reforming 2518.5.5 Steam-Naphtha Reforming 2538.6 Catalysts 2548.6.1 Reforming Catalysts 2548.6.2 Shift Conversion Catalysts 2568.6.3 Methanation Catalysts 2568.7 Hydrogen Purification 2578.7.1 Wet Scrubbing 2578.7.2 Pressure-Swing Adsorption Units 2578.7.3 Membrane Systems 2588.7.4 Cryogenic Separation 2588.8 Hydrogen Management 259References 2609 Gas Conditioning and Cleaning 2639.1 Introduction 2639.2 Gas Streams 2659.3 Synthesis Gas Cleaning 2709.3.1 Composition 2709.3.2 Process Types 2729.4 Water Removal 2749.4.1 Absorption 2759.4.2 Adsorption 2769.4.3 Cryogenics 2789.5 Acid Gas Removal 2789.5.1 Adsorption 2799.5.2 Absorption 2809.5.3 Chemisorption 2819.5.4 Other Processes 2859.6 Removal of Condensable Hydrocarbons 2899.6.1 Extraction 2919.6.2 Absorption 2929.6.3 Fractionation 2929.6.4 Enrichment 2939.7 Tar Removal 2949.7.1 Physical Methods 2949.7.2 Thermal Methods 2969.8 Other Contaminant Removal 2969.8.1 Nitrogen Removal 2969.8.2 Ammonia Removal 2989.8.3 Particulate Matter Removal 2989.8.4 Siloxane Removal 2989.8.5 Alkali Metal Salt Removal 2999.8.6 Biological Methods 2999.8.6.1 Biofiltration 3009.8.6.2 Bioscrubbing 3029.8.6.3 Bio-Oxidation 3039.9 Tail Gas Cleaning 3039.9.1 Claus Process 3049.9.2 SCOT Process 305References 306Part 2: Fuels and Chemicals from Synthesis Gas 31110 The Fischer-Tropsch Process 31310.1 Introduction 31310.2 History and Development of the Process 31710.3 Synthesis Gas 32010.4 Production of Synthesis Gas 32310.4.1 Feedstocks 32310.4.2 Product Distribution 32610.5 Process Parameters 32710.6 Reactors and Catalysts 33010.6.1 Reactors 33010.6.2 Catalysts 33210.7 Products and Product Quality 33610.7.1 Products 33610.7.2 Product Quality 33710.8 Fischer-Tropsch Chemistry 33910.8.1 Chemical Principles 34010.8.2 Refining Fischer-Tropsch Products 344References 34611 Synthesis Gas in the Refinery 34911.1 Introduction 34911.2 Processes and Feedstocks 35011.2.1 Gasification of Residua 35311.2.2 Gasification of Residua with Coal 35411.2.3 Gasification of Residua with Biomass 35411.2.4 Gasification of Residua with Waste 35611.3 Synthetic Fuel Production 35811.3.1 Fischer-Tropsch Synthesis 35911.3.2 Fischer-Tropsch Liquids 36011.3.3 Upgrading Fischer-Tropsch Liquids 36211.3.3.1 Gasoline Production 36311.3.3.2 Diesel Production 36511.4 Sabatier-Senderens Process 36611.4.1 Methanol Production 36711.4.2 Dimethyl Ether Production 36811.5 The Future 369References 37312 Hydrogen Production 37712.1 Introduction 37712.2 Processes 38112.2.1 Feedstocks 38212.2.2 Commercial Processes 38312.2.2.1 Hydrocarbon Gasification 38412.2.2.2 Hypro Process 38512.2.2.3 Hydrogen from Pyrolysis Processes 38612.2.2.4 Hydrogen from Refinery Gas 38712.2.2.5 Other Options 38712.2.3 Process Chemistry 38812.3 Hydrogen Purification 39012.3.1 Wet Scrubbing 39112.3.2 Pressure-Swing Adsorption 39112.3.3 Membrane Systems 39212.3.4 Cryogenic Separation 39312.4 Hydrogen Management 394References 39513 Chemicals from Synthesis Gas 39913.1 Introduction 39913.2 Historical Aspects and Overview 41013.3 The Petrochemical Industry 41213.4 Petrochemicals 41713.4.1 Primary Petrochemicals 41713.4.2 Products and End Use 41813.4.3 Production of Petrochemicals 41913.4.4 Gaseous Fuels and Chemicals 42513.4.4.1 Ammonia 42513.4.4.2 Hydrogen 42713.4.4.3 Synthetic Natural Gas 42713.4.5 Liquid Fuels and Chemicals 42813.4.5.1 Fischer-Tropsch Liquids 42813.4.5.2 Methanol 42813.4.5.3 Dimethyl Ether 42913.4.5.4 Methanol-to-Gasoline and Olefins 42913.4.5.5 Other Processes 42913.5 The Future 430References 43714 Technology Integration 43914.1 Introduction 43914.2 Applications and Products 44014.2.1 Chemicals and Fertilizers 44114.2.2 Substitute Natural Gas 44114.2.3 Hydrogen for Crude Oil Refining 44214.2.4 Transportation Fuels 44314.2.5 Transportation Fuels from Tar Sand Bitumen 44514.2.6 Power Generation 44514.2.7 Waste-to-Energy Gasification 44614.2.8 Biomass Gasification 44714.3 Environmental Benefits 44914.3.1 Carbon Dioxide 45014.3.2 Air Emissions 45014.3.3 Solids Generation 45014.3.4 Water Use 45014.4 A Process for Now and the Future 45114.4.1 The Process 45114.4.2 Refinery of the Future 45314.4.3 Economic Aspects 45414.4.4 Market Outlook 45514.5 Conclusions 455References 457Coversion Factors 459Glossary 463About the Author 489Index 491