Hydrogen and Syngas Production and Purification Technologies

KE LIU, PhD, MBA, is the Principal Scientist and Project Leader of the Energy and Propulsion Technologies Division of GE Global Research Center, working on different technologies related to gasification, IGCC, syngas, and fuel conversion. Currently, he leads a team of engineers to develop the dry feeding technology for next-generation GE gasifier for high-moisture, low-rank coal and biomass gasification. Dr. Liu started his career at Exxon-Mobil and then UTC Fuel Cells, working on various fuel and H2 production technologies. He is not only a leading expert on energy, fuels, and gasification, but also an industrial leader who led many large R&D projects funded by DOE and large U.S. energy corporations such as GE, Shell-UTC, and Exxon-Mobil. A recipient of numerous awards, including the 2006 National Emerald Honors Special Recognition Award, Dr. Liu has served as a board member and program chair of International Pittsburgh Coal Conference, a board member of the Energy Center of CalTech (PEER), and the associate editor of the Energy and Fuels Journal.CHUNSHAN SONG, PhD, is a Professor of Fuel Science and Chemical Engineering and the Director of the EMS Energy Institute at Pennsylvania State University. A recipient of numerous awards, he has been extensively published, and his research on clean fuels and catalysis has been funded by government and industry. Also, Dr. Song has served as chair for the ACS Division of Petroleum Chemistry; chair for ACS Fuel Chemistry Division; and advisory board chair and program chair for International Pittsburgh Coal Conference.VELU SUBRAMANI, PhD, is a Research Scientist working for the BP Refining and Logistics Technology team. He has over fifteen years of research experience in heterogeneous catalysis for fine chemicals synthesis, energy production, and environmental protection. He is the recipient of research fellowships from Switzerland and the Science and Technology Agency (STA) of Japan. Dr. Subramani is the author of over fifty peer-reviewed articles in international journals and the author or co-author of several patents. He served as the program chair for the ACS Division of Fuel Chemistry.

• Preface xiiiContributors xv1. Introduction to Hydrogen and Syngas Production and Purification Technologies 1Chunshan Song1.1 Importance of Hydrogen and Syngas Production 11.2 Principles of Syngas and Hydrogen Production 41.3 Options for Hydrogen and Syngas Production 61.4 Hydrogen Energy and Fuel Cells 81.5 Fuel Processing for Fuel Cells 91.6 Sulfur Removal 101.7 CO2 Capture and Separation 111.8 Scope of the Book 11Acknowledgments 12References 122. Catalytic Steam Reforming Technology for the Production of Hydrogen and Syngas 14Velu Subramani, Pradeepkumar Sharma, Lingzhi Zhang, and Ke Liu2.1 Introduction 142.2 Steam Reforming of Light Hydrocarbons 172.2.1 Steam Reforming of Natural Gas 172.2.2 Steam Reforming of C2–C4 Hydrocarbons 362.3 Steam Reforming of Liquid Hydrocarbons 462.3.1 Chemistry 462.3.2 Thermodynamics 472.3.3 Catalyst 522.3.4 Kinetics 582.3.5 Mechanism 612.3.6 Prereforming 612.4 Steam Reforming of Alcohols 652.4.1 Steam Reforming of Methanol (SRM) 652.4.2 Steam Reforming of Ethanol (SRE) 772.5 Carbon Formation and Catalyst Deactivation 1062.6 Recent Developments in Reforming Technologies 1092.6.1 Microreactor Reformer 1092.6.2 Plate Reformer 1102.6.3 Membrane Reformer 1102.6.4 Plasma Reforming (PR) 1122.7 Summary 112References 1123. Catalytic Partial Oxidation and Autothermal Reforming 127Ke Liu, Gregg D. Deluga, Anders Bitsch-Larsen, Lanny D. Schmidt, and Lingzhi Zhang3.1 Introduction 1273.2 Natural Gas Reforming Technologies: Fundamental Chemistry 1303.2.1 ATR 1303.2.2 Homogeneous POX 1323.2.3 CPO 1333.3 Development/Commercialization Status of ATR, POX, and CPO Reformers 1363.4 CPO Catalysts 1383.4.1 Nickel-Based CPO Catalysts 1383.4.2 Precious Metal CPO Catalysts 1423.5 CPO Mechanism and Kinetics 1463.5.1 Ni Catalyst Mechanism and Reactor Kinetics Modeling 1463.5.2 Precious Metal Catalyst Mechanism and Reactor Kinetics Modeling 1473.6 Start-Up and Shutdown Procedure of CPO 1493.7 CPO of Renewable Fuels 1503.8 Summary 151Acknowledgments 151References 1514. Coal Gasification 156Ke Liu, Zhe Cui, and Thomas H. Fletcher4.1 Introduction to Gasification 1564.2 Coal Gasification History 1584.3 Coal Gasification Chemistry 1604.3.1 Pyrolysis Process 1614.3.2 Combustion of Volatiles 1634.3.3 Char Gasification Reactions 1644.3.4 Ash–Slag Chemistry 1664.4 Gasification Thermodynamics 1694.5 Gasification Kinetics 1734.5.1 Reaction Mechanisms and the Kinetics of the Boudouard Reaction 1744.5.2 Reaction Mechanisms and the Kinetics of the Water-Gas Reaction 1754.6 Classification of Different Gasifiers 1764.7 GE (Texaco) Gasification Technology with CWS Feeding 1784.7.1 Introduction to GE Gasification Technology 1784.7.2 GE Gasification Process 1794.7.3 Coal Requirements of the GE Gasifier 1844.7.4 Summary of GE Slurry Feeding Gasification Technology 1864.8 Shell Gasification Technology with Dry Feeding 1874.8.1 Introduction to Dry-Feeding Coal Gasification 1874.8.2 Shell Gasification Process 1894.8.3 Coal Requirements of Shell Gasification Process 1934.8.4 Summary of Dry-Feeding Shell Gasifier 1944.9 Other Gasification Technologies 1954.9.1 GSP Gasification Technology 1954.9.2 East China University of Science and Technology (ECUST) Gasifier 1984.9.3 TPRI Gasifier 1994.9.4 Fluidized-Bed Gasifiers 1994.9.5 ConocoPhillips Gasifier 2024.9.6 Moving-Bed and Fixed-Bed Gasifiers: Lurgi’s Gasification Technology 2034.9.7 Summary of Different Gasification Technologies 2054.10 Challenges in Gasification Technology: Some Examples 2064.10.1 High AFT Coals 2064.10.2 Increasing the Coal Concentration in the CWS 2074.10.3 Improved Performance and Life of Gasifier Nozzles 2084.10.4 Gasifier Refractory Brick Life 2084.10.5 Gasifier Scale-Up 2094.11 Syngas Cleanup 2104.12 Integration of Coal Gasification with Coal Polygeneration Systems 215References 2165. Desulfurization Technologies 219Chunshan Song and Xiaoliang Ma5.1 Challenges in Deep Desulfurization for Hydrocarbon Fuel Processing and Fuel Cell Applications 2195.2 HDS Technology 2255.2.1 Natural Gas 2255.2.2 Gasoline 2265.2.3 Diesel 2335.3 Adsorptive Desulfurization 2435.3.1 Natural Gas 2445.3.2 Gasoline 2465.3.3 Jet Fuel 2565.3.4 Diesel 2585.4 Post-Reformer Desulfurization: H2S Sorption 2645.4.1 H2S Sorbents 2655.4.2 H2S Adsorption Thermodynamics 2685.5 Desulfurization of Coal Gasification Gas 2725.5.1 Absorption by Solvents 2755.5.2 Hot and Warm Gas Cleanup 2915.6 ODS 2935.6.1 Natural Gas 2935.6.2 Liquid Hydrocarbon Fuels 2955.7 Summary 298References 3006. Water-Gas Shift Technologies 311Alex Platon and Yong Wang6.1 Introduction 3116.2 Thermodynamic Considerations 3126.3 Industrial Processes and Catalysts 3136.3.1 Ferrochrome Catalyst for HTS Reaction 3136.3.2 CuZn Catalysts for LTS Reaction 3146.3.3 CoMo Catalyst for LTS Reaction 3146.4 Reaction Mechanism and Kinetics 3156.4.1 Ferrochrome Catalyst 3156.4.2 CuZn-Based Catalyst 3176.4.3 CoMo Catalyst 3176.5 Catalyst Improvements and New Classes of Catalysts 3186.5.1 Improvements to the Cu- and Fe-Based Catalysts 3186.5.2 New Reaction Technologies 3196.5.3 New Classes of Catalysts 321References 3267. Removal of Trace Contaminants from Fuel Processing Reformate: Preferential Oxidation (Prox) 329Marco J. Castaldi7.1 Introduction 3297.2 Reactions of Prox 3317.3 General Prox Reactor Performance 3337.3.1 Multiple Steady-State Operation 3377.3.2 Water–Oxygen Synergy 3397.4 Catalysts Formulations 3427.5 Reactor Geometries 3447.5.1 Monolithic Reactors 3457.5.2 SCT Reactors 3467.5.3 Microchannel Reactors 3497.5.4 MEMS-Based Reactors 3507.6 Commercial Units 352Acknowledgments 353References 3538. Hydrogen Membrane Technologies and Application in Fuel Processing 357David Edlund8.1 Introduction 3578.2 Fundamentals of Membrane-Based Separations 3588.3 Membrane Purification for Hydrogen Energy and Fuel Cell Applications 3638.3.1 Product Hydrogen Purity 3658.3.2 Process Scale 3678.3.3 Energy Efficiency 3688.4 Membrane Modules for Hydrogen Separation and Purification 3698.5 Dense Metal Membranes 3728.5.1 Metal Membrane Durability and Selectivity 3758.6 Integration of Reforming and Membrane-Based Purification 3788.7 Commercialization Activities 380References 3839. CO2-Selective Membranes for Hydrogen Fuel Processing 385Jin Huang, Jian Zou, and W.S. Winston Ho9.1 Introduction 3859.2 Synthesis of Novel CO2-Selective Membranes 3889.3 Model Description 3899.4 Results and Discussion 3919.4.1 Transport Properties of CO2-Selective Membrane 3919.4.2 Modeling Predictions 4009.5 Conclusions 408Glossary 410Acknowledgments 410References 41110. Pressure Swing Adsorption Technology for Hydrogen Production 414Shivaji Sircar and Timothy C. Golden10.1 Introduction 41410.2 PSA Processes for Hydrogen Purification 41810.2.1 PSA Processes for Production of Hydrogen Only 41810.2.2 Process for Coproduction of Hydrogen and Carbon Dioxide 42210.2.3 Processes for the Production of Ammonia Synthesis Gas 42510.3 Adsorbents for Hydrogen PSA Processes 42610.3.1 Adsorbents for Bulk CO2 Removal 42710.3.2 Adsorbents for Dilute CO and N2 Removal 42910.3.3 Adsorbents for Dilute CH4 Removal 43210.3.4 Adsorbents for C1–C4 Hydrocarbon Removal 43210.3.5 Other Adsorbent and Related Improvements in the H2 PSA 43410.4 Future Trends for Hydrogen PSA 43510.4.1 RPSA Cycles for Hydrogen Purification 43610.4.2 Structured Adsorbents 43810.4.3 Sorption-Enhanced Reaction Process (SERP) for H2 Production 43910.5 PSA Process Reliability 44110.6 Improved Hydrogen Recovery by PSA Processes 44110.6.1 Integration with Additional PSA System 44110.6.2 Hybrid PSA-Adsorbent Membrane System 44210.7 Engineering Process Design 44410.8 Summary 447References 44711. Integration of H2/Syngas Production Technologies with Future Energy Systems 451Wei Wei, Parag Kulkarni, and Ke Liu11.1 Overview of Future Energy Systems and Challenges 45111.2 Application of Reforming-Based Syngas Technology 45411.2.1 NGCC Plants 45411.2.2 Integration of H2/Syngas Production Technologies in NGCC Plants 45511.3 Application of Gasification-Based Syngas Technology 46511.3.1 IGCC Plant 46811.4 Application of H2/Syngas Generation Technology to Liquid Fuels 47711.4.1 Coal-to-H2 Process Description 47911.4.2 Coal-to-Hydrogen System Performance and Economics 48111.5 Summary 483References 48312. Coal and Syngas to Liquids 486Ke Liu, Zhe Cui, Wei Chen, and Lingzhi Zhang12.1 Overview and History of Coal to Liquids (CTL) 48612.2 Direct Coal Liquefaction (DCTL) 48812.2.1 DCTL Process 48812.2.2 The Kohleoel Process 49012.2.3 NEDOL (NEDO Liquefaction) Process 49112.2.4 The HTI-Coal Process 49412.2.5 Other Single-Stage Processes 49512.3 Indirect Coal to Liquid (ICTL) 49612.3.1 Introduction 49612.3.2 FT Synthesis 49812.4 Mobil Methanol to Gasoline (MTG) 51012.5 SMDS 51112.6 Hybrid Coal Liquefaction 51212.7 Coal to Methanol 51312.7.1 Introduction of Methanol Synthesis 51312.7.2 Methanol Synthesis Catalysts 51412.7.3 Methanol Synthesis Reactor Systems 51412.7.4 Liquid-Phase Methanol (LPMEOH™) Process 51612.8 Coal to Dimethyl Ether (DME) 519References 520Index 522

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