Preface p. xiii
Contributors p. xv
1 Introduction to Hydrogen and Syngas Production and Purification Technologies Chunshan Song p. 1
1.1 Importance of Hydrogen and Syngas Production p. 1
1.2 Principles of Syngas and Hydrogen Production p. 4
1.3 Options for Hydrogen and Syngas Production p. 6
1.4 Hydrogen Energy and Fuel Cells p. 8
1.5 Fuel Processing for Fuel Cells p. 9
1.6 Sulfur Removal p. 10
1.7 CO 2 Capture and Separation p. 11
1.8 Scope of the Book p. 11
Acknowledgments p. 12
References p. 12
2 Catalytic Steam Reforming Technology for the Production of Hydrogen and Syngas Velu Subramani and Pradeepkumar Sharma and Lingzhi Zhang and Ke Liu p. 14
2.1 Introduction p. 14
2.2 Steam Reforming of Light Hydrocarbons p. 17
2.2.1 Steam Reforming of Natural Gas p. 17
2.2.2 Steam Reforming of C 2 -C 4 Hydrocarbons p. 36
2.3 Steam Reforming of Liquid Hydrocarbons p. 46
2.3.1 Chemistry p. 46
2.3.2 Thermodynamics p. 47
2.3.3 Catalyst p. 52
2.3.4 Kinetics p. 58
2.3.5 Mechanism p. 61
2.3.6 Prereforming p. 61
2.4 Steam Reforming of Alcohols p. 65
2.4.1 Steam Reforming of Methanol (SRM) p. 65
2.4.2 Steam Reforming of Ethanol (SRE) p. 77
2.5 Carbon Formation and Catalyst Deactivation p. 106
2.6 Recent Developments in Reforming Technologies p. 109
2.6.1 Microreactor Reformer p. 109
2.6.2 Plate Reformer p. 110
2.6.3 Membrane Reformer p. 110
2.6.4 Plasma Reforming (PR) p. 112
2.7 Summary p. 112
References p. 112
3 Catalytic Partial Oxidation and Autothermal Reforming Ke Liu and Gregg D. Deluga and Anders Bitsch-Larsen and Lanny D. Schmidt and Lingzhi Zhang p. 127
3.1 Introduction p. 127
3.2 Natural Gas Reforming Technologies: Fundamental Chemistry p. 130
3.2.1 ATR p. 130
3.2.2 Homogeneous POX p. 132
3.2.3 CPO p. 133
3.3 Development/Commercialization Status of ATR, POX, and CPO Reformers p. 136
3.4 CPO Catalysts p. 138
3.4.1 Nickel-Based CPO Catalysts p. 138
3.4.2 Precious Metal CPO Catalysts p. 142
3.5 CPO Mechanism and Kinetics p. 146
3.5.1 Ni Catalyst Mechanism and Reactor Kinetics Modeling p. 146
3.5.2 Precious Metal Catalyst Mechanism and Reactor Kinetics Modeling p. 147
3.6 Start-Up and Shutdown Procedure of CPO p. 149
3.7 CPO of Renewable Fuels p. 150
3.8 Summary p. 151
Acknowledgments p. 151
References p. 151
4 Coal Gasification Ke Liu and Zhe Cui and Thomas H. Fletcher p. 156
4.1 Introduction to Gasification p. 156
4.2 Coal Gasification History p. 158
4.3 Coal Gasification Chemistry p. 160
4.3.1 Pyrolysis Process p. 161
4.3.2 Combustion of Volatiles p. 163
4.3.3 Char Gasification Reactions p. 164
4.3.4 Ash-Slag Chemistry p. 166
4.4 Gasification Thermodynamics p. 169
4.5 Gasification Kinetics p. 173
4.5.1 Reaction Mechanisms and the Kinetics Boudouard Reaction p. 174
4.5.2 Reaction Mechanisms and the Kinetics Reaction p. 175
4.6 Classification of Different Gasifiers p. 176
4.7 GE (Texaco) Gasification Technology with CWS Feeding p. 178
4.7.1 Introduction to GE Gasification Technology p. 178
4.7.2 GE Gasification Process p. 179
4.7.3 Coal Requirements of the GE Gasifier p. 184
4.7.4 Summary of GE Slurry Feeding Gasification Technology p. 186
4.8 Shell Gasification Technology with Dry Feeding p. 187
4.8.1 Introduction to Dry-Feeding Coal Gasification p. 187
4.8.2 Shell Gasification Process p. 189
4.8.3 Coal Requirements of Shell Gasification Process p. 193
4.8.4 Summary of Dry-Feeding Shell Gasifier p. 194
4.9 Other Gasification Technologies p. 195
4.9.1 GSP Gasification Technology p. 195
4.9.2 East China University of Science and Technology (ECUST) Gasifier p. 198
4.9.3 TPRI Gasifier p. 199
4.9.4 Fluidized-Bed Gasifiers p. 199
4.9.5 ConocoPhillips Gasifier p. 202
4.9.6 Moving-Bed and Fixed-Bed Gasifiers: Lurgi's Gasification Technology p. 203
4.9.7 Summary of Different Gasification Technologies p. 205
4.10 Challenges in Gasification Technology: Some Examples p. 206
4.10.1 High AFT Coals p. 206
4.10.2 Increasing the Coal Concentration in the CWS p. 207
4.10.3 Improved Performance and Life of Gasifier Nozzles p. 208
4.10.4 Gasifier Refractory Brick Life p. 208
4.10.5 Gasifier Scale-Up p. 209
4.11 Syngas Cleanup p. 210
4.12 Integration of Coal Gasification with Coal Polygeneration Systems p. 215
References p. 216
5 Desulfurization Technologies Chunshan Song and Xiaoliang Ma p. 219
5.1 Challenges in Deep Desulfurization for Hydrocarbon Fuel Processing and Fuel Cell Applications p. 219
5.2 HDS Technology p. 225
5.2.1 Natural Gas p. 225
5.2.2 Gasoline p. 226
5.2.3 Diesel p. 233
5.3 Adsorptive Desulfurization p. 243
5.3.1 Natural Gas p. 244
5.3.2 Gasoline p. 246
5.3.3 Jet Fuel p. 256
5.3.4 Diesel p. 258
5.4 Post-Reformer Desulfurization: H 2 S Sorption p. 264
5.4.1 H 2 S Sorbents p. 265
5.4.2 H 2 S Adsorption Thermodynamics p. 268
5.5 Desulfurization of Coal Gasification Gas p. 272
5.5.1 Absorption by Solvents p. 275
5.5.2 Hot and Warm Gas Cleanup p. 291
5.6 ODS p. 293
5.6.1 Natural Gas p. 293
5.6.2 Liquid Hydrocarbon Fuels p. 295
5.7 Summary p. 298
References p. 300
6 Water-Gas Shift Technologies Alex Platon and Yong Wang p. 311
6.1 Introduction p. 311
6.2 Thermodynamic Considerations p. 312
6.3 Industrial Processes and Catalysts p. 313
6.3.1 Ferrochrome Catalyst for HTS Reaction p. 313
6.3.2 CuZn Catalysts for LTS Reaction p. 314
6.3.3 CoMo Catalyst for LTS Reaction p. 314
6.4 Reaction Mechanism and Kinetics p. 315
6.4.1 Ferrochrome Catalyst p. 315
6.4.2 CuZn-Based Catalyst p. 317
6.4.3 CoMo Catalyst p. 317
6.5 Catalyst Improvements and New Classes of Catalysts p. 318
6.5.1 Improvements to the Cu- and Fe-Based Catalysts p. 318
6.5.2 New Reaction Technologies p. 319
6.5.3 New Classes of Catalysts p. 321
References p. 326
7 Removal of Trace Contaminants from Fuel Processing Reformate: Preferential Oxidation (Prox) Marco J. Castaldi p. 329
7.1 Introduction p. 329
7.2 Reactions of Prox p. 331
7.3 General Prox Reactor Performance p. 333
7.3.1 Multiple Steady-State Operation p. 337
7.3.2 Water-Oxygen Synergy p. 339
7.4 Catalysts Formulations p. 342
7.5 Reactor Geometries p. 344
7.5.1 Monolithic Reactors p. 345
7.5.2 SCT Reactors p. 346
7.5.3 Microchannel Reactors p. 349
7.5.4 MEMS-Based Reactors p. 350
7.6 Commercial Units p. 352
Acknowledgments p. 353
References p. 353
8 Hydrogen Membrane Technologies and Application in Fuel Processing David Edlund p. 357
8.1 Introduction p. 357
8.2 Fundamentals of Membrane-Based Separations p. 358
8.3 Membrane Purification for Hydrogen Energy and Fuel Cell Applications p. 363
8.3.1 Product Hydrogen Purity p. 365
8.3.2 Process Scale p. 367
8.3.3 Energy Efficiency p. 368
8.4 Membrane Modules for Hydrogen Separation and Purification p. 369
8.5 Dense Metal Membranes p. 372
8.5.1 Metal Membrane Durability and Selectivity p. 375
8.6 Integration of Reforming and Membrane-Based Purification p. 378
8.7 Commercialization Activities p. 380
References p. 383
9 CO 2 -Selective Membranes for Hydrogen Fuel Processing Jin Huang and Man Zou and W.S. Winston Ho p. 385
9.1 Introduction p. 385
9.2 Synthesis of Novel CO 2 -Selective Membranes p. 388
9.3 Model Description p. 389
9.4 Results and Discussion p. 391
9.4.1 Transport Properties of CO 2 -Selective Membrane p. 391
9.4.2 Modeling Predictions p. 400
9.5 Conclusions p. 408
Glossary p. 410
Acknowledgments p. 410
References p. 411
10 Pressure Swing Adsorption Technology for Hydrogen Production Shivaji Sircar and Timothy C. Golden p. 414
10.1 Introduction p. 414
10.2 PSA Processes for Hydrogen Purification p. 418
10.2.1 PSA Processes for Production of Hydrogen Only p. 418
10.2.2 Process for Coproduction of Hydrogen and Carbon Dioxide p. 422
10.2.3 Processes for the Production of Ammonia Synthesis Gas p. 425
10.3 Adsorbents for Hydrogen PSA Processes p. 426
10.3.1 Adsorbents for Bulk CO 2 Removal p. 427
10.3.2 Adsorbents for Dilute CO and N 2 Removal p. 429
10.3.3 Adsorbents for Dilute CH 4 Removal p. 432
10.3.4 Adsorbents for C 1 -C 4 Hydrocarbon Removal p. 432
10.3.5 Other Adsorbent and Related Improvements in the H 2 PSA p. 434
10.4 Future Trends for Hydrogen PSA p. 435
10.4.1 RPSA Cycles for Hydrogen Purification p. 436
10.4.2 Structured Adsorbents p. 438
10.4.3 Sorption-Enhanced Reaction Process (SERP) for H 2 Production p. 439
10.5 PSA Process Reliability p. 441
10.6 Improved Hydrogen Recovery by PSA Processes p. 441
10.6.1 Integration with Additional PSA System p. 441
10.6.2 Hybrid PSA-Adsorbent Membrane System p. 442
10.7 Engineering Process Design p. 444
10.8 Summary p. 447
References p. 447
11 Integration of H 2 /Syngas Production Technologies with Future Energy Systems Wei Wei and Parag Kulkarni and Ke Liu p. 451
11.1 Overview of Future Energy Systems and Challenges p. 451
11.2 Application of Reforming-Based Syngas Technology p. 454
11.2.1 NGCC Plants p. 454
11.2.2 Integration of H 2 /Syngas Production Technologies in NGCC Plants p. 455
11.3 Application of Gasification-Based Syngas Technology p. 465
11.3.1 IGCC Plant p. 468
11.4 Application of H 2 /Syngas Generation Technology to Liquid Fuels p. 477
11.4.1 Coal-to-H 2 Process Description p. 479
11.4.2 Coal-to-Hydrogen System Performance and Economics p. 481
11.5 Summary p. 483
References p. 483
12 Coal and Syngas to Liquids Ke Liu and Zhe Cui and Wei Chen and Lingzhi Zhang p. 486
12.1 Overview and History of Coal to Liquids (CTL) p. 486
12.2 Direct Coal Liquefaction (DCTL) p. 488
12.2.1 DCTL Process p. 488
12.2.2 The Kohleoel Process p. 490
12.2.3 NEDOL (NEDO Liquefaction) Process p. 491
12.2.4 The HTI-Coal Process p. 494
12.2.5 Other Single-Stage Processes p. 495
12.3 Indirect Coal to Liquid (ICTL) p. 496
12.3.1 Introduction p. 496
12.3.2 FT Synthesis p. 498
12.4 Mobil Methanol to Gasoline (MTG) p. 510
12.5 SMDS p. 511
12.6 Hybrid Coal Liquefaction p. 512
12.7 Coal to Methanol p. 513
12.7.1 Introduction of Methanol Synthesis p. 513
12.7.2 Methanol Synthesis Catalysts p. 514
12.7.3 Methanol Synthesis Reactor Systems p. 514
12.7.4 Liquid-Phase Methanol (LPMEOH脰) Process p. 516
12.8 Coal to Dimethyl Ether (DME) p. 519
References p. 520
Index p. 522