Hydrogen and Syngas Production and Purification Technologies

Hydrogen and Syngas Production and Purification Technologies......Page 5
Contents......Page 7
Preface......Page 15
Contributors......Page 17
1.1 Importance of Hydrogen and Syngas Production......Page 19
1.2 Principles of Syngas and Hydrogen Production......Page 22
1.3 Options for Hydrogen and Syngas Production......Page 24
1.4 Hydrogen Energy and Fuel Cells......Page 26
1.5 Fuel Processing for Fuel Cells......Page 27
1.6 Sulfur Removal......Page 28
1.8 Scope of the Book......Page 29
References......Page 30
2.1 Introduction......Page 32
2.2.1 Steam Reforming of Natural Gas......Page 35
2.2.2 Steam Reforming of C(2)–C(4) Hydrocarbons......Page 54
2.3.1 Chemistry......Page 64
2.3.2 Thermodynamics......Page 65
2.3.3 Catalyst......Page 70
2.3.4 Kinetics......Page 76
2.3.6 Prereforming......Page 79
2.4.1 Steam Reforming of Methanol (SRM)......Page 83
2.4.2 Steam Reforming of Ethanol (SRE)......Page 95
2.5 Carbon Formation and Catalyst Deactivation......Page 124
2.6.1 Microreactor Reformer......Page 127
2.6.3 Membrane Reformer......Page 128
References......Page 130
3.1 Introduction......Page 145
3.2.1 ATR......Page 148
3.2.2 Homogeneous POX......Page 150
3.2.3 CPO......Page 151
3.3 Development/Commercialization Status of ATR, POX, and CPO Reformers......Page 154
3.4.1 Nickel-Based CPO Catalysts......Page 156
3.4.2 Precious Metal CPO Catalysts......Page 160
3.5.1 Ni Catalyst Mechanism and Reactor Kinetics Modeling......Page 164
3.5.2 Precious Metal Catalyst Mechanism and Reactor Kinetics Modeling......Page 165
3.6 Start-Up and Shutdown Procedure of CPO......Page 167
3.7 CPO of Renewable Fuels......Page 168
References......Page 169
4.1 Introduction to Gasification......Page 174
4.2 Coal Gasification History......Page 176
4.3 Coal Gasification Chemistry......Page 178
4.3.1 Pyrolysis Process......Page 179
4.3.2 Combustion of Volatiles......Page 181
4.3.3 Char Gasification Reactions......Page 182
4.3.4 Ash–Slag Chemistry......Page 184
4.4 Gasification Thermodynamics......Page 187
4.5 Gasification Kinetics......Page 191
4.5.1 Reaction Mechanisms and the Kinetics of the Boudouard Reaction......Page 192
4.5.2 Reaction Mechanisms and the Kinetics of the Water-Gas Reaction......Page 193
4.6 Classification of Different Gasifiers......Page 194
4.7.1 Introduction to GE Gasification Technology......Page 196
4.7.2 GE Gasification Process......Page 197
4.7.3 Coal Requirements of the GE Gasifier......Page 202
4.7.4 Summary of GE Slurry Feeding Gasification Technology......Page 204
4.8.1 Introduction to Dry-Feeding Coal Gasification......Page 205
4.8.2 Shell Gasification Process......Page 207
4.8.3 Coal Requirements of Shell Gasification Process......Page 211
4.8.4 Summary of Dry-Feeding Shell Gasifier......Page 212
4.9.1 GSP Gasification Technology......Page 213
4.9.2 East China University of Science and Technology (ECUST) Gasifier......Page 216
4.9.4 Fluidized-Bed Gasifiers......Page 217
4.9.5 ConocoPhillips Gasifier......Page 220
4.9.6 Moving-Bed and Fixed-Bed Gasifiers: Lurgi's Gasification Technology......Page 221
4.9.7 Summary of Different Gasification Technologies......Page 223
4.10.1 High AFT Coals......Page 224
4.10.2 Increasing the Coal Concentration in the CWS......Page 225
4.10.4 Gasifier Refractory Brick Life......Page 226
4.10.5 Gasifier Scale-Up......Page 227
4.11 Syngas Cleanup......Page 228
4.12 Integration of Coal Gasification with Coal Polygeneration Systems......Page 233
References......Page 234
5.1 Challenges in Deep Desulfurization for Hydrocarbon Fuel Processing and Fuel Cell Applications......Page 237
5.2.1 Natural Gas......Page 243
5.2.2 Gasoline......Page 244
5.2.3 Diesel......Page 251
5.3 Adsorptive Desulfurization......Page 261
5.3.1 Natural Gas......Page 262
5.3.2 Gasoline......Page 264
5.3.3 Jet Fuel......Page 274
5.3.4 Diesel......Page 276
5.4 Post-Reformer Desulfurization: H(2)S Sorption......Page 282
5.4.1 H(2)S Sorbents......Page 283
5.4.2 H(2)S Adsorption Thermodynamics......Page 286
5.5 Desulfurization of Coal Gasification Gas......Page 290
5.5.1 Absorption by Solvents......Page 293
5.5.2 Hot and Warm Gas Cleanup......Page 309
5.6.1 Natural Gas......Page 311
5.6.2 Liquid Hydrocarbon Fuels......Page 313
5.7 Summary......Page 316
References......Page 318
6.1 Introduction......Page 329
6.2 Thermodynamic Considerations......Page 330
6.3.1 Ferrochrome Catalyst for HTS Reaction......Page 331
6.3.3 CoMo Catalyst for LTS Reaction......Page 332
6.4.1 Ferrochrome Catalyst......Page 333
6.4.3 CoMo Catalyst......Page 335
6.5.1 Improvements to the Cu- and Fe-Based Catalysts......Page 336
6.5.2 New Reaction Technologies......Page 337
6.5.3 New Classes of Catalysts......Page 339
References......Page 344
7.1 Introduction......Page 347
7.2 Reactions of Prox......Page 349
7.3 General Prox Reactor Performance......Page 351
7.3.1 Multiple Steady-State Operation......Page 355
7.3.2 Water–Oxygen Synergy......Page 357
7.4 Catalysts Formulations......Page 360
7.5 Reactor Geometries......Page 362
7.5.1 Monolithic Reactors......Page 363
7.5.2 SCT Reactors......Page 364
7.5.3 Microchannel Reactors......Page 367
7.5.4 MEMS-Based Reactors......Page 368
7.6 Commercial Units......Page 370
References......Page 371
8.1 Introduction......Page 375
8.2 Fundamentals of Membrane-Based Separations......Page 376
8.3 Membrane Purification for Hydrogen Energy and Fuel Cell Applications......Page 381
8.3.1 Product Hydrogen Purity......Page 383
8.3.2 Process Scale......Page 385
8.3.3 Energy Efficiency......Page 386
8.4 Membrane Modules for Hydrogen Separation and Purification......Page 387
8.5 Dense Metal Membranes......Page 390
8.5.1 Metal Membrane Durability and Selectivity......Page 393
8.6 Integration of Reforming and Membrane-Based Purification......Page 396
8.7 Commercialization Activities......Page 398
References......Page 401
9.1 Introduction......Page 403
9.2 Synthesis of Novel CO(2)-Selective Membranes......Page 406
9.3 Model Description......Page 407
9.4.1 Transport Properties of CO(2)-Selective Membrane......Page 409
9.4.2 Modeling Predictions......Page 418
9.5 Conclusions......Page 426
Acknowledgments......Page 428
References......Page 429
10.1 Introduction......Page 432
10.2.1 PSA Processes for Production of Hydrogen Only......Page 436
10.2.2 Process for Coproduction of Hydrogen and Carbon Dioxide......Page 440
10.2.3 Processes for the Production of Ammonia Synthesis Gas......Page 443
10.3 Adsorbents for Hydrogen PSA Processes......Page 444
10.3.1 Adsorbents for Bulk CO(2) Removal......Page 445
10.3.2 Adsorbents for Dilute CO and N(2) Removal......Page 447
10.3.4 Adsorbents for C(1)–C(4) Hydrocarbon Removal......Page 450
10.3.5 Other Adsorbent and Related Improvements in the H(2) PSA......Page 452
10.4 Future Trends for Hydrogen PSA......Page 453
10.4.1 RPSA Cycles for Hydrogen Purification......Page 454
10.4.2 Structured Adsorbents......Page 456
10.4.3 Sorption-Enhanced Reaction Process (SERP) for H(2) Production......Page 457
10.6.1 Integration with Additional PSA System......Page 459
10.6.2 Hybrid PSA-Adsorbent Membrane System......Page 460
10.7 Engineering Process Design......Page 462
References......Page 465
11.1 Overview of Future Energy Systems and Challenges......Page 469
11.2.1 NGCC Plants......Page 472
11.2.2 Integration of H(2)/Syngas Production Technologies in NGCC Plants......Page 473
11.3 Application of Gasification-Based Syngas Technology......Page 483
11.3.1 IGCC Plant......Page 486
11.4 Application of H(2)/Syngas Generation Technology to Liquid Fuels......Page 495
11.4.1 Coal-to-H(2) Process Description......Page 497
11.4.2 Coal-to-Hydrogen System Performance and Economics......Page 499
References......Page 501
12.1 Overview and History of Coal to Liquids (CTL)......Page 504
12.2.1 DCTL Process......Page 506
12.2.2 The Kohleoel Process......Page 508
12.2.3 NEDOL (NEDO Liquefaction) Process......Page 509
12.2.4 The HTI-Coal Process......Page 512
12.2.5 Other Single-Stage Processes......Page 513
12.3.1 Introduction......Page 514
12.3.2 FT Synthesis......Page 516
12.4 Mobil Methanol to Gasoline (MTG)......Page 528
12.5 SMDS......Page 529
12.6 Hybrid Coal Liquefaction......Page 530
12.7.1 Introduction of Methanol Synthesis......Page 531
12.7.3 Methanol Synthesis Reactor Systems......Page 532
12.7.4 Liquid-Phase Methanol (LPMEOH™) Process......Page 534
12.8 Coal to Dimethyl Ether (DME)......Page 537
References......Page 538
Index......Page 540