Hydrogen and Syngas Production and Purification Technologies

Preface xiii

Contributors xv

1. Introduction to Hydrogen and Syngas Production and Purification Technologies 1
Chunshan Song

1.1 Importance of Hydrogen and Syngas Production 1

1.2 Principles of Syngas and Hydrogen Production 4

1.3 Options for Hydrogen and Syngas Production 6

1.4 Hydrogen Energy and Fuel Cells 8

1.5 Fuel Processing for Fuel Cells 9

1.6 Sulfur Removal 10

1.7 CO₂ Capture and Separation 11

1.8 Scope of the Book 11

Acknowledgments 12

References 12

2. Catalytic Steam Reforming Technology for the Production of Hydrogen and Syngas 14
Velu Subramani, Pradeepkumar Sharma, Lingzhi Zhang, and Ke Liu

2.1 Introduction 14

2.2 Steam Reforming of Light Hydrocarbons 17

2.2.1 Steam Reforming of Natural Gas 17

2.2.2 Steam Reforming of C₂–C₄ Hydrocarbons 36

2.3 Steam Reforming of Liquid Hydrocarbons 46

2.3.1 Chemistry 46

2.3.2 Thermodynamics 47

2.3.3 Catalyst 52

2.3.4 Kinetics 58

2.3.5 Mechanism 61

2.3.6 Prereforming 61

2.4 Steam Reforming of Alcohols 65

2.4.1 Steam Reforming of Methanol (SRM) 65

2.4.2 Steam Reforming of Ethanol (SRE) 77

2.5 Carbon Formation and Catalyst Deactivation 106

2.6 Recent Developments in Reforming Technologies 109

2.6.1 Microreactor Reformer 109

2.6.2 Plate Reformer 110

2.6.3 Membrane Reformer 110

2.6.4 Plasma Reforming (PR) 112

2.7 Summary 112

References 112

3. Catalytic Partial Oxidation and Autothermal Reforming 127
Ke Liu, Gregg D. Deluga, Anders Bitsch-Larsen, Lanny D. Schmidt, and Lingzhi Zhang

3.1 Introduction 127

3.2 Natural Gas Reforming Technologies: Fundamental Chemistry 130

3.2.1 ATR 130

3.2.2 Homogeneous POX 132

3.2.3 CPO 133

3.3 Development/Commercialization Status of ATR, POX, and CPO Reformers 136

3.4 CPO Catalysts 138

3.4.1 Nickel-Based CPO Catalysts 138

3.4.2 Precious Metal CPO Catalysts 142

3.5 CPO Mechanism and Kinetics 146

3.5.1 Ni Catalyst Mechanism and Reactor Kinetics Modeling 146

3.5.2 Precious Metal Catalyst Mechanism and Reactor Kinetics Modeling 147

3.6 Start-Up and Shutdown Procedure of CPO 149

3.7 CPO of Renewable Fuels 150

3.8 Summary 151

Acknowledgments 151

References 151

4. Coal Gasification 156
Ke Liu, Zhe Cui, and Thomas H. Fletcher

4.1 Introduction to Gasification 156

4.2 Coal Gasification History 158

4.3 Coal Gasification Chemistry 160

4.3.1 Pyrolysis Process 161

4.3.2 Combustion of Volatiles 163

4.3.3 Char Gasification Reactions 164

4.3.4 Ash–Slag Chemistry 166

4.4 Gasification Thermodynamics 169

4.5 Gasification Kinetics 173

4.5.1 Reaction Mechanisms and the Kinetics of the Boudouard Reaction 174

4.5.2 Reaction Mechanisms and the Kinetics of the Water-Gas Reaction 175

4.6 Classification of Different Gasifiers 176

4.7 GE (Texaco) Gasification Technology with CWS Feeding 178

4.7.1 Introduction to GE Gasification Technology 178

4.7.2 GE Gasification Process 179

4.7.3 Coal Requirements of the GE Gasifier 184

4.7.4 Summary of GE Slurry Feeding Gasification Technology 186

4.8 Shell Gasification Technology with Dry Feeding 187

4.8.1 Introduction to Dry-Feeding Coal Gasification 187

4.8.2 Shell Gasification Process 189

4.8.3 Coal Requirements of Shell Gasification Process 193

4.8.4 Summary of Dry-Feeding Shell Gasifier 194

4.9 Other Gasification Technologies 195

4.9.1 GSP Gasification Technology 195

4.9.2 East China University of Science and Technology (ECUST) Gasifier 198

4.9.3 TPRI Gasifier 199

4.9.4 Fluidized-Bed Gasifiers 199

4.9.5 ConocoPhillips Gasifier 202

4.9.6 Moving-Bed and Fixed-Bed Gasifiers: Lurgi’s Gasification Technology 203

4.9.7 Summary of Different Gasification Technologies 205

4.10 Challenges in Gasification Technology: Some Examples 206

4.10.1 High AFT Coals 206

4.10.2 Increasing the Coal Concentration in the CWS 207

4.10.3 Improved Performance and Life of Gasifier Nozzles 208

4.10.4 Gasifier Refractory Brick Life 208

4.10.5 Gasifier Scale-Up 209

4.11 Syngas Cleanup 210

4.12 Integration of Coal Gasification with Coal Polygeneration Systems 215

References 216

5. Desulfurization Technologies 219
Chunshan Song and Xiaoliang Ma

5.1 Challenges in Deep Desulfurization for Hydrocarbon Fuel Processing and Fuel Cell Applications 219

5.2 HDS Technology 225

5.2.1 Natural Gas 225

5.2.2 Gasoline 226

5.2.3 Diesel 233

5.3 Adsorptive Desulfurization 243

5.3.1 Natural Gas 244

5.3.2 Gasoline 246

5.3.3 Jet Fuel 256

5.3.4 Diesel 258

5.4 Post-Reformer Desulfurization: H2S Sorption 264

5.4.1 H₂S Sorbents 265

5.4.2 H₂S Adsorption Thermodynamics 268

5.5 Desulfurization of Coal Gasification Gas 272

5.5.1 Absorption by Solvents 275

5.5.2 Hot and Warm Gas Cleanup 291

5.6 ODS 293

5.6.1 Natural Gas 293

5.6.2 Liquid Hydrocarbon Fuels 295

5.7 Summary 298

References 300

6. Water-Gas Shift Technologies 311
Alex Platon and Yong Wang

6.1 Introduction 311

6.2 Thermodynamic Considerations 312

6.3 Industrial Processes and Catalysts 313

6.3.1 Ferrochrome Catalyst for HTS Reaction 313

6.3.2 CuZn Catalysts for LTS Reaction 314

6.3.3 CoMo Catalyst for LTS Reaction 314

6.4 Reaction Mechanism and Kinetics 315

6.4.1 Ferrochrome Catalyst 315

6.4.2 CuZn-Based Catalyst 317

6.4.3 CoMo Catalyst 317

6.5 Catalyst Improvements and New Classes of Catalysts 318

6.5.1 Improvements to the Cu- and Fe-Based Catalysts 318

6.5.2 New Reaction Technologies 319

6.5.3 New Classes of Catalysts 321

References 326

7. Removal of Trace Contaminants from Fuel Processing Reformate: Preferential Oxidation (Prox) 329
Marco J. Castaldi

7.1 Introduction 329

7.2 Reactions of Prox 331

7.3 General Prox Reactor Performance 333

7.3.1 Multiple Steady-State Operation 337

7.3.2 Water–Oxygen Synergy 339

7.4 Catalysts Formulations 342

7.5 Reactor Geometries 344

7.5.1 Monolithic Reactors 345

7.5.2 SCT Reactors 346

7.5.3 Microchannel Reactors 349

7.5.4 MEMS-Based Reactors 350

7.6 Commercial Units 352

Acknowledgments 353

References 353

8. Hydrogen Membrane Technologies and Application in Fuel Processing 357
David Edlund

8.1 Introduction 357

8.2 Fundamentals of Membrane-Based Separations 358

8.3 Membrane Purification for Hydrogen Energy and Fuel Cell Applications 363

8.3.1 Product Hydrogen Purity 365

8.3.2 Process Scale 367

8.3.3 Energy Efficiency 368

8.4 Membrane Modules for Hydrogen Separation and Purification 369

8.5 Dense Metal Membranes 372

8.5.1 Metal Membrane Durability and Selectivity 375

8.6 Integration of Reforming and Membrane-Based Purification 378

8.7 Commercialization Activities 380

References 383

9. CO₂-Selective Membranes for Hydrogen Fuel Processing 385
Jin Huang, Jian Zou, and W.S. Winston Ho

9.1 Introduction 385

9.2 Synthesis of Novel CO₂-Selective Membranes 388

9.3 Model Description 389

9.4 Results and Discussion 391

9.4.1 Transport Properties of CO₂-Selective Membrane 391

9.4.2 Modeling Predictions 400

9.5 Conclusions 408

Glossary 410

Acknowledgments 410

References 411

10. Pressure Swing Adsorption Technology for Hydrogen Production 414
Shivaji Sircar and Timothy C. Golden

10.1 Introduction 414

10.2 PSA Processes for Hydrogen Purification 418

10.2.1 PSA Processes for Production of Hydrogen Only 418

10.2.2 Process for Coproduction of Hydrogen and Carbon Dioxide 422

10.2.3 Processes for the Production of Ammonia Synthesis Gas 425

10.3 Adsorbents for Hydrogen PSA Processes 426

10.3.1 Adsorbents for Bulk CO₂ Removal 427

10.3.2 Adsorbents for Dilute CO and N₂ Removal 429

10.3.3 Adsorbents for Dilute CH4 Removal 432

10.3.4 Adsorbents for C₁–C₄ Hydrocarbon Removal 432

10.3.5 Other Adsorbent and Related Improvements in the H₂ PSA 434

10.4 Future Trends for Hydrogen PSA 435

10.4.1 RPSA Cycles for Hydrogen Purification 436

10.4.2 Structured Adsorbents 438

10.4.3 Sorption-Enhanced Reaction Process (SERP) for H₂ Production 439

10.5 PSA Process Reliability 441

10.6 Improved Hydrogen Recovery by PSA Processes 441

10.6.1 Integration with Additional PSA System 441

10.6.2 Hybrid PSA-Adsorbent Membrane System 442

10.7 Engineering Process Design 444

10.8 Summary 447

References 447

11. Integration of H2/Syngas Production Technologies with Future Energy Systems 451
Wei Wei, Parag Kulkarni, and Ke Liu

11.1 Overview of Future Energy Systems and Challenges 451

11.2 Application of Reforming-Based Syngas Technology 454

11.2.1 NGCC Plants 454

11.2.2 Integration of H₂/Syngas Production Technologies in NGCC Plants 455

11.3 Application of Gasification-Based Syngas Technology 465

11.3.1 IGCC Plant 468

11.4 Application of H₂/Syngas Generation Technology to Liquid Fuels 477

11.4.1 Coal-to-H₂ Process Description 479

11.4.2 Coal-to-Hydrogen System Performance and Economics 481

11.5 Summary 483

References 483

12. Coal and Syngas to Liquids 486
Ke Liu, Zhe Cui, Wei Chen, and Lingzhi Zhang

12.1 Overview and History of Coal to Liquids (CTL) 486

12.2 Direct Coal Liquefaction (DCTL) 488

12.2.1 DCTL Process 488

12.2.2 The Kohleoel Process 490

12.2.3 NEDOL (NEDO Liquefaction) Process 491

12.2.4 The HTI-Coal Process 494

12.2.5 Other Single-Stage Processes 495

12.3 Indirect Coal to Liquid (ICTL) 496

12.3.1 Introduction 496

12.3.2 FT Synthesis 498

12.4 Mobil Methanol to Gasoline (MTG) 510

12.5 SMDS 511

12.6 Hybrid Coal Liquefaction 512

12.7 Coal to Methanol 513

12.7.1 Introduction of Methanol Synthesis 513

12.7.2 Methanol Synthesis Catalysts 514

12.7.3 Methanol Synthesis Reactor Systems 514

12.7.4 Liquid-Phase Methanol (LPMEOH^™) Process 516

12.8 Coal to Dimethyl Ether (DME) 519

References 520

Index 522