Direct natural gas conversion to value-added chemicals

Cover......Page 1
Half Title......Page 2
Title Page......Page 4
Copyright Page......Page 5
Table of Contents......Page 6
Preface......Page 8
Editors......Page 10
List of Contributors......Page 12
 1.1 Introduction......Page 16
 1.2 Electrochemical Direct Conversion of Methane......Page 18
   1.2.1.1 Electrochemical Oxidative Methane Coupling (EOMC)......Page 19
   1.2.1.2 Electrochemical Nonoxidative Methane Coupling (ENMC)......Page 21
  1.2.2 Electrochemical Methane Dehydro-Aromatization (EDMA)......Page 22
 1.3 Electrochemical Direct Conversion of Ethane......Page 24
  1.3.1 Electrochemical Oxidative Dehydrogenation (EODH)......Page 25
  1.3.2 Electrochemical Nonoxidative Dehydrogenation (ENDH)......Page 26
 1.4 Electrochemical Direct Conversion of Propane......Page 29
 1.5 Challenges and Opportunities......Page 31
 References......Page 35
Chapter 2 Microwaves in Nonoxidative Conversion of Natural Gas to Value-Added Products......Page 40
  2.2.1 Electromagnetic Waves......Page 41
  2.2.2 Interaction between Electromagnetic Fields and Dielectric Materials......Page 44
  2.2.4 Transmission-Reflection Line Method......Page 45
  2.2.5 Cavity Perturbation Method......Page 46
   2.2.6.1 Internal Heating, Rapid Heating, and Selective Heating......Page 47
  2.3.1 Microwave Source......Page 48
  2.3.2 E-H Tuners......Page 49
  2.3.3 Waveguide Cavity......Page 50
  2.3.5 Temperature Measurement......Page 51
  2.4.2 Reaction Chemistry......Page 52
 2.5 Microwave-Assisted Dehydroaromatization of Natural Gas......Page 54
   2.6.2.2 Reaction under Microwave Plasma without Catalyst......Page 58
   2.6.2.3 Reaction in Microwave-Heated Fixed-Bed Reactor......Page 59
 2.7 Numerical Modeling of Microwave–Material Interaction: Microwave-Assisted Methane Decomposition Example......Page 61
 References......Page 64
 3.1 Introduction......Page 68
  3.2.1 Direct Synthesis of Methanol from Methane......Page 69
  3.2.2 Conventional Methane Reforming......Page 70
  3.3.1 General......Page 71
  3.3.3 Thermal Catalysis versus Nonthermal Plasma Catalysis of Methane......Page 72
 3.4 Methane Conversion Using Microplasma......Page 73
  3.5.1 Effect of Reaction Temperature on Methanol Selectivity......Page 75
  3.5.3 Methane Conversion and Product Selectivity......Page 76
  3.6.2 Mechanism of Low-Temperature Methane Oxidation......Page 78
  3.6.3 Gas Phase Reaction Model......Page 79
 3.7 Conclusions......Page 81
 References......Page 82
 4.1 Introduction......Page 86
 4.2 Chemical Looping – The General Approach......Page 87
   4.3.1.1 Chemical Looping – Oxidative Coupling of Methane......Page 88
   4.3.1.2 Chemical Looping – Partial Oxidation or Reforming of Methane......Page 91
   4.3.2.1 Chemical Looping Oxidative Dehydrogenation of Ethane......Page 92
   4.3.2.2 Chemical Looping Oxidative Dehydrogenation of Propane......Page 95
  4.3.3 Naphtha-Based Ethylene Production......Page 96
 4.4 Chemical Looping Light Olefin Production – Advantages and Potential Opportunities......Page 97
 4.5 Summary......Page 100
 References......Page 101
Chapter 5 Oxidative Coupling of Methane......Page 110
 Abbreviations......Page 111
 5.1 Introduction......Page 112
  5.1.2 Evolution of Understanding of Oxidative Coupling of Methane......Page 113
   5.1.2.1 Reactions, Important Aspects, and Performance Indicators......Page 114
   5.1.2.2 Limitations of Catalysts, Reactors, and Process Performance......Page 115
   5.1.2.3 Highest Impact Parameters in a Practically Relevant Analysis Context......Page 116
  5.1.3 Remarks and Conclusions for Structuring This Chapter......Page 117
 5.2 Catalyst Research......Page 118
  5.2.1 Selecting Active Components for OCM Catalysts......Page 120
  5.2.2 Selecting Dopants and Promotors for OCM Catalysts......Page 121
  5.2.3 Impacts of Support on the Performance of OCM Catalysts......Page 122
  5.2.5 Efficient Characterizations Strategy for Systematic Analysis of the OCM Catalyst Performance......Page 123
   5.2.5.1 Comprehensive Analysis of an Mn-Na2WO4/SiO2 Catalyst......Page 125
   5.2.5.2 General Conclusions Based on Catalyst Material-Chemical-Structural Characteristics......Page 126
 5.3 Reactor Research......Page 127
  5.3.1 Fixed-Bed Reactor......Page 128
  5.3.2 Membrane Reactor......Page 129
  5.3.3 Fluidized-Bed Reactor......Page 130
  5.3.4 Other Types of OCM Reactors and General Design and Control Aspects......Page 131
 5.4 Interaction of the Catalyst and Reactor Research......Page 132
   5.4.1.2 Methane-to-Oxygen Ratio......Page 133
   5.4.1.4 Feed Flow or Gas Hourly Space Velocity (GHSV)......Page 134
  5.4.2 Thermal-Reaction Analysis......Page 135
   5.4.2.1 Stable, Transient, and Dynamic Behavior of OCM Reactors......Page 136
  5.5.1 Integration Potentials of OCM Reactors and other Reaction Systems......Page 137
  5.5.2 Process Integration via Downstream Units......Page 138
  5.5.4 Priorities for Future Research......Page 140
 References......Page 141
 6.1 Introduction......Page 148
 6.2 Challenges in Methane Activation and Functionalization......Page 149
  6.3.1 Criteria to Classify the Direct Methane Oxidation Processes......Page 150
  6.3.2 Nature of Oxidants......Page 153
  6.4.1 Homogeneous (Noncatalyzed) Direct Partial Oxidation of Methane to Oxygenates......Page 154
   6.4.1.2 Reaction Conditions......Page 155
   6.4.1.3 Additives (Reaction Initiators)......Page 157
   6.4.2.1 Homogeneous (Nonsolid) Catalyzed Direct Oxidation......Page 160
   6.4.2.2 Solid-Catalyzed Direct Oxidation......Page 166
 6.5 Direct Methane Oxidation to Higher Oxygenates......Page 179
 6.6 Conclusions and Outlook......Page 180
 References......Page 181
Chapter 7 Hydrogen and Solid Carbon Products from Natural Gas: A Review of Process Requirements, Current Technologies, Market Analysis, and Preliminary Techno Economic Assessment......Page 192
  7.1.1 Steam-Methane Reforming......Page 193
  7.1.2 Steam-Methane Reforming with Carbon Capture......Page 194
  7.1.3 Methane Pyrolysis......Page 196
 7.2 Engineering Review......Page 198
  7.2.1 Thermal (Noncatalytic) Reactions......Page 199
   7.2.2.1 Catalytic Reactors Types......Page 200
   7.2.2.2 Catalysts......Page 203
  7.2.3 Plasma Reactions......Page 206
 7.3 Process Technologies......Page 208
  7.3.1 Thermal Catalytic Processes......Page 210
  7.3.3 Plasma Processes......Page 211
 7.4 Market – Current and New Opportunities......Page 213
   7.4.1.2 Hydrogen......Page 214
   7.4.1.3 Carbon......Page 219
  7.4.2 New Market Opportunities for Methane Conversion to Carbon and Hydrogen......Page 221
   7.4.2.1 Graphite/Graphene......Page 222
   7.4.2.2 Carbon Fibers......Page 223
   7.4.2.3 Carbon Nanotubes......Page 225
  7.5.1 Break-Even Price of Carbon Products versus the Cost of Methane......Page 227
  7.5.2 ASPEN Process Modeling and Economic Analysis......Page 229
 7.6 Technology Barriers to Commercial Implementation and R&D Opportunities......Page 231
 7.7 Conclusions......Page 234
 References......Page 237
 8.1 Introduction......Page 244
  8.2.1 Base Metal SACs......Page 248
   8.2.1.1 Zeolite-Supported Base Metal SACs......Page 249
   8.2.1.2 MOF-Supported Base Metal SACs......Page 253
   8.2.1.3 Two-Dimensional Materials Supported Base Metal SACs......Page 254
   8.2.2.1 Rh SACs......Page 256
   8.2.2.2 Other Precious Metal SACs......Page 259
 8.3 Methane to Methanol over the SACs by Nonthermal Catalysis......Page 261
 References......Page 263
 9.1 Introduction......Page 270
 9.2 Thermodynamics and Reactivity......Page 271
 9.3 Generation of the Active Sites......Page 274
 9.4 Nature of the Active Sites......Page 276
 9.5 Conclusions......Page 285
 References......Page 286
 10.1 Introduction......Page 290
 10.3 Structure and Properties of Zeolites Used for Methane Activation......Page 292
  10.4.1 Nonoxidative Conversion of Methane over Metal-Based Catalyst......Page 293
   10.4.1.1 Mo-Based Catalysts......Page 294
   10.4.1.2 Zn-Based Catalysts......Page 296
   10.4.1.3 Transitional Metal Catalysts......Page 299
   10.4.1.4 Effect of Promoters......Page 301
   10.4.1.5 Addition of Other Hydrocarbons......Page 304
  10.4.2 Interaction of Methane with Different Catalyst Supports (Silica, Alumina, and H-ZSM-5)......Page 305
  10.4.3 Formation and Nature of Active Sites......Page 306
  10.4.4 Induction Period of Methane Dehydroaromatization Reaction......Page 307
  10.4.5 The Role of Brønsted Acid Sites......Page 309
  10.4.6 The Nature of the Carbonaceous Deposit and Its Role in the Reaction......Page 311
  10.4.7 Plasma Catalysis for Methane Activation......Page 312
 References......Page 313
  11.1.1 Natural Gas as an Alternative to Crude Oil......Page 320
  11.1.2 Gas-to-Liquid Conversion Pathways in Natural Gas Upgrading......Page 321
  11.1.3 Challenges in Direct Nonoxidative Methane Conversion......Page 322
 11.2 Membrane Reactor for Nonoxidative Methane Conversion......Page 323
  11.2.1 Hydrogen-Permeable Membrane Reactor......Page 324
   11.2.1.1 DNMC in Pd-Based Membrane Reactors......Page 325
   11.2.1.2 DNMC in Ceramic Membrane Reactors......Page 329
  11.2.2 Oxygen-Permeable Membrane Reactors......Page 332
  11.2.3 Membrane Reactor Coupled with External Circuit......Page 334
 11.3 Catalytic Wall Reactor for Direct Nonoxidative Methane Conversion......Page 336
  11.3.1 Catalytic Wall Reactor for Autothermal Operation......Page 337
  11.3.2 Direct Nonoxidative Methane Conversion in Catalytic Wall Reactor......Page 338
 References......Page 340
Chapter 12 Homogeneous Methane Functionalization......Page 346
 12.1 Introduction......Page 347
 12.2 Organization Structure......Page 349
  12.2.1 Organization Based on Practical Considerations......Page 350
  12.2.2 Organization Based on Mechanistic Considerations......Page 352
   12.2.2.1 Classification Details of Mechanistic Considerations......Page 354
 12.3 H2SO4/SO3 Systems for Methane Oxidation......Page 357
  12.4.1 Platinum Systems......Page 359
  12.4.2 Mercury Systems......Page 365
  12.4.3 Palladium Systems......Page 369
  12.4.4 Rhodium Systems......Page 374
  12.4.5 Iodine Systems......Page 378
  12.5.2 Palladium Systems......Page 380
  12.6.1 Europium Systems......Page 381
 12.7 CHO2 Stoichiometric Systems That Utilize O2/O2-Regenerable Oxidants and Operate by Nonchain, CH Oxidation Reactions......Page 382
 12.8 Summary and Conclusions......Page 383
 References......Page 384
 13.1 Introduction......Page 392
 13.2 Current Limitations of Gas-to-Liquid Biocatalysis......Page 393
 13.3 Biocatalyst Immobilization......Page 394
  13.3.1 Surface Immobilization Techniques......Page 395
  13.3.2 Entrapment or Encapsulation......Page 397
 13.4 Additive Manufacturing for Bioreactor Design......Page 398
   13.4.1.1 Photostereolithography......Page 399
   13.4.1.2 Extrusion-Based Bioprinting......Page 400
   13.4.1.3 Droplet-Based Bioprinting......Page 402
  13.4.2 3D Printing Reactors for Biocatalysis......Page 403
 13.5 Conclusions and Future Perspectives......Page 406
 References......Page 408
 14.1 Introduction......Page 412
 14.2 Methanotrophs and Their Biocatalytic Properties......Page 414
 14.3 Methanotrophic Resilience to Toxic Compounds......Page 418
 14.4 Culture Conditions for Natural Gas Bioconversion......Page 419
 14.5 Current Applications......Page 420
 14.6 Final Remarks......Page 421
 References......Page 422
 15.1 Introduction......Page 430
 15.2 Flowsheet Synthesis and Analysis......Page 431
 15.3 Process Integration and Multicriteria Decision Making......Page 432
 15.5 Integration of Shale-Gas Monetization into Industrial Symbiosis......Page 435
 15.6 Synergism between Systems Integration and Experimental Work......Page 436
 15.7 Conclusions......Page 437
 References......Page 438
 16.1 Introduction......Page 442
 16.2 Design of MW Reactors......Page 444
 16.3 MW Scale-Up Challenges and Alternatives......Page 445
 16.4 Natural Gas Conversion to Hydrocarbons......Page 449
 16.5 Direct Nonoxidative Conversion of Natural Gas to Aromatics: Plant-Wide Modeling and Techno-Economic Analysis......Page 450
 16.6 Conclusions......Page 458
 References......Page 459
Index......Page 462