Carbon Dioxide as Chemical Feedstock

Carbon Dioxide as Chemical Feedstock......Page 2
Contents......Page 10
Preface......Page 18
List of Contributors......Page 20
1.2 The Accumulation of CO2 in the Atmosphere, and the Effects that We Fear......Page 24
1.3 Technologies to Reduce CO2 Accumulation in the Atmosphere......Page 27
1.4 The Utilization of CO2......Page 29
1.6 CO2: Sources and Prices......Page 31
1.7 The Potential for CO2 Utilization, and the Content of This Book......Page 32
1.8 The Need for Research to Speed an Exploitation of the Utilization Option......Page 34
References......Page 36
2.2 Dense Carbon Dioxide as Solvent Medium for Chemical Processes......Page 38
2.3 Enzymatic Catalysis in Dense Carbon Dioxide......Page 41
2.4 Other Reactions in Dense Carbon Dioxide......Page 42
2.5 Polymer Synthesis in Supercritical Carbon Dioxide......Page 43
2.5.1 Chain Polymerizations: Synthesis of Fluoropolymers......Page 45
2.5.2 Step Polymerizations: Synthesis of Biodegradable Polymers......Page 49
Acknowledgments......Page 50
References......Page 51
3.1 Introduction......Page 56
3.2.1 The Calvin–Benson–Bassham (CBB) Cycle......Page 57
3.2.2 The Reductive Citric Acid Cycle (Arnon–Buchanan Cycle)......Page 60
3.2.3 The Reductive Acetyl-CoA Pathway (Wood–Ljungdahl Pathway)......Page 62
3.2.4 The 3-Hydroxypropionate/Malyl-CoA Cycle......Page 63
3.2.5 The 3-Hydroxypropionate/4-Hydroxybutyrate Cycle......Page 65
3.2.6 The Dicarboxylate/4-Hydroxybutyrate Cycle......Page 67
3.3 Rules to Explain the Diversity......Page 69
3.4 Evolutionary Aspects......Page 72
3.5 Chemical Aspects of CO2 Fixation......Page 73
References......Page 74
4.1 Introduction......Page 78
4.2 Carbon Dioxide Bonding to Metals......Page 79
4.3.1 Low-Temperature Matrix Isolation and Theoretical Studies......Page 82
4.3.2 Synthesis of Stable Complexes......Page 87
4.3.2.1 End-On Complexes......Page 88
4.3.2.4 Bridged Complexes Obtained by In-situ Synthesis......Page 90
4.4 Reactivity of CO2 Complexes......Page 92
4.4.1 C–O Bond Cleavage and O Transfer......Page 93
4.4.2 Reactions with Electrophiles......Page 95
4.4.3 Reactions with Nucleophiles......Page 96
4.5 CO2 Complexes as Reaction Intermediates in CO2 Utilization Processes......Page 98
4.5.1 Oxidative Coupling Reactions......Page 99
4.5.2 Reduction Reactions......Page 102
4.5.3 Catalytic Processes......Page 104
4.5.4 Bioinspired Reactions......Page 105
4.6 Conclusions......Page 107
References......Page 108
5.1 Introduction......Page 112
5.2.1 Kolbe–Schmitt Synthesis: Generalities......Page 113
5.2.2 Reaction Parameters and Mechanistic Studies of the Kolbe–Schmitt Synthesis......Page 114
5.2.3 Recent Applications of the Kolbe–Schmitt Carboxylation: Synthesis of 1,3-Dialkylimidazolium-2-Carboxylates......Page 120
5.2.4 Carboxylation of C–H-Acidic Compounds......Page 122
5.3.1 Generalities......Page 125
5.3.2.1 Pd/Sn Systems......Page 127
5.3.2.2 Rh/B and Cu/B......Page 130
5.3.2.3 Ni/Zn......Page 131
5.4 Palladium (0)-Catalyzed Telomerization of Butadiene with CO2: Synthesis of δ-Lactone......Page 135
References......Page 139
6.1 Introduction......Page 144
6.2 Synthesis of Carbamic Acids and Alkylammonium Carbamates......Page 145
6.3 Synthesis of Carbamate Esters......Page 148
6.3.1 Transfer of Carbamate Group to Alkyl Halides......Page 149
6.3.2 Transfer of Carbamate Group to Acylating Agents......Page 154
6.3.3 Transfer of Carbamate Group to Alcohols......Page 157
6.3.4 Transfer of Carbamate Group to Epoxides......Page 161
6.3.5 Transfer of Carbamate Group to C–C Double Bonds......Page 165
6.3.6 Transfer of Carbamate Group to C–C Triple Bonds......Page 168
6.4 Synthesis of Isocyanates......Page 171
6.5 Synthesis of Ureas......Page 177
References......Page 182
7.1 Introduction......Page 192
7.2.1 Market and Production......Page 193
7.2.2 Current Trends with CO2 as Feedstock......Page 195
7.2.3 Alcoholysis of Urea......Page 197
7.2.4 Direct Route......Page 198
7.2.5 The Future of CO2-Based Routes to Acyclic Carbonates......Page 203
7.3 Synthesis of Organic Cyclic Carbonates......Page 204
7.3.1.1 Use of Conventional Solvents......Page 205
7.3.1.2 Use of Ionic Liquids......Page 207
7.3.1.4 Combined Reaction Media: sc-CO2 and Ionic Liquids......Page 208
7.3.2.1 Use of Oxygen as Oxidant......Page 209
7.3.2.2 Use of Other Oxidants......Page 211
7.3.3.1 From Halohydrins......Page 212
7.3.3.2 From Halogenated Carbonates......Page 213
7.3.4 Synthesis of Cyclic Carbonates from Propargylic Alcohols......Page 214
7.3.5 Reaction Between Carbon Dioxide and Diols......Page 215
7.3.6 Reaction of Urea and Diols......Page 217
7.3.7 Reaction of Carbon Dioxide or Urea with Glycerol......Page 218
7.3.8 Reactivity of Cyclic Alkylene Carbonates......Page 221
7.4.1 Synthesis of Acyclic Carbonates......Page 223
7.4.2 Synthesis of Cyclic Carbonates......Page 227
References......Page 228
8.1 Introduction......Page 236
8.3 Metal Catalysts for the Copolymerization of Epoxides and CO2......Page 238
8.4.1 Early Studies......Page 251
8.4.2 Recent Studies using Transition Metal Catalysts......Page 252
8.5.1 Cyclohexene Oxide Monomer......Page 258
8.5.2 Propylene Oxide Monomer......Page 260
8.5.3 Oxetane Monomer......Page 262
8.6 Copolymer Isolation and Catalyst Recycling......Page 264
8.7 Copolymerization of Carbon Disulfide and Epoxides and Episulfides......Page 267
8.9 Concluding Remarks......Page 268
References......Page 269
9.1 Introduction......Page 272
9.2 Thermodynamic Analysis of Carbon Formation from CH4 or CO......Page 275
9.3 Thermodynamic Analysis of Carbon Formation in CO2 Reforming of Methane......Page 277
9.4 TEOM Measurement of Carbon Formation in CO2 Reforming of Methane......Page 279
9.5 TPO Analysis of Carbon Formation in CO2 Reforming......Page 280
9.6 TEM Analysis on Carbon Formed on Catalysts After CO2 Reforming of Methane......Page 282
9.7 Kinetic Study of Carbon Formation on PCH4 and PCO in CO2 Reforming......Page 283
9.8 H2O Effect on Carbon Formation in CO2 Reforming......Page 285
References......Page 286
Appendix A9.1......Page 287
10.1 Introduction......Page 290
10.2 Nonthermal Plasma Phenomena......Page 291
10.2.2 Atom/Ion/Molecule Reactions......Page 293
10.2.3 Heterogeneous Reactions......Page 294
10.3.1 CO2 Dissociation......Page 295
10.3.2 Reforming of CH4 with CO2......Page 296
10.3.3 Reforming of Aliphatic Hydrocarbons with CO2......Page 298
10.3.5 Reduction of CO2......Page 299
10.4.1 Oxidative Coupling of CH4 with CO2......Page 300
10.4.2 Hydrogenation of CO2/CO to C2 Hydrocarbons......Page 301
10.4.3 Higher Hydrocarbons from CH4 and CO2......Page 302
10.5.1 Methanol from CO2 Hydrogenation......Page 303
10.5.2 Methanol from CO2 and CH4......Page 304
10.5.4 Acetic Acid from CH4 and CO2......Page 305
10.5.5 Oxygenates from H2O and CO2......Page 306
10.6.1 Catalysts in Plasma Utilization of CO2......Page 307
10.6.2 Interaction Between Plasma and Catalyst......Page 308
10.7 Summary......Page 309
References......Page 310
11.1 Introduction......Page 314
11.2.1 General Considerations......Page 315
11.2.2.1 Ruthenium Complexes......Page 317
11.2.2.2 Rhenium Complexes......Page 318
11.3 Electrochemical Reduction......Page 319
11.3.1 Reduction in Aqueous Solutions at Metal Electrodes......Page 320
11.3.1.1 Reduction to CO and HCOOH......Page 321
11.3.1.2 Reduction to CH3OH and Alcohols......Page 322
11.3.1.3 Reduction to CH4 and Hydrocarbons......Page 323
11.3.2 Reduction in Nonaqueous Solutions at Metal Electrodes......Page 325
11.3.3.1 Transition Metal Complexes......Page 326
11.3.3.2 Macrocyclic Complexes......Page 327
11.4.1 Photoelectrochemical Semiconductor Electrode Systems......Page 328
11.4.1.1 Unmodified Semiconductor Electrode Interfaces......Page 329
11.4.1.2 Modified Semiconductor Electrodes......Page 330
11.4.1.3 Homogenous Solution Catalysts at Semiconductor Electrodes......Page 331
11.4.2.1 Unmodified Semiconductor Colloids and Powders......Page 332
11.4.2.2 Metal-Coated Semiconductor Colloids and Powders......Page 333
11.5 Concluding Remarks and Future Directions......Page 334
References......Page 335
12.1 Introduction......Page 340
12.2 Electrocarboxylation......Page 341
12.2.1 Electrocarboxylation of Organic Halides......Page 342
12.2.2 Electrocarboxylation of Aromatic Ketones......Page 347
12.2.3 Electrocarboxylation of Other Substrates......Page 349
12.3 The Electroreduction of Carbon Dioxide in Protic Media (Water and Alcohols)......Page 350
References......Page 353
13.1 Introduction......Page 358
13.2 The Natural Carbon Cycle......Page 359
13.3 The Utilization of Terrestrial Biomass......Page 360
13.3.1 Residual Biomass......Page 361
13.5 The New Generations of Biofuels......Page 362
13.5.1 Second-Generation Biofuels......Page 363
13.5.2 Third-Generation Biofuels......Page 364
13.6 Implementation of the Biorefinery Concept......Page 370
References......Page 372
14.1 Introduction: Inorganic Carbonate Uses and Natural Resources......Page 376
14.2 Natural Fixation of CO2 in Carbonates......Page 378
14.3.1 Material Resources......Page 380
14.3.2 Direct (Single-Step) Process Routes......Page 381
14.3.3.1 General Aspects of Calcium Carbonate Production......Page 382
14.3.3.2 Acetic Acid Route......Page 384
14.3.3.3 Two-Step Aqueous Carbonation of Solid Residues......Page 385
14.3.3.4 The pH-Swing Process......Page 386
14.4 Mineral Carbonation for Carbon Capture and Storage (CCS)......Page 387
14.4.1 Material Resources......Page 389
14.4.2.1 Gas–Solid Processes......Page 390
14.4.3.1 Gas–Solid Processes......Page 392
14.4.3.2 Aqueous Solution Processes......Page 395
14.5.1 Carbonation of Brines......Page 397
Acknowledgments......Page 398
References......Page 399
Index......Page 404