Liquid Phase Oxidation via Heterogeneous Catalysis

Liquid Phase Oxidation via Heterogeneous Catalysis: Organic Synthesis And Industrial Applications......Page 1
Contents......Page 5
Preface......Page 11
Contributors......Page 13
Abbreviations......Page 15
1.1 Introduction......Page 21
1.2 Oxygen Air......Page 23
1.3 Alkylhydroperoxides......Page 25
1.4 Hydrogen Peroxide......Page 29
1.5 Conclusions......Page 36
References......Page 37
2.1 Introduction......Page 41
2.2 Synthesis and Characterization of Zeolites......Page 42
2.2.1 Isomorphous Metal Substitution......Page 43
2.2.2 Synthesis of Titanium Silicalite-1 TS-1......Page 44
2.2.3 Characterization of Titanium Silicalite-1 TS-1......Page 46
2.2.4 Ti-Beta, Synthesis and Characterization......Page 50
2.2.5 Other Ti Zeolites......Page 52
2.2.6 Other Metal Zeolites......Page 53
2.3.1 Hydroxylation of Alkanes......Page 54
2.3.2 Hydroxylation of Aromatic Compounds......Page 60
2.3.3 Oxidation of Olefinic Compounds......Page 67
2.3.4 Oxidation of Alcohol and Ether Compounds......Page 79
2.3.5 Reactions of Carbonyl Compounds......Page 80
2.3.6 Oxidation of N-Compounds......Page 83
2.3.7 Oxidation of S-Compounds......Page 85
2.4.1 The Nature of Active Species......Page 86
2.4.2 Hydroxylation......Page 89
2.4.3 Epoxidation......Page 91
2.4.4 Oxidation of Alcohols......Page 92
2.4.5 Ammoximation......Page 93
2.4.7 Active Species, Adsorption and Catalytic Activity......Page 94
2.5 Stability of Metal-Substituted Zeolites to Reaction Conditions......Page 97
2.6 Conclusions......Page 98
References......Page 100
3.1 Introduction......Page 115
3.2.1 Microporous Aluminophosphates......Page 120
3.2.2 Mesoporous Aluminophosphates......Page 122
3.3 Characterization......Page 123
3.4.1 Oxidation of Hydrocarbons......Page 126
3.4.2 Oxidation of Olefins......Page 130
3.4.3 Oxidation of Alcohols......Page 131
3.4.4 Oxidation of Phenols......Page 133
3.4.5 Ammoximation and Ammoxidation......Page 134
3.5 Mechanistic Aspects......Page 136
3.6 Catalysts Stability......Page 138
3.7 Conclusion......Page 139
References......Page 140
4.1 Introduction......Page 147
4.2.1 General Synthetic Approaches......Page 148
4.2.2 Characterization Techniques......Page 149
4.2.3 Sol-Gel Synthesis of Amorphous Mixed Oxides......Page 152
4.2.5 Templated Synthesis of Ordered Metal Silicates......Page 156
4.2.6 Postsynthesis Modifications......Page 176
4.2.7 Organic?Inorganic Hybrid Materials......Page 182
4.3.1 Oxidation of Alkanes......Page 183
4.3.2 Oxidation of Aromatic Compounds......Page 187
4.3.3 Oxidation of Olefins......Page 192
4.3.4 Oxidation of Alcohols......Page 202
4.3.5 Oxidation of Ketones and Aldehydes......Page 203
4.3.6 Oxidation of S-compounds......Page 205
4.3.7 Oxidation of Amines......Page 208
4.4 Mechanistic Aspects......Page 209
4.5.1 Mechanisms of Deactivation......Page 214
4.5.2 Solving Problem of Hydrothermal Stability......Page 217
4.5.3 Hydrothermally Stable Catalysts: Scope and Limitations......Page 219
4.6 Conclusions and Outlook......Page 220
References......Page 221
5.1 Introduction......Page 241
5.2 Catalyst Preparation and Characterization......Page 242
5.3.1 Oxidation of Hydrocarbons......Page 244
5.3.2 Oxidation of Alcohols and Phenols......Page 248
5.3.3 Oxidation of Carbohydrates: The Case of Glucose......Page 261
5.3.4 Oxidation of Amines and Aminoalcohols......Page 264
5.3.5 Oxidative Polymerization of Aniline and Pyrrole......Page 265
5.4 Reaction Mechanisms......Page 270
5.5 Catalyst Stability......Page 274
References......Page 276
6.1 Introduction......Page 283
6.2.1 Choice of POM......Page 286
6.2.2 Embedding POM into Silica and Other Matrixes......Page 287
6.2.3 Adsorption on Active Carbon......Page 291
6.2.4 Electrostatic Attachment......Page 293
6.2.5 Dative and Covalent Binding......Page 303
6.3.1 Oxidation of Alkanes......Page 307
6.3.3 Oxidation of Olefins......Page 308
6.3.4 Oxidation of Alcohols......Page 317
6.3.5 Oxidation of Aldehydes......Page 318
6.3.6 Co-Oxidation of Alkenes and Aldehydes......Page 319
6.3.7 Oxidation of S-containing Compounds......Page 321
6.4 Mechanistic Aspects......Page 324
6.5 Stability......Page 327
6.6 Conclusions......Page 329
References......Page 331
7.1 Introduction......Page 341
7.2 Synthesis and Characterization......Page 343
7.2.1 General Synthetic Strategies......Page 344
7.2.2 Metal Porphyrins......Page 349
7.2.3 Metal Phthalocyanines......Page 351
7.2.4 Complexes with Other Macrocyclic Ligands......Page 356
7.2.5 Chiral Complexes......Page 357
7.3 Catalytic Properties and Stability......Page 358
7.3.1 Oxidation of Alkanes......Page 359
7.3.2 Oxidation of Olefins......Page 364
7.3.3 Oxidation of Aromatic Hydrocarbons......Page 372
7.3.4 Oxidation of Substituted Phenols......Page 373
7.3.5 Oxidation of Alcohols......Page 376
7.3.6 Miscellaneous Oxidations......Page 379
7.4 General Remarks on Stability......Page 382
7.5 Conclusion and Perspectives......Page 384
References......Page 385
8.1 Introduction......Page 391
8.2.1 Characteristics......Page 392
8.2.2 Structures......Page 394
8.2.3 Syntheses......Page 398
8.2.4 Active Sites......Page 400
8.3.1 Oxidation of Cycloalkanes......Page 408
8.3.2 Oxidation of Aromatic Compounds......Page 409
8.3.3 Oxidation of Olefins......Page 413
8.3.4 Oxidation of Alcohols and Phenols......Page 418
8.3.5 Oxidation of Sulfides......Page 419
8.4 Mechanistic Aspects......Page 420
8.5.1 Thermal and Chemical Stability......Page 422
8.5.2 Leaching of Active Metal Components......Page 424
References......Page 425
9.1 Introduction......Page 431
9.2.1 Titanium Dioxide......Page 433
9.2.2 Highly Dispersed Oxides......Page 436
9.2.3 Polyoxotungstates......Page 438
9.3.1 Oxidation of Alkanes......Page 442
9.3.2 Oxidation of Aromatic Compounds......Page 447
9.3.3 Oxidation of Alcohols......Page 450
9.3.4 Oxidation of Olefins......Page 456
9.4 Stability......Page 458
9.5 Conclusions......Page 463
References......Page 464
10.1.1 The Discovery of TS-1......Page 471
10.1.2 The Hydroxylation of Phenol......Page 472
10.1.3 The Industrial Process......Page 476
10.1.4 Other Processes Exploiting TS-1......Page 480
References......Page 481
10.2.1 Nylon-6 and ε-Caprolactam, Outlook and Industrial Production......Page 482
10.2.2 TS-1 Catalyzed Ammoximation......Page 486
10.2.3 Eni Cyclohexanone Ammoximation Process......Page 487
10.2.5 Other TS-1-Catalyzed Ammoximation Reactions and Related Processes of Industrial Relevance......Page 490
10.2.6 Conclusion......Page 491
References......Page 492
10.3 Production of Propylene Oxide......Page 494
10.3.1 Propylene Oxide Production via Ethylbenzene Hydroperoxide Route......Page 496
10.3.2 Propylene Oxide Production via Cumene Hydroperoxide Route......Page 500
10.3.3 Propylene Oxide Production via Hydrogen Peroxide Route......Page 503
10.3.4 Conclusions......Page 507
References......Page 514
10.4.1 Heterogeneous Liquid Phase Systems......Page 516
10.4.2 Temperature-Control Requirements......Page 519
10.4.3 Packed-Bed Reactors......Page 520
10.4.4 Three-Phase Systems ? Gas, Liquid, Solid......Page 521
10.4.5 Oxidant Selection......Page 523
10.4.6 Summary......Page 525
References......Page 526
Index......Page 527