Return to Books

New Trends in CO Activation

Editor
L. Guczi

Institute of Isotopes of the Hungarian Academy of Science, Budapest, Hungary

Elsevier Science Publishers

Copyright 1991

Chapter 1 - Rutger A. van Santene and Ad de Koster
Quantum Chemistry of CO Chemisorption and Activation
1.1 Introduction 2
1.2 The Coordination of CO 4
1.3 Crystal Face Dependence - Promoter Effects 16
1.4 CO Dissociation 26
1.5 Discussion and Conlcusions 31
1.6 References 33
Chapter 2 (Maya Kiskinova)
Interaction of CO with Single Crystal Metal Surfaces
2.1 Introduction 38
2.2 Experimental Techniques 39
2.2.1 Dynamical Methods 39
2.2.1.1 Thermal Desorption (TD) 39
2.2.1.2 Molecular Beam Technique 39
2.2.1.3 Electron and Photon stimulated Desorption (ESD and PSD) and Electron Stimulated Desorption Ionangular Distribution (ESDIAD) 40
2.2.1.4 Secondary Ion Mass Spectrometry (SIMS) 40
2.2.2 Static Methods 40
2.2.2.1 Emission Spectroscopies 40
2.2.2.2 Absorption Spectroscopies 41
2.2.2.3 Low Energy Electron Diffraction (LEED) 42
2.3 Electronic Structure of the Free CO Molecule and Molecular Orbital Model for CO Bonding to Metal Surfaces 42
2.3.1 Free CO Molecule 42
2.3.2 Molecular Orbital Model for CO - Metal surface Bonding 43
2.4 Molecular CO Adsorption on Clean Single Crystal Metal Surfaces 44
2.4.1 CO Adsorption Probability and the Mechanism of CO Adsorption 44
2.4.2 CO Adsorption Binding Energy and Mobility of the CO Molecule i the Adsorption Phase 47
2.4.3 Surface Structure of the CO Overlayers 53
2.4.4 Orientation of the Chemisorbed CO Molecule with Respect to the Substrate Surface and the Corresponding Surface - C and C - O Interaction Distances 57
2.4.5 Co Induced Work Function Changes and the Effective Charge Transfer during Formation of the Surface  - CO Bond 59
2.4.6 Influence of the Metal - Co Bonding on the CO Electron Core and Valence Level Binding Energies 62
4.1.2.1 Support Functions as a Promoter 121
4.1.2.2 A Closer Inspection of the Promoter Function 125
4.1.2.2.1 Transition Metals Pd, Pt, Ir and Co, Ru, Rh, in CH3OH 125
4.1.2.2.2 Copper Catalysts 127
4.1.2.2.3 Promoted Transition Metals as Catalysts for C2+-oxygenates 128
4.2 Adsorption of CO 130
4.2.1 Adsorption of CO on Metals 130
4.2.2 Adsorption of CO on Alloys 132
4.2.3 Alloy Based Catalysts 134
4.2.3.1 Group VIII - Ib Metals 134
4.2.3.2 Group VIII - Group VIII Metals 135
4.2.3.3 Group VIII Metals - Early Transition Metals 135
4.2.3.4 Group VIII Metals - Rare Earths 136
4.2.3.5 Copper - Early Transition Metals, Copper - Rare Earths 136
4.3 Promotion of Metals. Theories and their Verification 137
4.3.1 Some Physical Phenomena Relevant to the Promoter - Metal Interaction 137
4.3.1.1 Point Charge and Dipole Metal Interaction; Image Forces 137
4.3.1.2 Adsorption of Strongly Electrodonating Species 138
4.31.3 A Through-the-Metal Interaction of Coadsorbed Species 139
4.3.1.4 Chare Transfer Between Phases. Metal - Metal and Metal - Semiconductor Interaction 140
4.3.2 Modern theories of Promotion Effects in the Syngas Reaction 143
4.3.3 Theories and their Verification 145
4.4 Related Reactions 147
4.4.1 Water Gas Shift Reaction 147
4.4.2 Hydrogenation of Unsaturated Aldehydes 148
4.5 Acknowledgement 148
4.6 References 148
Chapter 5 (Calvin H. Bartholomew)
Recent Developments in Fischer-Tropsch Catalysis
5.1 Introduction 158
5.2 New Catalyst Developments 160
5.2.1 Chemical Modifications 160
5.2.1.1 Additives and Promoters 163
5.2.1.2 Effects of Support, Metal Loading and Dispersion 169
5.2.1.3 Interstitial Compounds 179
5.2.1.4 Bimetallics 184
5.2.1.5 Effects of Pretreatment and Preparation 186
5.2.1.5.1 General Developments in FT Catalyst Preparation/Pretreatment 186
5.2.1.5.1.1 Preparation 187
5.2.1.5.1.2 Pretreatment 190
5.2.2 Limitations of Chain Growth by Shape Selectivity 193
5.2.3 Interception of Intermediates 194
5.2.3.1 Interception in Multifunctional Catalysts 194
5.2.3.2 Selectivity/Structure Relationships and Design Principles 195
5.2.3.3 Recent Developments in Zeolite Catalyst Technology 198
5.2.3.4 Interception in Two-Step Processes 199
5.3 New Developments in Reactor and Process Design 199
5.3.1 Recent Developments in Reactor Design
5.3.1.1 Reactor Types and their Characteristics 199
5.3.1.2 Comparison of Attributes for Three Reactor Types 202
5.3.1.3 Recent Experimental and Modeling Studies of FT Reactors 203
5.3.2 Second Generation FT Processes 204
5.3.2.1 Second Generation Commercial Processes 204
5.3.2.2 Experimental/Conceptual Multi-Stage Processes 206
5.4 Conclusions and Recommendations 208
5.4.1 Assessment of Current Technology and Conclusions 208
5.4.2 Recommendations for Future Research and Development 211
5.5 References 214
Chapter 6 (Johannes Schwank)
Bimetallic Catalysts for CO Activation
6.1 Introduction 226
6.2 The Genesis and Nature of Surface Sites in Bimetallic Catalysts 227
6.3 The Effect of Catalyst Preparation on the Properties of the Support and the Consequences for Bimetallic Particle Formation 236
6.4 The Interaction of CO with Bimetallic Surfaces 242
6.5 The Interaction of Hydrogen with Bimetallic Surfaces 244
6.6 CO Activation over Bimetallic Catalysts 246
6.7 Effect of Second Metal Component on Catalyst Deactivation  251
6.8 New Reaction Pathways in CO Activation 253
6.9 References 255
Chapter 7 (Richard G. Herman)
Classical and Non-Classical Route for Alcohols Synthesis
7.1 Introduction 266
7.2 Methanol Synthesis Catalysts 268
7.2.1 Active State of Copper 271
7.2.2 Hydrogenation of CO vs CO2 272
7.2.3 Newer Methanol Synthesis Catalysts 274
7.2.3.1 Cs/Cu/ZnO Catalysts 274
7.2.3.2 Th/Cu Alloy Catalysts 275
7.2.3.3 Zr/Cu Catalysts 276
7.2.3.4 Ce/Cu Catalysts 277
7.2.3.5 Supported Pd Catalysts 279
7.2.3.6 NaH - RONa - M(OAc)2 Catalysts Suspended in Liquids 280
7.2.3.7 Homogeneous Methanol Synthesis Catalyst 280
7.2.4 Newer Methanol Synthesis Technology 281
7.2.4.1 New Reactor Systems for Gas Phase Methanol Synthesis 281
7.2.4.2 Liquid Phase Methanol Synthesis 283
7.2.5 Deactivation of Methanol Synthesis Catalysts 285
7.3 Higher Alcohol Synthesis Catalysts 289
7.3.1 Rationale for Higher Alcohols as Fuels 289
7.3.2 Background of Higher Alcohol Synthesis Catalysts 290
7.3.3 Historical Development of Higher Alcohol Synthesis 291
7.3.4 Newer Catalysts and Technology 293
7.3.5 Higher Alcohol Synthesis over Oxide-Based Catalysts 293
7.3.5.1 Alkali-Promoted Cu/ZnO Catalysts 293
7.3.5.2 Supported Alkali-Promoted Cu/ZnO/M2O3 Catalysts 296
7.3.5.3 Other Oxide Catalysts Containing Transition Metal Additives 300
7.3.6 Alcohol Synthesis over Alkali-Promoted MoS2 Catalysts 303
7.3.6.1 Effect of Alkali Doping of MoS2 on the Activity and Selectivity for Alcohol Synthesis 305
7.3.6.2 Effect of Cesium Concentration on the Activity and Selectivity of Alcohol Synthesis 308
7.3.6.3 Effect of Reaction Temperature and Pressure on the Selectivity to Alcohols at Different Cs Loadings 309
7.3.6.4 Effect of Reactant Contact Time 310
7.3.6.5 Effect of CO2, H2S, and Olefins in the Synthesis Gas 310
7.3.6.6 Effect of Adding Cobalt to the Alkali-Doped MoS2 Catalyst 314
7.3.7 Mechanistic Implications of the Promotional Effect of Alkali 315
7.3.8 Research Goals 316
7.4 Mechanisms of Alcohol Synthesis 317
7.4.1 Mechanistic Background of Higher Alcohol Synthesis over Oxide Catalysts 317
7.4.2 Formation of C2 Products over Cs/Cu/ZnO Catalysts 319
7.4.3 Formation of C3 and C4 Alcohols over Cs/Cu/ZnO Catalysts 321
7.4.4 Formation of Oxygenates and Hydrocarbons over Alkali/MoS2 Catalysts 325
7.4.5 Mechanistic Implications 328
7.5 Kinetic Models for the Synthesis of Alcohols 329
7.5.1 Introduction
7.5.2 Development of Kinetic Models for Higher Alcohol Synthesis 330
7.5.3 Kinetic Modelling of Alcohol Synthesis over Cs/Cu/ZnO Catalysts 335
7.5.4 Kinetic Modelling of Alcohol Synthesis over Alkali/MoS2-Based Catalysts 336
7.5.5 Kinetic Considerations 339
7.6 References 340
Chapter 8 (László Guczi)
Effect of Hydrogen in Controlling CO Hydrogenation
8.1 Introduction 351
8.2 Hydrogen Adsorption on Metal Surface 352
8.2.1 Quantumchemical Approach of the Hydrogen Bonding 352
8.2.2 Kinetics and Energetics of Hydrogen Adsorption on Metals 355
8.2.2.1 Kinetics of Hydrogen Adsorption 355
8.2.2.2 Extent and Stoichiometry of Hydrogen Adsorption 358
8.2.2.3 Weak and Strong Chemisorption of Hydrogen 359
8.3 Temperature Programmed Desorption of Hydrogen 362
8.3.1 Desorption of Hydrogen from Metals 362
8.3.2 Basic Knowledge about Temperature Programmed Desorption of Hydrogen 362
8.4 Effect of Hydrogen Bonding on the Selectivity in CO Hydrogenation 367
8.4.1 Hydrocarbon and Olefin Formation 367
8.4.2 Hydrogen Effect in Alcohol Formation 371
8.4.3 Effect of Promoters on the Activated Hydrogen 372
8.5 Conclusions 375
8.6 References 376
Chapter (Michael Röper)
CO Activiation by Homogeneous Catalysts
9.1 Introduction 382
9.2 Mechanistic Implications of CO Activation 384
9.2.1 Coordination of CO 384
9.2.2 Activation of the Reagent 385
9.2.3 Conversion of Coordinated CO 387
9.2.4 Product Elimination and Catalyst Regeneration 388
9.3 Homogeneous Hydrogenation of CO 389
9.3.1 Cobalt Catalysts 392
9.3.2 Rhodium Catalysts 393
9.3.3 Ruthenium Catalysts 395
9.4 Homogeneous Oxidation of CO 396
9.5 Functionalizing Reactions of CO 398
9.5.1 Carbonylation 399
9.5.1.1 Carbonylation of Alkynes 400
9.5.1.2 Carbonylation of Alkenes 402
9.5.1.3 Carbonylation of Alkadienes 404
9.5.1.4 Carbonylation of Alkanes 407
9.5.1.5 Carbonylation of Alkanols, Esters and Ethers 407
9.5.1.6 Carbonylation of Organic Halides 411
9.5.2 Hydrocarbonylation 413
9.5.2.1 Hydrocarbonylation of Alkenes 413
9.5.2.2 Hydrocarbonylation of Alkanols 420
9.5.2.3 Hydrocarbonylation of Alkanals 422
9.6 Conclusions 423
9.7 References 424
Chapter 10 (Helmut Papp and Manfred Baerns)
Industrial Application of CO Chemistry for the Production of Specialty Chemicals
10.1 Introduction 431
10.2 Carbonylation of Methanol and Related Processes 431
10.2.1 Synthesis of Acetic Acid by Carbonylation of Methanol 432
10.2.1.1 Catalytic Systems 433
10.2.1.2 Industrial Importance of Acetic Acid 434
10.2.2 Synthesis of Acetic Anhydride by Carbonylation of Methylacetate 435
10.2.2.1 Catalytic Systems 435
10.2.2.2 Industrial Importance of Acetic Anhydride 436
10.2.3 Synthesis of Acetaldehyde and Ethanol 438
10.2.4 Synthesis of Vinyl Acetate 440
10.2.5 Homologation of Carboxylic Acids and Esters 441
10.2.6 Oxidative Carbonylation of Alcohols and Production of Ethylene Glycol 442
10.3 Hydroformylation of Olefins (Oxo Process) 442
10.3.1 Catalysts 443
10.3.2 Mechanism 445
10.3.3 Commercial Applications 447
10.4 Reppe Carbonylation and Related Processes 449
10.4.1 Catalysts 450
10.4.2 Mechanism 451
10.4.3 Commercial Applications 452
10.4.4 Carbonylation of Organic Halides 454
10.5 Koch Reaction 455
10.6 References 457
Chapter 11 (Gábor A. Somorjai)
The Catalyzed Hydrogenation of Carbon Monoxide: An Overview and Future Directions
11.1 Introduction 463
11.2 The Chemisorption and Dissociation of Carbon Monoxide on Clean Transition Metals 464
11.2.1 Alkali Metal Induced CO Bond Weakening and Dissociation 464
11.2.2 CO Dissociation 465
11.3 The Kinetics of the CO/H2 Reaction 466
11.3.1 Evidence for Secondary Reactions 466
11.4 Promotion by the Oxide - Metal Interface 468
11.5 Control of Secondary Reactions during CO Hydrogenation by Contact Time Bimetallics and Zeolites 468
11.6 Future Directions of Research 468
11.7 References 469
Index