Catalysis: An Integrated ApproachSecond, revised and enlarged edition
Editors Van Santen, R. A. Schuit Institue of Catalysis, Eindhoven University of Technology, Eindhoven, The Netherlands
Van Leeuwen, P.W.N.M. Department of Inorganic Chemistry, University of Amsterdam, Amsterdam, The Netherlands
Moulijn, J. A. Section for Process Catalysis, Deft University of Technology, Delft, The Netherlands
Averill, B. A. E.C. Slater Institute, University of Amsterdam, Amsterdam, The Netherlands
Elsevier Scientific Publishing Company
First Edition 1993 Second, revised and enlarged edition 1999
Table of Contents
Chapter 1
History of Catalysis A. P. Kieboom, J. Moulijn, P.W.N.M. van Leeuwen and R.A. van Santen 1.1 Introduction
3
1.2 Industrial Catalysis 4 1.2.1 Sulphuric Acid 5 1.2.2 Ammonia Synthesis 5 1.2.3 Coal, Oil, Natural Gas 9 1.2.4 Catalytic Reforming 12 1.2.5 Hydrorefining 13 1.2.6 Acetaldehyde 13 1.2.7. Butanol 14 1.2.8 Acetic Acid 15 1.2.9 Polymerization 16 1.2.10 Metathesis 16 1.2.11 Motor Vehicle Emission Control 17 1.3 Biocatalysis 18 1.3.1 Fermentation 18 1.3.2 Microbial Transformation 19 1.3.3 Enzymatic Transformation 20 1.4 Summary 20 References 28 Chapter 2 Catalytic Processes in Industry A.P.G. Kieboom, J.A. Moulijn, R.A. Sheldon and P.W.N.M. van Leeuwen 2.1 Introduction 29 2.2 Catalytic Processes in the Oil Refinery 29 2.2.1 Catalytic Reforming 31 2.2.2 Catalytic Cracking 33 2.2.3 Hydrotreatment 36 2.3 Total Isomerization Process of Paraffins 39 2.4 Isotactic Polypropylene 42 2.5 Catalysts for Automotive Pollution Control 45 2.6 Ethene Oxide 47 2.7 Styrene and Propylene Oxide (SMPO Process) 49 2.8 Higher Olefins 52 2.9 Rhodium Catalyzed Hyrdoformylation of Propene 54 2.10 Methanol Synthesis 57 2.11 Maleic Anhydride 61 2.12 Methyl t-Butyl Ether (MTBE) 64 2.13 Caprolactam 68 2.14 Vitamin A Intermediates 70 2.15 Ibuprofen 72 2.16 Aminopenicillanic Acid (6-APA) 74 2.17 High Fructose Corn Syrup (HFCS) 76 2.18 Low-PHosphate Pig Faeces as Fertilizers 78 References 80 General Literature 80 Chapter 3 Chemical Kinetics of Catalyzed Reactions F. Kapteijn, J.A. Moulijn, R.A. van Santen and R. Wever 3.1 Introduction 81 3.2 Rate Expression (Single-Site Model) 82 3.3 Rate-Determining Step – Quasi-Equilibrium 85 3.4 Adsorption Isotherms 87 3.5 Rate Expressions – Other Models and Generalizations 89 3.6 Limiting Cases – Reactant And Product Concentrations 91 3.7 Temperature And Pressure Dependence 95 3.7.1 Transition-State Theory 95 3.7.2 Forward Reaction – Temperature and Pressure Dependence 96 3.7.3 Forward Reaction – Limiting Cases 98 3.8 Sabatier Principle – Volcano Plot 102 3.9 Concluding Remarks 104 Notation 105 References 106 Chapter 4 Bonding and Elementary Steps in Catalysis B.A. Averill, I.M.C.M. Rietjens, P.W.N.M. van Leeuwen and R.A. van Santen 4.1 Introduction 109 4.2 Bonding 110 4.2.1. General Introduction 110 4.2.2 Bonding in Transition Metal Complexes 117 4.3 Elementary Steps In Organometallic Complexes 129 4.3.1 Creation of a Vacant Site 129 4.3.2 Coordination of the Substrate 132 4.3.3 Insertions and Migrations 133 4.3.4 ß-Elimination and Deinsertion 136 4.3.5 Oxidative Addition 137 4.3.6 Reductive Elimination 139 4.3.7 α-Elimination and Reactions 140 4.3.8 Cyclometallation 142 4.3.9 Activation of a Substrate toward Nucleophilic Attack 143 4.3.10 σ-Bond Metathesis 146 4.3.11 Heterolytic Cleavage of Dihydrogen 147 4.4 Elementary Surface Reaction Steps 148 4.4.1 Elementary Surface Reaction Steps at Transition Metal Surfaces 148 4.5 Elementary Reaction Steps on Solid Acids 164 4.5.1 General Introduction 164 4.5.2 Mechanism of Protonation 169 4.5.3 Brønsted Acid-catalyzed Hydrocarbon Activation Reactions 172 4.6 Elementary Steps in Biocatalytic Reactions 175 4.6.1 Introduction 175 4.6.2 Classification of Enzymes 175 4.6.3 General Features of Enzymes 175 4.6.4 Factors Important in Enzymatic Catalysis 182 4.7 Elementary Steps in Biocatalytic Oxidation Reactions 186 4.7.1 Introduction 186 4.7.2 Electron Transfer Reactions 188 4.7.3 Heme-based Peroxidases 190 4.7.4 Monooxygenases 192 4.7.5 Dioxygenases 203 References 206 Chapter 5 Heterogeneous Catalysis B.K. Hodnett, F.J.J.G. Janssen, J.W. Niemantsverdriet, V. Ponec, R.A. van Santen and J.A.R. van Veen 5.1 Introduction 209 5.2 Synthesis Gas Conversion 210 5.2.1 The Fischer-Tropsch Mechanism and its Consequences for the Technology 210 5.2.2 Kinetics of the FTS and Methanation Reaction 212 5.2.3 Function of Promoters in the Hydrocarbon Synthesis 216 5.2.4 Synthesis of Higher Oxygenates 216 5.2.5 Synthesis of Methanol 218 5.3 Automotive Exhaust Catalysis 220 5.3.1 Air Pollution and Regulations 220 5.3.2 The Three-way Catalyst 222 5.3.3 The Catalytic Converter 223 5.3.4 Function of the Catalyst Components 223 5.3.5 Catalyst Deactivation 224 5.3.6 Catalytic Reactions in the Three-way Catalyst: Mechanism and Kinetics 225 5.3.7 Concluding Remarks 233 5.4 Selective Catalytic Reduction of NO by NH3 235 5.4.1 Introduction 235 5.4.2 SCR Catalysts 236 5.4.3 Species at the Catalyst Surface 237 5.4.4 Kinetics 239 5.4.5 Mechanisms 243 5.5 Selective Oxidation 249 5.5.1 Propene Oxidation to Acrolein 249 5.5.2 Epoxidation of Ethene 262 5.5.3 The Wacker Reaction; Vinylacetate Production 267 5.5.4 Epoxidation using Hyrdo- or Hydrogenperoxide 269 5.6 Electrocatalysis 270 5.6.1 Introduction 270 5.6.2 Electrochemical Evolution of Hydrogen 273 5.6.3 Electro-oxidation of Hydrogen 274 5.6.4 Electrochemical Evolution of Oxygen 276 5.6.5 Electroreduction of Oxygen 278 5.6.6 Electrochemical Oxidation of Alcohols 279 References 283 Chapter 6 Homogeneous Catalysis with Transition Metal Complexes G. van Koten and P.W.N.M. van Leeuwen 6.1 Introduction 289 6.2 Rhodium Catalyzed Hydroformylation 291 6.2.1 Introduction 291 6.2.2 Rhodium-based Hydroformylation 292 6.2.3 Ligand Effects 294 6.2.4 Phosphine Ligands 294 6.2.5 Ligand Effects in Rhodium Catalyzed Hydroformylation 296 6.2.6 Kinetic Studies 302 6.2.7 The Characterization of Intermediates 308 6.3 Zirconium Catalyzed Polymerization of Alkenes 314 6.3.1 Introduction 314 6.3.2 Supported Titanium Catalysts 314 6.3.3 Isotactic Polypropylene 315 6.3.4 The Cossee-Arlman Mechanism 316 6.3.5 Homogeneous versus Heterogeneous Catalysts 317 6.3.6 Site Control versus Chain-end Control 317 6.3.7 Chain-end Control: Syndiotactic Polymers 320 6.3.8 Chain-end Control: Isotactic Polymers 321 6.3.9 Site Control: Recent History 322 6.3.10 Site Control: Isotactic Polymers 323 6.3.11 Double Stereoselection: Chain-end Control and Site Control 327 6.3.12 Effect of Hydrogen 328 6.3.13 Further Work 329 6.4 Asymmetric Hydrogenation 330 6.4.1 Introduction 330 6.4.2 Cinnamic Acid Derivatives 331 6.4.3 BINAP Catalysis 335 6.4.4 Chiral Ferrocene Based Ligands 338 References 339 Chapter 7 Biocatalysis B.A. Averill, N.W.M. Laane, A.J.J. Straathof and J. Tramper 7.1 Introduction 343 7.2 Biocatalysis vs. Chemical Catalysis 344 7.2.1 Chemical Conversion vs. Biocatalysis 346 7.2.2 Isolated Enzyme versus Whole Cell 347 7.2.3 Free versus Immobilized Biocatalyst 351 7.2.4 Water versus Organic Solvent 351 7.2.5 Standard versus Novel Bioreactor 352 7.2.6 (Fed-)Batch versus Continuous Operation 353 7.2.7 Integration of Reactions/Process Steps/Overall Process 355 7.3 Areas of Enzyme Applications 357 7.3.1 Hydrolases 358 7.3.2 Lyases 360 7.3.3 Isomerases 362 7.3.4 Transferases 363 7.3.5 Ligases 364 7.3.6 Oxidoreductases 364 7.4 Conclusions 370 References 370 Chapter 8 Catalytic Reaction Engineering F. Kapteijn, G.B. Marin and J.A. Moulijn 8.1 Introduction 375 8.2 Industrial Reactors 376 8.2.1 Batch Reactors 376 8.2.2 Continuous-flow Reactors for Gas-Liquid Reactions (Homogeneous Catalysis) 377 8.2.3 Continuous-flow Reactors for Solid-catalyzed Reactions 379 8.3 Ideal Reactors – Mathematical Description 386 8.3.1 Batch Reactor 387 8.3.2 Plug-Flow Reactor (PFR) 390 8.3.3 Continuous-flow Stirred-Tank Reactor (CSTR) 391 8.3.4 Comparison of PFR and CSTR 393 8.4 Reaction Combined with Transport 395 8.4.1 Heterogeneous Catalysis 396 8.4.2 Homogeneous Catalysis 409 8.5 Experimental Determination of Reaction Kinetics 417 8.5.1 Scope 417 8.5.2 Reactors 417 Notation 427 References 430 Chapter 9 Preparation of Catalyst Supports, Zeolites and Mesoporous Materials E.B.M. Doesburg, K.P. de Jong and J.H.C. van Hooff 9.1 Introduction 433 9.2 Preparation of Silica Supports 434 9.2.1 Preparation of Silica Gel 434 9.2.2 Silica Precipitation from Vapour: Pyrogenic Silica 438 9.3 Preparation of Alumina Supports 439 9.3.1 Preparation of γ- A12O3 and η-A12O3 439 9.3.2 Structure of γ- A12O3 and η-A12O3 440 9.4 Carbon Supports 442 9.5 Synthesis of Zeolites and Mesoporous Materials 443 9.5.1 Introduction 443 9.5.2 Synthesis of Zeolite A 446 9.5.3 Synthesis of Zeolite Y 447 9.5.4 Synthesis of Mordenite 447 9.5.5 Synthesis of ZSM-5 448 9.5.6 Synthesis of mesoporous A1-MCM-41 448 9.6 Shaping of Catalyst Bodies 449 9.6.1 Introduction 449 9.6.2 Spray Drying 450 9.6.3 Granulation 451 9.6.4 Extrusion 453 9.6.5 Oil-Drop Method/Sol-Gel Method 454 References 456 Chapter 10 Preparation of Supported Catalysts J.W. Geus and J.A.R. van Veen 10.1 Introduction 459 10.2 Selective Removal 461 10.3 Application on a Separately Produced Support 462 10.3.1 Support Surface Chemistry 463 10.3.2 Impregnation 467 10.3.3 Deposition-Precipitation 477 Further Reading 484 Catalyst Characterization with Spectroscopic Techniques J.W. Niemantsverdriet 11.1 Introduction 489 11.1.1 Aim of Catalyst Characterization 489 11.2 Techniques 490 11.2.1 X-Ray Diffraction (XRD) 491 11.2.2 Electron Microscopy 494 11.2.3 Temperature Programmed Techniques 496 11.2.4 Surface Spectroscopy 498 11.2.5 Infrared Spectroscopy 508 11.2.6 Extended X-Ray Absorption Fine Structure (EXAFS) 513 11.2.7 Mössbauer Spectroscopy 516 11.3 Concluding Remarks 521 11.3.1 Research Strategies 522 References 523 Chapter 12 Catalyst Characterization and Mimicking Pretreatment Procedures by Temperature – Programmed Techniques F. Kapteijn, J.A. Moulijn and A. Tarfaoui 12.1 Introduction 525 12.2 Application of TPR 527 12.3 Thermodynamics 527 12.4 Apparatus 527 12.5 Example 1: Temperature-Programmed Reduction (TPR) of CoO/A12O3 529 12.6 Example 2: Temperature-Programmed Sulphiding (TPS) of MoO3/A12O3 531 12.7 Modelling 533 12.7.1 Theory 533 12.7.2 Reduction Kinetic Models 536 12.7.3 Activation energy 536 12.8 Example 3: Modelling of TPR of Fe2O3 537 References 541 Chapter 13 Adsorption Methods for the Assessment of the Specific Surface Area and the Pore Size Distribution of Heterogeneous Catalysts J.A. Lercher 13.1 Introduction 543 13.2 Physical Adsorption 544 13.3 Adsorption Isotherms 546 13.4 Classification of Pore Sizes 547 13.5 Porosity of Porous Substances 548 13.6 The Yardstick in the Determination of Specific Surface Areas 549 13.7 The Langmuir (Monolayer Adsorption) Description of Adsorption 550 13.8 The BET (Multilayer Adsorption) Description of Adsorption 551 13.9 The t Method, a Concept of a Standard Isotherm 554 13.10 Assessment of Mesopore Radii and Volumes via the Kelvin Equations 557 13.11 The Corrected Kelvin Equation 559 13.12 Mercury Porosimetry 560 13.13 Assessing Microporosity 561 13.14 Distribution of Micropores 563 13.15 General Conclusions and Recommendations 564 Acknowledgements 565 References 565 Subject Index 567