Industrial Catalysis

Jens Hagen gives vocational training seminars on catalysis throughout the world and until his retirement he was Professor of Technical Chemistry at Mannheim University of Applied Sciences (Germany). The input he received through his international courses had an active influence on the content of the current edition of "Industrial Catalysis". Jens Hagen completed his first degree in chemical engineering in Essen (Germany), before studying chemistry at RWTH Aachen (Germany). He gained his doctorate in 1975 in the field of catalysis and high-pressure synthesis. Following a period in industry at Henkel KGaA, Düsseldorf (Germany), he was appointed as Professor at Mannheim University of Applied Sciences in 1979. Professor Hagen's teaching and research at the faculty of Chemical and Process Engineering focused on chemical reaction engineering and technical catalysis. In addition, he was the head of the Steinbeis Transfer Center for Process Engineering, Biotechnology and Environmental Techniques for many years.

• Preface to the Third Edition XVAbbreviations XVII1 Introduction 11.1 The Phenomenon Catalysis 11.2 Mode of Action of Catalysts 21.2.1 Activity 41.2.1.1 Turnover Frequency TOF 61.2.1.2 Turnover Number TON 71.2.2 Selectivity 71.2.3 Stability 81.2.4 Mole Balance and Conversion 81.3 Classification of Catalysts 101.4 Comparison of Homogeneous and Heterogeneous Catalysis 11Exercises 14References 152 Homogeneous Catalysis with Transition Metal Catalysts 172.1 Key Reactions in Homogeneous Catalysis 182.1.1 Coordination and Exchange of Ligands 182.1.2 Complex Formation 202.1.3 Acid–Base Reactions 222.1.4 Redox Reactions: Oxidative Addition and Reductive Elimination 232.1.4.1 Oxidative Coupling and Reductive Cleavage 272.1.5 Insertion and Elimination Reactions 282.1.5.1 β-Elimination 302.1.5.2 α-Elimination 302.1.6 Reactions at Coordinated Ligands 312.2 Catalyst Concepts in Homogeneous Catalysis 322.2.1 The 16/18-Electron Rule 322.2.2 Catalytic Cycles 342.3 Characterization of Homogeneous Catalysts 352.3.1 Infrared Spectroscopy 382.3.2 NMR Spectroscopy 40Exercises 42References 453 Homogeneously Catalyzed Industrial Processes 473.1 Overview 473.2 Examples of Industrial Processes 483.2.1 Oxo Synthesis 503.2.2 Production of Acetic Acid by Carbonylation of Methanol 523.2.3 Selective Ethylene Oxidation by theWacker Process 553.2.4 Oxidation of Cyclohexane 573.2.5 Suzuki Coupling 583.2.6 Oligomerization of Ethylene (SHOP Process) 593.2.7 Telomerization of Butadiene 613.2.8 Adipodinitrile 633.3 Asymmetric Catalysis 633.3.1 Introduction 633.3.2 Catalysts 643.3.3 Commercial Applications 653.3.3.1 Asymmetric Hydrogenation 653.3.3.2 Enantioselective Isomerization: L-Menthol 673.3.3.3 Asymmetric Epoxidation 683.4 Alkene Metathesis 693.4.1 Examples of Heterogeneous Catalysis 723.5 Recycling of Homogeneous Catalysts 733.5.1 Overview 733.5.1.1 Precipitation of the Catalyst or of the Product(s) 733.5.1.2 Thermal Separation 733.5.1.3 Membrane Separation 733.5.1.4 Adsorption 743.5.1.5 Phase Separation/Extraction 743.5.2 Reactions in Two-Phase Liquid–Liquid Systems 74Exercises 76References 784 Biocatalysis 814.1 Introduction 814.1.1 Active Sites 834.1.2 Coenzymes 844.2 Kinetics of Enzyme-Catalyzed Reactions 844.3 Industrial Processes with Biocatalysts 904.3.1 Acrylamide from Acrylonitrile 904.3.2 Aspartame Through Enzymatic Peptide Synthesis 914.3.3 L-Amino Acids by Aminoacylase Process 924.3.4 Pharmaceuticals 934.3.5 Herbicides 954.3.5.1 4-Hydroxyphenoxypropionic Acid as Herbicide Intermediate 96Exercises 97References 975 Heterogeneous Catalysis: Fundamentals 995.1 Individual Steps in Heterogeneous Catalysis 995.2 Kinetics and Mechanisms of Heterogeneously Catalyzed Reactions 1015.2.1 The Importance of Adsorption in Heterogeneous Catalysis 1025.2.2 Kinetic Treatment 1065.2.3 Mechanisms of Heterogeneously Catalyzed Gas-Phase Reactions 1085.2.3.1 Langmuir–Hinshelwood Mechanism (1921) 1095.2.3.2 Eley–Rideal Mechanism (1943) 1115.3 Catalyst Concepts in Heterogeneous Catalysis 1135.3.1 Energetic Aspects of Catalytic Activity 1135.3.2 Steric Effects 1245.3.3 Electronic Factors 1345.3.3.1 Redox Catalysts 1345.3.3.2 Acid/Base Catalysts (Ionic Catalysts) 1355.3.3.3 Metals 1365.3.3.4 Bimetallic Catalysts 1405.3.3.5 Semiconductors 1445.3.3.6 Insulators: Acidic and Basic Catalysts 1575.4 Catalyst Performance 1645.4.1 FactorsWhich Affect the Catalyst Performance 1645.4.2 Supported Catalysts 1665.4.3 Promoters 1725.4.4 Inhibitors 1765.5 Catalyst Deactivation 1775.5.1 Catalyst Poisoning 1795.5.2 Poisoning of Metals 1795.5.3 Poisoning of Semiconductor Oxides 1825.5.4 Poisoning of Solid Acids 1825.5.5 Deposits on the Catalyst Surface 1835.5.6 Thermal Processes and Sintering 1855.5.7 Catalyst Losses via the Gas Phase 1865.6 Regeneration and Recycling of Heterogeneous Catalysts 1865.7 Characterization of Heterogeneous Catalysts 1895.7.1 Physical Characterization 1905.7.1.1 Temperature-Programmed Desorption 1955.7.2 Chemical Characterization and Surface Analysis 1955.7.2.1 Temperature-Programmed Reaction Methods 1965.7.2.2 Transmission Electron Microscopy 1975.7.2.3 Low-Energy Electron Diffraction (LEED) 1985.7.2.4 IR Spectroscopy 1995.7.2.5 Electron Spectroscopy for Chemical Analysis (ESCA) 1995.7.2.6 Auger Electron Spectroscopy (AES) 2015.7.2.7 Ion Scattering Spectroscopy (ISS) 2015.7.2.8 Secondary Ion Mass Spectrometry (SIMS) 202Exercises 203References 2096 Catalyst Shapes and Production of Heterogeneous Catalysts 2116.1 Introduction 2116.2 Bulk Catalysts 2126.2.1 Precipitation 2126.2.2 Fusion and Alloy Leaching 2146.2.3 Sol–Gel Synthesis 2156.2.4 Flame Hydrolysis 2176.2.5 Hydrothermal Synthesis 2176.2.6 Heteropolyacids 2196.3 Supported Catalysts 2196.3.1 Impregnation 2206.3.2 Coprecipitation 2256.3.3 Adsorption/Ion-Exchange 2266.3.3.1 Ion-Exchange Resins 2276.3.4 Anchoring/Grafting 2286.3.5 Monolithic Catalysts 2296.4 Shaping of Catalysts and Catalyst Supports 2306.5 Immobilization of Homogeneous Catalysts 2326.5.1 Supported Solid-Phase Catalysts (SSPC) 2346.5.2 Supported Liquid-Phase Catalysts (SLPC) 2366.5.3 Encapsulation 236Exercises 237References 2387 Shape-Selective Catalysis: Zeolites 2397.1 Composition and Structure of Zeolites 2397.2 Catalytic Properties of the Zeolites 2427.2.1 Shape Selectivity 2437.2.1.1 Reactant Selectivity 2437.2.1.2 Product Selectivity 2467.2.1.3 Restricted Transition State Selectivity 2467.2.2 Acidity of Zeolites 2477.3 Isomorphic Substitution of Zeolites 2517.4 Metal-Doped Zeolites 2527.5 Applications of Zeolites 255Exercises 258References 2598 Heterogeneously Catalyzed Processes in Industry 2618.1 Overview 2618.1.1 Production of Inorganic Chemicals 2618.1.2 Production of Organic Chemicals 2618.1.3 Refinery Processes 2628.1.4 Catalysts in Environmental Protection 2648.2 Examples of Industrial Processes – Bulk Chemicals 2668.2.1 Ammonia Synthesis 2668.2.2 Hydrogenation 2688.2.3 Methanol Synthesis 2708.2.4 Selective Oxidation of Propene 2728.2.4.1 Oxidation of Propene with H2O2 to Propylene Oxide 2778.2.5 Selective Oxidation of Hydrocarbons 2778.2.5.1 n-Butane to Maleic Anhydride 2788.2.5.2 o-Xylene to Phthalic Anhydride 2808.3 Fine Chemicals Manufacture 2818.3.1 Fine Chemicals andTheir Synthesis 2818.3.2 Selected Examples of Industrial Processes 2858.3.2.1 Hydrogenation 2868.3.2.2 Oxidation 2888.3.2.3 Catalytic C–C Linkage 2908.3.2.4 Acid/Base Catalysis 292Exercises 294References 2979 Refinery Processes and Petrochemistry 2999.1 Hydrotreating 3009.2 Catalytic Cracking 3029.3 Hydrocracking 3049.4 Catalytic Reforming 3069.5 Alkylation 3079.6 Hydroisomerization 3089.7 Synthesis Gas and Hydrogen by Steam Reforming 3109.8 Natural Gas Conversion to Fuels and Chemicals 3129.9 Fischer–Tropsch Synthesis 3139.10 Etherification Reactions 315Exercises 316References 31710 Electrocatalytic Processes 31910.1 Comparison Between Electrocatalysis and Heterogeneous Catalysis 31910.2 Electroorganic Syntheses 31910.2.1 Electrocatalytic Hydrogenation 32010.2.2 Electrocatalytic Oxidation 32210.2.3 Electrochemical Addition 32310.3 Electrocatalysis in Fuel Cells 32410.3.1 Basic Principles 32410.3.2 Types of Fuel Cell and Catalyst 32510.3.3 Important Reactions in Fuel Cell Technology 32810.3.3.1 The Anodic Reaction 32810.3.3.2 The Cathodic Reaction 32910.3.3.3 Methanol Oxidation 331Exercises 332References 33311 Environmental Catalysis and Green Chemistry 33511.1 Automotive Exhaust Catalysis 33511.2 NOx Removal Systems 33811.2.1 Selective Catalytic Reduction of Nitrogen Oxides 33811.2.2 NOx Storage-Reduction Catalyst for Lean-Burning Engines 34011.3 Catalytic Afterburning 34111.4 Green Chemistry and Catalysis 34411.4.1 Examples of Catalytical Processes 34511.4.1.1 Aldol Condensation 34511.4.1.2 Diels–Alder Reaction 34611.4.1.3 Hydrogenation 34711.4.1.4 Cyclization inWater 34711.4.1.5 Use of Ionic Liquids 34711.4.1.6 Green Solvents 349Exercises 350References 35112 Phase-Transfer Catalysis 35312.1 Definition 35312.2 Catalysts for PTC 35312.3 Mechanism and Benefits of PTC 35412.4 PTC Reactions 35512.5 Selected Industrial Processes with PTC 35612.5.1 Continuous Dehydrohalogenation to Produce the Large-Scale Monomer Chloroprene 35612.5.2 Polycarbonate Manufacture with Phosgene 35612.5.3 Etherification (O-Alkylation) 35712.5.4 Aldehydes by Oxidation of Alcohols with Hypochlorite 35712.5.5 Carbonylation 35712.5.6 2-Phenylbutyronitrile by Alkylation 358Exercises 359References 35913 Catalytic Processes with Renewable Materials 36113.1 Biofuels 36113.2 Biorefinery 36613.2.1 Lignocellulose Feedstock Biorefinery 36813.3 Chemicals from Biomass 36913.3.1 Chemicals from Biomass via Platform Molecules 36913.3.1.1 Carbohydrates 36913.3.1.2 Fats and Oils 37313.3.1.3 Terpenes 37513.3.2 Direct Biomass Conversion to End-Products 376Exercises 378References 37814 Polymerization Catalysis 38114.1 Introduction 38114.2 Fundamentals of Catalytical Polymerization Processes 38114.3 Coordination Polymerization 38314.3.1 Ziegler–Natta Catalysts 38314.3.1.1 Heterogeneous Ziegler–Natta Catalysts 38414.3.1.2 Homogeneous Ziegler–Natta Catalysts 38614.3.1.3 Metallocenes 38614.3.1.4 Ring-OpeningMetathetic Polymerization 38814.4 Examples of Catalytical Polymerization Processes 38914.4.1 Polyethylene Production 38914.4.2 Polypropylene Production 391Exercises 392References 39315 Planning, Development, and Testing of Catalysts 39515.1 Stages of Catalyst Development 39515.2 Development of a Catalytical Process: Hydrogenation of Benzene to Cyclohexane 39815.3 Selection and Testing of Catalysts in Practice 40115.3.1 Catalyst Screening 40115.3.2 Catalyst Test Reactors and Kinetic Modeling 40515.3.2.1 Differential Reactor 40515.3.2.2 Differential Circulating Reactor 40715.3.2.3 Integral reactor 41115.3.3 Kinetic Modeling and Simulation 41615.3.3.1 Hydrogenation of Benzaldehyde 41615.3.3.2 Modeling of a Trickle Bed Reactor 42015.3.4 Catalyst Discovery via High-Throughput Experimentation 427Exercises 430References 43016 Catalysis Reactors 43316.1 Plug Flow Reactor (PFR) 43316.2 Continuous Stirred-Tank Reactor (CSTR) 43516.3 Reactor Calculations 43616.4 Two-Phase Reactors 44016.4.1 Single-Bed Reactor 44116.4.2 Multibed Reactor 44116.4.3 Multitubular Reactors 44216.4.4 Shallow-Bed Reactors 44216.4.5 Fluidized-Bed Reactors 44316.5 Three-Phase Reactors 44316.5.1 Fixed-Bed Reactors 44516.5.2 Suspension Reactors 44716.6 Reactors for Homogeneously Catalyzed Reactions 45116.7 New Reactor Concepts 45216.7.1 Membrane Reactors 45216.7.2 Catalytic Reactive Distillation 45316.7.3 Catalytic Microreactors 454Exercises 455References 45717 Economic Importance of Catalysts 459References 46218 Future Development of Catalysis 46318.1 Homogeneous Catalysis 46318.2 Heterogeneous Catalysis 46518.2.1 Use of Other Cheaper Raw Materials 46718.2.2 Catalysts for Energy Generation 46818.2.3 Better Strategies for Catalyst Development 469References 472Solutions to the Exercises 473Index 513

"This is the third addition of Jens Hagen�s overview of the industrial application of catalytic science and engineering. As with previous editions this work covers a wide range of catalytic processes spanning heterogeneous and homogeneous catalysis, including chapters on biocatalysis and electrocatalysis. This edition has been extensively revised and includes additions not present in earlier versions. A key feature of the text is inclusion of exercises in each chapter, with solutions provided...[This book] would...be a useful reference for an introductory undergraduate course on catalysis, for whom the exercises would be particularly valuable, or to a researcher starting out in area unfamiliar to them......an excellent overview of catalysis and its applications more broadly..."(AOC review March 2017)