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Industrial Catalysis: A Practical Approach, 3rd Edition

Industrial Catalysis: A Practical Approach, 3rd Edition

Jens Hagen

ISBN: 978-3-527-68462-5

Sep 2015

544 pages

Description

Now in it's 3rd Edition, Industrial Catalysis offers all relevant information on catalytic processes in industry, including many recent examples. Perfectly suited for self-study, it is the ideal companion for scientists who want to get into the field or refresh existing knowledge.

The updated edition covers the full range of industrial aspects, from catalyst development and testing to process examples and catalyst recycling. The book is characterized by its practical relevance, expressed by a selection of over 40 examples of catalytic processes in industry. In addition, new chapters on catalytic processes with renewable materials and polymerization catalysis have been included. Existing chapters have been carefully revised and supported by new subchapters, for example, on metathesis reactions, refinery processes, petrochemistry and new reactor concepts.

"I found the book accesible, readable and interesting - both as a refresher and as an introduction to new topics - and a convenient first reference on current industrial catalytic practise and processes."
Excerpt from a book review for the second edition by P. C. H. Mitchell, Applied Organometallic Chemistry (2007)

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Preface to the Third Edition XV

Abbreviations XVII

1 Introduction 1

1.1 The Phenomenon Catalysis 1

1.2 Mode of Action of Catalysts 2

1.2.1 Activity 4

1.2.1.1 Turnover Frequency TOF 6

1.2.1.2 Turnover Number TON 7

1.2.2 Selectivity 7

1.2.3 Stability 8

1.2.4 Mole Balance and Conversion 8

1.3 Classification of Catalysts 10

1.4 Comparison of Homogeneous and Heterogeneous Catalysis 11

Exercises 14

References 15

2 Homogeneous Catalysis with Transition Metal Catalysts 17

2.1 Key Reactions in Homogeneous Catalysis 18

2.1.1 Coordination and Exchange of Ligands 18

2.1.2 Complex Formation 20

2.1.3 Acid–Base Reactions 22

2.1.4 Redox Reactions: Oxidative Addition and Reductive Elimination 23

2.1.4.1 Oxidative Coupling and Reductive Cleavage 27

2.1.5 Insertion and Elimination Reactions 28

2.1.5.1 β-Elimination 30

2.1.5.2 α-Elimination 30

2.1.6 Reactions at Coordinated Ligands 31

2.2 Catalyst Concepts in Homogeneous Catalysis 32

2.2.1 The 16/18-Electron Rule 32

2.2.2 Catalytic Cycles 34

2.3 Characterization of Homogeneous Catalysts 35

2.3.1 Infrared Spectroscopy 38

2.3.2 NMR Spectroscopy 40

Exercises 42

References 45

3 Homogeneously Catalyzed Industrial Processes 47

3.1 Overview 47

3.2 Examples of Industrial Processes 48

3.2.1 Oxo Synthesis 50

3.2.2 Production of Acetic Acid by Carbonylation of Methanol 52

3.2.3 Selective Ethylene Oxidation by theWacker Process 55

3.2.4 Oxidation of Cyclohexane 57

3.2.5 Suzuki Coupling 58

3.2.6 Oligomerization of Ethylene (SHOP Process) 59

3.2.7 Telomerization of Butadiene 61

3.2.8 Adipodinitrile 63

3.3 Asymmetric Catalysis 63

3.3.1 Introduction 63

3.3.2 Catalysts 64

3.3.3 Commercial Applications 65

3.3.3.1 Asymmetric Hydrogenation 65

3.3.3.2 Enantioselective Isomerization: L-Menthol 67

3.3.3.3 Asymmetric Epoxidation 68

3.4 Alkene Metathesis 69

3.4.1 Examples of Heterogeneous Catalysis 72

3.5 Recycling of Homogeneous Catalysts 73

3.5.1 Overview 73

3.5.1.1 Precipitation of the Catalyst or of the Product(s) 73

3.5.1.2 Thermal Separation 73

3.5.1.3 Membrane Separation 73

3.5.1.4 Adsorption 74

3.5.1.5 Phase Separation/Extraction 74

3.5.2 Reactions in Two-Phase Liquid–Liquid Systems 74

Exercises 76

References 78

4 Biocatalysis 81

4.1 Introduction 81

4.1.1 Active Sites 83

4.1.2 Coenzymes 84

4.2 Kinetics of Enzyme-Catalyzed Reactions 84

4.3 Industrial Processes with Biocatalysts 90

4.3.1 Acrylamide from Acrylonitrile 90

4.3.2 Aspartame Through Enzymatic Peptide Synthesis 91

4.3.3 L-Amino Acids by Aminoacylase Process 92

4.3.4 Pharmaceuticals 93

4.3.5 Herbicides 95

4.3.5.1 4-Hydroxyphenoxypropionic Acid as Herbicide Intermediate 96

Exercises 97

References 97

5 Heterogeneous Catalysis: Fundamentals 99

5.1 Individual Steps in Heterogeneous Catalysis 99

5.2 Kinetics and Mechanisms of Heterogeneously Catalyzed Reactions 101

5.2.1 The Importance of Adsorption in Heterogeneous Catalysis 102

5.2.2 Kinetic Treatment 106

5.2.3 Mechanisms of Heterogeneously Catalyzed Gas-Phase Reactions 108

5.2.3.1 Langmuir–Hinshelwood Mechanism (1921) 109

5.2.3.2 Eley–Rideal Mechanism (1943) 111

5.3 Catalyst Concepts in Heterogeneous Catalysis 113

5.3.1 Energetic Aspects of Catalytic Activity 113

5.3.2 Steric Effects 124

5.3.3 Electronic Factors 134

5.3.3.1 Redox Catalysts 134

5.3.3.2 Acid/Base Catalysts (Ionic Catalysts) 135

5.3.3.3 Metals 136

5.3.3.4 Bimetallic Catalysts 140

5.3.3.5 Semiconductors 144

5.3.3.6 Insulators: Acidic and Basic Catalysts 157

5.4 Catalyst Performance 164

5.4.1 FactorsWhich Affect the Catalyst Performance 164

5.4.2 Supported Catalysts 166

5.4.3 Promoters 172

5.4.4 Inhibitors 176

5.5 Catalyst Deactivation 177

5.5.1 Catalyst Poisoning 179

5.5.2 Poisoning of Metals 179

5.5.3 Poisoning of Semiconductor Oxides 182

5.5.4 Poisoning of Solid Acids 182

5.5.5 Deposits on the Catalyst Surface 183

5.5.6 Thermal Processes and Sintering 185

5.5.7 Catalyst Losses via the Gas Phase 186

5.6 Regeneration and Recycling of Heterogeneous Catalysts 186

5.7 Characterization of Heterogeneous Catalysts 189

5.7.1 Physical Characterization 190

5.7.1.1 Temperature-Programmed Desorption 195

5.7.2 Chemical Characterization and Surface Analysis 195

5.7.2.1 Temperature-Programmed Reaction Methods 196

5.7.2.2 Transmission Electron Microscopy 197

5.7.2.3 Low-Energy Electron Diffraction (LEED) 198

5.7.2.4 IR Spectroscopy 199

5.7.2.5 Electron Spectroscopy for Chemical Analysis (ESCA) 199

5.7.2.6 Auger Electron Spectroscopy (AES) 201

5.7.2.7 Ion Scattering Spectroscopy (ISS) 201

5.7.2.8 Secondary Ion Mass Spectrometry (SIMS) 202

Exercises 203

References 209

6 Catalyst Shapes and Production of Heterogeneous Catalysts 211

6.1 Introduction 211

6.2 Bulk Catalysts 212

6.2.1 Precipitation 212

6.2.2 Fusion and Alloy Leaching 214

6.2.3 Sol–Gel Synthesis 215

6.2.4 Flame Hydrolysis 217

6.2.5 Hydrothermal Synthesis 217

6.2.6 Heteropolyacids 219

6.3 Supported Catalysts 219

6.3.1 Impregnation 220

6.3.2 Coprecipitation 225

6.3.3 Adsorption/Ion-Exchange 226

6.3.3.1 Ion-Exchange Resins 227

6.3.4 Anchoring/Grafting 228

6.3.5 Monolithic Catalysts 229

6.4 Shaping of Catalysts and Catalyst Supports 230

6.5 Immobilization of Homogeneous Catalysts 232

6.5.1 Supported Solid-Phase Catalysts (SSPC) 234

6.5.2 Supported Liquid-Phase Catalysts (SLPC) 236

6.5.3 Encapsulation 236

Exercises 237

References 238

7 Shape-Selective Catalysis: Zeolites 239

7.1 Composition and Structure of Zeolites 239

7.2 Catalytic Properties of the Zeolites 242

7.2.1 Shape Selectivity 243

7.2.1.1 Reactant Selectivity 243

7.2.1.2 Product Selectivity 246

7.2.1.3 Restricted Transition State Selectivity 246

7.2.2 Acidity of Zeolites 247

7.3 Isomorphic Substitution of Zeolites 251

7.4 Metal-Doped Zeolites 252

7.5 Applications of Zeolites 255

Exercises 258

References 259

8 Heterogeneously Catalyzed Processes in Industry 261

8.1 Overview 261

8.1.1 Production of Inorganic Chemicals 261

8.1.2 Production of Organic Chemicals 261

8.1.3 Refinery Processes 262

8.1.4 Catalysts in Environmental Protection 264

8.2 Examples of Industrial Processes – Bulk Chemicals 266

8.2.1 Ammonia Synthesis 266

8.2.2 Hydrogenation 268

8.2.3 Methanol Synthesis 270

8.2.4 Selective Oxidation of Propene 272

8.2.4.1 Oxidation of Propene with H2O2 to Propylene Oxide 277

8.2.5 Selective Oxidation of Hydrocarbons 277

8.2.5.1 n-Butane to Maleic Anhydride 278

8.2.5.2 o-Xylene to Phthalic Anhydride 280

8.3 Fine Chemicals Manufacture 281

8.3.1 Fine Chemicals andTheir Synthesis 281

8.3.2 Selected Examples of Industrial Processes 285

8.3.2.1 Hydrogenation 286

8.3.2.2 Oxidation 288

8.3.2.3 Catalytic C–C Linkage 290

8.3.2.4 Acid/Base Catalysis 292

Exercises 294

References 297

9 Refinery Processes and Petrochemistry 299

9.1 Hydrotreating 300

9.2 Catalytic Cracking 302

9.3 Hydrocracking 304

9.4 Catalytic Reforming 306

9.5 Alkylation 307

9.6 Hydroisomerization 308

9.7 Synthesis Gas and Hydrogen by Steam Reforming 310

9.8 Natural Gas Conversion to Fuels and Chemicals 312

9.9 Fischer–Tropsch Synthesis 313

9.10 Etherification Reactions 315

Exercises 316

References 317

10 Electrocatalytic Processes 319

10.1 Comparison Between Electrocatalysis and Heterogeneous Catalysis 319

10.2 Electroorganic Syntheses 319

10.2.1 Electrocatalytic Hydrogenation 320

10.2.2 Electrocatalytic Oxidation 322

10.2.3 Electrochemical Addition 323

10.3 Electrocatalysis in Fuel Cells 324

10.3.1 Basic Principles 324

10.3.2 Types of Fuel Cell and Catalyst 325

10.3.3 Important Reactions in Fuel Cell Technology 328

10.3.3.1 The Anodic Reaction 328

10.3.3.2 The Cathodic Reaction 329

10.3.3.3 Methanol Oxidation 331

Exercises 332

References 333

11 Environmental Catalysis and Green Chemistry 335

11.1 Automotive Exhaust Catalysis 335

11.2 NOx Removal Systems 338

11.2.1 Selective Catalytic Reduction of Nitrogen Oxides 338

11.2.2 NOx Storage-Reduction Catalyst for Lean-Burning Engines 340

11.3 Catalytic Afterburning 341

11.4 Green Chemistry and Catalysis 344

11.4.1 Examples of Catalytical Processes 345

11.4.1.1 Aldol Condensation 345

11.4.1.2 Diels–Alder Reaction 346

11.4.1.3 Hydrogenation 347

11.4.1.4 Cyclization inWater 347

11.4.1.5 Use of Ionic Liquids 347

11.4.1.6 Green Solvents 349

Exercises 350

References 351

12 Phase-Transfer Catalysis 353

12.1 Definition 353

12.2 Catalysts for PTC 353

12.3 Mechanism and Benefits of PTC 354

12.4 PTC Reactions 355

12.5 Selected Industrial Processes with PTC 356

12.5.1 Continuous Dehydrohalogenation to Produce the Large-Scale Monomer Chloroprene 356

12.5.2 Polycarbonate Manufacture with Phosgene 356

12.5.3 Etherification (O-Alkylation) 357

12.5.4 Aldehydes by Oxidation of Alcohols with Hypochlorite 357

12.5.5 Carbonylation 357

12.5.6 2-Phenylbutyronitrile by Alkylation 358

Exercises 359

References 359

13 Catalytic Processes with Renewable Materials 361

13.1 Biofuels 361

13.2 Biorefinery 366

13.2.1 Lignocellulose Feedstock Biorefinery 368

13.3 Chemicals from Biomass 369

13.3.1 Chemicals from Biomass via Platform Molecules 369

13.3.1.1 Carbohydrates 369

13.3.1.2 Fats and Oils 373

13.3.1.3 Terpenes 375

13.3.2 Direct Biomass Conversion to End-Products 376

Exercises 378

References 378

14 Polymerization Catalysis 381

14.1 Introduction 381

14.2 Fundamentals of Catalytical Polymerization Processes 381

14.3 Coordination Polymerization 383

14.3.1 Ziegler–Natta Catalysts 383

14.3.1.1 Heterogeneous Ziegler–Natta Catalysts 384

14.3.1.2 Homogeneous Ziegler–Natta Catalysts 386

14.3.1.3 Metallocenes 386

14.3.1.4 Ring-OpeningMetathetic Polymerization 388

14.4 Examples of Catalytical Polymerization Processes 389

14.4.1 Polyethylene Production 389

14.4.2 Polypropylene Production 391

Exercises 392

References 393

15 Planning, Development, and Testing of Catalysts 395

15.1 Stages of Catalyst Development 395

15.2 Development of a Catalytical Process: Hydrogenation of Benzene to Cyclohexane 398

15.3 Selection and Testing of Catalysts in Practice 401

15.3.1 Catalyst Screening 401

15.3.2 Catalyst Test Reactors and Kinetic Modeling 405

15.3.2.1 Differential Reactor 405

15.3.2.2 Differential Circulating Reactor 407

15.3.2.3 Integral reactor 411

15.3.3 Kinetic Modeling and Simulation 416

15.3.3.1 Hydrogenation of Benzaldehyde 416

15.3.3.2 Modeling of a Trickle Bed Reactor 420

15.3.4 Catalyst Discovery via High-Throughput Experimentation 427

Exercises 430

References 430

16 Catalysis Reactors 433

16.1 Plug Flow Reactor (PFR) 433

16.2 Continuous Stirred-Tank Reactor (CSTR) 435

16.3 Reactor Calculations 436

16.4 Two-Phase Reactors 440

16.4.1 Single-Bed Reactor 441

16.4.2 Multibed Reactor 441

16.4.3 Multitubular Reactors 442

16.4.4 Shallow-Bed Reactors 442

16.4.5 Fluidized-Bed Reactors 443

16.5 Three-Phase Reactors 443

16.5.1 Fixed-Bed Reactors 445

16.5.2 Suspension Reactors 447

16.6 Reactors for Homogeneously Catalyzed Reactions 451

16.7 New Reactor Concepts 452

16.7.1 Membrane Reactors 452

16.7.2 Catalytic Reactive Distillation 453

16.7.3 Catalytic Microreactors 454

Exercises 455

References 457

17 Economic Importance of Catalysts 459

References 462

18 Future Development of Catalysis 463

18.1 Homogeneous Catalysis 463

18.2 Heterogeneous Catalysis 465

18.2.1 Use of Other Cheaper Raw Materials 467

18.2.2 Catalysts for Energy Generation 468

18.2.3 Better Strategies for Catalyst Development 469

References 472

Solutions to the Exercises 473

Index 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)