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Homogeneous Catalysis: Mechanisms and Industrial Applications

Sumit Bhaduri, Doble Mukesh

Copyright 2000 John Wiley & Sons, Inc.

ISBNs: 0-471-37221-8 (Hardback); 0-471-22038-8 (Electronic)

HOMOGENEOUS CATALYSIS

HOMOGENEOUS

CATALYSIS

Mechanisms and Industrial

Applications

SUMIT BHADURI

Department of Chemistry

Northwestern University

Evanston, Illinois

DOBLE MUKESH

ICI India R & T Centre

Thane, India

A John Wiley & Sons Publication.

New York • Chichester • Weinheim • Brisbane • Singapore • Toronto

Designations used by companies to distinguish their products are often claimed as trademarks. In all instances where John Wiley & Sons, Inc., is aware of a claim, the product names appear in initial capital or ALL CAPITAL LETTERS. Readers, however, should contact the appropriate companies for more complete information regarding trademarks and registration.

Copyright 2000 by John Wiley & Sons, Inc. All rights reserved.

No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic or mechanical, including uploading, downloading, printing, decompiling, recording or otherwise, except as permitted under Sections 107 or 108 of the 1976 United States Copyright Act, without the prior written permission of the Publisher. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 605 Third Avenue, New York, NY 10158-0012, (212) 850-6011, fax (212) 850-6008, E-Mil: PERMREQ@WILEY.com

This publication is designed to provide accurate and authoritative information in regard to the subject matter covered. It is sold with the understanding that the publisher is not engaged in rendering professional services. If professional advice or other expert assistance is required, the services of a competent professional person should be sought.

ISBN 0-471-22038-8

This title is also available in print as ISBN 0-471-37221-8.

For more information about Wiley products, visit our web site at www.Wiley.com.

For

Vrinda Nabar—my severest critic and best friend

—Sumit Bhaduri

and

My dear wife Geetha

—Doble Mukesh

CONTENTS

PREFACE

xiii

1 CHEMICAL INDUSTRY AND HOMOGENEOUS CATALYSIS

1

1.1Feed Stocks and Definitions / 1

1.2Feed Stock to Basic Building Blocks by Heterogeneous Catalysis / 2

1.3Basic Building Blocks to Downstream Products by Homogeneous Catalysis / 4

1.4Comparison Among Different Types of Catalysis / 5

1.5What Is To Follow—A Summary / 8 Problems / 10

Bibliography / 11

2 BASIC CHEMICAL CONCEPTS

13

2.1The Metal / 13

2.1.1Oxidation State and Electron Count / 13

2.1.2Coordinative Unsaturation / 15

2.1.3Rare Earth Metals / 17

2.2Important Properties of Ligands / 17

2.2.1CO, R2C—CR2, PR3, and H as Ligands / 17

2.2.2Alkyl, Allyl, and Alkylidene Ligands / 18

2.3Important Reaction Types / 19

2.3.1Oxidative Addition and Reductive Elimination / 19

vii

viiiCONTENTS

2.3.2Insertion Reactions / 22

2.3.3-Hydride Elimination / 23

2.3.4Nucleophilic Attack on a Coordinated Ligand / 23

2.4Energy Considerations—Thermodynamics and Kinetics / 25

2.5Catalytic Cycle and Intermediates / 25

2.5.1Kinetic Studies / 28

2.5.2Spectroscopic Studies / 29

2.5.3Model Compounds and Theoretical Calculations / 30 Problems / 33

Bibliography / 35

3 CHEMCAL ENGINEERING FUNDAMENTALS

37

3.1Reactor Design / 37

3.1.1Stirred Tank Reactors / 39

3.1.2Tubular Reactors / 41

3.1.3Membrane Reactors / 42

3.1.4Construction Materials / 43

3.2Operating Conditions / 43

3.3Mass Transfer in Multiphase Reactions / 44

3.4Heat Transfer / 45

3.5Catalyst Recovery / 46

3.6Unit Operations / 47

3.6.1Crystallization and Filtration / 47

3.6.2Distillation / 47

3.6.3Liquid–Liquid Extraction / 49

3.6.4Gas–Liquid Absorption (or Scrubbing) / 50

3.7Safety Aspects / 50

3.8Effluent and Waste Disposal / 51

3.9Economics / 51 Problems / 52 Bibliography / 54

4 CARBONYLATION

55

4.1Introduction / 55

4.2Manufacture of Acetic Acid / 56

4.2.1The Monsanto Process—The Catalytic Cycle / 56

4.2.2Mechanistic Studies and Model Compounds / 59

4.2.3The BASF Process—The Catalytic Cycle / 60

4.2.4BASF Process—Mechanistic Studies / 61

CONTENTS ix

4.3Water-Gas Shift Reaction and Rhodium-Catalyzed Carbonylation / 62

4.4Fischer–Tropsch Reaction and Cobalt-Catalyzed Carbonylation / 64

4.5Rhodium-Catalyzed Carbonylation of Other Alcohols / 66

4.6Carbonylation of Methyl Acetate / 68

4.6.1Mechanism and Catalytic Cycle / 69

4.7Carbonylation of Alkynes; Manufacture of Methyl Methacrylate / 70

4.7.1Mechanism and Catalytic Cycle / 71

4.8Other Carbonylation and Hydrocarboxylation Reactions / 74

4.9Engineering Aspects / 77 Problems / 79 Bibliography / 82

5 HYDROFORMYLATION

85

5.1Background / 85

5.2The Rhodium Process / 86

5.2.1The Catalytic Cycle / 86

5.2.2Product Selectivity / 88

5.2.3Mechanistic Studies / 88

5.2.4The Phosphorus Ligands and Selectivity / 90

5.2.5Water-Soluble Phosphines and Rhodium Recovery / 92

5.2.6Catalyst and Ligand Degradation / 95

5.3Cobalt-Based Hydroformylation / 96

5.4Other Hydroformylation Reactions / 98

5.5Engineering Aspects / 99 Problems / 99 Bibliography / 102

6 POLYMERIZATION

105

6.1Introduction / 105

6.1.1Polyethylene / 105

6.1.2Polypropylene / 106

6.2Catalysts for Polyethylene / 107

6.3Catalysts for Polypropylene / 108

6.4Catalytic Cycle for Alkene Polymerization / 109

6.4.1Cossee–Arlman Mechanism / 109

6.4.2Mechanism of Alkene Insertion / 111

6.4.3Mechanistic Evidence / 113

xCONTENTS

6.5Metallocene Catalysts / 113

6.5.1Structures of Metallocene Catalysts and the Co-catalysts / 114

6.5.2Special Features and Advantages of Metallocene Catalysts / 118

6.5.3Mechanism of Polymerization and Stereocontrol by Metallocene Catalysts / 119

6.6Chromocene and Heterogeneous Catalysts / 123

6.7Polymers of Other Alkenes / 125

6.8Engineering Aspects / 125 Problems / 127 Bibliography / 130

7 OTHER ALKENE-BASED HOMOGENEOUS

 

CATALYTIC REACTIONS

133

7.1Introduction / 133

7.2Isomerization of Alkenes / 133

7.2.1Catalytic Cycle / 134

7.3Hydrogenation of Alkenes / 135

7.3.1Catalytic Cycle / 136

7.3.2Mechanistic Evidence / 137

7.4Oligomerization of Ethylene / 138

7.4.1Shell Higher Olefin Process / 139

7.5Di-, Tri-, and Codimerization Reactions / 142

7.5.1Dimerization of Propylene / 142

7.5.2Diand Trimerization of Butadiene / 142

7.5.3Dimerization of Butadiene with Ethylene / 147

7.6Metathesis Reactions / 147

7.6.1Mechanistic Studies / 147

7.7Hydrocyanation / 151

7.7.1Catalysts for Hydrocyanation / 153

7.7.2Catalytic Cycle for the First Stage / 154

7.7.3Catalytic Cycle for the Second Stage / 156

7.8Hydrosilylation / 159

7.8.1Catalytic Cycle and Mechanism / 160

7.9C–C Coupling and Cyclopropanation Reactions / 161

7.9.1Catalytic Cycle for the Heck Reaction / 163

7.9.2Catalytic Cycle for Cyclopropanation / 163 Problems / 165

Bibliography / 168

CONTENTS xi

8 OXIDATION

171

8.1Introduction / 171

8.2Wacker Oxidation / 172

8.2.1The Background Chemistry / 173

8.2.2Catalytic Cycle and Mechanism / 174

8.3Metal-Catalyzed Liquid-Phase Autoxidation / 176

8.3.1Mechanism of Autoxidation / 177

8.3.2Special Features of Cyclohexane Oxidation / 179

8.3.3Special Features of p-Xylene Oxidation / 181

8.4Polymers (Polyesters and Polyamides) from Autoxidation Products / 182

8.5Epoxidation of Propylene / 183

8.5.1Catalytic Cycle and the Mechanism of Propylene Epoxidation / 184

8.6Oxo Complexes as Homogeneous Oxidation Catalysts / 186

8.6.1Mechanism of Oxidation by Oxo Compounds / 187

8.7Engineering and Safety Considerations / 188 Problems / 190

Bibliography / 193

9 ASYMMETRIC CATALYSIS

195

9.1Introduction / 195

9.2General Features of Chiral Ligands and Complexes / 196

9.3Mechanisms and Catalytic Cycles / 202

9.3.1Mechanism of Asymmetric Hydrogenation / 203

9.3.2Asymmetric Isomerization and Mechanism / 207

9.3.3Asymmetric Epoxidation of Allylic Alcohols and Mechanisms / 209

9.3.4Asymmetric Epoxidation of Alkenes other than Allyl Alcohols / 211

9.3.5Asymmetric Hydrolysis of Epoxides / 212

9.4Asymmetric Dihydroxylation Reaction / 215

9.4.1Mechanism of ADH Reaction / 216

9.5Asymmetric Catalytic Reactions of C–C Bond Formation / 217

9.5.1Asymmetric Hydroformylation Reaction / 218

9.5.2Mechanism of Asymmetric Hydroformylation Reaction / 221

9.5.3Asymmetric Hydrocyanation Reaction / 223

9.5.4Nitroaldol Condensation / 225

Problems / 227

Bibliography / 231

Index / 233

PREFACE

This book has grown out of a graduate-level course on homogeneous catalysis that one of us taught at Northwestern University several times in the recent past. It deals with an interdisciplinary area of chemistry that offers challenging research problems. Industrial applications of homogeneous catalysis are proven, and a much wider application in the future is anticipated. Numerous publications and patent applications testify to the fact that in both the academic and industrial research laboratories the growth in research activity in this area in the past decade or so has been phenomenal.

Written mainly from a pedagogical point of view, this book is not comprehensive but selective. The material presented was selected on the basis of two criteria. We have tried to include most of the homogeneous catalytic reactions with proven industrial applications and well-established mechanisms. The basic aim has been to highlight the connections that exist between imaginative academic research and successful technology. In the process, topics and reports whose application or mechanism appears a little far-fetched at this point, have been given lower priority.

A chapter on the basic chemical concepts (Chapter 2) is meant for readers who do not have a strong background in organometallic chemistry. A chapter on chemical engineering fundamentals (Chapter 3) is included to give nonchemical engineering students some idea of the issues that are important for successful technology development. Because of the industrial mergers, acquisitions, etc., that have taken place over the past 10 years or so, the present names of some of the chemical companies today differ from their names as given in this book.

We have covered the literature up to the start of 1999. Recent publications that are particularly instructive or that deal with novel concepts are referred to

xiii

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