57268

File Attachment

Coverjpg

INDUSTRIAL ORGANICCHEMICALS

Other Books by the Authors

The Phosphatides by Harold A Wittcoff Reinhold New York 1950

The Chemical Economy by Bryan G Reuben and Michael L Burstall Longman

London 1973

Industrial Organic Chemicals in Perspective Part 1 Raw Materials and Manufac-

ture Part 2 Technology Formulation and Use by Bryan G Reuben and Harold A

Wittcoff Wiley New York 1980

Industrial Organic Chemistry an ACS tape course by Harold A Wittcoff ACS

Washington DC 1984

The Pharmaceutical Industry ndash Chemistry and Concepts an ACS tape course

by Harold A Wittcoff and Bryan G Reuben ACS Washington DC 1987

The Cost of ldquoNon-Europerdquo in the Pharmaceutical Industry Research in the Cost

of ldquoNon-Europerdquo Basic Findings Volume 15 by Michael L Burstall and Bryan G

Reuben Commission of European Communities Luxembourg 1988

Pharmaceutical Chemicals in Perspective by Harold A Wittcoff and Bryan G

Reuben Wiley New York 1990

Cost Containment in the European Pharmaceutical Market by Michael L Burstall

and Bryan G Reuben Marketletter London 1992

Implications of the European Communityrsquos Proposed Policy for Self-Sufficiency in

Plasma and Plasma Products by Bryan G Reuben and Ian Senior Marketletter

London 1993

Outlook for the World Pharmaceutical Industry to 2010 by Michael L Burstall and

Bryan G Reuben Decision Resources Waltham MA 1999

Organic Chemical Principles and Industrial Practice byMM Green and Harold A

Wittcoff VCH Wiley Weinheim Germany 2003

Pharmaceutical RampD Productivity The Path to Innovation by Bryan G Reuben and

Michael L Burstall Cambridge Healthtech Advisors Massachusetts 2005

Bread A Slice of History by John SMarchant BryanG Reuben and Joan P Alcock

The History Press Stroud Gloucestershire 2008

INDUSTRIAL ORGANICCHEMICALS

THIRD EDITION

Harold A WittcoffScientific Adviser Nexant ChemSystems Inc (retired)Vice President of Corporate Research General Mills Inc (retired)

Bryan G ReubenProfessor Emeritus of Chemical TechnologyLondon South Bank University

Jeffrey S PlotkinDirector Process Evaluation and Research Planning ProgramNexant ChemSystems Inc

A JOHN WILEY amp SONS INC PUBLICATION

Cover design Michael Rutkowski

Cover photograph iStockphoto

Copyright 2013 by John Wiley amp Sons Inc All rights reserved

Published by John Wiley amp Sons Inc Hoboken New Jersey

Published simultaneously in Canada

No part of this publication may be reproduced stored in a retrieval system or transmitted in any

form or by any means electronic mechanical photocopying recording scanning or otherwise

except as permitted under Section 107 or 108 of the 1976 United States Copyright Act without

either the prior written permission of the Publisher or authorization through payment of the

appropriate per-copy fee to the Copyright Clearance Center Inc 222 Rosewood Drive Danvers

MA 01923 978-750-8400 fax 978-750-4470 or on the web at wwwcopyrightcom Requests

to the Publisher for permission should be addressed to the Permissions Department John Wiley amp

Sons Inc 111 River Street Hoboken NJ 07030 201-748-6011 fax 201-748-6008 or online

at httpwwwwileycomgopermission

Limit of LiabilityDisclaimer of Warranty While the publisher and author have used their best

efforts in preparing this book they make no representations or warranties with respect to the

accuracy or completeness of the contents of this book and specifically disclaim any implied

warranties of merchantability or fitness for a particular purpose No warranty may be created or

extended by sales representatives or written sales materials The advice and strategies contained

herein may not be suitable for your situation You should consult with a professional where

appropriate Neither the publisher nor author shall be liable for any loss of profit or any other

commercial damages including but not limited to special incidental consequential or other

damages

For general information on our other products and services or for technical support please contact

our Customer Care Department within the United States at 877-762-2974 outside the

United States at 317-572-3993 or fax 317-572-4002

Wiley also publishes its books in a variety of electronic formats Some content that appears in

print may not be available in electronic formats For more information about Wiley products visit

our web site at wwwwileycom

Library of Congress Cataloging-in-Publication Data

Wittcoff Harold A

Industrial organic chemicals Harold A Wittcoff Bryan G Reuben Jeffrey S Plotkin

ndash 3rd ed

p cm

Includes index

ISBN 978-0-470-53743-5 (cloth)

1 Organic compoundsndashIndustrial applications I Reuben B G II Plotkin Jeffrey S

III Title

TP247W59 2012

6618ndashdc23

2011040427

Printed in the United States of America

10 9 8 7 6 5 4 3 2 1

INDUSTRIAL ORGANICCHEMICALS

Other Books by the Authors

The Phosphatides by Harold A Wittcoff Reinhold New York 1950

The Chemical Economy by Bryan G Reuben and Michael L Burstall Longman

London 1973

Industrial Organic Chemicals in Perspective Part 1 Raw Materials and Manufac-

ture Part 2 Technology Formulation and Use by Bryan G Reuben and Harold A

Wittcoff Wiley New York 1980

Industrial Organic Chemistry an ACS tape course by Harold A Wittcoff ACS

Washington DC 1984

The Pharmaceutical Industry ndash Chemistry and Concepts an ACS tape course

by Harold A Wittcoff and Bryan G Reuben ACS Washington DC 1987

The Cost of ldquoNon-Europerdquo in the Pharmaceutical Industry Research in the Cost

of ldquoNon-Europerdquo Basic Findings Volume 15 by Michael L Burstall and Bryan G

Reuben Commission of European Communities Luxembourg 1988

Pharmaceutical Chemicals in Perspective by Harold A Wittcoff and Bryan G

Reuben Wiley New York 1990

Cost Containment in the European Pharmaceutical Market by Michael L Burstall

and Bryan G Reuben Marketletter London 1992

Implications of the European Communityrsquos Proposed Policy for Self-Sufficiency in

Plasma and Plasma Products by Bryan G Reuben and Ian Senior Marketletter

London 1993

Outlook for the World Pharmaceutical Industry to 2010 by Michael L Burstall and

Bryan G Reuben Decision Resources Waltham MA 1999

Organic Chemical Principles and Industrial Practice byMM Green and Harold A

Wittcoff VCH Wiley Weinheim Germany 2003

Pharmaceutical RampD Productivity The Path to Innovation by Bryan G Reuben and

Michael L Burstall Cambridge Healthtech Advisors Massachusetts 2005

Bread A Slice of History by John SMarchant BryanG Reuben and Joan P Alcock

The History Press Stroud Gloucestershire 2008

INDUSTRIAL ORGANICCHEMICALS

THIRD EDITION

Harold A WittcoffScientific Adviser Nexant ChemSystems Inc (retired)Vice President of Corporate Research General Mills Inc (retired)

Bryan G ReubenProfessor Emeritus of Chemical TechnologyLondon South Bank University

Jeffrey S PlotkinDirector Process Evaluation and Research Planning ProgramNexant ChemSystems Inc

A JOHN WILEY amp SONS INC PUBLICATION

Cover design Michael Rutkowski

Cover photograph iStockphoto

Copyright 2013 by John Wiley amp Sons Inc All rights reserved

Published by John Wiley amp Sons Inc Hoboken New Jersey

Published simultaneously in Canada

No part of this publication may be reproduced stored in a retrieval system or transmitted in any

form or by any means electronic mechanical photocopying recording scanning or otherwise

except as permitted under Section 107 or 108 of the 1976 United States Copyright Act without

either the prior written permission of the Publisher or authorization through payment of the

appropriate per-copy fee to the Copyright Clearance Center Inc 222 Rosewood Drive Danvers

MA 01923 978-750-8400 fax 978-750-4470 or on the web at wwwcopyrightcom Requests

to the Publisher for permission should be addressed to the Permissions Department John Wiley amp

Sons Inc 111 River Street Hoboken NJ 07030 201-748-6011 fax 201-748-6008 or online

at httpwwwwileycomgopermission

Limit of LiabilityDisclaimer of Warranty While the publisher and author have used their best

efforts in preparing this book they make no representations or warranties with respect to the

accuracy or completeness of the contents of this book and specifically disclaim any implied

warranties of merchantability or fitness for a particular purpose No warranty may be created or

extended by sales representatives or written sales materials The advice and strategies contained

herein may not be suitable for your situation You should consult with a professional where

appropriate Neither the publisher nor author shall be liable for any loss of profit or any other

commercial damages including but not limited to special incidental consequential or other

damages

For general information on our other products and services or for technical support please contact

our Customer Care Department within the United States at 877-762-2974 outside the

United States at 317-572-3993 or fax 317-572-4002

Wiley also publishes its books in a variety of electronic formats Some content that appears in

print may not be available in electronic formats For more information about Wiley products visit

our web site at wwwwileycom

Library of Congress Cataloging-in-Publication Data

Wittcoff Harold A

Industrial organic chemicals Harold A Wittcoff Bryan G Reuben Jeffrey S Plotkin

ndash 3rd ed

p cm

Includes index

ISBN 978-0-470-53743-5 (cloth)

1 Organic compoundsndashIndustrial applications I Reuben B G II Plotkin Jeffrey S

III Title

TP247W59 2012

6618ndashdc23

2011040427

Printed in the United States of America

10 9 8 7 6 5 4 3 2 1

Other Books by the Authors

The Phosphatides by Harold A Wittcoff Reinhold New York 1950

The Chemical Economy by Bryan G Reuben and Michael L Burstall Longman

London 1973

Industrial Organic Chemicals in Perspective Part 1 Raw Materials and Manufac-

ture Part 2 Technology Formulation and Use by Bryan G Reuben and Harold A

Wittcoff Wiley New York 1980

Industrial Organic Chemistry an ACS tape course by Harold A Wittcoff ACS

Washington DC 1984

The Pharmaceutical Industry ndash Chemistry and Concepts an ACS tape course

by Harold A Wittcoff and Bryan G Reuben ACS Washington DC 1987

The Cost of ldquoNon-Europerdquo in the Pharmaceutical Industry Research in the Cost

of ldquoNon-Europerdquo Basic Findings Volume 15 by Michael L Burstall and Bryan G

Reuben Commission of European Communities Luxembourg 1988

Pharmaceutical Chemicals in Perspective by Harold A Wittcoff and Bryan G

Reuben Wiley New York 1990

Cost Containment in the European Pharmaceutical Market by Michael L Burstall

and Bryan G Reuben Marketletter London 1992

Implications of the European Communityrsquos Proposed Policy for Self-Sufficiency in

Plasma and Plasma Products by Bryan G Reuben and Ian Senior Marketletter

London 1993

Outlook for the World Pharmaceutical Industry to 2010 by Michael L Burstall and

Bryan G Reuben Decision Resources Waltham MA 1999

Organic Chemical Principles and Industrial Practice byMM Green and Harold A

Wittcoff VCH Wiley Weinheim Germany 2003

Pharmaceutical RampD Productivity The Path to Innovation by Bryan G Reuben and

Michael L Burstall Cambridge Healthtech Advisors Massachusetts 2005

Bread A Slice of History by John SMarchant BryanG Reuben and Joan P Alcock

The History Press Stroud Gloucestershire 2008

INDUSTRIAL ORGANICCHEMICALS

THIRD EDITION

Harold A WittcoffScientific Adviser Nexant ChemSystems Inc (retired)Vice President of Corporate Research General Mills Inc (retired)

Bryan G ReubenProfessor Emeritus of Chemical TechnologyLondon South Bank University

Jeffrey S PlotkinDirector Process Evaluation and Research Planning ProgramNexant ChemSystems Inc

A JOHN WILEY amp SONS INC PUBLICATION

Cover design Michael Rutkowski

Cover photograph iStockphoto

Copyright 2013 by John Wiley amp Sons Inc All rights reserved

Published by John Wiley amp Sons Inc Hoboken New Jersey

Published simultaneously in Canada

No part of this publication may be reproduced stored in a retrieval system or transmitted in any

form or by any means electronic mechanical photocopying recording scanning or otherwise

except as permitted under Section 107 or 108 of the 1976 United States Copyright Act without

either the prior written permission of the Publisher or authorization through payment of the

appropriate per-copy fee to the Copyright Clearance Center Inc 222 Rosewood Drive Danvers

MA 01923 978-750-8400 fax 978-750-4470 or on the web at wwwcopyrightcom Requests

to the Publisher for permission should be addressed to the Permissions Department John Wiley amp

Sons Inc 111 River Street Hoboken NJ 07030 201-748-6011 fax 201-748-6008 or online

at httpwwwwileycomgopermission

Limit of LiabilityDisclaimer of Warranty While the publisher and author have used their best

efforts in preparing this book they make no representations or warranties with respect to the

accuracy or completeness of the contents of this book and specifically disclaim any implied

warranties of merchantability or fitness for a particular purpose No warranty may be created or

extended by sales representatives or written sales materials The advice and strategies contained

herein may not be suitable for your situation You should consult with a professional where

appropriate Neither the publisher nor author shall be liable for any loss of profit or any other

commercial damages including but not limited to special incidental consequential or other

damages

For general information on our other products and services or for technical support please contact

our Customer Care Department within the United States at 877-762-2974 outside the

United States at 317-572-3993 or fax 317-572-4002

Wiley also publishes its books in a variety of electronic formats Some content that appears in

print may not be available in electronic formats For more information about Wiley products visit

our web site at wwwwileycom

Library of Congress Cataloging-in-Publication Data

Wittcoff Harold A

Industrial organic chemicals Harold A Wittcoff Bryan G Reuben Jeffrey S Plotkin

ndash 3rd ed

p cm

Includes index

ISBN 978-0-470-53743-5 (cloth)

1 Organic compoundsndashIndustrial applications I Reuben B G II Plotkin Jeffrey S

III Title

TP247W59 2012

6618ndashdc23

2011040427

Printed in the United States of America

10 9 8 7 6 5 4 3 2 1

INDUSTRIAL ORGANICCHEMICALS

THIRD EDITION

Harold A WittcoffScientific Adviser Nexant ChemSystems Inc (retired)Vice President of Corporate Research General Mills Inc (retired)

Bryan G ReubenProfessor Emeritus of Chemical TechnologyLondon South Bank University

Jeffrey S PlotkinDirector Process Evaluation and Research Planning ProgramNexant ChemSystems Inc

A JOHN WILEY amp SONS INC PUBLICATION

Cover design Michael Rutkowski

Cover photograph iStockphoto

Copyright 2013 by John Wiley amp Sons Inc All rights reserved

Published by John Wiley amp Sons Inc Hoboken New Jersey

Published simultaneously in Canada

No part of this publication may be reproduced stored in a retrieval system or transmitted in any

form or by any means electronic mechanical photocopying recording scanning or otherwise

except as permitted under Section 107 or 108 of the 1976 United States Copyright Act without

either the prior written permission of the Publisher or authorization through payment of the

appropriate per-copy fee to the Copyright Clearance Center Inc 222 Rosewood Drive Danvers

MA 01923 978-750-8400 fax 978-750-4470 or on the web at wwwcopyrightcom Requests

to the Publisher for permission should be addressed to the Permissions Department John Wiley amp

Sons Inc 111 River Street Hoboken NJ 07030 201-748-6011 fax 201-748-6008 or online

at httpwwwwileycomgopermission

Limit of LiabilityDisclaimer of Warranty While the publisher and author have used their best

efforts in preparing this book they make no representations or warranties with respect to the

accuracy or completeness of the contents of this book and specifically disclaim any implied

warranties of merchantability or fitness for a particular purpose No warranty may be created or

extended by sales representatives or written sales materials The advice and strategies contained

herein may not be suitable for your situation You should consult with a professional where

appropriate Neither the publisher nor author shall be liable for any loss of profit or any other

commercial damages including but not limited to special incidental consequential or other

damages

For general information on our other products and services or for technical support please contact

our Customer Care Department within the United States at 877-762-2974 outside the

United States at 317-572-3993 or fax 317-572-4002

Wiley also publishes its books in a variety of electronic formats Some content that appears in

print may not be available in electronic formats For more information about Wiley products visit

our web site at wwwwileycom

Library of Congress Cataloging-in-Publication Data

Wittcoff Harold A

Industrial organic chemicals Harold A Wittcoff Bryan G Reuben Jeffrey S Plotkin

ndash 3rd ed

p cm

Includes index

ISBN 978-0-470-53743-5 (cloth)

1 Organic compoundsndashIndustrial applications I Reuben B G II Plotkin Jeffrey S

III Title

TP247W59 2012

6618ndashdc23

2011040427

Printed in the United States of America

10 9 8 7 6 5 4 3 2 1

Cover design Michael Rutkowski

Cover photograph iStockphoto

Copyright 2013 by John Wiley amp Sons Inc All rights reserved

Published by John Wiley amp Sons Inc Hoboken New Jersey

Published simultaneously in Canada

No part of this publication may be reproduced stored in a retrieval system or transmitted in any

form or by any means electronic mechanical photocopying recording scanning or otherwise

except as permitted under Section 107 or 108 of the 1976 United States Copyright Act without

either the prior written permission of the Publisher or authorization through payment of the

appropriate per-copy fee to the Copyright Clearance Center Inc 222 Rosewood Drive Danvers

MA 01923 978-750-8400 fax 978-750-4470 or on the web at wwwcopyrightcom Requests

to the Publisher for permission should be addressed to the Permissions Department John Wiley amp

Sons Inc 111 River Street Hoboken NJ 07030 201-748-6011 fax 201-748-6008 or online

at httpwwwwileycomgopermission

Limit of LiabilityDisclaimer of Warranty While the publisher and author have used their best

efforts in preparing this book they make no representations or warranties with respect to the

accuracy or completeness of the contents of this book and specifically disclaim any implied

warranties of merchantability or fitness for a particular purpose No warranty may be created or

extended by sales representatives or written sales materials The advice and strategies contained

herein may not be suitable for your situation You should consult with a professional where

appropriate Neither the publisher nor author shall be liable for any loss of profit or any other

commercial damages including but not limited to special incidental consequential or other

damages

For general information on our other products and services or for technical support please contact

our Customer Care Department within the United States at 877-762-2974 outside the

United States at 317-572-3993 or fax 317-572-4002

Wiley also publishes its books in a variety of electronic formats Some content that appears in

print may not be available in electronic formats For more information about Wiley products visit

our web site at wwwwileycom

Library of Congress Cataloging-in-Publication Data

Wittcoff Harold A

Industrial organic chemicals Harold A Wittcoff Bryan G Reuben Jeffrey S Plotkin

ndash 3rd ed

p cm

Includes index

ISBN 978-0-470-53743-5 (cloth)

1 Organic compoundsndashIndustrial applications I Reuben B G II Plotkin Jeffrey S

III Title

TP247W59 2012

6618ndashdc23

2011040427

Printed in the United States of America

10 9 8 7 6 5 4 3 2 1

To our wives Dorothy Catherine and Marisa children

grandchildren and great-grandchildren

CONTENTS

Preface xxiii

Preface to the First Edition xxv

Preface to the Second Edition xxvii

Acknowledgments xxix

Bryan Godel Reuben 1934ndash2012 xxxi

List of Acronyms and Abbreviations xxxiii

Introduction How to Use Industrial Organic Chemicals Third Edition 1

I1 Why This Book Was Written and How It Is Structured 2

I2 North American Industry Classification System 5

I3 Units and Nomenclature 5

I4 General Bibliography 6

I41 Encyclopedias 6

I42 Books 7

I43 Journals 8

I44 Patents 9

I45 Statistics and Internet Sources of Information 10

1 The Evolution of the Organic Chemicals Industry 13

11 The National Economy 13

12 Size of the Chemical Industry 16

13 Characteristics of the Chemical Industry 22

131 Capital Intensity and Economies of Scale 22

132 Criticality and Pervasiveness 24

133 Freedom of Market Entry 26

134 Strong Regulation 27

1341 European Legislation 29

1342 Political Factors 30

vii

135 High but Declining Research and Development

Expenditures 34

136 Dislocations 41

14 The Top Companies 43

15 The Top Chemicals 44

Endnotes 46

2 Globalization of the Chemical Industry 49

21 Overcapacity 51

211 Economic Cycles 55

22 Restructuring Mergers and Acquisitions 56

221 SuICIde of a UK Company 60

222 Private Equity 61

23 Participation in International Trade 63

24 Competition from Developing Countries 66

Endnotes 69

3 Transporting Chemicals 71

31 Shipping Petroleum 71

32 Shipping Gas 74

33 Shipping Chemicals 75

331 Gases 75

332 Liquids 77

333 Solids 85

34 Health and Safety 86

35 Economic Aspects 87

36 Trade in Specific Chemicals 88

37 Top Shipping Companies 90

Endnotes 91

4 Chemicals from Natural Gas and Petroleum 93

41 Petroleum Distillation 97

42 Shale Gas 100

421 Shale Gas Technology 101

43 Naphtha Versus Gaseous Feedstocks 102

viii CONTENTS

44 Heavier Oil Fractions 103

45 Steam Cracking and Petroleum Refining Reactions 104

451 Steam Cracking 106

452 Choice of Feedstock 108

453 Economics of Steam Cracking 110

46 Catalytic Cracking 114

47 Mechanisms of Steam and Catalytic Cracking 117

48 Catalytic Reforming 119

49 Oligomerization 122

410 Alkylation 124

411 Hydrotreating and Coking 125

412 Dehydrogenation 126

413 Isomerization 128

414 Metathesis 128

4141 Metathesis Outside the Refinery 129

4142 Mechanism of Metathesis 131

415 Function of the Refinery and the Potential Petroleum

Shortage 133

4151 Unleaded Gasoline and the Clean Air Act 134

416 Separation of Natural Gas 136

417 Oil from Tar Sands 137

Endnotes 137

5 Chemicals and Polymers from Ethylene 139

51 Ethylene Polymers 141

511 Discovery of Low and High Density Polyethylenes 142

512 Low Density Polyethylene 144

513 High Density Polyethylene 146

514 Linear Low Density Polyethylene 147

515 Very High Molecular Weight Polyethylene 148

516 Metallocene Polyethylenes 149

517 Very Low Density Polyethylene 149

518 Bimodal HDPE 149

519 ldquoGreenrdquo Polyethylene 150

CONTENTS ix

52 Ethylene Copolymers 151

521 Chlorosulfonated Polyethylene 151

522 Ethylene-Vinyl Acetate 151

523 Ionomers 152

524 Copolymer from ldquoIncompatiblerdquo Polymer Blends 152

525 EthylenendashPropylene Elastomers 153

526 Polyolefin Elastomers 153

53 Oligomerization 154

531 Dimerization 154

532 Ziegler Oligomerization of Ethylene 155

533 Other Ethylene Oligomerization Technologies 156

534 Shell Higher Olefins Process (SHOP) 158

54 Vinyl Chloride 160

55 Acetaldehyde 165

56 Vinyl Acetate 167

57 Ethylene Oxide 169

571 Ethylene Glycol 171

572 Proposed Non-Ethylene Oxide Processes for

Ethylene Glycol Production 174

58 Styrene 177

59 Ethanol 181

510 Major Chemicals from Ethylene ndash A Summary 182

511 Lesser Volume Chemicals from Ethylene 185

5111 Hydroformylation ndash Propionaldehyde

Propionic Acid and n-Propanol 185

5112 Ethyl Halides 186

5113 Acetaldehyde Chemistry 187

5114 Metal Complexes 191

5115 Ethylenediamine and Related Compounds 191

5116 Ethylene Oxide and Ethylene Glycol Derivatives 193

51161 Oligomers 193

51162 Glycol Ethers and Esters 194

51163 Ethylene Carbonate 197

51164 Aminoethyl Alcohols (Ethanolamines)

and Derivatives 198

51165 Ethyleneimine 199

x CONTENTS

51166 13-Propanediol 200

51167 Ethylene Glycol Derivatives 201

5117 Vinyl Chloride and Ethylene

Dichloride Derivatives 203

5118 Vinyl Fluoride and Vinylidene Fluoride 204

5119 Ethylene Dibromide 205

51110 Ethanol Derivatives 206

51111 Vinyl Esters and Ethers 207

Endnotes 208

6 Chemicals and Polymers from Propylene 211

61 On-Purpose Propylene Production Technologies and Propane

Dehydrogenation 214

611 Propylene Via Enhanced Fluidized

Catalytic Cracking 215

612 Propylene Via Selective C4C5 Cracking 215

62 Main Polymers and Chemicals from Propylene 217

621 Propylene Polymers and Copolymers 217

63 Oligomerization 221

64 Acrylic Acid 222

641 Biorenewable Processes to Acrylic Acid 225

642 Acrylic Acid Markets 226

65 Acrylonitrile 227

651 Uses of Acrylonitrile 230

66 CumenePhenol and Cumene Hydroperoxide 231

67 Acetone and Isopropanol 233

671 Methyl Methacrylate 235

672 Methyl Isobutyl Ketone and Other

Acetone Derivatives 242

68 Propylene Oxide 242

681 Other Propylene Oxide Processes 247

6811 Acetoxylation of Propylene 248

6812 Direct Oxidation 249

6813 Use of Peracids 249

6814 Electrochemical Processes 250

6815 Biotechnological Approaches 252

682 Propylene Oxide Applications 253

CONTENTS xi

69 n-Butyraldehyde and Isobutyraldehyde 255

691 Uses for Butyraldehyde Isobutyraldehyde

and n-Butanol 258

692 Other Oxo Products 260

610 Major Chemicals from Propylene ndash A Perspective 261

611 Lesser Volume Chemicals from Propylene 263

6111 Allyl Chloride and Epichlorohydrin 263

6112 Glycerol 266

6113 Acrylamide 266

6114 Acrolein 268

6115 Acrylonitrile Derivatives 270

Endnotes 270

7 Chemicals from the C4 Stream 273

71 Chemicals and Polymers from Butadiene 277

711 Tires 280

712 StyrenendashButadiene Elastomers 281

713 Polybutadienes and Other Elastomers 282

714 AcrylonitrilendashButadienendashStyrene Resins 283

715 Hexamethylenediamine 284

716 Lesser Volume Chemicals from Butadiene 289

7161 Cyclization 289

7162 Dimerization and Trimerization 291

7163 DielsndashAlder Reactions 293

7164 Adipic Acid 294

7165 14-Butanediol 294

7166 trans-14-Hexadiene 295

7167 Dimethyl-26-naphthalene

Dicarboxylate 295

7168 Butadiene Monoepoxide 296

72 Chemicals and Polymers from Isobutene 296

721 Methyl tert-Butyl Ether 297

722 Butyl Rubber 298

723 Polyisobutenes and Isobutene Oligomers

and Polymers 298

724 tert-Butanol 299

725 Methyl Methacrylate 299

726 Lesser Volume Chemicals from Isobutene 299

xii CONTENTS

73 Chemicals and Polymers from 1- and 2-Butenes 302

74 Chemicals from n-Butane 303

741 Acetic Acid 303

742 Maleic Anhydride 303

743 Succinic Malic Fumaric and Tartaric Acids 306

Endnotes 307

8 Chemicals from the C5 Stream 309

81 Separation of the C5 Stream 311

82 Isoprene 312

821 Natural Rubber 312

822 Vulcanization 313

823 Production of Petrochemical Isoprene 314

824 Applications of Isoprene 317

83 Cyclopentadiene and Dicyclopentadiene 319

84 Pentene-1 and Piperylene 321

Endnotes 321

9 Chemicals from Benzene 323

91 Phenol 326

911 Phenolic Resins 331

912 Bisphenol A 333

9121 Epoxy Resins 333

9122 Polycarbonate Resins 334

9123 Lesser Volume Uses for Bisphenol A 337

9124 Environmental Problems 340

913 Cyclohexanone 341

914 Alkylphenols 342

915 Chlorinated Phenols 342

916 26-XylenolCresols 343

917 Aniline from Phenol 344

92 Cyclohexane 344

921 Adipic Acid 344

9211 Nylons from Adipic Acid 349

922 Caprolactam 349

CONTENTS xiii

93 Aniline 354

931 440-Diphenylmethane Isocyanate 357

94 Alkylbenzenes 361

95 Maleic Anhydride 362

96 Chlorinated Benzenes 363

97 Dihydroxybenzenes 364

971 Hydroquinone 364

972 Resorcinol 368

973 Catechol 369

98 Anthraquinone 370

981 Hydrogen Peroxide 371

Endnotes 372

10 Chemicals from Toluene 375

101 Hydrodealkylation Disproportionation and Transalkylation 375

102 Solvents 378

103 Dinitrotoluene and Toluene Diisocyanate 378

104 Lesser Volume Chemicals from Toluene 380

Endnotes 382

11 Chemicals from Xylenes 383

111 o-Xylene and Phthalic Anhydride 386

1111 Plasticizers 387

1112 Alkyd Resins 391

1113 Unsaturated Polyester Resin 393

112 m-Xylene and Isophthalic Acid 395

1121 Uses of Isophthalic Acid 396

113 p-Xylene and Terephthalic AcidDimethyl Terephthalate 397

1131 Oxidation of p-Xylene 398

1132 Alternate Sources for Terephthalic Acid 400

1133 Poly(ethylene terephthalate) 400

1134 Lower Volume Polymers from Terephthalic Acid 403

Endnotes 404

xiv CONTENTS

12 Chemicals from Methane 407

121 Hydrocyanic Acid 408

122 Halogenated Methanes 411

1221 Chloromethane 412

1222 Dichloromethane 413

1223 Trichloromethane 413

1224 Fluorocarbons 414

1225 Tetrachloromethane and Carbon Disulfide 414

1226 Bromomethane 416

123 Acetylene 417

1231 14-Butanediol and 2-Methyl-13-propanediol 419

1232 Lesser Uses for Acetylene 423

124 Synthesis Gas 424

1241 Steam Reforming of Methane 425

1242 Variants of Steam Reforming 427

1243 Partial Oxidation of Hydrocarbons 428

1244 Solid Feedstocks 428

1245 Hydrogen 429

125 Chemicals from Synthesis Gas 429

1251 Ammonia and Its Derivatives 430

12511 The Crisis of Nitrogen Depletion 430

12512 Ammonia Manufacture 431

12513 Urea and Melamine Resins 434

1252 Methanol 435

12521 Formaldehyde 438

12522 Acetic Acid 439

12523 Acetic Anhydride 442

12524 Methanol to Gasoline 445

12525 Methanol to Olefins 446

12526 Lower Volume and Proposed Uses for Methanol 448

12527 C1-Based Development Processes 452

126 Carbon Monoxide Chemistry 454

1261 Proposed Chemistry Based on Carbon Monoxide 455

127 Gas-to-Liquid Fuels 459

1271 Sasol GTL Technology 459

1272 Shell Middle Distillate Synthesis 459

CONTENTS xv

1273 Other GTL Technologies 460

Endnotes 460

13 Chemicals from Alkanes 463

131 Functionalization of Methane 464

1311 Methane to MethanolFormaldehyde 464

1312 Dimerization of Methane 466

1313 Aromatization of Methane 467

132 Functionalization of C2ndashC4 Alkanes 468

1321 Oxidation of C2ndashC4 Alkanes 468

1322 Dehydrogenation of C2ndashC4 Alkanes 470

1323 Aromatization of C2ndashC4Alkanes 471

133 Carbon Black 472

Endnotes 473

14 Chemicals from Coal 475

141 Chemicals from Coke Oven Distillate 477

142 The FischerndashTropsch Reaction 480

143 Coal Hydrogenation 484

144 Substitute Natural Gas 485

145 SNG and Synthesis Gas Technology 485

146 Underground Coal Gasification 488

147 Calcium Carbide 488

1471 The Chinese Chemicals to Coal Program 489

148 Coal and the Environment 490

Endnotes 491

15 Fats and Oils 493

151 Markets for Fats and Oils 495

152 Purification of Fats and Oils 497

153 Fatty Acids 499

1531 Applications of Fatty Acids 501

154 Fatty Nitrogen Compounds 502

155 ldquoDimerrdquo Acid 504

xvi CONTENTS

156 Aminoamides and Imidazolines 506

157 Azelaic Pelargonic and Petroselinic Acids 507

158 Fatty Alcohols 508

159 Epoxidized Oils 509

1510 Ricinoleic Acid 510

1511 Glycerol 512

15111 Established Glycerol Uses 512

1512 Alcoholysis of Fats and Oils 513

15121 Cocoa Butter and Mothersrsquo Milk 513

151211 Mothersrsquo Milk 515

15122 Trans Fats and Interesterification 515

15123 Biodiesel and Lubricants 516

151231 Algae 518

1513 Alkyl Polyglycosides 519

1514 Non-Caloric Fat-like Substances 519

Endnotes 520

16 Carbohydrates 523

161 Sugars and Sorbitol 523

1611 Isosorbide 530

162 Furfural 530

163 Starch 532

164 Cellulose 535

1641 Miscellaneous Chemicals from Wood 539

16411 Vanillin 541

16412 Levulinic Acid 542

165 Gums 543

166 Fermentation and Biotechnology 544

1661 Amino Acids 547

16611 L-Glutamic Acid 547

16612 L-Lysine 547

16613 L-Aspartic Acid 548

16614 L-Cysteine 549

1662 Polymers 550

CONTENTS xvii

1663 Proteins by Recombinant DNA Technology 550

1664 Fermentation and Renewables Scenarios 551

1665 Biofuels 554

16651 The Brazilian Experience 554

16652 Is US Bioethanol a Renewable

Energy Source 555

16653 Biomass as Feedstock 556

16654 Catalytic Bioforming 556

16655 Biotechnology Versus Synthesis Gas 557

Endnotes 558

17 How Polymers Are Made 561

171 Polymerization 565

172 Functionality 568

173 Step Growth and Chain Growth Polymerizations 571

1731 Free Radical Polymerization 573

1732 Chain Transfer 575

1733 Copolymerization 577

1734 Molecular Weight 579

1735 Polymerization Procedures 580

17351 Photoinitiation 582

1736 Ionic Polymerization 584

1737 Living Polymers 589

1738 Block Copolymers 589

1739 Graft Copolymers 592

17310 Metal Complex Catalysts 593

17311 Metal Oxide Catalysts 598

17312 Metallocene and Other Single Site Catalysts 599

173121 Single Site Nonmetallocene Catalysts 602

173122 Late Transition Metal Catalysts 603

173123 Commercial Prospects of LLDPEs 604

174 Examples of Step Polymerization 605

1741 Phenoplasts and Aminoplasts 605

1742 Polyurethanes 606

1743 Epoxy Resins 611

1744 Dendritic and Hyperbranched Polymers 613

1745 Conducting Polymers 617

1746 Conducting and Semiconducting Inks 621

xviii CONTENTS

175 Polymer Properties 622

1751 Crystallinity 622

1752 Glass Transition Temperature Crystalline

Melting Point and Softening Temperature 626

1753 Molecular Cohesion 628

1754 StressndashStrain Diagrams 628

176 Classes of Polymers 630

177 Plastics Fabrication Techniques 631

Endnotes 635

18 Industrial Catalysis 637

181 Catalyst Choice 637

1811 Reaction Velocity and Selectivity 638

1812 Recovery of Unchanged Catalyst 641

1813 Catalyst Deactivation 642

1814 Access to Nonequilibrium Products 642

182 Homogeneous and Heterogeneous Catalysis 643

1821 Reactors for Heterogeneous Catalysts 644

1822 Immobilization of Homogeneous Catalysts 646

183 Catalyst Markets 647

184 Catalysis by Acids and Bases 651

185 Dual Function Catalysis 654

186 Catalysis by Metals Semiconductors and Insulators 655

1861 Catalysts for Automobile Emission Control 656

187 Coordination Catalysis 657

1871 Catalysts for Stereoregular Compounds 658

1872 Asymmetric Synthesis 660

188 Enzymes 661

1881 Catalytic Antibodies 663

189 Shape-Selective Catalysts 664

1810 Phase-Transfer and Fluorous Biphase Catalysis 669

1811 Nanocatalysis 670

1812 Catalysts of the Future 673

18121 Catalyst Design 673

18122 Higher Selectivities 673

CONTENTS xix

18123 Catalysts with Greater Activity 674

18124 Pollution Problems 675

18125 Catalysts for New Reactions 675

18126 Catalysts that Mimic Natural Catalysts 676

18127 Catalyst Discovery Via High Throughput

Experimentation 676

Endnotes 677

19 Green Chemistry 681

191 The Decline of Acetylene Chemistry 683

192 Nylon 683

193 Replacement of Phosgene 684

194 Monomethylation by Dimethyl Carbonate 685

195 Liquid and Supercritical Carbon Dioxide and Water 685

196 Ionic Liquids 687

197 Photocatalysts 690

198 Paired Electrosynthesis 691

199 ldquoGreenrdquo Pharmaceuticals 692

1991 Ibuprofen 692

1992 Sertraline 694

1993 Pharmaceuticals from ldquoRenewablesrdquo 696

1910 Catalytic Dehydrogenation of Diethanolamine 698

1911 Genetic Manipulation 698

1912 Biodegradable Packaging 698

19121 Polyhydroxyalkanoates 701

1913 The Presidential Green Chemistry Challenge Program 703

Endnotes 704

20 Sustainability 707

201 Climate Change 708

202 Resource Depletion 712

2021 Food Water and People 713

20211 Food 713

20212 Water 714

20213 People 715

xx CONTENTS

203 Energy Sources 717

2031 Wind Power 719

2032 Wave Power 720

2033 Solar Power 721

20331 Concentrated Solar Power 721

20332 Photovoltaic Cells 721

20333 Dye-Sensitized Solar Cells 722

20334 Artificial Photosynthesis 724

2034 Nuclear Energy 726

2035 Methane Hydrate 727

2036 The Hydrogen Economy 728

2037 Fuel Cells 729

2038 Electric Vehicles 735

204 Pollution 736

2041 The Ozone Layer 738

2042 Trace Chemicals 742

20421 Pesticides 742

20422 Nonpesticide Lipophiles 743

2043 Air Pollution 744

20431 Sulfur Dioxide Particulates 745

20432 Automobile Exhaust Emissions 748

2044 Water Treatment 750

2045 Solid Wastes 752

20451 Waste Prevention 753

20452 Recycling 754

20453 CombustionIncineration 755

20454 Sanitary Landfill 756

2046 Petrochemical Industry Wastes 758

2047 Other Environmental Problems 759

205 Valediction 759

Endnotes 761

Appendix A A Note on Cost Calculations 765

Appendix B Units and Conversion Factors 771

Appendix C Special Units in the Chemical Industry 773

Appendix D The Importance of Shale Gas and Shale Oil 775

Index 779

CONTENTS xxi

PREFACE

This third edition of Industrial Organic Chemicals is prompted by the impact of

globalization and of threats to the environment This is not to say that industrial

chemistry has stood still ndash very much the reverse and we have featured much new

chemistry All the same our earlier books were about the exciting new world of

petrochemical feedstocks and the ingenious new products that could be made

from them In this edition the exciting new processes have become the dull

traditional ones Well-established processes of technology transfer have carried

them to developing countries especially those that produce petrochemical feed-

stocks In addition humankindrsquos activities are seen both as depleting the resources

of the planet and of polluting it to the point at which humankind will drown in its

own effluvia The extent of these threats is hotly contested nonetheless the

chemical industry both contributes to the problems and is instrumental in trying to

solve them

There have been many developments since the second edition and the following

topics have gained especially in significance

The world chemical industry has migrated from the United States Western

Europe and Japan to theMiddle East and to Asia-Pacific especially ChinaWill

shale oil and gas bring it back (See Appendix D)

There is increased emphasis on environmental issues with pressure on com-

panies to clean up polluting processes or replace them with environmentally

friendly ones

Globalization has changed patterns of transportation of chemicals with for

example solid polymers rather than petrochemical feedstocks being shipped

from the Middle East

The discovery of vast reserves of shale gas has altered the long-term predictions

of resource depletion in the United States and other countries

Considerations of sustainability and the threat of climate change have prompted

research into processes (including electricity generation) that produce less or no

carbon dioxide or come from renewable resources

We have retained some material that is now largely of historical interest partly

for sentimental reasons but partly because the three authors have watched the

xxiii

meteoric rise of the chemical industry from its early days to its present-day

maturity We think there is a value in our readers observing how technology has

developed and the social technological and economic changes that have brought

it to its present position

HAROLD A WITTCOFF

xxiv PREFACE

PREFACE TO THE FIRST EDITION

In the early 1970s one of us (BGR) wrote a book celebrating the rapid growth of the

adolescent chemical industry The organic chemicals industry at the timewas growing

at four times the rate of the economy It was indicated nonetheless that ldquotrees do not

grow to the skyrdquo In 1980 in another book we both declared the industry to bemiddle-

aged with slow or zero growth In this totally revised and expanded version of our

earlier book we reflect that the industry at any rate in the developedworld is showing

many of the illnesses of late middle-age

The problems have arisen first from the undisciplined building of excess capacity

with consequent fierce competition and low prices Second the entry of numerous

developing countries into the industry has exacerbated the situation (Section 136)

and third there has beenmuch stricter government legislation (Section 137) There is

massive worldwide restructuring and continual shifting of commodity chemical

manufacturing to areas other than the United States Western Europe and Japan

The Middle East and Southeast Asia are the principal new players in the game

Perhaps this trend will continue and the present developed world will in the future

confine itself to themanufacture of specialties but the economic and political forces at

work are more complex than that We hope to be able to discuss their resolution in

another edition in about 10 yearsrsquo time

Meanwhile some things have not changed The organic chemicals industry is still

based on seven basic raw materials all deriving from petroleum and natural gas The

wisdom of teaching about the chemical industry on the basis of these seven building

blocks has been confirmed by the fact that since the publication of our first book one

of us (HAW) has delivered by invitation 300 courses in 28 countries on the

fundamentals of the industry based on this pattern Most of these courses are for

industrial personnel but academia has not been neglected

Furthermore some changes have been positive For example there have been

exciting new processes such as the development of metallocene catalysts (Section

15312) Section 461 describes new methyl methacrylate processes that give a

potentially cheaper product that do not produce ecologically undesirable ammonium

hydrogen sulfate by-product or (in another process) that eliminate the use of

dangerous hydrogen cyanide

In this book our main objective is still to present the technology of the organic

chemicals industry as an organized body of knowledge so that both the neophyte and

the experienced practitioner can see the broad picture Nonetheless we have

expanded its scope to include not only new processes but many apparently less

xxv

important reactions that are significant because they give rise to the more profitable

specialty chemicals The lesser volume chemicals have been clearly delineated as

such and the reader who wishes to see the industry on the basis of its large tonnage

products can omit these sections

We hope this bookwill be useful both to college students who have studied organic

chemistry and to graduates and industrial chemists whowork in or are interested in the

chemical industry Even though much of the chemistry has remained the same the

change in the way the industry looks at its problems provides ample justification for

our offering this edition as a fresh perspective on industrial organic chemicals

xxvi PREFACE TO THE FIRST EDITION

PREFACE TO THE SECOND EDITION

In the preface to the first edition we expressed the hope that we could comment on the

chemical industryrsquos evolution in 10 yearsrsquo time Dramatic changes have motivated us

to compress this time frame There have been unprecedented restructuring severe and

complicated feedstock problems and massive shifts of capacity to developing

countries whose economic and political stability is in doubt Possible terrorist

activity dictates elaborate safety and security procedures and the design of plants

with small inventories is a priority

To increase our cover particularly of the patent literature we have invited Dr

Jeffrey S Plotkin Director of the Process Evaluation and Research Planning program

at Nexant ChemSystems to join us as co-author

xxvii

CONTENTS

Preface xxiii

Preface to the First Edition xxv

Preface to the Second Edition xxvii

Acknowledgments xxix

Bryan Godel Reuben 1934ndash2012 xxxi

List of Acronyms and Abbreviations xxxiii

Introduction How to Use Industrial Organic Chemicals Third Edition 1

I1 Why This Book Was Written and How It Is Structured 2

I2 North American Industry Classification System 5

I3 Units and Nomenclature 5

I4 General Bibliography 6

I41 Encyclopedias 6

I42 Books 7

I43 Journals 8

I44 Patents 9

I45 Statistics and Internet Sources of Information 10

1 The Evolution of the Organic Chemicals Industry 13

11 The National Economy 13

12 Size of the Chemical Industry 16

13 Characteristics of the Chemical Industry 22

131 Capital Intensity and Economies of Scale 22

132 Criticality and Pervasiveness 24

133 Freedom of Market Entry 26

134 Strong Regulation 27

1341 European Legislation 29

1342 Political Factors 30

vii

135 High but Declining Research and Development

Expenditures 34

136 Dislocations 41

14 The Top Companies 43

15 The Top Chemicals 44

Endnotes 46

2 Globalization of the Chemical Industry 49

21 Overcapacity 51

211 Economic Cycles 55

22 Restructuring Mergers and Acquisitions 56

221 SuICIde of a UK Company 60

222 Private Equity 61

23 Participation in International Trade 63

24 Competition from Developing Countries 66

Endnotes 69

3 Transporting Chemicals 71

31 Shipping Petroleum 71

32 Shipping Gas 74

33 Shipping Chemicals 75

331 Gases 75

332 Liquids 77

333 Solids 85

34 Health and Safety 86

35 Economic Aspects 87

36 Trade in Specific Chemicals 88

37 Top Shipping Companies 90

Endnotes 91

4 Chemicals from Natural Gas and Petroleum 93

41 Petroleum Distillation 97

42 Shale Gas 100

421 Shale Gas Technology 101

43 Naphtha Versus Gaseous Feedstocks 102

viii CONTENTS

44 Heavier Oil Fractions 103

45 Steam Cracking and Petroleum Refining Reactions 104

451 Steam Cracking 106

452 Choice of Feedstock 108

453 Economics of Steam Cracking 110

46 Catalytic Cracking 114

47 Mechanisms of Steam and Catalytic Cracking 117

48 Catalytic Reforming 119

49 Oligomerization 122

410 Alkylation 124

411 Hydrotreating and Coking 125

412 Dehydrogenation 126

413 Isomerization 128

414 Metathesis 128

4141 Metathesis Outside the Refinery 129

4142 Mechanism of Metathesis 131

415 Function of the Refinery and the Potential Petroleum

Shortage 133

4151 Unleaded Gasoline and the Clean Air Act 134

416 Separation of Natural Gas 136

417 Oil from Tar Sands 137

Endnotes 137

5 Chemicals and Polymers from Ethylene 139

51 Ethylene Polymers 141

511 Discovery of Low and High Density Polyethylenes 142

512 Low Density Polyethylene 144

513 High Density Polyethylene 146

514 Linear Low Density Polyethylene 147

515 Very High Molecular Weight Polyethylene 148

516 Metallocene Polyethylenes 149

517 Very Low Density Polyethylene 149

518 Bimodal HDPE 149

519 ldquoGreenrdquo Polyethylene 150

CONTENTS ix

52 Ethylene Copolymers 151

521 Chlorosulfonated Polyethylene 151

522 Ethylene-Vinyl Acetate 151

523 Ionomers 152

524 Copolymer from ldquoIncompatiblerdquo Polymer Blends 152

525 EthylenendashPropylene Elastomers 153

526 Polyolefin Elastomers 153

53 Oligomerization 154

531 Dimerization 154

532 Ziegler Oligomerization of Ethylene 155

533 Other Ethylene Oligomerization Technologies 156

534 Shell Higher Olefins Process (SHOP) 158

54 Vinyl Chloride 160

55 Acetaldehyde 165

56 Vinyl Acetate 167

57 Ethylene Oxide 169

571 Ethylene Glycol 171

572 Proposed Non-Ethylene Oxide Processes for

Ethylene Glycol Production 174

58 Styrene 177

59 Ethanol 181

510 Major Chemicals from Ethylene ndash A Summary 182

511 Lesser Volume Chemicals from Ethylene 185

5111 Hydroformylation ndash Propionaldehyde

Propionic Acid and n-Propanol 185

5112 Ethyl Halides 186

5113 Acetaldehyde Chemistry 187

5114 Metal Complexes 191

5115 Ethylenediamine and Related Compounds 191

5116 Ethylene Oxide and Ethylene Glycol Derivatives 193

51161 Oligomers 193

51162 Glycol Ethers and Esters 194

51163 Ethylene Carbonate 197

51164 Aminoethyl Alcohols (Ethanolamines)

and Derivatives 198

51165 Ethyleneimine 199

x CONTENTS

51166 13-Propanediol 200

51167 Ethylene Glycol Derivatives 201

5117 Vinyl Chloride and Ethylene

Dichloride Derivatives 203

5118 Vinyl Fluoride and Vinylidene Fluoride 204

5119 Ethylene Dibromide 205

51110 Ethanol Derivatives 206

51111 Vinyl Esters and Ethers 207

Endnotes 208

6 Chemicals and Polymers from Propylene 211

61 On-Purpose Propylene Production Technologies and Propane

Dehydrogenation 214

611 Propylene Via Enhanced Fluidized

Catalytic Cracking 215

612 Propylene Via Selective C4C5 Cracking 215

62 Main Polymers and Chemicals from Propylene 217

621 Propylene Polymers and Copolymers 217

63 Oligomerization 221

64 Acrylic Acid 222

641 Biorenewable Processes to Acrylic Acid 225

642 Acrylic Acid Markets 226

65 Acrylonitrile 227

651 Uses of Acrylonitrile 230

66 CumenePhenol and Cumene Hydroperoxide 231

67 Acetone and Isopropanol 233

671 Methyl Methacrylate 235

672 Methyl Isobutyl Ketone and Other

Acetone Derivatives 242

68 Propylene Oxide 242

681 Other Propylene Oxide Processes 247

6811 Acetoxylation of Propylene 248

6812 Direct Oxidation 249

6813 Use of Peracids 249

6814 Electrochemical Processes 250

6815 Biotechnological Approaches 252

682 Propylene Oxide Applications 253

CONTENTS xi

69 n-Butyraldehyde and Isobutyraldehyde 255

691 Uses for Butyraldehyde Isobutyraldehyde

and n-Butanol 258

692 Other Oxo Products 260

610 Major Chemicals from Propylene ndash A Perspective 261

611 Lesser Volume Chemicals from Propylene 263

6111 Allyl Chloride and Epichlorohydrin 263

6112 Glycerol 266

6113 Acrylamide 266

6114 Acrolein 268

6115 Acrylonitrile Derivatives 270

Endnotes 270

7 Chemicals from the C4 Stream 273

71 Chemicals and Polymers from Butadiene 277

711 Tires 280

712 StyrenendashButadiene Elastomers 281

713 Polybutadienes and Other Elastomers 282

714 AcrylonitrilendashButadienendashStyrene Resins 283

715 Hexamethylenediamine 284

716 Lesser Volume Chemicals from Butadiene 289

7161 Cyclization 289

7162 Dimerization and Trimerization 291

7163 DielsndashAlder Reactions 293

7164 Adipic Acid 294

7165 14-Butanediol 294

7166 trans-14-Hexadiene 295

7167 Dimethyl-26-naphthalene

Dicarboxylate 295

7168 Butadiene Monoepoxide 296

72 Chemicals and Polymers from Isobutene 296

721 Methyl tert-Butyl Ether 297

722 Butyl Rubber 298

723 Polyisobutenes and Isobutene Oligomers

and Polymers 298

724 tert-Butanol 299

725 Methyl Methacrylate 299

726 Lesser Volume Chemicals from Isobutene 299

xii CONTENTS

73 Chemicals and Polymers from 1- and 2-Butenes 302

74 Chemicals from n-Butane 303

741 Acetic Acid 303

742 Maleic Anhydride 303

743 Succinic Malic Fumaric and Tartaric Acids 306

Endnotes 307

8 Chemicals from the C5 Stream 309

81 Separation of the C5 Stream 311

82 Isoprene 312

821 Natural Rubber 312

822 Vulcanization 313

823 Production of Petrochemical Isoprene 314

824 Applications of Isoprene 317

83 Cyclopentadiene and Dicyclopentadiene 319

84 Pentene-1 and Piperylene 321

Endnotes 321

9 Chemicals from Benzene 323

91 Phenol 326

911 Phenolic Resins 331

912 Bisphenol A 333

9121 Epoxy Resins 333

9122 Polycarbonate Resins 334

9123 Lesser Volume Uses for Bisphenol A 337

9124 Environmental Problems 340

913 Cyclohexanone 341

914 Alkylphenols 342

915 Chlorinated Phenols 342

916 26-XylenolCresols 343

917 Aniline from Phenol 344

92 Cyclohexane 344

921 Adipic Acid 344

9211 Nylons from Adipic Acid 349

922 Caprolactam 349

CONTENTS xiii

93 Aniline 354

931 440-Diphenylmethane Isocyanate 357

94 Alkylbenzenes 361

95 Maleic Anhydride 362

96 Chlorinated Benzenes 363

97 Dihydroxybenzenes 364

971 Hydroquinone 364

972 Resorcinol 368

973 Catechol 369

98 Anthraquinone 370

981 Hydrogen Peroxide 371

Endnotes 372

10 Chemicals from Toluene 375

101 Hydrodealkylation Disproportionation and Transalkylation 375

102 Solvents 378

103 Dinitrotoluene and Toluene Diisocyanate 378

104 Lesser Volume Chemicals from Toluene 380

Endnotes 382

11 Chemicals from Xylenes 383

111 o-Xylene and Phthalic Anhydride 386

1111 Plasticizers 387

1112 Alkyd Resins 391

1113 Unsaturated Polyester Resin 393

112 m-Xylene and Isophthalic Acid 395

1121 Uses of Isophthalic Acid 396

113 p-Xylene and Terephthalic AcidDimethyl Terephthalate 397

1131 Oxidation of p-Xylene 398

1132 Alternate Sources for Terephthalic Acid 400

1133 Poly(ethylene terephthalate) 400

1134 Lower Volume Polymers from Terephthalic Acid 403

Endnotes 404

xiv CONTENTS

12 Chemicals from Methane 407

121 Hydrocyanic Acid 408

122 Halogenated Methanes 411

1221 Chloromethane 412

1222 Dichloromethane 413

1223 Trichloromethane 413

1224 Fluorocarbons 414

1225 Tetrachloromethane and Carbon Disulfide 414

1226 Bromomethane 416

123 Acetylene 417

1231 14-Butanediol and 2-Methyl-13-propanediol 419

1232 Lesser Uses for Acetylene 423

124 Synthesis Gas 424

1241 Steam Reforming of Methane 425

1242 Variants of Steam Reforming 427

1243 Partial Oxidation of Hydrocarbons 428

1244 Solid Feedstocks 428

1245 Hydrogen 429

125 Chemicals from Synthesis Gas 429

1251 Ammonia and Its Derivatives 430

12511 The Crisis of Nitrogen Depletion 430

12512 Ammonia Manufacture 431

12513 Urea and Melamine Resins 434

1252 Methanol 435

12521 Formaldehyde 438

12522 Acetic Acid 439

12523 Acetic Anhydride 442

12524 Methanol to Gasoline 445

12525 Methanol to Olefins 446

12526 Lower Volume and Proposed Uses for Methanol 448

12527 C1-Based Development Processes 452

126 Carbon Monoxide Chemistry 454

1261 Proposed Chemistry Based on Carbon Monoxide 455

127 Gas-to-Liquid Fuels 459

1271 Sasol GTL Technology 459

1272 Shell Middle Distillate Synthesis 459

CONTENTS xv

1273 Other GTL Technologies 460

Endnotes 460

13 Chemicals from Alkanes 463

131 Functionalization of Methane 464

1311 Methane to MethanolFormaldehyde 464

1312 Dimerization of Methane 466

1313 Aromatization of Methane 467

132 Functionalization of C2ndashC4 Alkanes 468

1321 Oxidation of C2ndashC4 Alkanes 468

1322 Dehydrogenation of C2ndashC4 Alkanes 470

1323 Aromatization of C2ndashC4Alkanes 471

133 Carbon Black 472

Endnotes 473

14 Chemicals from Coal 475

141 Chemicals from Coke Oven Distillate 477

142 The FischerndashTropsch Reaction 480

143 Coal Hydrogenation 484

144 Substitute Natural Gas 485

145 SNG and Synthesis Gas Technology 485

146 Underground Coal Gasification 488

147 Calcium Carbide 488

1471 The Chinese Chemicals to Coal Program 489

148 Coal and the Environment 490

Endnotes 491

15 Fats and Oils 493

151 Markets for Fats and Oils 495

152 Purification of Fats and Oils 497

153 Fatty Acids 499

1531 Applications of Fatty Acids 501

154 Fatty Nitrogen Compounds 502

155 ldquoDimerrdquo Acid 504

xvi CONTENTS

156 Aminoamides and Imidazolines 506

157 Azelaic Pelargonic and Petroselinic Acids 507

158 Fatty Alcohols 508

159 Epoxidized Oils 509

1510 Ricinoleic Acid 510

1511 Glycerol 512

15111 Established Glycerol Uses 512

1512 Alcoholysis of Fats and Oils 513

15121 Cocoa Butter and Mothersrsquo Milk 513

151211 Mothersrsquo Milk 515

15122 Trans Fats and Interesterification 515

15123 Biodiesel and Lubricants 516

151231 Algae 518

1513 Alkyl Polyglycosides 519

1514 Non-Caloric Fat-like Substances 519

Endnotes 520

16 Carbohydrates 523

161 Sugars and Sorbitol 523

1611 Isosorbide 530

162 Furfural 530

163 Starch 532

164 Cellulose 535

1641 Miscellaneous Chemicals from Wood 539

16411 Vanillin 541

16412 Levulinic Acid 542

165 Gums 543

166 Fermentation and Biotechnology 544

1661 Amino Acids 547

16611 L-Glutamic Acid 547

16612 L-Lysine 547

16613 L-Aspartic Acid 548

16614 L-Cysteine 549

1662 Polymers 550

CONTENTS xvii

1663 Proteins by Recombinant DNA Technology 550

1664 Fermentation and Renewables Scenarios 551

1665 Biofuels 554

16651 The Brazilian Experience 554

16652 Is US Bioethanol a Renewable

Energy Source 555

16653 Biomass as Feedstock 556

16654 Catalytic Bioforming 556

16655 Biotechnology Versus Synthesis Gas 557

Endnotes 558

17 How Polymers Are Made 561

171 Polymerization 565

172 Functionality 568

173 Step Growth and Chain Growth Polymerizations 571

1731 Free Radical Polymerization 573

1732 Chain Transfer 575

1733 Copolymerization 577

1734 Molecular Weight 579

1735 Polymerization Procedures 580

17351 Photoinitiation 582

1736 Ionic Polymerization 584

1737 Living Polymers 589

1738 Block Copolymers 589

1739 Graft Copolymers 592

17310 Metal Complex Catalysts 593

17311 Metal Oxide Catalysts 598

17312 Metallocene and Other Single Site Catalysts 599

173121 Single Site Nonmetallocene Catalysts 602

173122 Late Transition Metal Catalysts 603

173123 Commercial Prospects of LLDPEs 604

174 Examples of Step Polymerization 605

1741 Phenoplasts and Aminoplasts 605

1742 Polyurethanes 606

1743 Epoxy Resins 611

1744 Dendritic and Hyperbranched Polymers 613

1745 Conducting Polymers 617

1746 Conducting and Semiconducting Inks 621

xviii CONTENTS

175 Polymer Properties 622

1751 Crystallinity 622

1752 Glass Transition Temperature Crystalline

Melting Point and Softening Temperature 626

1753 Molecular Cohesion 628

1754 StressndashStrain Diagrams 628

176 Classes of Polymers 630

177 Plastics Fabrication Techniques 631

Endnotes 635

18 Industrial Catalysis 637

181 Catalyst Choice 637

1811 Reaction Velocity and Selectivity 638

1812 Recovery of Unchanged Catalyst 641

1813 Catalyst Deactivation 642

1814 Access to Nonequilibrium Products 642

182 Homogeneous and Heterogeneous Catalysis 643

1821 Reactors for Heterogeneous Catalysts 644

1822 Immobilization of Homogeneous Catalysts 646

183 Catalyst Markets 647

184 Catalysis by Acids and Bases 651

185 Dual Function Catalysis 654

186 Catalysis by Metals Semiconductors and Insulators 655

1861 Catalysts for Automobile Emission Control 656

187 Coordination Catalysis 657

1871 Catalysts for Stereoregular Compounds 658

1872 Asymmetric Synthesis 660

188 Enzymes 661

1881 Catalytic Antibodies 663

189 Shape-Selective Catalysts 664

1810 Phase-Transfer and Fluorous Biphase Catalysis 669

1811 Nanocatalysis 670

1812 Catalysts of the Future 673

18121 Catalyst Design 673

18122 Higher Selectivities 673

CONTENTS xix

18123 Catalysts with Greater Activity 674

18124 Pollution Problems 675

18125 Catalysts for New Reactions 675

18126 Catalysts that Mimic Natural Catalysts 676

18127 Catalyst Discovery Via High Throughput

Experimentation 676

Endnotes 677

19 Green Chemistry 681

191 The Decline of Acetylene Chemistry 683

192 Nylon 683

193 Replacement of Phosgene 684

194 Monomethylation by Dimethyl Carbonate 685

195 Liquid and Supercritical Carbon Dioxide and Water 685

196 Ionic Liquids 687

197 Photocatalysts 690

198 Paired Electrosynthesis 691

199 ldquoGreenrdquo Pharmaceuticals 692

1991 Ibuprofen 692

1992 Sertraline 694

1993 Pharmaceuticals from ldquoRenewablesrdquo 696

1910 Catalytic Dehydrogenation of Diethanolamine 698

1911 Genetic Manipulation 698

1912 Biodegradable Packaging 698

19121 Polyhydroxyalkanoates 701

1913 The Presidential Green Chemistry Challenge Program 703

Endnotes 704

20 Sustainability 707

201 Climate Change 708

202 Resource Depletion 712

2021 Food Water and People 713

20211 Food 713

20212 Water 714

20213 People 715

xx CONTENTS

203 Energy Sources 717

2031 Wind Power 719

2032 Wave Power 720

2033 Solar Power 721

20331 Concentrated Solar Power 721

20332 Photovoltaic Cells 721

20333 Dye-Sensitized Solar Cells 722

20334 Artificial Photosynthesis 724

2034 Nuclear Energy 726

2035 Methane Hydrate 727

2036 The Hydrogen Economy 728

2037 Fuel Cells 729

2038 Electric Vehicles 735

204 Pollution 736

2041 The Ozone Layer 738

2042 Trace Chemicals 742

20421 Pesticides 742

20422 Nonpesticide Lipophiles 743

2043 Air Pollution 744

20431 Sulfur Dioxide Particulates 745

20432 Automobile Exhaust Emissions 748

2044 Water Treatment 750

2045 Solid Wastes 752

20451 Waste Prevention 753

20452 Recycling 754

20453 CombustionIncineration 755

20454 Sanitary Landfill 756

2046 Petrochemical Industry Wastes 758

2047 Other Environmental Problems 759

205 Valediction 759

Endnotes 761

Appendix A A Note on Cost Calculations 765

Appendix B Units and Conversion Factors 771

Appendix C Special Units in the Chemical Industry 773

Appendix D The Importance of Shale Gas and Shale Oil 775

Index 779

CONTENTS xxi

PREFACE

This third edition of Industrial Organic Chemicals is prompted by the impact of

globalization and of threats to the environment This is not to say that industrial

chemistry has stood still ndash very much the reverse and we have featured much new

chemistry All the same our earlier books were about the exciting new world of

petrochemical feedstocks and the ingenious new products that could be made

from them In this edition the exciting new processes have become the dull

traditional ones Well-established processes of technology transfer have carried

them to developing countries especially those that produce petrochemical feed-

stocks In addition humankindrsquos activities are seen both as depleting the resources

of the planet and of polluting it to the point at which humankind will drown in its

own effluvia The extent of these threats is hotly contested nonetheless the

chemical industry both contributes to the problems and is instrumental in trying to

solve them

There have been many developments since the second edition and the following

topics have gained especially in significance

The world chemical industry has migrated from the United States Western

Europe and Japan to theMiddle East and to Asia-Pacific especially ChinaWill

shale oil and gas bring it back (See Appendix D)

There is increased emphasis on environmental issues with pressure on com-

panies to clean up polluting processes or replace them with environmentally

friendly ones

Globalization has changed patterns of transportation of chemicals with for

example solid polymers rather than petrochemical feedstocks being shipped

from the Middle East

The discovery of vast reserves of shale gas has altered the long-term predictions

of resource depletion in the United States and other countries

Considerations of sustainability and the threat of climate change have prompted

research into processes (including electricity generation) that produce less or no

carbon dioxide or come from renewable resources

We have retained some material that is now largely of historical interest partly

for sentimental reasons but partly because the three authors have watched the

xxiii

meteoric rise of the chemical industry from its early days to its present-day

maturity We think there is a value in our readers observing how technology has

developed and the social technological and economic changes that have brought

it to its present position

HAROLD A WITTCOFF

xxiv PREFACE

PREFACE TO THE FIRST EDITION

In the early 1970s one of us (BGR) wrote a book celebrating the rapid growth of the

adolescent chemical industry The organic chemicals industry at the timewas growing

at four times the rate of the economy It was indicated nonetheless that ldquotrees do not

grow to the skyrdquo In 1980 in another book we both declared the industry to bemiddle-

aged with slow or zero growth In this totally revised and expanded version of our

earlier book we reflect that the industry at any rate in the developedworld is showing

many of the illnesses of late middle-age

The problems have arisen first from the undisciplined building of excess capacity

with consequent fierce competition and low prices Second the entry of numerous

developing countries into the industry has exacerbated the situation (Section 136)

and third there has beenmuch stricter government legislation (Section 137) There is

massive worldwide restructuring and continual shifting of commodity chemical

manufacturing to areas other than the United States Western Europe and Japan

The Middle East and Southeast Asia are the principal new players in the game

Perhaps this trend will continue and the present developed world will in the future

confine itself to themanufacture of specialties but the economic and political forces at

work are more complex than that We hope to be able to discuss their resolution in

another edition in about 10 yearsrsquo time

Meanwhile some things have not changed The organic chemicals industry is still

based on seven basic raw materials all deriving from petroleum and natural gas The

wisdom of teaching about the chemical industry on the basis of these seven building

blocks has been confirmed by the fact that since the publication of our first book one

of us (HAW) has delivered by invitation 300 courses in 28 countries on the

fundamentals of the industry based on this pattern Most of these courses are for

industrial personnel but academia has not been neglected

Furthermore some changes have been positive For example there have been

exciting new processes such as the development of metallocene catalysts (Section

15312) Section 461 describes new methyl methacrylate processes that give a

potentially cheaper product that do not produce ecologically undesirable ammonium

hydrogen sulfate by-product or (in another process) that eliminate the use of

dangerous hydrogen cyanide

In this book our main objective is still to present the technology of the organic

chemicals industry as an organized body of knowledge so that both the neophyte and

the experienced practitioner can see the broad picture Nonetheless we have

expanded its scope to include not only new processes but many apparently less

xxv

important reactions that are significant because they give rise to the more profitable

specialty chemicals The lesser volume chemicals have been clearly delineated as

such and the reader who wishes to see the industry on the basis of its large tonnage

products can omit these sections

We hope this bookwill be useful both to college students who have studied organic

chemistry and to graduates and industrial chemists whowork in or are interested in the

chemical industry Even though much of the chemistry has remained the same the

change in the way the industry looks at its problems provides ample justification for

our offering this edition as a fresh perspective on industrial organic chemicals

xxvi PREFACE TO THE FIRST EDITION

PREFACE TO THE SECOND EDITION

In the preface to the first edition we expressed the hope that we could comment on the

chemical industryrsquos evolution in 10 yearsrsquo time Dramatic changes have motivated us

to compress this time frame There have been unprecedented restructuring severe and

complicated feedstock problems and massive shifts of capacity to developing

countries whose economic and political stability is in doubt Possible terrorist

activity dictates elaborate safety and security procedures and the design of plants

with small inventories is a priority

To increase our cover particularly of the patent literature we have invited Dr

Jeffrey S Plotkin Director of the Process Evaluation and Research Planning program

at Nexant ChemSystems to join us as co-author

xxvii

135 High but Declining Research and Development

Expenditures 34

136 Dislocations 41

14 The Top Companies 43

15 The Top Chemicals 44

Endnotes 46

2 Globalization of the Chemical Industry 49

21 Overcapacity 51

211 Economic Cycles 55

22 Restructuring Mergers and Acquisitions 56

221 SuICIde of a UK Company 60

222 Private Equity 61

23 Participation in International Trade 63

24 Competition from Developing Countries 66

Endnotes 69

3 Transporting Chemicals 71

31 Shipping Petroleum 71

32 Shipping Gas 74

33 Shipping Chemicals 75

331 Gases 75

332 Liquids 77

333 Solids 85

34 Health and Safety 86

35 Economic Aspects 87

36 Trade in Specific Chemicals 88

37 Top Shipping Companies 90

Endnotes 91

4 Chemicals from Natural Gas and Petroleum 93

41 Petroleum Distillation 97

42 Shale Gas 100

421 Shale Gas Technology 101

43 Naphtha Versus Gaseous Feedstocks 102

viii CONTENTS

44 Heavier Oil Fractions 103

45 Steam Cracking and Petroleum Refining Reactions 104

451 Steam Cracking 106

452 Choice of Feedstock 108

453 Economics of Steam Cracking 110

46 Catalytic Cracking 114

47 Mechanisms of Steam and Catalytic Cracking 117

48 Catalytic Reforming 119

49 Oligomerization 122

410 Alkylation 124

411 Hydrotreating and Coking 125

412 Dehydrogenation 126

413 Isomerization 128

414 Metathesis 128

4141 Metathesis Outside the Refinery 129

4142 Mechanism of Metathesis 131

415 Function of the Refinery and the Potential Petroleum

Shortage 133

4151 Unleaded Gasoline and the Clean Air Act 134

416 Separation of Natural Gas 136

417 Oil from Tar Sands 137

Endnotes 137

5 Chemicals and Polymers from Ethylene 139

51 Ethylene Polymers 141

511 Discovery of Low and High Density Polyethylenes 142

512 Low Density Polyethylene 144

513 High Density Polyethylene 146

514 Linear Low Density Polyethylene 147

515 Very High Molecular Weight Polyethylene 148

516 Metallocene Polyethylenes 149

517 Very Low Density Polyethylene 149

518 Bimodal HDPE 149

519 ldquoGreenrdquo Polyethylene 150

CONTENTS ix

52 Ethylene Copolymers 151

521 Chlorosulfonated Polyethylene 151

522 Ethylene-Vinyl Acetate 151

523 Ionomers 152

524 Copolymer from ldquoIncompatiblerdquo Polymer Blends 152

525 EthylenendashPropylene Elastomers 153

526 Polyolefin Elastomers 153

53 Oligomerization 154

531 Dimerization 154

532 Ziegler Oligomerization of Ethylene 155

533 Other Ethylene Oligomerization Technologies 156

534 Shell Higher Olefins Process (SHOP) 158

54 Vinyl Chloride 160

55 Acetaldehyde 165

56 Vinyl Acetate 167

57 Ethylene Oxide 169

571 Ethylene Glycol 171

572 Proposed Non-Ethylene Oxide Processes for

Ethylene Glycol Production 174

58 Styrene 177

59 Ethanol 181

510 Major Chemicals from Ethylene ndash A Summary 182

511 Lesser Volume Chemicals from Ethylene 185

5111 Hydroformylation ndash Propionaldehyde

Propionic Acid and n-Propanol 185

5112 Ethyl Halides 186

5113 Acetaldehyde Chemistry 187

5114 Metal Complexes 191

5115 Ethylenediamine and Related Compounds 191

5116 Ethylene Oxide and Ethylene Glycol Derivatives 193

51161 Oligomers 193

51162 Glycol Ethers and Esters 194

51163 Ethylene Carbonate 197

51164 Aminoethyl Alcohols (Ethanolamines)

and Derivatives 198

51165 Ethyleneimine 199

x CONTENTS

51166 13-Propanediol 200

51167 Ethylene Glycol Derivatives 201

5117 Vinyl Chloride and Ethylene

Dichloride Derivatives 203

5118 Vinyl Fluoride and Vinylidene Fluoride 204

5119 Ethylene Dibromide 205

51110 Ethanol Derivatives 206

51111 Vinyl Esters and Ethers 207

Endnotes 208

6 Chemicals and Polymers from Propylene 211

61 On-Purpose Propylene Production Technologies and Propane

Dehydrogenation 214

611 Propylene Via Enhanced Fluidized

Catalytic Cracking 215

612 Propylene Via Selective C4C5 Cracking 215

62 Main Polymers and Chemicals from Propylene 217

621 Propylene Polymers and Copolymers 217

63 Oligomerization 221

64 Acrylic Acid 222

641 Biorenewable Processes to Acrylic Acid 225

642 Acrylic Acid Markets 226

65 Acrylonitrile 227

651 Uses of Acrylonitrile 230

66 CumenePhenol and Cumene Hydroperoxide 231

67 Acetone and Isopropanol 233

671 Methyl Methacrylate 235

672 Methyl Isobutyl Ketone and Other

Acetone Derivatives 242

68 Propylene Oxide 242

681 Other Propylene Oxide Processes 247

6811 Acetoxylation of Propylene 248

6812 Direct Oxidation 249

6813 Use of Peracids 249

6814 Electrochemical Processes 250

6815 Biotechnological Approaches 252

682 Propylene Oxide Applications 253

CONTENTS xi

69 n-Butyraldehyde and Isobutyraldehyde 255

691 Uses for Butyraldehyde Isobutyraldehyde

and n-Butanol 258

692 Other Oxo Products 260

610 Major Chemicals from Propylene ndash A Perspective 261

611 Lesser Volume Chemicals from Propylene 263

6111 Allyl Chloride and Epichlorohydrin 263

6112 Glycerol 266

6113 Acrylamide 266

6114 Acrolein 268

6115 Acrylonitrile Derivatives 270

Endnotes 270

7 Chemicals from the C4 Stream 273

71 Chemicals and Polymers from Butadiene 277

711 Tires 280

712 StyrenendashButadiene Elastomers 281

713 Polybutadienes and Other Elastomers 282

714 AcrylonitrilendashButadienendashStyrene Resins 283

715 Hexamethylenediamine 284

716 Lesser Volume Chemicals from Butadiene 289

7161 Cyclization 289

7162 Dimerization and Trimerization 291

7163 DielsndashAlder Reactions 293

7164 Adipic Acid 294

7165 14-Butanediol 294

7166 trans-14-Hexadiene 295

7167 Dimethyl-26-naphthalene

Dicarboxylate 295

7168 Butadiene Monoepoxide 296

72 Chemicals and Polymers from Isobutene 296

721 Methyl tert-Butyl Ether 297

722 Butyl Rubber 298

723 Polyisobutenes and Isobutene Oligomers

and Polymers 298

724 tert-Butanol 299

725 Methyl Methacrylate 299

726 Lesser Volume Chemicals from Isobutene 299

xii CONTENTS

73 Chemicals and Polymers from 1- and 2-Butenes 302

74 Chemicals from n-Butane 303

741 Acetic Acid 303

742 Maleic Anhydride 303

743 Succinic Malic Fumaric and Tartaric Acids 306

Endnotes 307

8 Chemicals from the C5 Stream 309

81 Separation of the C5 Stream 311

82 Isoprene 312

821 Natural Rubber 312

822 Vulcanization 313

823 Production of Petrochemical Isoprene 314

824 Applications of Isoprene 317

83 Cyclopentadiene and Dicyclopentadiene 319

84 Pentene-1 and Piperylene 321

Endnotes 321

9 Chemicals from Benzene 323

91 Phenol 326

911 Phenolic Resins 331

912 Bisphenol A 333

9121 Epoxy Resins 333

9122 Polycarbonate Resins 334

9123 Lesser Volume Uses for Bisphenol A 337

9124 Environmental Problems 340

913 Cyclohexanone 341

914 Alkylphenols 342

915 Chlorinated Phenols 342

916 26-XylenolCresols 343

917 Aniline from Phenol 344

92 Cyclohexane 344

921 Adipic Acid 344

9211 Nylons from Adipic Acid 349

922 Caprolactam 349

CONTENTS xiii

93 Aniline 354

931 440-Diphenylmethane Isocyanate 357

94 Alkylbenzenes 361

95 Maleic Anhydride 362

96 Chlorinated Benzenes 363

97 Dihydroxybenzenes 364

971 Hydroquinone 364

972 Resorcinol 368

973 Catechol 369

98 Anthraquinone 370

981 Hydrogen Peroxide 371

Endnotes 372

10 Chemicals from Toluene 375

101 Hydrodealkylation Disproportionation and Transalkylation 375

102 Solvents 378

103 Dinitrotoluene and Toluene Diisocyanate 378

104 Lesser Volume Chemicals from Toluene 380

Endnotes 382

11 Chemicals from Xylenes 383

111 o-Xylene and Phthalic Anhydride 386

1111 Plasticizers 387

1112 Alkyd Resins 391

1113 Unsaturated Polyester Resin 393

112 m-Xylene and Isophthalic Acid 395

1121 Uses of Isophthalic Acid 396

113 p-Xylene and Terephthalic AcidDimethyl Terephthalate 397

1131 Oxidation of p-Xylene 398

1132 Alternate Sources for Terephthalic Acid 400

1133 Poly(ethylene terephthalate) 400

1134 Lower Volume Polymers from Terephthalic Acid 403

Endnotes 404

xiv CONTENTS

12 Chemicals from Methane 407

121 Hydrocyanic Acid 408

122 Halogenated Methanes 411

1221 Chloromethane 412

1222 Dichloromethane 413

1223 Trichloromethane 413

1224 Fluorocarbons 414

1225 Tetrachloromethane and Carbon Disulfide 414

1226 Bromomethane 416

123 Acetylene 417

1231 14-Butanediol and 2-Methyl-13-propanediol 419

1232 Lesser Uses for Acetylene 423

124 Synthesis Gas 424

1241 Steam Reforming of Methane 425

1242 Variants of Steam Reforming 427

1243 Partial Oxidation of Hydrocarbons 428

1244 Solid Feedstocks 428

1245 Hydrogen 429

125 Chemicals from Synthesis Gas 429

1251 Ammonia and Its Derivatives 430

12511 The Crisis of Nitrogen Depletion 430

12512 Ammonia Manufacture 431

12513 Urea and Melamine Resins 434

1252 Methanol 435

12521 Formaldehyde 438

12522 Acetic Acid 439

12523 Acetic Anhydride 442

12524 Methanol to Gasoline 445

12525 Methanol to Olefins 446

12526 Lower Volume and Proposed Uses for Methanol 448

12527 C1-Based Development Processes 452

126 Carbon Monoxide Chemistry 454

1261 Proposed Chemistry Based on Carbon Monoxide 455

127 Gas-to-Liquid Fuels 459

1271 Sasol GTL Technology 459

1272 Shell Middle Distillate Synthesis 459

CONTENTS xv

1273 Other GTL Technologies 460

Endnotes 460

13 Chemicals from Alkanes 463

131 Functionalization of Methane 464

1311 Methane to MethanolFormaldehyde 464

1312 Dimerization of Methane 466

1313 Aromatization of Methane 467

132 Functionalization of C2ndashC4 Alkanes 468

1321 Oxidation of C2ndashC4 Alkanes 468

1322 Dehydrogenation of C2ndashC4 Alkanes 470

1323 Aromatization of C2ndashC4Alkanes 471

133 Carbon Black 472

Endnotes 473

14 Chemicals from Coal 475

141 Chemicals from Coke Oven Distillate 477

142 The FischerndashTropsch Reaction 480

143 Coal Hydrogenation 484

144 Substitute Natural Gas 485

145 SNG and Synthesis Gas Technology 485

146 Underground Coal Gasification 488

147 Calcium Carbide 488

1471 The Chinese Chemicals to Coal Program 489

148 Coal and the Environment 490

Endnotes 491

15 Fats and Oils 493

151 Markets for Fats and Oils 495

152 Purification of Fats and Oils 497

153 Fatty Acids 499

1531 Applications of Fatty Acids 501

154 Fatty Nitrogen Compounds 502

155 ldquoDimerrdquo Acid 504

xvi CONTENTS

156 Aminoamides and Imidazolines 506

157 Azelaic Pelargonic and Petroselinic Acids 507

158 Fatty Alcohols 508

159 Epoxidized Oils 509

1510 Ricinoleic Acid 510

1511 Glycerol 512

15111 Established Glycerol Uses 512

1512 Alcoholysis of Fats and Oils 513

15121 Cocoa Butter and Mothersrsquo Milk 513

151211 Mothersrsquo Milk 515

15122 Trans Fats and Interesterification 515

15123 Biodiesel and Lubricants 516

151231 Algae 518

1513 Alkyl Polyglycosides 519

1514 Non-Caloric Fat-like Substances 519

Endnotes 520

16 Carbohydrates 523

161 Sugars and Sorbitol 523

1611 Isosorbide 530

162 Furfural 530

163 Starch 532

164 Cellulose 535

1641 Miscellaneous Chemicals from Wood 539

16411 Vanillin 541

16412 Levulinic Acid 542

165 Gums 543

166 Fermentation and Biotechnology 544

1661 Amino Acids 547

16611 L-Glutamic Acid 547

16612 L-Lysine 547

16613 L-Aspartic Acid 548

16614 L-Cysteine 549

1662 Polymers 550

CONTENTS xvii

1663 Proteins by Recombinant DNA Technology 550

1664 Fermentation and Renewables Scenarios 551

1665 Biofuels 554

16651 The Brazilian Experience 554

16652 Is US Bioethanol a Renewable

Energy Source 555

16653 Biomass as Feedstock 556

16654 Catalytic Bioforming 556

16655 Biotechnology Versus Synthesis Gas 557

Endnotes 558

17 How Polymers Are Made 561

171 Polymerization 565

172 Functionality 568

173 Step Growth and Chain Growth Polymerizations 571

1731 Free Radical Polymerization 573

1732 Chain Transfer 575

1733 Copolymerization 577

1734 Molecular Weight 579

1735 Polymerization Procedures 580

17351 Photoinitiation 582

1736 Ionic Polymerization 584

1737 Living Polymers 589

1738 Block Copolymers 589

1739 Graft Copolymers 592

17310 Metal Complex Catalysts 593

17311 Metal Oxide Catalysts 598

17312 Metallocene and Other Single Site Catalysts 599

173121 Single Site Nonmetallocene Catalysts 602

173122 Late Transition Metal Catalysts 603

173123 Commercial Prospects of LLDPEs 604

174 Examples of Step Polymerization 605

1741 Phenoplasts and Aminoplasts 605

1742 Polyurethanes 606

1743 Epoxy Resins 611

1744 Dendritic and Hyperbranched Polymers 613

1745 Conducting Polymers 617

1746 Conducting and Semiconducting Inks 621

xviii CONTENTS

175 Polymer Properties 622

1751 Crystallinity 622

1752 Glass Transition Temperature Crystalline

Melting Point and Softening Temperature 626

1753 Molecular Cohesion 628

1754 StressndashStrain Diagrams 628

176 Classes of Polymers 630

177 Plastics Fabrication Techniques 631

Endnotes 635

18 Industrial Catalysis 637

181 Catalyst Choice 637

1811 Reaction Velocity and Selectivity 638

1812 Recovery of Unchanged Catalyst 641

1813 Catalyst Deactivation 642

1814 Access to Nonequilibrium Products 642

182 Homogeneous and Heterogeneous Catalysis 643

1821 Reactors for Heterogeneous Catalysts 644

1822 Immobilization of Homogeneous Catalysts 646

183 Catalyst Markets 647

184 Catalysis by Acids and Bases 651

185 Dual Function Catalysis 654

186 Catalysis by Metals Semiconductors and Insulators 655

1861 Catalysts for Automobile Emission Control 656

187 Coordination Catalysis 657

1871 Catalysts for Stereoregular Compounds 658

1872 Asymmetric Synthesis 660

188 Enzymes 661

1881 Catalytic Antibodies 663

189 Shape-Selective Catalysts 664

1810 Phase-Transfer and Fluorous Biphase Catalysis 669

1811 Nanocatalysis 670

1812 Catalysts of the Future 673

18121 Catalyst Design 673

18122 Higher Selectivities 673

CONTENTS xix

18123 Catalysts with Greater Activity 674

18124 Pollution Problems 675

18125 Catalysts for New Reactions 675

18126 Catalysts that Mimic Natural Catalysts 676

18127 Catalyst Discovery Via High Throughput

Experimentation 676

Endnotes 677

19 Green Chemistry 681

191 The Decline of Acetylene Chemistry 683

192 Nylon 683

193 Replacement of Phosgene 684

194 Monomethylation by Dimethyl Carbonate 685

195 Liquid and Supercritical Carbon Dioxide and Water 685

196 Ionic Liquids 687

197 Photocatalysts 690

198 Paired Electrosynthesis 691

199 ldquoGreenrdquo Pharmaceuticals 692

1991 Ibuprofen 692

1992 Sertraline 694

1993 Pharmaceuticals from ldquoRenewablesrdquo 696

1910 Catalytic Dehydrogenation of Diethanolamine 698

1911 Genetic Manipulation 698

1912 Biodegradable Packaging 698

19121 Polyhydroxyalkanoates 701

1913 The Presidential Green Chemistry Challenge Program 703

Endnotes 704

20 Sustainability 707

201 Climate Change 708

202 Resource Depletion 712

2021 Food Water and People 713

20211 Food 713

20212 Water 714

20213 People 715

xx CONTENTS

203 Energy Sources 717

2031 Wind Power 719

2032 Wave Power 720

2033 Solar Power 721

20331 Concentrated Solar Power 721

20332 Photovoltaic Cells 721

20333 Dye-Sensitized Solar Cells 722

20334 Artificial Photosynthesis 724

2034 Nuclear Energy 726

2035 Methane Hydrate 727

2036 The Hydrogen Economy 728

2037 Fuel Cells 729

2038 Electric Vehicles 735

204 Pollution 736

2041 The Ozone Layer 738

2042 Trace Chemicals 742

20421 Pesticides 742

20422 Nonpesticide Lipophiles 743

2043 Air Pollution 744

20431 Sulfur Dioxide Particulates 745

20432 Automobile Exhaust Emissions 748

2044 Water Treatment 750

2045 Solid Wastes 752

20451 Waste Prevention 753

20452 Recycling 754

20453 CombustionIncineration 755

20454 Sanitary Landfill 756

2046 Petrochemical Industry Wastes 758

2047 Other Environmental Problems 759

205 Valediction 759

Endnotes 761

Appendix A A Note on Cost Calculations 765

Appendix B Units and Conversion Factors 771

Appendix C Special Units in the Chemical Industry 773

Appendix D The Importance of Shale Gas and Shale Oil 775

Index 779

CONTENTS xxi

PREFACE

This third edition of Industrial Organic Chemicals is prompted by the impact of

globalization and of threats to the environment This is not to say that industrial

chemistry has stood still ndash very much the reverse and we have featured much new

chemistry All the same our earlier books were about the exciting new world of

petrochemical feedstocks and the ingenious new products that could be made

from them In this edition the exciting new processes have become the dull

traditional ones Well-established processes of technology transfer have carried

them to developing countries especially those that produce petrochemical feed-

stocks In addition humankindrsquos activities are seen both as depleting the resources

of the planet and of polluting it to the point at which humankind will drown in its

own effluvia The extent of these threats is hotly contested nonetheless the

chemical industry both contributes to the problems and is instrumental in trying to

solve them

There have been many developments since the second edition and the following

topics have gained especially in significance

The world chemical industry has migrated from the United States Western

Europe and Japan to theMiddle East and to Asia-Pacific especially ChinaWill

shale oil and gas bring it back (See Appendix D)

There is increased emphasis on environmental issues with pressure on com-

panies to clean up polluting processes or replace them with environmentally

friendly ones

Globalization has changed patterns of transportation of chemicals with for

example solid polymers rather than petrochemical feedstocks being shipped

from the Middle East

The discovery of vast reserves of shale gas has altered the long-term predictions

of resource depletion in the United States and other countries

Considerations of sustainability and the threat of climate change have prompted

research into processes (including electricity generation) that produce less or no

carbon dioxide or come from renewable resources

We have retained some material that is now largely of historical interest partly

for sentimental reasons but partly because the three authors have watched the

xxiii

meteoric rise of the chemical industry from its early days to its present-day

maturity We think there is a value in our readers observing how technology has

developed and the social technological and economic changes that have brought

it to its present position

HAROLD A WITTCOFF

xxiv PREFACE

PREFACE TO THE FIRST EDITION

In the early 1970s one of us (BGR) wrote a book celebrating the rapid growth of the

adolescent chemical industry The organic chemicals industry at the timewas growing

at four times the rate of the economy It was indicated nonetheless that ldquotrees do not

grow to the skyrdquo In 1980 in another book we both declared the industry to bemiddle-

aged with slow or zero growth In this totally revised and expanded version of our

earlier book we reflect that the industry at any rate in the developedworld is showing

many of the illnesses of late middle-age

The problems have arisen first from the undisciplined building of excess capacity

with consequent fierce competition and low prices Second the entry of numerous

developing countries into the industry has exacerbated the situation (Section 136)

and third there has beenmuch stricter government legislation (Section 137) There is

massive worldwide restructuring and continual shifting of commodity chemical

manufacturing to areas other than the United States Western Europe and Japan

The Middle East and Southeast Asia are the principal new players in the game

Perhaps this trend will continue and the present developed world will in the future

confine itself to themanufacture of specialties but the economic and political forces at

work are more complex than that We hope to be able to discuss their resolution in

another edition in about 10 yearsrsquo time

Meanwhile some things have not changed The organic chemicals industry is still

based on seven basic raw materials all deriving from petroleum and natural gas The

wisdom of teaching about the chemical industry on the basis of these seven building

blocks has been confirmed by the fact that since the publication of our first book one

of us (HAW) has delivered by invitation 300 courses in 28 countries on the

fundamentals of the industry based on this pattern Most of these courses are for

industrial personnel but academia has not been neglected

Furthermore some changes have been positive For example there have been

exciting new processes such as the development of metallocene catalysts (Section

15312) Section 461 describes new methyl methacrylate processes that give a

potentially cheaper product that do not produce ecologically undesirable ammonium

hydrogen sulfate by-product or (in another process) that eliminate the use of

dangerous hydrogen cyanide

In this book our main objective is still to present the technology of the organic

chemicals industry as an organized body of knowledge so that both the neophyte and

the experienced practitioner can see the broad picture Nonetheless we have

expanded its scope to include not only new processes but many apparently less

xxv

important reactions that are significant because they give rise to the more profitable

specialty chemicals The lesser volume chemicals have been clearly delineated as

such and the reader who wishes to see the industry on the basis of its large tonnage

products can omit these sections

We hope this bookwill be useful both to college students who have studied organic

chemistry and to graduates and industrial chemists whowork in or are interested in the

chemical industry Even though much of the chemistry has remained the same the

change in the way the industry looks at its problems provides ample justification for

our offering this edition as a fresh perspective on industrial organic chemicals

xxvi PREFACE TO THE FIRST EDITION

PREFACE TO THE SECOND EDITION

In the preface to the first edition we expressed the hope that we could comment on the

chemical industryrsquos evolution in 10 yearsrsquo time Dramatic changes have motivated us

to compress this time frame There have been unprecedented restructuring severe and

complicated feedstock problems and massive shifts of capacity to developing

countries whose economic and political stability is in doubt Possible terrorist

activity dictates elaborate safety and security procedures and the design of plants

with small inventories is a priority

To increase our cover particularly of the patent literature we have invited Dr

Jeffrey S Plotkin Director of the Process Evaluation and Research Planning program

at Nexant ChemSystems to join us as co-author

xxvii

44 Heavier Oil Fractions 103

45 Steam Cracking and Petroleum Refining Reactions 104

451 Steam Cracking 106

452 Choice of Feedstock 108

453 Economics of Steam Cracking 110

46 Catalytic Cracking 114

47 Mechanisms of Steam and Catalytic Cracking 117

48 Catalytic Reforming 119

49 Oligomerization 122

410 Alkylation 124

411 Hydrotreating and Coking 125

412 Dehydrogenation 126

413 Isomerization 128

414 Metathesis 128

4141 Metathesis Outside the Refinery 129

4142 Mechanism of Metathesis 131

415 Function of the Refinery and the Potential Petroleum

Shortage 133

4151 Unleaded Gasoline and the Clean Air Act 134

416 Separation of Natural Gas 136

417 Oil from Tar Sands 137

Endnotes 137

5 Chemicals and Polymers from Ethylene 139

51 Ethylene Polymers 141

511 Discovery of Low and High Density Polyethylenes 142

512 Low Density Polyethylene 144

513 High Density Polyethylene 146

514 Linear Low Density Polyethylene 147

515 Very High Molecular Weight Polyethylene 148

516 Metallocene Polyethylenes 149

517 Very Low Density Polyethylene 149

518 Bimodal HDPE 149

519 ldquoGreenrdquo Polyethylene 150

CONTENTS ix

52 Ethylene Copolymers 151

521 Chlorosulfonated Polyethylene 151

522 Ethylene-Vinyl Acetate 151

523 Ionomers 152

524 Copolymer from ldquoIncompatiblerdquo Polymer Blends 152

525 EthylenendashPropylene Elastomers 153

526 Polyolefin Elastomers 153

53 Oligomerization 154

531 Dimerization 154

532 Ziegler Oligomerization of Ethylene 155

533 Other Ethylene Oligomerization Technologies 156

534 Shell Higher Olefins Process (SHOP) 158

54 Vinyl Chloride 160

55 Acetaldehyde 165

56 Vinyl Acetate 167

57 Ethylene Oxide 169

571 Ethylene Glycol 171

572 Proposed Non-Ethylene Oxide Processes for

Ethylene Glycol Production 174

58 Styrene 177

59 Ethanol 181

510 Major Chemicals from Ethylene ndash A Summary 182

511 Lesser Volume Chemicals from Ethylene 185

5111 Hydroformylation ndash Propionaldehyde

Propionic Acid and n-Propanol 185

5112 Ethyl Halides 186

5113 Acetaldehyde Chemistry 187

5114 Metal Complexes 191

5115 Ethylenediamine and Related Compounds 191

5116 Ethylene Oxide and Ethylene Glycol Derivatives 193

51161 Oligomers 193

51162 Glycol Ethers and Esters 194

51163 Ethylene Carbonate 197

51164 Aminoethyl Alcohols (Ethanolamines)

and Derivatives 198

51165 Ethyleneimine 199

x CONTENTS

51166 13-Propanediol 200

51167 Ethylene Glycol Derivatives 201

5117 Vinyl Chloride and Ethylene

Dichloride Derivatives 203

5118 Vinyl Fluoride and Vinylidene Fluoride 204

5119 Ethylene Dibromide 205

51110 Ethanol Derivatives 206

51111 Vinyl Esters and Ethers 207

Endnotes 208

6 Chemicals and Polymers from Propylene 211

61 On-Purpose Propylene Production Technologies and Propane

Dehydrogenation 214

611 Propylene Via Enhanced Fluidized

Catalytic Cracking 215

612 Propylene Via Selective C4C5 Cracking 215

62 Main Polymers and Chemicals from Propylene 217

621 Propylene Polymers and Copolymers 217

63 Oligomerization 221

64 Acrylic Acid 222

641 Biorenewable Processes to Acrylic Acid 225

642 Acrylic Acid Markets 226

65 Acrylonitrile 227

651 Uses of Acrylonitrile 230

66 CumenePhenol and Cumene Hydroperoxide 231

67 Acetone and Isopropanol 233

671 Methyl Methacrylate 235

672 Methyl Isobutyl Ketone and Other

Acetone Derivatives 242

68 Propylene Oxide 242

681 Other Propylene Oxide Processes 247

6811 Acetoxylation of Propylene 248

6812 Direct Oxidation 249

6813 Use of Peracids 249

6814 Electrochemical Processes 250

6815 Biotechnological Approaches 252

682 Propylene Oxide Applications 253

CONTENTS xi

69 n-Butyraldehyde and Isobutyraldehyde 255

691 Uses for Butyraldehyde Isobutyraldehyde

and n-Butanol 258

692 Other Oxo Products 260

610 Major Chemicals from Propylene ndash A Perspective 261

611 Lesser Volume Chemicals from Propylene 263

6111 Allyl Chloride and Epichlorohydrin 263

6112 Glycerol 266

6113 Acrylamide 266

6114 Acrolein 268

6115 Acrylonitrile Derivatives 270

Endnotes 270

7 Chemicals from the C4 Stream 273

71 Chemicals and Polymers from Butadiene 277

711 Tires 280

712 StyrenendashButadiene Elastomers 281

713 Polybutadienes and Other Elastomers 282

714 AcrylonitrilendashButadienendashStyrene Resins 283

715 Hexamethylenediamine 284

716 Lesser Volume Chemicals from Butadiene 289

7161 Cyclization 289

7162 Dimerization and Trimerization 291

7163 DielsndashAlder Reactions 293

7164 Adipic Acid 294

7165 14-Butanediol 294

7166 trans-14-Hexadiene 295

7167 Dimethyl-26-naphthalene

Dicarboxylate 295

7168 Butadiene Monoepoxide 296

72 Chemicals and Polymers from Isobutene 296

721 Methyl tert-Butyl Ether 297

722 Butyl Rubber 298

723 Polyisobutenes and Isobutene Oligomers

and Polymers 298

724 tert-Butanol 299

725 Methyl Methacrylate 299

726 Lesser Volume Chemicals from Isobutene 299

xii CONTENTS

73 Chemicals and Polymers from 1- and 2-Butenes 302

74 Chemicals from n-Butane 303

741 Acetic Acid 303

742 Maleic Anhydride 303

743 Succinic Malic Fumaric and Tartaric Acids 306

Endnotes 307

8 Chemicals from the C5 Stream 309

81 Separation of the C5 Stream 311

82 Isoprene 312

821 Natural Rubber 312

822 Vulcanization 313

823 Production of Petrochemical Isoprene 314

824 Applications of Isoprene 317

83 Cyclopentadiene and Dicyclopentadiene 319

84 Pentene-1 and Piperylene 321

Endnotes 321

9 Chemicals from Benzene 323

91 Phenol 326

911 Phenolic Resins 331

912 Bisphenol A 333

9121 Epoxy Resins 333

9122 Polycarbonate Resins 334

9123 Lesser Volume Uses for Bisphenol A 337

9124 Environmental Problems 340

913 Cyclohexanone 341

914 Alkylphenols 342

915 Chlorinated Phenols 342

916 26-XylenolCresols 343

917 Aniline from Phenol 344

92 Cyclohexane 344

921 Adipic Acid 344

9211 Nylons from Adipic Acid 349

922 Caprolactam 349

CONTENTS xiii

93 Aniline 354

931 440-Diphenylmethane Isocyanate 357

94 Alkylbenzenes 361

95 Maleic Anhydride 362

96 Chlorinated Benzenes 363

97 Dihydroxybenzenes 364

971 Hydroquinone 364

972 Resorcinol 368

973 Catechol 369

98 Anthraquinone 370

981 Hydrogen Peroxide 371

Endnotes 372

10 Chemicals from Toluene 375

101 Hydrodealkylation Disproportionation and Transalkylation 375

102 Solvents 378

103 Dinitrotoluene and Toluene Diisocyanate 378

104 Lesser Volume Chemicals from Toluene 380

Endnotes 382

11 Chemicals from Xylenes 383

111 o-Xylene and Phthalic Anhydride 386

1111 Plasticizers 387

1112 Alkyd Resins 391

1113 Unsaturated Polyester Resin 393

112 m-Xylene and Isophthalic Acid 395

1121 Uses of Isophthalic Acid 396

113 p-Xylene and Terephthalic AcidDimethyl Terephthalate 397

1131 Oxidation of p-Xylene 398

1132 Alternate Sources for Terephthalic Acid 400

1133 Poly(ethylene terephthalate) 400

1134 Lower Volume Polymers from Terephthalic Acid 403

Endnotes 404

xiv CONTENTS

12 Chemicals from Methane 407

121 Hydrocyanic Acid 408

122 Halogenated Methanes 411

1221 Chloromethane 412

1222 Dichloromethane 413

1223 Trichloromethane 413

1224 Fluorocarbons 414

1225 Tetrachloromethane and Carbon Disulfide 414

1226 Bromomethane 416

123 Acetylene 417

1231 14-Butanediol and 2-Methyl-13-propanediol 419

1232 Lesser Uses for Acetylene 423

124 Synthesis Gas 424

1241 Steam Reforming of Methane 425

1242 Variants of Steam Reforming 427

1243 Partial Oxidation of Hydrocarbons 428

1244 Solid Feedstocks 428

1245 Hydrogen 429

125 Chemicals from Synthesis Gas 429

1251 Ammonia and Its Derivatives 430

12511 The Crisis of Nitrogen Depletion 430

12512 Ammonia Manufacture 431

12513 Urea and Melamine Resins 434

1252 Methanol 435

12521 Formaldehyde 438

12522 Acetic Acid 439

12523 Acetic Anhydride 442

12524 Methanol to Gasoline 445

12525 Methanol to Olefins 446

12526 Lower Volume and Proposed Uses for Methanol 448

12527 C1-Based Development Processes 452

126 Carbon Monoxide Chemistry 454

1261 Proposed Chemistry Based on Carbon Monoxide 455

127 Gas-to-Liquid Fuels 459

1271 Sasol GTL Technology 459

1272 Shell Middle Distillate Synthesis 459

CONTENTS xv

1273 Other GTL Technologies 460

Endnotes 460

13 Chemicals from Alkanes 463

131 Functionalization of Methane 464

1311 Methane to MethanolFormaldehyde 464

1312 Dimerization of Methane 466

1313 Aromatization of Methane 467

132 Functionalization of C2ndashC4 Alkanes 468

1321 Oxidation of C2ndashC4 Alkanes 468

1322 Dehydrogenation of C2ndashC4 Alkanes 470

1323 Aromatization of C2ndashC4Alkanes 471

133 Carbon Black 472

Endnotes 473

14 Chemicals from Coal 475

141 Chemicals from Coke Oven Distillate 477

142 The FischerndashTropsch Reaction 480

143 Coal Hydrogenation 484

144 Substitute Natural Gas 485

145 SNG and Synthesis Gas Technology 485

146 Underground Coal Gasification 488

147 Calcium Carbide 488

1471 The Chinese Chemicals to Coal Program 489

148 Coal and the Environment 490

Endnotes 491

15 Fats and Oils 493

151 Markets for Fats and Oils 495

152 Purification of Fats and Oils 497

153 Fatty Acids 499

1531 Applications of Fatty Acids 501

154 Fatty Nitrogen Compounds 502

155 ldquoDimerrdquo Acid 504

xvi CONTENTS

156 Aminoamides and Imidazolines 506

157 Azelaic Pelargonic and Petroselinic Acids 507

158 Fatty Alcohols 508

159 Epoxidized Oils 509

1510 Ricinoleic Acid 510

1511 Glycerol 512

15111 Established Glycerol Uses 512

1512 Alcoholysis of Fats and Oils 513

15121 Cocoa Butter and Mothersrsquo Milk 513

151211 Mothersrsquo Milk 515

15122 Trans Fats and Interesterification 515

15123 Biodiesel and Lubricants 516

151231 Algae 518

1513 Alkyl Polyglycosides 519

1514 Non-Caloric Fat-like Substances 519

Endnotes 520

16 Carbohydrates 523

161 Sugars and Sorbitol 523

1611 Isosorbide 530

162 Furfural 530

163 Starch 532

164 Cellulose 535

1641 Miscellaneous Chemicals from Wood 539

16411 Vanillin 541

16412 Levulinic Acid 542

165 Gums 543

166 Fermentation and Biotechnology 544

1661 Amino Acids 547

16611 L-Glutamic Acid 547

16612 L-Lysine 547

16613 L-Aspartic Acid 548

16614 L-Cysteine 549

1662 Polymers 550

CONTENTS xvii

1663 Proteins by Recombinant DNA Technology 550

1664 Fermentation and Renewables Scenarios 551

1665 Biofuels 554

16651 The Brazilian Experience 554

16652 Is US Bioethanol a Renewable

Energy Source 555

16653 Biomass as Feedstock 556

16654 Catalytic Bioforming 556

16655 Biotechnology Versus Synthesis Gas 557

Endnotes 558

17 How Polymers Are Made 561

171 Polymerization 565

172 Functionality 568

173 Step Growth and Chain Growth Polymerizations 571

1731 Free Radical Polymerization 573

1732 Chain Transfer 575

1733 Copolymerization 577

1734 Molecular Weight 579

1735 Polymerization Procedures 580

17351 Photoinitiation 582

1736 Ionic Polymerization 584

1737 Living Polymers 589

1738 Block Copolymers 589

1739 Graft Copolymers 592

17310 Metal Complex Catalysts 593

17311 Metal Oxide Catalysts 598

17312 Metallocene and Other Single Site Catalysts 599

173121 Single Site Nonmetallocene Catalysts 602

173122 Late Transition Metal Catalysts 603

173123 Commercial Prospects of LLDPEs 604

174 Examples of Step Polymerization 605

1741 Phenoplasts and Aminoplasts 605

1742 Polyurethanes 606

1743 Epoxy Resins 611

1744 Dendritic and Hyperbranched Polymers 613

1745 Conducting Polymers 617

1746 Conducting and Semiconducting Inks 621

xviii CONTENTS

175 Polymer Properties 622

1751 Crystallinity 622

1752 Glass Transition Temperature Crystalline

Melting Point and Softening Temperature 626

1753 Molecular Cohesion 628

1754 StressndashStrain Diagrams 628

176 Classes of Polymers 630

177 Plastics Fabrication Techniques 631

Endnotes 635

18 Industrial Catalysis 637

181 Catalyst Choice 637

1811 Reaction Velocity and Selectivity 638

1812 Recovery of Unchanged Catalyst 641

1813 Catalyst Deactivation 642

1814 Access to Nonequilibrium Products 642

182 Homogeneous and Heterogeneous Catalysis 643

1821 Reactors for Heterogeneous Catalysts 644

1822 Immobilization of Homogeneous Catalysts 646

183 Catalyst Markets 647

184 Catalysis by Acids and Bases 651

185 Dual Function Catalysis 654

186 Catalysis by Metals Semiconductors and Insulators 655

1861 Catalysts for Automobile Emission Control 656

187 Coordination Catalysis 657

1871 Catalysts for Stereoregular Compounds 658

1872 Asymmetric Synthesis 660

188 Enzymes 661

1881 Catalytic Antibodies 663

189 Shape-Selective Catalysts 664

1810 Phase-Transfer and Fluorous Biphase Catalysis 669

1811 Nanocatalysis 670

1812 Catalysts of the Future 673

18121 Catalyst Design 673

18122 Higher Selectivities 673

CONTENTS xix

18123 Catalysts with Greater Activity 674

18124 Pollution Problems 675

18125 Catalysts for New Reactions 675

18126 Catalysts that Mimic Natural Catalysts 676

18127 Catalyst Discovery Via High Throughput

Experimentation 676

Endnotes 677

19 Green Chemistry 681

191 The Decline of Acetylene Chemistry 683

192 Nylon 683

193 Replacement of Phosgene 684

194 Monomethylation by Dimethyl Carbonate 685

195 Liquid and Supercritical Carbon Dioxide and Water 685

196 Ionic Liquids 687

197 Photocatalysts 690

198 Paired Electrosynthesis 691

199 ldquoGreenrdquo Pharmaceuticals 692

1991 Ibuprofen 692

1992 Sertraline 694

1993 Pharmaceuticals from ldquoRenewablesrdquo 696

1910 Catalytic Dehydrogenation of Diethanolamine 698

1911 Genetic Manipulation 698

1912 Biodegradable Packaging 698

19121 Polyhydroxyalkanoates 701

1913 The Presidential Green Chemistry Challenge Program 703

Endnotes 704

20 Sustainability 707

201 Climate Change 708

202 Resource Depletion 712

2021 Food Water and People 713

20211 Food 713

20212 Water 714

20213 People 715

xx CONTENTS

203 Energy Sources 717

2031 Wind Power 719

2032 Wave Power 720

2033 Solar Power 721

20331 Concentrated Solar Power 721

20332 Photovoltaic Cells 721

20333 Dye-Sensitized Solar Cells 722

20334 Artificial Photosynthesis 724

2034 Nuclear Energy 726

2035 Methane Hydrate 727

2036 The Hydrogen Economy 728

2037 Fuel Cells 729

2038 Electric Vehicles 735

204 Pollution 736

2041 The Ozone Layer 738

2042 Trace Chemicals 742

20421 Pesticides 742

20422 Nonpesticide Lipophiles 743

2043 Air Pollution 744

20431 Sulfur Dioxide Particulates 745

20432 Automobile Exhaust Emissions 748

2044 Water Treatment 750

2045 Solid Wastes 752

20451 Waste Prevention 753

20452 Recycling 754

20453 CombustionIncineration 755

20454 Sanitary Landfill 756

2046 Petrochemical Industry Wastes 758

2047 Other Environmental Problems 759

205 Valediction 759

Endnotes 761

Appendix A A Note on Cost Calculations 765

Appendix B Units and Conversion Factors 771

Appendix C Special Units in the Chemical Industry 773

Appendix D The Importance of Shale Gas and Shale Oil 775

Index 779

CONTENTS xxi

PREFACE

This third edition of Industrial Organic Chemicals is prompted by the impact of

globalization and of threats to the environment This is not to say that industrial

chemistry has stood still ndash very much the reverse and we have featured much new

chemistry All the same our earlier books were about the exciting new world of

petrochemical feedstocks and the ingenious new products that could be made

from them In this edition the exciting new processes have become the dull

traditional ones Well-established processes of technology transfer have carried

them to developing countries especially those that produce petrochemical feed-

stocks In addition humankindrsquos activities are seen both as depleting the resources

of the planet and of polluting it to the point at which humankind will drown in its

own effluvia The extent of these threats is hotly contested nonetheless the

chemical industry both contributes to the problems and is instrumental in trying to

solve them

There have been many developments since the second edition and the following

topics have gained especially in significance

The world chemical industry has migrated from the United States Western

Europe and Japan to theMiddle East and to Asia-Pacific especially ChinaWill

shale oil and gas bring it back (See Appendix D)

There is increased emphasis on environmental issues with pressure on com-

panies to clean up polluting processes or replace them with environmentally

friendly ones

Globalization has changed patterns of transportation of chemicals with for

example solid polymers rather than petrochemical feedstocks being shipped

from the Middle East

The discovery of vast reserves of shale gas has altered the long-term predictions

of resource depletion in the United States and other countries

Considerations of sustainability and the threat of climate change have prompted

research into processes (including electricity generation) that produce less or no

carbon dioxide or come from renewable resources

We have retained some material that is now largely of historical interest partly

for sentimental reasons but partly because the three authors have watched the

xxiii

meteoric rise of the chemical industry from its early days to its present-day

maturity We think there is a value in our readers observing how technology has

developed and the social technological and economic changes that have brought

it to its present position

HAROLD A WITTCOFF

xxiv PREFACE

PREFACE TO THE FIRST EDITION

In the early 1970s one of us (BGR) wrote a book celebrating the rapid growth of the

adolescent chemical industry The organic chemicals industry at the timewas growing

at four times the rate of the economy It was indicated nonetheless that ldquotrees do not

grow to the skyrdquo In 1980 in another book we both declared the industry to bemiddle-

aged with slow or zero growth In this totally revised and expanded version of our

earlier book we reflect that the industry at any rate in the developedworld is showing

many of the illnesses of late middle-age

The problems have arisen first from the undisciplined building of excess capacity

with consequent fierce competition and low prices Second the entry of numerous

developing countries into the industry has exacerbated the situation (Section 136)

and third there has beenmuch stricter government legislation (Section 137) There is

massive worldwide restructuring and continual shifting of commodity chemical

manufacturing to areas other than the United States Western Europe and Japan

The Middle East and Southeast Asia are the principal new players in the game

Perhaps this trend will continue and the present developed world will in the future

confine itself to themanufacture of specialties but the economic and political forces at

work are more complex than that We hope to be able to discuss their resolution in

another edition in about 10 yearsrsquo time

Meanwhile some things have not changed The organic chemicals industry is still

based on seven basic raw materials all deriving from petroleum and natural gas The

wisdom of teaching about the chemical industry on the basis of these seven building

blocks has been confirmed by the fact that since the publication of our first book one

of us (HAW) has delivered by invitation 300 courses in 28 countries on the

fundamentals of the industry based on this pattern Most of these courses are for

industrial personnel but academia has not been neglected

Furthermore some changes have been positive For example there have been

exciting new processes such as the development of metallocene catalysts (Section

15312) Section 461 describes new methyl methacrylate processes that give a

potentially cheaper product that do not produce ecologically undesirable ammonium

hydrogen sulfate by-product or (in another process) that eliminate the use of

dangerous hydrogen cyanide

In this book our main objective is still to present the technology of the organic

chemicals industry as an organized body of knowledge so that both the neophyte and

the experienced practitioner can see the broad picture Nonetheless we have

expanded its scope to include not only new processes but many apparently less

xxv

important reactions that are significant because they give rise to the more profitable

specialty chemicals The lesser volume chemicals have been clearly delineated as

such and the reader who wishes to see the industry on the basis of its large tonnage

products can omit these sections

We hope this bookwill be useful both to college students who have studied organic

chemistry and to graduates and industrial chemists whowork in or are interested in the

chemical industry Even though much of the chemistry has remained the same the

change in the way the industry looks at its problems provides ample justification for

our offering this edition as a fresh perspective on industrial organic chemicals

xxvi PREFACE TO THE FIRST EDITION

PREFACE TO THE SECOND EDITION

In the preface to the first edition we expressed the hope that we could comment on the

chemical industryrsquos evolution in 10 yearsrsquo time Dramatic changes have motivated us

to compress this time frame There have been unprecedented restructuring severe and

complicated feedstock problems and massive shifts of capacity to developing

countries whose economic and political stability is in doubt Possible terrorist

activity dictates elaborate safety and security procedures and the design of plants

with small inventories is a priority

To increase our cover particularly of the patent literature we have invited Dr

Jeffrey S Plotkin Director of the Process Evaluation and Research Planning program

at Nexant ChemSystems to join us as co-author

xxvii

52 Ethylene Copolymers 151

521 Chlorosulfonated Polyethylene 151

522 Ethylene-Vinyl Acetate 151

523 Ionomers 152

524 Copolymer from ldquoIncompatiblerdquo Polymer Blends 152

525 EthylenendashPropylene Elastomers 153

526 Polyolefin Elastomers 153

53 Oligomerization 154

531 Dimerization 154

532 Ziegler Oligomerization of Ethylene 155

533 Other Ethylene Oligomerization Technologies 156

534 Shell Higher Olefins Process (SHOP) 158

54 Vinyl Chloride 160

55 Acetaldehyde 165

56 Vinyl Acetate 167

57 Ethylene Oxide 169

571 Ethylene Glycol 171

572 Proposed Non-Ethylene Oxide Processes for

Ethylene Glycol Production 174

58 Styrene 177

59 Ethanol 181

510 Major Chemicals from Ethylene ndash A Summary 182

511 Lesser Volume Chemicals from Ethylene 185

5111 Hydroformylation ndash Propionaldehyde

Propionic Acid and n-Propanol 185

5112 Ethyl Halides 186

5113 Acetaldehyde Chemistry 187

5114 Metal Complexes 191

5115 Ethylenediamine and Related Compounds 191

5116 Ethylene Oxide and Ethylene Glycol Derivatives 193

51161 Oligomers 193

51162 Glycol Ethers and Esters 194

51163 Ethylene Carbonate 197

51164 Aminoethyl Alcohols (Ethanolamines)

and Derivatives 198

51165 Ethyleneimine 199

x CONTENTS

51166 13-Propanediol 200

51167 Ethylene Glycol Derivatives 201

5117 Vinyl Chloride and Ethylene

Dichloride Derivatives 203

5118 Vinyl Fluoride and Vinylidene Fluoride 204

5119 Ethylene Dibromide 205

51110 Ethanol Derivatives 206

51111 Vinyl Esters and Ethers 207

Endnotes 208

6 Chemicals and Polymers from Propylene 211

61 On-Purpose Propylene Production Technologies and Propane

Dehydrogenation 214

611 Propylene Via Enhanced Fluidized

Catalytic Cracking 215

612 Propylene Via Selective C4C5 Cracking 215

62 Main Polymers and Chemicals from Propylene 217

621 Propylene Polymers and Copolymers 217

63 Oligomerization 221

64 Acrylic Acid 222

641 Biorenewable Processes to Acrylic Acid 225

642 Acrylic Acid Markets 226

65 Acrylonitrile 227

651 Uses of Acrylonitrile 230

66 CumenePhenol and Cumene Hydroperoxide 231

67 Acetone and Isopropanol 233

671 Methyl Methacrylate 235

672 Methyl Isobutyl Ketone and Other

Acetone Derivatives 242

68 Propylene Oxide 242

681 Other Propylene Oxide Processes 247

6811 Acetoxylation of Propylene 248

6812 Direct Oxidation 249

6813 Use of Peracids 249

6814 Electrochemical Processes 250

6815 Biotechnological Approaches 252

682 Propylene Oxide Applications 253

CONTENTS xi

69 n-Butyraldehyde and Isobutyraldehyde 255

691 Uses for Butyraldehyde Isobutyraldehyde

and n-Butanol 258

692 Other Oxo Products 260

610 Major Chemicals from Propylene ndash A Perspective 261

611 Lesser Volume Chemicals from Propylene 263

6111 Allyl Chloride and Epichlorohydrin 263

6112 Glycerol 266

6113 Acrylamide 266

6114 Acrolein 268

6115 Acrylonitrile Derivatives 270

Endnotes 270

7 Chemicals from the C4 Stream 273

71 Chemicals and Polymers from Butadiene 277

711 Tires 280

712 StyrenendashButadiene Elastomers 281

713 Polybutadienes and Other Elastomers 282

714 AcrylonitrilendashButadienendashStyrene Resins 283

715 Hexamethylenediamine 284

716 Lesser Volume Chemicals from Butadiene 289

7161 Cyclization 289

7162 Dimerization and Trimerization 291

7163 DielsndashAlder Reactions 293

7164 Adipic Acid 294

7165 14-Butanediol 294

7166 trans-14-Hexadiene 295

7167 Dimethyl-26-naphthalene

Dicarboxylate 295

7168 Butadiene Monoepoxide 296

72 Chemicals and Polymers from Isobutene 296

721 Methyl tert-Butyl Ether 297

722 Butyl Rubber 298

723 Polyisobutenes and Isobutene Oligomers

and Polymers 298

724 tert-Butanol 299

725 Methyl Methacrylate 299

726 Lesser Volume Chemicals from Isobutene 299

xii CONTENTS

73 Chemicals and Polymers from 1- and 2-Butenes 302

74 Chemicals from n-Butane 303

741 Acetic Acid 303

742 Maleic Anhydride 303

743 Succinic Malic Fumaric and Tartaric Acids 306

Endnotes 307

8 Chemicals from the C5 Stream 309

81 Separation of the C5 Stream 311

82 Isoprene 312

821 Natural Rubber 312

822 Vulcanization 313

823 Production of Petrochemical Isoprene 314

824 Applications of Isoprene 317

83 Cyclopentadiene and Dicyclopentadiene 319

84 Pentene-1 and Piperylene 321

Endnotes 321

9 Chemicals from Benzene 323

91 Phenol 326

911 Phenolic Resins 331

912 Bisphenol A 333

9121 Epoxy Resins 333

9122 Polycarbonate Resins 334

9123 Lesser Volume Uses for Bisphenol A 337

9124 Environmental Problems 340

913 Cyclohexanone 341

914 Alkylphenols 342

915 Chlorinated Phenols 342

916 26-XylenolCresols 343

917 Aniline from Phenol 344

92 Cyclohexane 344

921 Adipic Acid 344

9211 Nylons from Adipic Acid 349

922 Caprolactam 349

CONTENTS xiii

93 Aniline 354

931 440-Diphenylmethane Isocyanate 357

94 Alkylbenzenes 361

95 Maleic Anhydride 362

96 Chlorinated Benzenes 363

97 Dihydroxybenzenes 364

971 Hydroquinone 364

972 Resorcinol 368

973 Catechol 369

98 Anthraquinone 370

981 Hydrogen Peroxide 371

Endnotes 372

10 Chemicals from Toluene 375

101 Hydrodealkylation Disproportionation and Transalkylation 375

102 Solvents 378

103 Dinitrotoluene and Toluene Diisocyanate 378

104 Lesser Volume Chemicals from Toluene 380

Endnotes 382

11 Chemicals from Xylenes 383

111 o-Xylene and Phthalic Anhydride 386

1111 Plasticizers 387

1112 Alkyd Resins 391

1113 Unsaturated Polyester Resin 393

112 m-Xylene and Isophthalic Acid 395

1121 Uses of Isophthalic Acid 396

113 p-Xylene and Terephthalic AcidDimethyl Terephthalate 397

1131 Oxidation of p-Xylene 398

1132 Alternate Sources for Terephthalic Acid 400

1133 Poly(ethylene terephthalate) 400

1134 Lower Volume Polymers from Terephthalic Acid 403

Endnotes 404

xiv CONTENTS

12 Chemicals from Methane 407

121 Hydrocyanic Acid 408

122 Halogenated Methanes 411

1221 Chloromethane 412

1222 Dichloromethane 413

1223 Trichloromethane 413

1224 Fluorocarbons 414

1225 Tetrachloromethane and Carbon Disulfide 414

1226 Bromomethane 416

123 Acetylene 417

1231 14-Butanediol and 2-Methyl-13-propanediol 419

1232 Lesser Uses for Acetylene 423

124 Synthesis Gas 424

1241 Steam Reforming of Methane 425

1242 Variants of Steam Reforming 427

1243 Partial Oxidation of Hydrocarbons 428

1244 Solid Feedstocks 428

1245 Hydrogen 429

125 Chemicals from Synthesis Gas 429

1251 Ammonia and Its Derivatives 430

12511 The Crisis of Nitrogen Depletion 430

12512 Ammonia Manufacture 431

12513 Urea and Melamine Resins 434

1252 Methanol 435

12521 Formaldehyde 438

12522 Acetic Acid 439

12523 Acetic Anhydride 442

12524 Methanol to Gasoline 445

12525 Methanol to Olefins 446

12526 Lower Volume and Proposed Uses for Methanol 448

12527 C1-Based Development Processes 452

126 Carbon Monoxide Chemistry 454

1261 Proposed Chemistry Based on Carbon Monoxide 455

127 Gas-to-Liquid Fuels 459

1271 Sasol GTL Technology 459

1272 Shell Middle Distillate Synthesis 459

CONTENTS xv

1273 Other GTL Technologies 460

Endnotes 460

13 Chemicals from Alkanes 463

131 Functionalization of Methane 464

1311 Methane to MethanolFormaldehyde 464

1312 Dimerization of Methane 466

1313 Aromatization of Methane 467

132 Functionalization of C2ndashC4 Alkanes 468

1321 Oxidation of C2ndashC4 Alkanes 468

1322 Dehydrogenation of C2ndashC4 Alkanes 470

1323 Aromatization of C2ndashC4Alkanes 471

133 Carbon Black 472

Endnotes 473

14 Chemicals from Coal 475

141 Chemicals from Coke Oven Distillate 477

142 The FischerndashTropsch Reaction 480

143 Coal Hydrogenation 484

144 Substitute Natural Gas 485

145 SNG and Synthesis Gas Technology 485

146 Underground Coal Gasification 488

147 Calcium Carbide 488

1471 The Chinese Chemicals to Coal Program 489

148 Coal and the Environment 490

Endnotes 491

15 Fats and Oils 493

151 Markets for Fats and Oils 495

152 Purification of Fats and Oils 497

153 Fatty Acids 499

1531 Applications of Fatty Acids 501

154 Fatty Nitrogen Compounds 502

155 ldquoDimerrdquo Acid 504

xvi CONTENTS

156 Aminoamides and Imidazolines 506

157 Azelaic Pelargonic and Petroselinic Acids 507

158 Fatty Alcohols 508

159 Epoxidized Oils 509

1510 Ricinoleic Acid 510

1511 Glycerol 512

15111 Established Glycerol Uses 512

1512 Alcoholysis of Fats and Oils 513

15121 Cocoa Butter and Mothersrsquo Milk 513

151211 Mothersrsquo Milk 515

15122 Trans Fats and Interesterification 515

15123 Biodiesel and Lubricants 516

151231 Algae 518

1513 Alkyl Polyglycosides 519

1514 Non-Caloric Fat-like Substances 519

Endnotes 520

16 Carbohydrates 523

161 Sugars and Sorbitol 523

1611 Isosorbide 530

162 Furfural 530

163 Starch 532

164 Cellulose 535

1641 Miscellaneous Chemicals from Wood 539

16411 Vanillin 541

16412 Levulinic Acid 542

165 Gums 543

166 Fermentation and Biotechnology 544

1661 Amino Acids 547

16611 L-Glutamic Acid 547

16612 L-Lysine 547

16613 L-Aspartic Acid 548

16614 L-Cysteine 549

1662 Polymers 550

CONTENTS xvii

1663 Proteins by Recombinant DNA Technology 550

1664 Fermentation and Renewables Scenarios 551

1665 Biofuels 554

16651 The Brazilian Experience 554

16652 Is US Bioethanol a Renewable

Energy Source 555

16653 Biomass as Feedstock 556

16654 Catalytic Bioforming 556

16655 Biotechnology Versus Synthesis Gas 557

Endnotes 558

17 How Polymers Are Made 561

171 Polymerization 565

172 Functionality 568

173 Step Growth and Chain Growth Polymerizations 571

1731 Free Radical Polymerization 573

1732 Chain Transfer 575

1733 Copolymerization 577

1734 Molecular Weight 579

1735 Polymerization Procedures 580

17351 Photoinitiation 582

1736 Ionic Polymerization 584

1737 Living Polymers 589

1738 Block Copolymers 589

1739 Graft Copolymers 592

17310 Metal Complex Catalysts 593

17311 Metal Oxide Catalysts 598

17312 Metallocene and Other Single Site Catalysts 599

173121 Single Site Nonmetallocene Catalysts 602

173122 Late Transition Metal Catalysts 603

173123 Commercial Prospects of LLDPEs 604

174 Examples of Step Polymerization 605

1741 Phenoplasts and Aminoplasts 605

1742 Polyurethanes 606

1743 Epoxy Resins 611

1744 Dendritic and Hyperbranched Polymers 613

1745 Conducting Polymers 617

1746 Conducting and Semiconducting Inks 621

xviii CONTENTS

175 Polymer Properties 622

1751 Crystallinity 622

1752 Glass Transition Temperature Crystalline

Melting Point and Softening Temperature 626

1753 Molecular Cohesion 628

1754 StressndashStrain Diagrams 628

176 Classes of Polymers 630

177 Plastics Fabrication Techniques 631

Endnotes 635

18 Industrial Catalysis 637

181 Catalyst Choice 637

1811 Reaction Velocity and Selectivity 638

1812 Recovery of Unchanged Catalyst 641

1813 Catalyst Deactivation 642

1814 Access to Nonequilibrium Products 642

182 Homogeneous and Heterogeneous Catalysis 643

1821 Reactors for Heterogeneous Catalysts 644

1822 Immobilization of Homogeneous Catalysts 646

183 Catalyst Markets 647

184 Catalysis by Acids and Bases 651

185 Dual Function Catalysis 654

186 Catalysis by Metals Semiconductors and Insulators 655

1861 Catalysts for Automobile Emission Control 656

187 Coordination Catalysis 657

1871 Catalysts for Stereoregular Compounds 658

1872 Asymmetric Synthesis 660

188 Enzymes 661

1881 Catalytic Antibodies 663

189 Shape-Selective Catalysts 664

1810 Phase-Transfer and Fluorous Biphase Catalysis 669

1811 Nanocatalysis 670

1812 Catalysts of the Future 673

18121 Catalyst Design 673

18122 Higher Selectivities 673

CONTENTS xix

18123 Catalysts with Greater Activity 674

18124 Pollution Problems 675

18125 Catalysts for New Reactions 675

18126 Catalysts that Mimic Natural Catalysts 676

18127 Catalyst Discovery Via High Throughput

Experimentation 676

Endnotes 677

19 Green Chemistry 681

191 The Decline of Acetylene Chemistry 683

192 Nylon 683

193 Replacement of Phosgene 684

194 Monomethylation by Dimethyl Carbonate 685

195 Liquid and Supercritical Carbon Dioxide and Water 685

196 Ionic Liquids 687

197 Photocatalysts 690

198 Paired Electrosynthesis 691

199 ldquoGreenrdquo Pharmaceuticals 692

1991 Ibuprofen 692

1992 Sertraline 694

1993 Pharmaceuticals from ldquoRenewablesrdquo 696

1910 Catalytic Dehydrogenation of Diethanolamine 698

1911 Genetic Manipulation 698

1912 Biodegradable Packaging 698

19121 Polyhydroxyalkanoates 701

1913 The Presidential Green Chemistry Challenge Program 703

Endnotes 704

20 Sustainability 707

201 Climate Change 708

202 Resource Depletion 712

2021 Food Water and People 713

20211 Food 713

20212 Water 714

20213 People 715

xx CONTENTS

203 Energy Sources 717

2031 Wind Power 719

2032 Wave Power 720

2033 Solar Power 721

20331 Concentrated Solar Power 721

20332 Photovoltaic Cells 721

20333 Dye-Sensitized Solar Cells 722

20334 Artificial Photosynthesis 724

2034 Nuclear Energy 726

2035 Methane Hydrate 727

2036 The Hydrogen Economy 728

2037 Fuel Cells 729

2038 Electric Vehicles 735

204 Pollution 736

2041 The Ozone Layer 738

2042 Trace Chemicals 742

20421 Pesticides 742

20422 Nonpesticide Lipophiles 743

2043 Air Pollution 744

20431 Sulfur Dioxide Particulates 745

20432 Automobile Exhaust Emissions 748

2044 Water Treatment 750

2045 Solid Wastes 752

20451 Waste Prevention 753

20452 Recycling 754

20453 CombustionIncineration 755

20454 Sanitary Landfill 756

2046 Petrochemical Industry Wastes 758

2047 Other Environmental Problems 759

205 Valediction 759

Endnotes 761

Appendix A A Note on Cost Calculations 765

Appendix B Units and Conversion Factors 771

Appendix C Special Units in the Chemical Industry 773

Appendix D The Importance of Shale Gas and Shale Oil 775

Index 779

CONTENTS xxi

PREFACE

This third edition of Industrial Organic Chemicals is prompted by the impact of

globalization and of threats to the environment This is not to say that industrial

chemistry has stood still ndash very much the reverse and we have featured much new

chemistry All the same our earlier books were about the exciting new world of

petrochemical feedstocks and the ingenious new products that could be made

from them In this edition the exciting new processes have become the dull

traditional ones Well-established processes of technology transfer have carried

them to developing countries especially those that produce petrochemical feed-

stocks In addition humankindrsquos activities are seen both as depleting the resources

of the planet and of polluting it to the point at which humankind will drown in its

own effluvia The extent of these threats is hotly contested nonetheless the

chemical industry both contributes to the problems and is instrumental in trying to

solve them

There have been many developments since the second edition and the following

topics have gained especially in significance

The world chemical industry has migrated from the United States Western

Europe and Japan to theMiddle East and to Asia-Pacific especially ChinaWill

shale oil and gas bring it back (See Appendix D)

There is increased emphasis on environmental issues with pressure on com-

panies to clean up polluting processes or replace them with environmentally

friendly ones

Globalization has changed patterns of transportation of chemicals with for

example solid polymers rather than petrochemical feedstocks being shipped

from the Middle East

The discovery of vast reserves of shale gas has altered the long-term predictions

of resource depletion in the United States and other countries

Considerations of sustainability and the threat of climate change have prompted

research into processes (including electricity generation) that produce less or no

carbon dioxide or come from renewable resources

We have retained some material that is now largely of historical interest partly

for sentimental reasons but partly because the three authors have watched the

xxiii

meteoric rise of the chemical industry from its early days to its present-day

maturity We think there is a value in our readers observing how technology has

developed and the social technological and economic changes that have brought

it to its present position

HAROLD A WITTCOFF

xxiv PREFACE

PREFACE TO THE FIRST EDITION

In the early 1970s one of us (BGR) wrote a book celebrating the rapid growth of the

adolescent chemical industry The organic chemicals industry at the timewas growing

at four times the rate of the economy It was indicated nonetheless that ldquotrees do not

grow to the skyrdquo In 1980 in another book we both declared the industry to bemiddle-

aged with slow or zero growth In this totally revised and expanded version of our

earlier book we reflect that the industry at any rate in the developedworld is showing

many of the illnesses of late middle-age

The problems have arisen first from the undisciplined building of excess capacity

with consequent fierce competition and low prices Second the entry of numerous

developing countries into the industry has exacerbated the situation (Section 136)

and third there has beenmuch stricter government legislation (Section 137) There is

massive worldwide restructuring and continual shifting of commodity chemical

manufacturing to areas other than the United States Western Europe and Japan

The Middle East and Southeast Asia are the principal new players in the game

Perhaps this trend will continue and the present developed world will in the future

confine itself to themanufacture of specialties but the economic and political forces at

work are more complex than that We hope to be able to discuss their resolution in

another edition in about 10 yearsrsquo time

Meanwhile some things have not changed The organic chemicals industry is still

based on seven basic raw materials all deriving from petroleum and natural gas The

wisdom of teaching about the chemical industry on the basis of these seven building

blocks has been confirmed by the fact that since the publication of our first book one

of us (HAW) has delivered by invitation 300 courses in 28 countries on the

fundamentals of the industry based on this pattern Most of these courses are for

industrial personnel but academia has not been neglected

Furthermore some changes have been positive For example there have been

exciting new processes such as the development of metallocene catalysts (Section

15312) Section 461 describes new methyl methacrylate processes that give a

potentially cheaper product that do not produce ecologically undesirable ammonium

hydrogen sulfate by-product or (in another process) that eliminate the use of

dangerous hydrogen cyanide

In this book our main objective is still to present the technology of the organic

chemicals industry as an organized body of knowledge so that both the neophyte and

the experienced practitioner can see the broad picture Nonetheless we have

expanded its scope to include not only new processes but many apparently less

xxv

important reactions that are significant because they give rise to the more profitable

specialty chemicals The lesser volume chemicals have been clearly delineated as

such and the reader who wishes to see the industry on the basis of its large tonnage

products can omit these sections

We hope this bookwill be useful both to college students who have studied organic

chemistry and to graduates and industrial chemists whowork in or are interested in the

chemical industry Even though much of the chemistry has remained the same the

change in the way the industry looks at its problems provides ample justification for

our offering this edition as a fresh perspective on industrial organic chemicals

xxvi PREFACE TO THE FIRST EDITION

PREFACE TO THE SECOND EDITION

In the preface to the first edition we expressed the hope that we could comment on the

chemical industryrsquos evolution in 10 yearsrsquo time Dramatic changes have motivated us

to compress this time frame There have been unprecedented restructuring severe and

complicated feedstock problems and massive shifts of capacity to developing

countries whose economic and political stability is in doubt Possible terrorist

activity dictates elaborate safety and security procedures and the design of plants

with small inventories is a priority

To increase our cover particularly of the patent literature we have invited Dr

Jeffrey S Plotkin Director of the Process Evaluation and Research Planning program

at Nexant ChemSystems to join us as co-author

xxvii

51166 13-Propanediol 200

51167 Ethylene Glycol Derivatives 201

5117 Vinyl Chloride and Ethylene

Dichloride Derivatives 203

5118 Vinyl Fluoride and Vinylidene Fluoride 204

5119 Ethylene Dibromide 205

51110 Ethanol Derivatives 206

51111 Vinyl Esters and Ethers 207

Endnotes 208

6 Chemicals and Polymers from Propylene 211

61 On-Purpose Propylene Production Technologies and Propane

Dehydrogenation 214

611 Propylene Via Enhanced Fluidized

Catalytic Cracking 215

612 Propylene Via Selective C4C5 Cracking 215

62 Main Polymers and Chemicals from Propylene 217

621 Propylene Polymers and Copolymers 217

63 Oligomerization 221

64 Acrylic Acid 222

641 Biorenewable Processes to Acrylic Acid 225

642 Acrylic Acid Markets 226

65 Acrylonitrile 227

651 Uses of Acrylonitrile 230

66 CumenePhenol and Cumene Hydroperoxide 231

67 Acetone and Isopropanol 233

671 Methyl Methacrylate 235

672 Methyl Isobutyl Ketone and Other

Acetone Derivatives 242

68 Propylene Oxide 242

681 Other Propylene Oxide Processes 247

6811 Acetoxylation of Propylene 248

6812 Direct Oxidation 249

6813 Use of Peracids 249

6814 Electrochemical Processes 250

6815 Biotechnological Approaches 252

682 Propylene Oxide Applications 253

CONTENTS xi

69 n-Butyraldehyde and Isobutyraldehyde 255

691 Uses for Butyraldehyde Isobutyraldehyde

and n-Butanol 258

692 Other Oxo Products 260

610 Major Chemicals from Propylene ndash A Perspective 261

611 Lesser Volume Chemicals from Propylene 263

6111 Allyl Chloride and Epichlorohydrin 263

6112 Glycerol 266

6113 Acrylamide 266

6114 Acrolein 268

6115 Acrylonitrile Derivatives 270

Endnotes 270

7 Chemicals from the C4 Stream 273

71 Chemicals and Polymers from Butadiene 277

711 Tires 280

712 StyrenendashButadiene Elastomers 281

713 Polybutadienes and Other Elastomers 282

714 AcrylonitrilendashButadienendashStyrene Resins 283

715 Hexamethylenediamine 284

716 Lesser Volume Chemicals from Butadiene 289

7161 Cyclization 289

7162 Dimerization and Trimerization 291

7163 DielsndashAlder Reactions 293

7164 Adipic Acid 294

7165 14-Butanediol 294

7166 trans-14-Hexadiene 295

7167 Dimethyl-26-naphthalene

Dicarboxylate 295

7168 Butadiene Monoepoxide 296

72 Chemicals and Polymers from Isobutene 296

721 Methyl tert-Butyl Ether 297

722 Butyl Rubber 298

723 Polyisobutenes and Isobutene Oligomers

and Polymers 298

724 tert-Butanol 299

725 Methyl Methacrylate 299

726 Lesser Volume Chemicals from Isobutene 299

xii CONTENTS

73 Chemicals and Polymers from 1- and 2-Butenes 302

74 Chemicals from n-Butane 303

741 Acetic Acid 303

742 Maleic Anhydride 303

743 Succinic Malic Fumaric and Tartaric Acids 306

Endnotes 307

8 Chemicals from the C5 Stream 309

81 Separation of the C5 Stream 311

82 Isoprene 312

821 Natural Rubber 312

822 Vulcanization 313

823 Production of Petrochemical Isoprene 314

824 Applications of Isoprene 317

83 Cyclopentadiene and Dicyclopentadiene 319

84 Pentene-1 and Piperylene 321

Endnotes 321

9 Chemicals from Benzene 323

91 Phenol 326

911 Phenolic Resins 331

912 Bisphenol A 333

9121 Epoxy Resins 333

9122 Polycarbonate Resins 334

9123 Lesser Volume Uses for Bisphenol A 337

9124 Environmental Problems 340

913 Cyclohexanone 341

914 Alkylphenols 342

915 Chlorinated Phenols 342

916 26-XylenolCresols 343

917 Aniline from Phenol 344

92 Cyclohexane 344

921 Adipic Acid 344

9211 Nylons from Adipic Acid 349

922 Caprolactam 349

CONTENTS xiii

93 Aniline 354

931 440-Diphenylmethane Isocyanate 357

94 Alkylbenzenes 361

95 Maleic Anhydride 362

96 Chlorinated Benzenes 363

97 Dihydroxybenzenes 364

971 Hydroquinone 364

972 Resorcinol 368

973 Catechol 369

98 Anthraquinone 370

981 Hydrogen Peroxide 371

Endnotes 372

10 Chemicals from Toluene 375

101 Hydrodealkylation Disproportionation and Transalkylation 375

102 Solvents 378

103 Dinitrotoluene and Toluene Diisocyanate 378

104 Lesser Volume Chemicals from Toluene 380

Endnotes 382

11 Chemicals from Xylenes 383

111 o-Xylene and Phthalic Anhydride 386

1111 Plasticizers 387

1112 Alkyd Resins 391

1113 Unsaturated Polyester Resin 393

112 m-Xylene and Isophthalic Acid 395

1121 Uses of Isophthalic Acid 396

113 p-Xylene and Terephthalic AcidDimethyl Terephthalate 397

1131 Oxidation of p-Xylene 398

1132 Alternate Sources for Terephthalic Acid 400

1133 Poly(ethylene terephthalate) 400

1134 Lower Volume Polymers from Terephthalic Acid 403

Endnotes 404

xiv CONTENTS

12 Chemicals from Methane 407

121 Hydrocyanic Acid 408

122 Halogenated Methanes 411

1221 Chloromethane 412

1222 Dichloromethane 413

1223 Trichloromethane 413

1224 Fluorocarbons 414

1225 Tetrachloromethane and Carbon Disulfide 414

1226 Bromomethane 416

123 Acetylene 417

1231 14-Butanediol and 2-Methyl-13-propanediol 419

1232 Lesser Uses for Acetylene 423

124 Synthesis Gas 424

1241 Steam Reforming of Methane 425

1242 Variants of Steam Reforming 427

1243 Partial Oxidation of Hydrocarbons 428

1244 Solid Feedstocks 428

1245 Hydrogen 429

125 Chemicals from Synthesis Gas 429

1251 Ammonia and Its Derivatives 430

12511 The Crisis of Nitrogen Depletion 430

12512 Ammonia Manufacture 431

12513 Urea and Melamine Resins 434

1252 Methanol 435

12521 Formaldehyde 438

12522 Acetic Acid 439

12523 Acetic Anhydride 442

12524 Methanol to Gasoline 445

12525 Methanol to Olefins 446

12526 Lower Volume and Proposed Uses for Methanol 448

12527 C1-Based Development Processes 452

126 Carbon Monoxide Chemistry 454

1261 Proposed Chemistry Based on Carbon Monoxide 455

127 Gas-to-Liquid Fuels 459

1271 Sasol GTL Technology 459

1272 Shell Middle Distillate Synthesis 459

CONTENTS xv

1273 Other GTL Technologies 460

Endnotes 460

13 Chemicals from Alkanes 463

131 Functionalization of Methane 464

1311 Methane to MethanolFormaldehyde 464

1312 Dimerization of Methane 466

1313 Aromatization of Methane 467

132 Functionalization of C2ndashC4 Alkanes 468

1321 Oxidation of C2ndashC4 Alkanes 468

1322 Dehydrogenation of C2ndashC4 Alkanes 470

1323 Aromatization of C2ndashC4Alkanes 471

133 Carbon Black 472

Endnotes 473

14 Chemicals from Coal 475

141 Chemicals from Coke Oven Distillate 477

142 The FischerndashTropsch Reaction 480

143 Coal Hydrogenation 484

144 Substitute Natural Gas 485

145 SNG and Synthesis Gas Technology 485

146 Underground Coal Gasification 488

147 Calcium Carbide 488

1471 The Chinese Chemicals to Coal Program 489

148 Coal and the Environment 490

Endnotes 491

15 Fats and Oils 493

151 Markets for Fats and Oils 495

152 Purification of Fats and Oils 497

153 Fatty Acids 499

1531 Applications of Fatty Acids 501

154 Fatty Nitrogen Compounds 502

155 ldquoDimerrdquo Acid 504

xvi CONTENTS

156 Aminoamides and Imidazolines 506

157 Azelaic Pelargonic and Petroselinic Acids 507

158 Fatty Alcohols 508

159 Epoxidized Oils 509

1510 Ricinoleic Acid 510

1511 Glycerol 512

15111 Established Glycerol Uses 512

1512 Alcoholysis of Fats and Oils 513

15121 Cocoa Butter and Mothersrsquo Milk 513

151211 Mothersrsquo Milk 515

15122 Trans Fats and Interesterification 515

15123 Biodiesel and Lubricants 516

151231 Algae 518

1513 Alkyl Polyglycosides 519

1514 Non-Caloric Fat-like Substances 519

Endnotes 520

16 Carbohydrates 523

161 Sugars and Sorbitol 523

1611 Isosorbide 530

162 Furfural 530

163 Starch 532

164 Cellulose 535

1641 Miscellaneous Chemicals from Wood 539

16411 Vanillin 541

16412 Levulinic Acid 542

165 Gums 543

166 Fermentation and Biotechnology 544

1661 Amino Acids 547

16611 L-Glutamic Acid 547

16612 L-Lysine 547

16613 L-Aspartic Acid 548

16614 L-Cysteine 549

1662 Polymers 550

CONTENTS xvii

1663 Proteins by Recombinant DNA Technology 550

1664 Fermentation and Renewables Scenarios 551

1665 Biofuels 554

16651 The Brazilian Experience 554

16652 Is US Bioethanol a Renewable

Energy Source 555

16653 Biomass as Feedstock 556

16654 Catalytic Bioforming 556

16655 Biotechnology Versus Synthesis Gas 557

Endnotes 558

17 How Polymers Are Made 561

171 Polymerization 565

172 Functionality 568

173 Step Growth and Chain Growth Polymerizations 571

1731 Free Radical Polymerization 573

1732 Chain Transfer 575

1733 Copolymerization 577

1734 Molecular Weight 579

1735 Polymerization Procedures 580

17351 Photoinitiation 582

1736 Ionic Polymerization 584

1737 Living Polymers 589

1738 Block Copolymers 589

1739 Graft Copolymers 592

17310 Metal Complex Catalysts 593

17311 Metal Oxide Catalysts 598

17312 Metallocene and Other Single Site Catalysts 599

173121 Single Site Nonmetallocene Catalysts 602

173122 Late Transition Metal Catalysts 603

173123 Commercial Prospects of LLDPEs 604

174 Examples of Step Polymerization 605

1741 Phenoplasts and Aminoplasts 605

1742 Polyurethanes 606

1743 Epoxy Resins 611

1744 Dendritic and Hyperbranched Polymers 613

1745 Conducting Polymers 617

1746 Conducting and Semiconducting Inks 621

xviii CONTENTS

175 Polymer Properties 622

1751 Crystallinity 622

1752 Glass Transition Temperature Crystalline

Melting Point and Softening Temperature 626

1753 Molecular Cohesion 628

1754 StressndashStrain Diagrams 628

176 Classes of Polymers 630

177 Plastics Fabrication Techniques 631

Endnotes 635

18 Industrial Catalysis 637

181 Catalyst Choice 637

1811 Reaction Velocity and Selectivity 638

1812 Recovery of Unchanged Catalyst 641

1813 Catalyst Deactivation 642

1814 Access to Nonequilibrium Products 642

182 Homogeneous and Heterogeneous Catalysis 643

1821 Reactors for Heterogeneous Catalysts 644

1822 Immobilization of Homogeneous Catalysts 646

183 Catalyst Markets 647

184 Catalysis by Acids and Bases 651

185 Dual Function Catalysis 654

186 Catalysis by Metals Semiconductors and Insulators 655

1861 Catalysts for Automobile Emission Control 656

187 Coordination Catalysis 657

1871 Catalysts for Stereoregular Compounds 658

1872 Asymmetric Synthesis 660

188 Enzymes 661

1881 Catalytic Antibodies 663

189 Shape-Selective Catalysts 664

1810 Phase-Transfer and Fluorous Biphase Catalysis 669

1811 Nanocatalysis 670

1812 Catalysts of the Future 673

18121 Catalyst Design 673

18122 Higher Selectivities 673

CONTENTS xix

18123 Catalysts with Greater Activity 674

18124 Pollution Problems 675

18125 Catalysts for New Reactions 675

18126 Catalysts that Mimic Natural Catalysts 676

18127 Catalyst Discovery Via High Throughput

Experimentation 676

Endnotes 677

19 Green Chemistry 681

191 The Decline of Acetylene Chemistry 683

192 Nylon 683

193 Replacement of Phosgene 684

194 Monomethylation by Dimethyl Carbonate 685

195 Liquid and Supercritical Carbon Dioxide and Water 685

196 Ionic Liquids 687

197 Photocatalysts 690

198 Paired Electrosynthesis 691

199 ldquoGreenrdquo Pharmaceuticals 692

1991 Ibuprofen 692

1992 Sertraline 694

1993 Pharmaceuticals from ldquoRenewablesrdquo 696

1910 Catalytic Dehydrogenation of Diethanolamine 698

1911 Genetic Manipulation 698

1912 Biodegradable Packaging 698

19121 Polyhydroxyalkanoates 701

1913 The Presidential Green Chemistry Challenge Program 703

Endnotes 704

20 Sustainability 707

201 Climate Change 708

202 Resource Depletion 712

2021 Food Water and People 713

20211 Food 713

20212 Water 714

20213 People 715

xx CONTENTS

203 Energy Sources 717

2031 Wind Power 719

2032 Wave Power 720

2033 Solar Power 721

20331 Concentrated Solar Power 721

20332 Photovoltaic Cells 721

20333 Dye-Sensitized Solar Cells 722

20334 Artificial Photosynthesis 724

2034 Nuclear Energy 726

2035 Methane Hydrate 727

2036 The Hydrogen Economy 728

2037 Fuel Cells 729

2038 Electric Vehicles 735

204 Pollution 736

2041 The Ozone Layer 738

2042 Trace Chemicals 742

20421 Pesticides 742

20422 Nonpesticide Lipophiles 743

2043 Air Pollution 744

20431 Sulfur Dioxide Particulates 745

20432 Automobile Exhaust Emissions 748

2044 Water Treatment 750

2045 Solid Wastes 752

20451 Waste Prevention 753

20452 Recycling 754

20453 CombustionIncineration 755

20454 Sanitary Landfill 756

2046 Petrochemical Industry Wastes 758

2047 Other Environmental Problems 759

205 Valediction 759

Endnotes 761

Appendix A A Note on Cost Calculations 765

Appendix B Units and Conversion Factors 771

Appendix C Special Units in the Chemical Industry 773

Appendix D The Importance of Shale Gas and Shale Oil 775

Index 779

CONTENTS xxi

PREFACE

This third edition of Industrial Organic Chemicals is prompted by the impact of

globalization and of threats to the environment This is not to say that industrial

chemistry has stood still ndash very much the reverse and we have featured much new

chemistry All the same our earlier books were about the exciting new world of

petrochemical feedstocks and the ingenious new products that could be made

from them In this edition the exciting new processes have become the dull

traditional ones Well-established processes of technology transfer have carried

them to developing countries especially those that produce petrochemical feed-

stocks In addition humankindrsquos activities are seen both as depleting the resources

of the planet and of polluting it to the point at which humankind will drown in its

own effluvia The extent of these threats is hotly contested nonetheless the

chemical industry both contributes to the problems and is instrumental in trying to

solve them

There have been many developments since the second edition and the following

topics have gained especially in significance

The world chemical industry has migrated from the United States Western

Europe and Japan to theMiddle East and to Asia-Pacific especially ChinaWill

shale oil and gas bring it back (See Appendix D)

There is increased emphasis on environmental issues with pressure on com-

panies to clean up polluting processes or replace them with environmentally

friendly ones

Globalization has changed patterns of transportation of chemicals with for

example solid polymers rather than petrochemical feedstocks being shipped

from the Middle East

The discovery of vast reserves of shale gas has altered the long-term predictions

of resource depletion in the United States and other countries

Considerations of sustainability and the threat of climate change have prompted

research into processes (including electricity generation) that produce less or no

carbon dioxide or come from renewable resources

We have retained some material that is now largely of historical interest partly

for sentimental reasons but partly because the three authors have watched the

xxiii

meteoric rise of the chemical industry from its early days to its present-day

maturity We think there is a value in our readers observing how technology has

developed and the social technological and economic changes that have brought

it to its present position

HAROLD A WITTCOFF

xxiv PREFACE

PREFACE TO THE FIRST EDITION

In the early 1970s one of us (BGR) wrote a book celebrating the rapid growth of the

adolescent chemical industry The organic chemicals industry at the timewas growing

at four times the rate of the economy It was indicated nonetheless that ldquotrees do not

grow to the skyrdquo In 1980 in another book we both declared the industry to bemiddle-

aged with slow or zero growth In this totally revised and expanded version of our

earlier book we reflect that the industry at any rate in the developedworld is showing

many of the illnesses of late middle-age

The problems have arisen first from the undisciplined building of excess capacity

with consequent fierce competition and low prices Second the entry of numerous

developing countries into the industry has exacerbated the situation (Section 136)

and third there has beenmuch stricter government legislation (Section 137) There is

massive worldwide restructuring and continual shifting of commodity chemical

manufacturing to areas other than the United States Western Europe and Japan

The Middle East and Southeast Asia are the principal new players in the game

Perhaps this trend will continue and the present developed world will in the future

confine itself to themanufacture of specialties but the economic and political forces at

work are more complex than that We hope to be able to discuss their resolution in

another edition in about 10 yearsrsquo time

Meanwhile some things have not changed The organic chemicals industry is still

based on seven basic raw materials all deriving from petroleum and natural gas The

wisdom of teaching about the chemical industry on the basis of these seven building

blocks has been confirmed by the fact that since the publication of our first book one

of us (HAW) has delivered by invitation 300 courses in 28 countries on the

fundamentals of the industry based on this pattern Most of these courses are for

industrial personnel but academia has not been neglected

Furthermore some changes have been positive For example there have been

exciting new processes such as the development of metallocene catalysts (Section

15312) Section 461 describes new methyl methacrylate processes that give a

potentially cheaper product that do not produce ecologically undesirable ammonium

hydrogen sulfate by-product or (in another process) that eliminate the use of

dangerous hydrogen cyanide

In this book our main objective is still to present the technology of the organic

chemicals industry as an organized body of knowledge so that both the neophyte and

the experienced practitioner can see the broad picture Nonetheless we have

expanded its scope to include not only new processes but many apparently less

xxv

important reactions that are significant because they give rise to the more profitable

specialty chemicals The lesser volume chemicals have been clearly delineated as

such and the reader who wishes to see the industry on the basis of its large tonnage

products can omit these sections

We hope this bookwill be useful both to college students who have studied organic

chemistry and to graduates and industrial chemists whowork in or are interested in the

chemical industry Even though much of the chemistry has remained the same the

change in the way the industry looks at its problems provides ample justification for

our offering this edition as a fresh perspective on industrial organic chemicals

xxvi PREFACE TO THE FIRST EDITION

PREFACE TO THE SECOND EDITION

In the preface to the first edition we expressed the hope that we could comment on the

chemical industryrsquos evolution in 10 yearsrsquo time Dramatic changes have motivated us

to compress this time frame There have been unprecedented restructuring severe and

complicated feedstock problems and massive shifts of capacity to developing

countries whose economic and political stability is in doubt Possible terrorist

activity dictates elaborate safety and security procedures and the design of plants

with small inventories is a priority

To increase our cover particularly of the patent literature we have invited Dr

Jeffrey S Plotkin Director of the Process Evaluation and Research Planning program

at Nexant ChemSystems to join us as co-author

xxvii

69 n-Butyraldehyde and Isobutyraldehyde 255

691 Uses for Butyraldehyde Isobutyraldehyde

and n-Butanol 258

692 Other Oxo Products 260

610 Major Chemicals from Propylene ndash A Perspective 261

611 Lesser Volume Chemicals from Propylene 263

6111 Allyl Chloride and Epichlorohydrin 263

6112 Glycerol 266

6113 Acrylamide 266

6114 Acrolein 268

6115 Acrylonitrile Derivatives 270

Endnotes 270

7 Chemicals from the C4 Stream 273

71 Chemicals and Polymers from Butadiene 277

711 Tires 280

712 StyrenendashButadiene Elastomers 281

713 Polybutadienes and Other Elastomers 282

714 AcrylonitrilendashButadienendashStyrene Resins 283

715 Hexamethylenediamine 284

716 Lesser Volume Chemicals from Butadiene 289

7161 Cyclization 289

7162 Dimerization and Trimerization 291

7163 DielsndashAlder Reactions 293

7164 Adipic Acid 294

7165 14-Butanediol 294

7166 trans-14-Hexadiene 295

7167 Dimethyl-26-naphthalene

Dicarboxylate 295

7168 Butadiene Monoepoxide 296

72 Chemicals and Polymers from Isobutene 296

721 Methyl tert-Butyl Ether 297

722 Butyl Rubber 298

723 Polyisobutenes and Isobutene Oligomers

and Polymers 298

724 tert-Butanol 299

725 Methyl Methacrylate 299

726 Lesser Volume Chemicals from Isobutene 299

xii CONTENTS

73 Chemicals and Polymers from 1- and 2-Butenes 302

74 Chemicals from n-Butane 303

741 Acetic Acid 303

742 Maleic Anhydride 303

743 Succinic Malic Fumaric and Tartaric Acids 306

Endnotes 307

8 Chemicals from the C5 Stream 309

81 Separation of the C5 Stream 311

82 Isoprene 312

821 Natural Rubber 312

822 Vulcanization 313

823 Production of Petrochemical Isoprene 314

824 Applications of Isoprene 317

83 Cyclopentadiene and Dicyclopentadiene 319

84 Pentene-1 and Piperylene 321

Endnotes 321

9 Chemicals from Benzene 323

91 Phenol 326

911 Phenolic Resins 331

912 Bisphenol A 333

9121 Epoxy Resins 333

9122 Polycarbonate Resins 334

9123 Lesser Volume Uses for Bisphenol A 337

9124 Environmental Problems 340

913 Cyclohexanone 341

914 Alkylphenols 342

915 Chlorinated Phenols 342

916 26-XylenolCresols 343

917 Aniline from Phenol 344

92 Cyclohexane 344

921 Adipic Acid 344

9211 Nylons from Adipic Acid 349

922 Caprolactam 349

CONTENTS xiii

93 Aniline 354

931 440-Diphenylmethane Isocyanate 357

94 Alkylbenzenes 361

95 Maleic Anhydride 362

96 Chlorinated Benzenes 363

97 Dihydroxybenzenes 364

971 Hydroquinone 364

972 Resorcinol 368

973 Catechol 369

98 Anthraquinone 370

981 Hydrogen Peroxide 371

Endnotes 372

10 Chemicals from Toluene 375

101 Hydrodealkylation Disproportionation and Transalkylation 375

102 Solvents 378

103 Dinitrotoluene and Toluene Diisocyanate 378

104 Lesser Volume Chemicals from Toluene 380

Endnotes 382

11 Chemicals from Xylenes 383

111 o-Xylene and Phthalic Anhydride 386

1111 Plasticizers 387

1112 Alkyd Resins 391

1113 Unsaturated Polyester Resin 393

112 m-Xylene and Isophthalic Acid 395

1121 Uses of Isophthalic Acid 396

113 p-Xylene and Terephthalic AcidDimethyl Terephthalate 397

1131 Oxidation of p-Xylene 398

1132 Alternate Sources for Terephthalic Acid 400

1133 Poly(ethylene terephthalate) 400

1134 Lower Volume Polymers from Terephthalic Acid 403

Endnotes 404

xiv CONTENTS

12 Chemicals from Methane 407

121 Hydrocyanic Acid 408

122 Halogenated Methanes 411

1221 Chloromethane 412

1222 Dichloromethane 413

1223 Trichloromethane 413

1224 Fluorocarbons 414

1225 Tetrachloromethane and Carbon Disulfide 414

1226 Bromomethane 416

123 Acetylene 417

1231 14-Butanediol and 2-Methyl-13-propanediol 419

1232 Lesser Uses for Acetylene 423

124 Synthesis Gas 424

1241 Steam Reforming of Methane 425

1242 Variants of Steam Reforming 427

1243 Partial Oxidation of Hydrocarbons 428

1244 Solid Feedstocks 428

1245 Hydrogen 429

125 Chemicals from Synthesis Gas 429

1251 Ammonia and Its Derivatives 430

12511 The Crisis of Nitrogen Depletion 430

12512 Ammonia Manufacture 431

12513 Urea and Melamine Resins 434

1252 Methanol 435

12521 Formaldehyde 438

12522 Acetic Acid 439

12523 Acetic Anhydride 442

12524 Methanol to Gasoline 445

12525 Methanol to Olefins 446

12526 Lower Volume and Proposed Uses for Methanol 448

12527 C1-Based Development Processes 452

126 Carbon Monoxide Chemistry 454

1261 Proposed Chemistry Based on Carbon Monoxide 455

127 Gas-to-Liquid Fuels 459

1271 Sasol GTL Technology 459

1272 Shell Middle Distillate Synthesis 459

CONTENTS xv

1273 Other GTL Technologies 460

Endnotes 460

13 Chemicals from Alkanes 463

131 Functionalization of Methane 464

1311 Methane to MethanolFormaldehyde 464

1312 Dimerization of Methane 466

1313 Aromatization of Methane 467

132 Functionalization of C2ndashC4 Alkanes 468

1321 Oxidation of C2ndashC4 Alkanes 468

1322 Dehydrogenation of C2ndashC4 Alkanes 470

1323 Aromatization of C2ndashC4Alkanes 471

133 Carbon Black 472

Endnotes 473

14 Chemicals from Coal 475

141 Chemicals from Coke Oven Distillate 477

142 The FischerndashTropsch Reaction 480

143 Coal Hydrogenation 484

144 Substitute Natural Gas 485

145 SNG and Synthesis Gas Technology 485

146 Underground Coal Gasification 488

147 Calcium Carbide 488

1471 The Chinese Chemicals to Coal Program 489

148 Coal and the Environment 490

Endnotes 491

15 Fats and Oils 493

151 Markets for Fats and Oils 495

152 Purification of Fats and Oils 497

153 Fatty Acids 499

1531 Applications of Fatty Acids 501

154 Fatty Nitrogen Compounds 502

155 ldquoDimerrdquo Acid 504

xvi CONTENTS

156 Aminoamides and Imidazolines 506

157 Azelaic Pelargonic and Petroselinic Acids 507

158 Fatty Alcohols 508

159 Epoxidized Oils 509

1510 Ricinoleic Acid 510

1511 Glycerol 512

15111 Established Glycerol Uses 512

1512 Alcoholysis of Fats and Oils 513

15121 Cocoa Butter and Mothersrsquo Milk 513

151211 Mothersrsquo Milk 515

15122 Trans Fats and Interesterification 515

15123 Biodiesel and Lubricants 516

151231 Algae 518

1513 Alkyl Polyglycosides 519

1514 Non-Caloric Fat-like Substances 519

Endnotes 520

16 Carbohydrates 523

161 Sugars and Sorbitol 523

1611 Isosorbide 530

162 Furfural 530

163 Starch 532

164 Cellulose 535

1641 Miscellaneous Chemicals from Wood 539

16411 Vanillin 541

16412 Levulinic Acid 542

165 Gums 543

166 Fermentation and Biotechnology 544

1661 Amino Acids 547

16611 L-Glutamic Acid 547

16612 L-Lysine 547

16613 L-Aspartic Acid 548

16614 L-Cysteine 549

1662 Polymers 550

CONTENTS xvii

1663 Proteins by Recombinant DNA Technology 550

1664 Fermentation and Renewables Scenarios 551

1665 Biofuels 554

16651 The Brazilian Experience 554

16652 Is US Bioethanol a Renewable

Energy Source 555

16653 Biomass as Feedstock 556

16654 Catalytic Bioforming 556

16655 Biotechnology Versus Synthesis Gas 557

Endnotes 558

17 How Polymers Are Made 561

171 Polymerization 565

172 Functionality 568

173 Step Growth and Chain Growth Polymerizations 571

1731 Free Radical Polymerization 573

1732 Chain Transfer 575

1733 Copolymerization 577

1734 Molecular Weight 579

1735 Polymerization Procedures 580

17351 Photoinitiation 582

1736 Ionic Polymerization 584

1737 Living Polymers 589

1738 Block Copolymers 589

1739 Graft Copolymers 592

17310 Metal Complex Catalysts 593

17311 Metal Oxide Catalysts 598

17312 Metallocene and Other Single Site Catalysts 599

173121 Single Site Nonmetallocene Catalysts 602

173122 Late Transition Metal Catalysts 603

173123 Commercial Prospects of LLDPEs 604

174 Examples of Step Polymerization 605

1741 Phenoplasts and Aminoplasts 605

1742 Polyurethanes 606

1743 Epoxy Resins 611

1744 Dendritic and Hyperbranched Polymers 613

1745 Conducting Polymers 617

1746 Conducting and Semiconducting Inks 621

xviii CONTENTS

175 Polymer Properties 622

1751 Crystallinity 622

1752 Glass Transition Temperature Crystalline

Melting Point and Softening Temperature 626

1753 Molecular Cohesion 628

1754 StressndashStrain Diagrams 628

176 Classes of Polymers 630

177 Plastics Fabrication Techniques 631

Endnotes 635

18 Industrial Catalysis 637

181 Catalyst Choice 637

1811 Reaction Velocity and Selectivity 638

1812 Recovery of Unchanged Catalyst 641

1813 Catalyst Deactivation 642

1814 Access to Nonequilibrium Products 642

182 Homogeneous and Heterogeneous Catalysis 643

1821 Reactors for Heterogeneous Catalysts 644

1822 Immobilization of Homogeneous Catalysts 646

183 Catalyst Markets 647

184 Catalysis by Acids and Bases 651

185 Dual Function Catalysis 654

186 Catalysis by Metals Semiconductors and Insulators 655

1861 Catalysts for Automobile Emission Control 656

187 Coordination Catalysis 657

1871 Catalysts for Stereoregular Compounds 658

1872 Asymmetric Synthesis 660

188 Enzymes 661

1881 Catalytic Antibodies 663

189 Shape-Selective Catalysts 664

1810 Phase-Transfer and Fluorous Biphase Catalysis 669

1811 Nanocatalysis 670

1812 Catalysts of the Future 673

18121 Catalyst Design 673

18122 Higher Selectivities 673

CONTENTS xix

18123 Catalysts with Greater Activity 674

18124 Pollution Problems 675

18125 Catalysts for New Reactions 675

18126 Catalysts that Mimic Natural Catalysts 676

18127 Catalyst Discovery Via High Throughput

Experimentation 676

Endnotes 677

19 Green Chemistry 681

191 The Decline of Acetylene Chemistry 683

192 Nylon 683

193 Replacement of Phosgene 684

194 Monomethylation by Dimethyl Carbonate 685

195 Liquid and Supercritical Carbon Dioxide and Water 685

196 Ionic Liquids 687

197 Photocatalysts 690

198 Paired Electrosynthesis 691

199 ldquoGreenrdquo Pharmaceuticals 692

1991 Ibuprofen 692

1992 Sertraline 694

1993 Pharmaceuticals from ldquoRenewablesrdquo 696

1910 Catalytic Dehydrogenation of Diethanolamine 698

1911 Genetic Manipulation 698

1912 Biodegradable Packaging 698

19121 Polyhydroxyalkanoates 701

1913 The Presidential Green Chemistry Challenge Program 703

Endnotes 704

20 Sustainability 707

201 Climate Change 708

202 Resource Depletion 712

2021 Food Water and People 713

20211 Food 713

20212 Water 714

20213 People 715

xx CONTENTS

203 Energy Sources 717

2031 Wind Power 719

2032 Wave Power 720

2033 Solar Power 721

20331 Concentrated Solar Power 721

20332 Photovoltaic Cells 721

20333 Dye-Sensitized Solar Cells 722

20334 Artificial Photosynthesis 724

2034 Nuclear Energy 726

2035 Methane Hydrate 727

2036 The Hydrogen Economy 728

2037 Fuel Cells 729

2038 Electric Vehicles 735

204 Pollution 736

2041 The Ozone Layer 738

2042 Trace Chemicals 742

20421 Pesticides 742

20422 Nonpesticide Lipophiles 743

2043 Air Pollution 744

20431 Sulfur Dioxide Particulates 745

20432 Automobile Exhaust Emissions 748

2044 Water Treatment 750

2045 Solid Wastes 752

20451 Waste Prevention 753

20452 Recycling 754

20453 CombustionIncineration 755

20454 Sanitary Landfill 756

2046 Petrochemical Industry Wastes 758

2047 Other Environmental Problems 759

205 Valediction 759

Endnotes 761

Appendix A A Note on Cost Calculations 765

Appendix B Units and Conversion Factors 771

Appendix C Special Units in the Chemical Industry 773

Appendix D The Importance of Shale Gas and Shale Oil 775

Index 779

CONTENTS xxi

PREFACE

This third edition of Industrial Organic Chemicals is prompted by the impact of

globalization and of threats to the environment This is not to say that industrial

chemistry has stood still ndash very much the reverse and we have featured much new

chemistry All the same our earlier books were about the exciting new world of

petrochemical feedstocks and the ingenious new products that could be made

from them In this edition the exciting new processes have become the dull

traditional ones Well-established processes of technology transfer have carried

them to developing countries especially those that produce petrochemical feed-

stocks In addition humankindrsquos activities are seen both as depleting the resources

of the planet and of polluting it to the point at which humankind will drown in its

own effluvia The extent of these threats is hotly contested nonetheless the

chemical industry both contributes to the problems and is instrumental in trying to

solve them

There have been many developments since the second edition and the following

topics have gained especially in significance

The world chemical industry has migrated from the United States Western

Europe and Japan to theMiddle East and to Asia-Pacific especially ChinaWill

shale oil and gas bring it back (See Appendix D)

There is increased emphasis on environmental issues with pressure on com-

panies to clean up polluting processes or replace them with environmentally

friendly ones

Globalization has changed patterns of transportation of chemicals with for

example solid polymers rather than petrochemical feedstocks being shipped

from the Middle East

The discovery of vast reserves of shale gas has altered the long-term predictions

of resource depletion in the United States and other countries

Considerations of sustainability and the threat of climate change have prompted

research into processes (including electricity generation) that produce less or no

carbon dioxide or come from renewable resources

We have retained some material that is now largely of historical interest partly

for sentimental reasons but partly because the three authors have watched the

xxiii

meteoric rise of the chemical industry from its early days to its present-day

maturity We think there is a value in our readers observing how technology has

developed and the social technological and economic changes that have brought

it to its present position

HAROLD A WITTCOFF

xxiv PREFACE

PREFACE TO THE FIRST EDITION

In the early 1970s one of us (BGR) wrote a book celebrating the rapid growth of the

adolescent chemical industry The organic chemicals industry at the timewas growing

at four times the rate of the economy It was indicated nonetheless that ldquotrees do not

grow to the skyrdquo In 1980 in another book we both declared the industry to bemiddle-

aged with slow or zero growth In this totally revised and expanded version of our

earlier book we reflect that the industry at any rate in the developedworld is showing

many of the illnesses of late middle-age

The problems have arisen first from the undisciplined building of excess capacity

with consequent fierce competition and low prices Second the entry of numerous

developing countries into the industry has exacerbated the situation (Section 136)

and third there has beenmuch stricter government legislation (Section 137) There is

massive worldwide restructuring and continual shifting of commodity chemical

manufacturing to areas other than the United States Western Europe and Japan

The Middle East and Southeast Asia are the principal new players in the game

Perhaps this trend will continue and the present developed world will in the future

confine itself to themanufacture of specialties but the economic and political forces at

work are more complex than that We hope to be able to discuss their resolution in

another edition in about 10 yearsrsquo time

Meanwhile some things have not changed The organic chemicals industry is still

based on seven basic raw materials all deriving from petroleum and natural gas The

wisdom of teaching about the chemical industry on the basis of these seven building

blocks has been confirmed by the fact that since the publication of our first book one

of us (HAW) has delivered by invitation 300 courses in 28 countries on the

fundamentals of the industry based on this pattern Most of these courses are for

industrial personnel but academia has not been neglected

Furthermore some changes have been positive For example there have been

exciting new processes such as the development of metallocene catalysts (Section

15312) Section 461 describes new methyl methacrylate processes that give a

potentially cheaper product that do not produce ecologically undesirable ammonium

hydrogen sulfate by-product or (in another process) that eliminate the use of

dangerous hydrogen cyanide

In this book our main objective is still to present the technology of the organic

chemicals industry as an organized body of knowledge so that both the neophyte and

the experienced practitioner can see the broad picture Nonetheless we have

expanded its scope to include not only new processes but many apparently less

xxv

important reactions that are significant because they give rise to the more profitable

specialty chemicals The lesser volume chemicals have been clearly delineated as

such and the reader who wishes to see the industry on the basis of its large tonnage

products can omit these sections

We hope this bookwill be useful both to college students who have studied organic

chemistry and to graduates and industrial chemists whowork in or are interested in the

chemical industry Even though much of the chemistry has remained the same the

change in the way the industry looks at its problems provides ample justification for

our offering this edition as a fresh perspective on industrial organic chemicals

xxvi PREFACE TO THE FIRST EDITION

PREFACE TO THE SECOND EDITION

In the preface to the first edition we expressed the hope that we could comment on the

chemical industryrsquos evolution in 10 yearsrsquo time Dramatic changes have motivated us

to compress this time frame There have been unprecedented restructuring severe and

complicated feedstock problems and massive shifts of capacity to developing

countries whose economic and political stability is in doubt Possible terrorist

activity dictates elaborate safety and security procedures and the design of plants

with small inventories is a priority

To increase our cover particularly of the patent literature we have invited Dr

Jeffrey S Plotkin Director of the Process Evaluation and Research Planning program

at Nexant ChemSystems to join us as co-author

xxvii

73 Chemicals and Polymers from 1- and 2-Butenes 302

74 Chemicals from n-Butane 303

741 Acetic Acid 303

742 Maleic Anhydride 303

743 Succinic Malic Fumaric and Tartaric Acids 306

Endnotes 307

8 Chemicals from the C5 Stream 309

81 Separation of the C5 Stream 311

82 Isoprene 312

821 Natural Rubber 312

822 Vulcanization 313

823 Production of Petrochemical Isoprene 314

824 Applications of Isoprene 317

83 Cyclopentadiene and Dicyclopentadiene 319

84 Pentene-1 and Piperylene 321

Endnotes 321

9 Chemicals from Benzene 323

91 Phenol 326

911 Phenolic Resins 331

912 Bisphenol A 333

9121 Epoxy Resins 333

9122 Polycarbonate Resins 334

9123 Lesser Volume Uses for Bisphenol A 337

9124 Environmental Problems 340

913 Cyclohexanone 341

914 Alkylphenols 342

915 Chlorinated Phenols 342

916 26-XylenolCresols 343

917 Aniline from Phenol 344

92 Cyclohexane 344

921 Adipic Acid 344

9211 Nylons from Adipic Acid 349

922 Caprolactam 349

CONTENTS xiii

93 Aniline 354

931 440-Diphenylmethane Isocyanate 357

94 Alkylbenzenes 361

95 Maleic Anhydride 362

96 Chlorinated Benzenes 363

97 Dihydroxybenzenes 364

971 Hydroquinone 364

972 Resorcinol 368

973 Catechol 369

98 Anthraquinone 370

981 Hydrogen Peroxide 371

Endnotes 372

10 Chemicals from Toluene 375

101 Hydrodealkylation Disproportionation and Transalkylation 375

102 Solvents 378

103 Dinitrotoluene and Toluene Diisocyanate 378

104 Lesser Volume Chemicals from Toluene 380

Endnotes 382

11 Chemicals from Xylenes 383

111 o-Xylene and Phthalic Anhydride 386

1111 Plasticizers 387

1112 Alkyd Resins 391

1113 Unsaturated Polyester Resin 393

112 m-Xylene and Isophthalic Acid 395

1121 Uses of Isophthalic Acid 396

113 p-Xylene and Terephthalic AcidDimethyl Terephthalate 397

1131 Oxidation of p-Xylene 398

1132 Alternate Sources for Terephthalic Acid 400

1133 Poly(ethylene terephthalate) 400

1134 Lower Volume Polymers from Terephthalic Acid 403

Endnotes 404

xiv CONTENTS

12 Chemicals from Methane 407

121 Hydrocyanic Acid 408

122 Halogenated Methanes 411

1221 Chloromethane 412

1222 Dichloromethane 413

1223 Trichloromethane 413

1224 Fluorocarbons 414

1225 Tetrachloromethane and Carbon Disulfide 414

1226 Bromomethane 416

123 Acetylene 417

1231 14-Butanediol and 2-Methyl-13-propanediol 419

1232 Lesser Uses for Acetylene 423

124 Synthesis Gas 424

1241 Steam Reforming of Methane 425

1242 Variants of Steam Reforming 427

1243 Partial Oxidation of Hydrocarbons 428

1244 Solid Feedstocks 428

1245 Hydrogen 429

125 Chemicals from Synthesis Gas 429

1251 Ammonia and Its Derivatives 430

12511 The Crisis of Nitrogen Depletion 430

12512 Ammonia Manufacture 431

12513 Urea and Melamine Resins 434

1252 Methanol 435

12521 Formaldehyde 438

12522 Acetic Acid 439

12523 Acetic Anhydride 442

12524 Methanol to Gasoline 445

12525 Methanol to Olefins 446

12526 Lower Volume and Proposed Uses for Methanol 448

12527 C1-Based Development Processes 452

126 Carbon Monoxide Chemistry 454

1261 Proposed Chemistry Based on Carbon Monoxide 455

127 Gas-to-Liquid Fuels 459

1271 Sasol GTL Technology 459

1272 Shell Middle Distillate Synthesis 459

CONTENTS xv

1273 Other GTL Technologies 460

Endnotes 460

13 Chemicals from Alkanes 463

131 Functionalization of Methane 464

1311 Methane to MethanolFormaldehyde 464

1312 Dimerization of Methane 466

1313 Aromatization of Methane 467

132 Functionalization of C2ndashC4 Alkanes 468

1321 Oxidation of C2ndashC4 Alkanes 468

1322 Dehydrogenation of C2ndashC4 Alkanes 470

1323 Aromatization of C2ndashC4Alkanes 471

133 Carbon Black 472

Endnotes 473

14 Chemicals from Coal 475

141 Chemicals from Coke Oven Distillate 477

142 The FischerndashTropsch Reaction 480

143 Coal Hydrogenation 484

144 Substitute Natural Gas 485

145 SNG and Synthesis Gas Technology 485

146 Underground Coal Gasification 488

147 Calcium Carbide 488

1471 The Chinese Chemicals to Coal Program 489

148 Coal and the Environment 490

Endnotes 491

15 Fats and Oils 493

151 Markets for Fats and Oils 495

152 Purification of Fats and Oils 497

153 Fatty Acids 499

1531 Applications of Fatty Acids 501

154 Fatty Nitrogen Compounds 502

155 ldquoDimerrdquo Acid 504

xvi CONTENTS

156 Aminoamides and Imidazolines 506

157 Azelaic Pelargonic and Petroselinic Acids 507

158 Fatty Alcohols 508

159 Epoxidized Oils 509

1510 Ricinoleic Acid 510

1511 Glycerol 512

15111 Established Glycerol Uses 512

1512 Alcoholysis of Fats and Oils 513

15121 Cocoa Butter and Mothersrsquo Milk 513

151211 Mothersrsquo Milk 515

15122 Trans Fats and Interesterification 515

15123 Biodiesel and Lubricants 516

151231 Algae 518

1513 Alkyl Polyglycosides 519

1514 Non-Caloric Fat-like Substances 519

Endnotes 520

16 Carbohydrates 523

161 Sugars and Sorbitol 523

1611 Isosorbide 530

162 Furfural 530

163 Starch 532

164 Cellulose 535

1641 Miscellaneous Chemicals from Wood 539

16411 Vanillin 541

16412 Levulinic Acid 542

165 Gums 543

166 Fermentation and Biotechnology 544

1661 Amino Acids 547

16611 L-Glutamic Acid 547

16612 L-Lysine 547

16613 L-Aspartic Acid 548

16614 L-Cysteine 549

1662 Polymers 550

CONTENTS xvii

1663 Proteins by Recombinant DNA Technology 550

1664 Fermentation and Renewables Scenarios 551

1665 Biofuels 554

16651 The Brazilian Experience 554

16652 Is US Bioethanol a Renewable

Energy Source 555

16653 Biomass as Feedstock 556

16654 Catalytic Bioforming 556

16655 Biotechnology Versus Synthesis Gas 557

Endnotes 558

17 How Polymers Are Made 561

171 Polymerization 565

172 Functionality 568

173 Step Growth and Chain Growth Polymerizations 571

1731 Free Radical Polymerization 573

1732 Chain Transfer 575

1733 Copolymerization 577

1734 Molecular Weight 579

1735 Polymerization Procedures 580

17351 Photoinitiation 582

1736 Ionic Polymerization 584

1737 Living Polymers 589

1738 Block Copolymers 589

1739 Graft Copolymers 592

17310 Metal Complex Catalysts 593

17311 Metal Oxide Catalysts 598

17312 Metallocene and Other Single Site Catalysts 599

173121 Single Site Nonmetallocene Catalysts 602

173122 Late Transition Metal Catalysts 603

173123 Commercial Prospects of LLDPEs 604

174 Examples of Step Polymerization 605

1741 Phenoplasts and Aminoplasts 605

1742 Polyurethanes 606

1743 Epoxy Resins 611

1744 Dendritic and Hyperbranched Polymers 613

1745 Conducting Polymers 617

1746 Conducting and Semiconducting Inks 621

xviii CONTENTS

175 Polymer Properties 622

1751 Crystallinity 622

1752 Glass Transition Temperature Crystalline

Melting Point and Softening Temperature 626

1753 Molecular Cohesion 628

1754 StressndashStrain Diagrams 628

176 Classes of Polymers 630

177 Plastics Fabrication Techniques 631

Endnotes 635

18 Industrial Catalysis 637

181 Catalyst Choice 637

1811 Reaction Velocity and Selectivity 638

1812 Recovery of Unchanged Catalyst 641

1813 Catalyst Deactivation 642

1814 Access to Nonequilibrium Products 642

182 Homogeneous and Heterogeneous Catalysis 643

1821 Reactors for Heterogeneous Catalysts 644

1822 Immobilization of Homogeneous Catalysts 646

183 Catalyst Markets 647

184 Catalysis by Acids and Bases 651

185 Dual Function Catalysis 654

186 Catalysis by Metals Semiconductors and Insulators 655

1861 Catalysts for Automobile Emission Control 656

187 Coordination Catalysis 657

1871 Catalysts for Stereoregular Compounds 658

1872 Asymmetric Synthesis 660

188 Enzymes 661

1881 Catalytic Antibodies 663

189 Shape-Selective Catalysts 664

1810 Phase-Transfer and Fluorous Biphase Catalysis 669

1811 Nanocatalysis 670

1812 Catalysts of the Future 673

18121 Catalyst Design 673

18122 Higher Selectivities 673

CONTENTS xix

18123 Catalysts with Greater Activity 674

18124 Pollution Problems 675

18125 Catalysts for New Reactions 675

18126 Catalysts that Mimic Natural Catalysts 676

18127 Catalyst Discovery Via High Throughput

Experimentation 676

Endnotes 677

19 Green Chemistry 681

191 The Decline of Acetylene Chemistry 683

192 Nylon 683

193 Replacement of Phosgene 684

194 Monomethylation by Dimethyl Carbonate 685

195 Liquid and Supercritical Carbon Dioxide and Water 685

196 Ionic Liquids 687

197 Photocatalysts 690

198 Paired Electrosynthesis 691

199 ldquoGreenrdquo Pharmaceuticals 692

1991 Ibuprofen 692

1992 Sertraline 694

1993 Pharmaceuticals from ldquoRenewablesrdquo 696

1910 Catalytic Dehydrogenation of Diethanolamine 698

1911 Genetic Manipulation 698

1912 Biodegradable Packaging 698

19121 Polyhydroxyalkanoates 701

1913 The Presidential Green Chemistry Challenge Program 703

Endnotes 704

20 Sustainability 707

201 Climate Change 708

202 Resource Depletion 712

2021 Food Water and People 713

20211 Food 713

20212 Water 714

20213 People 715

xx CONTENTS

203 Energy Sources 717

2031 Wind Power 719

2032 Wave Power 720

2033 Solar Power 721

20331 Concentrated Solar Power 721

20332 Photovoltaic Cells 721

20333 Dye-Sensitized Solar Cells 722

20334 Artificial Photosynthesis 724

2034 Nuclear Energy 726

2035 Methane Hydrate 727

2036 The Hydrogen Economy 728

2037 Fuel Cells 729

2038 Electric Vehicles 735

204 Pollution 736

2041 The Ozone Layer 738

2042 Trace Chemicals 742

20421 Pesticides 742

20422 Nonpesticide Lipophiles 743

2043 Air Pollution 744

20431 Sulfur Dioxide Particulates 745

20432 Automobile Exhaust Emissions 748

2044 Water Treatment 750

2045 Solid Wastes 752

20451 Waste Prevention 753

20452 Recycling 754

20453 CombustionIncineration 755

20454 Sanitary Landfill 756

2046 Petrochemical Industry Wastes 758

2047 Other Environmental Problems 759

205 Valediction 759

Endnotes 761

Appendix A A Note on Cost Calculations 765

Appendix B Units and Conversion Factors 771

Appendix C Special Units in the Chemical Industry 773

Appendix D The Importance of Shale Gas and Shale Oil 775

Index 779

CONTENTS xxi

PREFACE

This third edition of Industrial Organic Chemicals is prompted by the impact of

globalization and of threats to the environment This is not to say that industrial

chemistry has stood still ndash very much the reverse and we have featured much new

chemistry All the same our earlier books were about the exciting new world of

petrochemical feedstocks and the ingenious new products that could be made

from them In this edition the exciting new processes have become the dull

traditional ones Well-established processes of technology transfer have carried

them to developing countries especially those that produce petrochemical feed-

stocks In addition humankindrsquos activities are seen both as depleting the resources

of the planet and of polluting it to the point at which humankind will drown in its

own effluvia The extent of these threats is hotly contested nonetheless the

chemical industry both contributes to the problems and is instrumental in trying to

solve them

There have been many developments since the second edition and the following

topics have gained especially in significance

The world chemical industry has migrated from the United States Western

Europe and Japan to theMiddle East and to Asia-Pacific especially ChinaWill

shale oil and gas bring it back (See Appendix D)

There is increased emphasis on environmental issues with pressure on com-

panies to clean up polluting processes or replace them with environmentally

friendly ones

Globalization has changed patterns of transportation of chemicals with for

example solid polymers rather than petrochemical feedstocks being shipped

from the Middle East

The discovery of vast reserves of shale gas has altered the long-term predictions

of resource depletion in the United States and other countries

Considerations of sustainability and the threat of climate change have prompted

research into processes (including electricity generation) that produce less or no

carbon dioxide or come from renewable resources

We have retained some material that is now largely of historical interest partly

for sentimental reasons but partly because the three authors have watched the

xxiii

meteoric rise of the chemical industry from its early days to its present-day

maturity We think there is a value in our readers observing how technology has

developed and the social technological and economic changes that have brought

it to its present position

HAROLD A WITTCOFF

xxiv PREFACE

PREFACE TO THE FIRST EDITION

In the early 1970s one of us (BGR) wrote a book celebrating the rapid growth of the

adolescent chemical industry The organic chemicals industry at the timewas growing

at four times the rate of the economy It was indicated nonetheless that ldquotrees do not

grow to the skyrdquo In 1980 in another book we both declared the industry to bemiddle-

aged with slow or zero growth In this totally revised and expanded version of our

earlier book we reflect that the industry at any rate in the developedworld is showing

many of the illnesses of late middle-age

The problems have arisen first from the undisciplined building of excess capacity

with consequent fierce competition and low prices Second the entry of numerous

developing countries into the industry has exacerbated the situation (Section 136)

and third there has beenmuch stricter government legislation (Section 137) There is

massive worldwide restructuring and continual shifting of commodity chemical

manufacturing to areas other than the United States Western Europe and Japan

The Middle East and Southeast Asia are the principal new players in the game

Perhaps this trend will continue and the present developed world will in the future

confine itself to themanufacture of specialties but the economic and political forces at

work are more complex than that We hope to be able to discuss their resolution in

another edition in about 10 yearsrsquo time

Meanwhile some things have not changed The organic chemicals industry is still

based on seven basic raw materials all deriving from petroleum and natural gas The

wisdom of teaching about the chemical industry on the basis of these seven building

blocks has been confirmed by the fact that since the publication of our first book one

of us (HAW) has delivered by invitation 300 courses in 28 countries on the

fundamentals of the industry based on this pattern Most of these courses are for

industrial personnel but academia has not been neglected

Furthermore some changes have been positive For example there have been

exciting new processes such as the development of metallocene catalysts (Section

15312) Section 461 describes new methyl methacrylate processes that give a

potentially cheaper product that do not produce ecologically undesirable ammonium

hydrogen sulfate by-product or (in another process) that eliminate the use of

dangerous hydrogen cyanide

In this book our main objective is still to present the technology of the organic

chemicals industry as an organized body of knowledge so that both the neophyte and

the experienced practitioner can see the broad picture Nonetheless we have

expanded its scope to include not only new processes but many apparently less

xxv

important reactions that are significant because they give rise to the more profitable

specialty chemicals The lesser volume chemicals have been clearly delineated as

such and the reader who wishes to see the industry on the basis of its large tonnage

products can omit these sections

We hope this bookwill be useful both to college students who have studied organic

chemistry and to graduates and industrial chemists whowork in or are interested in the

chemical industry Even though much of the chemistry has remained the same the

change in the way the industry looks at its problems provides ample justification for

our offering this edition as a fresh perspective on industrial organic chemicals

xxvi PREFACE TO THE FIRST EDITION

PREFACE TO THE SECOND EDITION

In the preface to the first edition we expressed the hope that we could comment on the

chemical industryrsquos evolution in 10 yearsrsquo time Dramatic changes have motivated us

to compress this time frame There have been unprecedented restructuring severe and

complicated feedstock problems and massive shifts of capacity to developing

countries whose economic and political stability is in doubt Possible terrorist

activity dictates elaborate safety and security procedures and the design of plants

with small inventories is a priority

To increase our cover particularly of the patent literature we have invited Dr

Jeffrey S Plotkin Director of the Process Evaluation and Research Planning program

at Nexant ChemSystems to join us as co-author

xxvii

93 Aniline 354

931 440-Diphenylmethane Isocyanate 357

94 Alkylbenzenes 361

95 Maleic Anhydride 362

96 Chlorinated Benzenes 363

97 Dihydroxybenzenes 364

971 Hydroquinone 364

972 Resorcinol 368

973 Catechol 369

98 Anthraquinone 370

981 Hydrogen Peroxide 371

Endnotes 372

10 Chemicals from Toluene 375

101 Hydrodealkylation Disproportionation and Transalkylation 375

102 Solvents 378

103 Dinitrotoluene and Toluene Diisocyanate 378

104 Lesser Volume Chemicals from Toluene 380

Endnotes 382

11 Chemicals from Xylenes 383

111 o-Xylene and Phthalic Anhydride 386

1111 Plasticizers 387

1112 Alkyd Resins 391

1113 Unsaturated Polyester Resin 393

112 m-Xylene and Isophthalic Acid 395

1121 Uses of Isophthalic Acid 396

113 p-Xylene and Terephthalic AcidDimethyl Terephthalate 397

1131 Oxidation of p-Xylene 398

1132 Alternate Sources for Terephthalic Acid 400

1133 Poly(ethylene terephthalate) 400

1134 Lower Volume Polymers from Terephthalic Acid 403

Endnotes 404

xiv CONTENTS

12 Chemicals from Methane 407

121 Hydrocyanic Acid 408

122 Halogenated Methanes 411

1221 Chloromethane 412

1222 Dichloromethane 413

1223 Trichloromethane 413

1224 Fluorocarbons 414

1225 Tetrachloromethane and Carbon Disulfide 414

1226 Bromomethane 416

123 Acetylene 417

1231 14-Butanediol and 2-Methyl-13-propanediol 419

1232 Lesser Uses for Acetylene 423

124 Synthesis Gas 424

1241 Steam Reforming of Methane 425

1242 Variants of Steam Reforming 427

1243 Partial Oxidation of Hydrocarbons 428

1244 Solid Feedstocks 428

1245 Hydrogen 429

125 Chemicals from Synthesis Gas 429

1251 Ammonia and Its Derivatives 430

12511 The Crisis of Nitrogen Depletion 430

12512 Ammonia Manufacture 431

12513 Urea and Melamine Resins 434

1252 Methanol 435

12521 Formaldehyde 438

12522 Acetic Acid 439

12523 Acetic Anhydride 442

12524 Methanol to Gasoline 445

12525 Methanol to Olefins 446

12526 Lower Volume and Proposed Uses for Methanol 448

12527 C1-Based Development Processes 452

126 Carbon Monoxide Chemistry 454

1261 Proposed Chemistry Based on Carbon Monoxide 455

127 Gas-to-Liquid Fuels 459

1271 Sasol GTL Technology 459

1272 Shell Middle Distillate Synthesis 459

CONTENTS xv

1273 Other GTL Technologies 460

Endnotes 460

13 Chemicals from Alkanes 463

131 Functionalization of Methane 464

1311 Methane to MethanolFormaldehyde 464

1312 Dimerization of Methane 466

1313 Aromatization of Methane 467

132 Functionalization of C2ndashC4 Alkanes 468

1321 Oxidation of C2ndashC4 Alkanes 468

1322 Dehydrogenation of C2ndashC4 Alkanes 470

1323 Aromatization of C2ndashC4Alkanes 471

133 Carbon Black 472

Endnotes 473

14 Chemicals from Coal 475

141 Chemicals from Coke Oven Distillate 477

142 The FischerndashTropsch Reaction 480

143 Coal Hydrogenation 484

144 Substitute Natural Gas 485

145 SNG and Synthesis Gas Technology 485

146 Underground Coal Gasification 488

147 Calcium Carbide 488

1471 The Chinese Chemicals to Coal Program 489

148 Coal and the Environment 490

Endnotes 491

15 Fats and Oils 493

151 Markets for Fats and Oils 495

152 Purification of Fats and Oils 497

153 Fatty Acids 499

1531 Applications of Fatty Acids 501

154 Fatty Nitrogen Compounds 502

155 ldquoDimerrdquo Acid 504

xvi CONTENTS

156 Aminoamides and Imidazolines 506

157 Azelaic Pelargonic and Petroselinic Acids 507

158 Fatty Alcohols 508

159 Epoxidized Oils 509

1510 Ricinoleic Acid 510

1511 Glycerol 512

15111 Established Glycerol Uses 512

1512 Alcoholysis of Fats and Oils 513

15121 Cocoa Butter and Mothersrsquo Milk 513

151211 Mothersrsquo Milk 515

15122 Trans Fats and Interesterification 515

15123 Biodiesel and Lubricants 516

151231 Algae 518

1513 Alkyl Polyglycosides 519

1514 Non-Caloric Fat-like Substances 519

Endnotes 520

16 Carbohydrates 523

161 Sugars and Sorbitol 523

1611 Isosorbide 530

162 Furfural 530

163 Starch 532

164 Cellulose 535

1641 Miscellaneous Chemicals from Wood 539

16411 Vanillin 541

16412 Levulinic Acid 542

165 Gums 543

166 Fermentation and Biotechnology 544

1661 Amino Acids 547

16611 L-Glutamic Acid 547

16612 L-Lysine 547

16613 L-Aspartic Acid 548

16614 L-Cysteine 549

1662 Polymers 550

CONTENTS xvii

1663 Proteins by Recombinant DNA Technology 550

1664 Fermentation and Renewables Scenarios 551

1665 Biofuels 554

16651 The Brazilian Experience 554

16652 Is US Bioethanol a Renewable

Energy Source 555

16653 Biomass as Feedstock 556

16654 Catalytic Bioforming 556

16655 Biotechnology Versus Synthesis Gas 557

Endnotes 558

17 How Polymers Are Made 561

171 Polymerization 565

172 Functionality 568

173 Step Growth and Chain Growth Polymerizations 571

1731 Free Radical Polymerization 573

1732 Chain Transfer 575

1733 Copolymerization 577

1734 Molecular Weight 579

1735 Polymerization Procedures 580

17351 Photoinitiation 582

1736 Ionic Polymerization 584

1737 Living Polymers 589

1738 Block Copolymers 589

1739 Graft Copolymers 592

17310 Metal Complex Catalysts 593

17311 Metal Oxide Catalysts 598

17312 Metallocene and Other Single Site Catalysts 599

173121 Single Site Nonmetallocene Catalysts 602

173122 Late Transition Metal Catalysts 603

173123 Commercial Prospects of LLDPEs 604

174 Examples of Step Polymerization 605

1741 Phenoplasts and Aminoplasts 605

1742 Polyurethanes 606

1743 Epoxy Resins 611

1744 Dendritic and Hyperbranched Polymers 613

1745 Conducting Polymers 617

1746 Conducting and Semiconducting Inks 621

xviii CONTENTS

175 Polymer Properties 622

1751 Crystallinity 622

1752 Glass Transition Temperature Crystalline

Melting Point and Softening Temperature 626

1753 Molecular Cohesion 628

1754 StressndashStrain Diagrams 628

176 Classes of Polymers 630

177 Plastics Fabrication Techniques 631

Endnotes 635

18 Industrial Catalysis 637

181 Catalyst Choice 637

1811 Reaction Velocity and Selectivity 638

1812 Recovery of Unchanged Catalyst 641

1813 Catalyst Deactivation 642

1814 Access to Nonequilibrium Products 642

182 Homogeneous and Heterogeneous Catalysis 643

1821 Reactors for Heterogeneous Catalysts 644

1822 Immobilization of Homogeneous Catalysts 646

183 Catalyst Markets 647

184 Catalysis by Acids and Bases 651

185 Dual Function Catalysis 654

186 Catalysis by Metals Semiconductors and Insulators 655

1861 Catalysts for Automobile Emission Control 656

187 Coordination Catalysis 657

1871 Catalysts for Stereoregular Compounds 658

1872 Asymmetric Synthesis 660

188 Enzymes 661

1881 Catalytic Antibodies 663

189 Shape-Selective Catalysts 664

1810 Phase-Transfer and Fluorous Biphase Catalysis 669

1811 Nanocatalysis 670

1812 Catalysts of the Future 673

18121 Catalyst Design 673

18122 Higher Selectivities 673

CONTENTS xix

18123 Catalysts with Greater Activity 674

18124 Pollution Problems 675

18125 Catalysts for New Reactions 675

18126 Catalysts that Mimic Natural Catalysts 676

18127 Catalyst Discovery Via High Throughput

Experimentation 676

Endnotes 677

19 Green Chemistry 681

191 The Decline of Acetylene Chemistry 683

192 Nylon 683

193 Replacement of Phosgene 684

194 Monomethylation by Dimethyl Carbonate 685

195 Liquid and Supercritical Carbon Dioxide and Water 685

196 Ionic Liquids 687

197 Photocatalysts 690

198 Paired Electrosynthesis 691

199 ldquoGreenrdquo Pharmaceuticals 692

1991 Ibuprofen 692

1992 Sertraline 694

1993 Pharmaceuticals from ldquoRenewablesrdquo 696

1910 Catalytic Dehydrogenation of Diethanolamine 698

1911 Genetic Manipulation 698

1912 Biodegradable Packaging 698

19121 Polyhydroxyalkanoates 701

1913 The Presidential Green Chemistry Challenge Program 703

Endnotes 704

20 Sustainability 707

201 Climate Change 708

202 Resource Depletion 712

2021 Food Water and People 713

20211 Food 713

20212 Water 714

20213 People 715

xx CONTENTS

203 Energy Sources 717

2031 Wind Power 719

2032 Wave Power 720

2033 Solar Power 721

20331 Concentrated Solar Power 721

20332 Photovoltaic Cells 721

20333 Dye-Sensitized Solar Cells 722

20334 Artificial Photosynthesis 724

2034 Nuclear Energy 726

2035 Methane Hydrate 727

2036 The Hydrogen Economy 728

2037 Fuel Cells 729

2038 Electric Vehicles 735

204 Pollution 736

2041 The Ozone Layer 738

2042 Trace Chemicals 742

20421 Pesticides 742

20422 Nonpesticide Lipophiles 743

2043 Air Pollution 744

20431 Sulfur Dioxide Particulates 745

20432 Automobile Exhaust Emissions 748

2044 Water Treatment 750

2045 Solid Wastes 752

20451 Waste Prevention 753

20452 Recycling 754

20453 CombustionIncineration 755

20454 Sanitary Landfill 756

2046 Petrochemical Industry Wastes 758

2047 Other Environmental Problems 759

205 Valediction 759

Endnotes 761

Appendix A A Note on Cost Calculations 765

Appendix B Units and Conversion Factors 771

Appendix C Special Units in the Chemical Industry 773

Appendix D The Importance of Shale Gas and Shale Oil 775

Index 779

CONTENTS xxi

PREFACE

This third edition of Industrial Organic Chemicals is prompted by the impact of

globalization and of threats to the environment This is not to say that industrial

chemistry has stood still ndash very much the reverse and we have featured much new

chemistry All the same our earlier books were about the exciting new world of

petrochemical feedstocks and the ingenious new products that could be made

from them In this edition the exciting new processes have become the dull

traditional ones Well-established processes of technology transfer have carried

them to developing countries especially those that produce petrochemical feed-

stocks In addition humankindrsquos activities are seen both as depleting the resources

of the planet and of polluting it to the point at which humankind will drown in its

own effluvia The extent of these threats is hotly contested nonetheless the

chemical industry both contributes to the problems and is instrumental in trying to

solve them

There have been many developments since the second edition and the following

topics have gained especially in significance

The world chemical industry has migrated from the United States Western

Europe and Japan to theMiddle East and to Asia-Pacific especially ChinaWill

shale oil and gas bring it back (See Appendix D)

There is increased emphasis on environmental issues with pressure on com-

panies to clean up polluting processes or replace them with environmentally

friendly ones

Globalization has changed patterns of transportation of chemicals with for

example solid polymers rather than petrochemical feedstocks being shipped

from the Middle East

The discovery of vast reserves of shale gas has altered the long-term predictions

of resource depletion in the United States and other countries

Considerations of sustainability and the threat of climate change have prompted

research into processes (including electricity generation) that produce less or no

carbon dioxide or come from renewable resources

We have retained some material that is now largely of historical interest partly

for sentimental reasons but partly because the three authors have watched the

xxiii

meteoric rise of the chemical industry from its early days to its present-day

maturity We think there is a value in our readers observing how technology has

developed and the social technological and economic changes that have brought

it to its present position

HAROLD A WITTCOFF

xxiv PREFACE

PREFACE TO THE FIRST EDITION

In the early 1970s one of us (BGR) wrote a book celebrating the rapid growth of the

adolescent chemical industry The organic chemicals industry at the timewas growing

at four times the rate of the economy It was indicated nonetheless that ldquotrees do not

grow to the skyrdquo In 1980 in another book we both declared the industry to bemiddle-

aged with slow or zero growth In this totally revised and expanded version of our

earlier book we reflect that the industry at any rate in the developedworld is showing

many of the illnesses of late middle-age

The problems have arisen first from the undisciplined building of excess capacity

with consequent fierce competition and low prices Second the entry of numerous

developing countries into the industry has exacerbated the situation (Section 136)

and third there has beenmuch stricter government legislation (Section 137) There is

massive worldwide restructuring and continual shifting of commodity chemical

manufacturing to areas other than the United States Western Europe and Japan

The Middle East and Southeast Asia are the principal new players in the game

Perhaps this trend will continue and the present developed world will in the future

confine itself to themanufacture of specialties but the economic and political forces at

work are more complex than that We hope to be able to discuss their resolution in

another edition in about 10 yearsrsquo time

Meanwhile some things have not changed The organic chemicals industry is still

based on seven basic raw materials all deriving from petroleum and natural gas The

wisdom of teaching about the chemical industry on the basis of these seven building

blocks has been confirmed by the fact that since the publication of our first book one

of us (HAW) has delivered by invitation 300 courses in 28 countries on the

fundamentals of the industry based on this pattern Most of these courses are for

industrial personnel but academia has not been neglected

Furthermore some changes have been positive For example there have been

exciting new processes such as the development of metallocene catalysts (Section

15312) Section 461 describes new methyl methacrylate processes that give a

potentially cheaper product that do not produce ecologically undesirable ammonium

hydrogen sulfate by-product or (in another process) that eliminate the use of

dangerous hydrogen cyanide

In this book our main objective is still to present the technology of the organic

chemicals industry as an organized body of knowledge so that both the neophyte and

the experienced practitioner can see the broad picture Nonetheless we have

expanded its scope to include not only new processes but many apparently less

xxv

important reactions that are significant because they give rise to the more profitable

specialty chemicals The lesser volume chemicals have been clearly delineated as

such and the reader who wishes to see the industry on the basis of its large tonnage

products can omit these sections

We hope this bookwill be useful both to college students who have studied organic

chemistry and to graduates and industrial chemists whowork in or are interested in the

chemical industry Even though much of the chemistry has remained the same the

change in the way the industry looks at its problems provides ample justification for

our offering this edition as a fresh perspective on industrial organic chemicals

xxvi PREFACE TO THE FIRST EDITION

PREFACE TO THE SECOND EDITION

In the preface to the first edition we expressed the hope that we could comment on the

chemical industryrsquos evolution in 10 yearsrsquo time Dramatic changes have motivated us

to compress this time frame There have been unprecedented restructuring severe and

complicated feedstock problems and massive shifts of capacity to developing

countries whose economic and political stability is in doubt Possible terrorist

activity dictates elaborate safety and security procedures and the design of plants

with small inventories is a priority

To increase our cover particularly of the patent literature we have invited Dr

Jeffrey S Plotkin Director of the Process Evaluation and Research Planning program

at Nexant ChemSystems to join us as co-author

xxvii

12 Chemicals from Methane 407

121 Hydrocyanic Acid 408

122 Halogenated Methanes 411

1221 Chloromethane 412

1222 Dichloromethane 413

1223 Trichloromethane 413

1224 Fluorocarbons 414

1225 Tetrachloromethane and Carbon Disulfide 414

1226 Bromomethane 416

123 Acetylene 417

1231 14-Butanediol and 2-Methyl-13-propanediol 419

1232 Lesser Uses for Acetylene 423

124 Synthesis Gas 424

1241 Steam Reforming of Methane 425

1242 Variants of Steam Reforming 427

1243 Partial Oxidation of Hydrocarbons 428

1244 Solid Feedstocks 428

1245 Hydrogen 429

125 Chemicals from Synthesis Gas 429

1251 Ammonia and Its Derivatives 430

12511 The Crisis of Nitrogen Depletion 430

12512 Ammonia Manufacture 431

12513 Urea and Melamine Resins 434

1252 Methanol 435

12521 Formaldehyde 438

12522 Acetic Acid 439

12523 Acetic Anhydride 442

12524 Methanol to Gasoline 445

12525 Methanol to Olefins 446

12526 Lower Volume and Proposed Uses for Methanol 448

12527 C1-Based Development Processes 452

126 Carbon Monoxide Chemistry 454

1261 Proposed Chemistry Based on Carbon Monoxide 455

127 Gas-to-Liquid Fuels 459

1271 Sasol GTL Technology 459

1272 Shell Middle Distillate Synthesis 459

CONTENTS xv

1273 Other GTL Technologies 460

Endnotes 460

13 Chemicals from Alkanes 463

131 Functionalization of Methane 464

1311 Methane to MethanolFormaldehyde 464

1312 Dimerization of Methane 466

1313 Aromatization of Methane 467

132 Functionalization of C2ndashC4 Alkanes 468

1321 Oxidation of C2ndashC4 Alkanes 468

1322 Dehydrogenation of C2ndashC4 Alkanes 470

1323 Aromatization of C2ndashC4Alkanes 471

133 Carbon Black 472

Endnotes 473

14 Chemicals from Coal 475

141 Chemicals from Coke Oven Distillate 477

142 The FischerndashTropsch Reaction 480

143 Coal Hydrogenation 484

144 Substitute Natural Gas 485

145 SNG and Synthesis Gas Technology 485

146 Underground Coal Gasification 488

147 Calcium Carbide 488

1471 The Chinese Chemicals to Coal Program 489

148 Coal and the Environment 490

Endnotes 491

15 Fats and Oils 493

151 Markets for Fats and Oils 495

152 Purification of Fats and Oils 497

153 Fatty Acids 499

1531 Applications of Fatty Acids 501

154 Fatty Nitrogen Compounds 502

155 ldquoDimerrdquo Acid 504

xvi CONTENTS

156 Aminoamides and Imidazolines 506

157 Azelaic Pelargonic and Petroselinic Acids 507

158 Fatty Alcohols 508

159 Epoxidized Oils 509

1510 Ricinoleic Acid 510

1511 Glycerol 512

15111 Established Glycerol Uses 512

1512 Alcoholysis of Fats and Oils 513

15121 Cocoa Butter and Mothersrsquo Milk 513

151211 Mothersrsquo Milk 515

15122 Trans Fats and Interesterification 515

15123 Biodiesel and Lubricants 516

151231 Algae 518

1513 Alkyl Polyglycosides 519

1514 Non-Caloric Fat-like Substances 519

Endnotes 520

16 Carbohydrates 523

161 Sugars and Sorbitol 523

1611 Isosorbide 530

162 Furfural 530

163 Starch 532

164 Cellulose 535

1641 Miscellaneous Chemicals from Wood 539

16411 Vanillin 541

16412 Levulinic Acid 542

165 Gums 543

166 Fermentation and Biotechnology 544

1661 Amino Acids 547

16611 L-Glutamic Acid 547

16612 L-Lysine 547

16613 L-Aspartic Acid 548

16614 L-Cysteine 549

1662 Polymers 550

CONTENTS xvii

1663 Proteins by Recombinant DNA Technology 550

1664 Fermentation and Renewables Scenarios 551

1665 Biofuels 554

16651 The Brazilian Experience 554

16652 Is US Bioethanol a Renewable

Energy Source 555

16653 Biomass as Feedstock 556

16654 Catalytic Bioforming 556

16655 Biotechnology Versus Synthesis Gas 557

Endnotes 558

17 How Polymers Are Made 561

171 Polymerization 565

172 Functionality 568

173 Step Growth and Chain Growth Polymerizations 571

1731 Free Radical Polymerization 573

1732 Chain Transfer 575

1733 Copolymerization 577

1734 Molecular Weight 579

1735 Polymerization Procedures 580

17351 Photoinitiation 582

1736 Ionic Polymerization 584

1737 Living Polymers 589

1738 Block Copolymers 589

1739 Graft Copolymers 592

17310 Metal Complex Catalysts 593

17311 Metal Oxide Catalysts 598

17312 Metallocene and Other Single Site Catalysts 599

173121 Single Site Nonmetallocene Catalysts 602

173122 Late Transition Metal Catalysts 603

173123 Commercial Prospects of LLDPEs 604

174 Examples of Step Polymerization 605

1741 Phenoplasts and Aminoplasts 605

1742 Polyurethanes 606

1743 Epoxy Resins 611

1744 Dendritic and Hyperbranched Polymers 613

1745 Conducting Polymers 617

1746 Conducting and Semiconducting Inks 621

xviii CONTENTS

175 Polymer Properties 622

1751 Crystallinity 622

1752 Glass Transition Temperature Crystalline

Melting Point and Softening Temperature 626

1753 Molecular Cohesion 628

1754 StressndashStrain Diagrams 628

176 Classes of Polymers 630

177 Plastics Fabrication Techniques 631

Endnotes 635

18 Industrial Catalysis 637

181 Catalyst Choice 637

1811 Reaction Velocity and Selectivity 638

1812 Recovery of Unchanged Catalyst 641

1813 Catalyst Deactivation 642

1814 Access to Nonequilibrium Products 642

182 Homogeneous and Heterogeneous Catalysis 643

1821 Reactors for Heterogeneous Catalysts 644

1822 Immobilization of Homogeneous Catalysts 646

183 Catalyst Markets 647

184 Catalysis by Acids and Bases 651

185 Dual Function Catalysis 654

186 Catalysis by Metals Semiconductors and Insulators 655

1861 Catalysts for Automobile Emission Control 656

187 Coordination Catalysis 657

1871 Catalysts for Stereoregular Compounds 658

1872 Asymmetric Synthesis 660

188 Enzymes 661

1881 Catalytic Antibodies 663

189 Shape-Selective Catalysts 664

1810 Phase-Transfer and Fluorous Biphase Catalysis 669

1811 Nanocatalysis 670

1812 Catalysts of the Future 673

18121 Catalyst Design 673

18122 Higher Selectivities 673

CONTENTS xix

18123 Catalysts with Greater Activity 674

18124 Pollution Problems 675

18125 Catalysts for New Reactions 675

18126 Catalysts that Mimic Natural Catalysts 676

18127 Catalyst Discovery Via High Throughput

Experimentation 676

Endnotes 677

19 Green Chemistry 681

191 The Decline of Acetylene Chemistry 683

192 Nylon 683

193 Replacement of Phosgene 684

194 Monomethylation by Dimethyl Carbonate 685

195 Liquid and Supercritical Carbon Dioxide and Water 685

196 Ionic Liquids 687

197 Photocatalysts 690

198 Paired Electrosynthesis 691

199 ldquoGreenrdquo Pharmaceuticals 692

1991 Ibuprofen 692

1992 Sertraline 694

1993 Pharmaceuticals from ldquoRenewablesrdquo 696

1910 Catalytic Dehydrogenation of Diethanolamine 698

1911 Genetic Manipulation 698

1912 Biodegradable Packaging 698

19121 Polyhydroxyalkanoates 701

1913 The Presidential Green Chemistry Challenge Program 703

Endnotes 704

20 Sustainability 707

201 Climate Change 708

202 Resource Depletion 712

2021 Food Water and People 713

20211 Food 713

20212 Water 714

20213 People 715

xx CONTENTS

203 Energy Sources 717

2031 Wind Power 719

2032 Wave Power 720

2033 Solar Power 721

20331 Concentrated Solar Power 721

20332 Photovoltaic Cells 721

20333 Dye-Sensitized Solar Cells 722

20334 Artificial Photosynthesis 724

2034 Nuclear Energy 726

2035 Methane Hydrate 727

2036 The Hydrogen Economy 728

2037 Fuel Cells 729

2038 Electric Vehicles 735

204 Pollution 736

2041 The Ozone Layer 738

2042 Trace Chemicals 742

20421 Pesticides 742

20422 Nonpesticide Lipophiles 743

2043 Air Pollution 744

20431 Sulfur Dioxide Particulates 745

20432 Automobile Exhaust Emissions 748

2044 Water Treatment 750

2045 Solid Wastes 752

20451 Waste Prevention 753

20452 Recycling 754

20453 CombustionIncineration 755

20454 Sanitary Landfill 756

2046 Petrochemical Industry Wastes 758

2047 Other Environmental Problems 759

205 Valediction 759

Endnotes 761

Appendix A A Note on Cost Calculations 765

Appendix B Units and Conversion Factors 771

Appendix C Special Units in the Chemical Industry 773

Appendix D The Importance of Shale Gas and Shale Oil 775

Index 779

CONTENTS xxi

PREFACE

This third edition of Industrial Organic Chemicals is prompted by the impact of

globalization and of threats to the environment This is not to say that industrial

chemistry has stood still ndash very much the reverse and we have featured much new

chemistry All the same our earlier books were about the exciting new world of

petrochemical feedstocks and the ingenious new products that could be made

from them In this edition the exciting new processes have become the dull

traditional ones Well-established processes of technology transfer have carried

them to developing countries especially those that produce petrochemical feed-

stocks In addition humankindrsquos activities are seen both as depleting the resources

of the planet and of polluting it to the point at which humankind will drown in its

own effluvia The extent of these threats is hotly contested nonetheless the

chemical industry both contributes to the problems and is instrumental in trying to

solve them

There have been many developments since the second edition and the following

topics have gained especially in significance

The world chemical industry has migrated from the United States Western

Europe and Japan to theMiddle East and to Asia-Pacific especially ChinaWill

shale oil and gas bring it back (See Appendix D)

There is increased emphasis on environmental issues with pressure on com-

panies to clean up polluting processes or replace them with environmentally

friendly ones

Globalization has changed patterns of transportation of chemicals with for

example solid polymers rather than petrochemical feedstocks being shipped

from the Middle East

The discovery of vast reserves of shale gas has altered the long-term predictions

of resource depletion in the United States and other countries

Considerations of sustainability and the threat of climate change have prompted

research into processes (including electricity generation) that produce less or no

carbon dioxide or come from renewable resources

We have retained some material that is now largely of historical interest partly

for sentimental reasons but partly because the three authors have watched the

xxiii

meteoric rise of the chemical industry from its early days to its present-day

maturity We think there is a value in our readers observing how technology has

developed and the social technological and economic changes that have brought

it to its present position

HAROLD A WITTCOFF

xxiv PREFACE

PREFACE TO THE FIRST EDITION

In the early 1970s one of us (BGR) wrote a book celebrating the rapid growth of the

adolescent chemical industry The organic chemicals industry at the timewas growing

at four times the rate of the economy It was indicated nonetheless that ldquotrees do not

grow to the skyrdquo In 1980 in another book we both declared the industry to bemiddle-

aged with slow or zero growth In this totally revised and expanded version of our

earlier book we reflect that the industry at any rate in the developedworld is showing

many of the illnesses of late middle-age

The problems have arisen first from the undisciplined building of excess capacity

with consequent fierce competition and low prices Second the entry of numerous

developing countries into the industry has exacerbated the situation (Section 136)

and third there has beenmuch stricter government legislation (Section 137) There is

massive worldwide restructuring and continual shifting of commodity chemical

manufacturing to areas other than the United States Western Europe and Japan

The Middle East and Southeast Asia are the principal new players in the game

Perhaps this trend will continue and the present developed world will in the future

confine itself to themanufacture of specialties but the economic and political forces at

work are more complex than that We hope to be able to discuss their resolution in

another edition in about 10 yearsrsquo time

Meanwhile some things have not changed The organic chemicals industry is still

based on seven basic raw materials all deriving from petroleum and natural gas The

wisdom of teaching about the chemical industry on the basis of these seven building

blocks has been confirmed by the fact that since the publication of our first book one

of us (HAW) has delivered by invitation 300 courses in 28 countries on the

fundamentals of the industry based on this pattern Most of these courses are for

industrial personnel but academia has not been neglected

Furthermore some changes have been positive For example there have been

exciting new processes such as the development of metallocene catalysts (Section

15312) Section 461 describes new methyl methacrylate processes that give a

potentially cheaper product that do not produce ecologically undesirable ammonium

hydrogen sulfate by-product or (in another process) that eliminate the use of

dangerous hydrogen cyanide

In this book our main objective is still to present the technology of the organic

chemicals industry as an organized body of knowledge so that both the neophyte and

the experienced practitioner can see the broad picture Nonetheless we have

expanded its scope to include not only new processes but many apparently less

xxv

important reactions that are significant because they give rise to the more profitable

specialty chemicals The lesser volume chemicals have been clearly delineated as

such and the reader who wishes to see the industry on the basis of its large tonnage

products can omit these sections

We hope this bookwill be useful both to college students who have studied organic

chemistry and to graduates and industrial chemists whowork in or are interested in the

chemical industry Even though much of the chemistry has remained the same the

change in the way the industry looks at its problems provides ample justification for

our offering this edition as a fresh perspective on industrial organic chemicals

xxvi PREFACE TO THE FIRST EDITION

PREFACE TO THE SECOND EDITION

In the preface to the first edition we expressed the hope that we could comment on the

chemical industryrsquos evolution in 10 yearsrsquo time Dramatic changes have motivated us

to compress this time frame There have been unprecedented restructuring severe and

complicated feedstock problems and massive shifts of capacity to developing

countries whose economic and political stability is in doubt Possible terrorist

activity dictates elaborate safety and security procedures and the design of plants

with small inventories is a priority

To increase our cover particularly of the patent literature we have invited Dr

Jeffrey S Plotkin Director of the Process Evaluation and Research Planning program

at Nexant ChemSystems to join us as co-author

xxvii

1273 Other GTL Technologies 460

Endnotes 460

13 Chemicals from Alkanes 463

131 Functionalization of Methane 464

1311 Methane to MethanolFormaldehyde 464

1312 Dimerization of Methane 466

1313 Aromatization of Methane 467

132 Functionalization of C2ndashC4 Alkanes 468

1321 Oxidation of C2ndashC4 Alkanes 468

1322 Dehydrogenation of C2ndashC4 Alkanes 470

1323 Aromatization of C2ndashC4Alkanes 471

133 Carbon Black 472

Endnotes 473

14 Chemicals from Coal 475

141 Chemicals from Coke Oven Distillate 477

142 The FischerndashTropsch Reaction 480

143 Coal Hydrogenation 484

144 Substitute Natural Gas 485

145 SNG and Synthesis Gas Technology 485

146 Underground Coal Gasification 488

147 Calcium Carbide 488

1471 The Chinese Chemicals to Coal Program 489

148 Coal and the Environment 490

Endnotes 491

15 Fats and Oils 493

151 Markets for Fats and Oils 495

152 Purification of Fats and Oils 497

153 Fatty Acids 499

1531 Applications of Fatty Acids 501

154 Fatty Nitrogen Compounds 502

155 ldquoDimerrdquo Acid 504

xvi CONTENTS

156 Aminoamides and Imidazolines 506

157 Azelaic Pelargonic and Petroselinic Acids 507

158 Fatty Alcohols 508

159 Epoxidized Oils 509

1510 Ricinoleic Acid 510

1511 Glycerol 512

15111 Established Glycerol Uses 512

1512 Alcoholysis of Fats and Oils 513

15121 Cocoa Butter and Mothersrsquo Milk 513

151211 Mothersrsquo Milk 515

15122 Trans Fats and Interesterification 515

15123 Biodiesel and Lubricants 516

151231 Algae 518

1513 Alkyl Polyglycosides 519

1514 Non-Caloric Fat-like Substances 519

Endnotes 520

16 Carbohydrates 523

161 Sugars and Sorbitol 523

1611 Isosorbide 530

162 Furfural 530

163 Starch 532

164 Cellulose 535

1641 Miscellaneous Chemicals from Wood 539

16411 Vanillin 541

16412 Levulinic Acid 542

165 Gums 543

166 Fermentation and Biotechnology 544

1661 Amino Acids 547

16611 L-Glutamic Acid 547

16612 L-Lysine 547

16613 L-Aspartic Acid 548

16614 L-Cysteine 549

1662 Polymers 550

CONTENTS xvii

1663 Proteins by Recombinant DNA Technology 550

1664 Fermentation and Renewables Scenarios 551

1665 Biofuels 554

16651 The Brazilian Experience 554

16652 Is US Bioethanol a Renewable

Energy Source 555

16653 Biomass as Feedstock 556

16654 Catalytic Bioforming 556

16655 Biotechnology Versus Synthesis Gas 557

Endnotes 558

17 How Polymers Are Made 561

171 Polymerization 565

172 Functionality 568

173 Step Growth and Chain Growth Polymerizations 571

1731 Free Radical Polymerization 573

1732 Chain Transfer 575

1733 Copolymerization 577

1734 Molecular Weight 579

1735 Polymerization Procedures 580

17351 Photoinitiation 582

1736 Ionic Polymerization 584

1737 Living Polymers 589

1738 Block Copolymers 589

1739 Graft Copolymers 592

17310 Metal Complex Catalysts 593

17311 Metal Oxide Catalysts 598

17312 Metallocene and Other Single Site Catalysts 599

173121 Single Site Nonmetallocene Catalysts 602

173122 Late Transition Metal Catalysts 603

173123 Commercial Prospects of LLDPEs 604

174 Examples of Step Polymerization 605

1741 Phenoplasts and Aminoplasts 605

1742 Polyurethanes 606

1743 Epoxy Resins 611

1744 Dendritic and Hyperbranched Polymers 613

1745 Conducting Polymers 617

1746 Conducting and Semiconducting Inks 621

xviii CONTENTS

175 Polymer Properties 622

1751 Crystallinity 622

1752 Glass Transition Temperature Crystalline

Melting Point and Softening Temperature 626

1753 Molecular Cohesion 628

1754 StressndashStrain Diagrams 628

176 Classes of Polymers 630

177 Plastics Fabrication Techniques 631

Endnotes 635

18 Industrial Catalysis 637

181 Catalyst Choice 637

1811 Reaction Velocity and Selectivity 638

1812 Recovery of Unchanged Catalyst 641

1813 Catalyst Deactivation 642

1814 Access to Nonequilibrium Products 642

182 Homogeneous and Heterogeneous Catalysis 643

1821 Reactors for Heterogeneous Catalysts 644

1822 Immobilization of Homogeneous Catalysts 646

183 Catalyst Markets 647

184 Catalysis by Acids and Bases 651

185 Dual Function Catalysis 654

186 Catalysis by Metals Semiconductors and Insulators 655

1861 Catalysts for Automobile Emission Control 656

187 Coordination Catalysis 657

1871 Catalysts for Stereoregular Compounds 658

1872 Asymmetric Synthesis 660

188 Enzymes 661

1881 Catalytic Antibodies 663

189 Shape-Selective Catalysts 664

1810 Phase-Transfer and Fluorous Biphase Catalysis 669

1811 Nanocatalysis 670

1812 Catalysts of the Future 673

18121 Catalyst Design 673

18122 Higher Selectivities 673

CONTENTS xix

18123 Catalysts with Greater Activity 674

18124 Pollution Problems 675

18125 Catalysts for New Reactions 675

18126 Catalysts that Mimic Natural Catalysts 676

18127 Catalyst Discovery Via High Throughput

Experimentation 676

Endnotes 677

19 Green Chemistry 681

191 The Decline of Acetylene Chemistry 683

192 Nylon 683

193 Replacement of Phosgene 684

194 Monomethylation by Dimethyl Carbonate 685

195 Liquid and Supercritical Carbon Dioxide and Water 685

196 Ionic Liquids 687

197 Photocatalysts 690

198 Paired Electrosynthesis 691

199 ldquoGreenrdquo Pharmaceuticals 692

1991 Ibuprofen 692

1992 Sertraline 694

1993 Pharmaceuticals from ldquoRenewablesrdquo 696

1910 Catalytic Dehydrogenation of Diethanolamine 698

1911 Genetic Manipulation 698

1912 Biodegradable Packaging 698

19121 Polyhydroxyalkanoates 701

1913 The Presidential Green Chemistry Challenge Program 703

Endnotes 704

20 Sustainability 707

201 Climate Change 708

202 Resource Depletion 712

2021 Food Water and People 713

20211 Food 713

20212 Water 714

20213 People 715

xx CONTENTS

203 Energy Sources 717

2031 Wind Power 719

2032 Wave Power 720

2033 Solar Power 721

20331 Concentrated Solar Power 721

20332 Photovoltaic Cells 721

20333 Dye-Sensitized Solar Cells 722

20334 Artificial Photosynthesis 724

2034 Nuclear Energy 726

2035 Methane Hydrate 727

2036 The Hydrogen Economy 728

2037 Fuel Cells 729

2038 Electric Vehicles 735

204 Pollution 736

2041 The Ozone Layer 738

2042 Trace Chemicals 742

20421 Pesticides 742

20422 Nonpesticide Lipophiles 743

2043 Air Pollution 744

20431 Sulfur Dioxide Particulates 745

20432 Automobile Exhaust Emissions 748

2044 Water Treatment 750

2045 Solid Wastes 752

20451 Waste Prevention 753

20452 Recycling 754

20453 CombustionIncineration 755

20454 Sanitary Landfill 756

2046 Petrochemical Industry Wastes 758

2047 Other Environmental Problems 759

205 Valediction 759

Endnotes 761

Appendix A A Note on Cost Calculations 765

Appendix B Units and Conversion Factors 771

Appendix C Special Units in the Chemical Industry 773

Appendix D The Importance of Shale Gas and Shale Oil 775

Index 779

CONTENTS xxi

PREFACE

This third edition of Industrial Organic Chemicals is prompted by the impact of

globalization and of threats to the environment This is not to say that industrial

chemistry has stood still ndash very much the reverse and we have featured much new

chemistry All the same our earlier books were about the exciting new world of

petrochemical feedstocks and the ingenious new products that could be made

from them In this edition the exciting new processes have become the dull

traditional ones Well-established processes of technology transfer have carried

them to developing countries especially those that produce petrochemical feed-

stocks In addition humankindrsquos activities are seen both as depleting the resources

of the planet and of polluting it to the point at which humankind will drown in its

own effluvia The extent of these threats is hotly contested nonetheless the

chemical industry both contributes to the problems and is instrumental in trying to

solve them

There have been many developments since the second edition and the following

topics have gained especially in significance

The world chemical industry has migrated from the United States Western

Europe and Japan to theMiddle East and to Asia-Pacific especially ChinaWill

shale oil and gas bring it back (See Appendix D)

There is increased emphasis on environmental issues with pressure on com-

panies to clean up polluting processes or replace them with environmentally

friendly ones

Globalization has changed patterns of transportation of chemicals with for

example solid polymers rather than petrochemical feedstocks being shipped

from the Middle East

The discovery of vast reserves of shale gas has altered the long-term predictions

of resource depletion in the United States and other countries

Considerations of sustainability and the threat of climate change have prompted

research into processes (including electricity generation) that produce less or no

carbon dioxide or come from renewable resources

We have retained some material that is now largely of historical interest partly

for sentimental reasons but partly because the three authors have watched the

xxiii

meteoric rise of the chemical industry from its early days to its present-day

maturity We think there is a value in our readers observing how technology has

developed and the social technological and economic changes that have brought

it to its present position

HAROLD A WITTCOFF

xxiv PREFACE

PREFACE TO THE FIRST EDITION

In the early 1970s one of us (BGR) wrote a book celebrating the rapid growth of the

adolescent chemical industry The organic chemicals industry at the timewas growing

at four times the rate of the economy It was indicated nonetheless that ldquotrees do not

grow to the skyrdquo In 1980 in another book we both declared the industry to bemiddle-

aged with slow or zero growth In this totally revised and expanded version of our

earlier book we reflect that the industry at any rate in the developedworld is showing

many of the illnesses of late middle-age

The problems have arisen first from the undisciplined building of excess capacity

with consequent fierce competition and low prices Second the entry of numerous

developing countries into the industry has exacerbated the situation (Section 136)

and third there has beenmuch stricter government legislation (Section 137) There is

massive worldwide restructuring and continual shifting of commodity chemical

manufacturing to areas other than the United States Western Europe and Japan

The Middle East and Southeast Asia are the principal new players in the game

Perhaps this trend will continue and the present developed world will in the future

confine itself to themanufacture of specialties but the economic and political forces at

work are more complex than that We hope to be able to discuss their resolution in

another edition in about 10 yearsrsquo time

Meanwhile some things have not changed The organic chemicals industry is still

based on seven basic raw materials all deriving from petroleum and natural gas The

wisdom of teaching about the chemical industry on the basis of these seven building

blocks has been confirmed by the fact that since the publication of our first book one

of us (HAW) has delivered by invitation 300 courses in 28 countries on the

fundamentals of the industry based on this pattern Most of these courses are for

industrial personnel but academia has not been neglected

Furthermore some changes have been positive For example there have been

exciting new processes such as the development of metallocene catalysts (Section

15312) Section 461 describes new methyl methacrylate processes that give a

potentially cheaper product that do not produce ecologically undesirable ammonium

hydrogen sulfate by-product or (in another process) that eliminate the use of

dangerous hydrogen cyanide

In this book our main objective is still to present the technology of the organic

chemicals industry as an organized body of knowledge so that both the neophyte and

the experienced practitioner can see the broad picture Nonetheless we have

expanded its scope to include not only new processes but many apparently less

xxv

important reactions that are significant because they give rise to the more profitable

specialty chemicals The lesser volume chemicals have been clearly delineated as

such and the reader who wishes to see the industry on the basis of its large tonnage

products can omit these sections

We hope this bookwill be useful both to college students who have studied organic

chemistry and to graduates and industrial chemists whowork in or are interested in the

chemical industry Even though much of the chemistry has remained the same the

change in the way the industry looks at its problems provides ample justification for

our offering this edition as a fresh perspective on industrial organic chemicals

xxvi PREFACE TO THE FIRST EDITION

PREFACE TO THE SECOND EDITION

In the preface to the first edition we expressed the hope that we could comment on the

chemical industryrsquos evolution in 10 yearsrsquo time Dramatic changes have motivated us

to compress this time frame There have been unprecedented restructuring severe and

complicated feedstock problems and massive shifts of capacity to developing

countries whose economic and political stability is in doubt Possible terrorist

activity dictates elaborate safety and security procedures and the design of plants

with small inventories is a priority

To increase our cover particularly of the patent literature we have invited Dr

Jeffrey S Plotkin Director of the Process Evaluation and Research Planning program

at Nexant ChemSystems to join us as co-author

xxvii

156 Aminoamides and Imidazolines 506

157 Azelaic Pelargonic and Petroselinic Acids 507

158 Fatty Alcohols 508

159 Epoxidized Oils 509

1510 Ricinoleic Acid 510

1511 Glycerol 512

15111 Established Glycerol Uses 512

1512 Alcoholysis of Fats and Oils 513

15121 Cocoa Butter and Mothersrsquo Milk 513

151211 Mothersrsquo Milk 515

15122 Trans Fats and Interesterification 515

15123 Biodiesel and Lubricants 516

151231 Algae 518

1513 Alkyl Polyglycosides 519

1514 Non-Caloric Fat-like Substances 519

Endnotes 520

16 Carbohydrates 523

161 Sugars and Sorbitol 523

1611 Isosorbide 530

162 Furfural 530

163 Starch 532

164 Cellulose 535

1641 Miscellaneous Chemicals from Wood 539

16411 Vanillin 541

16412 Levulinic Acid 542

165 Gums 543

166 Fermentation and Biotechnology 544

1661 Amino Acids 547

16611 L-Glutamic Acid 547

16612 L-Lysine 547

16613 L-Aspartic Acid 548

16614 L-Cysteine 549

1662 Polymers 550

CONTENTS xvii

1663 Proteins by Recombinant DNA Technology 550

1664 Fermentation and Renewables Scenarios 551

1665 Biofuels 554

16651 The Brazilian Experience 554

16652 Is US Bioethanol a Renewable

Energy Source 555

16653 Biomass as Feedstock 556

16654 Catalytic Bioforming 556

16655 Biotechnology Versus Synthesis Gas 557

Endnotes 558

17 How Polymers Are Made 561

171 Polymerization 565

172 Functionality 568

173 Step Growth and Chain Growth Polymerizations 571

1731 Free Radical Polymerization 573

1732 Chain Transfer 575

1733 Copolymerization 577

1734 Molecular Weight 579

1735 Polymerization Procedures 580

17351 Photoinitiation 582

1736 Ionic Polymerization 584

1737 Living Polymers 589

1738 Block Copolymers 589

1739 Graft Copolymers 592

17310 Metal Complex Catalysts 593

17311 Metal Oxide Catalysts 598

17312 Metallocene and Other Single Site Catalysts 599

173121 Single Site Nonmetallocene Catalysts 602

173122 Late Transition Metal Catalysts 603

173123 Commercial Prospects of LLDPEs 604

174 Examples of Step Polymerization 605

1741 Phenoplasts and Aminoplasts 605

1742 Polyurethanes 606

1743 Epoxy Resins 611

1744 Dendritic and Hyperbranched Polymers 613

1745 Conducting Polymers 617

1746 Conducting and Semiconducting Inks 621

xviii CONTENTS

175 Polymer Properties 622

1751 Crystallinity 622

1752 Glass Transition Temperature Crystalline

Melting Point and Softening Temperature 626

1753 Molecular Cohesion 628

1754 StressndashStrain Diagrams 628

176 Classes of Polymers 630

177 Plastics Fabrication Techniques 631

Endnotes 635

18 Industrial Catalysis 637

181 Catalyst Choice 637

1811 Reaction Velocity and Selectivity 638

1812 Recovery of Unchanged Catalyst 641

1813 Catalyst Deactivation 642

1814 Access to Nonequilibrium Products 642

182 Homogeneous and Heterogeneous Catalysis 643

1821 Reactors for Heterogeneous Catalysts 644

1822 Immobilization of Homogeneous Catalysts 646

183 Catalyst Markets 647

184 Catalysis by Acids and Bases 651

185 Dual Function Catalysis 654

186 Catalysis by Metals Semiconductors and Insulators 655

1861 Catalysts for Automobile Emission Control 656

187 Coordination Catalysis 657

1871 Catalysts for Stereoregular Compounds 658

1872 Asymmetric Synthesis 660

188 Enzymes 661

1881 Catalytic Antibodies 663

189 Shape-Selective Catalysts 664

1810 Phase-Transfer and Fluorous Biphase Catalysis 669

1811 Nanocatalysis 670

1812 Catalysts of the Future 673

18121 Catalyst Design 673

18122 Higher Selectivities 673

CONTENTS xix

18123 Catalysts with Greater Activity 674

18124 Pollution Problems 675

18125 Catalysts for New Reactions 675

18126 Catalysts that Mimic Natural Catalysts 676

18127 Catalyst Discovery Via High Throughput

Experimentation 676

Endnotes 677

19 Green Chemistry 681

191 The Decline of Acetylene Chemistry 683

192 Nylon 683

193 Replacement of Phosgene 684

194 Monomethylation by Dimethyl Carbonate 685

195 Liquid and Supercritical Carbon Dioxide and Water 685

196 Ionic Liquids 687

197 Photocatalysts 690

198 Paired Electrosynthesis 691

199 ldquoGreenrdquo Pharmaceuticals 692

1991 Ibuprofen 692

1992 Sertraline 694

1993 Pharmaceuticals from ldquoRenewablesrdquo 696

1910 Catalytic Dehydrogenation of Diethanolamine 698

1911 Genetic Manipulation 698

1912 Biodegradable Packaging 698

19121 Polyhydroxyalkanoates 701

1913 The Presidential Green Chemistry Challenge Program 703

Endnotes 704

20 Sustainability 707

201 Climate Change 708

202 Resource Depletion 712

2021 Food Water and People 713

20211 Food 713

20212 Water 714

20213 People 715

xx CONTENTS

203 Energy Sources 717

2031 Wind Power 719

2032 Wave Power 720

2033 Solar Power 721

20331 Concentrated Solar Power 721

20332 Photovoltaic Cells 721

20333 Dye-Sensitized Solar Cells 722

20334 Artificial Photosynthesis 724

2034 Nuclear Energy 726

2035 Methane Hydrate 727

2036 The Hydrogen Economy 728

2037 Fuel Cells 729

2038 Electric Vehicles 735

204 Pollution 736

2041 The Ozone Layer 738

2042 Trace Chemicals 742

20421 Pesticides 742

20422 Nonpesticide Lipophiles 743

2043 Air Pollution 744

20431 Sulfur Dioxide Particulates 745

20432 Automobile Exhaust Emissions 748

2044 Water Treatment 750

2045 Solid Wastes 752

20451 Waste Prevention 753

20452 Recycling 754

20453 CombustionIncineration 755

20454 Sanitary Landfill 756

2046 Petrochemical Industry Wastes 758

2047 Other Environmental Problems 759

205 Valediction 759

Endnotes 761

Appendix A A Note on Cost Calculations 765

Appendix B Units and Conversion Factors 771

Appendix C Special Units in the Chemical Industry 773

Appendix D The Importance of Shale Gas and Shale Oil 775

Index 779

CONTENTS xxi

PREFACE

This third edition of Industrial Organic Chemicals is prompted by the impact of

globalization and of threats to the environment This is not to say that industrial

chemistry has stood still ndash very much the reverse and we have featured much new

chemistry All the same our earlier books were about the exciting new world of

petrochemical feedstocks and the ingenious new products that could be made

from them In this edition the exciting new processes have become the dull

traditional ones Well-established processes of technology transfer have carried

them to developing countries especially those that produce petrochemical feed-

stocks In addition humankindrsquos activities are seen both as depleting the resources

of the planet and of polluting it to the point at which humankind will drown in its

own effluvia The extent of these threats is hotly contested nonetheless the

chemical industry both contributes to the problems and is instrumental in trying to

solve them

There have been many developments since the second edition and the following

topics have gained especially in significance

The world chemical industry has migrated from the United States Western

Europe and Japan to theMiddle East and to Asia-Pacific especially ChinaWill

shale oil and gas bring it back (See Appendix D)

There is increased emphasis on environmental issues with pressure on com-

panies to clean up polluting processes or replace them with environmentally

friendly ones

Globalization has changed patterns of transportation of chemicals with for

example solid polymers rather than petrochemical feedstocks being shipped

from the Middle East

The discovery of vast reserves of shale gas has altered the long-term predictions

of resource depletion in the United States and other countries

Considerations of sustainability and the threat of climate change have prompted

research into processes (including electricity generation) that produce less or no

carbon dioxide or come from renewable resources

We have retained some material that is now largely of historical interest partly

for sentimental reasons but partly because the three authors have watched the

xxiii

meteoric rise of the chemical industry from its early days to its present-day

maturity We think there is a value in our readers observing how technology has

developed and the social technological and economic changes that have brought

it to its present position

HAROLD A WITTCOFF

xxiv PREFACE

PREFACE TO THE FIRST EDITION

In the early 1970s one of us (BGR) wrote a book celebrating the rapid growth of the

adolescent chemical industry The organic chemicals industry at the timewas growing

at four times the rate of the economy It was indicated nonetheless that ldquotrees do not

grow to the skyrdquo In 1980 in another book we both declared the industry to bemiddle-

aged with slow or zero growth In this totally revised and expanded version of our

earlier book we reflect that the industry at any rate in the developedworld is showing

many of the illnesses of late middle-age

The problems have arisen first from the undisciplined building of excess capacity

with consequent fierce competition and low prices Second the entry of numerous

developing countries into the industry has exacerbated the situation (Section 136)

and third there has beenmuch stricter government legislation (Section 137) There is

massive worldwide restructuring and continual shifting of commodity chemical

manufacturing to areas other than the United States Western Europe and Japan

The Middle East and Southeast Asia are the principal new players in the game

Perhaps this trend will continue and the present developed world will in the future

confine itself to themanufacture of specialties but the economic and political forces at

work are more complex than that We hope to be able to discuss their resolution in

another edition in about 10 yearsrsquo time

Meanwhile some things have not changed The organic chemicals industry is still

based on seven basic raw materials all deriving from petroleum and natural gas The

wisdom of teaching about the chemical industry on the basis of these seven building

blocks has been confirmed by the fact that since the publication of our first book one

of us (HAW) has delivered by invitation 300 courses in 28 countries on the

fundamentals of the industry based on this pattern Most of these courses are for

industrial personnel but academia has not been neglected

Furthermore some changes have been positive For example there have been

exciting new processes such as the development of metallocene catalysts (Section

15312) Section 461 describes new methyl methacrylate processes that give a

potentially cheaper product that do not produce ecologically undesirable ammonium

hydrogen sulfate by-product or (in another process) that eliminate the use of

dangerous hydrogen cyanide

In this book our main objective is still to present the technology of the organic

chemicals industry as an organized body of knowledge so that both the neophyte and

the experienced practitioner can see the broad picture Nonetheless we have

expanded its scope to include not only new processes but many apparently less

xxv

important reactions that are significant because they give rise to the more profitable

specialty chemicals The lesser volume chemicals have been clearly delineated as

such and the reader who wishes to see the industry on the basis of its large tonnage

products can omit these sections

We hope this bookwill be useful both to college students who have studied organic

chemistry and to graduates and industrial chemists whowork in or are interested in the

chemical industry Even though much of the chemistry has remained the same the

change in the way the industry looks at its problems provides ample justification for

our offering this edition as a fresh perspective on industrial organic chemicals

xxvi PREFACE TO THE FIRST EDITION

PREFACE TO THE SECOND EDITION

In the preface to the first edition we expressed the hope that we could comment on the

chemical industryrsquos evolution in 10 yearsrsquo time Dramatic changes have motivated us

to compress this time frame There have been unprecedented restructuring severe and

complicated feedstock problems and massive shifts of capacity to developing

countries whose economic and political stability is in doubt Possible terrorist

activity dictates elaborate safety and security procedures and the design of plants

with small inventories is a priority

To increase our cover particularly of the patent literature we have invited Dr

Jeffrey S Plotkin Director of the Process Evaluation and Research Planning program

at Nexant ChemSystems to join us as co-author

xxvii

1663 Proteins by Recombinant DNA Technology 550

1664 Fermentation and Renewables Scenarios 551

1665 Biofuels 554

16651 The Brazilian Experience 554

16652 Is US Bioethanol a Renewable

Energy Source 555

16653 Biomass as Feedstock 556

16654 Catalytic Bioforming 556

16655 Biotechnology Versus Synthesis Gas 557

Endnotes 558

17 How Polymers Are Made 561

171 Polymerization 565

172 Functionality 568

173 Step Growth and Chain Growth Polymerizations 571

1731 Free Radical Polymerization 573

1732 Chain Transfer 575

1733 Copolymerization 577

1734 Molecular Weight 579

1735 Polymerization Procedures 580

17351 Photoinitiation 582

1736 Ionic Polymerization 584

1737 Living Polymers 589

1738 Block Copolymers 589

1739 Graft Copolymers 592

17310 Metal Complex Catalysts 593

17311 Metal Oxide Catalysts 598

17312 Metallocene and Other Single Site Catalysts 599

173121 Single Site Nonmetallocene Catalysts 602

173122 Late Transition Metal Catalysts 603

173123 Commercial Prospects of LLDPEs 604

174 Examples of Step Polymerization 605

1741 Phenoplasts and Aminoplasts 605

1742 Polyurethanes 606

1743 Epoxy Resins 611

1744 Dendritic and Hyperbranched Polymers 613

1745 Conducting Polymers 617

1746 Conducting and Semiconducting Inks 621

xviii CONTENTS

175 Polymer Properties 622

1751 Crystallinity 622

1752 Glass Transition Temperature Crystalline

Melting Point and Softening Temperature 626

1753 Molecular Cohesion 628

1754 StressndashStrain Diagrams 628

176 Classes of Polymers 630

177 Plastics Fabrication Techniques 631

Endnotes 635

18 Industrial Catalysis 637

181 Catalyst Choice 637

1811 Reaction Velocity and Selectivity 638

1812 Recovery of Unchanged Catalyst 641

1813 Catalyst Deactivation 642

1814 Access to Nonequilibrium Products 642

182 Homogeneous and Heterogeneous Catalysis 643

1821 Reactors for Heterogeneous Catalysts 644

1822 Immobilization of Homogeneous Catalysts 646

183 Catalyst Markets 647

184 Catalysis by Acids and Bases 651

185 Dual Function Catalysis 654

186 Catalysis by Metals Semiconductors and Insulators 655

1861 Catalysts for Automobile Emission Control 656

187 Coordination Catalysis 657

1871 Catalysts for Stereoregular Compounds 658

1872 Asymmetric Synthesis 660

188 Enzymes 661

1881 Catalytic Antibodies 663

189 Shape-Selective Catalysts 664

1810 Phase-Transfer and Fluorous Biphase Catalysis 669

1811 Nanocatalysis 670

1812 Catalysts of the Future 673

18121 Catalyst Design 673

18122 Higher Selectivities 673

CONTENTS xix

18123 Catalysts with Greater Activity 674

18124 Pollution Problems 675

18125 Catalysts for New Reactions 675

18126 Catalysts that Mimic Natural Catalysts 676

18127 Catalyst Discovery Via High Throughput

Experimentation 676

Endnotes 677

19 Green Chemistry 681

191 The Decline of Acetylene Chemistry 683

192 Nylon 683

193 Replacement of Phosgene 684

194 Monomethylation by Dimethyl Carbonate 685

195 Liquid and Supercritical Carbon Dioxide and Water 685

196 Ionic Liquids 687

197 Photocatalysts 690

198 Paired Electrosynthesis 691

199 ldquoGreenrdquo Pharmaceuticals 692

1991 Ibuprofen 692

1992 Sertraline 694

1993 Pharmaceuticals from ldquoRenewablesrdquo 696

1910 Catalytic Dehydrogenation of Diethanolamine 698

1911 Genetic Manipulation 698

1912 Biodegradable Packaging 698

19121 Polyhydroxyalkanoates 701

1913 The Presidential Green Chemistry Challenge Program 703

Endnotes 704

20 Sustainability 707

201 Climate Change 708

202 Resource Depletion 712

2021 Food Water and People 713

20211 Food 713

20212 Water 714

20213 People 715

xx CONTENTS

203 Energy Sources 717

2031 Wind Power 719

2032 Wave Power 720

2033 Solar Power 721

20331 Concentrated Solar Power 721

20332 Photovoltaic Cells 721

20333 Dye-Sensitized Solar Cells 722

20334 Artificial Photosynthesis 724

2034 Nuclear Energy 726

2035 Methane Hydrate 727

2036 The Hydrogen Economy 728

2037 Fuel Cells 729

2038 Electric Vehicles 735

204 Pollution 736

2041 The Ozone Layer 738

2042 Trace Chemicals 742

20421 Pesticides 742

20422 Nonpesticide Lipophiles 743

2043 Air Pollution 744

20431 Sulfur Dioxide Particulates 745

20432 Automobile Exhaust Emissions 748

2044 Water Treatment 750

2045 Solid Wastes 752

20451 Waste Prevention 753

20452 Recycling 754

20453 CombustionIncineration 755

20454 Sanitary Landfill 756

2046 Petrochemical Industry Wastes 758

2047 Other Environmental Problems 759

205 Valediction 759

Endnotes 761

Appendix A A Note on Cost Calculations 765

Appendix B Units and Conversion Factors 771

Appendix C Special Units in the Chemical Industry 773

Appendix D The Importance of Shale Gas and Shale Oil 775

Index 779

CONTENTS xxi

PREFACE

This third edition of Industrial Organic Chemicals is prompted by the impact of

globalization and of threats to the environment This is not to say that industrial

chemistry has stood still ndash very much the reverse and we have featured much new

chemistry All the same our earlier books were about the exciting new world of

petrochemical feedstocks and the ingenious new products that could be made

from them In this edition the exciting new processes have become the dull

traditional ones Well-established processes of technology transfer have carried

them to developing countries especially those that produce petrochemical feed-

stocks In addition humankindrsquos activities are seen both as depleting the resources

of the planet and of polluting it to the point at which humankind will drown in its

own effluvia The extent of these threats is hotly contested nonetheless the

chemical industry both contributes to the problems and is instrumental in trying to

solve them

There have been many developments since the second edition and the following

topics have gained especially in significance

The world chemical industry has migrated from the United States Western

Europe and Japan to theMiddle East and to Asia-Pacific especially ChinaWill

shale oil and gas bring it back (See Appendix D)

There is increased emphasis on environmental issues with pressure on com-

panies to clean up polluting processes or replace them with environmentally

friendly ones

Globalization has changed patterns of transportation of chemicals with for

example solid polymers rather than petrochemical feedstocks being shipped

from the Middle East

The discovery of vast reserves of shale gas has altered the long-term predictions

of resource depletion in the United States and other countries

Considerations of sustainability and the threat of climate change have prompted

research into processes (including electricity generation) that produce less or no

carbon dioxide or come from renewable resources

We have retained some material that is now largely of historical interest partly

for sentimental reasons but partly because the three authors have watched the

xxiii

meteoric rise of the chemical industry from its early days to its present-day

maturity We think there is a value in our readers observing how technology has

developed and the social technological and economic changes that have brought

it to its present position

HAROLD A WITTCOFF

xxiv PREFACE

PREFACE TO THE FIRST EDITION

In the early 1970s one of us (BGR) wrote a book celebrating the rapid growth of the

adolescent chemical industry The organic chemicals industry at the timewas growing

at four times the rate of the economy It was indicated nonetheless that ldquotrees do not

grow to the skyrdquo In 1980 in another book we both declared the industry to bemiddle-

aged with slow or zero growth In this totally revised and expanded version of our

earlier book we reflect that the industry at any rate in the developedworld is showing

many of the illnesses of late middle-age

The problems have arisen first from the undisciplined building of excess capacity

with consequent fierce competition and low prices Second the entry of numerous

developing countries into the industry has exacerbated the situation (Section 136)

and third there has beenmuch stricter government legislation (Section 137) There is

massive worldwide restructuring and continual shifting of commodity chemical

manufacturing to areas other than the United States Western Europe and Japan

The Middle East and Southeast Asia are the principal new players in the game

Perhaps this trend will continue and the present developed world will in the future

confine itself to themanufacture of specialties but the economic and political forces at

work are more complex than that We hope to be able to discuss their resolution in

another edition in about 10 yearsrsquo time

Meanwhile some things have not changed The organic chemicals industry is still

based on seven basic raw materials all deriving from petroleum and natural gas The

wisdom of teaching about the chemical industry on the basis of these seven building

blocks has been confirmed by the fact that since the publication of our first book one

of us (HAW) has delivered by invitation 300 courses in 28 countries on the

fundamentals of the industry based on this pattern Most of these courses are for

industrial personnel but academia has not been neglected

Furthermore some changes have been positive For example there have been

exciting new processes such as the development of metallocene catalysts (Section

15312) Section 461 describes new methyl methacrylate processes that give a

potentially cheaper product that do not produce ecologically undesirable ammonium

hydrogen sulfate by-product or (in another process) that eliminate the use of

dangerous hydrogen cyanide

In this book our main objective is still to present the technology of the organic

chemicals industry as an organized body of knowledge so that both the neophyte and

the experienced practitioner can see the broad picture Nonetheless we have

expanded its scope to include not only new processes but many apparently less

xxv

important reactions that are significant because they give rise to the more profitable

specialty chemicals The lesser volume chemicals have been clearly delineated as

such and the reader who wishes to see the industry on the basis of its large tonnage

products can omit these sections

We hope this bookwill be useful both to college students who have studied organic

chemistry and to graduates and industrial chemists whowork in or are interested in the

chemical industry Even though much of the chemistry has remained the same the

change in the way the industry looks at its problems provides ample justification for

our offering this edition as a fresh perspective on industrial organic chemicals

xxvi PREFACE TO THE FIRST EDITION

PREFACE TO THE SECOND EDITION

In the preface to the first edition we expressed the hope that we could comment on the

chemical industryrsquos evolution in 10 yearsrsquo time Dramatic changes have motivated us

to compress this time frame There have been unprecedented restructuring severe and

complicated feedstock problems and massive shifts of capacity to developing

countries whose economic and political stability is in doubt Possible terrorist

activity dictates elaborate safety and security procedures and the design of plants

with small inventories is a priority

To increase our cover particularly of the patent literature we have invited Dr

Jeffrey S Plotkin Director of the Process Evaluation and Research Planning program

at Nexant ChemSystems to join us as co-author

xxvii

175 Polymer Properties 622

1751 Crystallinity 622

1752 Glass Transition Temperature Crystalline

Melting Point and Softening Temperature 626

1753 Molecular Cohesion 628

1754 StressndashStrain Diagrams 628

176 Classes of Polymers 630

177 Plastics Fabrication Techniques 631

Endnotes 635

18 Industrial Catalysis 637

181 Catalyst Choice 637

1811 Reaction Velocity and Selectivity 638

1812 Recovery of Unchanged Catalyst 641

1813 Catalyst Deactivation 642

1814 Access to Nonequilibrium Products 642

182 Homogeneous and Heterogeneous Catalysis 643

1821 Reactors for Heterogeneous Catalysts 644

1822 Immobilization of Homogeneous Catalysts 646

183 Catalyst Markets 647

184 Catalysis by Acids and Bases 651

185 Dual Function Catalysis 654

186 Catalysis by Metals Semiconductors and Insulators 655

1861 Catalysts for Automobile Emission Control 656

187 Coordination Catalysis 657

1871 Catalysts for Stereoregular Compounds 658

1872 Asymmetric Synthesis 660

188 Enzymes 661

1881 Catalytic Antibodies 663

189 Shape-Selective Catalysts 664

1810 Phase-Transfer and Fluorous Biphase Catalysis 669

1811 Nanocatalysis 670

1812 Catalysts of the Future 673

18121 Catalyst Design 673

18122 Higher Selectivities 673

CONTENTS xix

18123 Catalysts with Greater Activity 674

18124 Pollution Problems 675

18125 Catalysts for New Reactions 675

18126 Catalysts that Mimic Natural Catalysts 676

18127 Catalyst Discovery Via High Throughput

Experimentation 676

Endnotes 677

19 Green Chemistry 681

191 The Decline of Acetylene Chemistry 683

192 Nylon 683

193 Replacement of Phosgene 684

194 Monomethylation by Dimethyl Carbonate 685

195 Liquid and Supercritical Carbon Dioxide and Water 685

196 Ionic Liquids 687

197 Photocatalysts 690

198 Paired Electrosynthesis 691

199 ldquoGreenrdquo Pharmaceuticals 692

1991 Ibuprofen 692

1992 Sertraline 694

1993 Pharmaceuticals from ldquoRenewablesrdquo 696

1910 Catalytic Dehydrogenation of Diethanolamine 698

1911 Genetic Manipulation 698

1912 Biodegradable Packaging 698

19121 Polyhydroxyalkanoates 701

1913 The Presidential Green Chemistry Challenge Program 703

Endnotes 704

20 Sustainability 707

201 Climate Change 708

202 Resource Depletion 712

2021 Food Water and People 713

20211 Food 713

20212 Water 714

20213 People 715

xx CONTENTS

203 Energy Sources 717

2031 Wind Power 719

2032 Wave Power 720

2033 Solar Power 721

20331 Concentrated Solar Power 721

20332 Photovoltaic Cells 721

20333 Dye-Sensitized Solar Cells 722

20334 Artificial Photosynthesis 724

2034 Nuclear Energy 726

2035 Methane Hydrate 727

2036 The Hydrogen Economy 728

2037 Fuel Cells 729

2038 Electric Vehicles 735

204 Pollution 736

2041 The Ozone Layer 738

2042 Trace Chemicals 742

20421 Pesticides 742

20422 Nonpesticide Lipophiles 743

2043 Air Pollution 744

20431 Sulfur Dioxide Particulates 745

20432 Automobile Exhaust Emissions 748

2044 Water Treatment 750

2045 Solid Wastes 752

20451 Waste Prevention 753

20452 Recycling 754

20453 CombustionIncineration 755

20454 Sanitary Landfill 756

2046 Petrochemical Industry Wastes 758

2047 Other Environmental Problems 759

205 Valediction 759

Endnotes 761

Appendix A A Note on Cost Calculations 765

Appendix B Units and Conversion Factors 771

Appendix C Special Units in the Chemical Industry 773

Appendix D The Importance of Shale Gas and Shale Oil 775

Index 779

CONTENTS xxi

PREFACE

This third edition of Industrial Organic Chemicals is prompted by the impact of

globalization and of threats to the environment This is not to say that industrial

chemistry has stood still ndash very much the reverse and we have featured much new

chemistry All the same our earlier books were about the exciting new world of

petrochemical feedstocks and the ingenious new products that could be made

from them In this edition the exciting new processes have become the dull

traditional ones Well-established processes of technology transfer have carried

them to developing countries especially those that produce petrochemical feed-

stocks In addition humankindrsquos activities are seen both as depleting the resources

of the planet and of polluting it to the point at which humankind will drown in its

own effluvia The extent of these threats is hotly contested nonetheless the

chemical industry both contributes to the problems and is instrumental in trying to

solve them

There have been many developments since the second edition and the following

topics have gained especially in significance

The world chemical industry has migrated from the United States Western

Europe and Japan to theMiddle East and to Asia-Pacific especially ChinaWill

shale oil and gas bring it back (See Appendix D)

There is increased emphasis on environmental issues with pressure on com-

panies to clean up polluting processes or replace them with environmentally

friendly ones

Globalization has changed patterns of transportation of chemicals with for

example solid polymers rather than petrochemical feedstocks being shipped

from the Middle East

The discovery of vast reserves of shale gas has altered the long-term predictions

of resource depletion in the United States and other countries

Considerations of sustainability and the threat of climate change have prompted

research into processes (including electricity generation) that produce less or no

carbon dioxide or come from renewable resources

We have retained some material that is now largely of historical interest partly

for sentimental reasons but partly because the three authors have watched the

xxiii

meteoric rise of the chemical industry from its early days to its present-day

maturity We think there is a value in our readers observing how technology has

developed and the social technological and economic changes that have brought

it to its present position

HAROLD A WITTCOFF

xxiv PREFACE

PREFACE TO THE FIRST EDITION

In the early 1970s one of us (BGR) wrote a book celebrating the rapid growth of the

adolescent chemical industry The organic chemicals industry at the timewas growing

at four times the rate of the economy It was indicated nonetheless that ldquotrees do not

grow to the skyrdquo In 1980 in another book we both declared the industry to bemiddle-

aged with slow or zero growth In this totally revised and expanded version of our

earlier book we reflect that the industry at any rate in the developedworld is showing

many of the illnesses of late middle-age

The problems have arisen first from the undisciplined building of excess capacity

with consequent fierce competition and low prices Second the entry of numerous

developing countries into the industry has exacerbated the situation (Section 136)

and third there has beenmuch stricter government legislation (Section 137) There is

massive worldwide restructuring and continual shifting of commodity chemical

manufacturing to areas other than the United States Western Europe and Japan

The Middle East and Southeast Asia are the principal new players in the game

Perhaps this trend will continue and the present developed world will in the future

confine itself to themanufacture of specialties but the economic and political forces at

work are more complex than that We hope to be able to discuss their resolution in

another edition in about 10 yearsrsquo time

Meanwhile some things have not changed The organic chemicals industry is still

based on seven basic raw materials all deriving from petroleum and natural gas The

wisdom of teaching about the chemical industry on the basis of these seven building

blocks has been confirmed by the fact that since the publication of our first book one

of us (HAW) has delivered by invitation 300 courses in 28 countries on the

fundamentals of the industry based on this pattern Most of these courses are for

industrial personnel but academia has not been neglected

Furthermore some changes have been positive For example there have been

exciting new processes such as the development of metallocene catalysts (Section

15312) Section 461 describes new methyl methacrylate processes that give a

potentially cheaper product that do not produce ecologically undesirable ammonium

hydrogen sulfate by-product or (in another process) that eliminate the use of

dangerous hydrogen cyanide

In this book our main objective is still to present the technology of the organic

chemicals industry as an organized body of knowledge so that both the neophyte and

the experienced practitioner can see the broad picture Nonetheless we have

expanded its scope to include not only new processes but many apparently less

xxv

important reactions that are significant because they give rise to the more profitable

specialty chemicals The lesser volume chemicals have been clearly delineated as

such and the reader who wishes to see the industry on the basis of its large tonnage

products can omit these sections

We hope this bookwill be useful both to college students who have studied organic

chemistry and to graduates and industrial chemists whowork in or are interested in the

chemical industry Even though much of the chemistry has remained the same the

change in the way the industry looks at its problems provides ample justification for

our offering this edition as a fresh perspective on industrial organic chemicals

xxvi PREFACE TO THE FIRST EDITION

PREFACE TO THE SECOND EDITION

In the preface to the first edition we expressed the hope that we could comment on the

chemical industryrsquos evolution in 10 yearsrsquo time Dramatic changes have motivated us

to compress this time frame There have been unprecedented restructuring severe and

complicated feedstock problems and massive shifts of capacity to developing

countries whose economic and political stability is in doubt Possible terrorist

activity dictates elaborate safety and security procedures and the design of plants

with small inventories is a priority

To increase our cover particularly of the patent literature we have invited Dr

Jeffrey S Plotkin Director of the Process Evaluation and Research Planning program

at Nexant ChemSystems to join us as co-author

xxvii

18123 Catalysts with Greater Activity 674

18124 Pollution Problems 675

18125 Catalysts for New Reactions 675

18126 Catalysts that Mimic Natural Catalysts 676

18127 Catalyst Discovery Via High Throughput

Experimentation 676

Endnotes 677

19 Green Chemistry 681

191 The Decline of Acetylene Chemistry 683

192 Nylon 683

193 Replacement of Phosgene 684

194 Monomethylation by Dimethyl Carbonate 685

195 Liquid and Supercritical Carbon Dioxide and Water 685

196 Ionic Liquids 687

197 Photocatalysts 690

198 Paired Electrosynthesis 691

199 ldquoGreenrdquo Pharmaceuticals 692

1991 Ibuprofen 692

1992 Sertraline 694

1993 Pharmaceuticals from ldquoRenewablesrdquo 696

1910 Catalytic Dehydrogenation of Diethanolamine 698

1911 Genetic Manipulation 698

1912 Biodegradable Packaging 698

19121 Polyhydroxyalkanoates 701

1913 The Presidential Green Chemistry Challenge Program 703

Endnotes 704

20 Sustainability 707

201 Climate Change 708

202 Resource Depletion 712

2021 Food Water and People 713

20211 Food 713

20212 Water 714

20213 People 715

xx CONTENTS

203 Energy Sources 717

2031 Wind Power 719

2032 Wave Power 720

2033 Solar Power 721

20331 Concentrated Solar Power 721

20332 Photovoltaic Cells 721

20333 Dye-Sensitized Solar Cells 722

20334 Artificial Photosynthesis 724

2034 Nuclear Energy 726

2035 Methane Hydrate 727

2036 The Hydrogen Economy 728

2037 Fuel Cells 729

2038 Electric Vehicles 735

204 Pollution 736

2041 The Ozone Layer 738

2042 Trace Chemicals 742

20421 Pesticides 742

20422 Nonpesticide Lipophiles 743

2043 Air Pollution 744

20431 Sulfur Dioxide Particulates 745

20432 Automobile Exhaust Emissions 748

2044 Water Treatment 750

2045 Solid Wastes 752

20451 Waste Prevention 753

20452 Recycling 754

20453 CombustionIncineration 755

20454 Sanitary Landfill 756

2046 Petrochemical Industry Wastes 758

2047 Other Environmental Problems 759

205 Valediction 759

Endnotes 761

Appendix A A Note on Cost Calculations 765

Appendix B Units and Conversion Factors 771

Appendix C Special Units in the Chemical Industry 773

Appendix D The Importance of Shale Gas and Shale Oil 775

Index 779

CONTENTS xxi

PREFACE

This third edition of Industrial Organic Chemicals is prompted by the impact of

globalization and of threats to the environment This is not to say that industrial

chemistry has stood still ndash very much the reverse and we have featured much new

chemistry All the same our earlier books were about the exciting new world of

petrochemical feedstocks and the ingenious new products that could be made

from them In this edition the exciting new processes have become the dull

traditional ones Well-established processes of technology transfer have carried

them to developing countries especially those that produce petrochemical feed-

stocks In addition humankindrsquos activities are seen both as depleting the resources

of the planet and of polluting it to the point at which humankind will drown in its

own effluvia The extent of these threats is hotly contested nonetheless the

chemical industry both contributes to the problems and is instrumental in trying to

solve them

There have been many developments since the second edition and the following

topics have gained especially in significance

The world chemical industry has migrated from the United States Western

Europe and Japan to theMiddle East and to Asia-Pacific especially ChinaWill

shale oil and gas bring it back (See Appendix D)

There is increased emphasis on environmental issues with pressure on com-

panies to clean up polluting processes or replace them with environmentally

friendly ones

Globalization has changed patterns of transportation of chemicals with for

example solid polymers rather than petrochemical feedstocks being shipped

from the Middle East

The discovery of vast reserves of shale gas has altered the long-term predictions

of resource depletion in the United States and other countries

Considerations of sustainability and the threat of climate change have prompted

research into processes (including electricity generation) that produce less or no

carbon dioxide or come from renewable resources

We have retained some material that is now largely of historical interest partly

for sentimental reasons but partly because the three authors have watched the

xxiii

meteoric rise of the chemical industry from its early days to its present-day

maturity We think there is a value in our readers observing how technology has

developed and the social technological and economic changes that have brought

it to its present position

HAROLD A WITTCOFF

xxiv PREFACE

PREFACE TO THE FIRST EDITION

In the early 1970s one of us (BGR) wrote a book celebrating the rapid growth of the

adolescent chemical industry The organic chemicals industry at the timewas growing

at four times the rate of the economy It was indicated nonetheless that ldquotrees do not

grow to the skyrdquo In 1980 in another book we both declared the industry to bemiddle-

aged with slow or zero growth In this totally revised and expanded version of our

earlier book we reflect that the industry at any rate in the developedworld is showing

many of the illnesses of late middle-age

The problems have arisen first from the undisciplined building of excess capacity

with consequent fierce competition and low prices Second the entry of numerous

developing countries into the industry has exacerbated the situation (Section 136)

and third there has beenmuch stricter government legislation (Section 137) There is

massive worldwide restructuring and continual shifting of commodity chemical

manufacturing to areas other than the United States Western Europe and Japan

The Middle East and Southeast Asia are the principal new players in the game

Perhaps this trend will continue and the present developed world will in the future

confine itself to themanufacture of specialties but the economic and political forces at

work are more complex than that We hope to be able to discuss their resolution in

another edition in about 10 yearsrsquo time

Meanwhile some things have not changed The organic chemicals industry is still

based on seven basic raw materials all deriving from petroleum and natural gas The

wisdom of teaching about the chemical industry on the basis of these seven building

blocks has been confirmed by the fact that since the publication of our first book one

of us (HAW) has delivered by invitation 300 courses in 28 countries on the

fundamentals of the industry based on this pattern Most of these courses are for

industrial personnel but academia has not been neglected

Furthermore some changes have been positive For example there have been

exciting new processes such as the development of metallocene catalysts (Section

15312) Section 461 describes new methyl methacrylate processes that give a

potentially cheaper product that do not produce ecologically undesirable ammonium

hydrogen sulfate by-product or (in another process) that eliminate the use of

dangerous hydrogen cyanide

In this book our main objective is still to present the technology of the organic

chemicals industry as an organized body of knowledge so that both the neophyte and

the experienced practitioner can see the broad picture Nonetheless we have

expanded its scope to include not only new processes but many apparently less

xxv

important reactions that are significant because they give rise to the more profitable

specialty chemicals The lesser volume chemicals have been clearly delineated as

such and the reader who wishes to see the industry on the basis of its large tonnage

products can omit these sections

We hope this bookwill be useful both to college students who have studied organic

chemistry and to graduates and industrial chemists whowork in or are interested in the

chemical industry Even though much of the chemistry has remained the same the

change in the way the industry looks at its problems provides ample justification for

our offering this edition as a fresh perspective on industrial organic chemicals

xxvi PREFACE TO THE FIRST EDITION

PREFACE TO THE SECOND EDITION

In the preface to the first edition we expressed the hope that we could comment on the

chemical industryrsquos evolution in 10 yearsrsquo time Dramatic changes have motivated us

to compress this time frame There have been unprecedented restructuring severe and

complicated feedstock problems and massive shifts of capacity to developing

countries whose economic and political stability is in doubt Possible terrorist

activity dictates elaborate safety and security procedures and the design of plants

with small inventories is a priority

To increase our cover particularly of the patent literature we have invited Dr

Jeffrey S Plotkin Director of the Process Evaluation and Research Planning program

at Nexant ChemSystems to join us as co-author

xxvii

203 Energy Sources 717

2031 Wind Power 719

2032 Wave Power 720

2033 Solar Power 721

20331 Concentrated Solar Power 721

20332 Photovoltaic Cells 721

20333 Dye-Sensitized Solar Cells 722

20334 Artificial Photosynthesis 724

2034 Nuclear Energy 726

2035 Methane Hydrate 727

2036 The Hydrogen Economy 728

2037 Fuel Cells 729

2038 Electric Vehicles 735

204 Pollution 736

2041 The Ozone Layer 738

2042 Trace Chemicals 742

20421 Pesticides 742

20422 Nonpesticide Lipophiles 743

2043 Air Pollution 744

20431 Sulfur Dioxide Particulates 745

20432 Automobile Exhaust Emissions 748

2044 Water Treatment 750

2045 Solid Wastes 752

20451 Waste Prevention 753

20452 Recycling 754

20453 CombustionIncineration 755

20454 Sanitary Landfill 756

2046 Petrochemical Industry Wastes 758

2047 Other Environmental Problems 759

205 Valediction 759

Endnotes 761

Appendix A A Note on Cost Calculations 765

Appendix B Units and Conversion Factors 771

Appendix C Special Units in the Chemical Industry 773

Appendix D The Importance of Shale Gas and Shale Oil 775

Index 779

CONTENTS xxi

PREFACE

This third edition of Industrial Organic Chemicals is prompted by the impact of

globalization and of threats to the environment This is not to say that industrial

chemistry has stood still ndash very much the reverse and we have featured much new

chemistry All the same our earlier books were about the exciting new world of

petrochemical feedstocks and the ingenious new products that could be made

from them In this edition the exciting new processes have become the dull

traditional ones Well-established processes of technology transfer have carried

them to developing countries especially those that produce petrochemical feed-

stocks In addition humankindrsquos activities are seen both as depleting the resources

of the planet and of polluting it to the point at which humankind will drown in its

own effluvia The extent of these threats is hotly contested nonetheless the

chemical industry both contributes to the problems and is instrumental in trying to

solve them

There have been many developments since the second edition and the following

topics have gained especially in significance

The world chemical industry has migrated from the United States Western

Europe and Japan to theMiddle East and to Asia-Pacific especially ChinaWill

shale oil and gas bring it back (See Appendix D)

There is increased emphasis on environmental issues with pressure on com-

panies to clean up polluting processes or replace them with environmentally

friendly ones

Globalization has changed patterns of transportation of chemicals with for

example solid polymers rather than petrochemical feedstocks being shipped

from the Middle East

The discovery of vast reserves of shale gas has altered the long-term predictions

of resource depletion in the United States and other countries

Considerations of sustainability and the threat of climate change have prompted

research into processes (including electricity generation) that produce less or no

carbon dioxide or come from renewable resources

We have retained some material that is now largely of historical interest partly

for sentimental reasons but partly because the three authors have watched the

xxiii

meteoric rise of the chemical industry from its early days to its present-day

maturity We think there is a value in our readers observing how technology has

developed and the social technological and economic changes that have brought

it to its present position

HAROLD A WITTCOFF

xxiv PREFACE

PREFACE TO THE FIRST EDITION

In the early 1970s one of us (BGR) wrote a book celebrating the rapid growth of the

adolescent chemical industry The organic chemicals industry at the timewas growing

at four times the rate of the economy It was indicated nonetheless that ldquotrees do not

grow to the skyrdquo In 1980 in another book we both declared the industry to bemiddle-

aged with slow or zero growth In this totally revised and expanded version of our

earlier book we reflect that the industry at any rate in the developedworld is showing

many of the illnesses of late middle-age

The problems have arisen first from the undisciplined building of excess capacity

with consequent fierce competition and low prices Second the entry of numerous

developing countries into the industry has exacerbated the situation (Section 136)

and third there has beenmuch stricter government legislation (Section 137) There is

massive worldwide restructuring and continual shifting of commodity chemical

manufacturing to areas other than the United States Western Europe and Japan

The Middle East and Southeast Asia are the principal new players in the game

Perhaps this trend will continue and the present developed world will in the future

confine itself to themanufacture of specialties but the economic and political forces at

work are more complex than that We hope to be able to discuss their resolution in

another edition in about 10 yearsrsquo time

Meanwhile some things have not changed The organic chemicals industry is still

based on seven basic raw materials all deriving from petroleum and natural gas The

wisdom of teaching about the chemical industry on the basis of these seven building

blocks has been confirmed by the fact that since the publication of our first book one

of us (HAW) has delivered by invitation 300 courses in 28 countries on the

fundamentals of the industry based on this pattern Most of these courses are for

industrial personnel but academia has not been neglected

Furthermore some changes have been positive For example there have been

exciting new processes such as the development of metallocene catalysts (Section

15312) Section 461 describes new methyl methacrylate processes that give a

potentially cheaper product that do not produce ecologically undesirable ammonium

hydrogen sulfate by-product or (in another process) that eliminate the use of

dangerous hydrogen cyanide

In this book our main objective is still to present the technology of the organic

chemicals industry as an organized body of knowledge so that both the neophyte and

the experienced practitioner can see the broad picture Nonetheless we have

expanded its scope to include not only new processes but many apparently less

xxv

important reactions that are significant because they give rise to the more profitable

specialty chemicals The lesser volume chemicals have been clearly delineated as

such and the reader who wishes to see the industry on the basis of its large tonnage

products can omit these sections

We hope this bookwill be useful both to college students who have studied organic

chemistry and to graduates and industrial chemists whowork in or are interested in the

chemical industry Even though much of the chemistry has remained the same the

change in the way the industry looks at its problems provides ample justification for

our offering this edition as a fresh perspective on industrial organic chemicals

xxvi PREFACE TO THE FIRST EDITION

PREFACE TO THE SECOND EDITION

In the preface to the first edition we expressed the hope that we could comment on the

chemical industryrsquos evolution in 10 yearsrsquo time Dramatic changes have motivated us

to compress this time frame There have been unprecedented restructuring severe and

complicated feedstock problems and massive shifts of capacity to developing

countries whose economic and political stability is in doubt Possible terrorist

activity dictates elaborate safety and security procedures and the design of plants

with small inventories is a priority

To increase our cover particularly of the patent literature we have invited Dr

Jeffrey S Plotkin Director of the Process Evaluation and Research Planning program

at Nexant ChemSystems to join us as co-author

xxvii

PREFACE

This third edition of Industrial Organic Chemicals is prompted by the impact of

globalization and of threats to the environment This is not to say that industrial

chemistry has stood still ndash very much the reverse and we have featured much new

chemistry All the same our earlier books were about the exciting new world of

petrochemical feedstocks and the ingenious new products that could be made

from them In this edition the exciting new processes have become the dull

traditional ones Well-established processes of technology transfer have carried

them to developing countries especially those that produce petrochemical feed-

stocks In addition humankindrsquos activities are seen both as depleting the resources

of the planet and of polluting it to the point at which humankind will drown in its

own effluvia The extent of these threats is hotly contested nonetheless the

chemical industry both contributes to the problems and is instrumental in trying to

solve them

There have been many developments since the second edition and the following

topics have gained especially in significance

The world chemical industry has migrated from the United States Western

Europe and Japan to theMiddle East and to Asia-Pacific especially ChinaWill

shale oil and gas bring it back (See Appendix D)

There is increased emphasis on environmental issues with pressure on com-

panies to clean up polluting processes or replace them with environmentally

friendly ones

Globalization has changed patterns of transportation of chemicals with for

example solid polymers rather than petrochemical feedstocks being shipped

from the Middle East

The discovery of vast reserves of shale gas has altered the long-term predictions

of resource depletion in the United States and other countries

Considerations of sustainability and the threat of climate change have prompted

research into processes (including electricity generation) that produce less or no

carbon dioxide or come from renewable resources

We have retained some material that is now largely of historical interest partly

for sentimental reasons but partly because the three authors have watched the

xxiii

meteoric rise of the chemical industry from its early days to its present-day

maturity We think there is a value in our readers observing how technology has

developed and the social technological and economic changes that have brought

it to its present position

HAROLD A WITTCOFF

xxiv PREFACE

PREFACE TO THE FIRST EDITION

In the early 1970s one of us (BGR) wrote a book celebrating the rapid growth of the

adolescent chemical industry The organic chemicals industry at the timewas growing

at four times the rate of the economy It was indicated nonetheless that ldquotrees do not

grow to the skyrdquo In 1980 in another book we both declared the industry to bemiddle-

aged with slow or zero growth In this totally revised and expanded version of our

earlier book we reflect that the industry at any rate in the developedworld is showing

many of the illnesses of late middle-age

The problems have arisen first from the undisciplined building of excess capacity

with consequent fierce competition and low prices Second the entry of numerous

developing countries into the industry has exacerbated the situation (Section 136)

and third there has beenmuch stricter government legislation (Section 137) There is

massive worldwide restructuring and continual shifting of commodity chemical

manufacturing to areas other than the United States Western Europe and Japan

The Middle East and Southeast Asia are the principal new players in the game

Perhaps this trend will continue and the present developed world will in the future

confine itself to themanufacture of specialties but the economic and political forces at

work are more complex than that We hope to be able to discuss their resolution in

another edition in about 10 yearsrsquo time

Meanwhile some things have not changed The organic chemicals industry is still

based on seven basic raw materials all deriving from petroleum and natural gas The

wisdom of teaching about the chemical industry on the basis of these seven building

blocks has been confirmed by the fact that since the publication of our first book one

of us (HAW) has delivered by invitation 300 courses in 28 countries on the

fundamentals of the industry based on this pattern Most of these courses are for

industrial personnel but academia has not been neglected

Furthermore some changes have been positive For example there have been

exciting new processes such as the development of metallocene catalysts (Section

15312) Section 461 describes new methyl methacrylate processes that give a

potentially cheaper product that do not produce ecologically undesirable ammonium

hydrogen sulfate by-product or (in another process) that eliminate the use of

dangerous hydrogen cyanide

In this book our main objective is still to present the technology of the organic

chemicals industry as an organized body of knowledge so that both the neophyte and

the experienced practitioner can see the broad picture Nonetheless we have

expanded its scope to include not only new processes but many apparently less

xxv

important reactions that are significant because they give rise to the more profitable

specialty chemicals The lesser volume chemicals have been clearly delineated as

such and the reader who wishes to see the industry on the basis of its large tonnage

products can omit these sections

We hope this bookwill be useful both to college students who have studied organic

chemistry and to graduates and industrial chemists whowork in or are interested in the

chemical industry Even though much of the chemistry has remained the same the

change in the way the industry looks at its problems provides ample justification for

our offering this edition as a fresh perspective on industrial organic chemicals

xxvi PREFACE TO THE FIRST EDITION

PREFACE TO THE SECOND EDITION

In the preface to the first edition we expressed the hope that we could comment on the

chemical industryrsquos evolution in 10 yearsrsquo time Dramatic changes have motivated us

to compress this time frame There have been unprecedented restructuring severe and

complicated feedstock problems and massive shifts of capacity to developing

countries whose economic and political stability is in doubt Possible terrorist

activity dictates elaborate safety and security procedures and the design of plants

with small inventories is a priority

To increase our cover particularly of the patent literature we have invited Dr

Jeffrey S Plotkin Director of the Process Evaluation and Research Planning program

at Nexant ChemSystems to join us as co-author

xxvii

meteoric rise of the chemical industry from its early days to its present-day

maturity We think there is a value in our readers observing how technology has

developed and the social technological and economic changes that have brought

it to its present position

HAROLD A WITTCOFF

xxiv PREFACE

PREFACE TO THE FIRST EDITION

In the early 1970s one of us (BGR) wrote a book celebrating the rapid growth of the

adolescent chemical industry The organic chemicals industry at the timewas growing

at four times the rate of the economy It was indicated nonetheless that ldquotrees do not

grow to the skyrdquo In 1980 in another book we both declared the industry to bemiddle-

aged with slow or zero growth In this totally revised and expanded version of our

earlier book we reflect that the industry at any rate in the developedworld is showing

many of the illnesses of late middle-age

The problems have arisen first from the undisciplined building of excess capacity

with consequent fierce competition and low prices Second the entry of numerous

developing countries into the industry has exacerbated the situation (Section 136)

and third there has beenmuch stricter government legislation (Section 137) There is

massive worldwide restructuring and continual shifting of commodity chemical

manufacturing to areas other than the United States Western Europe and Japan

The Middle East and Southeast Asia are the principal new players in the game

Perhaps this trend will continue and the present developed world will in the future

confine itself to themanufacture of specialties but the economic and political forces at

work are more complex than that We hope to be able to discuss their resolution in

another edition in about 10 yearsrsquo time

Meanwhile some things have not changed The organic chemicals industry is still

based on seven basic raw materials all deriving from petroleum and natural gas The

wisdom of teaching about the chemical industry on the basis of these seven building

blocks has been confirmed by the fact that since the publication of our first book one

of us (HAW) has delivered by invitation 300 courses in 28 countries on the

fundamentals of the industry based on this pattern Most of these courses are for

industrial personnel but academia has not been neglected

Furthermore some changes have been positive For example there have been

exciting new processes such as the development of metallocene catalysts (Section

15312) Section 461 describes new methyl methacrylate processes that give a

potentially cheaper product that do not produce ecologically undesirable ammonium

hydrogen sulfate by-product or (in another process) that eliminate the use of

dangerous hydrogen cyanide

In this book our main objective is still to present the technology of the organic

chemicals industry as an organized body of knowledge so that both the neophyte and

the experienced practitioner can see the broad picture Nonetheless we have

expanded its scope to include not only new processes but many apparently less

xxv

important reactions that are significant because they give rise to the more profitable

specialty chemicals The lesser volume chemicals have been clearly delineated as

such and the reader who wishes to see the industry on the basis of its large tonnage

products can omit these sections

We hope this bookwill be useful both to college students who have studied organic

chemistry and to graduates and industrial chemists whowork in or are interested in the

chemical industry Even though much of the chemistry has remained the same the

change in the way the industry looks at its problems provides ample justification for

our offering this edition as a fresh perspective on industrial organic chemicals

xxvi PREFACE TO THE FIRST EDITION

PREFACE TO THE SECOND EDITION

In the preface to the first edition we expressed the hope that we could comment on the

chemical industryrsquos evolution in 10 yearsrsquo time Dramatic changes have motivated us

to compress this time frame There have been unprecedented restructuring severe and

complicated feedstock problems and massive shifts of capacity to developing

countries whose economic and political stability is in doubt Possible terrorist

activity dictates elaborate safety and security procedures and the design of plants

with small inventories is a priority

To increase our cover particularly of the patent literature we have invited Dr

Jeffrey S Plotkin Director of the Process Evaluation and Research Planning program

at Nexant ChemSystems to join us as co-author

xxvii

PREFACE TO THE FIRST EDITION

In the early 1970s one of us (BGR) wrote a book celebrating the rapid growth of the

adolescent chemical industry The organic chemicals industry at the timewas growing

at four times the rate of the economy It was indicated nonetheless that ldquotrees do not

grow to the skyrdquo In 1980 in another book we both declared the industry to bemiddle-

aged with slow or zero growth In this totally revised and expanded version of our

earlier book we reflect that the industry at any rate in the developedworld is showing

many of the illnesses of late middle-age

The problems have arisen first from the undisciplined building of excess capacity

with consequent fierce competition and low prices Second the entry of numerous

developing countries into the industry has exacerbated the situation (Section 136)

and third there has beenmuch stricter government legislation (Section 137) There is

massive worldwide restructuring and continual shifting of commodity chemical

manufacturing to areas other than the United States Western Europe and Japan

The Middle East and Southeast Asia are the principal new players in the game

Perhaps this trend will continue and the present developed world will in the future

confine itself to themanufacture of specialties but the economic and political forces at

work are more complex than that We hope to be able to discuss their resolution in

another edition in about 10 yearsrsquo time

Meanwhile some things have not changed The organic chemicals industry is still

based on seven basic raw materials all deriving from petroleum and natural gas The

wisdom of teaching about the chemical industry on the basis of these seven building

blocks has been confirmed by the fact that since the publication of our first book one

of us (HAW) has delivered by invitation 300 courses in 28 countries on the

fundamentals of the industry based on this pattern Most of these courses are for

industrial personnel but academia has not been neglected

Furthermore some changes have been positive For example there have been

exciting new processes such as the development of metallocene catalysts (Section

15312) Section 461 describes new methyl methacrylate processes that give a

potentially cheaper product that do not produce ecologically undesirable ammonium

hydrogen sulfate by-product or (in another process) that eliminate the use of

dangerous hydrogen cyanide

In this book our main objective is still to present the technology of the organic

chemicals industry as an organized body of knowledge so that both the neophyte and

the experienced practitioner can see the broad picture Nonetheless we have

expanded its scope to include not only new processes but many apparently less

xxv

important reactions that are significant because they give rise to the more profitable

specialty chemicals The lesser volume chemicals have been clearly delineated as

such and the reader who wishes to see the industry on the basis of its large tonnage

products can omit these sections

We hope this bookwill be useful both to college students who have studied organic

chemistry and to graduates and industrial chemists whowork in or are interested in the

chemical industry Even though much of the chemistry has remained the same the

change in the way the industry looks at its problems provides ample justification for

our offering this edition as a fresh perspective on industrial organic chemicals

xxvi PREFACE TO THE FIRST EDITION

PREFACE TO THE SECOND EDITION

In the preface to the first edition we expressed the hope that we could comment on the

chemical industryrsquos evolution in 10 yearsrsquo time Dramatic changes have motivated us

to compress this time frame There have been unprecedented restructuring severe and

complicated feedstock problems and massive shifts of capacity to developing

countries whose economic and political stability is in doubt Possible terrorist

activity dictates elaborate safety and security procedures and the design of plants

with small inventories is a priority

To increase our cover particularly of the patent literature we have invited Dr

Jeffrey S Plotkin Director of the Process Evaluation and Research Planning program

at Nexant ChemSystems to join us as co-author

xxvii

important reactions that are significant because they give rise to the more profitable

specialty chemicals The lesser volume chemicals have been clearly delineated as

such and the reader who wishes to see the industry on the basis of its large tonnage

products can omit these sections

We hope this bookwill be useful both to college students who have studied organic

chemistry and to graduates and industrial chemists whowork in or are interested in the

chemical industry Even though much of the chemistry has remained the same the

change in the way the industry looks at its problems provides ample justification for

our offering this edition as a fresh perspective on industrial organic chemicals

xxvi PREFACE TO THE FIRST EDITION

PREFACE TO THE SECOND EDITION

In the preface to the first edition we expressed the hope that we could comment on the

chemical industryrsquos evolution in 10 yearsrsquo time Dramatic changes have motivated us

to compress this time frame There have been unprecedented restructuring severe and

complicated feedstock problems and massive shifts of capacity to developing

countries whose economic and political stability is in doubt Possible terrorist

activity dictates elaborate safety and security procedures and the design of plants

with small inventories is a priority

To increase our cover particularly of the patent literature we have invited Dr

Jeffrey S Plotkin Director of the Process Evaluation and Research Planning program

at Nexant ChemSystems to join us as co-author

xxvii

PREFACE TO THE SECOND EDITION

In the preface to the first edition we expressed the hope that we could comment on the

chemical industryrsquos evolution in 10 yearsrsquo time Dramatic changes have motivated us

to compress this time frame There have been unprecedented restructuring severe and

complicated feedstock problems and massive shifts of capacity to developing

countries whose economic and political stability is in doubt Possible terrorist

activity dictates elaborate safety and security procedures and the design of plants

with small inventories is a priority

To increase our cover particularly of the patent literature we have invited Dr

Jeffrey S Plotkin Director of the Process Evaluation and Research Planning program

at Nexant ChemSystems to join us as co-author

xxvii