Industrial Organic Chemicals Wittcoff 3th PDF

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INDUSTRIAL ORGANIC CHEMICALS 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, P...

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INDUSTRIAL ORGANIC CHEMICALS

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 Manufacture, 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 – Chemistry and Concepts, an ACS tape course, by Harold A. Wittcoff and Bryan G. Reuben, ACS, Washington DC, 1987. The Cost of “Non-Europe” in the Pharmaceutical Industry, Research in the Cost of “Non-Europe,” 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 Community’s 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, by M. M. Green and Harold A. Wittcoff, VCH Wiley, Weinheim, Germany, 2003. Pharmaceutical R&D 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 S. Marchant, Bryan G. Reuben, and Joan P. Alcock, The History Press, Stroud, Gloucestershire, 2008.

INDUSTRIAL ORGANIC CHEMICALS THIRD EDITION

Harold A. Wittcoff Scientific Adviser, Nexant ChemSystems Inc. (retired) Vice President of Corporate Research, General Mills, Inc. (retired)

Bryan G. Reuben Professor Emeritus of Chemical Technology London South Bank University

Jeffrey S. Plotkin Director, Process Evaluation and Research Planning Program Nexant ChemSystems Inc.

A JOHN WILEY & SONS, INC., PUBLICATION

Cover design: Michael Rutkowski Cover photograph: @iStockphoto Copyright
2013 by John Wiley & Sons, Inc. All rights reserved Published by John Wiley & 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 www.copyright.com. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, 201-748-6011, fax 201-748-6008, or online at http://www.wiley.com/go/permission. Limit of Liability/Disclaimer 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 www.wiley.com. Library of Congress Cataloging-in-Publication Data: Wittcoff, Harold A. Industrial organic chemicals / Harold A. Wittcoff, Bryan G. Reuben, Jeffrey S. Plotkin. – 3rd ed. p. cm. Includes index. ISBN 978-0-470-53743-5 (cloth) 1. Organic compounds–Industrial applications. I. Reuben, B. G. II. Plotkin, Jeffrey S. III. Title. TP247.W59 2012 661.8–dc23 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 Preface to the First Edition

xxiii xxv

Preface to the Second Edition

xxvii

Acknowledgments

xxix

Bryan Godel Reuben 1934–2012

xxxi

List of Acronyms and Abbreviations Introduction: How to Use Industrial Organic Chemicals, Third Edition

xxxiii 1

I.1 Why This Book Was Written and How It Is Structured

2

I.2 North American Industry Classification System

5

I.3 Units and Nomenclature

5

I.4 General Bibliography I.4.1 Encyclopedias I.4.2 Books I.4.3 Journals I.4.4 Patents I.4.5 Statistics and Internet Sources of Information 1. The Evolution of the Organic Chemicals Industry

6 6 7 8 9 10 13

1.1 The National Economy

13

1.2 Size of the Chemical Industry

16

1.3 Characteristics of the Chemical Industry 1.3.1 Capital Intensity and Economies of Scale 1.3.2 Criticality and Pervasiveness 1.3.3 Freedom of Market Entry 1.3.4 Strong Regulation 1.3.4.1 European Legislation 1.3.4.2 Political Factors

22 22 24 26 27 29 30 vii

viii

CONTENTS

1.3.5 High but Declining Research and Development Expenditures 1.3.6 Dislocations

34 41

1.4 The Top Companies

43

1.5 The Top Chemicals

44

Endnotes

46

2. Globalization of the Chemical Industry

49

2.1 Overcapacity 2.1.1 Economic Cycles

51 55

2.2 Restructuring, Mergers, and Acquisitions 2.2.1 SuICIde of a UK Company 2.2.2 Private Equity

56 60 61

2.3 Participation in International Trade

63

2.4 Competition from Developing Countries

66

Endnotes

69

3. Transporting Chemicals

71

3.1 Shipping Petroleum

71

3.2 Shipping Gas

74

3.3 Shipping Chemicals 3.3.1 Gases 3.3.2 Liquids 3.3.3 Solids

75 75 77 85

3.4 Health and Safety

86

3.5 Economic Aspects

87

3.6 Trade in Specific Chemicals

88

3.7 Top Shipping Companies

90

Endnotes

91

4. Chemicals from Natural Gas and Petroleum

93

4.1

Petroleum Distillation

97

4.2

Shale Gas 4.2.1 Shale Gas Technology

100 101

4.3

Naphtha Versus Gaseous Feedstocks

102

CONTENTS

ix

4.4

Heavier Oil Fractions

103

4.5

Steam Cracking and Petroleum Refining Reactions 4.5.1 Steam Cracking 4.5.2 Choice of Feedstock 4.5.3 Economics of Steam Cracking

104 106 108 110

4.6

Catalytic Cracking

114

4.7

Mechanisms of Steam and Catalytic Cracking

117

4.8

Catalytic Reforming

119

4.9

Oligomerization

122

4.10 Alkylation

124

4.11 Hydrotreating and Coking

125

4.12 Dehydrogenation

126

4.13 Isomerization

128

4.14 Metathesis 4.14.1 Metathesis Outside the Refinery 4.14.2 Mechanism of Metathesis

128 129 131

4.15 Function of the Refinery and the Potential Petroleum Shortage 4.15.1 Unleaded Gasoline and the Clean Air Act

133 134

4.16 Separation of Natural Gas

136

4.17 Oil from Tar Sands

137

Endnotes

137

5. Chemicals and Polymers from Ethylene 5.1

Ethylene 5.1.1 5.1.2 5.1.3 5.1.4 5.1.5 5.1.6 5.1.7 5.1.8 5.1.9

Polymers Discovery of Low and High Density Polyethylenes Low Density Polyethylene High Density Polyethylene Linear Low Density Polyethylene Very High Molecular Weight Polyethylene Metallocene Polyethylenes Very Low Density Polyethylene Bimodal HDPE “Green” Polyethylene

139 141 142 144 146 147 148 149 149 149 150

x

CONTENTS

5.2

Ethylene 5.2.1 5.2.2 5.2.3 5.2.4 5.2.5 5.2.6

Copolymers Chlorosulfonated Polyethylene Ethylene-Vinyl Acetate Ionomers Copolymer from “Incompatible” Polymer Blends Ethylene–Propylene Elastomers Polyolefin Elastomers

151 151 151 152 152 153 153

5.3

Oligomerization 5.3.1 Dimerization 5.3.2 Ziegler Oligomerization of Ethylene 5.3.3 Other Ethylene Oligomerization Technologies 5.3.4 Shell Higher Olefins Process (SHOP)

154 154 155 156 158

5.4

Vinyl Chloride

160

5.5

Acetaldehyde

165

5.6

Vinyl Acetate

167

5.7

Ethylene Oxide 5.7.1 Ethylene Glycol 5.7.2 Proposed Non-Ethylene Oxide Processes for Ethylene Glycol Production

169 171 174

5.8

Styrene

177

5.9

Ethanol

181

5.10 Major Chemicals from Ethylene – A Summary

182

5.11 Lesser Volume Chemicals from Ethylene 5.11.1 Hydroformylation – Propionaldehyde, Propionic Acid, and n-Propanol 5.11.2 Ethyl Halides 5.11.3 Acetaldehyde Chemistry 5.11.4 Metal Complexes 5.11.5 Ethylenediamine and Related Compounds 5.11.6 Ethylene Oxide and Ethylene Glycol Derivatives 5.11.6.1 Oligomers 5.11.6.2 Glycol Ethers and Esters 5.11.6.3 Ethylene Carbonate 5.11.6.4 Aminoethyl Alcohols (Ethanolamines) and Derivatives 5.11.6.5 Ethyleneimine

185 185 186 187 191 191 193 193 194 197 198 199

CONTENTS

5.11.6.6 1,3-Propanediol 5.11.6.7 Ethylene Glycol Derivatives 5.11.7 Vinyl Chloride and Ethylene Dichloride Derivatives 5.11.8 Vinyl Fluoride and Vinylidene Fluoride 5.11.9 Ethylene Dibromide 5.11.10 Ethanol Derivatives 5.11.11 Vinyl Esters and Ethers Endnotes 6. Chemicals and Polymers from Propylene 6.1

xi

200 201 203 204 205 206 207 208 211

On-Purpose Propylene Production Technologies and Propane Dehydrogenation 6.1.1 Propylene Via Enhanced Fluidized Catalytic Cracking 6.1.2 Propylene Via Selective C4/C5 Cracking

215 215

6.2

Main Polymers and Chemicals from Propylene 6.2.1 Propylene Polymers and Copolymers

217 217

6.3

Oligomerization

221

6.4

Acrylic Acid 6.4.1 Biorenewable Processes to Acrylic Acid 6.4.2 Acrylic Acid Markets

222 225 226

6.5

Acrylonitrile 6.5.1 Uses of Acrylonitrile

227 230

6.6

Cumene/Phenol and Cumene Hydroperoxide

231

6.7

Acetone and Isopropanol 6.7.1 Methyl Methacrylate 6.7.2 Methyl Isobutyl Ketone and Other Acetone Derivatives

233 235 242

Propylene Oxide 6.8.1 Other Propylene Oxide Processes 6.8.1.1 Acetoxylation of Propylene 6.8.1.2 Direct Oxidation 6.8.1.3 Use of Peracids 6.8.1.4 Electrochemical Processes 6.8.1.5 Biotechnological Approaches 6.8.2 Propylene Oxide Applications

242 247 248 249 249 250 252 253

6.8

214

xii

CONTENTS

6.9

n-Butyraldehyde and Isobutyraldehyde 6.9.1 Uses for Butyraldehyde, Isobutyraldehyde, and n-Butanol 6.9.2 Other Oxo Products

255 258 260

6.10 Major Chemicals from Propylene – A Perspective

261

6.11 Lesser 6.11.1 6.11.2 6.11.3 6.11.4 6.11.5

263 263 266 266 268 270

Volume Chemicals from Propylene Allyl Chloride and Epichlorohydrin Glycerol Acrylamide Acrolein Acrylonitrile Derivatives

Endnotes 7. Chemicals from the C4 Stream

270 273

7.1 Chemicals and Polymers from Butadiene 7.1.1 Tires 7.1.2 Styrene–Butadiene Elastomers 7.1.3 Polybutadienes and Other Elastomers 7.1.4 Acrylonitrile–Butadiene–Styrene Resins 7.1.5 Hexamethylenediamine 7.1.6 Lesser Volume Chemicals from Butadiene 7.1.6.1 Cyclization 7.1.6.2 Dimerization and Trimerization 7.1.6.3 Diels–Alder Reactions 7.1.6.4 Adipic Acid 7.1.6.5 1,4-Butanediol 7.1.6.6 trans-1,4-Hexadiene 7.1.6.7 Dimethyl-2,6-naphthalene Dicarboxylate 7.1.6.8 Butadiene Monoepoxide

277 280 281 282 283 284 289 289 291 293 294 294 295

7.2 Chemicals and Polymers from Isobutene 7.2.1 Methyl tert-Butyl Ether 7.2.2 Butyl Rubber 7.2.3 Polyisobutenes and Isobutene Oligomers and Polymers 7.2.4 tert-Butanol 7.2.5 Methyl Methacrylate 7.2.6 Lesser Volume Chemicals from Isobutene

296 297 298

295 296

298 299 299 299

CONTENTS

xiii

7.3 Chemicals and Polymers from 1- and 2-Butenes

302

7.4 Chemicals from n-Butane 7.4.1 Acetic Acid 7.4.2 Maleic Anhydride 7.4.3 Succinic, Malic, Fumaric, and Tartaric Acids

303 303 303 306

Endnotes

307

8. Chemicals from the C5 Stream

309

8.1 Separation of the C5 Stream

311

8.2 Isoprene 8.2.1 Natural Rubber 8.2.2 Vulcanization 8.2.3 Production of Petrochemical Isoprene 8.2.4 Applications of Isoprene

312 312 313 314 317

8.3 Cyclopentadiene and Dicyclopentadiene

319

8.4 Pentene-1 and Piperylene

321

Endnotes 9. Chemicals from Benzene

321 323

9.1 Phenol 9.1.1 Phenolic Resins 9.1.2 Bisphenol A 9.1.2.1 Epoxy Resins 9.1.2.2 Polycarbonate Resins 9.1.2.3 Lesser Volume Uses for Bisphenol A 9.1.2.4 Environmental Problems 9.1.3 Cyclohexanone 9.1.4 Alkylphenols 9.1.5 Chlorinated Phenols 9.1.6 2,6-Xylenol/Cresols 9.1.7 Aniline from Phenol

326 331 333 333 334 337 340 341 342 342 343 344

9.2 Cyclohexane 9.2.1 Adipic Acid 9.2.1.1 Nylons from Adipic Acid 9.2.2 Caprolactam

344 344 349 349

xiv

CONTENTS

9.3 Aniline 9.3.1 4,40 -Diphenylmethane Isocyanate

354 357

9.4 Alkylbenzenes

361

9.5 Maleic Anhydride

362

9.6 Chlorinated Benzenes

363

9.7 Dihydroxybenzenes 9.7.1 Hydroquinone 9.7.2 Resorcinol 9.7.3 Catechol

364 364 368 369

9.8 Anthraquinone 9.8.1 Hydrogen Peroxide

370 371

Endnotes 10. Chemicals from Toluene

372 375

10.1 Hydrodealkylation, Disproportionation, and Transalkylation

375

10.2 Solvents

378

10.3 Dinitrotoluene and Toluene Diisocyanate

378

10.4 Lesser Volume Chemicals from Toluene

380

Endnotes 11. Chemicals from Xylenes

382 383

11.1 o-Xylene and Phthalic Anhydride 11.1.1 Plasticizers 11.1.2 Alkyd Resins 11.1.3 Unsaturated Polyester Resin

386 387 391 393

11.2 m-Xylene and Isophthalic Acid 11.2.1 Uses of Isophthalic Acid

395 396

11.3 p-Xylene and Terephthalic Acid/Dimethyl Terephthalate 11.3.1 Oxidation of p-Xylene 11.3.2 Alternate Sources for Terephthalic Acid 11.3.3 Poly(ethylene terephthalate) 11.3.4 Lower Volume Polymers from Terephthalic Acid

397 398 400 400 403

Endnotes

404

CONTENTS

12. Chemicals from Methane

xv

407

12.1 Hydrocyanic Acid

408

12.2 Halogenated Methanes 12.2.1 Chloromethane 12.2.2 Dichloromethane 12.2.3 Trichloromethane 12.2.4 Fluorocarbons 12.2.5 Tetrachloromethane and Carbon Disulfide 12.2.6 Bromomethane

411 412 413 413 414 414 416

12.3 Acetylene 12.3.1 1,4-Butanediol and 2-Methyl-1,3-propanediol 12.3.2 Lesser Uses for Acetylene

417 419 423

12.4 Synthesis Gas 12.4.1 Steam Reforming of Methane 12.4.2 Variants of Steam Reforming 12.4.3 Partial Oxidation of Hydrocarbons 12.4.4 Solid Feedstocks 12.4.5 Hydrogen

424 425 427 428 428 429

12.5 Chemicals from Synthesis Gas 429 12.5.1 Ammonia and Its Derivatives 430 12.5.1.1 The Crisis of Nitrogen Depletion 430 12.5.1.2 Ammonia Manufacture 431 12.5.1.3 Urea and Melamine Resins 434 12.5.2 Methanol 435 12.5.2.1 Formaldehyde 438 12.5.2.2 Acetic Acid 439 12.5.2.3 Acetic Anhydride 442 12.5.2.4 Methanol to Gasoline 445 12.5.2.5 Methanol to Olefins 446 12.5.2.6 Lower Volume and Proposed Uses for Methanol 448 452 12.5.2.7 C1-Based Development Processes 12.6 Carbon Monoxide Chemistry 12.6.1 Proposed Chemistry Based on Carbon Monoxide

454 455

12.7 Gas-to-Liquid Fuels 12.7.1 Sasol GTL Technology 12.7.2 Shell Middle Distillate Synthesis

459 459 459

xvi

CONTENTS

12.7.3 Other GTL Technologies Endnotes 13. Chemicals from Alkanes

460 460 463

13.1 Functionalization of Methane 13.1.1 Methane to Methanol/Formaldehyde 13.1.2 Dimerization of Methane 13.1.3 Aromatization of Methane

464 464 466 467

13.2 Functionalization of C2–C4 Alkanes 13.2.1 Oxidation of C2–C4 Alkanes 13.2.2 Dehydrogenation of C2–C4 Alkanes 13.2.3 Aromatization of C2–C4 Alkanes

468 468 470 471

13.3 Carbon Black

472

Endnotes 14. Chemicals from Coal

473 475

14.1 Chemicals from Coke Oven Distillate

477

14.2 The Fischer–Tropsch Reaction

480

14.3 Coal Hydrogenation

484

14.4 Substitute Natural Gas

485

14.5 SNG and Synthesis Gas Technology

485

14.6 Underground Coal Gasification

488

14.7 Calcium Carbide 14.7.1 The Chinese Chemicals to Coal Program

488 489

14.8 Coal and the Environment

490

Endnotes 15. Fats and Oils

491 493

15.1

Markets for Fats and Oils

495

15.2

Purification of Fats and Oils

497

15.3

Fatty Acids 15.3.1 Applications of Fatty Acids

499 501

15.4

Fatty Nitrogen Compounds

502

15.5

“Dimer” Acid

504

CONTENTS

xvii

15.6

Aminoamides and Imidazolines

506

15.7

Azelaic, Pelargonic, and Petroselinic Acids

507

15.8

Fatty Alcohols
...