Harold a wittcoff, bryan g reuben, jeffery s plotkin industrial organic chemicals, 2nd edition wiley interscience (2004)

ffirs.qxd

29.5.04

11:13

Page i

INDUSTRIAL ORGANIC
CHEMICALS


ffirs.qxd

29.5.04

11:13

Page iii

INDUSTRIAL ORGANIC
CHEMICALS
Second Edition

HAROLD A. WITTCOFF
Scientific Adviser, Nexant ChemSystems Inc.; Vice President of Corporate
Research, General Mills, Inc. (ret.)

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

www.pdfgrip.com


ffirs.qxd

29.5.04

11:13

Page iv

Copyright © 2004 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
978-646-8600, 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.
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 please contact our Customer Care
Department within the U.S. at 877-762-2974, outside the U.S. 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,
however, may not be available in electronic format.
Library of Congress Cataloging-in-Publication Data:
Wittcoff, Harold.
Industrial organic chemicals.—2nd ed. / Harold A. Wittcoff, Bryan G. Reuben, Jeffrey S. Plotkin.
p. cm.
Includes index.
ISBN 0-471-44385-9 (Cloth)
1. Organic compounds—Industrial applications. I. Reuben, B. G. II. Plotkin, Jeffrey S. III. Title.
TP247.W59 2004
661.8—dc22
2003023097
Printed in the United States of America
10 9 8 7 6 5 4 3 2 1

www.pdfgrip.com


ffirs.qxd

29.5.04

11:13

Page v

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 Harold A. Wittcoff and
Bryan G. Reuben, 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 Vol. 15, by Michael L. Burstall and Bryan G.
Reuben, Commission of European Communities, Luxembourg, 1988.
Pharmaceutical Chemicals in Perspective, by Bryan G. Reuben and Harold A.
Wittcoff, 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 M. L. Burstall and
B. 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.
Outlook for the World Pharmaceutical Industry to 2015, by M. L. Burstall and

B. G. Reuben, Decision Resources, Waltham MA, 2004.

www.pdfgrip.com


ffirs.qxd

29.5.04

11:13

Page vii

To our wives, Dorothy, Catherine, and Marisa, and to our children,
grandchildren, and great-grandchildren.

www.pdfgrip.com


ffirs.qxd

29.5.04

11:13

Page ix

ACKNOWLEDGMENTS

We gratefully acknowledge the help of Professor Maurice Kreevoy, who reviewed

the chapter on catalysis and offered many helpful suggestions. Mrs. Denise Phillips
searched the literature diligently for us. We thank Ms. Carol Conti of Nexant
ChemSystems Inc. for many insights about the supply and demand situation for
many of the large volume petrochemicals and plastics. We are particularly grateful
to Nexant ChemSystems Inc., whose numerous multiclient reports provided detailed
information about reaction conditions and production economics. And we are grateful to our wives, who gave us encouragement at all stages of this enterprise.

www.pdfgrip.com


ftoc.qxd

29.5.04

11:15

Page xi

CONTENTS

PREFACE

xxiii

PREFACE TO THE FIRST EDITION

xxv

LIST OF ACRONYMS AND ABBREVIATIONS
CHAPTER 0 HOW TO USE INDUSTRIAL ORGANIC CHEMICALS,

SECOND EDITION

xxvii

1

0.1 Why this Book was Written and
how it is Structured / 1
0.2 North American Industry Classification / 3
0.3 Units and Nomenclature / 4
0.4 General Bibliography / 4
0.4.1 Encyclopedias / 5
0.4.2 Books / 6
0.4.3 Journals / 9
0.4.4 Patents / 9
0.4.5 Statistics / 11
0.4.6 CD-ROM and On-Line Databases / 12
CHAPTER 1

THE CHEMICAL INDUSTRY
1.1
1.2

15

The National Economy / 15
Size of the Chemical Industry / 20
xi

www.pdfgrip.com

ftoc.qxd

29.5.04

xii

11:15

Page xii

CONTENTS

1.3

Characteristics of the Chemical Industry / 21
1.3.1 Maturity / 21
1.3.1.1 Realignment of Business Segments / 26
1.3.2 Participation in International Trade / 28
1.3.3 Competition from Developing Countries / 29
1.3.4 Capital Intensity and Economies of Scale / 32
1.3.5 Criticality and Pervasiveness / 33
1.3.6 Freedom of Market Entry / 35
1.3.7 Strong Health and Safety Regulation / 36
1.3.8 High Research and Development Expenditures / 41
1.3.9 Dislocations / 46
1.4 The Top Chemical Companies / 48
1.5 The Top Chemicals / 50
Notes and References / 53

CHAPTER 2 CHEMICALS FROM NATURAL GAS AND
PETROLEUM
2.1
2.2

Petroleum Distillation / 61
Petroleum Refining Reactions / 67
2.2.1 Steam Cracking / 67
2.2.1.1 Choice of Feedstock / 70
2.2.1.2 Economics of Steam Cracking / 71
2.2.1.3 Mechanism of Cracking / 76
2.2.2 Catalytic Cracking / 76
2.2.3 Catalytic Reforming / 79
2.2.4 Oligomerization / 82
2.2.5 Alkylation / 84
2.2.6 Hydrotreating and Coking / 84
2.2.7 Dehydrogenation / 86
2.2.8 Isomerization / 87
2.2.9 Metathesis / 87
2.2.9.1 Metathesis Outside the Refinery / 89
2.2.9.2 Mechanism of Metathesis / 90
2.3 The Refinery—A Perspective / 92
2.3.1 The Function of the Refinery and the Potential
Petroleum Shortage / 92
2.3.2 Unleaded Gasoline and the Clean Air Act / 93
2.4 Separation of Natural Gas / 96
Notes and References / 96

www.pdfgrip.com

57


ftoc.qxd

29.5.04

11:15

Page xiii

CONTENTS

CHAPTER 3

CHEMICALS AND POLYMERS FROM ETHYLENE
3.1

3.2

3.3

3.4
3.5
3.6
3.7

3.8
3.9

3.10
3.11

xiii

100

Ethylene Polymers / 105
3.1.1 Discovery of Low- and High-Density
Polyethylenes / 105
3.1.2 Low-Density Polyethylene / 106
3.1.3 High-Density Polyethylene / 107
3.1.4 Linear Low-Density Polyethylene / 108
3.1.5 Very High Molecular Weight Polyethylene / 109
Ethylene Copolymers / 109
3.2.1 Chlorosulfonated Polyethylene / 109
3.2.2 Ethylene-Vinyl Acetate / 110
3.2.3 Ionomers / 111
3.2.4 Copolymer from “Incompatible” Polymer
Blends / 111
3.2.5 Ethylene–Propylene Elastomers / 111
3.2.6 Ultra-Low-Density Polyethylene / 112
3.2.7 Photodegradable Copolymers / 112
Oligomerization / 113
3.3.1 Dimerization / 113
3.3.2 Ziegler Oligomerization of Ethylene / 114
3.3.3 Other Ethylene Oligomerization Technologies / 115
3.3.4 The Shell Higher Olefins Process (SHOP) / 116
Vinyl Chloride / 119
Acetaldehyde / 121

Vinyl Acetate / 124
Ethylene Oxide / 126
3.7.1 Ethylene Glycol / 127
3.7.2 Proposed Non-Ethylene Oxide Processes
for Ethylene Glycol Production / 129
Styrene / 132
Ethanol / 135
Major Chemicals from Ethylene—A Summary / 137
Lesser Volume Chemicals from Ethylene / 139
3.11.1 Hydroformylation—Propionaldehyde, Propionic
Acid, and n-Propanol / 140
3.11.2 Ethyl Halides / 141
3.11.3 Acetaldehyde Chemistry / 142
3.11.4 Metal Complexes / 146
3.11.5 Ethylenediamine and Related Compounds / 147

www.pdfgrip.com


ftoc.qxd

29.5.04

xiv

11:15

Page xiv

CONTENTS

3.11.6

Ethylene Oxide and Ethylene Glycol
Derivatives / 149
3.11.6.1 Oligomers / 149
3.11.6.2 Glycol Ethers and Esters / 149
3.11.6.3 Ethylene Carbonate / 150
3.11.6.4 Aminoethyl Alcohols (Ethanolamines)
and Derivatives / 153
3.11.6.5 Ethylenimine / 154
3.11.6.6 1,3-Propanediol / 155
3.11.6.7 Ethylene Glycol Derivatives / 156
3.11.7 Vinyl Chloride and Ethylene Dichloride
Derivatives / 158
3.11.8 Vinyl Fluoride and Vinylidene Fluoride / 159
3.11.9 Ethylene Dibromide / 160
3.11.10 Ethanol Derivatives / 161
3.11.11 Vinyl Esters and Ethers / 162
Notes and References / 163
CHAPTER 4

CHEMICALS AND POLYMERS FROM PROPYLENE
4.1 On-Purpose Propylene Production Technologies and
Propane Dehydrogenation / 168
4.2 Propylene via Deep Catalytic Cracking / 169
4.3 Propylene via Olefin Metathesis / 169
4.4 Propylene via Selective C4/C5 Cracking / 171
4.5 Main Polymers and Chemicals from Propylene / 172
4.5.1 Propylene Polymers and Copolymers / 172

4.6 Oligomerization / 175
4.7 Acrylic Acid / 176
4.8 Acrylonitrile / 181
4.8.1 Uses of Acrylonitrile / 183
4.9 Cumene, Cumene Hydroperoxide, and Phenol / 184
4.10 Acetone and Isopropanol / 187
4.10.1 Methyl Methacrylate / 188
4.10.2 Methyl Isobutyl Ketone and other Acetone
Derivatives / 193
4.11 Propylene Oxide / 195
4.11.1 Propylene Oxide Applications / 198
4.11.2 Projected Propylene Oxide–Propylene Glycol
Processes / 199

www.pdfgrip.com

167


ftoc.qxd

29.5.04

11:15

Page xv

CONTENTS

xv

4.11.3 Other Novel Syntheses of Propylene Oxide / 200
4.11.3.1 Direct Oxidation / 200
4.11.3.2 Use of Peracids or Hydrogen
Peroxide / 201
4.11.3.3 Electrochemical Processes / 202
4.11.3.4 Biotechnological Approaches / 204
4.12 n-Butyraldehyde and Isobutyraldehyde / 205
4.12.1 Uses for Butyraldehyde and Isobutyraldehyde / 207
4.12.2 Other Oxo Products / 208
4.13 Major Chemicals from Propylene—A Perspective / 209
4.14 Lesser Volume Chemicals from Propylene / 211
4.14.1 Allyl Chloride and Epichlorohydrin / 211
4.14.2 Glycerol / 214
4.14.3 Acrylamide / 215
4.14.4 Acrolein / 216
4.14.5 Acrylonitrile Derivatives / 218
Notes and References / 218
CHAPTER 5 CHEMICALS AND POLYMERS FROM THE C4
STREAM
5.1

Chemicals and Polymers from Butadiene / 226
5.1.1 Acrylonitrile–Butadiene–Styrene
Resins (ABS) / 230
5.1.2 Hexamethylenediamine / 231
5.1.3 Lesser Volume Chemicals from Butadiene / 236
5.1.3.1 Cyclization / 236
5.1.3.2 Dimerization and Trimerization / 237
5.1.3.3 Diels–Alder Reactions / 239

5.1.3.4 Adipic Acid / 240
5.1.3.5 1,4-Butanediol / 241
5.1.3.6 trans-1,4-Hexadiene / 241
5.1.3.7 Dimethyl-2,6-naphthalene
Dicarboxylate / 241
5.1.3.8 Butadiene Monoepoxide / 241
5.2 Chemicals and Polymers from Isobutene / 242
5.2.1 Methyl tert-butyl Ether / 243
5.2.2 Butyl Rubber / 244
5.2.3 Polyisobutenes and Isobutene Oligomers and
Polymers / 244

www.pdfgrip.com

223


ftoc.qxd

29.5.04

xvi

11:15

Page xvi

CONTENTS

5.2.4 tert-Butanol / 245

5.2.5 Methyl Methacrylate / 245
5.2.6 Lesser Volume Chemicals from Isobutene / 245
5.3 Chemicals and Polymers from 1- and 2-Butenes / 248
5.4 Chemicals from n-Butane / 249
5.4.1 Acetic Acid / 249
5.4.2 Maleic Anhydride / 249
Notes and References / 251
CHAPTER 6 CHEMICALS AND POLYMERS FROM THE C5
STREAM

255

6.1 Separation of the C5 Stream / 256
6.2 Isoprene / 259
6.3 Cyclopentadiene and Dicyclopentadiene / 263
6.4 Pentene-1 and Piperylene / 265
Notes and References / 266
CHAPTER 7

CHEMICALS AND POLYMERS FROM BENZENE
7.1

7.2

7.3
7.4
7.5
7.6

267

Phenol / 269
7.1.1 Phenolic Resins / 275
7.1.2 Bisphenol A / 276
7.1.2.1 Epoxy Resins / 277
7.1.2.2 Polycarbonate Resins / 277
7.1.2.3 Lesser Volume Uses for
Bisphenol A / 280
7.1.3 Cyclohexanone / 281
7.1.4 Alkylphenols / 283
7.1.5 Chlorinated Phenols / 283
7.1.6 2,6-Xylenol and Cresols / 284
7.1.7 Aniline from Phenol / 284
Cyclohexane / 285
7.2.1 Adipic Acid / 285
7.2.1.1 Nylons from Adipic Acid / 289
7.2.2 Caprolactam / 290
Aniline / 294
7.3.1 4,4Ј-Diphenylmethane Diisocyanate (MDI) / 296
Alkylbenzenes / 299
Maleic Anhydride / 301
Chlorinated Benzenes / 301

www.pdfgrip.com


ftoc.qxd

29.5.04

11:15

Page xvii

CONTENTS

xvii

7.7 Dihydroxybenzenes / 302
7.8 Anthraquinone / 308
Notes and References / 309
CHAPTER 8

CHEMICALS AND POLYMERS FROM TOLUENE

312

8.1 Hydrodealkylation and Disproportionation / 313
8.2 Solvents / 314
8.3 Dinitrotoluene and Toluene Diisocyanate / 314
8.4 Lesser Volume Chemicals from Toluene / 316
Notes and References / 318
CHAPTER 9

CHEMICALS AND POLYMERS FROM XYLENES

320

9.1

o-Xylene and Phthalic Anhydride / 322
9.1.1 Uses of Phthalic Anhydride / 323
9.2 m-Xylene and Isophthalic Acid / 327
9.2.1 Uses of Isophthalic Acid / 328
9.3 p-Xylene and Terephthalic Acid—Dimethyl
Terephthalate / 329
9.3.1 Oxidation of p-Xylene / 329
9.3.2 Alternate Sources for Terephthalic Acid / 331
9.3.3 Poly(ethylene terephthalate) / 332
9.3.4 Lower Volume Polymers from Terephthalic
Acid / 334
9.4 Major Chemicals from Xylenes: A Summary / 335
Notes and References / 336
CHAPTER 10

CHEMICALS FROM METHANE
10.1
10.2

10.3

Hydrocyanic Acid / 338
Halogenated Methanes / 341
10.2.1 Chloromethane / 342
10.2.2 Dichloromethane / 343
10.2.3 Trichloromethane / 343
10.2.4 Tetrachloromethane and
Carbon Disulfide / 344
10.2.5 Bromomethane / 347
Acetylene / 347

10.3.1 1,4-Butanediol / 349
10.3.2 Lesser Uses for Acetylene / 352

www.pdfgrip.com

338


ftoc.qxd

29.5.04

xviii

11:15

Page xviii

CONTENTS

10.4

Synthesis Gas / 353
10.4.1 Steam Reforming of Methane / 354
10.4.2 Variants of Steam Reforming / 355
10.4.3 Partial Oxidation of Hydrocarbons / 356
10.4.4 Solid Feedstocks / 357
10.4.5 Hydrogen / 357
10.5 Chemicals from Synthesis Gas / 358
10.5.1 Ammonia and Its Derivatives / 358

10.5.1.1 Urea and Melamine Resins / 360
10.5.2 Methanol / 362
10.5.2.1 Formaldehyde / 364
10.5.2.2 Acetic Acid / 365
10.5.2.3 Acetic Anhydride / 368
10.5.2.4 Methanol to Gasoline / 370
10.5.2.5 Methanol to Olefins / 371
10.5.2.6 Lower Volume and Proposed Uses for
Methanol / 373
10.5.2.7 C1-Based Development Processes / 375
10.6 Carbon Monoxide Chemistry / 377
10.6.1 Proposed Chemistry Based on Carbon
Monoxide / 378
10.7 Gas-to-Liquid Fuels / 382
10.7.1 Sasol GTL Technology / 382
10.7.2 Shell Middle Distillate Synthesis / 383
10.7.3 Other GTL Technologies / 383
Notes and References / 384
CHAPTER 11

CHEMICALS FROM ALKANES
11.1

Functionalization of Methane / 388
11.1.1 Methane to Methanol–Formaldehyde / 388
11.1.2 Dimerization of Methane / 389
11.1.3 Aromatization of Methane / 390
11.2 Functionalization of C2–C4 Alkanes / 391
11.2.1 Oxidation of C2–C4 Alkanes / 391
11.2.2 Dehydrogenation of C2–C4 Alkanes / 393

11.2.3 Aromatization of C2–C4 Alkanes / 394
11.3 Carbon Black / 394
Notes and References / 395

www.pdfgrip.com

387


ftoc.qxd

29.5.04

11:15

Page xix

CONTENTS

CHAPTER 12

CHEMICALS FROM COAL

xix

399

12.1 Chemicals from Coke Oven Distillate / 400
12.2 The Fischer–Tropsch Reaction / 404
12.3 Coal Hydrogenation / 406

12.4 Substitute Natural Gas (SNG) / 407
12.5 Synthesis Gas Technology / 407
12.6 Calcium Carbide / 408
12.7 Coal and the Environment / 409
Notes and References / 409

CHAPTER 13

FATS AND OILS

411

13.1
13.2
13.3
13.4
13.5
13.6
13.7
13.8
13.9
13.10

Fatty Acids / 416
Fatty Nitrogen Compounds / 419
“Dimer” Acid / 421
Aminoamides and Imidazolines / 423
Azelaic, Pelargonic, and Petroselinic Acids / 423
Fatty Alcohols / 424
Epoxidized Oils / 426

Ricinoleic Acid / 426
Glycerol / 428
Alcoholysis of Fats and Oils / 428
13.10.1 Cocoa Butter / 429
13.11 The Future of Fat and Oil Chemistry / 430
13.11.1 Non-Caloric Fat-Like Substances / 430
13.11.2 Alkyl Polyglycosides / 430
13.11.3 Fatty Acid-Based Fuels and Lubricants / 431
Notes and References / 432

CHAPTER 14

CARBOHYDRATES
14.1
14.2
14.3
14.4
14.5

Sugars and Sorbitol / 435
14.1.1 Furfural / 442
Starch / 443
Cellulose / 446
Gums / 449
Fermentation and Biotechnology / 450
14.5.1 Amino Acids / 453

www.pdfgrip.com

435

ftoc.qxd

29.5.04

xx

11:15

Page xx

CONTENTS

14.5.2 Polymers / 454
14.5.3 Proteins by Recombinant DNA Technology / 455
14.5.4 A Fermentation Scenario / 455
14.5.5 Can Ethanol Be Justified as a Fuel? / 456
Notes and References / 457
CHAPTER 15

HOW POLYMERS ARE MADE
15.1
15.2
15.3

Polymerization / 464
Functionality / 465
Step- and Chain-Growth
Polymerizations / 469

15.3.1 Free Radical Polymerization / 471
15.3.2 Chain Transfer / 473
15.3.3 Copolymerization / 475
15.3.4 Molecular Weight / 477
15.3.5 Polymerization Procedures / 478
15.3.6 Ionic Polymerization / 480
15.3.7 Living Polymers / 486
15.3.8 Block Copolymers / 486
15.3.9 Graft Copolymers / 489
15.3.10 Metal Complex Catalysts / 489
15.3.11 Metal Oxide Catalysts / 493
15.3.12 Metallocene and Other Single-Site
Catalysts / 494
15.3.12.1 Single-Site Nonmetallocene
Catalysts / 498
15.3.12.2 Late Transition Metal
Catalysts / 498
15.3.12.3 Commercial Prospects / 500
15.4 Examples of Step Polymerization / 501
15.4.1 Phenoplasts and Aminoplasts / 501
15.4.2 Polyurethanes / 503
15.4.3 Epoxy Resins / 506
15.4.4 Dendritic and Hyperbranched
Polymers / 508
15.5 Polymer Properties / 512
15.5.1 Crystallinity / 512

www.pdfgrip.com

459

ftoc.qxd

29.5.04

11:15

Page xxi

CONTENTS

xxi

15.5.2 Glass Transition Temperature, Crystalline
Melting Point, and Softening
Temperature / 516
15.5.3 Molecular Cohesion / 517
15.5.4 Stress–Strain Diagrams / 518
15.6 Classes of Polymers / 520
Notes and References / 521
CHAPTER 16

INDUSTRIAL CATALYSIS
16.1

16.2

16.3
16.4

16.5
16.6

16.7

16.8
16.9
16.10
16.11

527

Catalyst Choice / 528
16.1.1 Reaction Velocity and Selectivity / 529
16.1.2 Recovery of Unchanged Catalyst / 531
16.1.3 Catalyst Deactivation / 532
16.1.4 Access to Nonequilibrium Products / 532
Homogeneous and Heterogeneous Catalysis / 533
16.2.1 Reactors for Heterogeneous Catalysts / 534
16.2.2 “Immobilization” of Homogeneous
Catalysts / 535
Catalyst Markets / 536
Catalysis by Acids and Bases / 539
Dual Function Catalysis / 543
Catalysis by Metals, Semiconductors, and Insulators / 544
16.6.1 Catalysts for Automobile Emission
Control / 545
Coordination Catalysis / 546
16.7.1 Catalysts for Stereoregular Compounds / 547
16.7.2 Asymmetric Synthesis / 549

Enzymes / 550
16.8.1 Catalytic Antibodies / 552
Shape-Selective Catalysts / 553
Phase-Transfer and Fluorous Biphase Catalysis / 556
Catalysts of the Future / 558
16.11.1 Catalyst Design / 558
16.11.2 Higher Selectivities / 559
16.11.3 Catalysts with Greater Activity / 559
16.11.4 Pollution Problems / 560
16.11.5 Catalysts for New Reactions / 560
16.11.6 Catalysts that Mimic Natural Catalysts / 560

www.pdfgrip.com


ftoc.qxd

29.5.04

xxii

11:15

Page xxii

CONTENTS

16.11.7

Catalyst Discovery via High Throughput

Experimentation / 561
Notes and References / 562
CHAPTER 17

SUSTAINABILITY AND GREEN CHEMISTRY
17.1

567

Energy Sources / 569
17.1.1 Wind Power / 570
17.1.2 Wave Power / 570
17.1.3 Solar Power / 571
17.1.3.1 Photovoltaic Cells / 571
17.1.3.2 Artificial Photosynthesis / 572
17.1.4 Methane Hydrate / 574
17.1.5 The Hydrogen Economy / 575
17.1.5.1 Fuel Cells / 576
17.2 Pollution / 580
17.2.1 The Ozone Layer / 581
17.2.2 Global Warming / 585
17.2.3 Trace Chemicals / 587
17.2.3.1 Pesticides / 587
17.2.3.2 Nonpesticide Lipophiles / 588
17.2.4 Air Pollution / 589
17.2.4.1 Sulfur Dioxide and Particulates / 589
17.2.4.2 Automobile Exhaust Emissions / 590
17.2.5 Water Treatment / 593
17.2.6 Solid Wastes / 594
17.2.6.1 Waste Prevention / 595

17.2.6.2 Recycling / 595
17.2.6.3 Combustion—Incineration / 596
17.2.6.4 Sanitary Landfill / 598
17.2.7 Petrochemical Industry Wastes / 599
17.2.8 Other Environmental Problems / 600
17.3 Green Chemistry / 601
17.3.1 The Decline in Acetylene Chemistry / 602
17.3.2 Nylon / 603
17.3.3 Replacement of Phosgene / 603
17.3.4 Monomethylation by Dimethyl Carbonate / 604
17.3.5 Liquid and Supercritical Carbon Dioxide
and Water / 605

www.pdfgrip.com


ftoc.qxd

29.5.04

11:15

Page xxiii

CONTENTS

xxiii

17.3.6
17.3.7

17.3.8
17.3.9
17.3.10

Ionic Liquids / 607
Photocatalysts / 608
Paired Electrosynthesis / 608
Sertraline Synthesis / 609
Catalytic Dehydrogenation of
Diethanolamine / 611
17.3.11 Genetic Manipulation / 611
17.3.12 Polyhydroxyalkanoates / 612
17.4 Valediction / 613
Notes and References / 614
APPENDIX 1

A NOTE ON COST CALCULATIONS

620

APPENDIX 2

UNITS AND CONVERSION FACTORS

624

APPENDIX 3

SPECIAL UNITS IN THE CHEMICAL INDUSTRY

626

INDEX

629

www.pdfgrip.com


fpref.qxd

29.5.04

11:14

Page xxv

PREFACE

In the preface to the first edition, we expressed the hope that we could comment on
the chemical industry’s evolution in 10 years 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.
In the years since the last edition, one of us (HAW) has increased his tally of
courses on the fundamentals of the industry to 300 in 28 countries. 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 Inc., to join us as co-author.

xxv

www.pdfgrip.com


flast.qxd

29.5.04

11:13

Page 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 time was growing at four times the rate of the economy. It was indicated nonetheless that “trees do
not grow to the sky.” In 1980, in another book, we both declared the industry to be
middle-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 developed world,
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 1.3.6),
and third, there has been much stricter government legislation (Section 1.3.7). 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 the manufacture 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 years’ 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 200 courses in 27 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.

xxvii

www.pdfgrip.com


flast.qxd

29.5.04

xxviii

11:13

Page xxviii

PREFACE TO THE FIRST EDITION

Furthermore, some changes have been positive. For example, there have been
exciting new processes such as the development of metallocene catalysts (Section
15.3.12). Section 4.6.1 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
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 book will be useful both to college students who have studied
organic chemistry and to graduates and industrial chemists who work 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.

www.pdfgrip.com


flast.qxd

29.5.04

11:13

Page xxix

LIST OF ACRONYMS AND
ABBREVIATIONS
ABS
ACS

AFC
AMOCO
AO
APPE
ARCO
BASF
BHA
BHT
BP
BPA
Btu
BTX
CAA
CEFIC
CFCs
CHP
CIA
CIS
CMA
CMC
CMRs
CNI
COCs
CRG
DCC
DDT
DEA
DMF

Acrylonitrile-butadiene-styrene

American Chemical Society
Alkali fuel cell
Formerly American Oil/Standard Oil of Indiana, now owned by BP
Acid Optimization
Association of Petrochemicals Producers in Europe
Formerly Atlantic Richfield Oil Company, now owned by Lyondell
German chemical company: formerly Badische Anilin und Soda Fabrik
Butylated hydroxyanisole
Butylated hydroxytoluene
British Petroleum
Bisphenol A
British Thermal Units (see appendix 2)
Benzene-toluene-xylene
Clean Air Act
Centre Européen des Fédérations de L’Industrie Chimique
Chlorofluorocarbons having no hydrogen atoms
Combined heat and power
UK Chemical Industries Association
Commonwealth of Independent States (formerly USSR)
Chemical Manufacturers’ Association
Carboxymethylcellulose
Carcinogens, mutagens, and reprotoxins
Chemical News Intelligence
Cyclic olefin copolymers
Catalytic rich gas
Deep catalytic cracking
Bis(chlorophenyl)trichloromethylmethane
Diethanolamine
Dimethylformamide

xxix

www.pdfgrip.com


flast.qxd

29.5.04

xxx
DMSO
DSM
EDTA
ENI
EP
EPA
EPDM
EVA
EVC
FCC
FDA
GATT
GLA
GMP
GTL
HTE
HCFCs
HCN
HDPE
HIPS

HMDA
HMDI
HMSO
ICI
IFP
IPDI
IR
ISP
IUPAC
KA
LAB
LDPE
LLDPE
LPG
LVN
M/F
MBS
MCFC
MDI
MEK
MOI
MON
MTBE
MTG
MTO
MTP
NAICS
NPRA
OSHA
P/F

PAFC
PAMAM
PAN
PBBs

11:13

Page xxx

LIST OF ACRONYMS AND ABBREVIATIONS

Dimethyl sulfoxide
Dutch chemical company; formerly Dutch State Mines
Ethylenediaminetetraacetic acid
Italian chemical company: Ente Nazionale Idrocarburi (Enichemi is a subsidiary)
Ethylene-propylene (rubber)
Environmental Protection Agency
Ethylene-propylene-diene-monomer
Ethylene-vinyl acetate
European Vinyls Corporation
Fluid catalytic cracking
Food and Drug Administration
General Agreement on Trade and Tariffs
Gamma-linolenic acid
Good Manufacturing Practice
Gas-to-liquid
High throughput experimentation
Hydrochlorofluorocarbons
Hydrocyanic acid and Hydrogen cyanide
High-density polyethylene

High-impact styrene
Hexamethylenediamine
Hexamethylene diisocyanate
Her Majesty’s Stationery Office
UK Chemical Company; formerly Imperial Chemical Industries
Institut Franỗais de Pộtrole
Isophorone diisocyanate
Infrared
International Specialty Products
International Union of Pure and Applied Chemistry
Ketone/alcohol
Linear alkylbenzene
low-density polyethylene
Linear low-density polyethylene
Liquid petroleum gas
Light virgin naphtha
Melamine-formaldehyde
Methyl acrylate-butadiene-styrene
Molten carbonate fuel cell
4,4-Diphenylmethane diisocyanate
Methyl ethyl ketone; 2-butanone
Mobil Olefin Interconversion
Motor Octane number
Methyl tert-butyl ether
Methanol to gasoline
Methanol to olefins
Methanol-to-propylene
North American Industry Classification System
National Petroleum Refiners Association
Occupational Safety and Health Act

Phenol-formaldehyde
Phosphoric acid fuel cell
Poly(amidoamine)
Peroxyacetyl nitrate
Polybrominated biphenyls

www.pdfgrip.com


flast.qxd

29.5.04

11:13

Page xxxi

LIST OF ACRONYMS AND ABBREVIATIONS

PBDEs
PBT
PDJ
PEEK
PEMFC
PEN
PERP
PET
PIMM
PMDA
PO

POX
PTA
PTFE
PVC
REACH
RIM
RIPP
RON
SABIC
SAN
SAPO
SBR
S-B-S
S-E-B-S
S-E-P-S
SHOP
SI
S-I-S
SMDS
SNG
SOFC
SOHIO
TAME
TBA
TDI
THF
TMA
TNT
TPA
U/F

UOP
USGC
USGS
USSR
UV
VGO
vPvBs
WIPO

Polybrominated diphenyl ethers
Persistent bioaccumulative toxic
Patents and Design Journal
Poly(ether ether ketone)
Polymer electrolyte-proton exchange membrane fuel cell
Poly(ethylene naphthalate)
Process Evaluation and Research Planning
Poly(ethylene terephthalate)
Process Integrated Management Methods
Pyromellitic dianhydride
Propylene oxide
Noncatalytic partial oxidation
Pure terephthalic acid
Polytetrafluoroethylene
Poly(vinyl chloride)
Registration, Authorization, and Evaluation of Chemicals
Reaction injection molding
Chinese Research Institute of Petroleum Processing
Research Octane number
Saudi Arabia Basic Industries Corporation
Styrene-acrylonitrile

Silicaaluminophosphate
Styrene-butadiene rubber
Styrene-butadiene-styrene
Styrene-ethylene-butylene-styrene
Styrene-ethylene-propylene-styrene
Shell Higher Olefins Process
Système International
Styrene-isoprene-styrene
Shell Middle Distillate Synthesis
Substitute natural gas
Solid oxide fuel cell
Was Standard Oil of Ohio; now part of BP
tert-Amyl methyl ether
tert-Butylbenzaldehyde
Toluene diisocyanate
Tetrahydrofuran
Trimellitic anhydride
Trinitrotoluene
Terephthalic acid
Urea-formaldehyde
Universal Oil Products
United States Gulf Coast
United States Geological Survey
Union of Soviet Socialist Republics (Soviet Union), now CIS
Ultraviolet
Vacuum gas oil
Very persistent bioaccumulative toxic chemicals
World Intellectual Property Organization

www.pdfgrip.com

xxxi