cover - download.e-bookshelf.de€¦ · 4.5 steam cracking and petroleum refining reactions 104...
TRANSCRIPT
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
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
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
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
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
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
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
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
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
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