Industrial Organic Chemicals, Third Edition

HAROLD A. WITTCOFF has taught industrial organic chemistry at the University of Minnesota, while serving as Vice President of Corporate Research for General Mills Inc. As scientific adviser to Nexant ChemSystems, he has presented 300 courses in industrial chemistry in twenty-eight countries. The late BRYAN G. REUBEN was Professor Emeritus of Chemical Technology at London South Bank University, and was the author or coauthor of 130 publications and a single patent. JEFFREY S. PLOTKIN is Vice President, Chemicals and Technology, at Nexant ChemSystems and is the author or coauthor of twenty-five technical publications and thirty patents.

Preface xxiii Preface to the First Edition xxv Preface to the Second Edition xxvii Acknowledgments xxix Bryan Godel Reuben 1934--2012 xxxi List of Acronyms and Abbreviations xxxiii Introduction: How to Use Industrial Organic Chemicals, Third Edition 1 I.1 Why This Book Was Written and How It Is Structured 2 I.2 North American Industry Classification System 5 I.3 Units and Nomenclature 5 I.4 General Bibliography 6 1. The Evolution of the Organic Chemicals Industry 13 1.1 The National Economy 13 1.2 Size of the Chemical Industry 16 1.3 Characteristics of the Chemical Industry 22 1.4 The Top Companies 43 1.5 The Top Chemicals 44 2. Globalization of the Chemical Industry 49 2.1 Overcapacity 51 2.3 Participation in International Trade 63 2.4 Competition from Developing Countries 66 3. Transporting Chemicals 71 3.1 Shipping Petroleum 71 3.2 Shipping Gas 74 3.3 Shipping Chemicals 75 3.4 Health and Safety 86 3.5 Economic Aspects 87 3.6 Trade in Specific Chemicals 88 3.7 Top Shipping Companies 90 4. Chemicals from Natural Gas and Petroleum 93 4.1 Petroleum Distillation 97 4.2 Shale Gas 100 4.3 Naphtha Versus Gaseous Feedstocks 102 4.4 Heavier Oil Fractions 103 4.5 Steam Cracking and Petroleum Refining Reactions 104 4.6 Catalytic Cracking 114 4.7 Mechanisms of Steam and Catalytic Cracking 117 4.8 Catalytic Reforming 119 4.9 Oligomerization 122 4.10 Alkylation 124 4.11 Hydrotreating and Coking 125 4.12 Dehydrogenation 126 4.13 Isomerization 128 4.14 Metathesis 128 4.15 Function of the Refinery and the Potential Petroleum Shortage 133 4.16 Separation of Natural Gas 136 4.17 Oil from Tar Sands 137 5. Chemicals and Polymers from Ethylene 139 5.1 Ethylene Polymers 141 5.2 Ethylene Copolymers 151 5.3 Oligomerization 154 5.4 Vinyl Chloride 160 5.5 Acetaldehyde 165 5.6 Vinyl Acetate 167 5.7 Ethylene Oxide 169 5.8 Styrene 177 5.9 Ethanol 181 5.10 Major Chemicals from Ethylene -- A Summary 182 5.11 Lesser Volume Chemicals from Ethylene 185 6. Chemicals and Polymers from Propylene 211 6.1 On-Purpose Propylene Production Technologies and Propane Dehydrogenation 214 6.2 Main Polymers and Chemicals from Propylene 217 6.3 Oligomerization 221 6.4 Acrylic Acid 222 6.5 Acrylonitrile 227 6.6 Cumene/Phenol and Cumene Hydroperoxide 231 6.7 Acetone and Isopropanol 233 6.8 Propylene Oxide 242 6.9 n-Butyraldehyde and Isobutyraldehyde 255 6.10 Major Chemicals from Propylene -- A Perspective 261 6.11 Lesser Volume Chemicals from Propylene 263 7. Chemicals from the C4 Stream 273 7.1 Chemicals and Polymers from Butadiene 277 7.2 Chemicals and Polymers from Isobutene 296 7.3 Chemicals and Polymers from 1- and 2-Butenes 302 7.4 Chemicals from n-Butane 303 8. Chemicals from the C5 Stream 309 8.1 Separation of the C5 Stream 311 8.2 Isoprene 312 8.3 Cyclopentadiene and Dicyclopentadiene 319 8.4 Pentene-1 and Piperylene 321 9. Chemicals from Benzene 323 9.1 Phenol 326 9.2 Cyclohexane 344 9.3 Aniline 354 9.4 Alkylbenzenes 361 9.5 Maleic Anhydride 362 9.6 Chlorinated Benzenes 363 9.7 Dihydroxybenzenes 364 9.8 Anthraquinone 370 9.8.1 Hydrogen Peroxide 371 10. Chemicals from Toluene 375 10.1 Hydrodealkylation, Disproportionation, and Transalkylation 375 10.2 Solvents 378 10.3 Dinitrotoluene and Toluene Diisocyanate 378 10.4 Lesser Volume Chemicals from Toluene 380 11. Chemicals from Xylenes 383 11.1 o-Xylene and Phthalic Anhydride 386 11.2 m-Xylene and Isophthalic Acid 395 11.3 p-Xylene and Terephthalic Acid/Dimethyl Terephthalate 397 12. Chemicals from Methane 407 12.1 Hydrocyanic Acid 408 12.2 Halogenated Methanes 411 12.3 Acetylene 417 12.4 Synthesis Gas 424 12.5 Chemicals from Synthesis Gas 429 12.6 Carbon Monoxide Chemistry 454 12.7 Gas-to-Liquid Fuels 459 13. Chemicals from Alkanes 463 13.1 Functionalization of Methane 464 13.2 Functionalization of C2--C4 Alkanes 468 13.3 Carbon Black 472 14. Chemicals from Coal 475 14.1 Chemicals from Coke Oven Distillate 477 14.2 The Fischer--Tropsch Reaction 480 14.3 Coal Hydrogenation 484 14.4 Substitute Natural Gas 485 14.5 SNG and Synthesis Gas Technology 485 14.6 Underground Coal Gasification 488 14.7 Calcium Carbide 488 14.8 Coal and the Environment 490 15. Fats and Oils 493 15.1 Markets for Fats and Oils 495 15.2 Purification of Fats and Oils 497 15.3 Fatty Acids 499 15.4 Fatty Nitrogen Compounds 502 15.5 "Dimer" Acid 504 15.6 Aminoamides and Imidazolines 506 15.7 Azelaic, Pelargonic, and Petroselinic Acids 507 15.8 Fatty Alcohols 508 15.9 Epoxidized Oils 509 15.10 Ricinoleic Acid 510 15.11 Glycerol 512 15.12 Alcoholysis of Fats and Oils 513 15.13 Alkyl Polyglycosides 519 15.14 Non-Caloric Fat-like Substances 519 16. Carbohydrates 523 16.1 Sugars and Sorbitol 523 16.2 Furfural 530 16.3 Starch 532 16.4 Cellulose 535 16.5 Gums 543 16.6 Fermentation and Biotechnology 544 17. How Polymers Are Made 561 17.1 Polymerization 565 17.2 Functionality 568 17.3 Step Growth and Chain Growth Polymerizations 571 17.4 Examples of Step Polymerization 605 17.5 Polymer Properties 622 17.6 Classes of Polymers 630 17.7 Plastics Fabrication Techniques 631 18. Industrial Catalysis 637 18.1 Catalyst Choice 637 18.2 Homogeneous and Heterogeneous Catalysis 643 18.3 Catalyst Markets 647 18.4 Catalysis by Acids and Bases 651 18.5 Dual Function Catalysis 654 18.6 Catalysis by Metals, Semiconductors, and Insulators 655 18.7 Coordination Catalysis 657 18.8 Enzymes 661 18.9 Shape-Selective Catalysts 664 18.10 Phase-Transfer and Fluorous Biphase Catalysis 669 18.11 Nanocatalysis 670 18.12 Catalysts of the Future 673 19. Green Chemistry 681 19.1 The Decline of Acetylene Chemistry 683 19.2 Nylon 683 19.3 Replacement of Phosgene 684 19.4 Monomethylation by Dimethyl Carbonate 685 19.5 Liquid and Supercritical Carbon Dioxide and Water 685 19.6 Ionic Liquids 687 19.7 Photocatalysts 690 19.8 Paired Electrosynthesis 691 19.9 "Green" Pharmaceuticals 692 19.10 Catalytic Dehydrogenation of Diethanolamine 698 19.11 Genetic Manipulation 698 19.12 Biodegradable Packaging 698 19.13 The Presidential Green Chemistry Challenge Program 703 20. Sustainability 707 20.1 Climate Change 708 20.2 Resource Depletion 712 20.3 Energy Sources 717 20.4 Pollution 736 20.5 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