Survey of industrial chemistry (3rd edition)

Survey of Industrial Chemistry Third Edition Philip ) Chenier University of Wisconsin-Eau Claire Eau Claire, Wisconsin Kluwer Academic / Plenum Publishers New York, Boston, Dordrecht, London, Moscow ISBN 0-306-47246-5 ©2002 Kluwer Academic/Plenum Publishers 233 Spring Street, New York, N.Y 10013 http://www.wkap.nl/ 10 A C.LP record for this book is available from the Library of Congress All rights reserved No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher Printed in the United States of America Preface This book arose from the need for a basic text dealing with industrial chemistry for use in a one-semester, three-credit senior level course taught at the University of Wisconsin-Eau Claire The course was added as a requirement for our B.S degree in Chemistry with Business Emphasis and is strongly recommended as an elective in our other chemistry majors, including our American Chemical Society-accredited program There are some good extensive texts and valuable reference works dealing with applied chemistry What was needed for our course, and what I believe will be useful for similar courses at the graduate or advanced undergraduate level, is a basic text of introductory material, sufficient to cover all important areas of the chemical industry, yet limited in scope so that completion of the book in 40 to 45 hours of lecture may be a reasonable goal The book is also an excellent resource and reference for persons working in the chemical and related industries It has sections on all important technology used by these industries and therefore is a one-step source for answers to most questions on practical applied chemistry Young scientists and engineers just entering the workforce will in particular find it useful as a readily available handbook to prepare them for a type of chemistry quite different from what they have seen in their traditional coursework, whether graduate or undergraduate Chemists and chemical engineers at every level of education and experience will have at their disposal a valuable resource Industrial chemistry means different things to different people Most will agree that the phrase includes the practical applied chemistry that bridges the gap between basic research and development and at least two other disciplines, chemical engineering and chemical marketing The present text attempts to lessen the lack of knowledge that most graduates have in both of these areas Some attempt is made to instill in chemists an appreciation for both the manufacturing and the economic problems facing the chemical industry on a day-to-day basis, as well as to introduce them to the chemistry used by our industry every day Although some space is devoted to economics and engineering, this is largely a chemistry book, and chemical reactions and processes, even mechanisms of reactions, are given full coverage In developing such a book the toughest job is always deciding what to include I have tried to cover a little of everything, since the text is meant to be a survey of important sectors of industrial chemistry The manufacture and uses of the top 100 basic chemicals are covered in detail The chemistry of all important industrial polymers is included and their applications are discussed Finally, certain selected specific technologies, the most important of the many areas that chemical manufacturing covers, are given one chapter each If one measures treatment in terms of the value of shipments, the book covers more than 90% of the chemical industry, as well as providing information on other industries separate from chemical manufacturing that also contain interesting chemistry and employ many chemists, such as the paper, petroleum and coal products industry, and the plastics and rubber products industry Perhaps the most challenging part of teaching this course and of writing a good text is to keep the important economic data current In some cases this is done easily; in others it is difficult Rather than having to revise this material yearly or even monthly with changing economic times, I have had recourse to some references to periodic updates that students can consult for the latest data An example of these series is "Chemical Profiles" in Chemical Marketing Reporter Government figures are a particular challenge, since official numbers for shipments are not available in Annual Survey of Manufactures until three years later But even those numbers give students a general feel for the economic trends of the industry It is virtually impossible for a text to remain economically accurate and complete for more than a year or two, and the present text is no exception In presenting this material in class I update these data periodically The graphs and charts are easily updated for a course The course material is also supplemented with over 200 color slides of various chemical plants, manufacturing sites, and research labs I have visited To attempt to thank everyone who has helped me expand my knowledge of this subject would be an impossible task, but certain organizations deserve a special mention A University of Wisconsin System Undergraduate Teaching Improvement Grant allowed me to plan the course initially during one summer University of Wisconsin-Eau Claire Faculty Development Grants enabled me to visit chemical plants throughout the United States to get firsthand experience in manufacturing They also funded some release time for one semester in which I wrote a portion of an earlier version of this book A number of companies let me visit their facilities, talk with their personnel, and obtain pictures for use in the course Their names are given in the figure captions I also thank the Department of Chemistry at UW-Eau Claire for allowing me to develop and teach the course, and to the students who have given me valuable feedback on the course and book In particular, I wish to thank the following students who have done research for me in connection with the preparation of materials used in the book: Danette Artibee, Lisa Bauer, Christine Benter, Leslie Bresina, Andrea Halberg, Kristin Halverson, Dawn Schroeder, Rich Vehlow, and Jennifer White Thanks also to Michael Carney, Melvin Gleiter, Ben Etzkorn, and Paul Houslet who helped with information and proofing Finally, I wish to thank one individual, Dr Harold Wittcoff, who first got me interested in teaching industrial chemistry when I audited his graduate course during a sabbatical at the University of Minnesota Philip J Chenier January 2002 About the Author Philip J Chenier is Emeritus Professor of Chemistry at the University of Wisconsin-Eau Claire, which he joined in 1970 He has worked for General Mills Chemicals and 3M Company Dr Chenier received his B.A from St Mary's College, Winona, Minnesota, and his Ph.D from Loyola University, Chicago, Illinois He has done post-doctoral work at the University of Minnesota He has published extensively in research and scholarly journals, and earlier versions of his book on industrial chemistry have been used by various schools since 1986 He has developed and taught an industrial chemistry course for the past twenty years Contents Preface v Introduction to the Chemical Industry: An Overview 1 The National Economy Definition and Divisions of the Chemical Industry Size and Current Economics of the Chemical Industry Location of the Chemical Industry Employment in the Chemical Industry Salaries of Chemists General Characteristics of the Chemical Industry 11 Top 50 Chemicals 16 Top Polymers 18 10 Top U.S Chemical Companies 22 11 Top World Chemical Companies 22 Sulfuric Acid and Its Derivatives 23 Introduction to Inorganic Chemicals 23 Sulfuric Acid (Oil of Vitriol) 27 Phosphoric Acid (Orthophosphoric Acid) 37 Aluminum Sulfate (Filter Alum or Papermaker's Alum) 39 Industrial Gases 41 Nitrogen 41 Oxygen 44 This page has been reformatted by Knovel to provide easier navigation ix x Contents Hydrogen 45 Carbon Dioxide 50 Economics of Industrial Gases 51 Inorganic Nitrogen Compounds 55 Ammonia 56 Nitric Acid 59 Ammonium Nitrate 61 Urea 62 Ammonium Sulfate 63 Chemicals from Limestone 65 Lime 65 Soda Ash (Sodium Carbonate) 69 Calcium Chloride 72 Sodium Silicate (Silica Gel) 73 Sodium Chloride Derivatives and Miscellaneous Inorganics 75 Sodium Chloride 75 Caustic Soda (Sodium Hydroxide, Caustic) 77 Chlorine 82 Economics of Caustic Soda and Chlorine 83 Hydrochloric Acid (Muriatic Acid) 84 Titanium Dioxide 86 Miscellaneous Inorganic Chemicals 87 Petroleum Refining Processes 91 Introduction 91 Distillation 96 Octane Number 98 Additives 101 This page has been reformatted by Knovel to provide easier navigation Contents xi Hydrotreating 105 Cracking 106 Reforming 110 Alkylation and Polymerization 112 Separation of Natural Gas: Methane Production 113 Basic Organic Chemicals 117 Ethylene (Ethene) 117 Propylene (Propene) 122 The C4 Stream 124 Butadiene (1,3-Butadiene) 124 Isobutylene (Isobutene) 126 Economic Aspects of Olefins 128 Benzene (Benzol) 130 Toluene (Toluol) 134 Xylenes (Xylols) 136 10 Economic Aspects of Aromatics 139 Derivatives of Ethylene 143 Ethylene Bichloride (EDC) 145 Vinyl Chloride (Vinyl Chloride Monomer, VCM) 147 Acetic Acid (Ethanoic Acid, Glacial Acetic Acid) 148 Vinyl Acetate 152 Ethylbenzene 154 Styrene (Vinylbenzene, Phenylethene) 156 Ethylene Oxide 158 Ethylene Glycol (Ethan-1,2-Diol) 160 10 Chemicals from Propylene and Butylene 163 Acrylonitrile (2-Propenonitrile) 163 Propylene Oxide (1,2-Epoxypropane) 167 Cumene (Isopropylbenzene) 171 This page has been reformatted by Knovel to provide easier navigation xii Contents Acetone (2-Propanone) 172 Bisphenol A (BPA) 176 n-Butyraldehyde (Butanal) 177 Chemicals from the C4 Fraction 179 Butadiene Derivatives 179 Methyl t-Butyl Ether (MTBE) 182 10 Other C4 Derivatives 182 11 Derivatives of the Basic Aromatics 185 Benzene Derivatives 185 Phenol (Carbolic Acid) 187 Cyclohexane (Hexahydrobenzene, Hexamethylene) 188 Adipic Acid (1,6-Hexandioic Acid) 189 Caprolactam 193 Nitrobenzene 195 Toluene Derivatives 197 Terephthalic Acid and Dimethyl Terephthalate 199 Phthalic Anhydride 201 12 Chemicals from Methane 205 Methanol (Wood Alcohol, Methyl Alcohol) 207 Formaldehyde (Methanal) 208 Acetic Acid 210 Chlorofluorocarbons and Fluorocarbons 211 13 The Second Fifty Industrial Chemicals 217 Introduction and Background 217 Characteristics of the Second 50 Chemicals 220 Derivatives of the Seven Basic Organics 221 Second 50 Chemical Pairs 222 Manufacture and Uses 222 This page has been reformatted by Knovel to provide easier navigation 522 Index terms methyl salicylate methyl t-butyl ether Links 425 15 104 182 241 methyl-3-butenonitrile 180 methylcyclopentadienyl manganese tricarbonyl 104 methylene chloride 240 methylene diisocyanate 223 methylene diphenyl diisocyanate 196 methylenedianiline 197 methylglutaronitrile 180 methylmercury 478 N-methylpyrrolidone 125 α-methylstyrene 173 metolachlor 169 457 220 228 386 M/F See melamine formaldehyde MIBK See methyl isobutyl ketone micelles 264 minocycline 442 462 MMT See methylcyclopentadienyl manganese tricarbonyl modulus 285 molecular weight of polymers 280 295 319 MON See motor octane number monoammonium phosphate monoethanolamine 395 48 monofilament 318 Monsanto process 151 Montreal Protocol 215 morphine 455 morpholine 160 motor octane number 211 236 99 ® Motrin See ibuprofen This page has been reformatted by Knovel to provide easier navigation 453 179 523 Index terms Links MSDS See Material Safety Data Sheets MTBE See methyl f-butyl ether multistriatin 378 ® Mylar See poly(ethylene terephthalate) N NAICS See North American Industry Classification System nalidixic acid naphtha naphthalene 443 96 107 118 124 130 242 201 230 252 131 134 122 375 453 naphthenes 96 naphthenic acid 97 ® Naprosyn See naproxen naproxen National Toxicology Program 453 458 133 202 369 383 306 490 Natta 253 278 280 335 341 342 natural gas 113 114 117 118 naval stores industry 412 185 195 196 NBR See nitrile rubber Neoprene® See polychloroprene Nernst 56 nicotine 365 nitric acid 59 nitrile rubber 343 nitrilotriacetate 473 nitrobenzene 61 227 nitrocellulose 61 This page has been reformatted by Knovel to provide easier navigation 524 Index terms Links nitrogen 41 nitroglycerin 58 Nobel Prize 61 215 253 367 369 430 438 440 458 nonene 224 238 471 nonylphenol 238 464 470 471 nonylphenol ethoxylates 470 noradrenaline 429 norepinephrine 429 norethindrone 446 North American Industry Classification System 430 ® Norvasc See amlodipine novolacs 268 NPE See nonylphenol ethoxylates NPK value 393 NR See rubber, natural NSP See superphosphate, normal NTP See National Toxicology Program Nutrasweet® See aspartame nylon 193 195 225 226 247 257 324 325 183 490 O Occupational Safety and Health Administration octane number 98 oleum 33 241 oligomers 122 124 omeprazole 424 organophosphorus compounds 366 372 OSHA See Occupational Safety and Health Administration OSP See superphosphate, ordinary This page has been reformatted by Knovel to provide easier navigation 246 525 Index terms oxo process oxychlorination of ethylene oxygen Links 177 178 184 205 224 238 242 105 146 148 213 333 334 478 479 97 234 347 348 353 381 412 91 361 399 223 237 146 41 ozone depletion 485 P paint Paper Manufacturing n-paraffins 237 paraformaldehyde 209 parathion 372 paroxetine 437 ® Paxil See paroxetine PCBs See polychlorinated biphenyls penicillins 440 pentachlorophenol 410 pentaerythritol tetranitrate 210 pentanal 184 1-pentanol 184 3-pentenonitrile 180 peracetic acid 150 242 151 perc See perchloroethylene perchloroethylene 146 persistent organic pollutants 369 pesticides 361 489 PET See poly(ethylene terephthalate) Petroleum and Coal Products Manufacturing petroleum refining 91 91 This page has been reformatted by Knovel to provide easier navigation 92 526 Index terms Links P/F See phenol-formaldehyde Pharmaceuticals 417 phase transfer catalyst 166 phenobarbital 433 phenol 187 188 phenol-formaldehyde resins 265 310 phenoxy herbicides 382 phenylmethylcarbinol 157 phenylpropane units 400 pheromones 378 phorate 373 phosgene 308 169 85 197 198 220 223 230 234 308 114 375 phosphate rock 37 38 76 237 389 394 phosphoric acid 37 phosphorus 37 44 220 237 238 372 389 397 138 199 201 202 203 230 231 233 276 351 435 phthalocyanine blue 350 351 physostigmine 374 phthalic anhydride pig iron 44 pigments 196 228 350 408 pine oil 413 pinenes 412 plasticizers 231 plastics 289 Plastics and Rubber Products Manufacturing 348 237 91 This page has been reformatted by Knovel to provide easier navigation 289 349 527 Index terms Links Platforming® 110 131 plywood adhesive 172 210 165 283 126 255 264 307 335 336 338 341 177 223 261 334 PMNs See premanufacturing notices polyacrylonitrile polyamides See nylons polybutadiene poly(butylene terephthalate) polycarbonate 201 82 308 polychlorinated biphenyls 369 483 polychloroprene 126 179 252 170 242 273 polyester See poly(ethylene terephthalate) polyether polyethylene 22 122 123 129 145 224 242 249 255 256 281 283 291 295 327 335 138 159 201 259 283 291 326 252 278 334 22 166 326 123 163 254 283 291 327 335 359 281 355 polyethylene terephthalate) poly(hexamethyleneadipamide) See nylon polyisoprene 335 340 polymers 246 poly(methyl methacrylate) 175 polyolefin polypropylene poly(propylene glycol) 171 polystyrene 122 158 264 283 291 295 This page has been reformatted by Knovel to provide easier navigation 528 Index terms polyurethanes Links 83 134 135 171 198 273 274 358 poly(vinyl acetate) 153 354 poly(vinyl butyral) 352 359 122 146 148 88 233 392 87 156 239 233 239 220 239 poly(vinyl chloride) POPs See persistent organic pollutants Portland cement 68 potash 87 393 potassium carbonate potassium chloride 28 87 88 432 466 potassium hydroxide 87 88 potassium nitrate 28 87 potassium sulfate 87 88 233 446 448 premanufacturing notices 490 ® Premarin See estrogens pressure-sensitive adhesives prills 357 61 ® Prilosec See omeprazole progesterone 445 prontosil 438 propanil 386 propellants 213 propoxyphene 454 propranolol 429 propylene: derivatives 163 economics 128 manufacture 122 propylene glycol 170 233 This page has been reformatted by Knovel to provide easier navigation 529 Index terms propylene oxide proton pump inhibitor Links 83 123 133 158 167 241 157 425 ® Prozac See fluoxetine PSAs See pressure-sensitive adhesives PTA See terephthalic acid pulp and paper 399 PVC See poly(vinyl chloride) pyrethrin 365 377 pyrethroids 366 377 ® Pyrex 72 pyrogallol 415 Q quat 465 quercetin 415 quicklime 65 4-quinolones 443 R rayon 33 228 277 322 324 338 315 45 46 56 103 110 112 117 130 89 333 338 RCRA See Resource Conservation and Recovery Act recyling of plastics reforming 301 232 reformulated gasoline 105 refrigerants 213 reinforcing agent, for elastomers 74 research octane number 99 reserpine 429 This page has been reformatted by Knovel to provide easier navigation 530 Index terms Links resorcinol 269 Resource Conservation and Recovery Act 485 RFG See reformulated gasoline (R + M)/2 value road deicing 100 225 rock salt 75 rofecoxib 454 76 RON See research octane number Rosin 224 rotenone 407 414 365 ® Roundup 384 See glyphosate rubber, natural rutile ore 330 336 86 349 S saccharin salaries of chemists saltpeter ® Saran 483 59 147 SBR See styrene-butadiene rubber Scotch® tape 357 second 50 industrial chemicals 217 selective serotonin reuptake inhibitor 428 sertraline 427 433 Seveso 383 484 437 ® Sevin See carbaryl shellac 347 short-term exposure limit 133 SIC See Standard Industrial Classification Silent Spring silica gel 482 73 74 This page has been reformatted by Knovel to provide easier navigation 157 415 531 Index terms Links silicones 231 silk 257 silver nitrate 371 61 silvex 383 sizing in paper 153 soaps 461 224 408 414 71 72 233 226 486 soda ash See sodium carbonate sodium bicarbonate 70 451 sodium bromide 241 sodium carbonate 69 sodium chlorate 408 sodium chloride 75 sodium cyanide 82 sodium dichromate 228 sodium hydroxide 77 sodium hypochlorite 80 sodium lauryl sulfate 468 sodium nitrate 59 72 sodium silicates 65 73 69 72 220 240 472 sodium sulfate 402 sodium tripolyphosphate 220 Solvay 69 sorbitol 239 spinning of yarns 318 240 SSRI See selective serotonin reuptake inhibitor Standard Industrial Classifications staple fibers 318 steam-reforming 45 steel manufacture 44 This page has been reformatted by Knovel to provide easier navigation 228 532 Index terms steroid drugs Links 444 STPP See sodium tripolyphosphate styrene 156 styrene-butadiene rubber 126 sulfa drugs 438 sulfadiazine 439 sulfanilamide sulfolane sulfur 262 336 438 439 440 131 135 27 sulfur dioxide 236 sulfuric acid 27 ® Super glue 359 superfund 486 487 superphosphate 394 395 surfactants 461 sylvinite 88 synthesis gas 45 46 124 161 205 207 227 236 220 224 407 414 415 466 Synthetic Organic Chemicals 16 ® Synthroid See levothyroxine T 2,4,5-T See 2,4,5-trichlorophenoxyacetic acid tall oil tannin 414 TCDD See 2,3,7,8-tetrachlorodibenzo-p-dioxin TCP See totally chlorine-free TDI See toluene diisocyanate TEG See triethylene glycol Temik® See aldicarb tenacity 318 This page has been reformatted by Knovel to provide easier navigation 533 Index terms tensile strength Links 258 285 295 305 306 307 314 318 319 333 terbufos 373 378 terephthalic acid 138 152 198 199 201 306 TEPP See tetraethyl pyrophosphate terpinolene 412 testosterone 445 2,3,7,8-tetrachlorodibenzo-p-dioxin 382 tetrachlorodibenzofuran 371 tetracyclines 418 tetraethyl pyrophosphate 372 tetraethylene glycol 131 236 15 102 104 tetrahydrofuran 209 238 411 tetrahydrotriazone 396 tetraethyllead 442 tetramethylene glycol See 1,4-butanediol thalidomide 482 thermoplastics 245 thermosets 265 489 THF See tetrahydrofuran threshold limit value 125 thyroid hormone 423 time weighted average 133 tinting strength 348 tires, automobile 337 titanium dioxide 45 75 86 87 157 243 349 408 titanium tetrachloride 133 351 86 TLV See threshold limit value This page has been reformatted by Knovel to provide easier navigation 534 Index terms toluene Links 134 135 139 140 197 2,4-toluenediamine 234 toluene diisocyanate 135 top 50 Chemicals 16 top Polymers 18 top U.S Chemical Companies 22 top World Chemical Companies 22 total reduced sulfur 406 totally chlorine-free 408 tower acid 198 488 29 Toxic Release Inventory 475 491 Toxic Substances Control Act 475 485 489 135 198 ® Treflan See trifluralin TRI See Toxic Release Inventory triamterene 2,4,5-trichlorophenoxyacetic acid 432 381 tricyclic antidepressants 435 triethylene glycol 236 trifluralin 386 trinitrotoluene 61 trioxane 209 triprolidine 457 trona ore 69 TRS See total reduced sulfur TSCA, TOSCA See Toxic Substances Control Act TSP See superphosphate, triple turpentine 412 TWA See time weighted average Tylenol® See acetaminophen This page has been reformatted by Knovel to provide easier navigation 480 535 Index terms Links U U.S Pharmacopeia 33 420 131 132 138 160 170 202 231 236 239 311 uranium 38 242 urea 62 63 urea-formaldehyde resins 63 209 269 270 310 396 408 13 30 31 Udex extraction U/F See urea-formaldehyde unsaturated polyester resins USP See U.S Pharmacopeia V valeraldehyde 242 ® Valium See diazepam value added vanadium pentoxide vanillin 411 varnish 347 vinyl acetate 152 vinyl chloride 133 vinyl coatings 352 vinylidene chloride 147 147 148 484 329 331 ® Vioxx See rofecoxib viscose 228 322 VOCs See volatile organic compounds volatile organic compounds 355 vulcanization 196 251 149 153 W Wacker process ® Weed-B-Gon 384 This page has been reformatted by Knovel to provide easier navigation 536 Index terms wet process for phosphoric acid Links 37 38 394 395 38 97 409 410 257 321 277 322 wood carbonization 412 wood distillation 412 wood preservatives wool X xanthate xylene 16 91 117 132 133 136 137 139 198 199 200 202 221 230 154 172 Y yarns 318 Z zeolites 136 137 237 473 Ziegler catalysts 223 470 zinc chloride 411 Zoloft® See sertraline This page has been reformatted by Knovel to provide easier navigation ... little of everything, since the text is meant to be a survey of important sectors of industrial chemistry The manufacture and uses of the top 100 basic chemicals are covered in detail The chemistry. .. example of these series is "Chemical Profiles" in Chemical Marketing Reporter Government figures are a particular challenge, since official numbers for shipments are not available in Annual Survey of. .. a sabbatical at the University of Minnesota Philip J Chenier January 2002 About the Author Philip J Chenier is Emeritus Professor of Chemistry at the University of Wisconsin-Eau Claire, which