Handbook of Industrial Chemistry Organic Chemicals Mohammad Farhat AIi, Ph.D King Fahd University of Petroleum & Minerals Dhahran, Saudi Arabia Bassam M El AIi, Ph.D King Fahd University of Petroleum & Minerals Dhahran, Saudi Arabia James G Speight, Ph.D CD&Wlnc Laramie, Wyoming McGraw-Hill New York Chicago San Francisco Lisbon London Madrid Mexico City Milan New Delhi San Juan Seoul Singapore Sydney Toronto CIP Data is on file with the Library of Congress Copyright © 2005 by The McGraw-Hill Companies, Inc AU rights reserved Printed in the United States of America Except as permitted under the United States Copyright Act of 1976, no part of this publication may be reproduced or distributed in any form or by any means, or stored in a data base or retrieval system, without the prior written permission of the publisher 1234567890 DOC/DOC 010987654 ISBN 0-07-141037-6 The sponsoring editor for this book was Kenneth P McCombs and the production supervisor was Pamela A Pelton It was set in Century Schoolbook by International typesetting and Composition The art director for the cover was Anthony Landi Printed and bound by RR Donnelley This book is printed on recycled, acid-free paper containing a minimum of 50% recycled, de-inked fiber McGraw-Hill books are available at special quantity discounts to use as premiums and sales promotions, or for use in corporate training programs For more information, please write to the Director of Special Sales, McGraw-Hill Professional, Two Penn Plaza, New York, NY 101212298 Or contact your local bookstore Information contained in this work has been obtained by The McGraw-Hill Companies, Inc ("McGraw-Hill") from sources believed to be reliable However, neither McGraw-Hill nor its authors guarantee the accuracy or completeness of any information published herein, and neither McGraw-Hill nor its authors shall be responsible for any errors, omissions, or damages arising out of use of this information This work is published with the understanding that McGraw-Hill and its authors are supplying information but are not attempting to render engineering or other professional services If such services are required, the assistance of an appropriate professional should be sought To our wives and families, and to all scientists and engineers who preceded us in such work ABOUTTHE EDITORS is Professor of Industrial and Petroleum Chemistry at King Fahd University of Petroleum & Minerals in Saudi Arabia An expert in characterization studies of heavy ends, residues, and asphalt, he is also knowledgeable about crude oils and products, refining process technology, waste oil recycling, and stability characteristics of jet fuels MOHAMMAD FARHAT ALI, PH.D., BASSAM M EL ALI, PH.D., is Professor of Industrial Chemistry at King Fahd University of Petroleum & Minerals in Saudi Arabia His specialties include homogenous and heterogeneous catalysis using transition metal complexes in hydrocarboxylation, hydroformylation, oxidation, coupling, hydrogenation, and other important processes; investigation of the organometallic intermediates and the mechanisms of various homogenous reactions; and synthesis, characterization, and application of various supported catalytic systems in the production of fine chemicals He has taught many industrial chemistry courses including Industrial Catalysis, Industrial Organic Chemistry, Industrial Inorganic Chemistry, and Petroleum Processes G SPEIGHT, PH.D., has more than 35 years' experience in fields related to the properties and processing of conventional and synthetic fuels He has participated in, and led, significant research in defining the uses of chemistry with heavy oil and coal The author of well over 400 professional papers, reports, and presentations detailing his research activities, he has taught more than 50 related courses Dr Speight is the author, editor, or compiler of a total of 25 books and bibliographies related to fossil fuel processing and environmental issues He lives in Laramie, Wyoming JAMES Contributors Hasan A Al-Muallem, Ph.D Department of Chemistry King Fahd University of Petroleum & Minerals Dhahran, Saudi Arabia Mohammad Farhat AIi, Ph.D Professor of Chemistry Department of Chemistry King Fahd University of Petroleum & Minerals Dhahran, Saudi Arabia Bassam M ElAIi, Ph.D Professor of Chemistry Department of Chemistry King Fahd University of Petroleum & Minerals Dhahran, Saudi Arabia Manfred J Mirbach, Ph.D Landis Kane Consulting R&D Management Fuellinsdorf, Switzerland Ahsan Shemsi Department of Chemistry King Fahd University of Petroleum & Minerals Dhahran, Saudi Arabia James G Speight, Ph.D CD&W Inc Laramie, Wyoming Preface The organic chemical industry is an important branch of industry and its structure usually centers on petroleum and hydrocarbon derived chemicals The volume text of available books is generally lacking in covering other very important nonpetroleum-based organic industries such as paints, dyes, edible oils, fats and waxes, soaps and detergents, sugars, fermentation, chemical explosives, and agrochemical industries This book focuses primarily on the chemical processing of raw materials other than petroleum and hydrocarbons These materials are usually converted into useful and profitable products that are, in general, used as consumer goods The book addresses the needs of both students and practicing chemists and chemical engineers It is intended to be a primary source of information for the young practicing professionals who wish to broaden their knowledge of the organic process industry as a whole The book may also serve as a textbook for advanced undergraduate students in industrial chemistry Chapter describes the development of the chemical industry and its role in welfare and employment around the world This chapter shows how raw materials are procured and converted to consumer products Chapter discusses safety aspects in organic industries and methods to protect the workers from hazards such as exposure to dangerous chemicals, heat, pressures, high electric fields, accelerating objects, and other sources of hazards Chapter deals with the sources of pollution caused by raw materials, products, and wastes in petroleum, petrochemicals, pharmaceuticals, food, and other industries The growing public concerns over the safety of chemicals in the environment, and the efforts by the governments and industries for their control, are discussed Chapter presents the chemistry and technology of edible oil, fat, and wax processing including refining, recovery, crystallization, interesterification, and hydrogenation The key oxidation reactions of lipids leading to quality deterioration of processed and unprocessed foods, and the mechanism of the action of the antioxidants in improving oxidation stability of foods are discussed Chapter highlights the soap and detergent industry The raw materials, important processes of production, and economic importance of the soap and detergent industry are elaborated Chapter covers one of the most widely distributed and abundant organic chemicals—the sugars The chemistry of saccharides, historical survey, and world production of sugar are presented The sugar recovery from the two principal sources—sugar cane and sugar beets—are discussed The chemistry and uses of nonsugar sweetening agents is also presented Chapter describes paints, pigments, and industrial coatings The major paint components, namely, pigments, binders, additives, and solvents are discussed in separate sections These are followed by the principles of formulation, application techniques, durability, and testing of paints Chapter is devoted to the industrially produced dyes with their classification, manufacture, properties, and main applications, as well as environmental and health aspects Chapter presents an overview of modern fermentation processes and their application in food, pharmaceutical, and industrial chemical industries The social and economic importance of fermentation processes is discussed The pharmaceutical industry is presented in Chapter 10 as one of the most important sectors of healthcare worldwide The discovery, the development, and the production of drugs are covered in this chapter The chapter also includes the correlation between the growth in the worldwide market for Pharmaceuticals and the increase of the world population as a result of higher life expectancy and changes in lifestyle Chapter 11 presents an overview of the agrochemical industry Beginning with the introduction and historical background, it leads to the modern trends in agriculture, chemical pest control, herbicides, fungicides, insecticides, and biological pest control agents Social and economic aspects of pesticides use are also discussed Chapter 12 presents the chemistry of explosives Chemical explosives and propellants are well-covered in this book because of their importance for peaceful uses They are considered chemical compounds in pure form or mixtures that rapidly produce a large volume of hot gases when properly ignited The destructive effects of explosives are much more spectacular than their peaceful uses However, it appears that more explosives have been used by industries for peaceful purposes than in all the wars Chapter 13 covers the conversion of crude oil into desired products in an economically feasible and environmentally acceptable manner Descriptions are provided for (1) desalting and dewatering; (2) separation processes, of which distillation is the prime example; (3) conversion processes, of which coking and catalytic cracking are prime examples; and (4) finishing processes, of which hydrotreating to remove sulfur is a prime example Descriptions of the various petroleum products (from fuel gas to asphalt and coke) are also given This chapter also includes a description of the petrochemical industry, and the production of the chemicals and compounds in a refinery that are destined for further processing, and used as raw material feedstocks for the fast-growing petrochemical industry Chapter 14 provides the basic principles of polymer science, and addresses the importance of this subject This chapter aims to give a broad and unified description of the subject matter—describing the polymerization reactions, structures, properties, and applications of commercially important polymers, including those used as plastics, fibers, and elastomers This chapter focuses on synthetic polymers because of the great commercial importance of these materials The chemical reactions by which polymer molecules are synthesized are addressed along with the process conditions that can be used to carry them out This chapter also discusses topics on degradation, stability, and environmental issues associated with the use of polymers This book is intended for university and college students who have studied organic chemistry, as well as for scientists and technicians who work in the organic chemical industry, and senior executives and specialists who wish to broaden their knowledge of the industrial organic processes as a whole At the end, we gratefully acknowledge the financial aid, facilities, and support provided by the Deanship of Scientific Research at King Fahd University of Petroleum & Minerals, Dhahran, Saudi Arabia Mohammad Farhat AU, Ph.D Bassam M ElAIi, Ph.D James G Speight, Ph.D Contents About the Editors vi Contributors vii Preface ix Introduction: an Overview of the Chemical Process Industry and Primary Raw Materials 1.1 The Chemical Process Industry 1.2 Development of the Chemical Industry 1.3 Characteristics of the Chemical Industry 1.4 Raw Materials, Manufacturing, and Engineering Environmental Aspects References Safety Considerations in Process Industries 11 1.5 2.1 Introduction 12 2.2 OSHA (Occupational Safety and Health Administration) and PSM (Process Safety Management) 14 2.3 Incident Statistics and Financial Aspects 16 2.4 Safety Decision Hierarchy 16 2.5 Hazard Analysis and Risk Assessment (HARA) 17 Types of Hazards in Industries 18 2.6.1 18 2.6 Heat and Temperature This page has been reformatted by Knovel to provide easier navigation v vi Contents 2.6.2 Pressure Hazards 19 2.6.3 Electrical Hazards 21 2.6.4 Mechanical Hazards 23 2.6.5 Toxic Materials 24 2.6.6 Fire and Explosion 27 2.6.7 Accelerator and Falling Objects 30 2.6.8 Confined Space 31 2.6.9 Radiation 33 2.6.10 Noise and Vibrations 37 2.6.11 Ergonomics 39 Risk Management Plan 40 2.7.1 The Role of Safety Personnel 40 2.7.2 Personal Protective Equipment (PPE) 41 Appraising Plant Safety and Practices 44 Planning for Emergencies 45 References 47 Industrial Pollution Prevention 49 2.7 2.7.3 2.7.4 3.1 Definition of Industrial Waste 50 3.2 Types of Industrial Wastes 51 3.2.1 Classification of Industrial Waste 52 3.3 Public Concern over Pollution 54 3.4 Legislation to Waste Management 56 3.5 Industrial Pollution Prevention 57 3.6 Assessment of Industrial Pollution Prevention 58 3.6.1 Assessment of Waste Generation 58 3.6.2 Feasibility of the Industrial Pollution Prevention 59 Feasibility Implementation 59 3.6.3 This page has been reformatted by Knovel to provide easier navigation 647 Index terms Links Pharmaceuticals (Continued) antidepressant 357 antiepileptic 359 antihypertensive 359 antipsychotic agents 362 antiulcer 361 aspirin 370 biopolymers 322 by biotransformation 319 capsules 376 chemical synthesis of 366 classical drug discovery 339 classification/chemistry of 347 clinical testing in development of 345 contraceptive 364 creams/ointments/pastes 377 development of 337 by direct fermentation 318 diuretic 363 economic aspects of 332 extraction process for 368 fermentation of 369 formulation/mixing/compounding 372 industrial processing of 365 liquid dosage forms 377 manufacturing of 370 modern development of 341 parenteral dosage forms 377 pre-clinical testing in development of 344 pyribenzamine 371 quality control of 378 R&D 366 369 This page has been reformatted by Knovel to provide easier navigation 648 Index terms Links Pharmaceuticals (Continued) sales of 332 suppositories 377 tablets 373 vitamin 364 Pharmacia 334 Pharmacophore 339 Phenyl keton uria (PKU) 195 Phosphates 144 Photosynthesis 167 375 Physical hazards 33 Physical waste treatment 69 70 Picric acid 433 441 Pigments (paints) 204 black 215 bleeding characteristics of 207 blue 214 classification of 208 color 213 extender 216 green 444 221 219 221 214 219 220 hiding power of 205 206 inorganic 209 light fastness of 207 metallic 215 orange 213 organic 217 particle size/shape of 207 red 214 218 refractive index of 206 207 tinting strength of 205 This page has been reformatted by Knovel to provide easier navigation 219 649 Index terms Links Pigments (paints) (Continued) white 209 yellow 213 Pipe reactors 218 PKU (phenyl keton uria) 195 Plant protection chemicals 385 Plants: as raw material source sucrose in Plastics Pollution 167 516 523 50 output sources prevention techniques public concern over 54 and waste management 53 (See also Industrial waste management) Polymerization 564 addition/chain-reaction 572 anionic 582 bulk 594 cationic 585 co- 600 condensation/step-reaction of 569 coordination 589 emulsion 597 free radical 573 group-transfer 592 interfacial 599 ionic 582 metathesis 591 precipitation 596 This page has been reformatted by Knovel to provide easier navigation 650 Index terms Links Polymerization (Continued) ring-opening 592 solution 596 suspension 597 Polymers 593 511 additives to 616 Asian production of 526 branched 514 Canadian production of 524 classification of 512 co- 521 comb 514 534 commodity/engineering 518 520 cross-linked 514 532 crystalline/amorphous state of 539 degradation/stability of 611 elastomer 515 European production of 525 European production of fiber 530 fiber 515 flexibility of 538 geometric isomerism of 535 head-to-head vs head-to-tail 521 homo- 520 ladder 528 516 522 528 514 532 533 linear 514 522 528 mechanical properties of 546 modification of synthetic 607 molecular interaction of 536 molecular weight of 560 plastic 516 This page has been reformatted by Knovel to provide easier navigation 651 Index terms Links Polymers (Continued) rheology of 556 shipments of paint/coating 529 solubility of 548 star-shape 514 534 structure of 520 528 structure-property relationships of 541 synthesis of high (see Polymerization) tacticity of 534 thermal properties of 541 thermoplastic/thermoset 516 U.S production of fiber 530 U.S production of plastic/synthetic-rubber 523 viscosity of 554 Postconsumer recycling Potassium hydroxide Potassium permanganate 64 126 75 Precipitation polymerization 596 Pre-clinical drug testing 344 Preconsumer recycling 64 Pressure hazards 19 Prilosec 334 Primary explosives 437 Primary metabolites 294 Process safety management 15 Procter and Gamble 131 Progesterone 321 Propellants 443 composite 451 composite rocket 454 double-base 450 449 451 This page has been reformatted by Knovel to provide easier navigation 532 652 Index terms Links Propellants (Continued) double-base rocket 454 gun 449 rocket 453 single-base 449 450 triple-base 451 452 Protective clothing 26 43 35 36 Protective equipment 26 434 442 Pseudomonas Purification methods 310 Pyranose form (glucose) 164 Pyrethrins 391 Pyribenzamine 371 Pyrotechnics 455 Q Quality control: of Pharmaceuticals 378 R Radars 36 Radiation 33 Radio frequency (RF) radiation 36 Radioactive substances 25 Radon gas 35 Raw materials R&D (see Research and development) RDX 433 461 Reactants This page has been reformatted by Knovel to provide easier navigation 653 Index terms Reactors Links Reclamation 65 Recycling 64 with energy recovery 66 with liquid-liquid-separation 67 with off-site recovery 66 on-site 65 with solid-liquid-separation 67 technologies for 66 with vapor-liquid-separation 66 Red pigments 214 218 Refining: of petroleum (see Petroleum) of raw sugar 180 of vegetable oils 108 Reforming processes (petroleum) 491 Refractive index (of pigments) 206 Regeneration 65 Renewable resources Research and development (R&D) in pharmaceutical industry 336 Pharmaceuticals 366 spending on and waste management 207 366 63 Reuse 65 Reverse osmosis 68 RF (see Radio frequency radiation) Ring-opening polymerization 592 Risk assessment hierarchy 16 Risk management plan 40 and appraisal of plant safety 593 44 This page has been reformatted by Knovel to provide easier navigation 219 654 Index terms Links Risk management plan (Continued) for emergencies 45 personal protective equipment in 41 safety personnel in 40 Rocket propellants 453 Rodenticides 396 Romans, ancient 123 Rotary kiln incinerators 78 Rotational crop system 382 Rupturing (of container) 19 399 S Saccharides 164 Saccharin 193 Safety decision hierarchy for with explosives 12 16 467 financial aspects of 16 and hazard analysis and risk assessment (HARA) 17 with pesticides risk management plan for ensuring 196 415 40 (See also Hazard(s)) Salicylic acid 338 Saponification 86 Saturated fats 87 Saturated fatty acids 88 Sauerkraut 305 Scurvy 305 Seawater desalination plants Seaweed 126 91 68 314 This page has been reformatted by Knovel to provide easier navigation 655 Index terms Links Secondary explosives 439 Secondary metabolites 295 Separation methods Serpxat 335 Shaving soaps 127 Silage 309 Silver azide 439 Single-base propellants 449 Site evacuation routes 46 Smoke-producing pyrotechnics Soap(s) 450 457 86 chemistry of 125 classification of 126 environmental aspects of 130 historical background 123 manufacturing of 127 raw materials for 125 98 (See also Detergents) Soda ash 124 Solid fats 94 Solid toxic materials 25 Solid wastes, disposal of 55 Solid-liquid separation 67 Solution polymerization 596 Solvay process 146 Solvent dyes 266 Solvents 27 Sorbitol 192 Sorghum 311 Sound-producing pyrotechnics 456 501 This page has been reformatted by Knovel to provide easier navigation 123 656 Index terms Links Soy sauce 306 Spray-drying process 155 Sprinklers, automatic 30 Starch sugars 188 Star-shape polymers 514 Step-reaction polymerization 569 Sternbach, Leo 340 Steroids 320 Strain 307 534 39 Stripping: air 71 steam 72 Sucralose 197 Sucrose: hydrolysis of 165 properties of 167 Sugar alcohols 192 Sugar beets 168 (See also Beet sugar) Sugar boiling 175 Sugarcane 168 Sugar coating 376 Sugar(s) 163 analysis of 197 beet 184 brown 190 by-products of 191 172 197 191 cane (see Cane sugar) chemistry of 164 consumption of 169 This page has been reformatted by Knovel to provide easier navigation 657 Index terms Links Sugar(s) (Continued) and fermentation 294 global production of 168 granulated 189 historical background 168 invert 191 liquid 191 properties of 167 sources of 187 starch 188 Sulfitation 186 Sulfonamides (sulfa drugs) 353 Sulfonation 135 Sulfonic acid 135 Sulfur dioxide 174 Sulfur dyes 266 Sulfur trioxide 135 Suppositories 377 Supradyn 337 Surface active agent, detergent as 130 Surfactants 133 136 amphoteric 133 143 cationic 133 142 nonionic 133 139 (See also Detergents) Suspension polymerization 597 Sweeteners 187 acesulfame-K 194 alitame 194 apartame 195 192 This page has been reformatted by Knovel to provide easier navigation 275 658 Index terms Links Sweeteners (Continued) cyclamate 195 saccharin 196 sucralose 197 (See also Sugar) Synthetic detergents 132 Synthetic dyes 260 Syrup, sugar 188 T Tablets (pharmaceuticals) 373 Talisman system 178 Tallow 125 Tenside 130 Terpolymers 601 Tetrazene 439 Tetryl 441 Textile dyes 268 Thermoplastic solidification 73 Thin juice (sugar production) 186 Tinting strength (of pigments) 205 TNT 433 Toilet soap 126 Toluene 193 Toxic materials 24 Toxic vapors 43 Toxic waste dumping 56 Tranquilizer drugs trans- (prefix) Triblock copolymers 375 441 69 340 91 602 This page has been reformatted by Knovel to provide easier navigation 446 659 Index terms Links -trienoic (suffix) 91 Triethanolamine 126 Triglycerides 86 chemical properties of 98 fats and oils as 92 HPLC of 118 methanolysis of 126 physical properties of 92 94 Triple-base propellants 451 452 Trisodium phosphate 144 Tylenol 349 96 U Ulcer medications 361 Ultimate disposal 81 Ultra-filtration 68 Ultraviolet radiation 35 V Vaccines 304 Valium 341 Vapor-liquid separation 66 Vat dyes 266 Venice 124 Verticillium dahliae 298 Vioxx 334 Visbreaking 486 Vitamins 305 Volatile liquids 316 20 This page has been reformatted by Knovel to provide easier navigation 364 660 Index terms Links W Washing: of clothing 124 of sugar beets 184 149 Waste management (see Industrial waste management) Waste-stabilization ponds 77 Wastewater 62 157 as fire suppressant 29 30 and perspiration 36 seawater desalination plants 68 Water: Water hardness Waxes components of petroleum-based 139 89 89 504 White pigments 209 Whole body radiography 345 Wind 18 Wurster process 376 X Xylitol 192 Y Yeast cells 311 Yellow pigments 213 218 Z Zambon Process 349 Zantac 337 This page has been reformatted by Knovel to provide easier navigation 661 Index terms Links Zeolites 131 Zocor 334 Zoloft 334 Zyprexa 334 Zyrtec 351 146 335 352 This page has been reformatted by Knovel to provide easier navigation 160 ... application of various supported catalytic systems in the production of fine chemicals He has taught many industrial chemistry courses including Industrial Catalysis, Industrial Organic Chemistry, Industrial. .. Chemistry King Fahd University of Petroleum & Minerals Dhahran, Saudi Arabia Mohammad Farhat AIi, Ph.D Professor of Chemistry Department of Chemistry King Fahd University of Petroleum & Minerals Dhahran,... • • • • Industrial inorganic chemicals Plastics, materials, and synthetics Drugs Soap, cleaners, and toilet goods Paints and allied products Industrial organic chemicals Agricultural chemicals