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McGRAW-HILL SERIES IN CHEMICAL ENGINEERING SIDNEY D. KIRKPATRICK, Consulting Editor THE CHEMICAL PROCESS INDUSTRIES McGRAW-HILL SERIES IN CHEMICAL ENGINEERING SIDNEY D. KIRKPATRICK, Consulting Editor EDITORIAL ADVISORY COMMITTEE MANSON BENEDICT' Professor of Nuclear Engineering, Massachusetts Institute of Technology CHARLES F. BONILLA' Professor of Chem- ical Engineering, Columbia University JOHN R. CALLAHAM • Editor, Chemical Engineering HARRY A. CURTIS • Commissioner, Ten- nessee Valley Authority .J. V. N. DORR • Chairman, The Dorr Company A. W. HIXSON • Professor Emeritus of Chemical Engineering, Columbia Uni- versity H. FRASER JOHNSTONE • Chairman, Divi- sion of Chemical Engineering, Univer- sity of Illinois WEBSTER N. JONES' Vice President, Car- negie Institute of Technology DONALD L. KATZ • Chairman, Depart- ment of Chemical and Metallurgical Engineering, University of Michigan W. K. LEWIS • Professor Emeritus of Chemical Engineering, Massachusetts Institute of Technology WALTER E. LOBO • Director, Chemical Engineering Division, The M. W. Kellogg Company PAUL D. V. MANNING' Vice President, International Minerals and Chemical Corporation R. S. McBRIDE • ConSUlting Chemical Engineer H. C. PARMELEE' Editor Emeritus, En, gineering and Mining Journal ROBERT L. PIGFORD • Chairman, Depart, ment of Chemical Engineering, Univerc sity of Delaware MOTT SOUDERS • Associate Director of Research, Shell Development Company E. R. WEIDLEIN • President, Mellon In- stitute of Industrial Research M. C. WHITAKER . Director, American Cyanamid Company WALTER G. WHITMAN • Chairman, De- partment of Chemical Engineering, Massachusetts Institute of Technology RICHARD H. WILHELM • Chairman, De- partment of Chemical Engineering, Princeton University BUILDING FOR THE FUTURE OF A PROFESSION Fifteen prominent chemical engineers first met in New York more than thirty years ago to plan a continuing literature for their rapidly growing profession. From industry came such pioneer practitioners as Leo H. Baekeland, Arthur D. Little, Charles L. Reese, John V. N. Dorr, M. C. Whitaker, and R. S. McBride. From the universities came such eminent educators as William H. Walker, Alfred H. White, D. D. Jackson, J. H. James, J. F. Norris, Warren K. Lewis, and Harry A .. Curtis. H. C. Parmelee, then editor of Chemical & Metallurgical Engineering, served as chairman and was joined subsequently by S. D. Kirkpatrick as consulting editor. After several meetings, this Editorial Advisory Committee submitted its report to the McGraw-Hill Book Company in September, 1925. In it were detailed specifica- tions for a correlated series of more than a dozen text and reference books, including a chemical engineers' handbook and basic textbooks on the elements and principles of chemical engineering, on industrial applications of chemical synthesis, on materials of construction, on plant design, on chemical-engineering economics. Broadly out- lined, too, were plans fori monographs on unit operations and processes and on other industrial subjects to be developed as the need became apparent. From this prophetic b~ginning has since come the McGraw-Hill Series in Chemical Engineering, which now numbers about thirty-five books. -More are always in prepa- ration to meet the ever~growing needs of chemical engineers in education and in industry. In .the aggregate these books represent the work of literally hundreds of authors, editors, and collaborators. But no small measure of credit is due the pioneering members of the original committee and those engineering educators and industrialists who have succeeded them in the task of building a permanent literature for the classical engineering profession. THE SERIES ARIES AND NEWTON-Chemical Engineering Cost Estimation BADGER AND BA!'ICHERo-Introduction to Chemical Engineering CLARKE-M anual for Proce.~s Engineering Calculations COMINGS-High Pressure Technology COULSON AND RICHARDSON-Chemical Engineering, Vols. 1 and 2 DODGE-Chemical Engineering Thermodynamics GRISWOLD-Fuels, Combustion, and Furnaces GROGGINs-Unit Processes in Organic Synthesis HUNTINGTON-Natural Gas and Natural Gasoline JOHNSTONE AND THRINa-Pilot Plants, Models, and Scale-up Methods in Chemical Engineering KIRKBRIDE-Chemical Engineering Fundamentals LEE-M aterials of Con.struction LEWIS, RADASCH, AND LEWIs-Industrial Stoichiometry MANTELL-Adsorption MANTELL-lndustrial Electrochemistry McADAMs-Heat Transmission MCCABE AND SMITH-Unit Operations of Chemical Engineering MICKLEY, SHERWOOD, AND REED-Applied Mathematics in Chemical Engineering NELSON-Petroleum Refinery Engineering PERRY (EDITOR)-Chemical Business Handbook PERRY (EDITOR)-Chemical Engineers' Handbook PETERs-Elementary Chemical Engineering PIERCE-Chemical Engineering for Production Supervision RHODES, F. H.-Technical Report Writing RHODES, T. J.-Industrial Instruments for Measurement and Control ROBINSON AND GILLILAND-Elements of Fractional Distillation SCHMIDT AND MARLIEs-Principles of High-polymer Theory and Practice SCHWEYER-PrOcess Engineering Economics SHERWOOD AND PIGFORD-Absorption and Extraction SHERWOOD AND REED-Applied Mathematics' in Chemical Engineering SHREVE-The Chemical Process Industries 'SMITH-Chemical Engineering Kinetics SMITH-Introduction to Chemjcal Engineering Thermodynamics STEPHENsoN-Introduction to Nuclear Engineering TREYBAIr-Liquid Extraction TREYBAIr-M ass-transfer Operations TYLER-Chemical Engineering Economics VILBRANDT-Chemical Engineering Plant Design WALKER, LEWIS, McADAMS, AND GILLILAND-Principles of Chemical Engilleerillg WILSON AND RIEs-Principles of Chemical Engineering Thermodynamics WILtlON ANI> WELLs-Coa.l, Coke, and Coal Chemicals WINDING AND HAScHE-Plastics, Theory and Practice The Chemical Process Industries R. NORRIS SHREVE Professor of Chemical Engineering Purdue University , Lafayette, Ind. INTERNATIONAL STUDENT EDITION McGRAW-HILL BOOK COMPANY, INC. New York /, Toronto London KOGAKUSHA COMPANY, LTD. Tokyo a,.U!. '" o. !( \ D '\ C-~O' b ~ 0 c - s. THE CHEMICAL PROCESS INDUSTRIES INTERNATIONAL STUDENT EDITION Exclusive rights by Kogakusha Co., Ltd., for manufacture and export from Japan. This book cannot be re-exported from the country to which it is consigned by Kogakusha Co., Ltd. Copyright @ 1956 by the McGraw-Hill Book Company, Inc. Copyright, 1945, by the McGraw-Hill Book Company, Inc. All rights reserved. This book, or parts thereof, may not be reproduced in any form without permission of the publishers. Library of Congress Catalog Card Number 55-8293 III TOSHO INSATSU PRINTING CO., LTD., TOKYO, JAPAN This book represents a lifetime of experience in the chemical industry. As such it should be and is dedicated to him who helped to give the .author his start in the chemical field EDWARD MALLINCKRODT, JR. PREFACE Chemical engineering underlies the chemical process industries, and the emphasis on this has been the main objective in writing this book. Other objectives, and the ways .in which they have been approached, are explained in detail in Chapter 1. This second edition represents a checking of the literature and of the chemical industry since the first edition appeared. The literature covered is to January 1954, with a very few notable articles which have been added while the manuscript was being put into print. The statistics for the inorganic field cover generally through 1952 because of the very serious delay in getting out the recent statistics on the part of the U.S. Bureau of the Census. However, most of the industries that fall within the organic field actually have many figures through December, 1954, because of the very prompt and up-to-date publications of these statistics by the U.S. Tariff Commission. The question of nomenclature is often a troublesome one, particularly for industrial usage. It is difficult to get people in industry to employ the scientific nomenclature such as has been adopted by Chemical Ab- stracts. In most cases this text follows the scientific nomenclature of Chemical Abstracts with the exception that for long, complicated organic names hyphens are inserted frequently to break these names into their component parts. This is much better than the writing of these names as separate words as is done so frequently in industry. An example is the writing of chloro-nitro-benzene rather than chloronitrobenzene or chloro nitro benzene. However, as a concession to wide industrial usage, glycerine is used rather than glycerol al_!d gelatine rather than gelatin. I This book has as an important part-many flow sheets. These have all been gone over care~ully by the author and by experts in the respective industries. Many have been corrected, some only in a minor way. Obsolete flow sheets have been discarded and new ones added. Many of the older references appearing in the first edition have been dropped unless there was a special reason for such retention. Newer references have been added. One of the most disputed points in the first edition, particularly from ix x PREFACE the point of view of teachers in chemical engineering, was concerned with the problems. The majority wanted these short problems dropped as not worthwhile; however, an influential group considered them very useful. After weighing the whole situation, these problems were removed from the ends of the chapters and placed in a special appendix arranged by chapter headings and supplemented very importantly by references to the book by Lewis, Radasch, and Lewis entitled "Industrial Stoichi- ometry." The book by Lewis, Radasch, and Lewis will be of very great service as a teaching aid particularly since the problems given by these authors have their principles fully discussed in this special problem book. Furthermore, comprehensive problems are included which are more useful than short special problems. The author in his teaching of this subject for over 25 years has found comprehensive problems particularly helpful. This book has a dual purpose. It is a college text to integrate various courses and to give the young chemical engineer some comprehension of the various fields into which he will enter or with which he will be affiliated even if only indirectly. It is also a reference book for practicing chemical engineers and chemists. For them the various outline flow sheets are supplemented with references to pictured flow sheets in Chemical Engineering which will furnish the details a practicing engineer will need but which would be confusing to students. Also the many references in the footnotes and under "Selected References" at the end of each chapter will be of most value to the practicing chemical engineer and chemist. However, the students should always look up the references to Perry's third edition of "Chemical Engineers' Handbook." If it had not been for the good coverage in Perry's Handbook on equipment, many more pages would have needed to be added to this textbook. As is true of a book of this nature, no one author can know the whole field. Therefore, the policy pursued in the first edition has been carried out in the second where chapters and-parts of chapters have been sub- mitted to experts for checking. Not only did many experienced teachers !.tnd practicing engineers help in the first edition but they have also cooperated in this, supplemented by many new ones. In particular, it is a pleasure to acknowledge· the following who have aided materially: Raymond H. Ewell, Robert C. Forney, George T. Austin, Charles H. Prien, Donald F. Othmer, Kenneth A. Kobe, H. A. Lubs, Otto Stall- mann, Brage Golding, Jacqueline Bailey, James D. Idol, H. M. Kurihara, Eskell Nordell, U. B. Yeager, H. S. Turner, H. J. Rose, A. R. PoweU, H. A. Gollm'ar, Carl Ulmer, Currey E. Ford, George W. Feus, W. W. Palmqhist, Stanley E. Zager, J. C. Radamaker, Paul D. V. Manning, R. W. Mumford, H. H. Bruhn, R. M. Hunter, R. C. Specht, W. M. Leaders, Charles D. Harrington, E. F. Richner, G. E. Matthe~vs, T. H. James, E. K. Carver, R. M. Evans, Max Spencer, R. E. Hall, G. P. Hal- PREFACE xi berstadt, Foster D. Snell, Sylvan B. Lee, Jerome Martin, R. J. Hickey, A. R. Miller, A. B. Welty, C. E. Springhorn, Gustav Egloff, HansZ. Lecher, Walter M. Ralph, W. B. Hardy, W. D. Appel, and J. D. Fennesbresque. The revision of this book could not have been done in this time without the meticulous and skilled help given by Marilyn G. Forney and Elizabeth Prentiss who have worked closely with me over the last few years. Mrs. Forney and Miss Prentiss have also prepared the indexes. As it is impossible to catch every mistake, the author requests that any errors that are found be brought to his attention for correction in subse- quent printings. R. NORRIS SHREVE ... ;' , \. Preface 1. OBJECTIVES 2. UNIT PROCESSES AND UNIT OPERATIONS 3. GENERAL FUNDAMENTALS . Materials of Construction, 23; Process Instrumentation, 29; Chemical Con- trol, 30; Containers, 31; Safety and Fire Protection, 33; Patents, 36; Research, 37; Waste Disposal, 38; Growth and Statistics, 39; Miscellaneous Aspects, 40. ' 4. WATER CONDITIONING AND \VASTE-WATER TREATMENT . Water Conditioning, 45; Methods of Conditioning Water, 46; Sewage and Industrial Waste-water Treatment, 59. 5. FUELS, POWER, AND AIR CONDITIONING. Fuels, 66; Power Generation, 71; Refrigeration, 76; Air' Conditioning, 78. 6. COAL CHEMICALS • The Destructive Distillation of Coal, 81; Coking of Coal, 85; Distillation of Coal Tar, 96; Miscellaneous Uses of Coal Tar, 100; Liquid Fuels, 100; Hydrogenolysis, 101. 7. FUEL GASES. Natural Gas, 106; Coal Gas, 116; Water Gas (Blue Gas), 117; Producer Gas, 121; Liquefied Petroleum Gases, 123. 8. INDUSTRIAL GASES-, Carbon Dioxide, 125; Hydrogen, 133; Hydrogen Manufacture, 134; Oxygen and Nitrogen, 139; Rare Gases of the Atmosphere, 145;' Helium, 147; Acety- lene, 147; Sulfur Dioxide, 149; Carbon Monoxide, 150; Nitrous Oxide, 150. 9. INDUSTRIAL CARBON Lampblack, 154; Carbon Black, 155; Carbon and Graphite Structural Ma- terials, 11)0; Activated Carbon, 163; Graphite, 167; Industrial Diamonds, 170. I 10. THE CERAMIC INDUSTRIES. Basic Raw Materi~ls, 175; Unit Processes Including Fundamental Ceramic Chemistry, 177; Whitewares, 179; Heavy Clay Products, 182; Refractories, 184; Enamels and Enameled Metal, 194; Kilns, 196. xiii ix 9 23 44 63 80 104 125 152 173 xiv CONTENTS 11. CEMENTS, CJ\LCIUM J\ND MJ\GNESIUM COMPOUNDS. Cement, 199; Cement Manufacture, 200; Special Cements, 211; Lime, 212; Lime Manufacture, 214; Gypsum, 218; Miscellaneous Calcium Compounds, 219; Magnesium Oxychloride Cement, 221; Magnesium Compounds, 221. 12. GLJ\SS INDUSTRIES . Manufacture, 230; Methods of Manufacture, 238; Manufacture of Special Glasses, 247; Rock or Mineral Wool, 250. 13. POTJ\SSIUM SJ\LTS AND MIXED FERTILIZERS. Potassium Chloride,' 254; Various Potassium Salts, 263; Mixed Fertilizers, 265. 14. SALT AND MISCELLANEOUS SODIUM COMPOUNDS Sodium Chloride or Common Salt, 271; Sodium Sulfate (Salt Cake and Glauber's Salt), 274; Sodium Bisulfate or Niter Cake, 276; Sodium Bisulfite, 276; Sodium Sulfite, 277; Sodium Hydrosulfite, 278; Sodium Sulfide, 278; Sodium Thiosulfate, 279; Sodium Nitrite, 280; Sodium Silicates, 280; Sodium Peroxide, 282; Sodium Perborate, 282; Sodium Amide, 282; Sodium Cyanide and' Ferrocyanide, 283. 199 229 253 271 15. SODA ASH, CAUSTIC SODA, AND CHLORINE 285 Manufacture of Soda Ash, 289; Manufacture of Sodium Bicarbonate, 295; Miscellaneous Alkalies, 295; Manufacture of Caustic Soda by the Lime-soda Process, 296; Manufacture of Electrolytic Caustic Soda and Chlorine, 298; Bleaching Powder, 309; Sodium Hypochlorite, 310; Sodium Chlorite, 311. 16. ELECTROLYTIC INDUSTRIES Aluminum, 315; Magnesium, 319; Sodium, 323; Hydrogen Peroxide, 324; Chlorates and Perchlorates, 326; Other Products, 327; Organic Compounds, 328; Primary and Secondary Cells, 328. 17. ELECTROTHERMAL INDUSTRIES Artificial Abrasives, 331; Calcium Carbide, 334; Miscellaneous Electro- thermal Products, 336. 18. PHOSPHORUS INDUSTRIES Calcium Phosphates, 338; Phosphorus, 349; Manufacture of Ph!)sphorus ! and Phosphoric Acid, 352; Sodium Phosphates, 355; Ammonium Phosphates, 359; Baking Powders, 360. - , 19. SULFUR AND SULFURIC ACID' . Mining and Manufacture of Sulfur, 363; Sulfuric Acid, 367; Manufacture by the Chamber Process, 371; Manufacture by the Contact Process, 383; Contact Process Equipment, 388. 312 330 338 362 20. NITROGEN INPUSTRIES. 394 I Cyan~mide, 397; Synthetic Ammonia, 399; Ammonium Sulfate, 410; Am- monium Phosphates, 410; Ammonium Nitrate, 410; Urea, 412; Nitric Acid, 413; Sodium Nitrate, 417. CONTENTS 21. HYilROCHLORIC ACID AND MISCELLANEOUS INORGANIC CHEMICALS Hydrochloric or Muriatic Acid, 420; Bromine, 425; Iodine, 428; Fluorine and Fluoro-chemicals, 431; Alumina, 434; Aluminum Sulfate and Alums, 435; Aluminum Chloride, 437; Ferrous Sulfate, 438; Copper Salts, 438; Molyb- denum Compounds, 439; Barium Salts, 439; Strontium Salts, 440; Lithium Salts, 440; Boron Compounds, 441; Silver Nitrate, 442; Radium and Ura- nium Salts, 442; Rare-earth Compounds, 446; Sodium Dichromate, 447. 22. EXPLOSIVES, PYROTECHNICS, AND CHEMICAL WARFARE Industrial and Military Explosives, 449; Military Explosives, 453; Industrial Explosives, 462; Chemical Warfare, 465; Pyrotechnics, 474; Matches, 475; Propellants of Rockets and Guided Missiles, 476; Atomic Bombs, 477. 23. THE PHOTOGRAPHIC INDUSTRY 24. PAINT, VARNISH, LACQUER, AND ALLIED INDUSTRIES Paints, 495; Pigments, 502; White Pigments, 502; Black Pigments, 510; Blue Pigments, 510; Red Pigments, 511; Yellow Pigments, 512; Green Pig- ments, 512; Brown Pigments, 513; Toners and Lakes, 513; Metallic Powders, 514; Pigment Extenders, 514; Oils, 515; Varnishes, 516; Enamels and Japans, 520; Lacquers, 520; Printing Inks, 524; Coated Fabrics, 525; Linoleum, 526. xv 420 449 480 494 25. LEATHER, GELATINE, AND GLUE. 528 Leather, 528; Animal Skins, 529; Manufacture, 531; Gelatine, 540; Glues and Adhesives, 544; Manufacture, 547. 26. PESTICIDES . Insecticides, 551; Rodenticides, 561; Fungicides, 561; ,Herbicides, 563; Germicides, Antiseptics, Disinfectants, 565. / 27. PERFUME AND FLAVORING INDUSTRIES . The Perfume Industry, 569; Vehicle, 570; Fixative, 571; Odorous Substances, 573; Condensation Processes, 581; Esterification Processes, 582; Grignard Processes, 583; Nitration Processes, 583; Oxidation Processes, 584; Miscel- laneous Processes, 587; Perfume Formulation, 588; Industrial Applications , of Perfumery, 589; The Flavoring Industry, 590; Natural Fruit Concen- trates, 590; Flavor Essence Formulation, 594. 550 569 28. OILS, FATS, WAXES: 595 Vegetable Oils, 599;iAnimal Fats and Oils, 607; Waxes, 609; Hydrogenation, 610. I 2!J. SOAP, DETERGENTS,: AND RELATED COMPOUNDS 615 Soap Manufacture, 1617; Detergents or Surface-active Agents (Other than Soaps), 629; Glycerfne Manufacture, 635. 30. SUGAR AND STARCH INDUSTRIES . Sugar, 640; Manufacture of Sugar, 642; Starches and Related Products, 654; Miscellaneous'Starches, 661. 31. FERMENTATION INDUSTRIES . Industrial Alcohol, 667; Manufacture of Industrial Alcohol, 671; Absolute or Anhydrous Alcohol, 676; Beers, Wines, and Liquors, 680; Butyl Alcohol 640 664

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