the chemical process industries

1013 Pages·2007·24.8 MB·English

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