Chemical Process Industries Books

McGRAW-HILL SERIES IN CHEMICAL ENGINEERING
SIDNEY

D.

KIRKPATRICK,

Consulting Editor

THE CHEMICAL PROCESS INDUSTRIES

McGRAW-HILL SERIES IN CHEMICAL ENGINEERING
D. KIRKPATRICK, Consulting Editor

SIDNEY

EDITORIAL ADVISORY COMMITTEE
MANSON BENEDICT' Professor of Nuclear
Engineering, Massachusetts Institute
of Technology
CHARLES F. BONILLA' Professor of Chemical Engineering, Columbia University

JOHN R. CALLAHAM • Editor, Chemical
Engineering
HARRY A. CURTIS • Commissioner, Tennessee Valley Authority
.J. V. N. DORR • Chairman, The Dorr
Company
A. W. HIXSON • Professor Emeritus of
Chemical Engineering, Columbia University
H. FRASER JOHNSTONE • Chairman, Division of Chemical Engineering, University of Illinois
WEBSTER N. JONES' Vice President, Carnegie Institute of Technology
DONALD L. KATZ • Chairman, Department 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 Institute of Industrial Research
M. C. WHITAKER . Director, American
Cyanamid Company
WALTER G. WHITMAN • Chairman, Department of Chemical Engineering,
Massachusetts Institute of Technology
RICHARD H. WILHELM • Chairman, Department 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 specifications 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 outlined, 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 ｢ｾｧｩｮ＠
has since come the McGraw-Hill Series in Chemical
Engineering, which now numbers about thirty-five books. -More are always in prepaneeds of chemical engineers in education and in
ration to meet the ･ｶｲｾｧｯｷｩｮ＠
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

NEWTON-Chemical Engineering Cost Estimation
BA!'ICHERo-Introduction to Chemical Engineering
CLARKE-M anual for ｐｲｯ｣･Ｎｾｳ＠
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
ARIES AND

BADGER AND

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 ' \

ｃＭｾｏＧ＠

b ｾ＠

c - s.

0

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 Abstracts. 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 ｣｡ｲ･ｾｵｬｹ＠
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 Stoichiometry." 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 submitted 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 Stallmann, 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.
T. H.
Leaders, Charles D. Harrington, E. F. Richner, G. E. ｍ｡ｴｨ･ｾｶｳＬ＠
James, E. K. Carver, R. M. Evans, Max Spencer, R. E. Hall, G. P. Hal-

xi

PREFACE

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 subsequent printings.

R.

NORRIS SHREVE

...

,

;'

\.

ix

Preface

1.

OBJECTIVES

2.

UNIT PROCESSES AND UNIT OPERATIONS

3.

GENERAL FUNDAMENTALS .

9
23

Materials of Construction, 23; Process Instrumentation, 29; Chemical Control, 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

.

44

Water Conditioning, 45; Methods of Conditioning Water, 46; Sewage and
Industrial Waste-water Treatment, 59.
5.

FUELS, POWER, AND

6.

COAL CHEMICALS

AIR

CONDITIONING.

63

Fuels, 66; Power Generation, 71; Refrigeration, 76; Air' Conditioning, 78.
•

80

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.

104

FUEL GASES.

Natural Gas, 106; Coal Gas, 116; Water Gas (Blue Gas), 117; Producer Gas,
121; Liquefied Petroleum Gases, 123.

8.

INDUSTRIAL GASES-,

125

Carbon Dioxide, 125; Hydrogen, 133; Hydrogen Manufacture, 134; Oxygen
and Nitrogen, 139; Rare Gases of the Atmosphere, 145;' Helium, 147; Acetylene, 147; Sulfur Dioxide, 149; Carbon Monoxide, 150; Nitrous Oxide, 150.
9.

INDUSTRIAL CARBON

152

Lampblack, 154; Carbon Black, 155; Carbon and Graphite Structural Materials, 11)0; Activated Carbon, 163; Graphite, 167; Industrial Diamonds, 170.
10.

I

THE CERAMIC INDUSTRIES.

Basic Raw ｍ｡ｴ･ｲｩｾｬｳＬ＠
175; Unit Processes Including Fundamental Ceramic
Chemistry, 177; Whitewares, 179; Heavy Clay Products, 182; Refractories,
184; Enamels and Enameled Metal, 194; Kilns, 196.
xiii

173

xiv
11.

CONTENTS
CEMENTS, CJ\LCIUM J\ND MJ\GNESIUM COMPOUNDS.

199

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 .

229

Manufacture, 230; Methods of Manufacture, 238; Manufacture of Special
Glasses, 247; Rock or Mineral Wool, 250.
13.

POTJ\SSIUM SJ\LTS AND MIXED FERTILIZERS.

253

Potassium Chloride,' 254; Various Potassium Salts, 263; Mixed Fertilizers,
265.
14.

SALT AND MISCELLANEOUS SODIUM COMPOUNDS

271

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.
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

312

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

330

Artificial Abrasives, 331; Calcium Carbide, 334; Miscellaneous Electrothermal Products, 336.
18.

!
19.

PHOSPHORUS INDUSTRIES

338

Calcium Phosphates, 338; Phosphorus, 349; Manufacture of Ph!)sphorus
and Phosphoric Acid, 352; Sodium Phosphates, 355; Ammonium Phosphates,
359; Baking Powders, 360.
,
SULFUR AND SULFURIC ACID' .

362

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.
20.

NITROGEN INPUSTRIES.

ｃｹ｡ｮｾｭｩ､･Ｌ＠

I

397; Synthetic Ammonia, 399; Ammonium Sulfate, 410; Ammonium Phosphates, 410; Ammonium Nitrate, 410; Urea, 412; Nitric Acid,
413; Sodium Nitrate, 417.

394

xv

CONTENTS

21. HYilROCHLORIC ACID AND MISCELLANEOUS INORGANIC CHEMICALS

420

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; Molybdenum Compounds, 439; Barium Salts, 439; Strontium Salts, 440; Lithium
Salts, 440; Boron Compounds, 441; Silver Nitrate, 442; Radium and Uranium Salts, 442; Rare-earth Compounds, 446; Sodium Dichromate, 447.
22. EXPLOSIVES, PYROTECHNICS, AND CHEMICAL WARFARE

449

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

480

24. PAINT, VARNISH, LACQUER, AND ALLIED INDUSTRIES

494

Paints, 495; Pigments, 502; White Pigments, 502; Black Pigments, 510;
Blue Pigments, 510; Red Pigments, 511; Yellow Pigments, 512; Green Pigments, 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.
25. LEATHER, GELATINE, AND GLUE.

528

Leather, 528; Animal Skins, 529; Manufacture, 531; Gelatine, 540; Glues and
Adhesives, 544; Manufacture, 547.
550

26. PESTICIDES .
Insecticides, 551; Rodenticides, 561; Fungicides, 561; ,Herbicides, 563;
Germicides, Antiseptics, Disinfectants, 565.
/

27. PERFUME AND FLAVORING INDUSTRIES .

569

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; Miscellaneous Processes, 587; Perfume Formulation, 588; Industrial Applications
, of Perfumery, 589; The Flavoring Industry, 590; Natural Fruit Concentrates, 590; Flavor Essence Formulation, 594.
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 .

640

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

664

xvi

CONTENTS

and Acetone, 686; Vinegar and Acetic Acid, 690; Citric Acid, 691; Lactic
Acid, 692; Antibiotics, 694.
32.

700

WOOD CHEMICALS .

Distillation of Hardwood, 701; Manufacture, 703; Products from Softwood,
710; Manufacture, 713; Hydrolysis of Wood, 716; Cellulose Derivatives, 718.
33.

720

PULP AND PAPER INDUSTRIES.

Manufacture of Pulp for Paper, 722; Manufacture of Paper, 736; Paperboard, 741.
34.

743

SYNTHETIC FIBERS.

Rayon and Acetate, 744; Reactions, 747; Viscose Manufacturing Process,
748; Cuprammonium Manufacturing Process, 753; Cellulose Acetate Manufacturing Process, 754; Synthetic Fibers Other Than Rayon, and Acetate,
756; Melt Spun Fibers, 757; Dry Spun Fibers, 761; Wet Spun Fibers, 762;
Finishing of Textiles, 763.
35.

766

PLASTICS.

Thermosetting Resins, 778; Thermoplastics Based on Cellulose, 783;
Thermoplastic Resins, 785; Miscellaneous Plastics, 793; Manufacture of
Laminates, 794.
36.

797

NATURAL AND SYNTHETIC RUBBER

Natural Rubber, 797; Manufacture, 798; Synthetic Rubber, 806; Manufacture, 807.
37.

820

THE PETROLEUM INDUSTRY

Constituents of Petroleum, Including Petroleum Gases, 828; Products of
Refining, 832; Petroleum Chemicals or Petrochemicals, 834; Manufacture or
Refining, 836.
38.

INTERMEDIATES, DYES, AND THEIR ApPLICATION

.

861

Intermediates, 867; Nitration, 869; Amination by Reduction, 871; Amination by Ammonolysis, 874; Halogenation, 876; Sulfonation, 877; Hydrolysis,
880; Oxidation, 884; Alkylation, 887; Condensation and Addition Reactions
(Friedel-Crafts), 889; Miscellaneous Unit Processes, 892; Dyes, 892; Manufacture of Dyes, 901.
39.

I

ORGANIC CHEMICALS, NOT OTHERWISE CLASSIFIED

930

Nitration, 933; Esterification, 935; Amination by RedU!ltion, 937; Amination
by Ammonolysis, 937; Halogenation, 939; Sulfonation, 943; Hydrolysis and
Hydration, 943; Oxidation, 945; Hydrogenation, 949; Alkylation, 950; Condensation, 954; Miscellaneous Unit Processes, 954.

Appendix:

PROBLEMS

961

Name Index.

975

Subject Index

987

CHAPTER

1

OBJECTIVESl

Chemical engineering has been well defined for the American Institute
of Chemical Engineers as follows:
Chemical engineering is that branch of engineering concerned with the development and application of manufacturing processes in which chemical or certain
physical changes of materials are involved. These processes may usually be
resolved into a coordinated series of unit physical operations and unit chemical
processes. The work of the chemical engineer is concerned primarily with the
design, construction, and operation of equipment and plants in which these unit
operations and processes are applied. Chemistry, physics, and mathematics are
the underlying sciences of chemical engineering, and economics its guide in
practice. 2

These unit operations or physical changes and these unit processes or
chemical changes may be accepted as the units or blocks into which we
can break down the manufacturing processes of the various chemical
industries. Many now hold that these two concepts bring unifying
principles into what was previously a large, diversified group of apparently unrelated industries. Beginning in Chap. 2, this book correlates
these two concepts as they are applied to the various chemical process
industries.
Chemical engineering has been defined more fundamentally and yet i
more precise terms in the new Constitution, 1954, of the America
Institute of Chemical Engineers as "the application of the principles 0
the physical sciences together with the principles of economics and huma
relations to fields that pertain directly to processes and process equip
ment in which matter is ｴｲｾ｡･､＠
to effect a change in state, energy con ten
or composition."
The objectives ｳｯｾｧｨｴ＠
are to present a cross section of the manu
facturing procedures employed by modern chemical industries, largel.
I This short chapter is act,ually an introduction to this book, its aims and methods.
The author would strongly urge that, when the book is employed as a text, the instruc
tor assign this chapter tq the students for study and discussion so that they may earl
gain a comprehension ofl the fundamental viewpoints as well as the objectives sought.
'NEWMAN, Development of Chemical Engineering Education, Trans. Am. Inst.
Chem. Engrs., Supplement to 34 (3a), 6 (July 25, 1938); see also Trans. Am. Inst.
Chem. Engrs., 32, 568 (1936).
1

2

OBJECTIVES

separated into their unit chemical processes and unit physical operations
through the help of flow charts. The presentation is from the viewpoint
of the fundamental chemistry involved in the changes necessary to make
the processes operate and of the energy released or absorbed in the
reactions, as well as the energy required for evaporation, fusion, and
related operations. Because we must have a yardstick to evaluate these
industries, domestic statistics of production and consumption are frequently cited with dollar values where available. Likewise costs and other
phases of the economic picture are included. Because these are industrial
processes, the equipment necessary to carry out the chemical reactions on
an industrial scale is of paramount importance.
These chemical process industries not only involve the manufacture
of chemicals as such, but they embrace many manufacturing processes
based on important chemical changes. Such processes naturally include
a considerable variety of operations based on data and principles from
other branches of science and engineering. Therefore, it may well be
maintained that the chemical process industries represent the summation
or the integration of the contributions of many scientists, engineers, and
technologists. Specifically, any description of these industries should show
the reason why a chemical engineer or an industrial chemist should be
interested in inorganic or organic chemistry, physical chemistry, analytical chemistry, physics, mathematics, as well as the modern concept of
chemical engineering in its twofold application of unit operations and
unit processes. Nor should we forget, of course, that all these activities
are carried on to make money and hence exist under the enveloping
mantle of sound economics and business principles. Included in this
integration should be such other divisions of engineering as strength of
materials and the fundamentals of electrical engineering. Hence, to the
stud-ent, this book may well be the link, or tie, between many of ·his
basic scientific and technical courses, .on the one nand, and their industrial
application, on the other.
Because of space limitations, very 1ittle has been included pertaining
Ito the chemical industries of foreign countries. Their practice is available
from the detailed presentations,l in many volumes, by Thorpe arrd Ullmann, to which references are given at the end of this chapter. Nor is any
attempt made here to supply the names of companies in the various
branches of chemical industry, although there is an occasional reference
1 Reports on German and Japanese technology covering the period 1939-1945 are
obtainable from the Office of Technical Services, U.S. Department of Commerce,
Washington, D.C.,· and from the British Intelligence Objectives Sub-Committee (the
BIOS reports), 32 Bryanston Square, London, W. I. Many foreign processes are also
covered in KIRK and OTHMER, "Encyclopedia of Chemical Technology," 15 vols., The
Interscience Encyclopedia, Inc., New York, 1947-1956. However, this most excellent
encyclopedia deals mainly with United States technology. Hereafter, this will be
referred to as KIRK and OTHMER, op. cit.

OBJECTIVES

3

to a specific company. However, the full listing of such companies is
obtainable from a number of trade directories and from the pages of
various chemical publications, including the "Chemical Engineering
Catalog."
Most chemical engineers do not have intimate contact with more than
one industry. With this in mind, the text emphasizes not details but
broad principles, or a distinguishing characteristic of a certain process
or industry. These should be a part of the working knowledge of even
the engineer who becomes a specialist, for he never knows when he can
translate to his own field a principle that has been put into practice in
another process. For the growing number of chemical engineers who
enter sales, executive, or management positions, a broader acquaintance
with the chemical industry in its entirety is essential. For all these, the
specialist, the salesman, and the manager, the flow sheets will present in a
connected logical manner an over-all viewpoint of many processes, from
raw materials to salable products, such as has been developed so excellently by our competitive system under the economic stimulus and wise
temporary protection of our patent laws.
The presentation of the chemical process industries around the flow
sheets and the energy changes ought to lead to a logical following through
of a connected series of unit operations and unit processes, rather than
to the memorizing of purely descriptive matter. These will emphasize
the why rather than the how of industrial procedures, or thinking rather
than memorizing.
An engineer has to do with the direction and cm).trol of energy. This
energy may be expended in the moving of raw materials by ship, rail, or
pipe line, it may be employed in the form of heat or steam or electricity, or
it may be the energy,that is given out in exothermic reactions or that
which is absorbed in endothermic chemical reactions. The chemical engineer works with chemical change involving chemical reactions but, on the
other hand, in these modern competitive times serious consideration
should be given to the other types of energy expenditure connected
particularly with the' process with which he is concerned. The unit
processes consider the 'change in chemical energy and the resultant effects.
Unit operations include the physical changes in energy or position, such
as heat flow, liquid flow, or separation; these frequently are an essential
part of the fundamental unit process. It is thoroughly believed that the
chemical engineer should also consider other broad energy expenditures,
such as those represented by the transportation of raw materials. All
of these enter into the cost.
The cost of things bust be always in ｴｨｾ＠
consciousness of the engineer,
industrial system. One of the primary objectives
since he is a part of ｾｵｲ＠
of the engineer's endeavor should be to deliver the best product or the
most efficient service' at the lowest cost to the consuming public. There-

4

OBJECTIVES

fore, we may well say, quoting from Dean Emeritus A. A. Potter of
Purdue University, "No matter what the numerator may be in an
equation one may place before the students in an engineering institution,
the dollar sign should appear in the denominator, either apparent or
latent."
Every chemical engineer should be familiar with the current selling
prices of the principal chemicals with which he is concerned. There is no
use in publishing such a list in a book of this nature; these costs change
too much and too frequently. To be of any value, such quotations must
be secured when the chemical engineer is interested in them. They can
be readily obtained from such journals as the Oil, Paint and Drug Reporter
and Chemical and Engineering N eW8. Indeed, a corollary to the obtaining
of a list of current market prices is the introduction of the chemical
engineer to these essential periodicals.
Although this book is not a study in cost determination, there are
included many data on the basis of which a cost estimate can be made.
Particularly in the flow sheets and in a few other selected parts of the
book, approximate figures are given leading to at least the material cost
of the product considered, or to labor and material (the so-called L. & M.)
costs. On the other hand, it is impossible adequately to present or understand the determination of costs without long experience in a particular
industry, and too much emphasis cannot be placed upon the inadequacy
of the labor and material costs without there being added the various
so-called overhead costs, such as research and develOpment expense,
depreciation and obsolescence of plant and process, provision for taxes
and insurance, and interest on invested capital. These overhead and fixed
items often equal or exceed the direct labor and material charges. The
cost of chemicals tends to drop as processes are perfected and as production rises.
This book contains no separate chapters on equipment. Specialized
books on the subject are available. It was thought better to emphasize
equipment in conjunction with the description of the various processes
and with the flow sheets representing< those processes. On the other hand,
/ any chemical engineer should start early to familiarize himself with industrial equipment such as pumps, filter presses, nitrators, ;:tnd sulfonators.
The "Chemical Engineering Catalog'" includes the most available
and convenient information concerning the actual equipment that can
be supplied by various manufacturers. In short, it is a yearly resume of
the different catalogs put out by these suppliers. It should be employed
as the current apparatus supplement. When this book is used as a text,
it is suggested that the instructor so conduct his course that, from time
to tiqle, the students are required to go through this catalog and select
1 Reinhold Publishing Corporation, New York. Distributed annually to practicing
chemical engineers.

OBJECTIVES

5

therefrom the various pumps or filter presses or reactors that would be
most suitable for the process or flow sheet being studied.
Every chemical engineer, whether in training or in practice, should
have as his constant companion the current edition of Perry's" Chemical
Engineers' Handbook."1 Not only are its voluminous tables of data
essential to the chemical engineer but also the descriptions and illustrations of apparatus present more about these tools than are contained in
any other one volume. The colleetion of formulas with illustrations is
also unexcelled elsewhere. Finally, each section starts with well-selected
references for anyone desiring even more details. Because of the excellence of this handbook, particularly covering equipment, many specific
references are given to it here when otherwise fuller presentation would
have been necessary.
Because of the very eonsiderable number of flow sheets included and
the desire to eonserve space, not many pictures or line drawings to
illustrate the proeess industries are included in this text. On the other
hand, as visual presentation of equipment is extremely helpful, it is
advised that instructors, to supplement this text, gather appropriate
photographs of plants and equipment from the industries being studied.
Quite frequently pictures can be obtained of plants which the students
have visited or are planning to visit on their inspection trips. By having
all these pictures on lantern slides, they can be used in the appropriate
places and in much greater number than would be possible in these pages.
The texts and advertising pages of such journals as Industrial and
Engineering Chemistry, Chemical Engineering, Chemjcal and Engineering
News, Chemical Engineering Progress, Chemical Week, together with the
very many specialized journals such as Modern Plastics, Sugar, Petroleum
Refiner, and many others, should be consulted by the chemical engineer
for up-to-date information on equipment and fundamental data.
Usually a chapter is assigned to a given process industry like glass,
paper, rubber, or sulfuric acid. Such a chapter has its contents arranged
in somewhat the following order:
After a brief introduction, aimed to epitomize the industry, some aspect is
given of the historical side or background of the particular process. This is followed by a consideration of Uses and Economics, including statistical tabulations
by which the importance of the industry can be judged. It is well recognized that
trends in production, \\:hether on the increase or decrease, are found of more
statement that so many pounds or so many dollars'
importance than the ｭｾｲ｣＠
worth of a given substance are being manufactured. This is shown by parallel
columns for different years and by statistical cunes. Under Manufacture, this
I

II., cdiior-in-chicf, with a staff 'of specialists, "Chemical Engineers'
Handbook," 3d ed., McGraw-Hill Book Company, Inc., New York, 1950, 1,942 pages
of tabulated data and epitomized information. Hereafter this book will be referred
to as Perry, op. cit.
1 PERRY, JOHN

6

OBJECTIVES

being a book on chemical engineering, energy change, unit operations, and unit
processes are particularly brought to the attention of the reader. For some of the
important processes, the principal unit operations and unit processes are tabulated. Dividing the industries into these units helps greatly in the transference
of information from one industry to another. Indeed, flow sheets do this same
thing in a visual manner. It is felt that by this breakdown the reader will gain
a clearer comprehension that filtration or evaporation or hydrogenation or nitration is employed in a considerable number of industries. The source of the raw
materials and their relationship to the manufacturing procedures are discussed
in their economic and chemical relationship. The product of one industry is
frequently the raw material of another-indeed, it has been remarked frequently
that the chemical industry is its own best customer.l Ultimately chemicals stem
TABLE

1. ULTIMATE GEOLOGIC RAW MATERIALS FOR 150 IMPORTANT

INDUSTRIAL CHEMICALSa •b
Index
number"
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.

Water ................... .
Air ...................... .
COal. ............. " .... .

Sulfur ................... .
Mineral salt .............. .
Limestone ............... .
Sulfide ores .............. .
Brines ................... .
Petroleum ............... .
Natural gas ........ , .. " ..
Saltpeter ................ .
Potassium minerals ....... .
Gypsum ................. .
Lead ores ................ .
Sand .................... .
Aluminum minerals ..... , .,
Chromium ores ........... .

99
96
91
88
75

63
32
24
23
16
13
11

10

9
9
8
7

Index
number'
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.

Iron ores .................
Phosphate rock ...........
Sea water ................
Copper ores ..............
Fluorine minerals ..........
Arsenic minerals ..........
Magnesium minerals .......
Mercury ores .............
Zinc ores ..........: .......
Antimony minerals ........
Barium minerals ..........
Boron minerals ............
Manganese ores ...........
Tin ores ..................
Bismuth minerals .........
Silver ores ....... " ., .....
Titanium ores .............

6
6
5

4
4

3
3
3
3

2
2
2
2
2
1
I
1

KELLER and QUIRKE, Ind. Eng. Chern.,_News Ed., '17, 444 (1939).
Note that coal, petroleum, and natural gas combined equal 130; sulfur and sulfide
ores combined equal 120; and salt, brines, and sea water combined equal 104.
/
, Index numbers indicate relative frequency in use. The names of the 150 chemicals
are tabulated in the reference.I
a

b

from the minerals as shown in Table 1 (see also Fig. 1 in Chap. 39). The actual
manufacturing procedures, in the case of the principal industries, are woven in
and around the various flow sheets. Here the raw materials entering into unit
operations and unit processes, carried on in industrial equipment, are all connected ｴｯｧ･ｾｲＮ＠
This is the heart,of each industry and, although the flow sheets
1 EWELL, Past and Future Growth at the Chemical Industry, Chem. Eng. New8,
29, 5228 (1950).

OBJECTIVES

7

show the general sequence of operations and processes, the text supplements this
and refers to the literature for further details.

The order of chapters was determined very largely from a teaching
viewpoint. When this book is used in college, the student will frequently
be taking physical chemistry and organic chemistry simultaneously.
Primarily because of this, it was thought wise to place first those chapters which would be easiest for the student to learn. Hence, such a
chapter as that presenting sulfuric acid, involving applications of equilibriums and certain other phases of physical chemistry, is placed after the
more purely descriptive chapters pertaining to water, fuels, distillation
of coal, gases, and carbon. The sequence of presentation as used in this
book has been employed in the classes at Purdue University for a number
of years, with an increased ease of learning on the part of students. This
seems much better than starting at the beginning of the year with a
chapter on sulfuric acid and trying to get the student to comprehend
the physical and chemical reasons for some of the procedures that have
been applied industrially in the manufacture of this important acid.
If" an instructor wishes to vary the order of the chapters, it will" be very
simple for him to make a mimeographed sheet, giving the sequence he
desires his students to use.
As the aim of a book such as this is to impress upon the reader the
quantitative engineering aspects and to lead him to think from raw
materials to salable products, the working of problems 1 is of great importance. They also disclose whether the reader has sufficiently mastered the
given industry to make calculations concerning its Procedures. Therefore,
at the end of the book there are a few typical problems pertaining to
many of the industries c!)ncerned. However, when this volume is used
as a college text, each instructor should supplement these problems with
some of his own devising which, for obvious reasons, should be changed
ｦｲｾｭ＠
year to year. Since these problems are the so-called simple ones, it
would be very helpful if each instructor toward the end of the course
would devise comprehensive problems to be given to his class, involving
one or more industries, s"\lch as are given out each year by the American
Institute of Chemical Engineers. 2 In certain universities such comprehensive problems ｡ｲｾ＠
included in a special problem course. Too much
emphasis cannot be Iplaced upon quantitative thinking whethe!" in the
practice of chemical engineering or in the living of life in general.
I

1 PERRY, op. cit., pp. 333-357; HOUGEN, WATSON, and RAGATZ, "Chemical Process
Principles," Part 1, Material and Energy Balances, 2d ed., John Wiley & Sons, Inc.,
RADASCH, and LEWIS,' "Industrial Stoichiometry," 2d ed.,
New York, 1954; ｌｅｗｉｾ［＠
McGraw-HilI Book Company, Inc., New York, 1954.
2 "A.I.Ch.E. Student Contest Prohlems, and the Prize Winning SBlntions,"
American Institute of Chemical Engineers, New York, 1950.

8

OBJECTIVF.s

The objectives sought in this volume may be summarized by stating
that it has been the endeavor to present the various chemical processes
in a generalized form through the correlation into flow sheets and descriptive text of the following:'
1. Unit processes: chemical change.
2. Unit operations: physical change.
3. Physical chemistry: equilibriums and reaction rates.
4. Economics: costs, statistics, and consumption.
5. Energy and power: chemical as well as electrical and mechanical.
SELECTED REFERENCES
General:
Kirk, R. E., and D. F. Othmer, "Encyclopedia of Chemical Technology," 14 vois.,
The Interscience Encyclopedia, Inc., New York, 1947-.
Richter, Otto, "The German Chemical Industry," Badgandersheim, Hartz, 1954.
Ullmann, Fritz, "Enzyklopaedie der technischen Chemie," 3d ed., 13 vols., Urban &
Schwarzenberg, Berlin and Vienna, 1950--.
Thorpe, T. E., "Dictionary of Applied Chemistry," 4th ed., Longmans, Green & Co.,
Inc., New York, 1937.
Turner, F. M., "The Condensed Chemical Dictionary," 4th ed., Reinhold Publishing
Corporation, New York, 1950.
Haynes, Williams, "This Chemical Age, The Miracle of Man-made Materials,"
Alfred A. Knopf, Inc., New York, 1942.
Perry, John H., editor-in-chief, "Chemical Engineers' Handbook," 3d ed., McGrawHill Book Company, Inc., New York, 1950.
Costs and Economics:

"Chemical Economics Handbook," Stanford Research Institute, Stanford, Calif.,
1950--. Revised yearly.
Perry, John H., editor-in-chief, "Chemical Business Handbook," McGraw-Hill Book
Company, Inc., New York, 1954.
Perry, op. cit., pp. 1827-1845, with other references oni p. 1828.
1 It is recognized that the limitations of one volume have restricted the full application of all these factors to every process. However, frequent references from text as
well as in the Selected References at the end of each chapter will serve to supplement
what has been given. The author will welcome criticism of what has been chosen
/ as well as suggestions regarding what should be added.'

CHAPTER

2

UNIT PROCESSES AND UNIT OPERATIONS

In an inexact but expressive manner we may define chemical engineering in its modern sense by the following equation:
Chemical engineering = unit processes
(chemical changes)

+

unit operations
(physical changes)

The unit process is a very useful concept for technical chemical change
and has been described 1 as "the commercialization of a chemical reaction
under such conditions as to be economically profitable. This naturally
includes the machinery needed and the economics involved, as weli as the
physical and chemical phases." The unit operation is a physical change
connected with the industrial handling of chemicals or allied materials;
it frequently is tied in with the unit process as when heat flows into an
endothermic chemical reaction or out of an exothermic reaction. The
unit operation may also be distinctly separated from the chemical
change as when, by "flow of fluid," a liquid is movegfrom one part of an
industrial establishment to another.
Chemical engineering, if successfully practiced, requires that the
respective unit processes and operations be applied to the various manufacturing proQedures. The study of the unit operations on the one hand
and of the unit processes on the other is the characteristic of the present
stage of this branch of engineering. Indeed, the development of chemical
is largely through flow sheets which are
manufacturing ｰｲｯ｣･､ｵｾｳ＠
definitely constructed Ifrom a coordinated sequence of unit processes and
operations that fabricate the raw materials into the finished product and
by-products. In the actual technical application, both unit processes
and unit operations are carried on either simultaneously or independently
in suitable equipment under the guidance of skilled labor supervised by
chemical engineers. ｔｾｩｳ＠
is often called a chemical process.
These unit processes and unit operations are the common bond between
otherwise widely div!-lrgent chemical manufacturing procedures. They,
of course, are applied differently under the,necessarily varying conditions.
Although we hope that we shall have formulas that will enable the
1 SHREVE,

Unit ProceSses, Background and Objects, 11"d. Eng. Chern., 811, 145

(1940).

9

10

UNIT PROCESSES ANi> UNIT OPERATIONS

chemical engineer to calculate at his desk what is going to happen in the
factory, this millennium has not arrived. There are many more formulations for the unit operations than for the unit processes, as the latter
are more complicated and have only lately been receiving the attention
of chemical engineers. Indeed, broad experience is still necessary to
apply wisely and economically the formulas and knowledge that are
available. In the words of the eminent chemical engineer, W. L. Badger,'
• . . the engineer is the man who must build equipment, assemble it into a
process, and make it run, whether or not he, has all the theoretical data necessary
for its calculation. He must think of equipment in terms not of strictly solved
differential equations but of actual chunks of cast iron and steel that somebody
shall be able to fabricate, assemble, and operate in terms of a working, practical,
economical process.

The characteristics of unit processes as applied to the manufacture of
chemicals may be summarized as follows:
1. Each unit process points out the unitary or like aspects in a group
of numerous individual reactions. This unitary aspect, apart from the
TABLE 1. PRINCIPAL UNIT PROCESSES AND UNIT OPERATIONS

Unit processes

/

1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
I

Combustion
Oxidation
Neutralization
Silicate formation
Causticization
Electrolysis
Double decomposition
Calcination, dehydration
Nitration
Esterification (Bulfation)
Reduction
Ammonolysis
Halogenation
Sulfonation
Hydrolysis, hydration
Hydrogenation, hydrogeriolysis
Alkylation
Condensation
Polymerization
Diazotization and coupling
Fermentation
Pyrolysis, cracking
Aromatization
Isomerization
Hydroformylation (oxa)
Ion exchange

Unit
1.

2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.

ｯｰ･ｲ｡ｴｩｾｮｳ＠

Fluid dynamics
Heat transfer VS. cooling
Evaporation VB. evaporative cooling
Humidification
Gas absorption
Solvent extraction
Adsorption
Distillation and sublimation
Drying, high-vacuum distillation
Mixing
Classification or sedimentation VB.
fluidization
Filtration
Screening
Crystallization vs. extraction
Centrifugation
Size reduction ·vs./size enlargement
Materials handling

BADGER, Education, Experience and Engineers, Ind. Eng. Chem., 33, 1103 (1941).

UNIT PROCESSES AND UNIT OPERATIONS

11

basic chemical family, may be a similarity in energy change or corrosion
or pressure or reaction time or equilibrium or raw materials.
2. Frequently there is a factory segregation by unit processes wherein
a building or section of a building may be devoted to the making of many
chemicals under a given unit process as diazotization and coupling or
nitration or hydrogenation or esterification or fermentation or alkylation.
3. There frequently is a close relationship in the equipment used for
making many examples under a unit process. For instance, the cast-iron
well-agitated reactor, provided with cooling coils, called a nitrator, is
used for conducting the nitration unit process in the manufacture of a
number of chemicals such as nitro-benzene, nitro-naphthalene, or T.N.T.
4. Equipment may be conveniently transferred from the making of
one chemical to that of another within the same unit process. It is the
aim of a chemical superintendent to keep all his equipment constantly in
use. To do this he frequently mu