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CHEMICAL AND
PROCESS DESIGN
HANDBOOK
James G. Speight
FM_Speight_HB1 11/8/01 3:43 PM Page iii
Library of Congress Cataloging-in-Publication Data
Speight, J. G.
Chemical and process design handbook / James Speight.
p. cm.
Includes index.
ISBN 0-07-137433-7 (acid-free paper)
1. Chemical processes. I. Title.
TP155.7 .S63 2002
660′.2812—dc21 2001052555
Copyright © 2002 by The McGraw-Hill Companies, Inc. All 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 sys-
tem, without the prior written permission of the publisher.
1234567890 DOC/DOC 0987654321
ISBN 0-07-137433-7
The sponsoring editor for this book was Kenneth P. McCombs, the editing super-
visor was David E. Fogarty, and the production supervisor was Pamela A.
Pelton. It was set in the HB1A design in Times Roman by Kim Sheran, Deirdre
Sheean, and Vicki Hunt of McGraw-Hill Professional’s Hightstown, New Jersey,
composition unit.

Alkylation / 1.3
Amination / 1.6
Condensation and Addition / 1.12
Dehydration / 1.13
Dehydrogenation / 1.14
Esterfication / 1.16
Ethynylation / 1.17
Fermentation / 1.18
Friedel-Crafts Reactions / 1.19
Halogenation / 1.21
Hydration and Hydrolysis / 1.24
Hydroformylation / 1.27
Hydrogenation / 1.29
Nitration / 1.32
Oxidation / 1.36
Oxo Reaction / 1.40
Polymerization / 1.41
Sulfonation / 1.43
Vinylation / 1.46
Part 2 Manufacture of Chemicals
Acetaldehyde / 2.3
Acetal Resins / 2.7
Acetaminophen / 2.10
Acetic Acid / 2.11
Acetic Anhydride / 2.14
Acetone / 2.16
Acetone Cyanohydrin / 2.18
Acetophenetidine / 2.19
Acetylene / 2.20
Acrolein / 2.23

Barbiturates / 2.68
Barium Carbonate / 2.69
Barium Salts / 2.70
Barium Sulfate / 2.71
Barium Sulfide / 2.72
Bauxite / 2.73
Benzaldehyde / 2.74
Benzene / 2.75
Benzine / 2.80
Benzodiazepines / 2.81
Benzoic Acid / 2.83
Benzyl Acetate / 2.84
Benzyl Alcohol / 2.85
Bisphenol A / 2.86
Borax / 2.87
Boron Compounds / 2.88
Bromal / 2.89
Bromine / 2.90
Bromoacetaldehyde / 2.92
BTX Aromatics / 2.93
Butadiene / 2.95
Butane / 2.98
Butanediol / 2.99
Iso-butane / 2.102
Butene-1 / 2.103
Butenediol / 2.104
Iso-butene / 2.106
n-Butene / 2.107
Butyl Acrylate / 2.108
Iso-butyl Alcohol / 2.109

Carbon Monoxide / 2.150
Carbon Tetrachloride / 2.151
Cellulose / 2.152
Cellulose Acetate / 2.153
Cellulose Nitrate / 2.154
Cement / 2.156
Cephalosporins / 2.158
Chloral / 2.159
Chlorinated Solvents / 2.160
Chlorine / 2.161
Chlorine Dioxide / 2.164
Chloroacetaldehyde / 2.165
Chlorofluorocarbons / 2.166
Chloroform / 2.167
Chloroprene / 2.168
Chromic Oxide / 2.169
Cimetidine / 2.170
Cinnamic Aldehyde / 2.171
Citric Acid / 2.172
Coal Chemicals / 2.174
Cocaine / 2.179
Codeine / 2.180
Coke / 2.181
Copper Sulfate / 2.182
Cumene / 2.183
Cyclohexane / 2.185
Cyclohexanol / 2.186
Cyclohexanone / 2.187
Darvon / 2.188
Detergents / 2.190

Ferric Oxide / 2.235
Ferrocyanide Blue / 2.236
Fertilixers / 2.237
Fluorine / 2.240
Fluorocarbons / 2.242
Formaldehyde / 2.244
Furosemide / 2.246
Gasoline / 2.247
Glass / 2.249
Glutamic Acid / 2.250
Glycerol / 2.251
Graphite / 2.254
Gypsum / 2.255
Helium / 2.256
Herbicides / 2.257
Hexamethylenediamine / 2.258
Hexamethylenetetramine / 2.259
Hexamine / 2.260
Hexanes / 2.261
Hexylresorcinol / 2.262
Hydrochloric Acid / 2.263
Hydrofluoric Acid / 2.265
Hydrogen / 2.266
Hydrogen Cyanide / 2.269
Hydrogen Peroxide / 2.270
Ibuprofen / 2.271
Insecticides / 2.272
Insulin / 2.274
Iodine / 2.276
Isoniazid / 2.279

Malathion / 2.312
Maleic Acid / 2.313
Maleic Anhydride / 2.314
Melamine Resins (Malamine-Formadehyde Polymers) / 2.316
Mercury Fulminate / 2.317
Metaldehyde / 2.318
Methane / 2.319
Methyl Acetate / 2.321
Methyl Alcohol / 2.322
Methylamines / 2.324
Methyl Chloride / 2.325
Methylene Chloride / 2.326
Methylene Diphenyl Diisocyanate / 2.327
Methyl Ethyl Ketone / 2.328
Methyl Mathacrylate / 2.330
Methyl Tertiary Butyl Ether / 2.331
Methyl Vinyl Ether / 2.333
Molybdenum Compounds / 2.334
Monosodium Glutamate / 2.335
Morphine / 2.337
Naphtha / 2.339
Napthalene / 2.344
Natural Gas / 2.346
Natural Gas (Substitute) / 2.349
Neon / 2.351
Nicotine / 2.352
Nicotinic Acid and Nicotinamide / 2.353
Nitric Acid / 2.354
Nitrobenzene / 2.356
Nitrocellulose / 2.357

Phthalic Anhydride / 2.404
Phthalocyanine Blue / 2.405
Phthalocyanine Green / 2.406
Picric Acid / 2.407
Piperazine Citrate / 2.408
Polyacetaldehyde / 2.409
Polyamides / 2.410
Polycarbonates / 2.412
Polychlorinated Biphenyls / 2.413
Polyesters / 2.414
Polyesters (Unsaturated) / 2.416
Polyhydric Alcohols / 2.417
Polyimides / 2.418
Polysulfones / 2.419
Polyurethane Foams / 2.420
Potassium Chlorate / 2.421
Potassium Compounds / 2.422
Potassium Hydroxide / 2.423
Potassium Nitrate / 2.424
Potassium Perchlorate / 2.425
Producer Gas / 2.426
Propane / 2.427
Propanol Hydrochloride / 2.428
Propargyl Alcohol / 2.429
Propene / 2.431
Iso-propyl Alcohol / 2.433
Propylene Glycol / 2.434
Propylene Oxide / 2.435
Pulp and Paper Chemicals / 2.438
Pyridine / 2.440

Sodium Phosphate / 2.479
Sodium Pyrosulfite / 2.480
Sodium Silicate / 2.481
Sodium Sulfate / 2.482
Sodium Sulfite / 2.483
Sodium Triphosphate / 2.484
Steroids / 2.485
Streptomycin / 2.489
Styrene / 2.490
Sulfonamides / 2.493
Sulfur / 2.494
Sulfur Dioxide / 2.496
Sulfuric Acid / 2.497
Sulfurous Acid / 2.500
Sulfur Trioxide / 2.501
Superphosphates / 2.502
Surfactants / 2.503
Surfactants (Amphoteric) / 2.504
Surfactants (Anionic) / 2.505
Surfactants (Cationic) / 2.506
Surfactants (Nonionic) / 2.507
Synthesis Gas / 2.508
Talc / 2.511
Tall Oil / 2.512
Terephthalic Acid / 2.513
Tetrachloroethylene / 2.515
Tetracyclines / 2.516
Tetrahydofuran / 2.517
Tetrazine / 2.518
Tetryl / 2.519

xii CONTENTS
FM_Speight_HB1 11/8/01 3:44 PM Page xii
PREFACE
Chemicals are part of our everyday lives. The hundreds of chemicals that
are manufactured by industrial processes influence what we do and how
we do it. This book offers descriptions and process details of the most pop-
ular of those chemicals. The manufacture of chemicals involves many
facets of chemistry and engineering which are exhaustively treated in a
whole series of encyclopedic works, but it is not always simple to rapidly
grasp present status of knowledge from these sources. Thus, there is a
growing demand for a text that contains concise descriptions of the most
important chemical conversions and processes of industrial operations.
This text will, therefore, emphasize the broad principles of systems of
chemicals manufacture rather than intimate and encyclopedic details that
are often difficult to understand. As such, the book will allow the reader to
appreciate the chemistry and engineering aspects of important precursors
and intermediates as well as to follow the development of manufacturing
processes to current state-of-the-art processing.
This book emphasizes chemical conversions, which may be defined as
chemical reactions applied to industrial processing. The basic chemistry
will be set forth along with easy-to-understand descriptions, since the
nature of the chemical reaction will be emphasized in order to assist in
the understanding of reactor type and design. An outline is presented
of the production of a range of chemicals from starting materials into
useful products. These chemical products are used both as consumer
goods and as intermediates for further chemical and physical modifica-
tion to yield consumer products.
Since the basis of chemical-conversion classification is a chemical one,
emphasis is placed on the important industrial chemical reactions and
chemical processes in Part 1 of this book. These chapters focus on the var-

AIChE Journal (AIChE J.)
Canadian Journal of Chemistry
Canadian Journal of Chemical Engineering
Chemical and Engineering News (Chem. Eng. News)
ChemTech
Chemical Week (Chem. Week)
Chemical Engineering Progress (Chem. Eng. Prog.)
Chemical Processing Handbook, J. J. McKetta (ed.), Marcel Dekker,
New York.
Encyclopedia of Chemical Technology, 4th ed., It. E. Kirk, and D. F.
Othmer(eds.) Wiley-Interscience, New York
Chemical Engineers' Handbook, 7th ed., R. H. Perry and D. W. Green
(eds.), McGraw-Hill, New York.
Chemical Processing
xiv PREFACE
FM_Speight_HB1 11/8/01 3:44 PM Page xiv
Handbook of Chemistry and Physics, Chemical Rubber Co.
Hydrocarbon Processing
Industrial and Engineering Chemistry (Ind. Eng. Chem.)
Industrial and Engineering Chemistry Fundamentals (Ind. Eng. Chem.
Fundamentals)
Industrial and Engineering Chemistry Process Design and Development
(Ind. Eng. Chem. Process Des. Dev.)
Industrial and Engineering Chemistry Product Research and Devel-
opment (Ind. Eng. Chem. Prod. Res. Dev.)
International Chemical Engineering
Journal of Chemical and Engineering Data (J. Chem. Eng. Data)
Journal of the Chemical Society
Journal of the American Chemical Society
Lange's Handbook of Chemistry, 12th ed., J. A. Dean (ed.). McGraw-Hill,

OH → C
6
H
5
N(CH
3
)
2
+ 2H
2
O
Thus, aniline, with a considerable excess of methyl alcohol and a catalytic
amount of sulfuric acid, is heated in an autoclave at about 200
o
C for 5 or
6 hours at a high reaction pressure of 540 psi (3.7 MPa). Vacuum distilla-
tion is used for purification.
In the alkylation of aniline to diethylaniline by heating aniline and ethyl
alcohol, sulfuric acid cannot be used because it will form ether; conse-
quently, hydrochloric acid is employed, but these conditions are so corrosive
that the steel used to resist the pressure must be fitted with replaceable enam-
eled liners.
Alkylation reactions employing alkyl halides are carried out in an acidic
medium. For example, hydrobromic acid is formed when methyl bromide
is used in the alkylation leading, and for such reactions an autoclave with
a replaceable enameled liner and a lead-coated cover is suitable.
In the petroleum refining industry, alkylation is the union of an olefin
with an aromatic or paraffinic hydrocarbon:
CH
2

Stripper
Hydrogen
fluoride recycle
Deisobutanizer
Debutanizer
To depropanizer
Heavy alkylate
Light alkylate
Butane
FIGURE 1 Alkylation using hydrogen fluoride.
Alkylation is accomplished by using either of two catalysts: (1) hydro-
gen fluoride and (2) sulfuric acid. In the alkylation process using liquid
hydrogen fluoride (Fig. 1), the acid can be used repeatedly, and there is
virtually no acid-disposal problem. The acid/hydrocarbon ratio in the con-
tactor is 2:1 and temperature ranges from 15 to 35
o
C can be maintained
since no refrigeration is necessary. The anhydrous hydrofluoric acid is
regenerated by distillation with sufficient pressure to maintain the reac-
tants in the liquid phase.
In many cases, steel is suitable for the construction of alkylating equip-
ment, even in the presence of the strong acid catalysts, as their corrosive
effect is greatly lessened by the formation of esters as catalytic intermedi-
ate products.
In the petroleum industry, the sulfuric acid and hydrogen fluoride
employed as alkylation catalysts must be substantially anhydrous to be
effective, and steel equipment is satisfactory. Where conditions are not
anhydrous, lead-lined, monel-lined, or enamel-lined equipment is satisfac-
tory. In a few cases, copper or tinned copper is still used, for example, in
the manufacture of pharmaceutical and photographic products to lessen

)
by the reduction of nitrobenzene (C
6
H
5
NO
2
) in the liquid phase (Fig. 1)
or in the vapor phase in a fluidized bed reactor (Fig. 2). For many
decades, the only method of putting an amino group on an aryl nucleus
involved adding a nitro (–NO
2
) group, then reduction to the amino
(–NH
2
) group.
Without high-pressure vessels and catalysts, reduction had to be done
by reagents that would function under atmospheric pressure. The common
reducing agents available under these restrictions are:
1. Iron and acid
2. Zinc and alkali
3. Sodium sulfide or polysulfide
4. Sodium hydrosulfite
5. Electrolytic hydrogen
6. Metal hydrides
Now liquid- and gas-phase hydrogenations can be performed on a vari-
ety of materials.
RNO
2
+ 3H

Reactor
Nitrobenzene
Hydrogen
Hydrogen recycle
Water
Crude aniline still
Purification still
Aniline
Water, to
treatment
Water
plus
reject
Separator
FIGURE 2 Vapor phase reduction of nitrobenzene to aniline.
Speight_Part 1_A 11/7/01 3:04 PM Page 1.7
immersed in a molten salt bath. The nitrogen that accompanies the gener-
ated hydrogen is inert.
Amination is also achieved by the use of ammonia (NH
3
), in a process
referred to as ammonolysis. An example is the production of aniline
(C
6
H
5
NH
2
) from chlorobenzene (C
6

2
+ H
2
O
Ammonia is a comparatively low cost reagent, and the process can
be balanced to produce the desired amine. The other routes to amines
1.8 REACTION TYPES
Phenol
Ammonia
Catalytic
reactor
Ammonia recovery column
Dehydrating column
Purification column
Bottoms removal column
Ammonia recycle Water Aniline Azeotrope
Azeotrope recycle
Diphenylamine
FIGURE 3 Aniline and diphenylamine production from phenol.
Speight_Part 1_A 11/7/01 3:04 PM Page 1.8
through reduction use expensive reagents (iron, Fe, zinc, Zn, or hydrogen,
H
2
, gas) that make ammonolysis costs quite attractive. Substituted amines
can be produced by using substituted ammonia (amines) in place of sim-
ple ammonia. The equipment is an agitated iron pressure vessel; stainless
steel is also used for vessel construction.
Amination by reduction is usually carried out in cast-iron vessels (1600
gallons capacity, or higher) and alkali reductions in carbon steel vessels of
desired sizes. The vessel is usually equipped with a nozzle at the base so

) catalyst
(Bucherer reaction) yields 2-naphthylamine
3. Ethylene oxide yields monoethanolamine (HOCH
2
CH
2
NH
2
),
diethanolamine [(HOCH
2
CH
2
)
2
NH)], and triethanolamine
[(HOCH
2
CH
2
)
3
N)]
4. Glucose plus nickel catalyst yields glucamine
5. Cyclohexanone plus nickel catalyst yields cyclohexylamine
Methylamines are produced by reacting gaseous methanol with a cata-
lyst at 350 to 400
o
C and 290 psi (2.0 MPa), then distilling the reaction mix-
ture. Any ratio of mono-, di-, or trimethylamines is possible by recycling

2
O + NH
3
→ (HOCH
2
CH
2
)
2
NH + 2H
2
O
diethanolamine
3CH
2
CH
2
O + NH
3
→ (HOCH
2
CH
2
)
3
N + 3H
2
O
triethanolamine
After the strongly exothermic reaction, the reaction products are recov-

ing the correct alcohol with anhydrous ammonia in the vapor phase.
AMINATION 1.11
Speight_Part 1_A 11/7/01 3:04 PM Page 1.11