industrial inorganic chemistry 2nd

Karl Heinz Buchel
Hans-Heinrich Moretto
Peter Woditsch
Industrial
Inorganic Chemistry
Industrial
Karl Heinz Buchel
Hans-Heinrich Moretto
Peter Wodi
t
sc
h
Second, Completely
Revised Edition
inorganic
Translated by
C
hemi
s
trv
David R. Terrell
BWILEY-VCH
Weinheim
-
New York
Chichester
-
Brisbane
Singapore
-

Toronto
Professor Dr. Dr.
h.
c. mult. Karl Heinz Buchel
Member of the Board of Directors
of
Bayer
AG
D-5 I368 Leverkuaen
Professor Hans-Heinrich Moretto
Bayer
AG
Central Research
D-5 1368 Leverkusen
Professor Dr. Peter Woditsch
Bayer
AG
CH-BS
D-47829 Krefeld
This book was carefully produced. Nevertheless, authors, translator and publisher do not warrant the information
contained therein to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedu-
ral details or other items may inadvertently be inaccurate.
First Edition 1989
Second, Completely Revised Edition
2000
First Reprint 2003
Library
of
Congress Card
No.:

Applied for.
British Library Cataloguing-in-Publication Data:
A
catalogue record for this book is available from the Britiah Library.
Deutsche Bibliothek Cataloguing-in-Publication Data:
A
catalogue record for this publication is available from Die Deutsche Bibliothek
0
WILEY-VCH Verlag CmbH. D-69469 Weinheim (Federal Republic of Germany), 2000
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No
part
of
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-
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-
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Printed in the Federal Republic of Germany
Preface to the Second English Edition
In the more than 10 years, since the publication of the first edition of the book “Industrial Inorganic
Chemistry”, the structure of inorganic industrial chemistry has not changed fundamentally.
In most sectors the “state of the art” has been expanded and refined. This
is
addressed together
with the updating
of
the economic data in this new edition.
The pressure for change in the meantime was due in particular to globalization of the World
economy and the resulting pressure for cost reduction through new and optimalized processes and
to
an expanding knowledge
of
ecological requirements e.g. energy saving and new production and
development principles such
as
quality assurance and responsible care.
To the extent that it is discernible in the products and processes, appropriate aspects have been
incorporated in the revision, for example see membrane technology in the chloralkali and
hydrochloric acid electrolysis.
Expansion of the sections on the products of silicon chemistry, silanes, heavy duty ceramics and
photovoltaics reflects their increased importance.
Chapter
6
over the Nuclear Fuel Cycle has been updated
as

regards technical developments and
in
particular as regards its societal and political context.
In inorganic chemistry there have been important changes particularly in inorganic materials
such as new composite materials and so-called nano-materials, in the area of photovoltaics and in
catalysis. Since these have not yet been widely used industrially, they have not been covered
in
the
second edition of this book.
In the revision of this book numerous colleagues have assisted
us,
we particularly wish to thank:
Dr.
J.
Becker, Uranerzbergbau GmbH,
Dr. H D. Block, Bayer AG
Frau G. Blum, Bayer AG
Dr.
U.
Brekau, Bayer AG
Dip1 Ing. A. Bulan, Bayer AG
Dr. G. Buxbaum, Bayer AG
Dr. L. Puppe, Bayer AG
Dr.
F.
Gestermann, Bayer AG
Dr. Ch. Holzner, Bayer AG
Wesseling
Dr.
H.

Lange, Bayer AG
Dr.
J.
Liicke, CFI GmbH
&
Co.
KG, Rodenthal
Dr. R. Miinstedt, Bayer AG
Dr.
W.
Ohlendorf, Bayer AG
Dr.
K.
Tagder, Wirtschaftsverband
Frau Dr.
H.
Volker, Gottingen
Dr. G. Wagner, Bayer AG
Frau
M.
Wiegand, Bayer AG
Dr.
K.
Wussow, Bayer AG
Kernbrennstoff-Kreslauf e.V., Bonn
We also thank Wiley-VCH for their patience and understanding in the production of the new
edition and its excellent presentation.
Leverkusen. Autumn
1999
The Authors

VI
Preface
Preface to the First English Edition
“Industrial Inorganic Chemistry” was first published in German
in
1984. The book was well
received by students and teachers alike, leading to the publication of a second German edition
in
1986. The publishers, VCH Verlagsgesellschaft, were convinced that a wide circle of readers
would welcome the appearance of our book
in
the English language, and their encouragement has
led to the preparation of the present up-dated and revised edition in English.
The basic structure
of
the German Edition has been retained. Changes in the industrial importance
of some compounds and processes since the appearance of the German edition have been taken
into account and data relating to the
US
market have been emphasised. Thus the chapter on
potassium permanganate has been considerably abridged and that on the membrane process for the
manufacture of chlorine and sodium hydroxide expanded.
We are indebted to Dr Podesta and Dr Heine from Bayer AG for their assistance
in
the revision of
the German edition in addition to the institutions and colleagues mentioned
in
the preface to the
German edition.
The book was translated by Dr D.

R.
Terrell from Agfa-Gevaert
NV,
to whom we are particularly
grateful for the patience and care he devoted
to
this difficult task. We also wish to acknowledge the
contribution
of
VCH Verlagsgesellschaft in producing this edition.
Leverkusen. Autumn 1988
K.
H.
Buchel
Preface
VII
Preface to the First German Edition
The book “Industrielle Anorganische Chemie” will fill
a
long term need, which has become even
more apparent since the appearance of “Industrielle Organische Chemie” by Wessermel and Arpe*.
Although there are comprehensive chapters on this branch of chemistry in
a
number of
encyclopedias and handbooks, a single volume text is lacking that describes concisely the current
state of industrial inorganic chemistry.
The authors have been made aware of this need in discussions with students, young chemists,
colleagues in neighboring fields, teachers
and
university lecturers and willingly accepted the

suggestion of the publishers to write this text. Changes
in
the supply of raw materials and their
markets and economic and ecological requirements are responsible for the continual reshaping of
the inorganic chemical industry. As
a
result the treatment of industrial processes in the available
textbooks seldom keeps pace with these developments.
The inorganic chemical industry is an important branch of industry and its structure is particularly
diverse: including
a
large number of finished products (mineral fertilizers, construction materials,
glass, enamels and pigments to name but
a
few) and basic products for the organic chemical
industry such
as
mineral acids, alkalis, oxidizing agents and halogens. Modern developments in
other branches
of
industry, such
as
chips for microelectronics, video cassettes and optical fibers
have only been possible due to the continuous development of the inorganic chemical industry.
This book emphasises the manufacturing processes, economic importance and applications of
products. In the sections on production the pros and cons are considered in the context of the raw
material situation, economic and ecological considerations and energy consumption, the different
situations in different countries also being taken into account. Processes which are no longer
operated are at most briefly mentioned. The properties
of

the products are only considered to the
extent that they are relevant for production or applications.
It was necessary to restrict the material to avoid overextending the brief. Metallurgical processes
have not been included, except for the manufacture
of
“chemical” metals (e.g. alkali metals) which
is briefly described. Several borderline areas with organic chemistry are considered (e.g. organo-
phosphorus, -silicon and -fluoro products), others are deliberately excluded. A whole chapter is
devoted to the nuclear fuel cycle, since it involves
so
much industrial scale inorganic chemistry and
is currently
so
important.
The layout follows that of its sister book “Industrielle Organische Chemie” with the
main
text
being supplemented by marginal notes. These are essentially summaries of the main text and
enable the reader to obtain a rapid grasp of the most important facts. The equations are printed on a
gray background for the same reason.
At the end of each main section
a
generally subtitled list of references is provided. This should
enable the reader to obtain more detailed information on particular matters with the minimum of
effort. In addition to references to original papers and reviews, readers are referred to the important
VIII
Prejuce
handbooks: Ullmann, Winnacker-Kuchler and Kirk-Othmer. The Chemical Economic Handbook
of the Stanford Research Institute has frequently been used for economic data.
The documentation system at Bayer AG was invaluable in gathering the important facts for this

book. Numerous colleagues have assisted us:
Outside Bayer AG our thanks are due to Prof. P. Eyerer from Stuttgart University, Dr H. Grewe
from Krupp AG, Essen, Dr Ch. Hahn from Hutschenreuther AG, Selb, Dr G. Heymer from
Hoechst AG, Knapsack Works, Dr P. Kleinschmit from Degussa, Dr G. Konig from Martin
&
Pagenstecher GmbH, Krefeld, Dr R, Kroebel from the Kernforschungszentrum Karlsruhe, Dr G.
Kuhner from Degussa
AG,
Prof.
F.
W. Locher from the Forschungsinstitut der Zementindustrie,
Dusseldorf, H. Schmidt from the
Ziegeleiforschungsinstitut,
Essen, Dr
M.
Schwarzmann and his
colleagues from BASF AG and Dr E. Wege from Sigri Elektrographit GmbH, Meitingen, for
technical advice and critical perusal of sections of the manuscript.
Inside Bayer AG our thanks are due to Dr H P. Biermann, Dr G, Franz, Dr P. Kiemle, Dr M.
Mansmann, Dr H. H. Moretto and Dr
H.
Niederprum, who with many other colleagues have helped
with the technical realization of the text. In particular we would like to thank Dr Hanna Soll, who
with her many years of experience has substantially contributed to the editing of this book.
We also thank Verlag Chemie, which has assimilated the suggestions of the authors with much
understanding and has produced this book in such an excellent form.
Leverkusen, Spring
1984
K. H. Buchel
Contents

1
Primary Inorganic Materials
1
1.1
Water
1
1.1.1 Economic Importance
1
1.1.2 Production
of
Potable Water 2
1.1.2.1 Break-Point Chlorination and Ozonization
3
I.
1.2.2 Flocculation and Sedimentation 4
1
.I
.2.3 Filtration 5
1.1.2.4
1.1.2.5 Activated Charcoal Treatment 7
1.1.2.6 Safety Chlorination 8
1.1.2.7 Production of Soft or Deionized Water 8
1.1.3 Production of Freshwater from Seawater and Brackish Water
10
1.1.3.1 Production by Multistage Flash Evaporation
10
1.1.3.2
References for Chapter 1.1
:
Water 13

Removal of Dissolved Inorganic Impurities
5
Production using Reverse Osmosis
11
1.2
Hydrogen
14
I
.2.1 Economic Importance
I4
1.2.2 Hydrogen Manufacture
I5
1.2.2.
I
Petrochemical Processes and Coal Gasification 15
1.2.2.2 Electrolysis of Water 16
I
.2.2.3 Other Manufacturing Processes for Hydrogen
I7
I
.2.2.4
I
.2.3 Hydrogen Applications 18
References for Chapter 1.2: Hydrogen 19
Production of Hydrogen
as
a
Byproduct 18
1.3
1.3.1

1.3.
I.
I
1.3.1.2
1.3.1.3
1.3.2
1.3.2.1
1.3.2.2
I
.3.2.3
I
.3.2.4
I
.3.2.5
Hydrogen Peroxide and Inorganic Peroxo Compounds
20
Economic Importance 20
Hydrogen Peroxide 20
Sodium Perborate and Sodium Carbonate Perhydrate 20
Alkali Peroxodisulfates and Sodium Peroxide 2
1
Production 21
Hydrogen Peroxide 21
Sodium Perborate 24
Sodium Carbonate Perhydrate
25
Alkali Peroxodisulfate 26
Sodium Peroxide 26
X
Contents

1.3.3 Applications 27
1.3.3.1
1.3.3.2 Alkali Peroxodisulfates and Sodium Peroxide 28
References for Chapter 1.3: Hydrogen Peroxide and Inorganic Peroxo Compounds 28
Hydrogen Peroxide, Sodium Perborate and Sodium Carbonate Perhydrate 27
1.4
1.4.1 Ammonia 29
1.4.1.1 Economic Importance 29
1.4.1.2 Synthetic Ammonia Manufacture 29
1.4.1.2.1
General Information 29
1.4.1.2.2 Ammonia Synthesis Catalysts
30
1.4.1.2.3 Synthesis Gas Production 32
1.4.1.2.4
1.4.
I
.2.5
1.4.1.3 Ammonia Applications 43
References for Chapter
I
.4: Nitrogen and Nitrogen Compounds 43
1.4.2 Hydrazine 43
1.4.2.1 Economic Importance 43
1.4.2.2 Manufacture of Hydrazine 44
I
.4.2.2.1 Raschig Process 44
1.4.2.2.2 Urea Process 45
1.4.2.2.3 Bayer Process 46
1.4.2.2.4 H,Oz Process

47
1.4.2.3 Applications of Hydrazine 48
References for Chapter 1.4.2: Hydrazine 49
I
.4.3 Hydroxylamine
50
1.4.3.1
I
.4.3.2 Manufacture
50
1.4.3.2.1 Raschig Process 5
1
1.4.3.2.2
I
.4.3.2.3
References for Chapter 1.4.3: Hydroxylamine 53
1.4.4 Nitric Acid 53
1.4.4.1 Economic Importance 53
1.4.4.2 Manufacture 53
I
.4.4.2.
I
Fundamentals of Nitric Acid Manufacture 53
1.4.4.2.2 Plant Types 57
1.4.4.2.3 Process Description 58
1.4.4.2.4
1.4.4.2.5
Tail
Gases from Nitric Acid Manufacture 62
1.4.4.3 Nitric Acid Applications 64

References for Chapter 1.4.4: Nitric Acid 65
Nitrogen and Nitrogen Compounds
29
Conversion of Synthesis Gas
to
Ammonia 39
Integrated Ammonia Synthesis Plants
41
Economic Importance and Applications
50
Nitrogen(I1) Oxide Reduction Process
5
1
Nitrate Reduction Process (DSM/HPO-Stamicarbon) 52
Manufacture
of
Highly Concentrated Nitric Acid 59
1.5
1.5.1
1.5.1.
I
Raw Materials 65
Phosphorus and its Compounds
65
Phosphorus and Inorganic Phosphorus Compounds 65
Contents
XI
1.5.1.2 Products 67
1.5.1.2.1 Phosphoric Acid 67
1.5.1.2.2 Phosphoric Acid Salts

75
1.5.1.2.3 Phosphorus
80
I
.5.
I
.2.4
References for Chapter 1.5.1
:
Phosphorus and Inorganic Phosphorus Compounds 90
1.5.2 Organophosphorus Compounds
9
1
1.5.2.1 Neutral Phosphoric Acid Esters 9
1
1.5.2.2 Phosphoric Ester Acids 94
1.5.2.3 Dithiophosphoric Ester Acids 94
1.5.2.4
1.5.2.5
1.5.2.6 Phosphonic Acids 99
References for Chapter 1.5.2: Organophosphorus Compounds 101
Products Manufactures from Phosphorus
85
Neutral Esters of Thio- and Dithio-Phosphoric Acids 95
Neutral Di- and Triesters
of
Phosphorous Acid 97
1.6
1.6.
I

1.6.1.1
1.6.1.2
1.6.1.2.1
1.6.1.2.2
1.6.1.2.3
1.6.1.3
1.6.1.4
1.6.2
1.6.2.1
1.6.2.2
1.6.2.2.1
1.6.2.2.2
1.6.2.3
1.6.3
1.6.4
1.6.5
1.6.6
I
.6.7
1.6.8
1.6.9
1.6.10
1.6.11
1.6.12
1.6.13
1.6.14
1.6.15
1.6.16
1.6.17
Sulfur

and
Sulfur Compounds
101
Sulfur 101
Occurrence 10 1
Economic Importance 102
Sulfur from Elemental Sulfur Deposits 102
Sulfur from Hydrogen Sulfide and Sulfur Dioxide 102
Sulfur from Pyrites 103
Economic Importance
I04
Applications 104
Sulfuric Acid 104
Economic Importance 104
Starting Materials for Sulfuric Acid Manufacture 105
Sulfuric Acid from Sulfur Dioxide 105
Sulfuric Acid from Waste Sulfuric Acid and Metal Sulfates
1
13
Applications of Sulfuric Acid 115
100% Sulfur Dioxide
1
16
100% Sulfur Trioxide 117
Disulfur Dichloride
I
18
Sulfur Dichloride
1
18

Thionyl chloride 119
Sulfuryl Chloride
1
19
Chlorosulfonic Acid 120
Fluorosulfonic Acid 120
Sulfurous Acid Salts 120
Sodium Thiosulfate, Ammonium Thiosulfate 12
1
Sodium Dithionite and Sodium Hydroxymethanesulfinate 122
Hydrogen Sulfide 124
Sodium Sulfide I24
Sodium Hydrogen Sulfide 125
Carbon Disulfide 126
References for Chapter 1.6: Sulfur and Sulfur Compounds 126
XI1
Contents
1.7
1.7.1
1.7.1.1
1.7.1.1.
I
1.7.1.1.2
1.7.1.
I
.3
1.7.1.2
1.7.1.2.1
1.7.1.2.2
1.7.1.2.3

1.7.1.2.4
1.7.1.2.5
1.7.1.2.6
I
.7.1.2.7
1.7.1.2.8
1.7.1.2.9
1.7.1.3
Halogens
and
Halogen
Compounds
127
Fluorine and Fluorine Compounds I27
Fluorspar 127
Fluorspar Extraction 128
Qualities and Utilization of Fluorspar 128
Fluorapatite 130
Fluorine and Inorganic Fluorides I30
Fluorine 130
Hydrogen Fluoride I32
Aluminum Fluoride 138
Sodium Aluminum Hexafluoride (Cryolite) 140
Alkali Fluorides 141
Hexafluorosilicates 142
Uranium Hexafluoride 142
Boron Trifluoride and Tetrafluoroboric Acid 142
Sulfur Hexafluoride 143
Organofluoro Compounds by Electrochemical Fluorination I44
-

References for Chapter 1.7.1
:
Halogens and Halogen Compounds 145
1.7.2
1.7.2.1 Economic Importance 146
1.7.2.2 Starting Materials 148
I
.7.2.3 Manufacturing Processes
151
I
.7.2.3.1 Mercury Process 152
1.7.2.3.2 Diaphragm Process 154
1.7.2.3.3 Membrane Process 157
1.7.2.3.4
1.7.2.4
1.7.2.4.1 Chlorine 159
1.7.2.4.2 Sodium Hydroxide 160
References for Chapter
1.7.2:
Chloralkali-Electrolysis
161
1.7.3
1.7.3.1
I
.7.3.2
1.7.3.3
1.7.3.4
References for Chapter 1.7.3: Hydrochloric Acid
-
Hydrogen Chloride 165

1.7.4 Chlorine-Oxygen Compounds 166
1.7.4.1 Economic Importance 166
I
.7.4.2
I
.7.4.2.1 Hypochlorite 167
I
.7.4.2.2 Chlorites 170
I
.7.4.2.3 Chlorates 170
I
.7.4.2.4 Perchlorates and Perchloric Acid 172
1.7.4.2.5 Chlorine Dioxide 173
I
.7.4.3
Chloralkali Electrolysis, Chlorine and Sodium Hydroxide
146
Evaluation
of
Mercury, Diaphragm and Membrane Processes
158
Applications of Chlorine and Sodium Hydroxide 159
Hydrochloric Acid
-
Hydrogen Chloride 162
Manufacture of Hydrogen Chloride
162
Economic Importance
of
Hydrogen Chloride and Hydrochloric Acid 163

Electrolysis
of
Hydrochloric Acid 163
Non-Electrolytic Processes for the Manufacture of Chlorine from Hydrogen Chloride 164
Manufacture of Chlorine-Oxygen Compounds I67
Applications of Chlorine-Oxygen Compounds 174
Contents
XI11
References for Chapter 1.7.4: Chlorine-Oxygen Compounds 175
1.7.5
1.7.5.1
I
.7.5.2
1.7.5.2.1 Bromine 176
1.7.5.2.2 Hydrogen Bromide I78
1.7.5.2.3
1.7.5.2.4 Alkali Bromates 179
1.7.5.3
References for Chapter
I
.7.5: Bromine and Bromine Compounds
18
1
1.7.6
1.7.6.1
1.7.6.2
1.7.6.2.1 Iodine 182
1.7.6.2.2 Hydrogen Iodide 183
1.7.6.2.3 Alkali Iodides 183
1.7.6.2.4 Alkali Iodates 184

1.7.6.3 Applications of Iodine and Iodine Compounds 184
References for Chapter
I
.7.6: Iodine and Iodine Compounds 185
Bromine and Bromine Compounds 175
Natural Deposits and Economic Importance 175
Manufacture of Bromine and Bromine Compounds 176
Alkali Bromides, Calcium Bromide, Zinc Bromide 179
Applications for Bromine and Bromine Compounds 179
Iodine and Iodine Compounds
18
1
Economic Importance
I
8
I
Manufacture of Iodine and Iodine Compounds 182
2
2.1
2.1.1
2.1.1.1
2.1.1.2
2.1.1.3
2.
I.
I
.4
2.1.1.5
2.1.1.6
2.1.2

2.1.2.1
2.1.2.2
2.1.2.3
2.1.2.4
2.2
2.2.1
2.2.1.1
2.2.1.2
2.2.
I
.3
2.2.
I
.4
2.2.2
2.2.2.
I
Mineral Fertilizers
187
Phosphorus-Containing Fertilizers
187
Economic Importance I87
General Information 187
Importance
of
Superphosphate 188
Importance
of
Triple Superphosphate 188
Importance of Ammonium Phosphates I89

Importance
of
Nitrophosphates I89
Importance and Manufacture
of
Thermal (Sinter, Melt) and
Manufacture of Phosphorus-Containing Fertilizers
I
90
Superphosphate 190
Triple Superphosphate 19
1
Ammonium Phosphates 192
Nitrophosphates 195
Basic Slag (Thomas) Phosphates 189
Nitrogen-Containing Fertilizers
196
Economic Importance 196
General Information 196
Importance of Ammonium Sulfate 197
Importance
of
Ammonium Nitrate 197
Importance
of
Urea I98
Manufacture of Nitrogen-Containing Fertilizers 199
Ammonium Sulfate 199
XIV
Contents

2.2.2.2 Ammonium Nitrate 200
2.2.2.3 Urea 201
2.3 Potassium-Containing Fertilizers 205
2.3.1 Occurrence
of
Potassium Salts 205
2.3.2
2.3.3
2.3.3.1 Potassium Chloride 208
2.3.3.2 Potassium Sulfate 2 10
2.3.3.3 Potassium Nitrate 210
References for Chapter 2: Mineral Fertilizers 2
1
1
Economic Importance of Potassium-Containing Fertilizers 206
Manufacture
of Potassium-Containing Fertilizers 208
3
3.1
3.1.1
3.1.1.1
3.1.1.2
3.1.1.2.1
3.1.1.2.2
3.1.1.2.3
3.1.1.3
3.1.1.3.1
3.1.1.3.2
3.1
.I

.3.3
3.1.1.3.4
3.1.1.3.5
3.1.1.3.6
3.1.1.3.7
3.1.1.4
3.1.1.4.1
3.1.1.4.2
3.1.1.4.3
3.1.1.4.4
Metals and their
Compounds 213
Alkali and Alkaline Earth Metals and their Compounds 213
Alkali Metals and their Compounds 2 13
General Information 213
Lithium and its Compounds 2 13
Natural Deposits and Economic Importance 2 13
Metallic Lithium 214
Lithium Compounds 2 14
Sodium and its Compounds 216
General Information 216
Metallic Sodium 217
Sodium Carbonate 2 18
Sodium Hydrogen Carbonate 222
Sodium Sulfate 223
Sodium Hydrogen Sulfate 225
Sodium Borates 225
Potassium and its Compounds 227
General Information 227
Metallic Potassium 227

Potassium Hydroxide 227
Potassium Carbonate 228
References for Chapter 3.1.1: Alkali Metals and their Compounds 229
3.1.2
3.1.2.1 General Information 230
3.1.2.2
3.1.2.3
3.1.2.3.1 Natural Deposits 231
3.1.2.3.2 Metallic Magnesium 232
3.1.2.3.3 Magnesium Carbonate 234
3.1.2.3.4 Magnesium Oxide 235
3.1.2.3.5 Magnesium Chloride 236
3.1.2.3.6 Magnesium Sulfate 237
Alkaline Earth Metals and their Compounds 230
Beryllium and its Compounds 23
1
Magnesium and its Compounds 231
Contents
XV
3.1.2.4
3.1.2.4.1 Natural Deposits 237
3.1.2.4.2 Metallic Calcium 238
3.1.2.4.3 Calcium Carbonate 238
3.1.2.4.4
3.1.2.4.5 Calcium Chloride 240
3.1.2.4.6 Calcium Carbide 240
3.1.2.5
3.1.2.6
3.1.2.6.1
3.1.2.6.2 Barium Carbonate 243

3.1.2.6.3 Barium Sulfide 245
3.1.2.6.4 Barium Sulfate 245
References for Chapter 3.
I
.2: Alkaline Earth Metals and their Compounds 245
Calcium and its Compounds 237
Calcium Oxide and Calcium Hydroxide 239
Strontium and its Compounds 242
Barium and its Compounds 242
Natural Deposits and Economic Importance 242
3.2
3.2.1
3.2.2
3.2.3
3.2.3.1
3.2.3.2
3.2.3.3
3.2.4
3.2.4.1
3.2.4.2
3.2.4.3
3.2.5
3.2.5.1
3.2.5.2
3.2.5.3
3.2.6
3.2.6.1
3.2.6.2
3.2.6.3
3.2.7

Aluminum and
its
Compounds
246
General Information 246
Natural Deposits 247
Metallic Aluminum 248
Economic Importance 248
Manufacture 248
Applications 249
Aluminum Oxide and Aluminum Hydroxide 250
Economic Importance 250
Manufacture 250
Applications 25
1
Aluminum Sulfate 252
Economic Importance 252
Manufacture 252
Applications 253
Aluminum Chloride 253
Economic Importance 253
Manufacture 253
Applications 254
Sodium Aluminate 254
References for Chapter 3.2: Aluminum and its Compounds 255
3.3
3.3.1
3.3.1.1
3.3.1.2
3.3.1.3

3.3.1.3.1
3.3.1.3.2
3.3.
I
.3.3
3.3.1.3.4
Chromium Compounds and Chromium
255
Chromium Compounds 255
Economic Importance
255
Raw Material: Chromite 257
Manufacture of Chromium Compounds 258
Chromite Digestion to Alkali Chromates 258
Alkali Dichromates 260
Chromium(V1) Oxide (“Chromic Acid”) 262
Chromium(II1) Oxide 264
XVI
Contents
3.3.1.3.5
3.3.1.4
3.3.2 Metallic Chromium 266
3.3.2.1 Economic Importance 266
3.3.2.2 Manufacture of Chromium Metal 267
3.3.2.2.1 Chemical Reduction 267
3.3.2.2.2 Electrochemical Reduction of Chrome Alum 267
3.3.2.2.3
References for Chapter 3.3: Chromium Compounds and Chromium 268
Basic Chromium(II1) Salts (Chrome Tanning Agents) 265
Applications for Chromium Compounds 266

Electrochemical Reduction of Chromium(V1) Oxide 268
3.4
3.4.1 Elemental Silicon 269
3.4.1.1
3.4.1.2 Manufacture 270
3.4.1.2.1
3.4.1.2.2
3.4.1.3 Silicon Applications 278
3.4.2 Inorganic Silicon Compounds 279
References for Chapter 3.4: Silicon and its Inorganic Compounds 281
Silicon and its Inorganic Compounds 269
General Information and Economic Importance 269
Ferrosilicon and Metallurgical Grade Silicon 270
Electronic Grade Silicon (Semiconductor Silicon) 272
3.5
3.5.1 Manganese Compounds 282
3.5.1.1 Economic Importance 282
3.5.1.2 Raw Materials 283
3.5.1.3
3.5.1.3.1 Manganese(I1) Compounds 284
3.5.1.3.2
3.5.1.3.3 Manganese(1V) Oxide 286
3.5.1.3.4 Potassium Permanganate 289
3.5.1.4 Applications of Manganese Compounds 292
3.5.2 Manganese
-
Electrochemical Manufacture, Importance and Applications 292
References for Chapter 3.5: Manganese Compounds and Manganese 293
Manganese Compounds and Manganese
282

Manufacture of Manganese Compounds 284
Manganese(I1,III) Oxide (Mn,Od) and Manganese(II1) Oxide (Mn,O?) 286
4
Organo-Silicon Compounds
295
4.1
Industrially Important Organo-Silicon Compounds, Nomenclature 295
4.2
4.2.1
4.2.2
4.2.2.1
4.2.2.2
4.2.2.3
4.2.2.4
4.2.2.5
Industrially Important Silanes 296
Organohalosilanes 296
Industrial Important Silicon-functional Organo-Silanes 298
Organoalkoxysilanes 299
Acyloxysilanes 300
Oximino- and Aminoxy-Silanes 300
Amidosilanes, Silazanes 301
Organohydrogensilanes 30
1
Contents
XVII
4.2.3 Organofunctional Silanes 302
4.2.3.1 Alkenylsilanes 302
4.2.3.2 Halo-organosilanes 303
4.2.3.3 Organoaminosilanes 303

4.2.3.4 Organomercaptosilanes, Organosulfidosilanes 304
4.2.3.5 Other Organofunctional Silanes 304
References for Chapter 4.1 and 4.2: Organo-Silicon Compounds 305
4.3
4.3.1
4.3.2
4.3.3
4.3.3.1
4.3.3.2
4.3.3.3
4.3.3.4
4.3.3.5
4.3.3.6
4.3.3.7
4.3.4
4.4
4.4.1
4.4.2
4.4.3
4.4.3.1
4.4.3.2
4.4.3.3
4.4.3.4
4.4.3.5
4.4.4
4.4.5
Silicones
305
Structure and Properties, Nomenclature 305
Economic Importance 306

Linear and Cyclic Polyorganosiloxanes 307
Manufacture 307
Hydrolysis 307
Methanolysis 309
Cyclization 3 10
Polymerization 310
Polycondensation 3 I2
Industrial Realization of Polymerization 3 I3
Manufacture of Branched Polysiloxanes 3 14
Industrial Silicone Products
307
Silicone Oils 307
Products Manufactured from Silicone Oils 3
16
Silicone Rubbers 3 17
Room Temperature Vulcanizable Single Component Silicone Rubbers 3 I7
Two
Component Room Temperature Vulcanizable Silicone Rubbers 3
19
Hot Vulcanizable Peroxide Crosslinkable Silicone Rubbers 320
Hot Vulcanizable Addition Crosslinkable Silicone Rubbers 320
Properties of Silicone Rubber 322
Silicone Resins 322
Silicone Copolymers, Block Copolymers and Graft Copolymers 323
References for Chapters 4.3 and 4.4: Silicones 324
5
5.1
5.1.1
5.1
.l.

I
5.1.1.2
5.1.1.3
5.
I.
1.4
5.1.1.4.
I
5.
I.
1.4.2
5.1.1.4.3
Inorganic Solids 325
Silicate Products 325
Glass 325
Economic Importance 325
Structure 32.5
Glass Composition 326
Glass Manufacture 329
Glass Raw Materials 329
Melting Process 33
I
Melting Furnaces 332
XVIII
Contents
5.1.1.5
Forming 334
5.1.1.6
References for Chapter
5.1

.l:
Glass 337
5.1.2 Alkali Silicates 338
5.1.2.1
5.1.2.2 Manufacture of Alkali Silicates 338
5.1.2.3 Applications 340
References for Chapter 5.1.2: Alkali Silicates 340
Glass Properties and Applications 336
General and Economic Importance 338
5.
I
.3
5.1.3.1
5.1.3.2
5.1.3.3
5.1.3.4
5.1.3.4.1
5.1.3.4.2
5.1.3.4.3
5.1.3.5
5.1.3.6
5.1.3.7
5.1.3.7.1
5.1.3.7.2
5.1.3.7.3
5.1.3.7.4
5.1.3.7.5
Zeolites 340
Economic Importance 340
Zeolite Types 34

1
Natural Zeolites 344
Manufacture of Synthetic Zeolites 344
From Natural Raw Materials 344
From Synthetic
Raw
Materials 344
Modification of Synthetic Zeolites by Ion Exchange 346
Forming of Zeolites 346
Dehydration
of
Zeolites 347
Applications for Zeolites 347
As Ion Exchangers 347
As an Adsorption Agent 347
For Separation Processes 348
As Catalysts 349
Miscellaneous Applications 349
References for Chapter 5.1.3: Zeolites 350
5.2
5.2.1
5.2.1.1
5.2.1.2
5.2.1.3
5.2.1.4
5.2.1
.5
5.2.2
5.2.2.1
5.2.2.2

5.2.2.3
5.2.3
5.2.3.
I
5.2.3.2
5.2.3.3
5.2.4
5.2.5
5.2.5.1
5.2.5.2
5.2.5.3
Inorganic Fibers
351
Introduction 35 1
Definitions, Manufacture and Processing 35
1
Economic Importance 352
Properties 352
Classification and Applications 354
Physiological Aspects 354
Asbestos Fibers 356
General and Economic Importance 356
Occurrence and Extraction 359
Applications of Asbestos Fibers 361
Textile Glass Fibers 364
General and Economic Importance 364
Manufacture 366
Applications 369
Optical Fibers 370
Mineral Fiber Insulating Materials 372

General Information and Economic Importance 372
Manufacture 373
Applications 377
Contents
XIX
5.2.6
Carbon Fibers
377
5.2.6.1
5.2.6.2
Manufacture and Applications
380
5.2.7
Metal Fibers
384
5.2.7.
I
5.2.7.2
Boron Fibers
386
5.2.8
Ceramic Reinforcing Fibers
388
5.2.8.1
5.2.8.2
Oxide Fibers
389
5.2.8.3
Non-oxide Fibers
39

1
5.2.8.4
Whiskers
394
References for Section
5.2:
Inorganic Fibers
395
General Information and Economic Importance
377
Steel and Tungsten Fibers
384
General information and Economic Importance
388
5.3
5.3.1
5.3.2
5.3.2.1
5.3.2.2
5.3.2.3
5.3.2.4
5.3.2.4.1
5.3.2.4.2
5.3.2.4.3
5.3.2.5
5.3.2.6
5.3.3
5.3.3.1
5.3.3.2
5.3.3.3

5.3.3.3.1
5.3.3.3.2
5.3.3.3.3
5.3.3.3.4
5.3.3.4
5.3.3.5
5.3.3.6
5.3.3.7
5.3.3.8
5.3.3.9
5.3.4
5.3.4.1
5.3.4.2
5.3.4.3
5.3.4.4
5.3.4.5
5.3.4.6
Construction
Materials
396
General Introduction
396
Lime
397
Economic lmportance
397
Raw Materials
398
Quicklime
398

Slaked Lime
400
Wet Slaking of Quicklime
400
Dry Slaking of Quicklime
401
Lime Hydrate from Calcium Carbide
401
Steam-Hardened Construction Materials
402
Applications of Lime
402
Cement
403
Economic Importance
403
Composition of Cements
404
Portland Cement
405
Raw Materials
405
Composition of Portland Cement Clinkers
405
Manufacture
of
Portland Cement
405
Applications
of

Portland Cement
409
Slag Cement
409
Pozzolan Cements
410
Alumina Cement
41
I
Asbestos Cement
41
I
Miscellaneous Cement Types
41
1
Processes
in
the Solidification
of
Cement
4 12
Gypsum
415
Economic Importance
4
I5
Modifications of Calcium Sulfate
416
Natural Gypsum
4 18

Natural Anhydrite
420
Fluoroanhydrite
420
Byproduct Gypsum
420
xx
Contents
5.3.4.6.1
5.3.4.6.2
5.3.4.6.3 Phosphogypsum 421
5.3.4.7
5.3.5
5.3.6 Expanded Products 425
5.3.6.1
General lnformation 425
5.3.6.2
5.3.6.2.1 Raw Materials 425
5.3.6.2.2
5.3.6.2.3
5.3.6.3
5.3.6.4
References for Chapter 5.3: Construction Materials 43
1
Byproduct Gypsum from the Manufacture and Purification of Organic Acids 420
Byproduct Gypsum from Flue Gas Desulfurization 42
1
Processes in the Setting of Plaster 423
Coarse Ceramic Products for the Construction Industry 424
Expanded Products from Clays and Shales 425

Gas-forming Reactions in the Manufacture of
Manufacture of Expanded Products 429
Expanded Products from Glasses (Foam Glass) 430
Applications of Expanded Products 430
Expanded Products 428
5.4
5.4.1
5.4.2
5.4.3
5.4.3.1
5.4.3.2
5.4.4
5.4.4.
I
5.4.4.2
5.4.4.2.1
5.4.4.2.2
5.4.4.3
5.4.5
Enamel
430
General Information 432
Classification of Enamels 433
Enamel Frit Manufacture 437
Raw Materials 437
Smelting of Frits 437
Enameling 438
Production of Coatable Systems 438
Coating Processes 439
Wet Application Processes 439

Dry
Application Procesres 440
Stoving of Enamels 441
Applications of Enamel 442
References for Chapter 5.4: Enamel 442
5.5
5.5.
I
5.5.2
5.5.3
5.5.4
5.5.4.1
5.5.4.2
5.5.4.3
5.5.4.4
5.5.4.4.1
5.5.4.4.2
5.5.4.4.3
5.5.4.5
5.5.4.6
5.5.4.6.1
Ceramics
443
General Information 443
Classification of Ceramic Products 443
General Process Steps
in
the Manufacture of Ceramics 444
Clay Ceramic Products 445
Composition and Raw Materials 445

Extraction and Treatment of Raw Kaolin 447
Manufacture of Clay Ceramic Batches 447
Forming Processes 448
Casting Processes 449
Plastic Forming 450
Forming by Powder Pressing 45
1
Drying Processes 452
Firing of Ceramics 452
Physical-Chemical Processes 452
Contents
XXI
5.5.4.6.2
5.5.4.6.3
5.5.4.7
5.5.4.7.1
5.5.4.7.2
5.5.4.7.3
5.5.4.7.4
5.5.4.8
5.5.5
5.5.5.1
5.5.5.1
.I
5.5.5.1.2
5.5.5.
I
.3
5.5.5.1.4
5.5.5.

I
.5
5.5.5.
I
.6
5.5.5.2
5.5.5.2.1
5.5.5.2.2
5.5.5.3
5.5.5.3.1
5.5.5.3.2
5.5.5.3.3
5.5.5.3.4
5.5.5.3.5
5.5.5.3.6
5.5.5.3.7
5.5.5.4
5.5.5.4.1
5.5.5.4.2
5.5.5.4.3
5.5.5.4.4
5.5.5.4.5
5.5.5.4.6
5.5.5.4.7
5.5.5.4.8
Firing Conditions 454
Glazes 455
Properties and Applications of Clay Ceramic Products 455
Fine Earthenware 45.5
Stoneware 456

Porcelain 456
Rapidly Fired Porcelain 457
Economic Importance of Clay Ceramic Products 458
Specialty Ceramic Products 458
Oxide Ceramics 458
General Information 458
Aluminum Oxide 460
Zirconium Oxide 46
I
Beryllium Oxide 462
Uranium Oxide and Thorium Oxide 462
Other Oxide Ceramics 463
Electro- and Magneto-Ceramics 464
Titanates 464
Ferrites 465
Refractory Ceramics 468
Definition and Classification 468
Alumina-Rich Products 470
Fireclay Products 470
Silicate Products 47
1
Basic Products 472
Specialty Refractory Products 473
Economic Importance 473
Nonoxide Ceramics 474
Economic Importance 475
Manufacturing Processes for Silicon Carbide 475
Refractory Silicon Carbide Products 477
Fine Ceramic Silicon Carbide Products 477
Fine Silicon Nitride Ceramic Products 478

Manufacture and Properties of Boron Carbide 480
Manufacture and Properties
of
Boron Nitride 48
1
Manufacture and Properties of Aluminum Nitride 482
References for Chapter
5.5:
Ceramics 482
5.6
5.6.1
5.6.2
5.6.3
5.6.3.1
5.6.3.2
5.6.4
5.6.4.1
Metallic Hard Materials
484
General Information 484
General Manufacturing Processes and Properties of Metal Carbides 485
Carbides of the Subgroup of the IVth Group 487
Titanium Carbide 487
Zirconium Carbide and Hafnium Carbide 488
Carbides of the Subgroup of the Vth Group 488
Vanadium Carbide 488
XXII
Contents
5.6.4.2
5.6.5

5.6.5.1
Chromium Carbide
489
5.6.5.2
Molybdenum Carbide
489
5.6.5.3
Tungsten Carbide
489
5.6.5.4
5.6.6
5.6.7
Metal Nitrides
492
5.6.8
Metdl Borides
493
5.6.9
Metal Silicides
494
References
for
Chapter
5.6:
Metallic Hard Materials
495
Niobium Carbide and Tantalum Carbide
488
Carbides
of

the Subgroup
of
the VIth Group
489
Cemented Carbides Based
on
Tungsten Carbide
490
Thorium Carbide and Uranium Carbide
491
5.7
5.7.
I
5.7.2
5.7.2.1
5.7.2.2
5.7.2.3
5.7.2.4
5.7.3
5.7.3.1
5.7.3.2
5.7.3.3
5.7.4
5.7.4.1
5.7.4.2
5.1.4.3
5.7.4.3.
I
5.7.4.3.2
5.7.4.3.3

5.7.4.3.4
5.7.4.4
5.7.4.4.1
5.7.4.4.2
5.7.4.4.3
5.7.4.4.4
5.7.4.4.5
5.7.4.5
5.7.4.6
5.7.5
5.7.5.1
5.7.5.2
5.7.5.3
5.7.6
5.7.6.1
5.7.6.2
Carbon Modifications
496
Introduction
496
Diamond
496
Economic Importance
496
Mining of Natural Diamonds
497
Manufacture
of
Synthetic Diamonds
498

Properties and Applications
500
Natural Graphite
500
Economic Importance
500
Natural Deposits and Mining
502
Properties and Applications
503
Large Scale Production of Synthetic Carbon and Synthetic Graphite 505
Economic Importance
505
General Information about Manufacture
505
Manufacture of Synthetic Carbon
506
Raw Materials
506
Processing
507
Densification and Forming
507
Carbonization
508
Graphitization of Synthetic Carbon
509
General Information
509
Acheson Process

509
Castner Process
5
10
Other Graphitization Processes
5
10
Purification Graphitization
5
1 1
Impregnation and Processing of Carbon and Graphite Articles
5
1
1
Properties and Applications
5
12
Special Types of Carbon and Graphite
5
13
Pyrolytic Carbon and Pyrolytic Graphite
5
13
Glassy Carbon and Foamed Carbon
5
I5
Graphite Foils and Membranes
5
16
Carbon Black

5
17
Economic Importance
5
18
Manufacture
5
I8
Contents
XXIII
5.7.6.2.1 General Information 51
8
5.7.6.2.2
5.7.6.2.3
5.7.6.2.4 Posttreatment 523
5.7.6.3 Properties and Applications 524
5.7.7 Activated Carbon 527
5.7.7.1 Economic Importance 527
5.7.7.2 Manufacture
528
5.7.7.2.1 General Information 8
5.7.7.2.2
5.7.7.2.3
5.7.7.3
5.7.7.4
References for Chapter
5.7:
Carbon Modifications 534
Pyrolysis Processes in the Presence of Oxygen 519
Pyrolysis Processes in the Absence of Oxygen 522

Activated Carbon by “Chemical Activation” 529
Activated Carbon by “Gas Activation”
530
Reactivation and Regeneration of Used Activated Carbon 532
Applications of Activated Carbon 532
5.8
5.8.1
5.8.3
5.8.3.1
5.8.3.2
5.8.3.3
5.8.4
5.8.4.1
5.8.4.1.1
5.8.4.
I
.2
5.8.4.1.3
5.8.4.1.4
5.8.4.1
.5
5.8.4.2
5.8.4.3
5.8.4.4
5.8.4.5
5.8.5
5.8.2
Fillers
535
General Information 535

Economic Importance 536
Natural Fillers 536
Silicon-Based Fillers 536
Other Natural Fibers 538
Beneficiation of Natural Fillers 538
Synthetic Fillers 539
Silicas and Silicates 539
Pyrogenic Silicas 539
Wet Chemically Manufactured Silicas and Silicates 540
Posttreatment
of
Silicas 541
Glasses 542
Cristobalite 542
Aluminum Hydroxide 542
Carbonates 543
Sulfates
544
Other Synthetic Fillers 545
Properties and Applications 545
References for Chapter
5.8:
Fillers 546
5.9
5.9.1
5.9.2
5.9.2.1
5.9.2.2
5.9.2.2.1
5.9.2.2.2

5.9.2.2.3
5.9.2.2.4
5.9.2.3
Inorganic
Pigments
548
General Information and Economic Importance 548
White Pigments 552
General Information 552
Titanium Dioxide Pigments
553
Economic Importance 553
Raw Materials for Ti02 Pigments 553
Manufacturing Processes for TiOz Pigments
555
Applications for Ti02 Pigments
558
Lithopone and Zinc Sulfide Pigments 559
XXIV
Contents
5.9.2.4
5.9.2.4.1
5.9.2.4.2
5.9.3
5.9.3.1
5.9.3.1.1
5.9.3.1.2
5.9.3.2
5.9.3.2.1
5.9.3.2.2

5.9.3.3
5.9.3.4
5.9.3.5
5.9.3.6
5.9.3.7
5.9.4
5.9.5
5.9.5.
I
5.9.5.2
5.9.5.3
5.9.6
5.9.7
5.9.7.1
5.9.7.2
Zinc Oxide White Pigments
560
Manufacture
560
Applications
561
Colored Pigments
561
Iron Oxide Pigments
561
Natural Iron Oxide Pigments
561
Synthetic Iron Oxide Pigments
563
Chromium(II1) Oxide Pigments

567
Manufacture
567
Properties and Applications
of
Chromium(II1) Oxide
569
Chromate and Molybdate Pigments
570
Mixed-Metal Oxide Pigments and Ceramic Colorants
571
Cadmium Pigments
573
Cyanide Iron Blue Pigments
575
Ultramarine Pigments
577
Corrosion Protection Pigments
578
Luster Pigments
580
Metal Effect Pigments
580
Nacreous Pigments
581
Interference Pigments
581
Luminescent Pigments
581
Magnetic Pigments

582
General Information and Properties
582
Manufacture of Magnetic Pigments
584
References for Chapter
5.9:
Inorganic Pigments
586
6
6.1
6.2
6.3
6.4
6.4.1
6.4.2
6.4.2.1
6.4.2.2
6.4.3
6.4.3.1
6.4.3.2
6.4.4
6.4.5
Nuclear Fuel Cycle
587
Economic Importance
of
Nuclear Energy
587
General Information about the Nuclear Fuel Cycle

591
Availability
of
Uranium 592
Nuclear Reactor Types 594
General Information
594
Light-water Reactors
594
Boiling Water Reactors
594
Pressurized Water Reactors
595
Graphite-Moderated Reactors
595
Gas-Cooled
595
Light-Water Cooled
597
Heavy-Water Reactors
597
Fast Breeder Reactors
598
Contents
XXV
6.5
6.5.1
6.5.1.1
6.5.1.1,
I

6.5.1.1.2
6.5.1.1.3
6.5.1.2
6.5.1.3
6.5.2
6.5.2.1
6.5.2.2
6.5.2.3
6.5.3
6.5.4
6.5.4.1
6.5.4.1.1
6.5.4.1.2
6.5.4.1.3
6.5.4.1.4
6.5.4.2
6.5.5
6.6
6.6.1
6.6.2
6.6.2.1
6.6.2.2
6.6.2.3
6.6.2.4
6.6.2.5
Nuclear Fuel Production
599
Production of Uranium Concentrates (“Yellow Cake”) 600
Uranium from Uranium Ores
600

Leaching Processes 600
Separation of Uranium from the Leaching Solutions 602
Manufacture of Marketable Uranium Compounds (“Yellow Cake”) 603
Uranium from Phosphate Ores and Wet Phosphoric Acid 605
Uranium from Seawater 606
Conversion of Uranium Concentrates to Uranium Hexafluoride 607
General Information 607
Wet Process for Uranium(V1) Fluoride Manufacture 607
Dry Process for Uranium(V1) Fluoride Manufacture 609
*%-Enrichment 609
Reconversion
of
Uranium(V1) Fluoride into Nuclear Fuel 6
I0
Into Uranium(1V) Oxide 610
General Information 610
Uranium(1V) Oxide by Wet Processes 61
1
Uranium(1V) Oxide by the
Dry
(IDR) Process
6
I2
Manufacture
of
Uranium(1V) Oxide Pellets 61 2
Other Uranium Nuclear Fuels 6 13
Fuel Element Manufacture 614
Disposal
of

Waste from Nuclear Power Stations
615
General Information
6
15
Stages in Nuclear Waste Disposal 617
Interim Storage of Spent Fuel Elements 6 17
Reprocessing of Spent Fuel Elements 617
Further Processing of Uranium and Plutonium Solutions 620
Treatment of Radioactive Waste 621
Permanent Storage of Radioactive Waste 623
References for Chapter 6: Nuclear Fuel Cycle 624
Company Abbreviations Index 627
Subject Index 63
1