Industrial inorganic chemistry, second, completely revised edition by karl heinz büchel, hans heinrich moretto, peter woditsch

1.5.2.4 1.5.2.5 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- a

Karl Heinz Buchel Hans-Heinrich Moretto Peter Woditsch

Industrial

Inorganic Chemistry

Professor Dr Dr h c mult Karl Heinz Buchel

Member of the Board of Directors of Bayer AG

First Edition 1989

Second, Completely Revised Edition 2000

First Reprint 2003

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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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All rights reserved (including those of translation in other languages) No part of this book may be reproduced in any form - by fotoprinting, microfilm, or any other means - nor transmitted or translated into a machine language without written permission from :he publishers Registered names, trademarks, etc used in this book, even when not hpecifically marked as such, are not to be considered unprotected by law

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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

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

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

second edition of this book

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

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

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

potassium permanganate has been considerably abridged and that on the membrane process for the manufacture of chlorine and sodium hydroxide expanded

the German edition in addition to the institutions and colleagues mentioned in the preface to the German edition

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

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

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,

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

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

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

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

Contents

1 Primary Inorganic Materials 1

1.1.2.4

1.1.3.2

Removal of Dissolved Inorganic Impurities 5

References for Chapter 1.2: Hydrogen 19

Sodium Perborate and Sodium Carbonate Perhydrate 20

X Contents

1.3.3.1

References for Chapter 1.3: Hydrogen Peroxide and Inorganic Peroxo Compounds 28

Hydrogen Peroxide, Sodium Perborate and Sodium Carbonate Perhydrate 27

References for Chapter 1.4.4: Nitric Acid 65

Conversion of Synthesis Gas to Ammonia 39

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

Phosphorus and Inorganic Phosphorus Compounds 65

1.5.2.4

1.5.2.5

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

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

Applications of Sulfuric Acid 115

Sulfurous Acid Salts 120

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

Halogens and Halogen Compounds 127

Fluorine and Fluorine Compounds I27

Applications of Chlorine and Sodium Hydroxide 159

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

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

Importance of Triple Superphosphate 188

Importance of Ammonium Phosphates I89

Importance and Manufacture of Thermal (Sinter, Melt) and

Manufacture of Phosphorus-Containing Fertilizers I 90

Importance of Ammonium Sulfate 197

Manufacture of Nitrogen-Containing Fertilizers 199

Ammonium Sulfate 199

Economic Importance of Potassium-Containing Fertilizers 206 Manufacture of Potassium-Containing Fertilizers 208

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

Alkaline Earth Metals and their Compounds 230

Magnesium and its Compounds 231

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

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

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

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

References for Chapter 3.5: Manganese Compounds and Manganese 293

Manufacture of Manganese Compounds 284

Manganese(I1,III) Oxide (Mn,Od) and Manganese(II1) Oxide (Mn,O?) 286

References for Chapter 4.1 and 4.2: Organo-Silicon Compounds 305

Industrial Realization of Polymerization 3 I3

Manufacture of Branched Polysiloxanes 3 14

Industrial Silicone Products 307

Silicone Oils 307

Silicone Rubbers 3 17

Room Temperature Vulcanizable Single Component Silicone Rubbers 3 I7

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

References for Chapter 5.1.2: Alkali Silicates 340

Glass Properties and Applications 336

General and Economic Importance 338

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

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

References for Section 5.2: Inorganic Fibers 395

Processes in the Solidification of Cement 4 12

Byproduct Gypsum from the Manufacture and Purification of Organic Acids 420

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

Wet Application Processes 439

Dry Application Procesres 440

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

Rapidly Fired Porcelain 457

Economic Importance of Clay Ceramic Products 458

Specialty Ceramic Products 458

Uranium Oxide and Thorium Oxide 462

Other Oxide Ceramics 463

Electro- and Magneto-Ceramics 464

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 Aluminum Nitride 482

References for Chapter 5.5: Ceramics 482

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

References for Chapter 5.6: Metallic Hard Materials 495

General Information about Manufacture 505

Manufacture of Synthetic Carbon 506

Properties and Applications 5 12

Special Types of Carbon and Graphite 5 13

Graphite Foils and Membranes 5 16

Economic Importance 5 18

Manufacture 5 I8

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

Reactivation and Regeneration of Used Activated Carbon 532

Applications of Activated Carbon 532

Other Natural Fibers 538

Beneficiation of Natural Fillers 538

Other Synthetic Fillers 545

Properties and Applications 545

References for Chapter 5.8: Fillers 546

Raw Materials for Ti02 Pigments 553

Manufacturing Processes for TiOz Pigments 555

Lithopone and Zinc Sulfide Pigments 559

References for Chapter 5.9: Inorganic Pigments 586

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

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

Into Uranium(1V) Oxide 610

General Information 610

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

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

1 Primary Inorganic Materials

1.1 Water

1.1.1 Economic Importance

Water is a raw material which is available on Earth in

unlimited quantities Water is not consumed since, after

use, it is fed back sooner or later into the Earth's water

circulation The local availability of water (e.g in arid

regions), especially with the purity necessary for the

particular application, is another matter Cheap high purity

water is required for many applications

Statistics for the Federal Republic of Germany serve to

illustrate the origin and production of water for an

water was produced (corresponding to about 80 m3 per

inhabitant) which comprises:

4015 lo6 m3 ground- and spring water, of which

1725 1 Oh m3 surface water, of which

529 lo6 m3 is augmented ground water and

46.44' loy m3 of water was extracted (= demand) in

this quantity, reflecting the multiple usage of the cooling

water

In rain starved regions (southern Mediterranean, northern

desert belt) potable water is produced on an industrial scale

from sea- and brackish water using distillation plants (older

technology), reverse osmosis (newer technology) and to a

small extent electrodialysis plants (brackish water)

Water: a raw material in principle available

in unlimited quantities, since used water is fed back into the Earth's water circulation

FRG 1991:

Public supply of water:

6 I 10') inR = 80 m3 per inhabitant per year

46.44 I 0' id

Total water extraction:

Industrial inorganic Chemistry

Karl Heinz Bbchel Hans-Heinrich Moretto & Peter Woditsch

copyright0 WlLEY VCH Verldg GmbH, 2MlO

2 1 Primary Inorganic Materials

1995 8900 plants worldwide, with a capacity of 1 0 lo6

stage) vacuum distillation plants (MSF, multistage flash), ca

35 lo of the capacity is in plants utilizing the more recent

electrodialysis technology RO-plants dominate because they are more compact to build and consume much less energy, although this is expensive electrical energy, than MSF-plants which essentially use thermal energy

1.1.2 Production of Potable Water

Only good spring water can be used as potable water without further treatment

The untreated water is more or less contaminated

In obtaining potable water some or all of

the following steps have to be carried out:

Break.point chlorination or ozonizat,on

pH adjustment

entirely upon the quality of the untreated water In the case

prevent infection from mains water In the case of strongly polluted water (e.g water filtered through the banks of the Rhine or Ruhr) almost all the steps are necessary In this way potable water can be obtained even from strongly contaminated water However, industrial water with lower purity, e.g for cooling purposes, requires fewer purification steps

1.1 Wuter 3

Additional purification steps are necessary if the water

contains large quantities of hardeners (calcium and

magnesium ions), unbound carbon dioxide and iron and

manganese ions

Certain applications require deionized water This can be

obtained by ion exchange

1.1.2.1 Break-Point Chlorination and Ozonization

In the case of strongly polluted surface water, chlorination

is the first purification step and is carried out after removal

of any coarse foreign matter Sufficient chlorine is added to

ensure a free chlorine concentration of ca 0.2 to 0.5 mg/L

in the water after treatment (break-point chlorination)

Chlorine reacts with water forming hydrochloric acid and

the hypochlorite anion, depending upon the pH

Chlorination results in:

elimination of pathogenic germs, deactivation of viruses,

oxidation of cations such as iron(I1) or manganese(I1) to

higher valency states,

chlorination of ammonia to chloramines or nitrogen

trichloride,

chlorination of phenols to chlorophenols, and

chlorination of organic impurities, particularly humic

acid, e.g to aliphatic chlorohydrocarbons

The last two processes are undesirable: chlorophenols have

very strong taste and some of the aliphatic

chlorohydrocarbons (e.g chloroform) are also suspected of

being carcinogenic It is therefore usual to perform the

chlorination only up to the chloramine stage and to carry out

the further elimination of impurities, e.g microbiological

degradation processes, on activated charcoal

The most important alternative to chlorination of water is

ozonization in which the above-mentioned disadvantages

ozonization is a problem Ozonization helps subsequent

flocculation and biological degradation on activated

alternative is treatment with chlorine dioxide (from sodium

organochloro-compounds than in the case of chlorination

remove free carbon dioxide and iron and manganese ions

Break-point chlorination:

addition of sufficient chlorine to ensure

0.2 to 0.5 mg/L of free chlorine in the water after treatment

Chlorination results in:

elimination of pathogenic organisms chlorination of ammonia

formation of undesirable organochloro- compounds!

Ozonization as an alternative to chlorination:

advantages:

~ no formation of organochloro-

- subsequent flocculation made easier

- higher costs compounds disadvantages:

4 I Primary Inorganic Materials

In the Federal Republic of Germany ozoniLation, as pre-

break-point chlorination

Aeration is sufficient to oxidize and thereby tlocculate out iron and manganese ions in the treatment of

expelling the unbound carbon dioxide

1.1.2.2 Flocculation and Sedimentation

Preliminary purification by flocculation is necessary, if the

hydroxide is precipitated:

Flocculation:

removal of inorganic and organic colloids

by adsorption on (in situ produced)

aluminum and iron(II1) hydroxide flakes

If necessary flocculation aids are added

neutralize the acid formed, alkali has to be added (e.g

flocculation aids such as poly(acry1amide) or starch

which precipitate are positively charged and adsorb the negatively charged colloidal organic materials and clay particles

out the flocculation process and the separation of the flocculated materials producing a well-defined sludge suspension layer, which can be removed Some plant operates with sludge feedback to enable more efficient adsorption Sludge flocks can also be separated by flotation

1.1 Water 5

1.1.2.3 Filtration

filtered The water is generally filtered downwards through

impurities this increases the filter resistance and it is then

cleaned by flushing upwards together with air, if necessary

Alternatively, a multiple-layer filter can be used, optionally

separation ,,, undissolved sand filter, optionally combined with an anthracite filter Flushing with water or water/air when the filter is covered

Figure 1.1-1 Construction of a two layer filter

a) inlet; b) outlet; c ) bottom; d) sand; e) filter charcoal;

f ) water distribution

1.1.2.4 Removal of Dissolved Inorganic Impurities

carbonate forms, upon heating, a precipitate consisting

mainly of calcium carbonate (carbonate hardness, boiler

calcium hydroxide and separation of the

The carbonate hardness can be removed by adding acid,

whereupon the more soluble calcium sulfate is formed:

6 I Primary Inorganic Materials

The resulting carbon dioxide has to be expelled, as

carbonate can be removed by the addition of calcium hydroxide:

In an industrial variant of this process the calcium

hydrogen carbonate-containing water and the mixture passed over calcium carbonate beads, upon which the freshly formed calcium carbonate is deposited Fresh beads form on the crystal nuclei added and those beads which become too large are separated off

Carbon dioxide must also be expelled from soft water containing a high concentration of carbonic acid, a simultaneous hardening can be obtained by filtering over semi-calcined dolomite

Iron and manganese are present as bivalent ions in many waters They are removed by oxidation to their oxide

Removal of iron(II) and manganese(,,) ions

by oxidation of the bivalent ions with air,

or if necessary, with chlorine and

separation of the oxide hydrates formed

Dissolved carbon dioxide also expelled

during air oxidation

hydrates, preferably with air, and if necessary after increasing the pH These are then filtered off Treatment with air expels the dissolved carbon dioxide at the same time If air is an insufficiently powerful oxidation agent,

such as chlorine or ozone are used

Small quantities of phosphates are desirable in household effluent to protect household equipment from corrosion by suppressing heavy metal dissolution Reservoirs can contain too much phosphate due to run off from intensively used agricultural areas This is then precipitated by flocculation with iron or aluminum salts

Dedicated nitrate removal is hardly used despite known processes for denitrification, the mandatory minimum concentrations being obtained by mixing Decomposition

activated charcoal filters

1.1 Water 7

1.1.2.5 Activated Charcoal Treatment

If after the above-mentioned treatment steps, water still

contains nonionic organic impurities e.g phenolic matter or

by treatment with activated charcoal is advisable

Activated charcoal provides an additional safety element

for dealing with sporadic discharges, e.g accidental, into

river-water of organic substances e.g mineral oil,

tempering oils

So-called absorber resins based on poly(styrene) are

recommended as an alternative to activated charcoal, but

have as yet found little application Chlorohydrocarbons

and phenols are efficiently adsorbed by activated charcoal

Humic acid is less well adsorbed, its detection being a sign

of activated charcoal filter exhaustion

If powdered charcoal is added (widely used in the USA)

adsorption can be carried out simultaneously with

flocculation, but passing through a bed of granular

activated charcoal beds is more widely used in Europe

Use of powdered charcoal has the advantage that the

amount used can be easily adjusted to the impurity level of

the water and that the investment costs are low Powdered

charcoal is, however, not easy to regenerate, whereas

granular activated charcoal can be regenerated thermally

Since the composition of the impurities varies from water

to water, the conditions required for the treatment of water

with granular activated charcoal (e.g number of filters,

contact time) have to be established empirically The

release of already adsorbed compounds e.g chloro-alkanes

into the eluant due to displacement by more easily adsorbed

compounds (chromatographic effect) has, however, to be

avoided

of organic carbon are on average removed from water per

day This value is higher, if the water is not break-point

ozone

Back flushing is used to remove the sludge from the

activated charcoal filter Thermal reactivation of the filters

under similar conditions to activated charcoal production

has to be performed periodically to avoid break-through of

pollutants This can be carried out either at the waterworks

or by the manufacturer of the activated charcoal

The activated charcoal treatment also has effects other

than the elimination of dissolved organic impurities:

Between SO and ISO g mC/rn’ water

removed by activated carbon per day

Regeneration of charcoal by back flushing and periodic t h e r d re~tivation

8 1 Primary Inorganic Materials

Activated charcoal treatment also leads to:

decomposition of excess chlorine

biological oxidation of ammonia and

organic compounds by microbiological

processes o n the activated charcoal

surface

removal of iron and manganese ions

Safety chlorination:

avoidance of reinfection of potable water

in the distribution network by adding 0.1 to

0.2 mg/L chlorine

excess chlorine is decomposed

*ammonia and some of the organic compounds are iron and manganese oxide hydrates are removed

biologically oxidized

1.1.2.6 Safety Chlorination

After the water treatment is finished a safety chlorination is

distribution network This is also necessary after prior

chlorine

1.1.2.7 Production of Soft or Deionized Water

Treatment of water with cation exchangers: Water with a lower hardener content than that produced

required for a range of industrial processes This can be accomplished by ion exchange with solid polymeric organic acids, the “ion exchangers”

When the sodium salt of sulfonated poly(styrene) is used

as the cation exchanger, calcium and magnesium ions are exchanged for sodium ions:

Exchange of Ca2+ and Mg2+ for Na+ or H+

[PS poly(styrene)]

Regeneration of ion exchangers charged with calcium

charged with ca 40 g of CaO) can be accomplished by reversing the above equation by (countercurrent) elution

are present as hydrogen carbonate, the eluant becomes alkaline upon heating:

If ion exchangers are used in the acid form, then the eluant will be acidic:

(M+: monovalent metal ion or equivalent of a multivalent ion)

I I Water 9

If (weakly acidic) resins containing carboxy-groups are

used, only those hardeners present as hydrogen carbonates

are removed, as only the weak carbonic acid can be

released:

For very high purity water (for applications such as high

performance boilers or in the electronics industry) virtually

ion-free water is required This is achieved in alternate

layers of cation and anion exchangers or so-called “mixed

bed exchangers” In these, both strongly acid cationic

exchangers in the proton form and basic ion exchangers

based on poly(styrene) modified with amino- or

ammonium-groups are present, e.g

water with less than 0.02 I n g / ~ can be obtained by stepwise treatment over cation and anion exchange beds Or j n

beds” Rehidual organic impurities can be

by OslnOsiS

Basic ion exchangers remove anions and are regenerated

with sodium hydroxide, e.g

PS-N(CH,),+OH- + CI- + PS-N(CH3)3+Cl- + OH-

Upon passing salt-containing water through a mixed bed,

the cations are replaced by protons and the anions by

hydroxide ions Protons and hydroxide ions together form

water, making the resulting water virtually ion-free with an

exchangers (than cationic exchangers) makes the

regeneration of mixed beds possible The mixed bed ion-

exchange columns are flushed from the bottom upwards

with such a strong current of water that the resins are

transported into separate zones, in which they can be

regenerated independently of one another

remove dissolved nonionic organic compounds Distillation

(“distilled water”) is no longer economic

10 I Primary lnorgunic Materials

1.1.3 Production of Freshwater from Seawater and Brackish Water

1.1.3.1 Production by Multistage Flash Evaporation

salts, for the most part sodium chloride Calcium, magnesium and hydrogen carbonate ions are also present

The removal of such quantities of salt from seawater

freshwater from seawater: using ion exchangers would be totally uneconomic

Distillation processes are currently mainly used in the production of potable and irrigation water from seawater Distillation is carried out by multistage (vacuum) flash

linportant process for the production of

Multistage (vacuum) flash evaporation

vapor

1 '

concentrated brine condensate

Fig 1.1-2 Flowchart of a multistage distillation plant

V evaporator; K heat exchanger (preheater); E expansion valve

Seawater freed of particulate and biological impurities is

also the coolant for condensing the stream produced and in so

first (hottest) stage the energy required for the complete system is supplied by stream using a heat exchanger The temperature of the ever more concentrated salt solution decreases from stage to stage as does the prevailing pressure Additional seawater is necessary in a supplementary circuit for cooling the steam produced in the last (coolest) stages This is returned directly to the sea, which represents a considerable energy loss The rest of the prewarmed water is used as feed-water and is heated by the final heater and

1 I Wuter 11

subjected to evaporation The concentrate, which is not

recycled to the final heater, is run off The “concentration

the seawater Disposal of this concentrate also represents an

energy loss

The quality of the seawater has to fulfill certain

requirements: in addition to the removal of coarse foreign

matter and biological impurities, hardener removal or

stabilization is necessary Calcium carbonate and

magnesium hydroxide (Brucite) are deposited from

untreated seawater onto the heat exchanger surfaces with

loss of carbon dioxide, resulting in a strong decrease in the

distillation performance of the plant

sulfuric acid, whereupon the fairly soluble calcium and

quantities of acid are required and desalination plants are

necessary, underdosing leading to encrustation and

overdosing leading to corrosion Therefore polyphosphates

are currently used for hardener stabilization in under-

stoichiometric quantities in the first (hottest) stage at

temperatures of up to ca 90°C Above 90°C polyphosphates

(sodium tripolyphosphate) hydrolyze too rapidly, thereby

losing their activity and forming precipitates In plants

operating above 90”C, poly(maleic acid) is almost

exclusively used for hardener stabilization It is usual to use

sludge balls for removing encrustation Above 120°C

calcium sulfate precipitates out as anhydrite (the solubility

of calcium sulfate decreases with increasing temperature),

which in practice limits the final heater temperature to

120°C

The cost of potable water production from seawater is

mainly dependent upon the cost of the energy consumed It

is, however, considerably higher than that for potable water

adding:

polyphosphate quantities of sulfuric ttcid or poly(maleic acid) derivatives in under-stoichiometric quantities

1.1.3.2 Production using Reverse Osmosis

Currently another process for the production of potable

product,On of wiiter from brackish

small plants Therefore almost 70% of all plants operate

permeation of water with a low salt content through a semipermeable ,nembrane by applying pressure to the hide containing

12 I Primary Inorganic Muteriuls

to a concentrated solution resulting in a hydrostatic pressure increase in the concentrated solution This process proceeds spontaneously In reverse osmosis, water with a low salt content is produced by forcing a salt-containing

pressure applied must be substantially higher than the

for water production, the higher the pressure on the feed water side the higher the permeation of water However, the salt concentration in the water thus produced increases with increasing pressure, as the membrane is unable to retain the salt completely A multistep process has sometimes to be used

The membranes are manufactured from acetylcellulose

or, more preferably, polyamide The technical construction

is complicated and made expensive by the large pressure differences and the need for thin membranes Bundles of

from the ends of the cylinder through plastic sealing layers

Of the (high salt content)-water fed into the cylinder from

the capillaries and the rest is run off as concentrate and disposed of An intensive and expensive pretreatment of the feed water is also necessary: in addition to the removal of all colloidal and biological impurities, treatment of the feed water is also necessary e.g by acid addition The use of feed water from wells in the neighborhood of beaches is particularly favored

Membranes lnostly made of acetylcellulose

or more preferably polyamide Large

pressure differences mean complicated

desalination plant construction (in some

cases multistage) Pretreatment of water

necessary as for distillation plants

I I Wuter 13

inlet tube with

raw wa

inlet

brine outlet

Fig 1.1.3 Schematic lay-out of a RO-module

In water production, reverse osmosis requires less than

(8 to 10.6 kWh for freshwater for a capacity of 19 lo3

m3/d)

Freshwater production by reverse osmosis

~.~~i~!~hly cheaper than flash

References for Chapter 1.1: Water

Water supply in the Federal Republic of Germany:

Statjstisches Jahrbuch der BR Deutschland 1994

Ojentliche Wasserversorung und Ahwasserbeseiti~Sung

1991, 26/Umwelt, 131

Trinkcvnssrr-cc~f~errirlmRsrrc.hnik, Stuttg Ber

Siedlungswasserwirtschaft, 157 - 182

e V (BGW), (Hrsg) 1997 108 Wu.wrJrutisrik

Bundesrepuhlik Deurschlund, Berichtsiuhr 1996,

Wirtschafts- uiid Verlagsgesellschaft Gas und Wasser,

Bonn

qualitat westdeutscher Trinknasserressourcen, VCH

Verlagsgesellschaft, Weinheim

Der Wussrrbedurf'in rler Bimdcsrepublik Deumhlultd his

iuin Jobre 2010 - Studie erstellt im Auftrage des

Umweltbundesamtes, Berlin, 198 1

Flinspach, D 1993 Sfand der

Bundesverband der deutschen Gas- und Wasserwirtschaft

Schleyer, R u Kerndorff, H 1992 Die Grundwnsser-

Reviews:

Ullmann's Encyclopedia of Industrial Chemistry 1996

5 Ed Vol A 28, I - 101, VCH Verlagsgesellschaft,

Weinheini

1998.4 Ed., Vol 25, 361 - 569, John Wiley & Sons,

New York

Kirk-Othmer, Encyclopedia of Chemical Technology

Chemie und Uniwelt, VCI - Waxser (Verhand dei

Cheniischen Industrie, Frankfurt/Main, Hrsg.)

Adsorption:

Sontheimer, H., Crittenden, J C., Summers, R S 1988

Artiv~ited CUVbOJI ,fiw Wuler Treutmc,nt, 2 Ed DVGW- Forschungsstelle, Karlsruhe

Demineralization:

Applebaurn, S B 1968 Deminrrrr/izfitinii !~y I o n

E ~ c h ~ i i g e , Academic Press, New York - London

Flocculation:

Jekel, M., Liefifeld, R 1985 Dic Flockunji in drr

W~/.r.vPrcri/fl,ereifiin,~, DVGW-Schriftenreihe Waaser 42 Filtration:

Degremont 1991, Water Treatinent Handbook, Voh 1 +

2, Lavoisier Publ., Paris

Treatment of Seawater:

Coghlan, A I99 I, Fresh cturer,pont rhr SL'N, New

Scientist 3 1, 37 - 40

Finan M A, et al 1989 &,/jiurd@ E V - IS,wtirs e.rpe-

riencr iti scale control Desalination 73, 341 - 357 Heitmann, H G (Ed.) 1990 Suline Wuter Proc~essinji

VCH Verlagsgesllschaft, Weinheim

14 I Primary Inorganic Materials

Mulder, M 1991 Basic Principles ofMembrune

Technology, Kluwer Academic Publ., Dordrecht

Hydrogen is the most widespread element

in the Universe, but only the ninth most

common element in the Earth’s crust

Further development of hydrogen

technology requires cheap primary energy

Rest of the World 25 I

Only a small part of the hydrogen

produced is marketed, most is directly

utilized by the producer

Desalination of Water:

International Desalination Association 1995

Proceedings, IDA World Congress on Drsalincition und

Water Sciences A h Dhahi, Topsfield, Mass., USA

A Coghlan, A 1991 Fresh Wuterfrom the Sea, New Scientist 3 I , 37 - 40

1.2 Hydrogen

1.2.1 Economic Importance

Hydrogen is by far the most widespread element in the universe, but on Earth (litho-, bio- and atmosphere) it is only the ninth most common element with 1% by weight (or 1.5 atomic 96) Hydrogen is almost exclusively present

as water, hydrates, in the biomass and in fossilized raw materials

chemical raw material and industrial chemical However, particularly since the 1973/74 oil crisis, there has been increasing, if largely speculative, interest in hydrogen as an almost inexhaustible (secondary) energy source (for power and combustion purposes) This instead of, or in addition

to, electricity, due to its high energy density per unit mass (121 kJ/g compared with 50.3 kJ/g for methane), its high environmental compatibility, its being nonpoisonous and the ease of its transport and storage

in certain application up to 10% per year The recorded

m3, although the actual consumption was certainly somewhat higher, since the quantities produced as a byproduct in refineries and used in other sites are not included in these figures

hydrogen was marketed, most of the hydrogen produced, e.g as a byproduct, being directly used by the producer as

in Western Europe Since refineries are increasingly using hydrogen from the plants of third parties rather than from their own hydrogen plants, the proportion of marketed hydrogen should increase in the future