Chemistry of Waste Minimization

Chemistry of Waste Minimization

edited by

J.R. Clark
Professor of Chemistry
The University of York

SPRINGER-SCIENCE+BUSINESS MEDIA, B.V.

First edition 1995
© 1995 Springer Science+Business Media Dordrecht
Originally published by Chapman & HalI in 1995
Softcover reprint ofthe hardcover Ist edition 1995

Typeset in 10/12 Times by Acom Bookwork, Salisbury, Wilts

ISBN 978-94-010-4273-4 ISBN 978-94-011-0623-8 (eBook)

DOI 10.1007/978-94-011-0623-8
Apart rrom any rair dealing for the purposes of research or private study,
or criticism or review, as permitted under the UK Copyright Designs and
Patents Act, 1988, this publication may not be reproduced, stored, or
transmitted, in any form or by any means, without the prior permission in
writing of the publishers, or in the case of reprographic reproduction only
in accordance with the terms of the licences issued by the Copyright
Licensing Agency in the UK, or in accordance with the terms of licences
issued by the appropriate Reproduction Rights Organization outside the
UK. Enquiries conceming reproduction outside the terms stated here
should be sent to the publishers at the Glasgow address printed on this
page.
The publisher makes no representation, express or implied, with regard to
the accuracy of the information contained in this book and cannot accept
any legal responsibility or liability for any errors or omissions that may be
made.
A catalogue record for this book is available from the British Library
Library of Congress Catalog Card Number: 95-76130

t§Printed on acid-free text paper, manufactured in accordance with ANSI/

NISO Z39.48-1992 (Permanence of Paper)
(Cover depicts suspension polymerised styrene-divinylbenzene beads)
Editorial introduction

The chemical industry is one of the most successful and diverse sectors of
manufacturing industry. The explosive growth of the chemical industry in
the 1960s and 1970s has been followed by a period of slower growth
although it still exceeds that of manufacturing industry as a whole by a
factor of 1.5-2. Chemical manufacturing plants have capacities ranging
from a few tonnes per year in the fine chemicals area to 500000 tonnes
per year in the petrochemicals area. The range of chemical products is
enormous and these products make an invaluable contribution to the
quality of our lives. However, these manufacturing processes also lead to
millions of tonnes of waste, and the reduction or elimination of this waste
is now a central issue to the industry, the authorities and the general
public.
New national and trans-national (e.g. European) legislation is likely to
lead to a revolution in the chemical industry. Public pressure and the
work of action groups have played a major role in forcing action from the
authorities on environmental issues. It is clear that governments, local
authorities and many companies now believe in being proactive in envir-
onmental issues rather than simply reactive. The need for companies to
'clean-up their act' should not simply be a result of meeting the require-
ments of more demanding laws; high standards will be a lifeline to profit-
ability in the increasingly competitive global and community markets of
the future. The benefits of an effective and dynamic corporate waste mini-
mization policy as part of a sound environmental programme are not just
to the environment or to the public image of the company, they will
increasingly be to the bottom line.
The drive towards clean technology in the chemical industry with an
increasing emphasis on the reduction of waste at source will require a
level of innovation and new technology that the chemical industry has not
seen in many years. Mature chemical processes, that are often based on
technology developed in the first half of the 20th century, may no longer
be acceptable in these environmentally conscious days. 'Enviro-economics'
will become the driving force for new products and processes. The cost of
running chemical plants more cleanly and safely will be high and will
increasingly make it important to use the best technology-the environ-
mental overhead is already featuring in cost calculations. It has been esti-
mated that expenditure in the 1990s on clean process technology will
exceed £140 billion in the UK alone with the level of spending in the Eur-
vi EDITORIAL INTRODUCTION

opean Union exceeding the current R&D expenditure of the European

chemical industries. This level of expenditure will bring with it unprece-
dented opportunities for the introduction of new technology and for
applied research aimed at developing new and more environmentally
friendly chemical processes. The Chemistry of Waste Minimization covers
many of the most important and most exciting topics in chemistry that are
relevant to clean synthesis, the reduction of waste at source, catalysis, new
techniques and waste treatment. By bringing together leading scientists in
industry, academia and the public sector, the book provides an author-
itative and timely guide to the problems that the industry faces and the
solutions that modern chemistry can offer.
The public image of the chemical industry has badly deteriorated in the
last ten years and this is largely due to concerns over adverse environ-
mental impact. The industry is reacting to this negative perception
through corporate environmental policies and through the introduction of
industry-wide initiatives that seek continuous improvements in all aspects
of health, safety and environmental protection. The introduction of
cleaner processes and the development of new more environmentally
friendly technologies are now encouraged through various national and
trans-national schemes and programmes. These issues of public percep-
tion, environmental programmes and the response of industry, including
the successful introduction of new technology, are discussed in chapter I
which serves as an introduction to all of the topics in this book.
The main objective of the Chemical Industry is to generate profit using
chemical processes to add value to basic raw materials. The additional
costs of 'clean up', forced on the industry by environmental legislation,
are placing severe demands on the profitability of the industry, yet an
effective corporate policy of waste minimization can actually bring con-
siderable financial rewards. In chapter 2, the industrial aspects of waste
minimization are carefully examined. The costs and benefits are analysed
and the entire manufacturing process from laboratory development to
marketing is studied and illustrated through real examples.
The tarnished image of the chemical industry has in part been respon-
sible for increasingly demanding environmental legislation and the devel-
opment and impact of this legislation are the subjects of chapter 3.
Environmental control in the UK, Europe and the USA are critically con-
sidered as is the response of the chemical industry and the likely long term
effects of legislation on its prosperity.
Catalysts played a major role in establishing the economic strength of
the chemical industry in the first half of the 20th century and the environ-
mental revolution in the industry will place new demands on catalysis and
catalytic processes. Remarkably, while it has been estimated that some
90% of the important new chemical processes introduced in the last 50
years depend on catalysis, the market growth potential for catalysis is still
 EDITORIAL INTRODUCTION vii

considerable. Chapters 4-6 address some of the most significant recent

developments in catalysis that will have an impact on inefficient chemical
processes, notably those in the fine and speciality chemical industries
where catalysis has traditionally played a relatively minor role. Some of
the major goals of waste minimization are to increase process selectivity,
to enable easy and efficient recovery of reagents and catalysts and to
replace stoichiometric processes with catalytic ones. The use of inorganic
solids as catalysts or supports for other reagents can go a long way to
achieving all of these goals and these topics are discussed via a range of
examples in chapter 4. The problem of bringing together substances of
markedly different polarities has been a continual challenge to chemists
and methods based on the use of toxic or reactive solvents are becoming
increasingly unacceptable. Phase transfer catalysis is a well established
technique for overcoming this problem and is likely to find increasing
application in cleaner processes. This is the subject of chapter 5 which
also includes further consideration of the important possibility of immobi-
lizing the catalysts so as to enhance their value in clean synthesis. Organic
polymers are important and versatile alternatives to inorganic materials as
catalyst supports and their value in synthesis goes back to the pioneering
work of Merrifield. Chapter 6 provides a detailed description of the design
and application of polymers and polymer supported reagents with the
emphasis on recent and strategically important developments in the
context of waste reduction at source. The great importance of catalysis to
waste minimization is further illustrated through its inclusion in later
chapters on clean synthesis.
While most drug substances derived from natural sources are single
enantiomer compounds, the majority of chiral drugs produced by syn-
thetic means are racemates. The trend, however, is rapidly changing to
enantiopurity largely as a result of increasingly demanding legislation
which, while not necessarily prohibiting racemic drugs, requires detailed
pharmacodynamic and pharmacokinetic information on all isomers. The
highly important subject of the industrial synthesis of optically active
compounds is the subject of chapter 7. This covers environmental aspects,
the chirality pool, resolution and catalytic asymmetric synthesis.
One of the most topical of all environmental issues is the use of chloro-
fluorocarbons. Here the goal is the minimization of chlorine and bromine
originating from CFCs and perhalogenocarbons containing bromide. The
remarkable level of public interest in this subject has resulted in the extre-
mely rapid development of 'drop-in' replacements with a resulting lag in
the fundamental principles of the associated chemistry. Understanding
and identifying areas of ignorance are major concerns and are addressed
in chapter 8 which also places emphasis on new catalytic methods of
synthesis.
The chemical industry is still largely using processes which originated
viii EDITORIAL INTRODUCTION

before effluent considerations formed an integral part of process design

and selection. Hence, there is currently much activity in dealing with end-
of-pine problems so as to meet the more stringent environmental stan-
dards necessary for existing processes to continue to operate. Hydrogen
peroxide is a particularly important chemical in the context of waste treat-
ment and its chemistry and use in effluent treatment are discussed in
chapter 9. New chemical plants will increasingly be based on an integrated
design approach where prevention of waste will be the guiding principle.
In the context of oxidation processes which are so important to many
sectors of the chemical industry, hydrogen peroxide will also find an
increasing role at the process end, largely because the only inorganic side-
product is water. The use of hydrogen peroxide in organic synthesis is also
described in this chapter as are other important applications including
product purification.
While the increased use of catalytic methods, the use of more envir-
onmentally friendly reagents and more careful consideration of process
routes will all play important roles in waste minimization, it is also likely
that the environmental revolution will demand better use of alternative
techniques in the process. Sonochemistry and electrochemistry have much
to offer in this context and are the subjects of chapters lO and 11, respec-
tively. Sonochemistry has moved a long way from its beginnings in the
1940s and is now a major new technology for many applications. Here its
applications in the context of waste minimization are considered including
its use in chemical synthesis, environmental protection and waste control,
sonoelectrochemistry and the scale up of sonochemical systems. Electro-
chemistry is an established technology with many important applications.
There are also rapidly developing roles for electrochemistry in effluent
treatment and in recycling as well as some exciting possibilities for elec-
trochemical synthesis, and these applications for waste minimization are
considered here.
The importance of solvents in batch processes for the manufacture of
many fine chemicals, chemical intermediates and other high-value pro-
ducts cannot be overestimated. These processes normally run in solvents
and often involve solvents in the work-up and separation stages. Since
solvents are often the major components in such processes, they are also
likely to be the major source of waste. Controls on the release of volatile
organic compounds, restrictions on the use of chlorinated and some other
solvents, and the growing concerns over the use of dipolar aprotic solvents
make the solvent issue of vital importance to many chemical companies in
the industrial world. The nature of solvent effects, the parameters that are
used to describe solvent power, and the role of solvents in chemical reac-
tions are discussed in chapter 12 along with a consideration of some alter-
natives to the more commonly used solvents.
Despite the shift in emphasis in pollution control from end-of-pipe
 EDITORIAL INTRODUCTION IX

technology to the reduction of waste at source, no one will pretend that

we can expect to achieve zero waste in chemical processes. We must there-
fore continue to address the problems of dealing with chemical waste.
Rather than seek methods for the safe disposal of waste, recycling the
waste is a more attractive option and a popular view is that we should
expect most if not all chemical products to have more than one useful life
even if the second life is only as a fuel. The great benefits that the
'polymer age' has given us has also, however, resulted in a polymer waste
mountain of enormous proportions that probably represents the greatest
challenge for recycling. The problems of polymer waste, the methods of
polymer recycling, and the interesting opportunities available through the
use of biodegradable polymers are discussed in chapter 13.
Chemical waste containing a mixture of inorganic and organic compo-
nents is particularly difficult to deal with and the presence of toxic metal
ions makes the problem greater. These difficulties and the various
methods, old and new, that can be used to clean up metal-contaminated
waste including the exciting new possibilities offered by biological treat-
ment, are described in chapter 14.
Even after employing methods to selectively remove especially toxic
species from chemical waste, we will continue to have to dispose of quan-
tities of chemical waste. While many types of waste can be dealt with by
incineration, often on site, some types of waste will demand chemical
treatment to render them safe. Oxidation is very important in this context
and apart for hydrogen peroxide and wet air, the use of supercritical
water offers some exciting possibilities for the total oxidation of chemical
waste. Chapter 15 deals with this powerful technique including a discus-
sion of the remarkable properties of supercritical liquids as well as con-
sideration of engineering aspects of the technology such as corrosion and
plant design.
There are many exciting benefits available to companies who have a
more proactive policy towards environmental legislation. These include
the development of more environmentally friendly products and processes
that are likely to win new customers and which may even be imposed
upon competitor companies through 'best available technique' legislation.
In chapter 16, the many and exciting opportunities for the new envir-
onmentally friendly catalytic processes described earlier are illustrated
through a description of new solid catalysts that are being used to replace
toxic and corrosive reagents currently used in commercial oxidation,
Friedel-Crafts and other acid-catalysed reactions.
Future generations are likely to view the 1990s as a watershed in the
chemical industry. Change is being forced upon the industry by increas-
ingly tight environmental legislation encouraged by a hostile public per-
ception. This tarnished image can only be improved by a positive, visible
and dynamic policy towards waste minimization coupled with greater
x EDITORIAL INTRODUCTION

efforts by the authorities, industry, scientists and educationalists to

improve the public understanding of science. With the great challenges
ahead there are also great opportunities and the clean technology revolu-
tion will provide considerable scope for chemists and chemical engineers
to develop and apply new processes and products. Innovation was at the
heart of the development of the chemical industry in the early 20th
century, and, on the eve of the 21st century, we can see that innovation
will again prove vital in the next phase of development of the industry.
In conclusion, I would like to thank all of the contributors to this book
for accepting their tasks cheerfully and for completing their assignments
so effectively.

James Clark
York, March 1995
Contributors

B.M. Adger Chiroscience, 283 Cambridge Science Park, Milton

Road, Cambridge CB4 4WE, UK
J.H. Atherton Zeneca Fine Chemicals Manufacturing Organisation,
Process Studies Group, Leeds Road, Huddersfield
HD2 IFF, UK
S.J. Barlow Contract Chemicals Ltd., Penrhyn Road, Knowsley
Industrial Park South, Merseyside L34 9HY, UK
M.J. Braithwaite Industry Consultant, 12 Heath Gardens, Manor
Heath Road, Halifax, West Yorkshire HX3 OBD,
UK
A.J. Butterworth The University of York, Department of Chemistry,
Heslington, York YOI 5DD, UK
J.H. Clark The University of York, Department of Chemistry,
Heslington, York YOI 5DD, UK
A.A. Clifford The University of Leeds, Department of Chemistry,
Leeds LS2 9JT, UK
C.V. Fry University of Wales, Swansea, Department of Chem-
istry, Singleton Park, Swansea SA2 8PP, UK
I.K. Jones Zeneca Fine Chemicals Manufacturing Organisation,
Process Studies Group, Leeds Road, Huddersfield
HD2 IFF, UK
P.J. Kinley Contract Chemicals Ltd., Penrhyn Road, Knowsley
Industrial Park, Prescot, Merseyside L34 9HY, UK
T.E. Lester Deft Technology and Design, 11 Nightingale Road,
Hampton, Middlesex TWl2 3HU, UK
(formerly of BP International)
T.J. Mason University of Coventry, School of Natural and
Environmental Sciences, Coventry CVl 5FB, UK
S.S. Phull University of Coventry, School of Natural and
Environmental Sciences, Coventry CVl 5FB, UK
XII CONTRIBUTORS

M.J. Ramsden The University of York, Department of Chemistry,

Heslington, York YOI 5DD, UK
W.R. Sanderson Solvay Interox Research and Development, PO Box
51, Widnes WAS OFE, UK
K. Scott University of Newcastle upon Tyne, Department of
Chemical and Process Engineering, Newcastle upon
Tyne NEI 7RU, UK
D.C. Sherrington University of Strathc1yde, Department of Pure
& Applied Chemistry, Thomas Graham Building,
295 Cathedral Street, Glasgow G 1 lXL, UK
K. Smith University of Wales, Swansea, Department of Chem-
istry, Singleton Park, Swansea SA2 8PP, UK
S.J. Tavener The University of York, Department of Chemistry,
Heslington, York YOI 5DD, UK
M. Tzimas University of Wales, Swansea, Department of Chem-
istry, Singleton Park, Swansea SA2 8PP, UK
P.H. Walton The University of York, Department of Chemistry,
Heslington, York YOI 5DD, UK
G. Webb University of Glasgow, Department of Chemistry,
Glasgow G12 8QQ, UK
J.M. Winfield University of Glasgow, Department of Chemistry,
Glasgow G 12 8QQ, UK
Contents

1 Introduction 1
T. LESTER

1.1 Public image of the industry I

1.2 Waste minimisation 3
1.3 Sources of waste 6
1.3.1 Stoichiometric reactions - wastes to byproducts 6
1.3.2 Secondary side reactions 8
1.3.3 Further reactions 9
1.4 Commodity vs. fine chemical manufacture II
1.5 Cleaner process initiatives \3
References 15

2 Waste minimisation - the industrial approach 17

M. BRAITHWAITE

2.1 The industrial process 17

2.1.1 Introduction 17
2.1.2 Raw materials and waste minimisation 17
2.1.3 General factors relating to waste generation in the chemical
industry 18
2.1.4 Summary 22
2.2 Waste minimisation - the cost/benefit ratio 22
2.2.1 Costs 23
2.2.2 Benefits of waste minimisation 25
2.2.3 Financial impacts of waste minimisation 25
2.3 The process 27
2.3.1 Process flow diagrams 28
2.3.2 The role of the process development chemist 30
2.3.3 Catalysts as auxiliary reagents 34
2.3.4 Batch vs. continuous processes 41
2.3.5 Recovery and recycle/reuse of solvents and byproducts 45
2.3.6 End-of-pipe recycling vs. cleaner process technology 48
2.3.7 Good housekeeping 51
2.3.8 Industrial examples 54
2.4 Developing products to help others minimise waste 57
2.4.1 The role of marketing 57
2.4.2 Effect chemicals for cleaner technology 59
2.5 Conclusions 63
References 64

3 The development and impact of environmental legislation on the

chemical industry 66
PJ. KINLEY

3.1 Introduction 66
3.2 The development of environmental legislation 66
XIV CONTENTS

3.2.1 An overview of UK legislation 67

3.2.2 European regulatory control 69
3.2.3 US environmental control 71
3.3 The chemical industry's response ~ change due to market forces or
regulatory pressure? 74
3.4 Future developments ~ can the industry progress? 82
3.5 Conclusions 83
Bibliography 85

4 The use of solid supports and supported reagents in liquid phase

organic reactions 86
K. SMITH, c.y. FRY and M. TZIMAS

4.1 Introduction 86
4.2 Electrophilic aromatic substitution 89
4.2.1 Chlorination 89
4.2.2 Bromination 89
4.2.3 Nitration 90
4.2.4 Sulfonylation 91
4.2.5 Alkylation 91
4.2.6 Acylation 92
4.2.7 Fischer~Indole synthesis 92
4.3 Reactions on nitrogen 93
4.3.1 Alkylation 93
4.3.2 Acylation 93
4.3.3 Arylation 93
4.4 Reactions on oxygen 94
4.4.1 Ester formation 94
4.4.2 Acetal formation 94
4.4.3 Ring opening of epoxides 95
4.5 Eliminations 96
4.6 Aldol condensations 97
4.7 Isomerisations and rearrangements 97
4.8 Reduction reactions 99
4.8.1 Reduction of compounds containing double bonds 99
4.8.2 Reduction of epoxides 100
4.8.3 Mimicking a naturally occurring reducing agent 101
4.9 Oxidation reactions 101
4.9.1 Oxidation of alcohols 101
4.9.2 Oxidation of alkanes, alkenes and alkyl groups 103
4.9.3 Oxidation of carbonyl compounds 104
4.9.4 Porphyrin catalysts in oxidation reactions 104
4.10 Addition reactions 105
4.10.1 Addition of water or alcohols to alkenes 105
4.10.2 Addition of hydrogen halides to alkenes 105
4.10.3 Addition of halogens to alkenes 106
4.10.4 Michael additions 106
4.10.5 Additions to silyl ketene acetals 106
4.10.6 Additions of thiols 107
4.11 Cycloaddition reactions 108
4.11.1 Diels~Alder reactions 108
4.11.2 Other cycloadditions 109
4.12 Miscellaneous 109
4.12.1 Allylic chlorination 109
4.12.2 Fluorination 110
4.12.3 Thioacetalisation 110
4.12.4 Acetaldehyde trimerisation 110
 CONTENTS xv

4.12.5 Benzodioxepination 111

4.12.6 Addition-cyclisation 111
4.13 Conclusion 111
References 112

5 Phase transfer catalysis 116

S.J. TAVENER and J.H. CLARK
5.1 Introduction 116
5.2 What is a phase transfer catalyst? 116
5.3 What can phase transfer catalysis do for you? 117
5.4 How phase transfer catalysis works 118
5.5 Types of phase transfer reactions 119
5.5.1 Anion displacement reactions 119
5.5.2 Phase transfer under alkaline conditions 120
5.5.3 Aromatic fluorinations 123
5.5.4 Oxyhalogenation of aromatic molecules 123
5.5.5 Cationic reactions under phase transfer catalysis 125
5.5.6 Triphase catalysis 125
5.6 The rates of phase transfer reactions 128
5.6.1 The catalyst 128
5.6.2 The effect of anions 13l
5.6.3 The concentration of the catalyst 132
5.6.4 The organic solvent 133
5.6.5 The role of water 134
5.7 Phase transfer catalysis and large molecules 135
5.7.1 Polymer preparation by phase transfer 135
5.7.2 Rotaxanes 137
5.7.3 Dendrimers as phase transfer catalysts 137
5.8 Concluding remarks 138
References 138

6 Polymer-supported synthesis 141

D.C. SHERRINGTON
6.1 Introduction 141
6.1.1 Earlier review literature 142
6.1.2 Polymer supports, scope, 'pros and cons' 143
6.2 Synthesis and structure of polymer supports 147
6.2.1 Physical characteristics of supports 150
6.2.2 Introduction of reactive groups 154
6.2.3 Thermo-oxidatively stable polymer supports 157
6.3 Use of polymer-supported species in synthesis 164
6.3.1 Polymeric reagents 164
6.3.2 Polymeric protecting groups 166
6.3.3 Polymer-supported catalysts 170
6.4 Novel formats for polymer supports 193
6.5 Conclusion 195
Acknowledgements 196
References 196

7 Industrial synthesis of optically active compounds 201

B.M.ADGER
7.1 Introduction 201
7.2 Chirality and biological activity 201
XVI CONTENTS

7.3 Methods for obtaining optically active compounds 204

7.3.1 The chirality pool 205
7.3.2 Resolution of racemates 206
7.3.3 From prochiral substrates 206
7.4 Environmental aspects 206
7.5 Methodology 207
7.5.1 Microbial synthesis 207
7.5.2 The chirality pool 209
7.5.3 Resolution by preferential crystallisation 213
7.5.4 Diastereomer resolution 214
7.5.5 Kinetic enzyme resolution 215
7.5.6 Catalytic asymmetric synthesis 217
7.6 Conclusions 219
References 220

8 CFC alternatives and new catalytic methods of synthesis 222

G. WEBB and I.M. WINFIELD
8.1 Introduction 222
8.2 An historical perspective 222
8.3 Current CFC and Halon alternatives 224
8.4 Heterogeneous catalytic routes to HFCs and HCFCs 225
8.4.1 General considerations 225
8.4.2 The heterogeneous catalytic fluorinations HCFC-133a .....
HFC-134a and HCFC-123a ..... HFC-125 227
8.4.3 Heterogeneous catalytic halogen exchange involving
chlorofluoroethanes 229
8.4.4 Hydrogenolysis of CF 3CChF and related compounds 231
8.4.5 Catalytic fluorination of CCl4 and dismutation of C, HFCs
under heterogeneous conditions 233
8.4.6 Supported organic layer catalysts for room temperature
catalytic fluorination 234
8.5 Homogeneous catalytic fluorination 236
8.6 Catalytic decomposition of CFCs 238
8.7 Some properties of fluorination catalysts 239
8.8 Conclusions and possible future developments 243
Acknowledgements 243
References 243

9 Hydrogen peroxide in clean processes 247

W.R. SANDERSON

9.1 Introduction 247

9.2 Background and technology 247
9.2.1 The role of hydrogen peroxide 247
9.2.2 Relevant issues in industrial processes 249
9.2.3 Recent developments 249
9.3 Basic chemistry 251
9.3.1 Neutral hydrogen peroxide 252
9.3.2 Active oxygen species 253
9.3.3 Peroxygen intermediates 255
9.3.4 Inorganic oxidant systems 259
9.3.5 Peroxide stabilisation 264
9.4 Safety principles 265
9.4.1 Potential energy (condensed phase hazards) 266
9.4.2 Oxygen release (vapour phase hazards) 267
9.4.3 Hazardous by-products (formation hazards) 268
 CONTENTS xvii

9.4.4 Peroxide residuals (concentration hazards) 268

9.5 Chemical industry applications 269
9.5.1 In-process uses of peroxygens 269
9.5.2 Effluent treatment with peroxygens 298
9.6 Other industries 304
9.6.1 Pulp and paper 304
9.6.2 Hydrometallurgy and metal finishing 308
Acknowledgements 315
References 315

10 Sonochemistry in waste minimisation 328

TJ. MASON and S.S. PHULL

10.1 Introduction 328

10.1.1 Sonochemistry 328
10.1.2 Power ultrasound 329
10.2 Sonochemistry in chemical synthesis 333
10.2.1 Acceleration of reaction rates and enhancement in product yields 334
10.2.2 Simplification of procedure and the amelioration of conditions 337
10.2.3 Activation of catalysts 340
10.2.4 Modification of reaction pathway 343
10.3 Sonoelectrochemistry 344
10.3.1 Ultrasound in electroplating 344
10.3.2 Ultrasound in electrochemistry 345
10.4 Ultrasound in environmental protection and waste control 347
10.4.1 Wastewater treatment 347
10.4.2 Sonochemistry in the recycling of polymers 351
10.4.3 Sonochemically enhanced extraction 351
10.5 Large scale sonochemistry 352
10.5.1 Batch treatment 352
10.5.2 Flow systems 353
10.6 Conclusions 356
References 358

11 Electrochemical aspects of chemical waste minimisation 360

K. SCOTT

11.1 The scope of electrochemical waste minimisation 360

11.2 Electrochemistry of waste minimisation 361
11.2.1 Electrode potential and multiple reactions 363
11.2.2 Influence of the counter electrode reaction 364
11.3 Recovery and recycling of metal ions 365
11.3.1 Applications of electrodeposition 366
11.3.2 Combined electrochemical processes 373
11.3.3 Integration of electrodeposition with other separations 374
11.3.4 Electrochemical ion exchange 376
11.3.5 Cementation 378
11.4 Electrochemical treatment of inorganic compounds and gaseous effluents 378
11.4.1 Cyanides and thiocyanates 378
11.4.2 Treatment of chromium liquors 380
11.4.3 Other waste treatment applications 381
11.4.4 Electrochemical treatment of gases 382
11.5 Treatment of process and effluent streams containing organic compounds 389
11.5.1 Direct anodic oxidation 389
11.5.2 Indirect oxidation processes 391
11.5.3 Chloride and chlorinated compounds 393
XVlll CONTENTS

11.5.4 Sterilisation of water and waste 394

11.5.5 Photoelectrochemical oxidation 396
11.5.6 Electroflotation 397
11.5.7 Electrosorption 397
11.6 Electrochemical membrane processes 397
11.6.1 Electrodialysis cells 398
11.6.2 Applications of electrodialysis 399
11.6.3 Electrohydrolysis 400
11.6.4 Bipolar membranes 402
11.7 Waste minimisation and electrochemical synthesis 406
11.7.1 Metal salt preparation 407
11.7.2 Electrochemical generation of arsine 408
11.7.3 Solution based synthesis 408
References 413

12 Solvent selection 417

J.H. ATHERTON and I.K. JONES

12.1 Introduction 417

12.2 Solvent effects on reaction rates - the transition state approach 417
12.3 Solvent parameters 419
12.3.1 Dielectric constant 420
12.3.2 Hildebrand solubility parameter 420
12.3.3 Donor number 420
12.3.4 Acceptor number 421
12.3.5 Solvatochromic parameters 422
12.4 Solvation of inorganic ions 422
12.5 Solvent effects on reaction rate 424
12.6 Solvent effects on regioselectivity 428
12.7 Two-phase reaction systems 429
12.7.1 Extractive reaction 429
12.7.2 Phase-transfer catalysis 432
12.7.3 Catalytic two-phase reactions 432
12.8 Inorganic solvents 434
12.8.1 Sulphuric acid 434
12.8.2 Liquid sulphur dioxide 434
12.8.3 Hydrogen fluoride 435
12.8.4 Carbon dioxide 436
12.8.5 Liquid ammonia 436
12.9 Solvent recovery 437
12.10 Conclusions 438
References 438
General bibliography 440

13 Polymer recycling 441

MJ. RAMSDEN

13.1 Introduction and background 441

13.2 Technologies available 443
13.3 Tertiary recycling 445
13.4 Secondary recycling 446
13.4.1 The chemistry in thermal reprocessing 447
13.4.2 Thermally reprocessed product quality 451
13.5 Primary recycling 452
13.5.1 Pyrolysis 452
13.5.2 Hydrogenation 454
 CONTENTS xix

13.5.3 Chemolysis 454

13.6 Reuse 454
13.7 Energy recovery 455
13.7.1 Incineration 455
13.7.2 Gasification 456
13.8 Degradable polymers 456
13.8.1 Biodegradable polymers 457
13.8.2 Photodegradable polymers 458
13.9 Summary 459
Abbreviations 460
References 460

14 Methods of metal capture from effiuent 462

P.H. WALTON

14.1 Metals in industry: an environmental hazard 462

14.2 Metal toxicities 462
14.3 Legislation 463
14.4 Industries at risk 464
14.5 Natural occurrence of metals 465
14.6 Chemistry of metals 466
14.6.1 Oxidation state 467
14.6.2 pH 467
14.6.3 Organic complexing agents 469
14.6.4 Solvent 469
14.7 Clean-up techniques 470
14.7.1 Precipitation 470
14.7.2 Ion-exchange 474
14.7.3 Electrochemical methods 482
14.7.4 Biological methods 489
14.7.5 Solvent extraction 495
14.7.6 Reverse osmosis (ultrafiltration) 497
14.8 Conclusions 500
List of abbreviations 501
References 502

15 Chemical destruction using supercritical water 504

A.A. CLIFFORD

15.1 Introduction 504

15.2 Supercritical fluids 505
15.3 Properties of supercritica1 water 508
15.4 Reactions in supercritical water 514
15.5 Supercritical water oxidation and other destructive processes 516
15.6 Wet air oxidation 519
15.7 Corrosion problems 519
References 520

16 The use of catalysis for the manufacture of fine chemicals and

chemical intermediates 522
AJ. BUTTERWORTH, SJ. TAVENER and S.J. BARLOW

16.1 Introduction 522

16.2 Catalysis in the chemical industry 523
16.3 The preparation of fine chemicals via enzyme catalysis 523
xx CONTENTS

16.4 General acid catalysis 525

16.4.1 Zeolites 526
16.4.2 Envirocat EPIC: a versatile solid acid 529
16.5 Friedel-Crafts catalysis 531
16.5.1 Friedel-Crafts benzoylations 534
16.5.2 Friedel-Crafts sulfonylations 536
16.5.3 Friedel-Crafts benzylations 537
16.6 Oxidation of organic substrates 538
16.7 Summary and concluding remarks 541
References 542

Index 545