T. v. Arden D.SC., PH.D., F.R.I.C., C.eng., M.I.M.M., P.a.I.W.E. (Auth.) - Water Purification by Ion Exchange-Springer US (1995)

WATER PURIFICATION BY ION EXCHANGE
Fronlispiece. Polystyrene sulphonic acid calion exchange bead (Magnijicalion 10 x, reduced

5/9ths on reproduction)
WATER PURIFICATION
BY ION EXCHANGE
T. V. ARDEN, D.Se., Ph.D., F.R.I.C., C.Eng.,

M.I.M.M., P.A.I.W.E.
Chcmical Director, The Permutit Company Ltd.
NEW YORK
PLENUM PRESS
LONDON
BUTTERWORTHS
Published in the U.S.A. by
PLENUM PRESS
a division of
PLENUM PUBLISHING CORPORATION
227 West 17th Street, New York, N.Y. 10011
First published by
Butterworth and Co. (Publishers) Ltd.
ISBN 978-1-4684-9038-1 ISBN 978-1-4684-9036-7 (eBook)

DOT 10.1007/978-1-4684-9036-7
©
Butterworth and Co. (Publishers) Ltd.
1968
Softcover reprint of the hardcover 1st edition 1968
Suggested U.D.C. No. 541.183.12:628.16

Suggested additional No. 661.183.12
Libra~y qfCongress Catalogue Card Number 68-54310
CONTENTS
PREFACE VII
1. INDUSTRIAL W ATERS
Hard Water . Soft Water . Units . Typical Waters and Their
Uses' Laundering, Wool Scouring, Bottle Washing, etc .. Chemi-
cal Pracessing, Metal finishing, etc .. Boiler Feed Water.
2. THE ION EXCHANGE PROCESS 13

Intraduction . The Development of Ion Exchange Resins.
3. EQlJILIBRIA AND KINETICS, AS APPLIED TO

WATER TREATMENT 26
General Cation Exchange' Hydragen Ion Exchange, Sulphonic
Resin· Hydrogen Ion Exchange, Carboxylic Resins . General
Anion Exchange' Hydroxide Ion Exchange, Strang Base Resins
. Acid Absorption, \Veak Base Resins . Kinetics.
4. UNIT WATER TREATMENT PROCESSES 49

Water Softening by Sodium Exchange· Alkalinity Removal with
Carboxylic Resins . Sulphonic Resins . Hydrogen Ion Exchange
. Acid Absorption by Weak Base Resins . Acid Absorption by
Strang Base Resins . Mixed Beds
5. COMBINATION PROCESSES 80
1. Weak Acid Cation. Sodium Exchange Cation. Degas
(WAC-Na-DG)
2. Strong Acid Cation. Weak Base Anion. Degas (SAC-WBA-DG)
3. Strong Acid Cation. Degas. Strong Base Anion (SAC-DG-SBA)
4. Strong Acid Cation. Weak Base Anion. Degas. Mixed Bed
(SAC-WBA-DG-MB)
5. Strang Acid Cation. Degas. Strang Base Anion Mixed Bed
(SAC-DG-SBA-MB)
6. Weak Acid Cation. Degas. Mixed Bed (WAC-DG-MB)
7. Weak Acid Cation. Strang Acid Cation. Degas. Anion. Mixed
Bed (WAC-SAC-Degas-(WBA)-MB)
(SBA2)
(SBAI)
8. Strang Acid Cation. Weak Base Anion. Mixed bed. Mixed Bed
(SAC-WBA-MB-MB)
9. Strong Acid Cation. Degas. Weak Base Anion. Strang Base
Anion (SAC-DG-WBA-SBA)
v
CONTENTS
6. ORGANIC POISONING OF ANION EXCHANGE

RES INS 90
The Problem' Organic Matter in Water . Poisoning of Resins
. Cleaning Poisoned Resins . The Effect of Resin Structure . Non-
poisoning Resins . The Protection of Mixed Beds . Prevention of
Poisoning, Summary
7. EQUIPMENT AND SPECIAL PROCESSES 113

Standard Resin Columns . Counterftow Units . Continuous Ion
Exchange . Advantages of Continuous Ion Exchange . Special
Problems of Continuous Ion Exchange . Types of Continuous
Plant . Condensate Polishing for High Pressure Boilers . Brackish
Water Desalination by Ion Exchange· Electrodialysis
8. INDUSTRIAL APPLICATIONS 150

The Treatment of Water-Soluble Organic Compounds . Recovery
of Water and By-products from Industrial Wastes . Chromium
Plating, Recovery of Water . Anodizing, Recovery of Water and
Chromic Acid· Gold Plating, Recovery of Gold· Photographic
Solutions, Recovery of Silver . Reactivition of Metal Finishing
Solutions . Recovery of Metals by Complex Anion Formation .
Elution Chromatography . Ion Exchange as a Manufacturing
Process . Liquid Liquid Ion Exchange
INDEX 181
VI
PREFACE
This book is an attempt to fill a gap in the existing literature on
ion exchange. The many excellent works already available are of
three main types, general introductions to the subject, specialist
discussions of analytical and laboratory techniques, and advanced
theoretical treatises. In practice, in spite of the vast number of
processes which have been developed for la bora tory use, 99 per
cent of all ion exchange resins produced in the world are used in
water treatment, or closely allied applications. This book is intended
as a general survey of the principles governing the practical uses of
ion exchange resins, for the benefit of students encountering the
subject for the first time, and for the chemists and engineers in
many branches of industry whose work brings them into contact
with water treatment, but who do not have the time to study more
advanced volumes of basic theory. The background presented has
been simplified to the maximum extent found possible without
falsification, and an attempt has been made to relate each aspect
of theory to its practical consequences in full scale water treatment.
Mathematical methods have been avoided and pictorial or graphical
presentation methods used wherever possible. As the book is
concerned with general principles, rather than details of any
particular research work, references to original papers and patents
have been omitted except in the cases of special processes, which
have a single clearly defined origin. The bibliography, included at
the end, consists of books and review papers covering the various
sections of this book, and giving the detailed original references
which may be useful at a later stage of study.
The practice, adopted in several earlier works, of including
tables of equivalent resins produced by different manufacturers,
has not been followed. The total number of resins now available
is so large that a comprehensive table would be a massive item.
Moreover, as knowledge in the field has increased in recent years,
differences between individual resins previously classified as
equivalent to each other have become increasingly important.
Whenever a type of resin is described, a few examples are given
of individual resins commonly used in Great Britain, but the lists
are not intended to be comprehensive. Moreover, even in these
cases, it must be emphasized that the classification is purely the
result of my own studies of the res ins concerned. The manufacturers
VlJ
PREFACE
of ion exchange resins rarely publish their exact structures, or

manufacturing methods, and the attribution of structures to named
resins should be considered, not as statements of fact, but as per-
sonal deductions from the analysis and general properties of the
materials mentioned.
The tables and graphs of operating results are quoted, with
thanks, from the records of The Permutit Company Limited. They
apply in principle to all other resins in the same general categories,
but should not be taken to apply quantitatively to any one. Readers
requiring the detailed operating characteristics of individual ion
exchange resins can obtain the figures from the information sheets
issued by all the major manufacturers; and it is hoped that a
knowledge of the general principles set out here will facilitate
understanding and comparison of the manufacturers' literature.
Certain conventions of the water treatment industry have been
followed. The hydrogen ion is written as H+, hydration being
ignored. The terms 'silica', or 'SiOz' are used, in the absence of
any more accurate general words, to refer to the various silicon-
containing anions present in water. The word 'absorb' and its
derivatives are given their most generally understood meaning,
that of uptake by permeation. No particular thermodynamic
mechanism is implied.
Grateful thanks are due to Dr. T. R. E. Kressman, Mr. J. Pilot
and Mr. B. A. Sard, whose comments on the original typescript
induced a proper sense of humility, and helped to eliminate the
more glaring errors.
V11l
CHAPTER 1
INDUSTRIAL WATERS
The water used by industry for boiler feed or process purposes may
be taken from public supplies, or abstracted directly from wells,
lakes or rivers. In Great Britain, town mains water will have been
treated to render it largely clear and colourless, free from odour,
and bacteriologically sterile. I t is thus directly suitable for many
industrial purposes such as cooling, and in cases where ion exchange
treatment is used, town mains water can normally be fed directly
into the columns. Many large industrial users abstract water from
natural sources for their own use. Where these are deep wells, the
water is normally clear, colourless, and directly treatable by ion
exchange; but in cases where water is taken directly from rivers or
lakes, clarification by the classical methods of coagulation and
filtration is normally necessary. These techniques are fully described
elsewhere, and for the purposes of this book, the starting point of all
industrial ion exchange processes is a supply of clear water, free
from suspended and colloidal matter.
HARD WATER
The range of minerals contained in most natural waters is quite
limited. The cations present are normally calcium, magnesium
and sodium, while the anions are mainly chloride, sulphate and
bicarbonate, with lower concentrations of nitrate, phosphate and
silica. There are also traces of organic matter. For the majority
of natural waters, analysis of the ions mentioned above will give
the total dissolved so lids in the water. Waters occurring in regions
of unusual rock formation may differ considerably from this pattern,
but the principles which are to be discussed apply equally to waters
of unusual composition.
I t is customary to refer to waters as 'hard' or 'soft'. The former
are waters containing appreciable concentrations (over 50 p. p.m.)
of calcium and magnesium, which in Great Britain have normally
been derived from the leaching of limestone or dolomitic rocks,
by water containing free carbon dioxide. Significant concentrations
of bicarbonate are therefore also present. Calcium may be derived
INDUSTRIAL WATERS
from other types of rock, for example gypsum, CaS04.2H20, in

which case the principle ions present will be calcium and sulphate.
1t is a common convention in the water treatment industry to
refer to ions in solution in terms of certain hypothetical combina-
tions. Thus calcium, magnesium and bicarbonate ions, when present
together in solution, are grouped under the term 'temporary
hardness', because on heating, all are substantially removed by
precipitation of the corresponding insoluble carbonates, with loss
of carbon dioxide into the atmosphere. Calcium and magnesium
co-existing with sulphate or chloride are known as 'permanent
hardness', since the solutions are stable to heat at normal pressure.
These imaginary combinations have no real significance, but the
two terms are convenient forms of abbreviation, and will be used in
this book in places where they cannot give rise to misunderstanding.
SOFT WATER
While the meaning of hardness is gene rally understood, the term
'soft water' is often subject to confusion. Soft waters are those which
contain less than about 20 p.p.m. Ca2 + and M g2+, and in many
areas of Great Britain, such as the hilly regions of Wales and
Scotland, these soft waters have very low total dissolved solids:
indeed, the total of all ions may be below 50 p.p.m. As a result, it
is not uncommon to find among non-technical water users in
industry, a belief that all soft waters, including those artificially
softened, have a low mineral content. The misconception that ion
exchange softening gives results equivalent to those of distillation
is still not unknown; and it is a fairly common experience for a water
treatment contractor to be asked to supply a softener, when abrief
study of the proposed use of the water shows that complete de-
mineralizing, that is, removal of aH dissolved salts, is required.
A water may, therefore, be soft, while still containing consider-
able concentrations of dissolved salts. WeH waters in low-lying
areas near to the sea are often of this type, owing to ingress of sea-
water through porous rock. Waters containing a preponderance
of sodium bicarbonate are also not uncommon in some countries.
EquaHy, a water containing low total solids consisting largely of
calcium salts, which is soft by ordinary standards, will be hard from
the point of view of ion exchange reactions, since the cation resin
on exhaustion will be almost fuHy loaded with calcium. For the
purpose of this book, the concept of hardness will be separated from
that of total mineral content. The terms 'hard' and 'soft' will be
used to indicate the presence or absence of calcium and magnesium
2
UNITS
ions. Where a broad indication of total dissolved solids is required,

the convenient expressions 'thin' and 'thick' waters will be used to
indicate values ofless than 100 p.p.m. and greater than 300 p.p.m.,
respectively.
UNITS
The water treatment industry in the Anglo-Saxon countries is
bedevilled by the most complex and illogical set of units ever
devised by the wit of man. The European measures both the water
and the ion exchange resin in litres, or cubic metres. He then quotes
the solution analyses, the quantities of regenerants and the resin
capacities in gramm es or milligramm es per litre, and the resultant
calculations are simple. The British or American chemist measures
the resin in cubic feet, and the water in gallons. Not, of course,
the same gallons, as many an unwary supplier has found when
quoting to American specifications. Until a few years ago, he
quoted the resin loadings in kilograins/cubic foot and the water
analyses in grains/gallon, which if horrible, was at least consistent.
In recent years however, water analysts have followed the general
chemical practice of quoting results in milligrammes/litre, or
p.p.m. (parts per million), while retaining kilograins/cubic foot
for resin capacities, and, to ensure complete absence of uniformity,
pounds/cubic foot for the regenerant quantities.
A convention which has been widely used was to refer to total
calcium plus magnesium content as 'degree of hardness'. Three
different units have been used. One English degree (l°E), is
equivalent to 1 grain CaC03 per Imperial gallon, or 14 p.p.m. as
CaC03. A French degree (1°F) is 10 p.p.m. as CaC03, while a
German degree (loG) is 10 p.p.m. as CaO, or 18 p.p.m. as CaC03.
The terms are, fortunately, in the process of disappearing, and will
not be used in this book.
In an attempt to make the book intelligible, while still permitting
the reader to compare its tables and graphs with those published
by the British and American resin manufacturers, both the metric
and the British scales of units will be used, and a table of conversion
factors has been included.
There is one further convention, of almost universal application
by both Anglo-Saxon and European users, which is to quote
analyses and resin loadings (but not regeneration levels) in terms
of calcium carbonate, chosen because the molecular weight of
CaC0 3 is 100. It is unfortunate that the equivalent weight is 50,
which destroys much of the value of the device. Thus a sodium
3
INDUSTRIAL WATERS
chloride solution of concentration O·OOlN, contains 23 p.p.m. Na+

and 35·5 p.p.m. CI-; but both are recorded as 50 p.p.m. as CaCOa.
The system has the advantage of permitting concentrations of
different ions to be added directly, prior to making calculations of
ion exchange capacity requirements. The fundamental worker in
the ion exchange field achieves this result more logically, by
quoting both his solution analyses and his resin capacities in
gramme equivalents/litre, or mg.equiv./ml, but in ac cord with
common practice, the CaCO a convention will be used in this book.
TYPICAL WATERS AND THEIR USES

Table 1 gives the analyses in p.p.m. as CaCOa, offour typical waters.
Water A is thin, and therefore automatically soft. Its mineral
content is however, largely in the form of calcium and magnesium
salts, so that its dissolved solids consist chiefly of permanent hard-
ness. Water B is medium, from the point ofview of both hardness
and total solids. The bicarbonate content equals the total of
calcium and magnesium, and the hardness is thus entirely tem-
porary. Consequently, this water will give rise to considerable
deposition on heating, unless it is softened before use. Water C
is thick, with high temporary and some permanent hardness, while
D is fairly typical of supplies found in many desert areas. It
contains enough temporary hardness to cause deposition on heating,
but its principle characteristic is a high content of sodium and
chloride. This water is just potable, but in many parts of the world,
the only available supplies are undrinkable brackish waters having
similar general characteristics to D but with individual concentra-
tions up to six times those recorded.
Table 1. Typical Waters
A B C D
Ca 2 + 20 60 300 40
M g 2+ 5 20 50 20
Na+ 5 40 50 440
C12- 10 20 50 350
S04 2 + 10 20 50 50
HC03- I
I 10 80 300 100
- - - - -I
TOTAL , 30 120 400 500
i
Considering in turn some of the main processes for which water

1S used in large quantities, certain general principles may be laid
4
LAUNDERING, WOOL SCOURING, BOTTLE WASHING, ETC.
down for the treatment of these waters. The methods of achieving

the required results are considered in later chapters.
LAUNDERING, WOOL SCOURING, BOTTLE

WASHING, ETC.
In spite of the increasing general use of synthetic detergents, fatty
acid soaps are still very widely used in laundering, and in addition,
there is usually a certain amount of in situ soap formation due to
the presence of grease and fats in the articles being washed. To
avoid precipitation of calcium stearate scum, and also to economize
in soap, softening is required for waters Band C. In the case of A,
it may not always be necessary, but as the cast of softening this
water is trivial because of its low hardness, it is a common sense
precaution to use the process to ensure freedom from problems.
D represents a difficult case in which care must be used. With its
high chloride content, this water, under typical laundry or bottle
washing conditions of varying temperature, coupled with agitation
and aeration, is likely to give corrosion of unprotected mild steel.
The corrosion effect would be slightly increased by softening, since
the protective effect of light calcium carbonate scale on the equip-
ment would be lost. Consequently, although the correct solution is
to reduce or eliminate the chloride content, by partial 01' complete
demineralizing, it may often be expedient to leave the water un-
treated, and to protect steelwork by suitable coatings.
Wool-scouring is an extension of the principle of laundering.
Calcium soaps are so readily formed with the natural fats of the
wool, that complete softening of the four waters is essential, to
avoid deposits of scum which would interfere seriously with sub-
sequent dyeing. Waters C and D, even after softening, would be
unattractive for wool processing because of their high content of
dissolved solids, and for this reason, the woollen industry is estab-
lished in the regions where the water supplies are of types A and
B. If waters C and D were the only ones available, partial de-
mineralizing to reduce the solids content would be advisable.
Automatie bottle washing machines normally use hot alkaline
solutions, containing sodium carbonate, phosphate or metasilicate,
in the form of sprays, followed by aperiod of draining and final
drying by hot air. As the intention is to produce bright, sparkling
glassware, the water used must be reasonably soft, to avoid the
precipitation of calcium compounds on the glass. Complete soften-
ing is not necessary, as the presence of phosphate ensures ftuffy,
non-adherent calcium precipitates, provided the total hardness is
5
INDUSTRIAL WATERS
not too high. Waters A and B can be used without ion exchange
treatment. There is, however, an economic advantage in softening
water B, since this process permits a substantial reduction in the
usage of chemicals, which would otherwise be lost by reaction with
calcium and magnesium. Water C must be softened, while D, should
preferably have its dissolved solids reduced.
One further difficulty can arise with waters C and D. Automatie
washers normally dry the bottles fairly rapidly by means of hot
air, and if this is applied without adequate drainage time, visible
deposits can be formed from a thick water by simple evaporation.
This is not normally a problem with well designed industrial
machines and if it does occur, partial demineralizing of the water
provides the solution to the problem.
CHEMICAL PROCESSING, METAL FINISHING, ETC.

The range of water used in the chemical industry is so great that
no absolute rules can be laid down, but a high proportion of the
water is consumed either for temperature control, or in the chemical
processes themselves. Many processes are carried out in reactors,
fitted with jackets or interna I coils used for heating and cooling
the contents of the vessels at different stages of the reactions. These
alternating conditions give the possibility of heavy deposition from
waters containing temporary hardness. Scale formation is par-
ticularly obnoxious in the cooling circuits of chemical reactors, not
only because of the danger of blockage, but because rapid removal
ofheat is frequently necessary, and insulation ofthe cooling surfaces
by scale is accordingly intolerable. Complete softening is therefore
anormal requirement. However, chemical equipment often pro-
vides the conditions for bimetallic corrosion. Stainless steel reactors
with mild steel jackets are widely used, and other combinations
of metals can occur. In the case of water D, it would be advisable
to demineralize before use, the cost of this process being minimized
by the use of a closed-circuit cooling system, including an evapora-
tive cooling tower.
Process water is normally required to be of a higher standard of
purity than can be achieved by simple softening, and demineral-
ized water is almost universally used.
A rough general standard for process water is that it should be
similar to industrial distilled water in quality, with 1-2 p.p.m. total
dissolved solids and a conductivity of 10-15 /-LS/cm, chiefly due to
residual carbon dioxide. These results can be obtained readily and
economically, in the case of waters A-C, by simple two-bed
6
BOILER FEED WATER
demineralizing, using a weak base anion resin (see Chapter 4) followed

by aeration to remove the free carbon dioxide which is left in a
supersaturated solution by this process. Thick waters such as D
again prove difficult, for reasons discussed in Chapter 5, and it is
necessary to use more complex systems involving three or more
columns. Certain processes, of which transistor manufacture is a
typical example, require water whose purity is as near to perfection
as is technically achievable. In cases such as these, multi-column
systems of the type described in Chapter 5 are required, irrespec-
tive ofthe type offeed-water.
In general, a chemical company will have exact knowledge of
the impurity levels it can tolerate in process water, but in the metal
finishing industry, the situation is normally less weIl understood.
In the past, it has been customary to use untreated water for the
rinses which follow metal pickling, before paint spraying or electro-
plating, but experience has shown that remarkable improvements
can be made in the quality of both finishes, if demineralized water
is used for all rinse stages, to avoid salt deposition on the metal.
The same principle applies to allied processes such as mirror
silvering, where the use of de-ionized water eliminates the problem
of brown staining of the finished mirrors.
BOILER FEED WATER

The quality of water required for boiler feed purposes is dependent
on the boiler design, its operating pressure, and the purpose for
which it is being used. If the use is simply hot water production
in a closed circuit system, then any of the waters can be used
without extern al treatment. The light calcium carbonate scale
which forms on the metal surfaces is advantageous in preventing
corrosion, and in a weIl designed system it does not increase to an
obnoxious level, since evaporation losses, and corresponding
additions ofnew water to the circuit, are trivial. Water D, because
of its high chloride content, should preferably be treated with a
little caustic soda and tannin to reduce corrosion.
Steam Generating Boilers

Boilers producing steam are in a completely different category,
and their make-up water must be treated to avoid four separate,
but interrelated, occurrences:
(a) Scale formation, leading to blocking oftubes in a water-tube
boiler, or coating of heat transfer surfaces in any type of boiler,
with resultant localized insulation, overheating, and tube failures.
7
INDUSTRIAL WATERS
(b) Decomposition of bicarbonate, with liberation of carbon

dioxide which passes over with the steam to cause corrosion of the
condenser system and return lines.
(c) Concentration of salts in the boiler, causing priming, that is
carry-over of water in the steam, and localized saturation and
solidification of salts, with results similar to (a).
(d) Corrosion of the boiler, leading to tube failure by direct
penetration, or by local overheating due to deposition of corrosion
products.
In the traditional low pressure Lancashire boiler of up to 250
Ibjin2 (Figure l(a)) it was possible to deal with all these problems in
(0)
Steam space 20811 3
Water surface 187ft Z
(b)
Steam space 41 ft3

Water surface 64ft z
Figure 1. (a) Lancashire boiler 10,000 tb/h (b) Package boiler 10,000 lb/h
in a fairly simple manner. The boiler was large in relation to its

steam output, it contained a considerable volume ofwater, and had
a large steam space with low steam velocity. Consequently, scale
formation and excessive carbon dioxide liberation was prevented
by the addition of conditioning chemicals, normally sodium
hydroxide, sodium phosphate, and tannin, which gave rise to a
voluminous sludge which settled in the bottom of the boiler, and
was removed from time to time by opening a valve on the underside,
and allowing some water to be forced out under steam pressure.
BOILER FEED WATER
This process of 'blowing down', simultaneously reduced the total

dissolved solids in the boiler, which in any case could tolerate
high concentrations, often up to 10,000 p.p.m. without priming,
because of the low steam velocity and large steam chest, which
allowed entrained water droplets to fall back, before the steam left
the boiler.
The rivetted construction of these boilers did on occasion give
rise to a difficulty known as 'caustic embrittlement'. Boiler water
forced into crevices by steam pressure evaporated to dryness, and
the contact of sodium hydroxide with hot steel caused slow changes
in the crystal structure to a brittle condition which finally caused
failure of the boiler. However, this condition could be prevented
by maintaining a Na2S04/NaOH weight ratio of over 2·5/1·0,
and the sulphate could be added to the water as sulphite, to give
simultaneous removal of dissolved oxygen and suppression of oxygen
corrosion. No ion exchange treatment was necessary.
During the last 50 years, there have been constant improvements
in boiler design, to give higher steam pressures, and more efficient
consumption of heat. Boilers became smaller, in relation to their
output, and were made more economic by passing the hot gases
twice through the boiler drum, to give greater extraction of heat
from them. The increase in general temperature, and the even
greater localized heating due to the gas movement system, accen-
tuated the four dangers mentioned above. Consequently in the case
of an economic boiler, it is advisable to soften waters Band C, in
addition to supplying internal conditioning as before. The total
dissolved solids tolerable by the boiler are also somewhat reduced,
and if the amount of condensate available for re-use in the boiler is
fairly smalI, partial demineralizing of waters C and D mayaiso be
necessary. Water C would thus require two processes, and a com-
bined method, known as 'Starvation-base exchange', (page 56)
was developed for this purpose. All the waters would also require
virtually complete oxygen removal, by the addition of sodium
sulphite to the make-up, or preferably by using a de-aerator, a
unit in which the incoming cold water is sprayed into a steam-
filled chamber, which is vented so as to dis charge a mixture of
steam and the gases released from the water. In the case ofwater D,
corrosion due to chloride could be a problem, and although it can
be minimized by maintaining a high pH in the boiler, together with
a permanent positive level of sulphite, these steps could be in-
sufficient in certain conditions, and demineralizing would then be
necessary. There is no simple rule relating the water treatment to the
9
B
INDUSTRIAL WATERS
type of boiler, and much depends on the conditions of use. If there

is a high degree of condensate recovery, and a correspondingly low
level of make-up, the impurity level in the make-up water is
relatively unimportant, and the treatment can be correspondingly
simple. Even if the condensate availability is not very great, the
total solids in the boiler can often be kept within reasonable bounds
by maintaining a sufficient level of blowdown. Rowever, blow-
down is expensive, in that it wastes not only water, but also the
heat which has been put in it, and for thick waters such as C or D,
demineralizing may be justified on grounds of economy alone.
Packaged Boilers
Further improvements in boiler efficiency have beenachieved with
the introduction of the 'packaged' boilers. These units, which are
available for steam generation at up to 10,000 lbjh, and 250 Ibjin2
pressure, are designed to be factory assembled, and delivered to
site ready for immediate operation. Consequently, they are reduced
to the minimum possible size. Figure 1 shows a schematic comparison.
The packaged boiler, Figure l(b) as compared with the Lancashire
boiler, has a very low total water content, small water surface area
and steam space, with correspondingly high steam disengagement
and horizontal velocities and an extremely high rate ofheat transfer
across the metal to water surface of the boiler tubes.
These factors ren der the boiler highly efficient, but also increase
its sensitivity to water conditions. The total dissolved solids (T.D.S.)
must be kept below 4,000 p.p.m. and preferably below 2,500 p.p.m.
in order to minimize priming and resultant impure steam. At the same
time, the extent to which boiler solids can be controlled by blow-
down is limited, because of the small water content of the boiler.
Finally, formation of sludge inside the boiler, which was standard
practice with earlier units, must be avoided, since blockage can
readily take place in the small gaps between the fire-tubes.
Undoubtedly, the simplest technical solution to packaged boiler
water problems is to provide good operating conditions, by de-
mineralizing the make-up. However, the user, having purchased
a small and economical boiler unit, is normally unwilling to con-
sider more than the minimum tolerable treatment of the make-up
water. This minimum consists of ion exchange softening, oxygen
removal, and caustic soda dosing to give pR 10 in the boiler. How-
ever, simple arithmetic shows that more is required in the case of
waters C and D. If the boiler is producing process steam, and the
retumed condensate is only 50 per cent of the total feed water, the
10
BOILER FEED WATER
make-up is 50 per cent and the T.D.S. of the feed water is 200
p.p.m. The addition of sodium sulphite and caustic soda raises this
to about 300 p.p.m., and it is thus impossible to maintain the total
solids in the boiler below 2,500 p.p.m., other than by blowing-
down ab out 15 per cent of the boiler water, which is an intolerable
figure. Partial demineralizing, by the Starvation process, thus
be comes essential for these waters.
Goil Boilers
In recent years, coil boilers, or vapour generators, have become
increasingly popular. These are essentially water tube boilers, in
which the tube is in the form of a long continuous coil passing
through the flame region. They are available only for fairly small
output, up to 7,500 lbjh, and have the advantage of very rapid
start-up and shut-down. The general water conditions are similar
to those of packaged boilers, with two significant differences,
according to the type of coil boiler. One system makes no attempt
to supply dry steam directly and liquid water is present in all parts
ofthe coil. A highly efficient steam separator forms an essential part
of the boiler, the separated water being returned to the input end of
the coil. The avoidance ofpriming has no meaning, since the steam
coil is effectively priming continuously. This type of coil boiler can
therefore tolerate somewhat higher dissolved solids in the feed
water than can a packaged boiler, but the water treatment con-
ditions are otherwise unchanged. Other types are operated under
conditions which cause complete evaporation in the coil, with
delivery of dry superheated steam. Under these conditions, full
demineralizing of the feed water is essential to avoid deposition and
steam contamination.
High Pressure Boilers

For the higher press ure boilers, 1,000 Ibjin2 and above, which are
used for power generation, demineralizing is required for all waters,
not only to protect the boiler itself, but also to prevent carry-over
of solids by the steam, and consequent damage to the turbine
blades. For many years, the standard of make-up water quality
was a conductivity ofless than 1·0 /LSjcm (S = mho), correspond-
ing to about 0·3 p.p.m. T.D.S., and a silica content of less than
0·05 p.p.m. These requirements were readily met by means of
mixed-bed demineralizing (Chapter 4). In recent years, boiler
press ures have been increasing still further, values of 1,500 Ibjin2
now being quite normal, while units operating at over 2,000 Ib/in2
11
INDUSTRIAL WATERS
are increasingly common. The feed water quality for these boilers
must be extremely high.
In Great Britain, the Central Electricity Generating Board now
specifies make-up water of conductivity <0·1 p.S/cm which cor-
responds with total ionized solids of weIl under 0·05 p.p.m. and
there is also a requirement for less than 0·02 p.p.m. total silica.
To achieve these results, multi-column systems are required, and the
treatment methods are unchanged in principle, whichever type
of water is available. In other words, the differences between
waters A-D are no longer fundamentally significant. They affect
the running cost of the process, and the number of ion exchange
columns used, but not the methods or results. The feed water
quality requirements are so high, that the returned condensate
itself can no longer be considered as pure water, even though its
total dissolved solids may be less than 0·5 p.p.m. Traces of corrosion
products, or salts resulting from condenser leakage, cannot be
permitted to return to the boiler. It is now becoming standard
practice to filter and demineralize the returned condensate, before
it enters the boiler feed system.
It is interesting to realize that, as economical large scale power
production necessitates the use of high temperatures and pressures,
the modem electrical generating industry could not have been
developed, but for the availability of the demineralizing process.
There is no other technique capable of producing water of the
required quality.
12
CHAPTER2
THE ION EXCHANGE PROCESS
INTRODUCTION
It has become so customary to associate the term 'ion exchange'
with the standard technique of causing water to flow through
columns of resin, that it tends to be forgotten that the principle of
the process itselfis neither new, nor unduly complex. It has probably
been used by every living chemist in the earliest stages ofhis studies.
The experiment of detecting chloride in solution, by the addition
of silver nitrate solution, typifies the commonest type of ion ex-
change reaction:
Na+CI- + Ag+N03- = Na+N03- + Ag+CI- {, .... (1)

The sodium and silver cations have exchanged the chloride and
nitrate anions which were their partners in the original solutions.
In contrast, if sodium chloride and lithium nitrate solutions are
mixed, there is no corresponding reaction.
Na+CI- + Li+NO- 3 =I- Na+N0 3- + Li+CI- .... (2)
In the mixed solution, all four ions are freely mobile, and have no
tendency to form any particular pairs. When the two reactions
above are written more correctly, to represent the true conditions
in solution, the difference is obvious.
Na+ + CI- + Ag+ + N03- = Na+ + N0 3- + Ag+CI- {, ... (3)

Na+ + CI- + Li+ + N0 3- = Na+ + N03- + Li+ + CI- .. (4)
Ions are therefore uniformly mixed in solution, and to make a
recognizable exchange of partners possible, there must be some
mechanical means of separating them into two groups, each of
which must of necessity contain equivalent numbers of anions and
cations to preserve electrical neutrality. In practice, the separation
is achieved by the use of two separate phases, and it follows that the
achievement of an ion exchange reaction requires four conditions.
13
(a) Two phases.

(b) Four ions (two positive and two negative).
(c) Free passage of one type of ion (e.g. positive) between the
phases.
(d) No passage of the opposite type of ion between the phases.
Any of the following pairs of phases may form the basis of an
exchange system.
(i) Solid-liquid.
(ii) Two immiscible liquids.
(iii) Two miscible liquids, or two sampIes of the same liquid,
separated by a membrane which will pass only one type of ion.
Systems involving two solids, as in mixed crystals, or solid and gas,
••
t
l ,
•• '00 0
• ' o•
• '0 0 0
•
100 0
•• •.-4-' o.
' 0 0
,
1 0
00 0
e-t- 0 0
o •
I.
• Na+
••o
.-..1-0 1 0 0 0
10 0 0 Li+
o '0 0
•
-4f-{) 0
Cl-
• ,,
,: 0 10 •
0
0
• .,0 0 0 0
NO;
• ~: •
0 0
0
0 • • : 0 0
, 0 o·
•
0
•°• , 0
, °0 0
0
•
. , 00 0
el 0 0
, ·1 0
0 • . 0 : 0 000
0 000
• 1 0 00 o• 1'00 00
(a)
o. (b)
i
Figure 2. Exchange across a cation permeable membrane (a) Static (b) Left-hand side flowing
in an electric are, are not theoretically impossible, but have no

practical significance. In practice, an overwhelmingly high propor-
tion of industrial processes are carried out in solid-liquid systems,
but the fundamental nature of the process is best understood by
first considering case (iii), that of two aqueous solutions separated
bya semi-permeable membrane. In Figure 2(a), sodiu,m chloride and
lithium nitrate solutions are separated by a membrane permeable
only to cations. Over a long period, sodium and lithium ions will
14
INTRODUCTION
diffuse through the membrane, the driving force being the concen-
tration difference on each side of it. As this difference decreases,
the rate of exchange reduces, until finally equilibrium is reached
and no further change takes place.
At this stage, an exactly equal number of sodium and lithium
ions will have crossed the barrier, to preserve electrical neutrality,
and as the initial concentration of LiN0 3 on the right has been
shown as higher than that of NaCI on the left, it follows that at
equilibrium, there will be different concentrations of sodium ions on
each side of the barrier. The equilibrium state is governed by the
law of mass action
Na+CI- Na+N0 3-
LEFT RIGHT LEFT RIGHT .... (5)
[Na+]R represents the concentration ofsodium ions in the right-hand

compartment etc. *
I t follows that the higher the concentration ratio between the two
solutions, the more complete will be the replacement of sodium by
lithium on the left. Nevertheless, absolute removal of sodium is
impossible.
Figure 2(b) presents the effect offlowing the dilute sodium chloride
solution past the concentrated lithium nitrate. At the top of the
column, the conditions are virtually identical with those of Figure
2(a) but as the descending liquid is constantly being brought into
contact with new LiN03 solution containing no sodium, the term
[Na+]R of equation 6 remains at nominal zero, and more sodium
ions must cross the barrier to res tore equilibrium. The whole effect
is virtually a complete stripping of sodium ions from the advancing
wavefront.
* NOTE. Strictly, the law of mass action applies to ionic activities, not con-
centrations, and the terms above should read [Na+]R yNa+R etc., where y
is the activity coefficient. For the simplified theory used throughout the book,
activities will be neglected, and concentrations only will be used. This simplifica-
tion does not effect the validity of the principles to be discussed.
lS
If the sodium chloride solution continues to flow, then at the

upper end of the column, the concentration of lithium on the left
[LiJL, remains at nominal zero, and to restore equilibrium, Li + ions
will diffuse to the left, and equal quantities of Na + ions will travel
right. In due course [Na+]R will exceed [Na+JL, but nevertheless,
the Na + ions will continue to diffuse through the barrier, under the
driving force of the constant new supply of ions. Thus finally, the
supply of lithium ions will be exhausted, and the solution will be
sodium nitrate.
In understanding this process, three factors are of prime impor-
tance. The first is that complete exchange on bothsides ofthe barrier
is not possible simultaneously. Complete stripping of sodium occurs
on the left only at the start of the process, while fulllithium removal
on the right occurs only at the end.
The net effect of this process on the analysis of the solution
energing from the left-hand cell is shown in Figure 3. The break-
through curve is asymptotic to the horizontal axis at each end and
Breakthrough
of Na +
Percentage 1 0 0 1 - - - - - - - - -....
replacement
of Na + by Li'
in emergent
liquor
Exhaustion of
supply of Li'
A B
OL-------------~~--------=---
Increasing volume ~
Figure 3. Breakthrough curve
therefore it has in theory no finite length. In practice, the length is

arbitrarily fixed by the limits of analytical detection of the two ions,
and if the test method is too sensitive to provide a satisfactory
arbitrary limit, it is convenient to select a fixed breakthrough
percentage, for example 1 per cent of the input concentration. If
this is done the length of the curve of varying compo~ition, or
wavefront, is fixed for a given set of conditions and is represented
by A B in Figure 3.
The second point is that the mechanism of the process so far
described is not necessarily a chemical one, and does not depend
fundamentally on affinities, cross-linking, or any other resin
16
INTRODUCTION
properties which will be considered later. Exactly the same pair of

experiments could be carried out using two vibrating columns
filled with black and white spheres and cubes, separated by asolid
plate perforated with circular holes through which the cubes cannot
pass. Such a system would obey the law of mass action, and per-
fectly reproduce the process of ion exchange through a membrane,
so long as there were always the same number of spheres and cubes
in any one compartment.
The final general factor concems the reversibility of the process.
If a solution of lithium chloride is passed through the left-hand
compartment of the equipment shown in Figure 2(b), which now
contains sodium nitrate in the right-hand cell, then the previous
process will be precisely reversed. In this ideal case there is no
question of relative affinities and the reverse exchange will follow
an identical curve to the forward process. When using ion exchange
resins, the general nature of the process is unchanged but the shapes
of the breakthrough curves are modified by resin affinities (see
Chapter 3).
The process of exchange by diffusion through a membrane,
described above, can be achieved under laboratory conditions; but
it is so slow and requires such a large membrane area that it has no
practical significance, although a modification of the process known
as electrodialysis (see Chapter 7) is used on the industrial scale.
In order to achieve the required results on the large scale it is
necessary to use a very large number of extremely small units so as
to present a vast surface barrier across which exchange can take
place. If, in the example given, the single membrane separating
the two solutions could be replaced by millions of tiny sacs each
containing lithium nitrate and surrounded by a membrane, then
the same overall process would be achieved at a high degree of
efficiency. As this is not a practical possibility, the same effect must
be obtained by dispensing with the membrane as such, and locking
one of the ions (in this case the nitrate ion) into small particles or
globules which can be produced in enormous numbers.
One method of achieving this is to use liquid/liquid ion exchange
(see Chapter 8). By using finely dispersed droplets of an inert water
immiscible solvent such as a paraffin, having dissolved in it an
organic acid possessing a long hydrocarbon tail to render it hydro-
phobie, the anion of this acid is locked into the oil droplet while
cations can pass freely in and out from the surrounding aqueous
solution. The organic anion thus replaces the nitrate of Figure 2 and
conditions for ion exchange have been established.
17
This method of operating the ion exchange process is of compara-

tively recent origin, but is now frequently used for specialized
industrial processes such as the recovery of certain valuable metals
from solution. It is not, however, in general industrial use and for
this reason will be described only briefly in Chapter 8.
The method which, with this minor exception, is used throughout
the ion exchange industry, is liquid/solid ion exchange. The oil
droplets of the liquid/liquid process are replaced by solid insoluble
particles which are freely permeable by water and contain ionic
groups locked into their structure. Two of the most common groups
used are the sulphonic group -S03-H+, for cation exchange
resins, and the quatemary ammonium group -CH2-N-(CH3)3+
(0) (b)
Figure 4. Comparison of cation exchange resin bead with sulphuric acid droplet (a) Schematie
section through cation exchange (b) Imaginary drop let of sulphurie acid surrounded by eation
permeable membrane
OH- for anion exchange materials. The cation exchange resin is

shown diagrammatically in Figure 4. The sulphonic groups are
immovably attached to the resin skeleton, while the corresponding
hydrogen ions are free to move throughout the structure. Thus a
sodium ion can enter freely, causing the ejection of a hydrogen ion,
whereas a chloride ion approaching the surface of the bead is
repelled by the fixed negative charges, and cannot ehter. The effect is
thus exactly as if the bead were a droplet of sulphuric acid solution,
surrounded by a membrane through which cations, but not anions,
can pass. A column of resin beads can thus exactly replace the right-
hand cells shown in Figure 2(a) and (b), and the exchange process
will be govemed by reactions 5 and 6.
In the same way, a quaternary ammonium anion exchange resin
bead resembles in principle a droplet of sodium hydroxide solution
18
INTRODUCTION
surrounded by a membrane through which only anions can pass.

This comparison is important for the full understanding of the
ion exchange process. It is a common misconception that ion
exchange is a surface effect, taking place on the outside of an inert
solid partide. In fact, the res in bead has all the characteristics of a
fairly concentrated aqueous solution, and its surface is merely the
barrier through which the appropriate ions must pass to enter the
solution. More precisely, the modern ion exchange resin is a
water-swollen organic gel. The exchangeable ions travel freely in
the water, while the counter-ions are held immobile in the gel
structure.
THE DEVELOPMENT OF ION EXCHANGE RESINS

Many different types of chemical compounds can be used to form
ion exchange materials. Indeed the most common ion exchange
material in the world is ordinary day soil in which the crystalline
alumino-silicate structure gives the locked anion, while cations can
freely replace each other in the crystal network.
The first observation of the existence of ion exchange was made in
1845 by Thompson and Spence who, in studying the mechanism of
soil fertilization using ammonium 'sulphate, found that when a
solution of it was passed through a tube of soil the ammonium was
absorbed and calcium sulphate solution emerged from the column.
Systematic studies of this process were made by Way from 1850
onwards. He showed that the exchange process was a general
phenomenon, that the quantities of cations exchanged were exactly
chemically equivalent to each other and that some ions were held
more strongly than others. Way also prepared the first laboratory
sampIes of synthetic alumino-silicate minerals having ion exchange
properties; and he thus laid the foundation of modern ion exchange
theory and technology with a remarkable degree of completeness.
Nevertheless, the process was not used for any practical purpose,
until in 1905 Gans in Germany softened water on the industrial
scale by replacing the calcium and magnesium ions with sodium,
by means of a bed of a natural or a synthetic alumino-silicate
material, Zeolite, which was subsequently reconverted to the
sodium form with brine. The Gans patents for this technique were
taken up by companies in every part of the world and du ring the
next 30 years ion exchange water softening became universally used.
One of the most commonly used materials was a natural alumino-
silicate green-sand found in certain parts of America and Australia,
and even today there are numerous old green-sand water softeners
19
still in use. The synthetic alumino-silicates, however, had a con-

siderably higher capacity and they had largely superseded green-
sand by about 1935.
The alumino-silicate materials had one serious disadvantage,
their instability in the presence of mineral acid, which rendered the
Heat
catalyst"
Styrene Linear polystyrene
~=CH'
CH=CH2
Divinyl benzene
Crossli nked polyslyrene
~ HzS04
Calion exchange resin

Figure 5. Preparation 01 sulphonic cation exchange resin
hydrogen ion exchange process impossible. In 1934 two new types

of material without this defect were invented almost simultaneously.
The first was sulphonated coal, developed by Leibknecht in
20
Germany, and the second was the synthetic phenolformaldehyde type

of material invented by Adams and Holmes in Britain. Adams and
Holmes simultaneously prepared the first anion exchange material
and thus made possible the demineralizing process which has
subsequently become by far the most important application of ion
exchange. The anion exchange resins were made by condensing
aromatic amines with formaldehyde and, like the corresponding
cation exchange materials, were relatively unstable by modern
standards. Nevertheless, they were of considerable industrial value
and subsequent progress was so rapid that by 1937 the first industrial
scale demineralizing plant in the world had been installed in
Great Britain.
The next step forward occurred in 1942 with the invention by
D' Alelio of sulphonated crosslinked polystyrene, followed in 1949 by
the corresponding polystyrene anion exchange resin invented by
McBurney. Both these developments took place in the U.S.A. The
polystyrene resins are chemically very stable and are almost ideal
ion exchangers from every point of view. Consequently they have
now become almost universally used; and this situation is likely to
continue for a considerable time, even though many perfectly
usable ion exchange resins have been prepared on the basis of other
polymers such as sulphonated polyethylene or aminated polyvinyl
chloride. In recent years there has been some revival of interest in
inorganic exchangers, based on insoluble gel structures such as
zirconium phosphate, but these materials are at present largely of
academic interest, and the polymeric organic products are used
almost exclusively in industry.
Styrene is readily polymerized under the inftuence of heat and a
peroxide catalyst to form linear polystyrene (Figure 5). If the poly-
merization is carried out while the liquid monomer is dispersed in
water in the form of fine globules, the final solid resin is in the form
of perfect spheres of high purity and clearly defined particle size.
If this product is sulphonated, it forms linear polystyrene sulphonic
acid, which is water soluble and is therefore useless as an ion
exchange material. The essential step in the D'Alelio process was to
co-polymerize divinyl benzene with the styrene so as to give a
crosslinked structure. The hydrocarbon beads are then insoluble in
organic solvents, although readily swelled by them, while the
sulphonated product is completely insoluble in water although
swollen and freely permeable by it. The standard industrial grades
of crosslinked polystyrene sulphonic acid resins, such as Amberlite
IR-120, Dowex 50, Lewatit S 100, or Zeo Karb 225 contain about
21
50 per cent water in their structure, but are so insoluble that,there

are now many examples of resin beds which have been in industrial
use for 20 years and are still virtually unchanged .
../ /'
CH
/CH
/CHz
A
/CH
/c",c~J: /CH2
U
../CHz U ../CH2
../CH
CHzCl
Crosslinked polyslyrene
N(CH,J, NH(CH,J2
./
/CH
/CHl
/,CH
/CH1QCH
/,CH
CH
../ 1 CH2NH(CH3)~ Cl-
(b)
Figure 6. Preparation 01 anion exchange resins (a) Strongly basic anion exchange resin
(b) Weakly basic (tertiary amine) anion exchange resins
The sulphonic acid cation exchange resins made by different

manufacturers are chemically similar to each other, although there
are differences in the molecular structure of the skeleton which affect
the physical strength and rate of reaction of the different products.
The case of the polystyrene anion exchange resins is somewhat
different. They are prepared by chloromethylating and aminating
22
the hydrocarbon beads. The process is shown in Figure 6. When a

tertiary amine is used, the final product is a quaternary ammonium
compound whose basic strength is extremely high, being similar
to that of potassium hydroxide. The most commonly used amine is
trimethylamine, which gives resins of the highest basic strength
obtainable. Examples of such resins are Amberlite IRA-400.
De-Acidite FF jIP, Dowex 1 and Lewatit M.500. The use of di-
methylethanolamine gives a resin of slightly lower basic strength,
although such materials, including Amberlite IRA-4IO, De-Acidite
NjIP, Dowex 2 and Lewatit M.600, are still essentially strong base
in contrast with weak base resins. The use of other amines such as
triethylamine has been mentioned in the literature and it is not
impossible that some of these are used industrially.
When the amine used in the resin manufacture is a primary or
secondary one, the resuIt is a secondary or tertiary amine resin
respectively, and these products are weakly basic in nature (Figure
6(b)). The number of available amines is very great, and conse-
quently there are commercially available a large number of different
weak base resins which, while broadly equivalent to each other in
their functions, are nevertheless quite different chemically and have
widely varying capacities and rates of reaction.
The fourth type of ion exchange resin is the weak acid cation
exchange material which contains carboxylic instead of sulphonic
groups, and is thus the parallel of the secondary or tertiary amine
weak base resins. Carboxylic resins can be manufactured by inserting
the -COOH group into the polystyrene skeleton, but there are
simpler methods of preparation. Copolymerization of acrylic or
methacrylic acid with divinylbenzene gives a resin whose structure
is indicated in Figure 7, while similar resuIts can be achieved by the
use of crosslinked polyacrylonitrile which is subsequently hydrolysed.
As these resins are based on an aliphatic rather than an aromatic
chain they have lower equivalent weights and correspondingly
higher total capacities than the polystyrene materials. The total
capacity is not however achievable in practice for the reasons given
in Chapter 3. Materials of this type are Amberlites IRC-50 and
IRC-84, Kastel C.IOO, Lewatit CNP and Zeo Karb 226.
Finally, extremely valuable carboxylic materials can be made by
the carboxylation of phenol formaldehyde condensation products.
Whereas all other condensation ion exchange resins are now virtually
obsolete, these carboxylic resins are widely used for water treatment
because of their exceptionally high regeneration efficiency. Resins
of this type are Lewatit CNO and Zeo Karb 216.
23
Irrespective of their method of manufacture, the ion exchange

resins are all crosslinked gels, containing a high proportion of water
which is an essential part of their structure. The water can be
removed by heat or vacuum, whereupon the molecular chains lie
closer together, and the beads shrink. On being re-wetted, the
beads swell, the ions contained in them becoming hydra ted. If the
resin structure were not constrained by crosslinking, the swelling
would be infinite, that is the product would be soluble. The degree of
CH 3
I
C=CH2
I
COOH
Methacrylic C~ C~
acid I I
-TH-CH2-~CH CH2-~H-
~H'
COOH COOH
CH3
I
-CH-CH z -CH -CHz-CH-
CH=CHz
Divinyl benzene booH tOOH
Figure 7. Preparation 0/ carboxylic cation exchange resins
swelling is related precisely to the crosslinking. When this is at the

level of 1 per cent, the beads contain only 5-10 per cent dry solids,
the remainder being water. They are nevertheless, solid spherical
particles which are perfectly usable for laboratory ion exchange
experiments, although too soft and gelatinous to have any industrial
value. As the crosslinking increases, the water content decreases,
until at 8 per cent crosslinking, which is the optimum for most
industrial purposes, the beads contain about 50 per cent water. They
are then hard and tough, and almost infinitely durable. Materials
crosslinked to more than 25 per cent are extremely hard and brittle,
while their water content has fallen too low for the satisfactory
functioning of most ion exchange processes.
In reading the literature of ion exchange, frequent references are
found to the porosity of resins. These can be extremely misleading.
With the single exception of the macroporous resins (see Chapter 6)
which have a special structure, ion exchange resins do not have any
features which can correctly be described as pores. They are
24
essentially continuous gel structures, of greater or lesser solids

content. The resins described variously in the literature as 'porous',
'more porous' or 'highly porous' are normally found to be materials
of low crosslinking, giving them a low solids and a high water
content.
Although the gel structures are continuous, and. appear homo-
geneous when observed by optical or even electron microscopy they
are, in fact, distinctly heterogeneous on the molecular scale. Owing
to the nature of the polymerization process by which the original
hydrocarbon skeleton is manufactured, the first copolymer molecules
which form in the drop lets of liquid monomer contain a higher
proportion of crosslinks than the monomer mixture. The chains
which are initiated later are correspondingly less crosslinked than
the average. The final gel is accordingly not uniform but consists of
a collection of tightly knotted regions, separated by more loosely
crosslinked areas. The effect of this structure on the action of the
res ins is considered in Chapter 6.
25
c
CHAPTER 3
EQUILIBRIA AND KINETICS, AS APPLIED TO

WATER TREATMENT
While the reactions of ion exchange resins are all fundamentally

similar, they may be classified according to their purpose. The first
of these is the general cation exchange process, whose industrial
application is in water softening.
GENERAL CATION EXCHANGE

Na+Rc - + Li+CI- ~ Li+R c - + Na+CI- .... (7)*
2Na+Rc - + Caz+Clz- ~ Ca z+Rc2- + 2Na+CI- .... (8)
3Na+Rc - + Fe3+Cla- ~ Fe 3 +Rc3- + 3Na+CI- · ... (9)
4Na+Rc - + Th4+CI4- ~ Th4+Rc4 - + 4Na+CI- · ... (10)
Reactions 7-10 all concern the removal of metals from solution
by sodium form resin, while thc reverse reactions give the corres-
ponding regeneration of the resin by sodium chloride solution, used
because of its low cost, and because all common sodium salts are
soluble.
Applying the law of mass action to equation 7:
[Li+] [Na +]
'Affinityconstant' KLi = ~~~._-- · ... (11)
Na [Na+] [Li+]
or
JLi+] = KLi J!:-i+]
· ... (12)
[Na+] Na [Na+]
This would indicate that the concentration ratios of the two ions in
* The terms Rc - and RA+ are used to indicate one equivalent unit of a cation
and anion exchange respectively. The terms [IT+] and [Li+] are used to indicate
the respective concentrations of these ions in the resin and in solution.
26
the resin are always directly proportional to their concentration

ratios in the surrounding solution, and if K~~ were 1·0, the relative
concentrations in the resin would always equal those in solution.
In practice, the reaction constants for various pairs of univalent
ions differ. The affinity of a resin for a given ion is govemed by the
size of the hydra ted ion. The larger this is, the more the resin must
swell to accommodate it in the structure, and as the swelling is
opposed by the constraining of the crosslinks, larger ions require
a greater force to cause them to enter. This force is supplied by the
relative concentrations of the ions in the surrounding solution
[Li +Jj[Na +J. *
As the hydrated lithium ion is larger than thatof sodium, its affinity
for the resin is lower, and the relative concentration inside the resin
bead is always less than in the surrounding solution, and K~~ is
accordingly less than 1·0.
The inhomogeneous nature of the resin structure causes a compli-
cation. As lithium ions enter, displacing sodium, they seek first the
10·0,-----------------.
Theoretieally perteel
_~_r~u~ _ _ _
/
Practical results
0·1
Xli'
Figure 8. Variation rif affiniry coefficient with resin loading
regions most favourable to them, that is, the loosely crosslinked part
of the resin. As XLi, the fraction of the resin occupied by Li +,
increases towards 1·0, new ions are entering regions increasingly
unfavourable to them, and the proportion entering becomes pro-
gressively less than would be calculated from equation 11. The
'affinity constant' ~ia thus varies as in Figure 8. For this reason, it is
• Note: This statement is a simplification. Factors additional to hydrated ion size

also influence affinity relationships. The theory of this subject is still under study
by many groups of workers, and complete agreement has not yet been reached.
27
EQUILIBRIA AND KINETICS
customary to abandon the word 'constant', and refer to it as the

affinity coefficient, or selectivity coefficient.
The series ofions Li+, Na+, K+, Rb+ and Cs+ have decreasing
hydra ted ionic size, and the energy required to swell the resin bead
against the constraining forces of its crosslinking decreases corres-
pondingly. Thus the affinities of the resin for these ions increases
markedly in the direction Li+ to Cs+, and if a mixed solution of
these ions is passed through a resin column in some other ionic
form (e.g. H+ form), the order ofemergence ofions is H+, Li+, Na+,
K +, Rb+ and Cs+. The relation between affinity, hydra ted ionic
size, and resin swelling is a precise one, and is readily observed in
practice. A bead of resin shrinks visibly as it changes from the Li +
to the Cs+ form, and the change in the diameter, measured with a
microscope eyepiece scale, can be related directly to thc affinity
coefficient as calculated from equation 11.
In the case of bivalent ions (equation 8) the mass action equation
becomes
.... (13)
If Xca and X Ca represent the equivalent fractions of calcium in

the resin and in solution, and if [r) and [T) are the total concentra-
tions of both cations in the resin and solution,
then
X ca [TJ X ca
KCa . - - - - - - - .... (14)
(1 - Xca)2 Na [T) (1 - Xca)2
[rJ is constant, neglecting the comparatively small changes in resin

water content which occur during the exchange process, and it
follows that if the ionic ratio in solution remains unchanged, while
the overall concentration [T] decreases, the uptake of calcium by
the resin will increase in approximate proportion to the dilution.
Conversely, increasing total concentration of ions in solution
favours the absorption of sodium. Figure 9 gives aseries of curves
relating the fraction of the resin capacity occupied by sodium X Na +,
to the sodium content of water which is in equilibrium with the
resin, expressed as a fraction of the total ions present, XNa+. At
concentrations in solution greater than 3N (Curve B) the affinities
of calcium and sodium for the resin are similar. Because of the
28
varying affinity coefficient effect noted above, sodium is preferen-

tially absorbed when XNa+ is less than 0,5, while calcium is taken
up more strongly at higher values of ~a+. With decreasing concen-
tration, the equilibria increasingly favour calcium absorption,
until at 0,005N, or 250 p.p.m. as CaCO a (Curve F), calcium uptake
is so pronounced that resin 80 per cent in the calcium form
is in equilibrium with water whose sodium :calcium ratio is
99: 1. The mass action effect of equation 13 thus completely out-
1·0 r - -- - - - -- - - - - - ---:I
/
/
..
/
/
' /
I~ 0'8 /
/
c /
' Vi /
/
~ /
.!:: 0 ' 6 /
/..
+/11
Z
'0 0"
c
~
oa. '
E 0,2
0..
0'6
Proportion of Na' in water (X Na')
Figure 9. Na+(Ca 2 + equilibria
weighs the effect of decreasing affinity coefficient, and resin which

is almost fully exhausted is still capable of softening water virtually
completely.
The effect of these equilibria on the full softening cycle is shown
in Figure 10, in which curves Band F are repeated from Figure 9.
If water containing 250 p.p.m. total hardness is passed through a
new column of resin, fully in the sodium form, the starting condi-
tions throughout the column are represented by point P. The column
never returns to these conditions in its future operating life. As the
solution continues to pass, X Na+ remains high er than 0·99, i.e., the
water is fully softened, until the resin at the base ofthe column, which
29
governs the quality of the emergent water, is 80 per cent in the

calcium form (Point QB). At this stage, the first traces of hardness
can be detected in the treated water. The resin above the lowest
layer of the column is, of course, more fuHy converted to the calcium
form, the top layers being almost fuHy exhausted (Point QT), and
the average condition throughout the column being over 95 per cent
,·Or - -- - -- - -- - -- - -- -. p
0 '8
0·6
O·{. 0'&
Os
--- -- - -- - -- - 0'8
o Qr 0'2 o·t. . 0'6

X a'
Softening
Tr -q>r =Variation in conditions of column top
Ts -Cfls = Variation in conditions of column base
Regeneration
RT-S r =Variation in conditions of column top
Rs---Ss = Variation in conditions of column base
Figure 10. The softelling cycle (O·OOSN so/n .)
calcium form (Point QAV)' Thus, in this first operation, the res in
has absorbed calcium equal to 95 per cent of its total capa city
(2,25 mg.equiv.jl), that is, it has taken up 2·1 mg.equiv.jl of hard-
ness, or 105 g jl as CaC03.
If 3N sodium chloride solution is now passed into the column, the
resin immediately starts to re-establish a new series of equilibria
along Curve B . At the top of the column, X Na+ is almost zero,
30
while XNa+ is 1·0. Thus the first few drops of regenerant solution
entering the column are almost completelr, stripped of sodium ions,
and XNa+ reaches an equilibrium with XNa+, in which both are
very low, point R T • Similar, as the first traces of 3N solution, reach
the bottom of the column, a new equilibrium state RB is reached,
and the average condition of the resin is represented by RA V. If
the total quantity of sodium chloride passed through the column is
100 g/l (approx: 6 Ib/ft3), it is found in practice that the total
quantity of calcium removed from the resin is equivalent to about
half the total capacity of the resin, that is 1·13 mg.equiv./g, or
57 g/l as CaC0 3 (25 kgr/ft 3). The average condition of the resin is
now represented by point SA v, where XNa is 0·55. The top of the
column is, of course, more highly regenerated than this, its condition
being represented by ST, while the bottom-most layer is still about
55 per cent in the calcium form (point SB). Nevertheless, when the
released calcium chloride and excess sodium chloride have been
rinsed from the resin bed,.and the solution concentration has been
returned to 0·005N, aIl parts ofthe bed have returned to the vertical
portion of curve F (points TT, TA v and TB), so that the emergent
water is completely soft, (XNa+ > 0'99). In the second and sub-
sequent absorption stages, the column again returns to the condition
represented by the curve Q,T-(2.B. The quality ofthe emergent water
at the end of the run is represented by Q,B, while the operating
capacity, that is the amount of calcium absorbed, is equal to the
quantity removed during regeneration, that is 50 per cent of the
total c~acity ofthe resin, repres~ting the vertical distance between
TA V (XCa2+ = 0,45) and Q,A v(Xca2+ = 0'95).
I t should be noted that if the total dissolved salts in the feed
water are much higher (e.g. Curve D, Figure 9, O'IN or 5,000 p.p.m.
as CaC03), then the termination point on the absorption cyde
occurs much earlier, at a higher value of XNa+ (Point U, Figure 9),
and the available operating capacity is correspondingly reduced.
This value, now about 40 per cent of the total capacity of
the resin, cannot be restored by extra regenerant, since the system
obviously cannot be taken beyond point P. The quantitative
effects of these graphs are considered in Chapter 4 (Figures 20
and 21).
This practical effect of equation 13 was known, and used in
industrial water softening, weIl before the theoretical reasons for it
were appreciated. A second result ofthe equation is, however, much
less commonly realized. It is that, just as a decrease in the total
ionic concentration in solution favours the absorption of Ca 2 +, so a
31
decrease in total ionic concentration in the resin favours the absorp-

tion ofNa+.
Industrial grade cation exchange resins are 8 per cent crosslinked,
and have a water content of about 1·0 g H20/g dry resin. If the
crosslinking is reduced to 2 per cent, the water content is now about
4·0 g H 20/g dry resin, and the internal ionic concentration is
reduced from SN to 1·2N. This is still so much greater than the
typical concentration of natural waters, that the efficiency of
calcium absorption is hardly affected, but removal by a 3N sodium
chloride solution is now noticeably more efficient, because the
relative concentrations in the solution and in the resin now favour
sodium absorption. The overall efficiency of the combined absorp-
tion/regeneration process is thus improved.
Unfortunately, the effect is of no industrial value. Loosely
crosslinked res ins are soft and gelatinous, and when used in resin
columns they deform and pack down under press ure, causing
restriction of flow through the bed, and eventual physical destruc-
tion of the resin itself. Loosely crosslinked resins are, however, used
for a variety of special laboratory purposes, which are outside the
scope of this book.
The mass action equations corresponding with equation 9,
(FeH) and equation 10, (Th4+) contain terms [Na+]3 and [Na]4
respectively and application of the reasoning given above for
calcium shows that the uptake of FeH and Th4+ increases as the
square and cube of the dilution respectively. As a result, ferric iron
is very strongly absorbed from dilute solution by cation exchange
resins and is difficult to remove from them on regeneration. Con-
sequently, it can be a cause of difficulty in the water softening
process. Fortunately, four-valent metals which would give still
greater difficulty, are rare and are not found in normal water
treating practice.
HYDROGEN ION EXCHANGE. SULPHONIC RESIN

Fundamentally, there is no difference between the reactions of the
hydrogen ion*, and the sodium ion with a sulphonic resin. Thus
.... (15)
.... (16)
'" Throughout this book, the hydration of the hydrogen ion will be ignored, and
it will be written as H+, ralher than H30+.
32
HYDROGEN ION EXCHANGE. SULPHONIC RESIN
The corresponding mass action equations are similar to equations

11 and 13 respectively, and it follows that calcium (and correspond-
ingly magnesium), are much more strongly absorbed than sodium
from dilute solutions. Similarly, hecause of the ionic size effect,
already discussed for Li+ and Na+, Ca 2+ is more strongly absorbed
than M g2+, so that, when a water containing predominantly these
three ions is passed through a cation column in the hydrogen form,
the order ofemergence ofions is H+, Na+, M g2+ and Ca 2+. Thus,
irrespective of the relative concentrations in the inftuent water,
termination of the absorption cyde is always indicated by the
emergence of sodium ions.
It might be deduced from this fact, that the operating capacity
of the resin for these ions would be in the order Na + < M g 2 +
< Ca 2+, but this would be incorreet. If the resin is initially fully in
the H+ form, and treatment is continued until it is exhausted, then
the total capacity for all ions is equal, the value for anormal
industrial grade resin being 5·0 mg.equiv./g, or 2·2 mg.equiv./ml,
based on the weight and volume of the resin measured in the
hydrogen form.
In water treatment practice, for reasons to be considered later
(Chapter 4), regeneration is always carried out with a quantity
of acid much less than would be needed to reeonvert the resin fully
to the H+ form. Consequently, the operating capacity during the
next absorption eyde is governed solely by the extent to which the
resin has been reconverted to the H + form. This is lowest for calcium,
which has the highest affinity, and the operating capacities are
therefore in the order
Na + > M g2+ > Ca 2+.
When hydrochlorie acid is used for regeneration, the effect is a
comparatively small one, because the acid can be used at about
1·5N concentration, which is high enough to ren der the concentra-
tion/valency effect small. Sulphuric acid, however, cannot be used
to regenerate fully calcium-loaded resin at coneentrations higher
than 1·5 per cent or 0·3N, because calcium sulphate, the regenera-
tion product, is only sparingly soluble, whereas magnesium or
sodium-Ioaded resins can be regenerated with acid at higher concen-
trations. Consequently the concentration/valency effect is enhanced
during regeneration, and as a result, the practical working capacity
of a resin for calcium may be only half that for sodium.
Whereas the operating capa ci ti es ofresins on the sodium cyde are
independent of the anions present in the water, the corresponding
33
values for resins operating on the hydrogen cyde are affected by the
anions present in solution. The reactions:
.... (17)
.... (18)
are for all practical purposes not equilibria, but proceed to comple-
tion. Indeed, a suspension in water of the hydrogen form resin can
be titrated with sodium hydroxide just as if it were a dissolved acid.
In the commonly occurring waters which contain bicarbonate,
rather than chloride or sulphate ion, the reactions become:
;:=" Na+Rc- + H 20 + C02 t

.... (19)
2H+Rc-+Ca2+(HCOa)2-;:=" Ca 2+Rc2- + 2H 20 + 2C0 2 t

.... (20)
These reactions are nearly as complete as reactions 17 and 18

because they are displaced to the right by loss of carbon dioxide, or,
if it is maintained in solution by press ure, by the low degree of
dissociation of the weak acid H2COa.
The absorption part of the exchange cyde is thus considerably
more efficient in the presence of HCO a-, than when Cl- is the
anion. The operating capacities for a given regeneration level are
thus high, and the differences between Ca 2+ and Na+ are reduced.
Treated Water Q;.ialiry

If the resin is fuHy used in the hydrogen condition, then the ca ti on
leakage until the breakthrough point is always below 1 per cent,
irrespective of the nature of the cation. It is, of course, never zero,
for reasons discussed in connection with Figure 3. However, as in
practice the resin is never reconverted fuHy to the H + form, the
cation/H+ ratio in the emergent water depends on the cation/H+
ratio in the res in at the end of regeneration, and consequently on
the quality of acid used for regeneration. The equilibrium curves
for Ca 2+/R+ are very similar to those of Figure 9, so that calcium
leakage is quite smalI, even at low regeneration levels. The Na +IR +
affinities are, however, almost equal, so that ifthe res in is regenerated
only to the extent ofaround 50 per cent, which is anormal industrial
34
HYDROGEN ION EXCHANGE. CARBOXYLIC RESINS
practice, the sodium leakage is extremely high. The effects of this

are considered in Chapter 4.
HYDROGEN ION EXCHANGE. CARBOXYLIC RESINS

The case of carboxylic resins is different again. They are, effec-
tively, very weak acids which are virtually non-ionized, and
therefore non-reactive, in acid solution. Thus reactions 15 and 16
are impossible, because the acid produced causes immediate
reversal of the equilibrium. Reactions 17 and 18, on the other
hand, are equally efficient for carboxylic and sulphonic resins.
"Cl

G 80~----~----~~----+f----~
Q.
u
o
'"
Q.
::l
0 60
L.
Ol

.~
+'
u 40
'"
--
0

Ol
C'"

20
~

a..
O~~--~----L-----~--~
2'0
Figure 11. Carboxylic resin equilibria
In the case of reactions 19 and 20 there is a most interesting

difference. For reasons already discussed in connection with the
sulphonic resins, the affinity of Ca 2 + is much high er than Na +.
The difference is even greater in the case ofthe carboxylic materials,
and effectively, the presence of Ca 2 + ions forces the resin to remain
active at a pH lower than is possible in the case of Na +. The effect
is illustrated in Figure 11, which shows resin capacity as a function
of pH, when titrated with NaOH and Ca(OH)2 respectively. In
practice, the difference is so great that a carboxylic resin of the
35
polymethacrylic acid type will absorb calcium and magnesium from

bicarbonate solution, to the complete exclusion of sodium
H+Rc + NaHC03 - ----- no action .... (21)
If a solution of sodium carbonate is passed through a hydrogen form

methacrylic resin, precisely half the sodium is removed, the emerg-
ent solution containing sodium bicarbonate. The more modern
carboxylic resins, such as Amberlite IRC-84, Kastel C.100 Lewatit
CNP and Zeo Karb 226 based on acrylic groups, are slightly
stronger acids, and they do absorb some sodium from bicarbonate
solution, although to a much lower capacity than for calcium. The
most efficient resins from this point of view are the condensation
materials, Lewatit C.N.O. and Zeo Karb 216 which absorb sodium
from bicarbonate waters without difficulty.
It is, of course, obvious from the discussion above, that the re-
generation of carboxylic resins is always extremely efficient, irrespec-
tive of the acid used, or its concentration. Virtually 100 per cent
usage of regeneration acid can be achieved. As the carboxylic
resins, irrespective of type, absorb calcium much more readily than
sodium, whereas both ions are released with equal ease on regenera-
tion, it follows that the operating capacity for calcium must always
be higher than for sodium. This is precisely the opposite effect to
that observed with the sulphonic resins, whose overall operating
results are governed by the regeneration, and not, as here, by the
absorption process.
GENERAL ANION EXCHANGE

The use of anion exchange resins for exchanging ions in solution,
by the anionic paralleIs of reactions 7-10, is comparatively rare in
water treatment, although widely used for special chemical purposes
(see Chapter 8). There are only two significant applications in
water treatment. The first is the rem oval of fulvic and humic acids,
by exchange for chloride. (see Organic Traps. Chapter 6).
RA +CI- + Na + (Fulvate) - ~ RA + (Fulvate) -- + Na +CI-

.... (22)
The second is the conversion of temporary to permanent hardness

36
HYDROXIDE ION EXCHANGE. STRONG BASE RESINS
by removing bicarbonate from solution, and replacing it with

chloride, so as to produce a water which is stable to heat.
HYDROXIDE ION EXCHANGE. STRONG BASE RESINS

The important use of anion exchange resins is in the removal of
acids produced by cation exchange res ins by reactions 15 and 16.
This is the second stage of the demineralizing process.
· ... (23)
· ... (24)
or
2RA +OH- + H 2+ S04 2- ~ (RA +)2S042- + 2H 20 · ... (25)
Reactions 24 and 25 take place simultaneously. If the resin lS In

excess, reaction 25 predominates, whereas with an excess of solution
reaction 24 is the important one. In practice, this means that as
sulphuric acid solution enters the anion exchange res in column in
the -OH form, the top of the column is first converted to the
sulphate form. As the sulphate wave proceeds down the column,
the top, now in the presence of excess sulphuric acid, becomes
converted to the bisulphate form. At breakthrough of sulphate, the
resin is in a mixed HS0 4-/S0 42- condition. For this reason, if, as
is commonly the case in water treatment practice, the capacity is
calculated in terms of S042- only, the measured figures appear
abnormally high, and can apparently exceed the total capacity of
the resin. A similar effect occurs during the absorption of carbon
dioxide. The resin is converted first to the carbonate, and subse-
quently to the bicarbonate forms. In this case, however, the final
state is almost completely bicarbonate, which occurs in neutral or
slightly alkaline conditions, whereas fairly strong acidity is required
to convert the resin fuHy to the bisulphate form.
Of the ions normally occurring in water, the order of affinities is
HS0 4- > Cl- > HCO a - > Si02. As in the case of cation resins,
the working capacities should be in the reverse order, but in
practice, the results are modified in two ways. The first is the false
calculation of sulphate capacity, which by convention is used
throughout the industry; and the second is the extremely complex
nature of silica and silicate chemistry, which means that the ions
present in water are far from being simple HSiOa-. In practice, the
working capacities as quoted by different resin manufacturers vary
37
to some extent, with 'sulphate' and bicarbonate being higher than

chloride, while silica (always quoted as SiO z) is slightly less than
chloride.
Regeneration rif Strong Base Resins

In the discussion of cation exchange resins, it was pointed out that
reactions 17 and 18 are not equilibria, but are effectively complete.
The same applies to the anion exchange reactions 23-25. Thus,
.... -._._.
----.---.
N~Cl
A -e_ -e_e-e_.
t",-..... - -
1'2 1-4 1-6 1·8 2·0 2'2 4·6 1,,8 5·0
Bed volu mes input
Figure 12. Regeneration of strongly basic resin with NaOH
provided that the water entering the column contains only mineral
acids, free from neutral salts, the emergent water is completely
de-ionized throughout the run, until the breakthrough point, at
which there is a sharp rise in conductivity, and drop in pH. The
process of regeneration is correspondingly inefficient. The quater-
nary ammonium resins are such strong bases, that they have
extremely high affinities for all anions, and it is difficult to displace
these ions with hydroxide. Indeed, it is virtually impossible to
convert them completely to the hydroxide form, irrespective of the
quantity or concentration ofregenerant used. A typical regeneration
curve is shown in Figure 12, which illustrates the removal of chloride
from the resin, using 5 per cent sodium hydroxide solution. The
first 0·45 bed volumes of emergent liquor consist solely of the voids
water displaced from between the resin beads, after which the spent
regenerant liquor builds up to the full input concentration du ring
the next 0·35 bed volumes. Allowing for this dilution factor, one
bed volume of 5 per cent NaOH has passed through the column by
point A. This contains 50 g NaOH/1 resin (3 Ib/ft 3 ), which is the
normal industriallevel. At this stage, only 60 per cent of the available
38
ACID ABSORPTION. WEAK BASE RESINS
chloride has been removed from the resin. After 5 bed volumes input,
when a total of 220 g NaOH/1 resin (13,5 Ib/ft3) have passed
completely through the column, the removal of chloride is still far
from complete.
ACID ABSORPTION. WEAK BASE RESINS

The absorption of mineral acids by weak base resins, while funda-
mentally an ion exchange reaction, has the characteristics of an
addition process. The weak base material has, for all practical
purposes, no hydroxide form, just as a simple organic base such as
aniline does not have a hydroxide. The salts are thus not chlorides
but hydrochlorides.
C 6 H sNH 2 + HCI ~ C 6 H sNH3+ CI- · ... (26)

Aniline
Similarly
· ... (27)
The corresponding process of regeneration is
· ... (28)
Both these processes have the characteristics, not of equilibria, but

of direct acid-base reactions which proceed virtually to completion.
The overall efficiency of regenerant usage is therefore over 70 per
cent, and can be raised to 90 per cent under suitable conditions,
whereas the corresponding figures for strong base resins rarely
exceed 40 per cent. Moreover, reaction 28 proceeds equaIly weIl
even when a less powerful regenerant than caustic soda, such as
sodium carbonate or ammonia, is used. As sodium carbonate is
considerably cheaper than an equivalent quantity of caustic soda,
it is frequently preferred.
Finally, the weak base resin is unable to absorb acids as weak as
CO 2 or Si02, and the whole of its capacity is thus available for the
absorption of chloride and sulphate. As a treated water free from
all mineral salts, but containing CO 2 and Si02, is perfectly satis-
factory for a large range of purposes, weak base resins have con-
siderable industrial value.
Treated Water Qpality

When anion exchange resins, whether weak or strong base, are
used for the absorption of pure mineral acids, the resultant water is
39
neutral and ofvery low conductivity, almost irrespective ofthe state

of regeneration of the resin column. In the case of weakly basic
resins, the treated water quality does depend on the regeneration
level, to the extent that hydrochloride left on the res\n by serious
under-regeneration will bleed out slowly by hydrolysis during the
subsequent operating cyde. This effect is a minor one, the total
concentration of HCI found in the treated water from this cause
rarelyexceeding 1·0 p.p.m. It follows that if a natural water supply
is submitted first to hydrogen ion exchange by equations 15 and 16,
and subsequently to hydroxide ion exchange 23-25 or acid absorp-
tion 27, the water will, with the above proviso, be completely
purified, provided that the cation exchange process itself has
proceeded to completion.
In industrial practice, as has been indicated above, the regenera-
tion levels used are govemed by economics, and are never sufficient
to convert the cation resin fully to the hydrogen form. There is
always a certain degree of cation leakage, which is normally in the
form of sodium, the least strongly retained ion. Thus the solution
entering the anion exchange column contains a mixture ofhydrogen
and sodium ions, together with chloride, sulphate, carbon dioxide
and silica. In the case of weak base resins, the C02 and Si02 pass
through unchanged, the free mineral acids, i.e., the hydrogen ions
and an equivalent quantity of mineral anions, are absorbed, and the
sodium ions pass through, together with an equivalent quantity of
chloride. The presence of this chloride is one of the most frequent
sources of misunderstanding in the water treatment industry.
Because it is easily detectable by simple analysis, whereas sodium is
not, the attention of the plant chemist is more easily drawn to it.
Consequently, on finding high chlorides in the treated water, his
normal re action is to raise the regeneration level of the anion ex-
change unit, and when this fails, to suspect some kind of chemical
failure of the resin. In fact, the chloride content of the final dem in-
eralized water is normally equal to the sodium concentration, and
by far the most common cause of high chlorides in the treated water
is sodium slip from the cation units. Under these circumstances, the
corrective action is to improve the regeneration, not of the anion
column, but of the cation unit. If really low chloride levels, below
0·5 p.p.m. are required, in cases where the raw water contains
appreciable concentrations of sodium, it is virtually impossible to
achieve the required results in a two-bed system using a weakly
basic resin, since the quantity of acid required to regenerate the
cation unit to the required level is economically intolerable. In
40
TREATED WATER QUALITY
these cases, the two-bed system must be followed by a mixed bed

unit (see Chapter 4).
When, in a two-bed demineralizing system, the anion column
contains a strong base res in, then the C02 and Si02 are absorbed,
in addition to the mineral anions. If the cation column is leaking
traces of sodium, then the associated chloride does not pass through
the anion unit, but is removed by hydroxide exchange.
The resulting water has a fairly high pH and conductivity, which

may be in the region of 10·0 and 25 p.S/cm respectively. If the cation
resin is exhausted before the anion material, the pH and conduc-
tivity both rise, as the whole of the metallic salts present are now
being converted to hydroxide by re action 29. The rise is, however,
comparatively slow. It is customary to calculate the plant to have
excess cation exchange capacity, so that at the exhaustion of the
anion material, the pH drops rapidly to around 3·0, while the
conductivity, after a momentary fall, rises correspondingly to
around 50-60. This gives a sharp and unambiguous end-point.
There is a further cffect of sodium leakage on the quality of
water treated by strong base resins. Although silica is only weakly
held by these materials, it is difficult to remove, because of its
tendency to form polymerie moleeules or micelles in the resin
structure. On completion of regeneration, a certain proportion
of silica always remains on the resin, distributed throughout the
bed. The caustic soda formed by reaction 29 during the subsequent
absorption cyde, although of low concentration, nevertheless
causes a partial further desorption of the silica left in the resin.
Consequently, the silica level in the treated water depends on the
degree of regenera tion both of the cation and of the anion exchange
unit, and to achieve low residual figures, excessive quantities of
regenerant must be used for each. If the final silica level is to be
suitable for high press ure boilers, that is, below 0·02 p.p.m., mixed
bed treatment is the only reliable method.
KINETICS
The discussion above of equilibria and their results are all based
on the principle that the time scales of the processes have been long
enough to allowequilibrium to be reached. In practice, this is not so,
and the observed results are influenced not only by ionic concentra-
tions and resin affinities, but also bythe rate of diffusion ofthe ions from
41
D
the solution into the resin, and then through the gel structure of
the res in itself. The theoretical background of ion exchange kinetics
is considerably more complex than that of equilibria, and it is
virtually impossible to reduce it to a simple mathematical expression
which can be applied by the industrial user of resins, so as to
determine the effect of changes in flow rate, or regeneration time
on resin capacity, and treated water quality.
Na+
/'
"- \ Na+
/
/'
"-
\ Na+
\
H+
I
I
H+
H+
\
!
\ Na+
~ Solution
flow
H+
\
,; (H~ I
/
/
Na;'
\ H+
"
/- / {
Na;'
H+
I
Particle Film
d illusion diffusion
Figure 13. Ion diffusion
Perhaps because of this difficulty, the whole subject of exchange

kinetics is virtually ignored in most of the practical literature on
water treatment. In particular, the resin data sheets issued by most
manufacturers make no mention of the influence of flow rates and
cycle times on the operating results. It is common to find consider-
able detail relating the capacity and treated water quality to the
input analysis and regeneration Joevel. It is rarelY made clear that
the observed values may be considerably inferior to the figures
quoted, if the flow rates used are higher than those employed by
the resin manufacturer in the tests from which the data were cal-
culated.
In the following section, a brief qualitative description will be
made of the factors influencing exchange rates, together with curves
showing the effect of exchange kinetics on practical results.
Strongly Acidic and Basic Resins

The effect ofexchange rates are illustrated by considering a cation
exchange resin bead in the H+ form, past which flows a solution
42
STRONGLY ACIDIC AND BASIC RESINS
containing Na+ ions (Figure 13). In the bulk of the solution, there
is effectively an infinite quantity of new Na + ions, at a constant
concentration, but around each bead, there is a static layer ofwater
held by friction. Sodium ions pass through this layer to the resin
purely by diffusion. The diffusion rate is constant for a given con-
centration of sodium ions in the bulk solution, and is quite indepen-
dent of the nature of the resin itself. H, as is true in the case of
strongly acidic and basic resins in dilute solutions, the rate of flow
of ions through the resin itself is faster than the diffusion through
the surrounding static film, this film becomes denuded of sodium
ions, and controls the rate at which the ion exchange reaction
proceeds. The kinetics are then stated to be F-type, or film con-
trolled. If the solution flows past the beads so slowly that the rate
1"0~---------~---~---:::==-'"
+
I
+
+",
.~
Z
o~--~~--~----~--------------~
A3
Increasing volu me ---
Figure 14. Breakthrough curves
of arrival of new ions is similar to the rate of diffusion through the

static film, then the resin is always virtually at equilibrium with the
solution. In a column originally of H+ form resin, with Na+Cl-
flowing down, there would be a sharp demarcation of 'wavefront'
between an upper layer of beads entirely in the sodium form,
surrounding Na+CI-, and a lower layer of beads in the hydrogen
form, surrounded by H+CI-. The analysis of the effiuent liquor, or
the 'breakthrough curve', would be as in Figure 14, curve 1.
As the solution flow rate increases, ions are presented to the beads
at a faster rate than they can diffuse through the static film, and
some must pass the bead, to enter another lower down. The sharp
barrier between H+ form and Na+ form resin disappears, and is
replaced by a region of varying composition, so that the wavefront
has become diffuse. Correspondingly in solution, there is a
43
concentration gradient ofNa+Cl- between zero and its input value,

and the efHuent curve is as in Figure 14 (2). The total quantity of
Na + ions absorbed, after passage of excess solution, would be the
same in each case, but in industrial water treatment, the practice
is to terminate the run at the breakthrough point, i.e., Al for curve
(1) and A2 for curve (2). The observed capacity is thus lower at the
higher ftow rate. If the ftow rate corresponding with curve (2)
is doubled, the region of varying composition is increased, and the
breakthrough capacity reduced to a value represented by point
A 3. If the static film were always unchanged in thickness, A3AI
would be exactly double A 2 A I , and the recorded loss of capacity,
as compared with the total available figure, would be proportional
to the ftow rate. In fact, the film itself decreases in thickness with
increasing water velocity, so the observed loss of capacity is pro-
portional to a complex but fairly small function of the rate of
presentation of ions. This rate is itself the product of the ftow rate
and ionic concentration of the water, and it follows that all break-
through capacities should be recorded in relation to these two
parameters. In practice, it is convenient to combine the two, by
plotting capacity against the total time to breakthrough. This time,
in the absence of kinetic effects, would be inversely proportional to
the product offtow rate and concentration.
The strongly acidic and basic materials, both ofwhich exhibit film
controlled kinetics in dilute solution, are comparatively rapid in
action. For purely engineering reasons, such as the necessity for
avoiding heavy press ure losses through the bed, flow rates for
industrial plants are normally limited to less than 20 gal ft- 2 min-1
(60 m 3 m- 2 h-1 )which with a bed depth of6 ft (1'85m), corresponds
with 3·3 gal ft- 3 min-1 (32 m 3m- 3h- I ). At this rate, and with a
typical input water analysis of 250 p.p.m. total dissolved solids,
the operating cyde lasts about 6 h, which is in excess of the time
required for the exchange process in the resin. Accordingly, all the
resin in the bed, except the last few inches, reaches full equilibrium
with the solution, so that kinetic considerations are almost without
inftuence, and variations in ftow rate do not significantly affect the
capacity of the res in , or the quality of the water produced. When
the ftow rate is increased so as to reducc the total operating run
below about 5 h, film diffusion kinetics begin to take effcct and
the operating capacity falls, as illustratcd in Figure 15. Thc curves
shown refer to normal waters, whosc total dissolvcd solids are in the
region 50-500 p.p.m. With incrcasing ionic concentration in the
water, the rate of diffusion of ions through the static film rises,
44
STRONGLY ACIDIC AND BASIC:RESINS
and the 'critical' operating period is correspondingly reduced.

Regeneration kinetics have a different control mechanism.
Because the solutions used are concentrated, the rate of diffusion of
ions through the statie film is greatly inereased, and beeomes
greater than the rate of diffusion through the resin bead itself.
The overall proeess is therefore eontrolled by the resin, and the
system is said to exhibit P-type, or particle eontrolled kineties.
Under these cireumstances, curves similar to those of Figure 14
are aga in obtained, exeept that the length of the wavefront now
bears a linear relation to the flow rate. Thus, if the solution veloeity
Eo; r:::--
>
~
:J
E~
x c
ra 0
-E:;:;
~
o 
C
01<1>
2 g'
f
If
c '-
~ C
L


>
- - Strong ly ac idic resin
Cl 'o, - - Strongly ba sic resin
::; ra
~~
U ....
ra-
:i~
U..c
01 ra
C c
:;:; 'iij
~:i5
g
 0
0 3 6 9 12
Tot al absorpt ion time ,h
o 5 10 15 20
Tota l regenerat io n time, min
Figure 15. Eifect of absorption and regeneration times
for eurve 3 is twice that of eurve 2, A 3 Al is twiee A2Al. Under the

influence of the high eoneentration gradient through the resin, the
particle diffusion rate is mueh more rapid than is the ease during
the absorption eycle. Aeeordingly, overall regeneration tim es ean
be mueh shorter than absorption times, and values in the region
of 15 min are adequate. At flow rates resulting in shorter total times
full equilibrium is not aehieved, the rem oval of ions is ineomplete,
and the resin eapacity is correspondingly lm.ver during the sub-
sequent absorption eycle. The effeet is illustrated in Figure 15.
45
Reaction rate is, of course, a function of particle size. The time

taken for an ion to travel to the centre of a 30 mesh bead from a
decinormal solution is about 20 sec, a fact which can readily be
confirmed by placing an indicator-dyed anion resin bead, in the
OH- form, in a drop of acid under a microscope. The indicator
change can be observed to pass inwards from the surface to the
centre of the bead. The time decreases with decreasing particle
size, and it follows that from the chemical viewpoint it is advan-
tageous to use the finest possible particle grading. In industrial
practice, hydraulic considerations govern the minimum size which
can be used, a particle range of 16-50 mesh being normal. For
laboratory work, the resins used may be as small as 15 p. in diameter.
Weak(y Acidic and Basic Resins

The position with regard to the carboxylic cation, and the weak
base anion materials is completely different from the strongly
ionized resins. The fully regenerated materials are almost com-
pletely non-ionized, so that the process of regeneration involves,
not only diffusion of ions through the resin, but also the making or
breaking of a covalent bond
-",
~-NH+.OH- .... (30)
/
~-COO-.H+ .... (31)
Reactions 30 and 31 are comparatively slow, and in consequence,

the weakly ionized ion exchange materials are much more rate-
sensitive than the strongly ionized ones. These materials are, in
fact, always governed by particle diffusion, which is now much
slower than the film diffusion rate. As a result, the capa city-time
relationship is much less favourable than with the strongly ionized
resin. Until fairly recently, most weakly basic resins were based
on the use of polyamines, which yielded products with high total
capacities, but low exchange rates. In recent years, the importance
ofincreasing the rate ofreaction has been generally realized, and the
modern tendency is to use tertiary amine resins, which, in general,
are more rapid than the polyamine materials. Dimethylamine,
(CH 3 )zNH, gives the active group -CH 2-N(CH 3 )2 (see Figure
6( b), Chapter 2), which is the smallest, and most rapidly
acting group possible in a polystyrene structure. Resins made in
this wal' are monofunctional, so far as their weak base content is
46
WEAKLY ACIDIC AND BASIC RESINS
concerned, hut they normally contain a proportion of strong hase

groups formed hy the secondary reaction:
/0
CHz
CH
/ 'CHzCl
CHz
/
I + (CH 3liNH ---:-
/0
CHz
CH
/ CHp
CHz
/
•••• (82)
60
25
50
0'
u
208'"
<'11 <'11
U U
1.0
-- ':..
....;
~
Cl
1 5~
--....
u
<'11 30 ~
a. u
<'11 <'11
u a.
Cl ro
c 10 u
20 Cl
C
~
CI>
a. iii
....
CI>
0 a.
50
10
o 6 12 18 21.
Total absorpt ion t i me. h
Figure 16
47
The presence of these groups is advantageous, since they increase

the overall ionization of the resin. The tertiary amine resins have
lower total capacities than the polyamine materials, but their greater
exchange rates result in improved capacity/time curves. A typical
polyamine resin, and a dimethylamine resin based on the same
polystyrene skeleton, are compared in Figure 16. This figure also
indudes the effect ofpoisoning, which is discussed in Chapter 6.
In carrying out laboratory test work on weakly basic resins, it is
vital to complete all absorption cycles without stopping the experi-
ment. Most research laboratories opera te a time-table covering
about 9 h, and if the first two are occupied in preparing a resin
column for its test run, there is a natural tendency to operate for
the remaining 7 h, shut down, and recommence next day. The
dependence of capacity on time is due solely to the slow rate at
which internal equilibrium in the resin is established. This process
is independent of the flow of water and continues during the over-
night shut-down, with the result that the interrupted experiment
frequently re cords a much higher capacity than would be achieved
by the same resin column in an unbroken run at the same flow
rate. In the author's laboratory, to permit correct testing of weak
base anion resins without undue night working by the laboratory
staff, automatie devices are used to switch on the columns under
test at about 3 a.m., so that they reach the crucial part of their
cyde during the middle ofthe next working day.
48
CHAPTER4
UNIT WATER TREATlvlENT PROCESSES
WATER SOFTENING BY SODIUM EXCHANGE

\Vater softening, which under its earlier name of base exchange
softening was the first industrial ion exchange process, is still
by far the most widely used: the total production of polystyrene
sulphonic resins, used for this purpose, is several times higher than
the total output of the corresponding anion exchange materials.
For the reasons given in Chapter 3 the process is fundamentally
very efficient and the basic operating techniques have changed very
little over the last 50 years. The process is usually carried out down-
ftow with a settled resin bed and after a backwash in the upftow
direction to regrade the resin bed and remove any loose dirt which
may have accumulated in it, regeneration is also carried out down-
ftow. There is now an increasing general tendency to use counter-
ftow operation, the advantages of which will be discussed later in
this chapter. The gain which can be made by counterftow operation
in the case of water softening is, however, comparatively marginal
and the counterftow process is therefore mainly used in demineraliz-
ing plants. One industrial company in the Uni ted Kingdom
produces a range of packed bed automatie counterftow softening
units, but the purpose is to give simplicity in design rather than
changes in chemical efficiency. The figures which follow in this
section apply equally to co-ftow and counterftow regeneration
procedures.
Industrial softeners are manufactured in diameters ranging from
1 to 12 ft, (0·3-3·6 m) with bed depths varying from 3 to 10 ft
(1-3 m). The rates of ftow used are normally between 5 and 20
gal ft- 2 min-1 (0·25-1·0 m 3m- 2min-1 or 15-60 m 3m- 2h-1 ). With
a bed depth of 6·6 ft (2 m), these figures represent 0·125-0·5 bed
vol./min. For hydraulic reasons it is frequently necessary to combine
large diameters with sm all bed depths in order to reduce the pump-
ing head required to feed water through the beds. Resin beds of
this type have a most unfavourable geometry as compared with the
typical tall narrow la bora tory units; but, nevertheless, the capacities
49
UNIT WATER TREATMENT PROCESSES
o btained in them should be wi thin 15 per cent of the corresponding

laboratory results, provided the unit has been designed to give
even distribution and collection ofwater.
If, in practice, the capacity figures differ by more than this figure,
the reason is unlikely to be due to resin kinetics, but is more prob-
ably connected with asymmetric entry of water to the plant. At
high flow rates in a large unit, this can cause a preferential flow
through one part ofthe resin bed, with the result that breakthrough of
hardness is detected in the effiuent water at a stage when part of the
bed is still far from exhausted.
Figure 17 gives the capacity of a typical polystyrene sulphonic
acid resin, as a function of regeneration level and flow rate, for a
water containing about 250 p.p.m. hardness. Similar curves are
..,
o
~ 70~--+---~~~--~---r~=r--
u
Regeneration level g/l. NaCl
Figure 17. Capacity /or hardness removal. A. Calculated results at 100 per cent efficiency·
B. Operating results 0/0,1 bed volumes/min. C. Operating results 0/0,3 bed volumes/min·
D. Operating results rif 0·5 bed volumes/min. E. Operating results 0/0,8 bed volumes/min
published by most resin manufacturers; but the effect of flow rate

is not always taken into account, and the curves given are related
to the conditions of test used by the manufacturer. If the flow rate
used exceeds 0·1 bed vol./min, it is wise to apply to any published
curves correction factors taken from Figure 17.
Polystyrene sulphonic resins are normally supplied fully in the
sodium form, and removal of hardness on the first run is complete
until a sharply defined breakthrough point is reached. At this
SO
WATER SOFTENING BY somUM EXCHANGE
stage the res in is almost completely in the calcium and magnesium

form and continuation of the run beyond the breakthrough point
leads to complete saturation of the resin almost immediately. The
sharpness of the breakthrough is of course dependent on the flow
rate, for the reason discussed in connection with Figure 13, Chapter 3.
It is for this reason that the operating capacities shown in Figure 17
are rate-dependent, since the total capacity of the res in is constant
but the operating run is always terminated at the point of break-
through and not at the point of final exhaustion.
The total capacity of a polystyrene sulphonic resin is normally
about 2·25 g.equiv.jl or 50 kgr CaC03jft3. In the unattainable
conditions of perfect regeneration the resin would require 2·25 X
58·6 or 132 gjl NaCI (8·25 Ibjft 3) to convert it fully to the sodium
form, and curve A of Figure 17 gives the capacity which would
\
10 I
QI
Cl
ru
C
\\
QI
~
QI
0.
0. 5
'"
-
''""
QI ~
C
...ru
"U "'-...
~
:J: 0
20 40 60 80 100 120 g/l. NaCl
2'5 5·0 7·5 lbltt 3 NaCl
Regeneration level
Figure 18. Hardness slip
result from different regeneration levels if complete exchange were

obtained. In the practical case represented by Curve B, regeneration
efficiency is virtually 100 per cent at NaCI levels below 30 gjl
(2 Ibjft 3) and is still over 70 per cent at 100 gjl (6·5Ib/ft 3).
As the resin is virtually fully in the calcium form at the end of the
operating cyde and as the total capacity of the resin is 114 gjl as
CaC0 3, it is dear that a regeneration level as low as 30 gjl NaCl,
which gives an exchange capacity of 26 gjl as CaC0 3, has left the
resin after regeneration only 23 per cent in the sodium form.
Nevertheless, it is seen from Figure 18 that resin which has been
regenerated only to this minor extent will still remove about 95
51
per cent of the hardness from the water, reducing it to a level which
is acceptable for many industrial purposes. Under the conditions
more normally used in industrial softening practice, it is almost
unnecessary to consider the possibility of slip.
The only compromise to be made is between a low regeneration
level, which gives a low running cost but high capital cost, and a
high level which has the reverse effect. In British practice the
optimum regeneration level is around 90-100 g/l NaCI (6 Ib/ft 3 )
which gives a salt usage efficiency of about 70 per cent, with a slip
of under 1 per cent. In countries where the price of salt is much
higher than in Great Britain the compromise would be at a some-
what lower salt input.
To avoid possible confusion later, it should be noted that this
statement applies only to softening, and not to demineralizing.
As will be seen later, sodium slip is always a significant feature ofthe
hydrogen exchange stage of the demineralizing process, and a more
complex compromise is necessary between the confticting require-
ments of treated water quality, regenerant cost, and plant size.
In the case of softening, the presence of sodium in the raw water
must theoretically reduce the res in capacity by disturbing the
equilibrium of equation 8 (page 26) to the left. In practice, the
effect is insignificant unless the sodium concentration is much
higher than is normally found in natural water supplies. Figure
19 gives a correction curve to be applied to the results of Figure 17
for waters with high sodium contents. In certain special cases high
alkali metal competition does occur. In the softening of sugar juices
(Chapter 8) resin capacities are considerably lower than those found
in water treatment practice, because of the relatively high con-
centration of potassium commonly present in the liquor. As potas-
sium has a higher affinity for the resin than for sodium, its effect
is greater than indicated in Figure 19 and it is inadvisable to attempt
to calculate the operating capacity from curves of this type. The
figures for plant design must be determined by direct experiment
with the liquors which are to be treated.
In cases of high total hardness there is a further capacity loss as
indicated in Figure 20. This is partly due to the overall concentration
effect discussed in Chapter ~~, but is more closely connected with
the fact that after regeneration the resin must be rinsed to remove
the mixture of sodium and calcium chloride from it. The total
quantity of rinse water required to re du ce the chlorides to an
acceptable level is quite high, being five to six times the total
volume of the resin bed. In normal industrial practice, the rinsing
52
WATER SOFTENING BY somUM EXCHANGE
is carried out with raw water, with the result that the top layers of
the bed are being exhausted while the lower layers are still being
rinsed. The effect is unnoticeable when the hardness of the raw
water is less than 500 p.p.m. but be comes increasingly important
7020 40 60 80 100
Na+ percentage of total
cations
Figure 19. Capacity correction Jor sodium in raw water
at high er concentrations. It can, of course, be eliminated by rinsing

the resin with softened water instead ofraw water; but the quantity
of treated water which is was ted is equal to the amount of raw
water which would have been used and the net capacity, as
measured in terms of available treated water, is thus unchanged.
100 -=---,---,-----,--.,..---r---,
--r--f--
~
ra
C~
~:; 90 L---L---~===t:::±::~==~
.... '-
8.g,
.~~ 801--+-+--+--1---4------1
~ 0
a.
ra
u 70500 1,000 1,500 2,000
Raw water hardness p.p.m. CaC03
Figure 20. Capacity correctionJor hardness oJ raw water
It is dear from Figures 17-20 that the softening of sea-water,

which contains 500 m.equiv./l sodium and 50 m.equiv./l hardness,
is a theoretical possibility although the resin capacities will be
considerably less than those obtained in normal water treatment
practice. Sea-water softening may become a subject of increasing
importance, in order to prevent scale formation in the evaporators
used for the large scale production of drinking water in arid
coastal areas, such as the oil producing regions of the Middle East.
53
In principle, it is possible to soften the sea-water to an acceptable

level, after which the resin is regenerated with the softened con-
centrated brine which is available as a by-product of a multi-
stage evaporation system. In practice, the results obtained with
conventional equipment fall far short of the ideal figures, and fairly
complex multi-stage counterflow equipment may be needed.
Difficulties Due To Iron

Mention has already been made (Chapter 3) of the problems
which can be caused by the presence of iron in water to be softened.
This problem rarely occurs with surface waters, where any iron
originally present has been oxidized naturally to the ferric state,
and hydrolysed to precipitate ferric hydroxide, which has settled or
been removed in filters. Some deep weIl waters, particularly those
containing dissolved carbon dioxide, may contain traces of ferrous
iron, FeH, which is taken up with the calcium by ion exchange.
Its affinity for the resin is similar to that of calcium, and if it re-
mained in the ferrous state, it would be removed without difficulty
during regeneration. In practice, however, the act of pumping the
water to the surface can introduce air, and a sam pIe of this type of
water which is allowed to stand normally develops a faint yellow
haze, as the oxidized iron hydrolyses to precipitate ferric hydroxide
in an extremely fine, or possibly colloidal state. The ferric colloid is
positively charged, and is strongly attracted to the negative charge
on the resin structure, so that it coagulates on the resin beads. The
affinity of the resin for FeH is such that the precipitate then slowly
redissolves, the iron being absorbed by the resin, with the pro duc-
tion of an equivalent amount of NaOH. Ferrous iron remaining
in solution is also absorbed, and slowly oxidized by dissolved
oxygen which penetrates the resin beads.
When iron has entered the res in , by either mechanism, it is not
fuHy removed at the normal regeneration level of 6 lb NaCI/ft 3 .
It is clear from Figure 17 that this quantity removes only about 50
per cent of the calcium held in the resin, and as the affinity of ferric
iron is high er than that of calcium, it is largely unaffected by
regeneration, and builds up on the r<:sin, causing a gradual reduc-
tion in capacity for calcium. In the U.S.A., a commonly used
method for overcoming this problem is to add a powerful reducing
agent such as sodium hydrosulphite to the regenerant. This is, how-
ever, a rather expensive procedure, and it is preferable to remove
the iron from the system before the ion exchange step, byaeration,
coagulation and filtration, or by means of an oxidizing filter
54
ALKALINI1Y REMOVAL WITH CARBOXYLIC RESINS
containing a mixture of pyrolusite (manganese dioxide) and

standard filter sand.
ALKALINITY REMOVAL WITH CARBOXYLIC RES INS
The 'Starvation' Process

The first cation exchange material which could be used indus-
trially on the hydrogen cyde was sulphonated coal, which, although
now completely superseded by the high capacity polystyrene
resins, was in fact superior to the modern materials in one respect.
Sulphonated coal was not monofunctional, but possessed a mixture
of sulphonic, carboxylic and phenolic groups, of widely differing
acid strength. When fairly high regeneration levels were used, the
phenolic and carboxylic groups, together with a considerable pro-
portion of the sulphonic groups, were converted to the hydrogen
form, and the material was thus able to convert neutral and alkaline
salts to their free acids by equations 15, 16 and 20
H+Rc-+ Na+Cl- ~ Na+Rc- + H+Cl- .... (15)
2H+Rc- + Ca +Cb- ~ Ca +Rc2- + 2H+Cl-
2 2 .... (16)
2H+R c - + Ca2+(HC03-)2 ~ Ca 2 +Rc2 - + 2H 20 + C0 2t (20)
H, however, the regenerant quantity was reduced to a level equiva-

lent to slightly less than the total weak acid groups, the sulphonic
groups remained in the salt form, and the resin was then able to
operate by reaction 20 only. This system of depriving the resin of
regenerant gave rise to the name 'Starvation Process'. The con-
sumption of acid during the regeneration was virtually 100 per
cent, and as the carbon dioxide resulting from the process could be
removed cheaply in a degassing tower, the process gave an extremely
economical method of partial demineralizing, without the use of
anion exchange resins, which has remained in wide use ever since.
A typical water from a limestone region has an analysis which can
be summarized as folIows.
Table 2
Raw water After
p.p.m. starvation treatment
Total hardness as CaC03 300 70
Sodium as CaC03 50 50
Bicarbonate as CaC03 250 20
Mineral anions ad RaC03 100 100
55
The total hardness is thus greater than the alkalinity, and the
Starvation Process removes about 70 per cent of the dissolved
solids, while stillleaving a significantly hard water. Passage of this
water through a degassing tower and a sodium form sulphonic
resin gives a soft, and reasonably thin water, which is eminently
suitable for use as make-up to medium press ure boilers. This com-
bined 'Starvation-Base Exchange' process, whose operating cost
is less than that of softening, and considerably lower than that of
demineralizing, is now increasingly being used for packaged
boilers, for which, as indicated in Chapter 1, thick waters can
present serious problems unless the total dissolved solids are con-
siderably reduced.
The use of sulphonated coal has been completely abandoned
in recent years, and the Starvation Process now uses carboxylic
resins, which have considerably high er intrinsic capacities. In
addition, they are virtually incapable of carrying out reactions
15 and 16 and use almost their total available capacity on reaction
20. They have, in consequence, much higher operating figures
than the earlier coal-based products. The manufacture and use of
the carboxylic resins is a rather more complex procedure than in the
case of the polystyrene sulphonic materials. Consequently, whereas
the latter are made under a variety of trade names, by alm ost
every ion exchange resin producer in the world, weak acid materials
are manufactured by comparatively few companies. There are three
types in use.
(a) Polyphenol-formaldehyde condensation products, which have
been subsequently carboxylated. Lewatit CNO and Zeo Karb 216.
(b) Crosslinked polymethacrylic acid. Amberlite IRC.50.
(c) Crosslinked polyacrylic acid, or hydrolysed polyacryloni-
trile possibly containing minor properties of methacrylic acid
Amberlite IRC.84, Kastel C.I00, Lewatit CNP, Zeo Karb 226.
The methacrylic materials have largely been replaced by the
acrylic resins, which have high er capacities, and are more rapid
in action. Even the acrylics, however, are considerably slower than
the condensation materials, which consequently give better ratings
at high ftow rates, even though their total capacities are less
than half those of the acrylic products. The latter can record
capa ci ti es as high as 80 kgr/ft 3 (180 g/l) as CaC03, when used
with waters containing high hardness and alkalinity, but the total
time required to achieve this capacity is so great that the operating
ftow rate is impracticably slow, and the plant size unnecessarily
large in relation to its output. Figure 21 gives the operating capacities
56
ALKALINITY REMOVAL WITH CARBOXYLIC RES INS
of the two types of resin as a function of absorption time. Above

10 h, the acrylic resin is superior, but below this value, the con-
densation product shows a considerable advantage. In practice, the
condensation resins are used even more widely than is suggested
by Figure 21, since their cost i.. much lower than that ofthe acrylics,
and the capacityfcost ratio is higher than that ofthe acrylics under
almost all conditions. The operating cost is, of course, the same in
both cases, since regeneration efficiency is virtually 100 per cent.
This statement is, in fact, a slight over-simplification, which is
strictly correct only under controlled conditions. If the resin is
C 100
<lJ
u
L.. 40
<lJ
0.
0
Q 80 35
-u
ro
>.
C
0 ""
C <lJ 30 ~
u
'~:g 60
251;
Cu;
.....
..... c L..
ro 0 20 ~
",,'-
S ~ 40 ~
ro <lJ
15 rou
u C
<lJ 0.
-'-:0)
..... <lJ
ru
0) L.. 20 10 u
~
u
ro 5
0.
ro
u
10 20 30
Operating cycle, h
Figure 21. Capacity / time relationship Jor weakly acidic resins
operated to breakthrough in each cyde, it will be almost completely

in the calcium and magnesium form. If the regeneration level used
is then chosen to equal the required capacity, taken from Figure 21,
the acid consumption will be 100 per cent and a substantially
neutral regeneration effiuent will result. During the subsequent
operating cyde, the treated water will then have an almost con-
stant alkalinity of 10-20 p.p.m. until the breakthrough point, when
alkalinity and conductivity will rise sharply (Figure 22, Curve A).
These conditions are required for the Starvation-base exchange
process for low-pressure boiler make-up, since a constant quality
and permanent freedom from acidity are essential.
57
E
However, the condensation type carboxylic resins have such a

high affinity for bivalent ions, that they are capable of carrying
out reaction 16 to a limited extent, although reaction 15 is for all
practical purposes impossible. Among the various multi-column
demineralizing units discussed in Chapter 5, there are included
some in which the first stage is a column of carboxylic resin. In these
cases, there is no objection to the production of an acid water, from
the first column, and it is possible to raise the operating capacity of
the resin by using regenerant quantities slightly higher than those
indicated in Figure 21. The efficiency of acid consumption remains
over 99 per cent and the water quality then varies throughout the
30~----------~----------~-,----~--~
Alkalinity 20
p.p.m. 10 A
as CaC0 3
- - - - -Ol""""'--------+--------!-----+----I
Acidity 10
p.p.m. 20
as CaC0 3 30
40
50~~--~--~~----~--~~__--~----~
o 100 200 300
Bed volumes effluent
Figure 22. Treated water qualitiesfrom carboxylic resin. Input water: Alkaliniry 200 p.p.m.
as CaC03. Mineral anions 110 p.p.m. as CaCO a. Total hardness 280 p.p.m. as CaCOa.
Regeneration level and operating capaciry. Curve A 19·3 kgrfft 3 (43,6 gjl) as CaC03.
Curve B 28·5 kgrjft3 (65 gjl) as CaC03
cycle from low to high pR. Figure 22, Curve B shows the effect on
water quality of changes in regeneration level, using Zeo Karb 216.
The effect of resin reaction rate on plant size, which applies
equally to weak base resins, results in an interesting anomaly which
is rarely understood by water treatment plant users. At first sight,
it would appear that, for a fixed flow of water, of fixed analysis, the
resin volume required must be inversely proportional to the res in
capacity. As a first approximation, this is true for strong acid and
strong base materials. The weakly ionized resins, however, have
capacities which increase as a function of the total cycle time, that
is inversely with the input flow rate per cubic foot of resin. I t
follows that, for a fixed total rate of flow, higher capacities are
achieved only by reducing the ftow rate per cubic foot. As the total
58
ALKALINITY REMOVAL WITH CARBOXYLIC RESINS
input is fixed, this involves increasing the total quantity of resin,

which leads to the apparent anomaly that the overall plant size
increases with increasing resin capacity. As the operating costs of
all weak acids resins are identical, there is no financial advantage
to set against the high capital cost of the greater usage of capacity.
It follows that the most advantageous weak resins are those with
the highest reaction rate, and not those with the highest intrinsic
capacity. This fact is not widely recognized, since figures for the
effect of flow rate or reaction time are rarely given in manu-
facturers' literature, and capacity figures are frequently quoted
which are not realizable under practical operating conditions.
Waters whose alkalinity is considerably greater than their hard-
ness are rare in Great Britain, but do occur in other parts of the
world, particularly in the Argentine, where sodium bicarbonate
concentrations of over 700 p.p.m. as CaCOa are common. These
waters are, of course, completely softened by the Starvation pro-
cess alone. The methacrylic resins will absorb only bivalent metals
from such waters, but the acrylic materials, which are slightly
stronger acids, will remove sodium, although their capacity for this
duty is normally less than half the values obtained with hard
alkaline waters. The condensation type materials are more strongly
acidic still, and will give good sodium removal from waters of this
type.
When using weak acid resins for this purpose, considerable care
must be taken with the plant design and mode of operation. All
carboxylic resins show an extremely high swelling ratio between
the largely non-ionized hydrogen form, and the fully swollen
sodium form. The increase in volume of the resin bed may be as
much as 100 per cent. The corresponding increase in swelling for
the hydrogen-calcium exchange is only about 5 per cent. Most
resins are relatively undamaged by slow alternate swelling and
shrinking, so long as they are physically unconfined during both
processes. In practice, however, a cylindrical resin column is con-
fined on all sides except the top, and while the bed rises vertically
during exhaustion, it is also attempting to expand outwards against
the column walls. The total force which can be exerted is very
large. Indeed, hydrogen form carboxylic resin which has been
treated rapidly with caustic soda has been known to buckle and
distort heavy steel cylinders and internal pipework. Consequently,
the weakly acidic resins, when used with soft alkaline waters, have
a noticeable tendency to physical breakdown, due to the crushing
forces which they exert against the cylinder walls. The effect may
59
be minimized by using broad, shallow beds, and artificially restrict-

ing the operating capacity by the use of low regeneration levels.
For high sodium waters, it is also advantageous to interrupt the
treatment run at intervals and backwash the bed to lift the resin,
and allow it to resettle in its partially swollen state. Hard waters
give no problem, and there are many recorded cases of Starvation
plants operating continuously for over 10 years, without any loss of
capacity or physical damage to the resin.
SULPHONIC RESINS. HYDROGEN ION EXCHANGE

The basic considerations given in Chapter 3 for the hydrogen ion
exchange process may be summarized as follows:
1. The relative affinities during absorption from dilute solution
are in the order Ca 2+>Mg2+}>Na+. As a result, it is relatively
easy to obtain full absorption of bivalent metals, but solutions high
in sodium give rise to considerable slip.
2. In solutions containing a high ratio of bicarbonate to other
anions, the absorption of all cations is efficient, and the slip effect
is minimized.
3. With sulphuric acid regeneration, because of the low con-
centration used and the incomplete dissociation of the acid, removal
of Ca 2+ and M g2+ from the resin is difficult, and the operating
capacities increase in the order Ca 2+ <Mg2+ <Na +.
4. Hydrochloric acid regeneration can be carried out in con-
centrations up to I·sN, minimizing the concentrationJvalency
effect on affinities. Accordingly, capacities are higher, and the
differences between ions smaller, than with sulphuric acid. Sodium
slip is correspondingly reduced.
5. Provided the operating cyde is over 6 h, and the regeneration
time over 15 min, ftow rate variations can largely be ignored, but
faster ftow rates result in lower capacities.
It follows that, in order to predict exactly the capacity and slip
figures for every given case, the user would need to have available to
hirn curves relating each of these factors to
(a) Regeneration level.
(h) Total ionic concentration.
(e) Ca2+JNa+ ratio.
(d) Ca 2 +JMg2+ ratio.
(e) HC03-J(CI- + S042 -) ratio.
(1) Absorption time.
(g) Regeneration time.
The presentation of the whole of this information, over an adeq ua te
60
range of values for each parameter, involves an enormous total

number of curves, which must be repeated for sulphuric and
hydrochloric acid, and strictly for nitric also, since this acid is
occasionally used in industrial practice. No resin manufacturer
attempts to give the whole of the information, the usual procedure
being to present blocks of curves for certain key items, with correc-
tion factors governing the effect of others. The corrections cannot
strictly be applied with complete accuracy to every point on every
curve, and this method of information presentation must lead to
some inaccuracy. It is possible, however, to maintain a maximum
error of under 5 per cent while still keeping the total number of
curves within reasonable bounds.
80
ra Na as p.rcentage of total cations
0 A A 100 D 40
<lI B 80 E 20
01 60
C 60
~
c U)
<lI C
u 0 B
:v :;: 40
D-ra
VI u
ra c
<lI
01
20
ra D
"""C1l
<lI
...J
0 15·0 (b/ft3
0 240 g/l.
Regeneration level
Figure 23. Sodium slip I,sulphuric acid)
In calculating the operating conditions of a hydrogen ion exchange

unit, the first consideration must be the cation leakage, or slip,
which can be tolerated. When the water is hard, the slip is negligible,
but for soft waters, the figure is extremely high. Figure 23 gives the
sodium slip, as a function of sulphuric acid regeneration level, for
waters of various cation ratios. For a fully soft water, free from
alkalinity, the slip is still 10 per cent, even when the acid usage i~
240 g/l (15 Ib/ft 3 ), which is an impossibly high figure for industrial
purposes. Much better results are obtained with hydrochloric
acid (Figure 24). The terms 'slip' and 'leakage' although universally
used, are in fact misleading. The sodium ions which emerge from
the resin are not apart ofthose entering, but are the ones left behind
from the previous cyde. The total capacity of a typical polystyrene
61
sulphonic acid resin is approximately 50 kgJft 3 or 2·25 g.equiv.JI.

At the levels of regeneration dicta ted by industrial economies, it is
rare to operate at a capacity ofmore than about30 kgrJft 3 , so that the
80r---~---.------------------,
....o
C1I
Na as percentage of total calions
A 100
B 80
~ 60~------~+ C 60
C1I
~u c::.
Ul
~.~40r---~-----r----~~--+----------;
o./ij
Ul U
C1I
~ 20~~----~+----------+------~~
Cl C
C1I
""C1I
-'
o 2-5 5·0 7· 5lb/ft 3
o 40 80 120 g/l.
Regeneration level
Figure 24. Sodium slip (hydrochloric acid)
resin bed, which is 80-90 per cent exhausted at the end of the
service cyde, is still 20-30 per cent in the sodium form following
regeneration. If this process has been carried out downflow, the
sodium proportion varies down the column as shown in Figure 25(a).
(a)start (b)25 % (c) 50 % (d)75% (e)End

of cycle of cycle of cycle
Effluent
water 50% 30% 15% 20% 50%
'leakage'
Figure 25. Leakage during co-jlow operation
During the subsequent service cyde, the treated water leaving the
column is in equilibrium with the last layers of resin it encounters,
62
and as the affinities of sodium and hydrogen ion for the resin are
almost equal, the Na +:H + ratio in the effiuent water will be, as a
first approximation, the same as in the resin. If service is co-flow
to regeneration, the Na +:H + ratios in the resin vary throughout
the run as in Figure 25. As sodium ions are absorbed at the top of
the column, the exchanged H + ions are reabsorbed lower down,
yielding equivalent concentrations of Na + ions. The lower layers of
resin are thus increasingly converted to the H+ form, and the treated
water quality, which initially is very poor, improves steadily, until
just before the end of the absorption cyde, when the Na+:H+
i: 80
.!
c
.; 70
~
Regenerant Sodium, as percenta!§e .. 60
;;j
level (g/l.) of neutralsalts L.
A 64 100 ~ 50
c
8 64 70
C 144 100
D 224 100
E' 144 70
F 224 70
"
.
~
..
t7I
'.."
~
..Ii:
• ...J 20 40 60 80 100
Percentage of operating cycl e
Figure 26. Leakage with sulphuric acid co-current regeneration
ratio in the bottom layer of the resin increases, and the treated
water quality falls off correspondingly.
The quantitative effect of this process is shown in Figure 26, for
various waters, and regeneration levels. The wide variation of the
apparent slip throughout the operating cyde means that the
average slip values recorded in Figures 23 and 24 are not really
reliable in cases where they exceed 10 per cent.
The acid input level having been chosen, the resultant capacity
can be read from Figure 27(a)-(d), which covers four ra ti os ofMg2+
to bivalent ions, and four ratios of Na2+ to bivalent ions, assuming
63
(0) (b)
25
20
15 0'
u
~~~~---+--~--~
...
~~ __~ __- L __~ __~ 10 U ~
-... .....
Cl
(c) (d)
~ 80 r--r---r--.--.--=
...u ?:
:i 70f-~--+- -ü
30 :t
U
u
...
25
10
80 120 160 200 240 4'=-0--,8f:0:-----,1~2-:-0---'-!,6:"::0---:-20L:-:0~2 40
g/t. g/t.
2-5 5-0 7-5 10 -0 12-5 15 -0 2-5
5 -0 7 -5 10-0 12-5 15-0
lbltt 3 Ibltt3
Regeneration level
---Ideal c-urve 100percent regeneration efficiency
Figure 27_ Capacity qf sulphonic resins with H 2 S04 regeneration (a) MgO (h) Mg 25 per
cent qf divalent cations (c) Mg 50 per cent 0/ divalent cations (d) Mg 75 per cent 0/
divalent cations
in all cases that bicarbonate forms 50 per cent of total anions. The
corrections for other bicarbonate levels are given in the following
notes.
Notes I. With waters containing und er 50 per cent Na, no alka-
linity correction is necessary.
2_ With waters containing over 50 per cent Na, the following

corrections are needed.
64
(a) (Figures 27(a), (h) and 28). For each 10 per cent increase or
decrease in alkalinity, add or subtract 2 per cent.
(h) (Figures 27(c) and (d). Thecorrespondingcorrectionis only 1 per
cent.
Regeneration with 5 per cent HGI solution gives a much simpler
picture (Figure 28). The alkalinity corrections are as before .
..,
8 70 1---1--r-:>"I-
~
U
10
20 L...--4.1.0-.J.SO:---:a'-:-0-10~0~1~270-1:-'4-=0-:1~6 0 g 11.
2·5 5·0 7·5 10 ' 0 lb/ft J
Regeneration level
Figure 28. Capacity of sulphonic resins with HCl regeneration
The shapes of the capacity/regenerant curves, indicate a rapidly

decreasing acid efficiency, as the quantity used increases. In order
to achieve low running costs, acid levels below 64 g/l H 2S04
(4 Ib/ft 3 ), are preferable, but it is seen from Figures 23 and 24 that
leakage must be high under these conditions, unless the input water
is hard. The two requirements for low running cost and high
quality are thus incompatible, and various different compromises
must be made according to the conditions. In the case of the smalI,
manually operated two-bed demineralizers used in factories for
producing fairly small quantities of treated water (less than about
25 m 3 , or 5,000 gal/day), chemical costs are small compared with
labour costs. Accordingly, there is every advantage in using very
high regeneration levels, preferably with HGI to give good quality,
a small plant, and maximum time between regenerations, to econo-
mize on labour. For large automatic plants, running costs become
the overriding factor, and it is then essential to keep down the
regenerant levels, even if this results in a poor quality of treated
65
water. The quality is then dealt with in a completely separate unit,

a bed ofmixed resins, which follows the demineralizing pair.
The choice of acid, except for small plants, is dicta ted purely
by economics. Knowing the costs of bulk acids, which in Great
Britain are 1·2d per lb for H2S04, and 3·6d per lb for HGI (both
considered as 100 per cent) it is easy to construct new capacity
curves, showing kgr/ft 3 as a function of pence/ft3 regeneration
cost. In Great Britain, the curve for H 2S04 falls below that for HGI
under all conditions, and sulphuric acid is therefore universally
used. In Germany, hydrochloric acid prices are much lower than in
Great Britain, while sulphuric acid prices are similar to U.K.
~
~
.! ~
'"
~2
'"
Oll
.
'E....
Cl.. 1 "-....10(7
o 20 40 60 80
Ca 2' as percentage total cations
Figure 29. Permissible H2S04 concentration
figures. It is therefore more economical to use HGI, which is

accordingly standard practice there. In other countries, the cost
curves for the two acids can cross, according to the water analysis,
and the decision as to which is more economic must be based on
individual calculations for each case.
Hydrochloric acid gives minor complications in plant design,
since the special chloride-resistant stainless steels are expensive,
but with the increasing availability of a wide range of plastics for
construction purposes, this factor no longer represents a serious
restriction. Another difficulty can occur if the concentration used
is too high. Osmotic dehydration of the resin beads takes place,
66
ACID ABSORPTION BY WEAK BASE RESINS
leading to resin shrinkage and packing of the bed. During the rinse
stage, the resin re-swells and the beads can become broken by
crushing. This effect is avoided by keeping the HCI concentration
below 7·5 %wjv. Sulphuric acid presents a more difficult problem,
owing to the necessity of avoiding the precipitation of gypsum,
CaS04.2H20, in the resin bed. The acid strength which can be
used is controlled by the input water analysis, and when this is high
in calcium, the concentrationmust be kept down to 1·5 %wjv, which
results in a considerable consumption ofwater during regeneration.
Figure 29 gives the range of permissible acid strengths as a function
of water analysis. These figures are indicative rather than exact.
The saturation concentration of gypsum is only about 0'14% wjv,
and the ability to use even 1,5% H 2S04 is made possible by the
fact that gypsum forms super-saturated solutions which remain
stable for periods of up to 1 h. The permissible acid level is there-
fore infiuenced by the time taken for regeneration, and by the plant
design.

The water produced by the hydrogen ion exchange process con-
tains all the anions originally present, together normally with
sodium representing a small proportion of the original cations.
When a weak base resin is used to complete the demineralizing pair,
the mineral acids present are removed by equation 27 (page 39),
leaving in solution the wh oie of the silica originally present, a
supersaturated solution of carbon dioxide and a low concentration
of sodium chloride resulting from the cation column slip. The
carbon dioxide can readily be reduced to a low level by passing the
water down a degassing tower, filled with ceramic rings, and
subjected to an up-draught of air, but it is usually uneconomic to
reduce the sodium chloride residual to below about 1·0 p.p.m. With
soft water the figure may be much higher. It is again emphasized
that this figure is purely a function of the cation resin operating
conditions, and cannot be altered by any modification of the anion
exchange procedure. However, even if the solution entering the
anion exchange column contains no metallic cations, the removal
of acid by a weak base resin column is never perfect, and a final
chloride residual ofO'1-0'3 p.p.m. is normal. When a better quality
than this is required, strong base res ins must be used, preferably in
a mixed bed system. For this reason, no practical purpose is served in
attempting to calculate the water quality resulting from demineral-
izing with a weak base resin, and the only figure of importance is
67
the operating capacity. Four main factors influence this value.

(a) The regeneration level-The efficiency of regeneration of weak
base resins is not as high as that of weak acid materials, but is
normally in the region of 70 per cent.
(h) The Free Mineral Acidiry (F.M.A.)-Because the weak base
resins are weakly ionized, their capacities are strongly influenced
by the concentration of acid to be absorbed.
(c) The rate ofpresentation 01 ions-In order to obtain fuU equilibrium
loadings, time cycles of 24 h maybe required.
~---r--~----+---~ao
~---+----+----4--~A 70
30
o'"
u
u'"
~ 25
........
Cl
..><
~20
u
'a." '.oL--+------l1. 0
u '"
15
~~~---+----~--~ 30
10
1...JU-~~--~--~~~20
o 200 1,00 600 aoo 200 1,00 600 aoo
Free mineral acidity p.p.m. as CaC03
0) ~)
Figure 30. Polyamine res in capacities (a) Sulphate (b) Chloride
(d) The chloride-sulphate ratio-This is a largely artificial effect, due

to the convention of recording sulphate loadings in terms of S04 2 -,
whereas absorption is given as a mixture of S04 2 - and HS04-.
Figures 29 and 30(h) give the chloride and sulphate capacities of
De-Acidite M jIP, a typical high capacity polyamine resin, as
functions of F.M.A. and total run time. The regeneration level is
1·6 g.equiv.jl of resin which is the optimum value für this resin.
Higher values do not give a proportionate gain in capacity, while
68
lower levels give a greater overall efficiency, at the expense of a

reduction in efHuent quality. The extremely wide range of capaci-
ties, from 20-80 g/l, obtained from a constant regeneration level
under different service conditions, is typieal of the high capacity
polyamine res ins, and in cases where manufacturers' literature
quotes a single high value without qualification, it should not be
relied upon to apply to all circumstanees.
The polyamine materials were completely satisfactory in the days
when plants were smalI, and manually regenerated, since to econo-
mize on labour it was customary to design them to operate for one
or more days between regenerations. Under these cireumstances,
advantage eould be taken oftheir high total eapaeities. They remain
of value for this type of equipment, and they have great advantages
for the treatment of very thiek waters, where high eapaeity is more
important than any other faetor. Nevertheless, under modem
eonditions of large fuHy automatie plants, eeonomie eonsiderations
normally direet all efforts to the reduetion of plant size and resin
quantity, by the use of high flow rates, and short eyde times, whieh
may be of only 5-6 h duration. For this reason, there have been
developed the rapidly aeting tertiary amine resins deseribed in
Chapter 3, in whieh Figure 16 eompares the eapaeity/time relation-
ship of the two types of resin. If, for a given flow of water of fixed
analysis, the eyde time is to be over 24 h, then the polyamine resin
is dearly superior, sinee its operating capacity is higher for the same
regenerant eonsumption. If, however, the flow rate is inereased, so
as to reduee the eyde time to 6 h, then the tertiary amine resin gives
the more favourable results. Examples of this type of resin are
Amberlite IRA-93, De-Aeidite H-IP and Lewatit MP.60. Typical
capacity figures are given in Figures 31 and 32. They are not exaet
for eaeh resin, sinee the polymer struetures used by different manu-
faeturers for anion exchange resins differ eonsiderably. It is essential
to refer to the data sheets issued for the individual resins being used
in any partieular ease.
The eapaeity/time relationship for weakly ionized res ins is not
universaHy appreciated. Many resin manufaeturers quote in their
literature, capacity figures obtained under ideal laboratory eondi-
tions, and it is not always apparent to the reader that the values
obtained in praetiee may be eonsiderably lower. It is impossible to
calculate aeeurately the size of a weakly basic resin unit unless the
eapaeity-time eurve is known. The first stage of the ealculation is a
deeision on the required duration of the operating eyde between
regenerations. The capacity is then read from eurves such as those
69
of Figures 30(a), (b) and 32 after which the plant size may be calculated
from a knowledge of the water analysis and flow rate. Calculations
made from published information whieh does not indude time or
55 21.
501----+-
... o
...
8<G 45 t---t---~ '=*_==--=1 20 ~
U u
'l.-
18 :;::
~---+-----r----+---~----~ ~
.?;o .!o<:
·ü 16 Z;-
:1 351----I-----.-+----,-c- u
<G
~ a.
14 ~
301----1-----1----4---~--~
12
25~--~--~--~L---~--~
o 20 1.0 60 80 100% 504
100 80 60 1.0 20 0 %Gl
504/Cl equivalent ratio in water
Figure 31. Tertiary amine resin capacities
.... /
~
o _ 110
111"'>
~
<G Cb ~
Z;- 3 100
. - t:l) ~
liii: /'/
~ 90
.,./
......
60 80 100 200 300 1.00
Total salt content p.p.m. as GaC0 3
Figure 32. Gorrectionfor total salt content of water. Note: Figures apply to cycle times of
over 8 h. Reduce by 5 % per hour down to 5 h. Gycles at less than 5 h are [iable to be
erratic
rate curves may lead to serious under-design ofthe equipment, unless
the operating eyde is long enough to be on the flat part of the
curve.
ACID ABSORPTION BY STRONG BASE RESINS

It has already been explained that when water from a hydrogen
exchanger is passed through a bed of strong base res in, the siliea
and earbon dioxide are absorbed, while any neutral salts present
70
ACID ABSORPTION BY STRONG BASE RES INS
are converted to sodium hydroxide, leaving the water more com-

pletely stripped of anions than when a weak base resin is used. It
is obvious that in a direct two-bed system, there must be a great
waste of anion resin capacity, due to the absorption of carbon diox-
ide, which could otherwise be removed at very low cost with a
degassing tower. Nevertheless, for many purposes, such as the small
portable two-bed deionizers used for producing pure water in
laboratories, the system strong acid resinjstrong base resin is used,
since the chemical cost is unimportant in comparison with the
convenience of producing pure water quickly and without com-
plication. For large scale industrial use, where running costs may
not be neglected, removal of carbon dioxide, by degassing between
the two ion exchange units, is standard practice.
Water produced in this way contains 0·1-0·2 p.p.m. Si02, a
slightly lower concentration of chloride, and a few p.p.m. ofNaOH,
dependent on the slip from the cation unit. It is thus directly
suitable for use as make-up to medium pressure boilers, up to about
1,000 Ibjin 2 , since a slightly alkaline feed water is advantageous.
It is obvious that the treated water purity can be further improved
by increasing the regenerant consumption of both cation and anion
resins to very high levels, but this procedure is uneconomic, even
though part of the excess acid and caustic can be recovered by
collecting the later portions of spent regenerant in a catch tank, for
re-use in the next cycle. Again, improvement in quality can be made
by warming the regenerant solutions, to obtain better kinetic effects,
or by adopting counterflow techniques, but there is little object in
trying to stretch the duties of a two-bed deionizer too far, since water
of greater purity can be produced with complete certainty by means
of the mixed bed system (see below). Two-bed systems, considered
in the context of very pure water, have one other difficulty, which
cannot be cured by the methods mentioned above, but which is
eliminated in mixed bed work (q.v.). This is the problem of ex-
cessive rinse. During regeneration a proportion of sodium hydroxide
penetrates the beads, although its concentration there is much lower
than in the surrounding regenerant solution. The absorbed caustic
soda is rinsed out only very slowly, and a total time of several hours
may be required to reach a really high water purity. Wastage of
water may be prevented by rejecting to drain the first two-bed
volumes of rinse, which contain over 95 per cent of the regenerant
left in the bed, after which the rinse water is recycled by pumping
back to the cation resin inlet. The two resins can then be rinsed in
closed-circuit until the conductivity drops to the required level.
71
Types of Strong Base Resin

Any soluble tertiary amine will react with chloromethylated cross-
linked polystyrene to produce a quatemary ammonium resin,
which will always be a strong base material. The most widely used
amine is trimethylamine, N(CHa)a, which forms the benzyl
trimethylammonium group
All resin manufacturers include in their series at least one resin of

this type, notable examples being Amberlite IRA-400 and 900,
De-Acidite FFjIP, Dowex I, and Duolite A,101, Lewatit M.500
and MP.500. Materials of this type are such strong bases, that
their affinity for all anions is extremely high. Accordingly, when
correctly used, they produce water of the highest purity obtainable
by any means, but they are difficult to regenerate, and regeneration
efficiencies are low. Figure 33 gives typical capacity values, as a
function of water analysis and regenerant level. It is impossible
to utilize the full intrinsic capacity of the resin, however great an
excess of regenerant is used, and at normal regeneration levels of
2-4 lb NaOHjft a (32-64 gjl), only about half the res in capacity is
brought into service.
Resins of this type have become generally known as Type 1
materials. Type 2 resins, the second major group, are made from
dimethylethanolamine, N(CHa)zC2H40H, and thus contain the
groups
72
TYPES OF STRONG BASE RESIN
These are also strong base materials, capable of absorbing weak

acids such as CO 2 and Si0 2 without difficulty, but their basic
40.---,---~----r---~--~
16 0
~35~---+----~--- , ~~----l (,)
111
8<1l 14 ;'
.....
~ 301-----+-
:::::Cl
12 ~--
-'"
~25~--~--~~
u
>.
<1l
0.
10:;:;
<1l <1l
0.
(,) 201---=o~~-- <1l
8(,)
60 80 100 % 504
40 20 o %Cl
504/Cl equivalent ratio
Figure 33. Type 1 quaternary resin (De-Acidite FF/IP) capacity
~___+-~~____~20 0
~
(,)
~___ \~~4-____~__-+____~18~
....
--Cl ~
W~
~35~---+~--~~--~---+----~
u
<1l
0.
<"5301----+-
r _ _....,.
25L-__-L____L -__~--~~~~
o 20 40 80 100 %S04
100 80 60 20 0 %Cl
504/Cl equivalent ratio
Figure 34. Type 2 quaternary resin (De-Acidite N/IP) capacity. Note: Figures 33 and 34
apply to exhaustion times of over 8 h. Reduce capacities by 5% per hour for times down to
5 h. Cycles of less than 5 h
strength is somewhat lower than that of the Type 1 resins. Conse-

quently, their regeneration is much more efficient, and the operating
capacity may be 40 per cent high er than that ofthe Type 1 products
under similar conditions. Typical results are given in Figure 34.
73
F
1t must, of course, follow that the removal of silica by Type 2

resins is not quite so good as with the Type 1 materials. A further
minor disadvantage of the dimethylethanolamine resins lies in their
lower chemical stability. Anion resins in general are less stable than
cation exchange materials, and have a shorter operating life. Type 1
materials, used at ambient temperatures will give good results
for 7-8 years, the operating capacity to silica end-point falling
during that period to about 70 per cent of the starting value. Type 2
resins suffer the same overallloss in about 5 years. The degradation
process is complex, and is not completely defined. Degradation
occurs by two main routes, which are similar in principle for both
Type 1 and Type 2 resins.
• ••• (33)
/-0
GHz
GH
/ GHzN(GH3)z + GH30H
GH2
/
Whereas the loss of amine by reaction 33 gives a direct reduction in

capacity, reaction 34 causes no loss in acid absorbing power, but
merely a change of some groups from quaternary (strong base) to
tertiary (weak base). Since most waters contain far higher concen-
trations of mineral anions than silica, and since carbon dioxide is
normally removed by degassing, it follows that the long-term
decomposition of the resin by equation 34 does not necessarily
lower its working capacity provided this is not judged solelyon
silica rem oval. 1ndeed, it may increase it slightly, since the weak
base groups are more readily regenerated than the strong, and the
operating capa city for a given caustic soda usage is higher. Type 1
resins te nd to degrade chiefly by the first route, with loss of the active
group, whereas Type 2 materials decompose mainly by the second.
Because of this phenomenon, the relative instability of the Type 2
74
TYPES OF STRONG BASE RESIN
resins is much less important than might appear at first sight, pro-
vided they are used correctly. This was not always the case during
the early years after their development, and this type of resin gained
an exaggerated reputation for instability. The reason was that,
while in Great Britain mixed bed demineralizing rapidly achieved
favour for the production of very pure water, the practice in the
U.S.A. for many years favoured two-bed operation, using very high
regeneration levels, to obtain the required quality. Under these
conditions, the Type 2 resins gave excellent capacities, with corres-
pondingly low running costs, and were for some years highly
favoured. However, when the resins had been in service for a year
or two, the conversion of strong base to weak base capacity resulted
in a reduction of silica absorption, and as the operating runs were
terminated at silica breakthrough, the recorded capacities fell
rapidly. Consequently, it became an established principle that the
excellent capacity of Type 2 materials was a purely temporary
phenomenon, and that after 1-2 years service, the total loadings
were lower than for the Type 1 resins. The dimethylethanolamine
resins thus fell into disfavour, and their general usage was consider-
ably reduced. This attitude was, in fact, misguided, and due only to
the method of operation which had been chosen. If Type 2 resins
are used in multi-column systems (see Chapter 5) in which the last
column is a mixed bed containing a Type 1 resin, the final treated
water quality is govemed by the last column. Under these circum-
stances the gradual change of the Type 2 material from strong to
weak base makes virtually no difference to its operating capacity,
but merely gives a slight increase in leakage of silica, which is
absorbed in the final column. At ambient temperature, the resin
retains 50-60 per cent of its strong base groups unchanged, even
after 5 years, and when used in this way gives constant overall
results for at least this length of time.
The terms Type 1 and Type 2 can no longer be assumed to cover
all strong base resins. In re cent years, a number of materials have
appeared, whose operating results are intermediate between the
two types. Resin manufacturers have not generally disclosed the
nature of these materials, but as a number of suitable amines are
industrially availableitmay be that such res ins are based on different
active groups.
MIXED BEDS
Attempts to prepare extremely pure water by two-stage demineral-
izing must inevitably lead to very high operating costs, due to the
75
regenerant levels required to reduce slip to low levels. Moreover,

the process is to some extent self-defeating, since the excess regen-
erant is difficuIt to remove from the resin, and the rinse period
following regeneration may be prolonged to an extent which involves
a major waste ofwater. With waters such as example D, Chapter 1,
it is impossible to achieve really pure water, with a conductivity of
less than 0·1 p.Sjcm (S = Siemen = mho) and a T.D.S. ofless than
25 p.p.b., by any practicable two-bed process.
If, with such a water, economical regeneration levels of about
5lb H 2S04jft3 (80 gjl) are used, the leakage from a demineralizing
pair will be at least 10 per cent ofthe initial T.D.S., that is 40 p.p.m.
When a strong base resin is used in the second bed, the contamina-
tion of the treated water will be largely due to NaOH. If a second
pair is added, in series with the first, the proportionate leakage is
now greatly reduced, due to the ease ofuptake ofsodium hydroxide,
the residual total solids being about 1 p.p.m. The addition of more
demineralizing pairs will improve the quality still further. The
complication of a large number of units is avoided by the use of a
column of intimately mixed cation and anion exchange beads,
which acts effectively as an infinite series of demineralizing pairs.
A mixed bed containing strong acid and strong base resins will
readily produce water whose conductivity is less than 0·05 p.Sjcm,
and reliable records exist of values as low as 0,04, which is virtually
identical with the conductivity of completely pure water (0,037 at
18°C). At the same time, dissolved silica can be reduced to less than
0·002 p.p.m. In industrial practice, because of the inevitable
reduction of hydraulic efficiency in large diameter units, a single
mixed bed cannot be relied upon to produce these figures, aIthough
they do often occur. Practical values for large single units are-
conductivity 0·2-0'5 and silica 0·02-0·05.
These results are achieved with great ease, at low regeneration
levels, and almost independently of the incoming water analysis.
The mixed bed process has, accordingly, become completely
standard wherever water of the highest purity is required, and there
is no object in considering any other technique. Modern high
press ure boilers, operating at 100 atm and above, require to be
fed with water of almost absolute purity, on an extremely large
scale, and to compensate for the somewhat lower efficiency resulting
from hydraulic effects in large units, it is normal to place two mixed
beds in series or to use a demineralizing pair followed by a mixed
bed. These systems, operating on the scale of millions of gallons per
day, give results equal to those obtained under ideal laboratory
76
MIXED BEDS
conditions. A mixed bed in good operating condition is character-

ized by an extremely sharp end-point. The conductivity remains at
a constant low value until either of the resins becomes exhausted,
after which it rises steeply. At this stage, the resins must be separated
for regeneration. This process is achieved by means of an upftow of
water, distributed evenly into the bottom of the bed at a rate of
2,5-3,0 gal min- 1 ft- 2 (7'5-9 mjh). The resin bed becomes ftuidized,
and as the anion resin has a lower specific gravity (1' 1) than the
cation material (1'4), two clearly defined layers are formed. The
upper layer is then regenerated with sodium hydroxide solution,
passing from distributors just above the bed, to collectors situated
at the interface of the two resins. The regenerant is followed by a
brief rinse of 4 voids volumes, or 1·6 resin volumes, to remove the
Raw
Water
Pure Raw
water water
Operation Separation Regeneration
Anion Cation Remixing
resin resin
Figure 35. Regeneration sequence for mixed bed demineralizing
majority of the spent regenerant, without attempting to eliminate

it completely. The acid for the cation exchange resin is now passed
through the interface piping, which now becomes the distributor,
and is collected at the bottom of the unit, once again followed by a
brief rinse. The resins are then remixed with an upftow of air, and
the unit is put back into downftow operation. (Figure 35.) In a weIl
designed unit, the conductivity of the emergent water will be very
high for 2 or 3 min, and will then drop suddenly to the final value
of under 0·5 /LSjcm. This phenomenon of rapid rinse, which is
characteristic of mixed beds, is due to the fact that any remaining
traces of acid, alkali or salt remaining in different parts of the bed
77
are rapidly absorbed by one or other resin. The waste of capacity in

this process is negligible, and the overall time required for mixed
bed regeneration is noticeably less than for a two-bed system, giving
a correspondingly higher proportion of time in service.
There is, of course, a smallioss of capacity at the resin interface,
where some acid and alkali must diffuse into the wrong resin, but
this is a small penalty to pay for the advantages of mixed bed
operation. The effect can, in any case, be minimized by the use of
hydraulic buffers. Water is passed upflow through the cation resin
during regeneration of the anion, and downflow through the anion
during regeneration of the cation. These processes reduce interface
diffusion to a very low level. I t has been suggested that both resins
should be regenerated simultaneously, the acid passing upflow from
the bottom, and the caustic soda downflow from the top, both leav-
ing simultaneously from the interface collector. The system is
perfectly practicable, and can be used in small units without
difficulty. For large scale operation, however, the problems of
control of the balanced flows and pressures add unnecessarily to the
cost of the equipment, and the system is rarely used.
When used with waters substantially free from organic matter,
mixed beds will operate for many years, with unchanged character-
istics of short rinse, low conductivity, and sharp breakthrough
point. They are, however, particularly susceptible to poisoning by
organic matter, largely because the water quality they produce is
so high that the effect of impurity is more noticeable than in other
systems.
Organic fouling, which is dealt with more fully in a succeeding
chapter, causes an increase in the rinse water requirement and in
the treated water conductivity. The same symptoms can be given
by bad resin separation and remixing. H, during the separation
stage, anion exchange resin is left undisturbed at the bottom of the
unit, it will come into contact with the sulphuric acid used for
regenerating the cation resin, and become converted fully to the
bisulphate form. Hit is again left in place, by the inefficiency of the
air mix process, the bisulphate ion hydrolyses slowly, with libera-
tion of sulphuric acid into the treated water.
. ... (35)
The effect does not of course occur when hydrochloric acid is used
for regeneration, and it can in any case be prevented by good re-
mixing, even if the original separation was poor.
78
MIXED BEDS
While there is no difficulty in remixing the resins, with an adequate

volume of air, it is virtually impossible to maintain them in a fully
mixed condition, when the air supply is cut off to allow the bed to
settle for re-use. As soon as positive mixing ceases, the resins tend to
reclassify themselves while falling through the surrounding water,
with the result that industrial mixed beds normally have a 6 in top
layer consisting largely of anion exchange resin, a corresponding
bottom layer chiefly containing cation material, with a varying
mixture in between. In normal water treatment practice, this
pattern does not cause any difficulty, since the strong base anion
resin layer converts neutral salts to the corresponding metallic
hydroxides, which are then absorbed by cation resin lower in the
bed. The re-separation phenomenon does, however, prevent the
efficient use of weak base resins in mixed beds, since any weak
anion material unpreceded by cation resin is effectively inert.
Except for rare special cases, therefore, only strong base anion
resins are used in mixed beds.
79
CHAPTER 5
COMBINATION PROCESSES
While many of the unit processes described in Chapter 4 may be used

individually, or in pairs, there are technical and economic advant-
ages to be gained in large scale operations, by grouping together
larger numbers of units. The combinations normally used in
practice are considered below in increasing order of complexity.
The results are indicative ofthe trends given by the various processes,
and are not intended to be absolute values for all cases. The systems
described are shown schematically in Figure 36.
1. WEAK ACID CATION. SODIUM EXCHANGE CATION.

DEGAS
( WAC-Na-DG)
This process, using an acid regenerated carboxylic resin in
series with a salt regenerated sulphonic exchanger, is the most
economical method for reducing total dissolved solids, with simul-
taneous softening, so as to produce water suitable for low pressure
boilers and simple process purposes. Considering the four prototype
waters listed in Chapter 1 (page 4), the following results are
obtained. Figures recorded as 'nil' are of course formalized. In
practice, trace quantities are observed.
Table 3. WAC-Na-Degas
I A B C D
--
Ca NIL I NIL NIL NIL
Mg
Na
I NIL
30
NIL
45
NIL
115
NIL
440
CI 10 20 50 250
S04 10 20 50 50
HC03 10 15 15 40
Total
Regeneration efficiency
30 I 45 115 440
Carboxylic Not used I 100% 100% 100%
Sulphonic 75% 75% 75% Not used
I i
80
WEAK ACID CATION. somUM EXCHANGE CATION. DEGAS.
The carboxylic resins, when opera ted by the 'Starvation' method,

do not remove bicarbonate completely from the water, but leave
10-20 p.p.m. in solution. Accordingly, the first column is virtually
without action for water A. In the case ofwater D, there is an excess
5 (a) and (b)
(a) SBA 2 (b) SBA 1
Figure 36. Combination processes
of alkalinity over total hardness, so that virtually complete softening

is achieved by the carboxylic resin, and the following sulphonic
column is unnecessary. By raising the acid level used for the first
column, a small reduction in sodium is obtained, at the expense of
a reduction in acid efficiency.
81
COMBINATION PROCE88E8
2. STRONG ACID CATION. WEAK BASE ANION. DEGAS

(SAC-WBA-DG)
This, the classical demineralizing method gives results which vary
according to the regeneration procedure used for the cation exchange
unit. The regeneration level of the anion exchange resin has
comparatively little effect on the treated water quality. Table 4
gives the results, for waters A-D, at two different acid levels for the
cation unit. Columns 'H' refer to a high level, 10 lb H2S04jft3 or
160 gjl, while column 'L' gives the results at low level, 4lbjft 3 0r64 gjl.
Table 4. SAC-WBA-Degas
A B C D
H L H L H L H L
Ca2+ NIL NIL NIL NIL NIL NIL NIL NIL
Mg2+ NIL NIL NIL NIL NIL NIL NIL NIL
Na+ 0·1 1·0 0·5 2·0 0·1 0·2 25 70
Cl+ 0·3 1·3 0·3 2·5 0·3 0·6 24 60
804 2+ NIL NIL NIL NIL NIL NIL 1 10
C02 10 10 15 15 15 15 15 15
Approx: pH 5 5 5 5 5 5 5 5
Conductivity 10 12 12 15 14 12 50 130
Cation- exch.
capacity g/l 38 25 44 29 37 25 55 37
kgr{ft 2 17 11 19 13 17 11 24 17
The cations and anions in the treated water no longer balance in

Table 4, since the hydrogen ion is not included, and the waters
produced by this system are always faintly acid. Water A, having
only 30 p.p.m. T.D.S. before treatment, gives good results under
both conditions, although some sodium slip, and equivalent chloride
leak, is observed in the 'L' column. The leakage is higher for water
B, in which the ratio Na :hardness is increased, whereas a purer
water is obtained from C than from B, in spite of its higher input
concentration. This is because of the high hardness of C, which
gives good absorption characteristics, at the expense of lower resin
capacity. Water D is completely unfavourable, and gives poor
quality even at the higher acid level. Simple two-bed demineraliz-
ing is unsuitable for this water.
3. STRONG ACID CATION. DEGAS. STRONG BASE ANION

(SAC-DG-SBA)
The results obtained with this system may be compared directly
with those of System 2. The cation exchange results are unchanged,
82
STRONG ACID CATION. DEGAS. STRONG BASE ANION
but the sodium salts are converted almost entirely to sodium

hydroxide on passage through the anion exchange column. Pro-
vided that anion exchange regeneration levels are over 2·5 Ib/ft 3
(40 g/l), this conversion is virtually complete in all cases except
water D, where the concentration ofneutral salts leaving the cation
material is high enough to give a noticeable chloride slip, on passage
through the anion exchange resin. This leakage is due to the fact
that the anion reaction is no longer a simple acid absorption, but a
chloride-hydroxide exchange, which is the anionic equivalent to
equation 15.
. ... (15)
Chloride leakage from the anion column is thus dependent on

regeneration level just as sodium leakage is governed by cation
regeneration level. Reliable figures for the calculation of chloride
slip are not available, and the only satisfactory method for full
purification of the water is by the use of a mixed bed.
Table 5. SAC-DG-SBA
II A B C D
, H L I H L
I H L H L
Ca2+ NIL NIL NIL NIL NIL NIL NIL NIL
M g 2+ NIL NIL NIL NIL NIL NIL NIL NIL
Na+ 0·1 1·0 0·5 2·0 0·1 0·2 25 70
Cl- NIL NIL NIL NIL NIL NIL 2 10
S04 NIL NIL NIL NIL NIL NIL NIL NIL
C02 NIL NIL I NIL NIL NIL NIL NIL NIL
OH- 0·1 1·0 0·5 2·0 0·1 0·2 23 60
I
Approx. pH 8 9·5 9 10 8 8·5 10·5 11·5
Approx.
conductivity 0·5 4 I 2 8 0·5 1 100 300
Silica
No silica content was included in the typical waters, and in cases
where it is present, it will of course be unchanged by the treatments
of Systems 1 and 2. The results in case 3 are variable, the silica in the
treated water being increased by increasing input concentration,
operating flow rate, regeneration flow rate, and sodium slip. 1t is
decreased by increasing regeneration level, regenerant temperature
83
and ratio of mixed anions to silica in the input water. Some resin
manufacturers provide tables or graphs relating some of these
figures, but the factors governing silica absorption and removal from
the resin are so complex, that the calculations have little significance.
In general terms, it may be said that for waters A-C, the system
SA-Degas-SB will give silica figures in the region ofO·1-O·3 p.p.m.,
for any value of input silica likely to be encountered in practice.
In almost all cases in which silica needs to be removed, these
figures are unacceptably high, and it is necessary to use mixed bed
treatment, in order to achieve reliable values of under 0·05 p.p.m.
4. STRONG ACID CATION. WEAK BASE ANION. DEGAS.

MIXED BED
(SAC-WBA-DG-MB)
In cases where water of high quality is required, mixed bed de-
mineralizing is essential. For small installations, the provision of a
single mixed bed unit may be all that is required. For larger units,
treating more than 5,000 galjh (22 m 3 jh) the operating cost becomes
a factor of considerable importance, and various combinations of
columns may be used to reduce it. The first of these is the system
SA-WB-Degas-MB. The largest single item of running cost is
the value ofthe caustic soda used for regenerating the anion exchange
resin. The cost of sodium hydroxide is approximately three times
that of the equivalent quantity of sulphuric acid, and as the re-
generation efficiency of both cation and anion exchange resins is
about 40 per cent, anion regeneration represents 75 per cent of the
total operating expense. The use of a weak base resin, at a regenera-
tion efficiency of 70 per cent, gives a major reduction, while the
removal of carbon dioxide by degassing, rather than by ion exchange,
represents a much greater total saving. Degassing may take place be-
fore or after the weak base resin without greatly affecting the results.
A further final economy can be made by a process known as
'thoroughfare' regeneration. The caustic soda solution is passed
first through the strong base anion resin in the mixed bed, and then
through the preceding weak base unit. About 40 per cent is con-
sumed by the strong base material, and 70 per cent ofthe remainder
by the weak base resin, giving an overall efficiency of 80 per cent.
A satisfactory overall economy is thus achieved, while still providing
water of mixed bed quality. The system can, however, have one
disadvantage. As the mineral anions and carbon dioxide are
removed before the mixed bed stage, the final anion resin be comes
loaded almost entirely with silica. Under these circumstances, the
84
STRONG ACID CATION. DEGAS. STRONG BASE ANION. MIXED BED
silica content of the resin may be as much as 1·5 lb/ft 3 (24 g/l), and
the total quantity of sodium silicate which can be produced on
regeneration is correspondingly 2·2 Ib/ft 3 (36 g/l). It is difficult to
rinse all traces of a comparatively viscous sodium silicate solution
from the column, and slow leakage in the subsequent operating
cyde may yield a treated water containing over 0·05 p.p.m. Si0 2 •
5. STRONG ACID CATION. DEGAS. STRONG BASE ANION.

MIXED BED
(SAC-DG-SBA-MB)
(a) Type 2 Anion (SBA2). The silica effect noted above may be
eliminated, with only a minor change in the operating costs, by
replacing the weak base resin with a Type 2 strong base anion
exchange resin, such as Amberlite IRA-4IO, De-Acidite N/IP,
Dowex 2 or Lewatit MP-600. The degassing tower must then be
placed ahead of the anion stage, to avoid wasting capacity on
carbon dioxide absorption. By the use of thoroughfare regeneration,
an overall caustic soda consumption of 70 per cent can be achieved,
while the treated water quality approach es the ultimate possible
purity. Conductivities of 0·2 p.S/cm, and silica concentrations of
0·02 p.p.m. are readily obtained by this process.
(b) Type 1 Anion (SBAl). For boilers of the highest pressures,
where deposition on the boiler tubes and turbine blades must be
reduced to the lowest obtainable levels, to avoid corrosion, the
system SA-Degas-SBI-MB is used. Thoroughfare regeneration
gives a minor saving in caustic soda consumption, and has the
much greater advantage ofpermitting a very high regeneration level
to be applied to the final mixed bed, through which passes the whole
of the soda required for both anion resins. The overall caustic
regenerant efficiency is 50-60 per cent, while the final dissolved
solids, irrespective of the input analysis, or the scale of operation,
can be reduced to the values in Table 6.
Table 6. SAC-DG-SBI-MB
Total bivalent metals < 0·01 p.p.m.

Na+ < 0·005 p.p.m.
Total anions < 0·015 p.p.m.
Silica < 0·010 p.p.m.
Conductivity < 0·1 p.S/cm
The same result can be achieved by the system SA-Degas-MB

-MB, but for reasons connected with organic poisoning (q.v.)
85
this method is unattractive in many cases. With either combination

it is important, if the ultimate in purity is required, to ensure that
the final mixed bed acts purely as a polishing unit. The absorption
process is stopped, and regeneration initiated, as soon as there is any
detectable leakage of ions from the anion unit, or first mixed bed.
6. WEAK ACID CATION. DEGAS. MIXED BED

( WAC-DG-MB)
Another method of improving the economy of mixed bed operation,
applicable to waters of high alkalinity, involves the use of a car-
boxylic resin, followed by degassing and a mixed bed. The final
water purity is identical with that obtained with a mixed bed
alone, while the running cost is greatly reduced, since the whole of
the acid, incIuding that used in the mixed bed, can be thoroughfared
through the weak acid column, and used at 100 per cent efficiency,
while the whole of the bicarbonate can be removed by degassing.
Table 3 shows a residual bicarbonate of15 p.p.m. when the 'Starva-
tion' process is used. When there is a following mixed bed, the
requirement for a neutral or alkaline water from the cation section
no longer holds, and by increasing the acid level to about 20 per
cent more than that of the normal 'Starvation' process elimination
of bicarbonate is made complete, whiIe acid efficiency remains
virtually 100 per cent.
The system WA-Degas-MB has no real value for water A, for
which the cost of demineralizing is in any case so low that the
reduction does not justify the extra complication in the equipment.
Similarly, the system is not of great interest for water D, whose high
chloride content requires the use of a weak base resin (System 4)
for maximum economy. Waters B andC, however are ideally suited
to System 7, which gives really important economies for water C.
7. WEAK ACID CATION. STRONG ACID CATION. DEGAS.

ANION. MIXED BED
(WAC-SAC-Degas-( WBA)-MB)
(SBA2)
(SBAl)
As the total quantity of water to be treated per hour increases, the
total quantity of resin required, and the number of columns needed
to contain it, are correspondingly greater. It is thus possible, in
suitable cases, to use combinations of greater complexity, without
adding to the overall plant size. By this means, running costs can
be reduced to their ultimate level.
86
WEAK ACID CATION. STRONG ACID CATION., ETC
For a water such as C, with high hardness and alkalinity, the

ideal system for large scale operation is
WAC-SAC-DG-WBA-MB
The strong and weak base anion resins are regenerated in thorough-
fare, giving maximum possible acid economy. The bicarbonate,
which forms 75 per cent of the anion load, is removed by degassing,
while the mixed bed and weak base resins are regenerated in
thoroughfare, to give 80 per cent overall caustic soda efficiency,
together with a high regeneration level for the mixed bed anion
resin to ensure good silica removal, down to a residual of < 0·05
p.p.m. When lower silica values are required, the weak base resin
can be replaced by a Type 2 strong base resin, with only a minor
change in running cost, while the purest obtainable water with
soluble silica of under 0·01 p.p.m. is produced by using a Type 1
resin in the same position. For alkaline waters, the system
WAC-SAC-DG-SB1-MB
is thus the best possible combination for producing at low cost the
very pure water needed for modem high press ure boilers.
An interesting development of this process, which is increasingly
being used, is to place the two cation resins in the same unit. The
acrylic resins are less dense than the sulphonic materials, and
form a discrete layer on top of them. By carrying out the absorption
cycle downflow, and the regeneration process upflow, thoroughfare
regeneration ofthe pair, together with true countercurrent operation
of each resin, is achieved. At the same time, the number of units is
reduced by one. Methods of operating counterflow regeneration
are considered in Chapter 7. A similar system can be used in the
anion exchange column, by placing a weak base over a strong base
resin, in the same unit.
One problem can arise with System 7, in any of its forms. It
occurs with water D, and more particularly with slightly brackish
waters ofthe same general type as D, but with greater total dissolved
solids. Because the carboxylic resin gives preferential removal of
Ca 2 + and M g 2+, the sulphonic resin is effectively treating a water
containing only mineral salts of sodium. The sodium slip is thus
very high, and silica removal by the anion resin is correspondingly
less complete. The final mixed bed is thus fed with a dilute solution
of sodium silicate, with a considerable excess of sodium hydroxide,
87
and the final treated water may fall short of the ideal, from the point
of view of silica removal, aIthough residuals in the region of 0·02
p.p.m. should be obtained. When better results are required, for
this type ofwater, the following system is most satisfactory.
8. STRONG ACID CATION. WEAK BASE ANION. MIXED

BED. MIXED BED
(SAC-WBA-MB-MB)
For fairly thick waters, in which sodium chloride predominates,
and particularly those of low alkalinity, this system forms the best
method of attaining the highest possible purity at tolerable running
costs, using conventional ion exchange resins and techniques.
Possible new systems are considered in Chapter 7. The bulk of the
work is carried out by the first two columns and the degassing
tower, leaving the first mixed bed to deal with the residual sodium
chloride and silica. The final mixed bed acts purely as a polisher.
One of the largest plants of this type in the world was built in 1964
at Gela, Sicily, by a British company. Four parallel lines, each
treating 250 m 3 jh (55,000 galjh) operate under full automatie
control, treating a water highly contaminated with organic matter,
and with mineral salt concentration varying from 300-1,500 p.p.m.
Each line consists of:
Organic trap - <: A-WB
SA-WB
>-MB-MB
The parallel placing ofthe SA-WB pairs is due to the fact that the
units, 12 ft 0 in diameter, and containing 1,100 ft3 of resin, were
the largest which could be made, and were still insufficient to give
the required capacity when working singly. The significance of the
organic trap will be considered later. The mixed beds of each line
are regenerated in thoroughfare, and since the original installation,
have consistently given silica residuals ofO·05 p.p.m., from the first,
and less than 0·005 p.p.m. from the second. The corresponding
conductivities are 0·5 and 0·1 fkSjcm respectively. A photograph of
this plant is shown in Plate 1.
9. STRONG ACID CATION. DEGAS. WEAK BASE ANION.

STRONG BASE ANION
(SAC-DG-WBA-SBA)
AIthough this system is favoured by many users of ion exchange
equipment, it is considered by the author to be less satisfactory
88
STRONG ACID CATION. DEGAS. WEAK BASE ANION, ETC.
technically than other methods of achieving the same results, such

as Systems 4 and 5. The object of System 9 is to achieve a treated
water of high purity, together with the economy resulting from the
use of a weak base resin. In practice, it is clear from the general
discussions of the previous chapters, that unless the regeneration
level of the SAG column is very high, the final water will contain
appreciable concentrations of caustic soda, and will have a corres-
pondingly high pH and conductivity. The problem is increased by
the fact that, as the carbon dioxide and mixed anions are almost
completely removed by the degassing tower and the WBA unit
respectively, the final SBA unit is used almost exclusively for the
removal of silica, with which it be comes very heavily loaded. In
order to ensure a low silica residual in the treated water, it is
necessary to use a high regeneration level on this unit, figures of
6·0 Ib/ft 3 NaOH (96 g/l) being normal. The use of such large
quantities of regenerant renders rinsing difficult, and tends to
increase the pH and conductivity of the water still further. The
method is perfectly workable, especially with fairly thin waters, but
it is sensitive to changes in input water quality, and inadvisable for
thick waters, especially those containing appreciable proportions
ofsodium.
89
G
CHAPTER 6
ORGANIC POISONING OF ANION EXCHANGE

RESINS
THE PROBLEM
Until recent years, water treatment by ion exchange was considered
as a largely inorganic process and resins were judged solely by their
ability to exchange or remove mineral ions. The total organic
content of natural water supplies is considerably lower than the
inorganic content, and when the standard of water purity required
for industrial purposes was 1-2 Jl-S/cm (S = mhos), organic con-
tamination of the input water was rarely sufficient to cause notice-
able changes in the quality of the treated water, or the apparent
working capacity of the resins. The greater purity requirements of
modern boilers, necessitating conductivities of down to 0·1 Jl-S/cm,
have converted into severe problems phenomena which were
virtually unrecognized until the 1950's. The nature of the problem
is best illustrated in Figure 37 which shows typical results of mixed
bed operation under a number of conditions. If the input water
contains no organic matter, then results such as Curve Bare
readily obtainable, and under ideal conditions, the treated water
quality can be as good as in Curve A. Typical results for London
water, a mixed and variable supply with about 300 p.p.m. T.D.S,
and 1-2 p.p.m. O.A, are given in Curve C, while old mixed beds
which have become poisoned will do no better than Curve D.
Indeed, some of the thin, organic-Ioaded waters occurring for
example in Wales will rapidly foul a conventional mixed bed to a
much greater extent, the conductivities being around 2-3 Jl-S/cm.
In the four cases shown, the total capacities of the resins are
proportional to the area (allowing for the logarithmic vertical
scale) between curves A-D and the horizontalline representing the
input water. The difference between the best and worst case is only
0·2 per cent. The operating capacity, on the other hand, is entirely
dependent on the quality of the water required. If a conductivity
below 1·0 is adequate, the total usable operating run for Curve A
is 9·5 kgr /ft 3 (21'8 g/l) while that of Curve D is 7·5 kgr /ft 3 (17'2 g/l),
90
THE PROBLEM
an operating capacity loss of 21 per cent. In 1950, therefore, this

unit would have been considered to be in quite serviceable condition.
With the quality standard of 0·5 fl-S /cm, the unit represented by
Curve D is giving no usable water at all, and since 1960, when this
standard has been commonly applied, its capacity would have been
regarded as zero.
500
_~~_~~e~~~~u.:.t~ iY_ _ __ _ ___ _____
100
E
u
I
~ 10'0
)
:1.
Z;o
~u
J
-go ' -0 I~ 0
U
0-5
X
I'=:: - - - - - -c- - - -X' - - - - - - - - - ?)Y
0'3 - - -
0 '1 8
A
0 2-01 4-0 1 6-0 I B-O 11(-Okgr/ftl
5 10 15 20 g/l.
Total an ions absor bed as CaC0 3
Figure 37. The effect of organic poisoning
By the same standard, Curve C shows an operating run XY of

9 kgr/ft3 (20,6 g/l), which is only 5 per cent less than the ideal case,
but a tightening of the conductivlty specification to 0·3 fl-S/cm
immediately reduces the operating capacity by 50 per cent to
X'Y', and the slightest deterioration in the results would result in
the whole of the water being rejected. Finally, no conditions except
the absence of organic matter (Curves A and B) give any treated
water, to the modern standard ofO·l fl-S /cm.
It follows that symptoms of organic poisoning can be discussed
only in relation to the standards of water purity required, and
91
ORGANIC POISONING OF ANION EXCHANGE RESINS
statements in the ion exchange literature of the 1955-1960 period,

before this fact was realized, are accordingly often misleading.
ORGANIC MATTER IN WATER

Water originating from deep wells or springs is normally almost free
from organic matter, and can be treated by ion exchange without
special precautions. Problems arise in the case of surface waters,
such as rivers, lakes, or reservoirs, which contain organic matter
resulting from the decomposition of grass, ferns and leaves on the
land from which the water is collected. The most difficult cases are
the soft, thin coloured waters found in peaty regions such as Scotland
and parts of Wales, which contain both dissolved and colloidal
organic matter. There is no absolute method of measuring the
total quantity of organic matter present, and it is customary to use
one of a number of generally accepted empirical tests. A commonly
used method is the O.A. test, in which the oxygen absorbed from
potassium permanganate solution in 4 h at 27°C is measured. All
results quoted in this chapter refer to this method. Another widely
used test is similar, but carried out for 30 min in a thermostat
bath at 100°C. Finally, in the Kubel test, which is favoured in
Europe, the sampie is boiled für 10 min. The high temperature
tests tend to be slightly less reprüducible than the 27°C method, and
if the chloride content of the water is high, re action between chlo-
ride and permanganate yields indicated O.A. figures which are
slightly too high, and require a correction. There is no absolute
relationship between the results of the three methods, but for most
surface waters, a reasonably reliable general relations hip is
Kubel : 30 min 100°C: 4 h 27°C = 3 : 1·5 : 1

Typical values for the 4 h O.A. for various waters are as follows.
Deep well waters 0·1-0·4 p.p.m. as O 2
Normal surface waters 0,8-2,0
Peaty waters 5·0-10·0
The exact nature ofthe organic matter is not yet fully established,
and a considerable volume of research is being carried out by
authorities in many parts of the world. The methods in general are
based on removing the organic matter from the water by a suitable
anion exchange res in, eluting it from the resin with brine, and
dialysing the concentrated eluate to remove the salto Chromato-
graphie separations of the organic constituents are then carried out
92
ORGANIC MATTER IN WATER
by ion exchange or gel filtration, the fractions being examined by

the standard techniques of organic analysis. It has been established
that natural organic matter consists almost entirely of a mixture of
polycarboxylic acids, of fairly high molecular weight, and of acid
strength similar to that of formic acid. The acids are conveniently
grouped into two main types, humic acids which are insoluble in
HCI at pH 1,0, and fulvic acids which are soluble under these
conditions. Humic acids have less carboxyl groups than fulvic, and
in general have a higher molecular weight. They are thus less
hydrophylic, and are not so readily absorbed by ion exchange
r··
2'0
1·5 ....,. /'--. \ / '.

E 1\
•• /'-., /
;.. \\ ... .
, \ • \.
1\
Cl. 1.0 .....,. •• '. _.... ,_ ...... I- •
Cl. r--'. .' .....- - -'. • ...
r-- '.'
"~ 0'5~J~M~M~~J~S~N~I~J~M~MLLJ~~S~N~I~J~M~MLLJ~S~~N~IJ~M~M~J~
~ FAJAODFAJAODFAJAODFAJA
~ 1956 I 1957 I 1958 I 1959
'~" 2'0
Cl
>.
)(
o 1·5
0·5 A 0 D F A J A 0 D F A J A 0 F A J A 0 0 F
5 NIJM MJ 5 NIJM MJ S NIJM MJ 5 NIJ
1959 1960 1961 19q2 1963
Figure 38. Seasonal variation in organic content of London water
resins. Once absorbed, however, they are very firmly held by normal
resins, and are difficult to remove. Both types are found in a range
of molecular weights, removability becoming more difficult as the
size of the molecule increases, with the larger humic molecules
presenting the most serious problem.
Studies of a large number of different surface waters in Great
Britain have shown that the organic content varies seasonally in a
regular fashion. A typical set of results is shown in Figure 38 for
London water over several years. The variation is due principaHy
93
to the fact that as vegetation decays in the autumn, its decomposition

products are leached by rain and find their way into rivers and
lakes, whose organic content therefore rises in October and is at a
maximum in the winter. With the new growth of vegetation in
spring the organic content falls and is at a minimum in summer.
There is some correlation between the heights of the peaks and the
type of weather in autumn. A warm wet autumn, giving rapid
wet degradation of the vegetation, gives rise to early high peaks,
while a dry autumn gives lower and more widespread maxima.
The seasonal effect is slightly enhanced by the fact that the bio-
logical degradation of the organic matter present in rivers and
lakes is higher in the warm weather than during the winter.
The nature of the organic matter itself varies according to the
time of the year and it has been shown in the author's laboratories
that water taken from a river in midsummer is much less poisoning
to ion exchange resins than the same water taken in midwinter.
The effect is greater than can be accounted for by the difference
in total organic content. It seems clear that there is a variation in
the ratio of humic and fulvic acids according to the seasons. In
winter time the type of organic matter present can cause severe
poisoning of ion exchange resins, while in summer the same water
may have no poisoning properties at all. The water supply at
Pontyclun, in South Wales contains organic matter which in
summer time totals less than 0·5 p.p.m., appears to have neg-
ligible ion exchange properties and is almost unabsorbed by any
type of resin. The same supply in winter may have an O.A. of 1·0
p.p.m. ofwhich 90 per cent is absorbed by anion exchange resins.
POISONING OF RESINS
In considering the poisoning of anion exchange resins by organic
matter, it is important to distinguish between the chemical effects
of soluble organic ions and the purely mechanical effect of the
presence of insoluble matter in the water, causing blocking of the
resin beds and consequently faulty operation. These two quite
different phenomena are often confused, since they give the same
symptoms of long rinse and poor water quality, and it is not un-
common to find water treatment plant users undertaking expensive
programmes of resin cleaning, or even replacement, when the
real requirement is efficient filtration of the incoming water,
together with a programme of vigorous agitation and backwashing
of the resin to remove physical blocking of the bed, which has
already occurred.
94
POISONING OF RES INS
In between the extremes of soluble and suspended organic matter

is the twilight zone of colloidal material, which is somewhat diffi-
cult to define. Colloidal organic matter is readily removed by the
standard methods of coagulation with alum or ferric sulphate, but
a proportion of the soluble organic material is also removed by
these processes. The two cannot therefore be distinguished by this
means. As a very rough generalization, it may be said that when
the O.A. is less than 1·5 p.p.m., the organic matter is likely to be
largely soluble, and removable by purely ion exchange procedures.
As the O.A. increases above this figure, the probability of colloidal
matter increases, and waters recording O.A. values of more than
2·5-3·0 p.p.m. nearly always contain sufficient colloidal material
to render coagulation necessary as aprecursor of a demineralizing
unit. Colloidal organic matter is negatively charged, and becomes
attracted to the surface ofthe anion beads, where it becomes attached
to the outer layers of the resin network, interfering with the free
transfer of normal ions. This action is not significantly modified by
changes in the resin structure, whereas, as will be shown, the nature
of the resin skeleton has a profound effect on the degree of poisoning
by soluble organic matter.
It is also important to realize that uptake of organic matter by
a resin does not necessarily imply poisoning. The two processes are
often mentioned in the literature as if they were identical, a con-
cept which was partly true of the classical polystyrene-divinyl-
benzene anion exchange resins, which were not fully reversible
to the humate and fulvate anions. As a result, there have been pro-
posed various tests for poisoning, based on titrating the resin with
oxidizing agents such as dichromate. Such experiments merely give
a measure of the oxidizable organic matter present in the resin,
and give no indication of whether or not the resin is being poisoned
by it. If, for example, a resin were used to absorb simple organic
acids as formic or acetic, which do not cause poisoning of any type
of anion exchange resin, the dichromate test would show high
values after the first use of the resin. Similarly, natural organic
acids in water, when absorbed by resin, must always lead to a
positive dichromate test, even if they are of low molecular weight,
and correspondingly harmless. The symptoms of true organic
poisoning can be classified under three main headings.
(a) Strong Base Resins in Single Columns

This is the simplest case. Ifthe resin structure is such that organic
matter is absorbed irreversibly, then there is a steady decrease in
95
ORGANIC POISONING OF ANION EXCHANGE RES INS
capacity as the resin is used, due to the blocking of ion exchange

sites by organic molecules. In addition, poisoned resin absorbs
sodium ions from the regenerant solution, and subsequently
releases them during the rinse. This process is slow, and the result
is a long period of rinsing, before the treated water conductivity
descends to an acceptable level. New resin normally requires about
5 bed volumes of water for adequate rinsing, whereas the require-
ment for poisoned material can rise to ten times this figure. The
emergent rinse water, while not sufficiently pure to be suitable for
service, is nevertheless very largely demineralized, and has thus
consumed some of the capacity of the resin. The operating capacity
of the resin is correspondingly reduced.
(b) Weak Base Resins in Single Columns

The problem in this case is more complex. In addition to a
primary action similar to case (a) there is a rate effect, which is
considerably more important. The exchange rate of the dassical
polyamine weak base resins is considerably lower than that of the
strong base materials, and as a result the operating capacity which
can be obtained, from the start of the exhaustion run to the point
at which the water quality deteriorates, is strongly dependent on
the rate of presentation of ions to the column. This value is itself
proportional to the product of the water flow rate, and the ionic
concentration. For a fixed resin capacity, the time taken für the
operating cyde is inversely proportional to this product, and it is
thus convenient to record the observed capacity against the length
in hours of the operating cyde. As has already been shown (Figure
16), the dassical polystyrene polyamine resins show capacity
reductions at short cyde times, and the effect is still more marked
with organically fouled materials.
In the earlier years of demineralizing practice, it was common
to use manually opera ted plants, which were calculated to run for
24 h or more between regenerations, in order to economize on
labour costs. Modern plants are increasingly being planned for
fully automatic operation, and to reduce capital costs, they are
designed to opera te at high flow rates, and short cyde times, down
to about 5 h. Under these conditions, the classical weak base res ins
show serious reductions in operating capacity after only a few
months service with surface waters, and the modern requirement is for
materials whose total exchange capacity may be lower than that ofthe
polyamine materials, but whose exchange rate is rapid, and unaffected
by the presence of organic matter in the water under treatment.
96
POISONING OF RES INS
(c) Mixed Beds

The symptoms of mixed bed poisoning are similar to those of
case (a), but are more immediately recognizable, because of the
high quality of water demanded from mixed bed operation. In
addition, the anion resin of a mixed bed can show signs of severe
poisoning, and yet yield perfectly normal results if it is removed
from the unit, and operated in a two-bed system.
This effect is due largely to the method of operation of a mixed
bed, and is not directly connected with the structure of the resin
itself. Anion exchange resin which has taken up natural organic
matter, but is not necessarily poisoned by it, is at each regeneration
cyde brought into contact with the mineral acid solution used for
regenerating the cation exchange resin. The humic acids present
become precipitated in and around the resin beads. After re-mixing
the res in, a fraction of this anion material will have found its way
to the bottom of the bed and during the subsequent rinse and
service cydes the humic acids slowly re-dissolve and are re-absorbed
by the anion exchange resin with emission of a corresponding
concentration of inorganic acid. This is the reason for the charac-
teristic phenomenon of high rinse and conductivity associated with
organically loaded mixed beds.
The correctness of the mechanism described above can be readily
demonstrated by taking a sam pie of old, organically loaded,
strong base resin and placing it in a laboratory mixed bed regener-
ated in the normal fashion. The bed will show all the usual signs of
poisoning. On the next cyde the resins are separated and great care
is taken to prevent any anion material being left mixed with the
cation resin. The two resins are then regenerated separately and
re-mixed. During the next cyde the rinse is rapid and the quality
is excellent throughout the run. Finally, the reverse experiment is
carried out in which, during the res in separation stage, a pro-
portion of the anion exchange resin is deliberately left with the
cation resin. After normal regeneration and re-mixing, the operat-
results are extremely bad and the conductivity may never fall
below 5·0.
It is thus seen that if organic ions are present in the raw water
reaching a mixed bed of dassical design, then part of the humic
fraction must become precipitated, and the bed must in due course
show the symptoms of poisoning. This action occurs, even if the
anion exchange resin is one of the non-poisoning types, freely
reversible to organic matter which are described below. It follows,
that, while non-poisoning resins are preferable for mixed beds, as
97
for every other duty, their use is in itself insufficient to ensure good
results. While good design of the mixed bed unit will minimize the
degree of acid contact, it is impossible to eliminate it. Consequently
it is essential to remove the organic matter from the water, before
it reaches the mixed bed unit.
CLEANING POISONED RESINS

Two methods of removing organic matter from poisoned res ins
have been regularly practised during the last 10-15 years. The
first is to soak the resin in a mixture of brine and hypochlorite,
containing about 2 per cent available chlorine, for 12-24 h. This
procedure usually has a marked effect on the colour of the resin,
which in the poisoned condition is dark brown or black, but after
hypochlorite treatment is often restored almost to its original
colour. The treatment does improve the operating results, but not
as greatly as would be expected from the change in appearance of
the resin. It is clear that the organie matter present is bleached in
situ, rather than removed or destroyed. When resins of classical type
are used under severely poisoning conditions, cleaning may be
required at intervals of a few weeks, and under these circumstances,
the hypo chlorite treatment gives rise to sufficient chemical attack
on the res in to cause a marked reduction in capacity over 2-3
years life.
A more reliable method is to treat the resin with about 1·5 bed
volumes of a solution containing 10% NaCI and 1 % NaOH, which is
allowed to percolate through the bed during aperiod of 1 h or 2 h.
If the circumstances of operation permit an overnight soaking in
the solution, this procedure is advantageous. The treatment removes
a great deal of coloured organic matter from the resin, the emergent
liquor being black. I t will not normally restore the resin to new
condition, but will always effect a considerably improvement in
the results, and as it does not damage the resin, it can be carried
out as frequently as required.
I t is important, when treating poisoning waters, to carry out the
alkaline brine cleaning as a routine maintenance procedure, at
intervals of about one month, rather than to wait until the operating
results have seriously deteriorated. Organic matter becomes more
difficult to remove as the total quantity in the resin increases.
In a typical case known to the author, three mixed beds operating
in parallel on an uncoagulated water in South Wales consistently
gave results inferior to those of Curve D (Figure 37). A system was
introduced of treating one unit with alkaline brine every week, so
98
THE EFFECT OF RESIN STRUCTURE
that each one ran for 3 weeks between treatments. The operating
results then recovered until the conductivities were consistently
about 0·5 p.Sjcm.

The method of manufacture of the divinylbenzene crosslinked ion
exchange resins has been given in Chapter 2. The processes
described are correct in principle, and are presented in the same
way as in most textbooks on ion exchange resins. In one respect,
however, the diagrams are misleading, since they give the impression
that the final product possesses a flat, rectangular, and almost
crystalline molecular structure. This concept has been tacitly
accepted by many workers in the ion exchange field for many years,
because it gave a simplified picture of the resin structure which,
while not completely correct, has been accurate enough for the
understanding of simple industrial processes involving only small
inorganic ions. Some of the earliest work on this subject, was
carried out in 1949 by Duncan and Lister, who first demonstrated
that the selectivity coefficient for cation exchange was not constant,
but became smaller with increasing loading of the resin. The prob-
lem was studied for some years by a section of the Chemical Re-
search Laboratory, D.S.I.R., and in 1955, Reichenberg demon-
strated that the effect was associated with differences in the
environment of different sulphonic groups in the resin. He postu-
lated that groups occurring in loosely crosslinked regions, being
readily accessible would show different K values from those in
tightly knotted regions. Among much evidence produced for this
theory, there was a simple and convincing experiment, in which
different sampies of the same batch of hydrocarbon beads were
separately sulphonated so as to attach the active groups first to
the accessible parts of the structure, and secondly to whole mole-
cules. The two resulting cation exchange resins differed considerably
from each other in the way he had predicted. This inhomogeneity
of the crosslinked hydrocarbon polymer structures, which applies
equally to the cation and anion exchange resins made from them,
has subsequently been confirmed by many other workers.
Knowledge of crosslinked polymer structure in general and ion
exchange resins in particular, is less advanced than that of the
linear polymers, since many of the standard methods of investiga-
tion are carried out with solutions of the polymers. This approach
is impossible in the case of crosslinked materials, which are insol-
uble, and structure must be inferred from other measurements.
99
It is of the greatest importance in connection with the mobility

in the resin of large organic ions such as the humates and fulvates,
which can become entangled with the tight regions of the polymer
network. During the polymerization of styrene with divinylbenzene,
or indeed with any other crosslinking agent, two major forms of
inhomogeneity are introduced.
(a) Chain Entanglement

The mechanism of vinyl polymerization, with peroxide catalysts,
implies that new molecular chains starts at each catalytic initiation
centre. The chains are long, and since they are crosslinked, they
must spread out in three dimensions, and cannot lie parallel. The
crosslinked structure is thus aseries of separate 3-dimensional
networks, each of which grows independently of the others from a
single starting point, and it is clear that the resulting networks
must be intertwined. The effect is illustrated in Figure 39 in which
A and B represent parts of two 8 per cent D.V.B. crosslinked
styrene molecules, formed separately, and lying alongside each
other, without entanglement. Figure 39(c) shows the same two mole-
l~~
A
1~~ B C
Figure 39. Chain entanglement
cules, which have grown through each other du ring polymerization,

and cannot now be unlocked. Resin C is still 8 per cent crosslinked,
but is a very much tighter structure than A or B, with corres-
pondingly smaller pores. In practice, for the reasons given, resins
as normally manufactured resemble C rather than A and B in
structure.
The hypo thesis has been proved by the work of Millar et al. In
addition to any natural entanglement produced during normal
polymerization, they introduced controlled degrees of extra entangle-
ment by ta king the finished beads on a polymer containing, say,
4 per cent D.V.B. imbihing into them some ofthe original monomer
100
mixture, and repolymerizing. The final solid polymer still contained

4 per cent D.V.B. yet when it was converted to a cation exchange
resin by sulphonation, it had the swelling characteristics of an 8 per
cent crosslinked material, as normally produced. Similarly, a
2 per cent crosslinked polymer can be given the properties of an
8 per cent material, by reswelling it several times with its own
monomer mixture, and a 1 per cent can be converted to the same
condition also by multiple reswellings. It is, in fact, quite possible
that a material could be made with all the characteristics of a
normally crosslinked res in, while containing virtually no cross-
links at all, but purely an exceptionally high degree of entangle-
ment. Although all these materials are similar in appearance,
capacity, water content, and similar readily measured character-
istics, they do differ appreciably in their equilibrium and kinetic
results. For example, the reswollen 4 per cent D.V.B. material
retains the kinetics of a simple 4 per cent D.V.B. polymer, com-
bined with the swelling characteristics of anormal 7-8 per cent
material, and the equilibrium coefficients of anormal 15 per cent
resin.
In addition to producing extra entanglement, it is equally
possible to arrange for deliberate disentanglement during manu-
facture. To the monomer mixture is added a miscible solvent such
as toluene, which is compatible with the final polymer, but which
takes no part in the reaction. The polymer chains are thus forced
to grow in the toluene solution, in an expanded, less entangled
form. On completion of the reaction the toluene is removed, and
the expanded structure collapses, while remaining disentangled. It
thus has all the measured properties of a more loosely crosslinked
resin. It is possible to prepare aseries of resins, all closely similar
to each other by increasing the proportion of toluene while simul-
taneously increasing the D.V.B. content to produce extra crosslinks
to replace the lost entanglement. In this way there can be made, for
example, a 20 per cent crosslinked material with the measured
characteristics of an 8 per cent resin.
It is thus possible to produce a complete range ofmaterials, with
almost infinitely variable divinylbenzene content, and with pro-
perties not directly dependent on the D.V.B. content. This principle
is illustrated in Figure 40 where resins along diagonal lines of the
diagram have virtually identical swelling and capacity properties
although their D.V.B. contents are widely different.
The process of disentanglement by means of toluene can be
carried to the extent that the solid polymer chains are stretched,
101
and rigidly locked so that on removal of the solvent, the structure

does not collapse, but contains genuine holes, of up to 1000 A
diameter, which form water channels. The rigid over-expanded, or
highly disentangled structures are known as 'macroporous', and as
will be shown later, are one of the available types of resins resistant
to organic poisoning. The deliberately re-entangled structures have
no industrial use at present.
Multiple
'"ova re-entangled
~e-entangled 'Normal' Disentangled'
2
1if ~
4
~ ~ 1j
8
• • ~~
16 4t
~
-=
Figure 40. Varying structural types
11
A different method of making macropores is also available. In
this process a solvent is used with which the monomers are miscible,
but with which the final polymer is incompatible. During poly-
merization, micelIes of polymer precipitate out from the monomer,
later joining together to form a 'sintered' structure. The final
result (Figure 41) is very similar to that produced by the compatible
102
solvent system, and gives another type of macroporous or macro-

reticular resin which is also used industrially.
There are thus four main types of resin structure, which are not
distinct, but merge into each other. Theyare
Entangled
'Normal'
Disentangled
Sintered.
The 'normal' resin has no fundamental meaning, and is merely one
containing the average degree of entanglement occurring under
the polymerization conditions used, and the structure thus contains
a considerable degree of inhomogeneity, with wide variations in
pore size in different parts of the moleeule.
Figure 41. Sintered structure
(b) Differential Polymerization

A second effect, completely independent of the entanglement
process, is due to the fact that in a mixture of divinylbenzene and
styrene, three different polymerizations are possible. In practice,
there are more, since ethylstyrene is also present, but for simplicity
this monomer is ignored.
Styrene-styrene
Styrene-divinylbenzene
Divinylbenzene-divinylbenzene
The reaction rates of these three processes increase in the order
given above, so that as polymerization starts round the initial
catalytic centres, the first polymers chains formed are excessively
rich in D.V.B. and the remaining monomer mixture is correspond-
ingly poorer. The chains which grow later are in consequence
progressively more lightly crosslinked. The resultant polymer
103
ORG ANIC POISONING OF ANION EXCHANGE RESINS
therefore is not uniform but has aseries of tightly linked centres

separated by more loosely linked regions as shown in Figure 42.
It follows that the pore sizes differ 'very widely from the average,
and a material which is nominally 8 per cent crosslinked, for
example, may have in the moleeule regions whose crosslinking
varies from as little as 3 per cent to as much as 30 per cent, with a
gaussian variation between. This structure is fundamental to all
copolymer networks which can be used in ion exchange resin
manufacture, and gives a second source of inhomogeneity.
From a knowledge ofthe resin structure, it is possible to build up a
picture of the mechanism of organic poisoning of the copolymer
anion exchange resins which, while difficult to demonstrate In
Early Final
Initiation stages copolymer
Figure 42. Progress of co-polymerization
detail, has nevertheless proved sufficiently accurate to explain the

observed effects, and provide at least two different means of over-
coming them. As the large organic anions travel through the resin
structure to exchange sites in the interior of the beads, they must
inevitably pass through both lightly and excessively crosslinked
regions. The knotted regions form bottlenecks in which the large
organic ions tend to collect. They can become entangled with each
other, and are unable to leave the structure to be replaced by OH-
ions during the normal process of regeneration. The quantity of
organic matter present in the water is normally insufficient to fill
more than a very small proportion of the highly crosslinked sites
in any one operating cyde, but as the resin continues to be used,
these sites become increasingly blocked by a concentration of
organic matter, thus making them unavailable for normal in-
organic ion exchange. The total capacity of the res in thus falls
slowly to a level which may be 80-90 per cent of the value für a
104
facing jwge IO.f
Plate 2. Fully automatic demineralizing plant at a large paper mill in Kent
THE EFFECT OF RESIN1STRUCTURE
new resin, according to the proportion of knotted regions in the

particular resin sam pie. The process of poisoning then stops, and
the resin continues to operate at its reduced total capacity for very
long periods. The poisoned regions of the resin molecule have,
however, completely changed their character. The anion exchange
properties have been lost, since the positively charged exchange sites
are blocked. These regions now contain fixed carboxylic groups,
contained in the organic molecules which are now anchored
immovably in the resin structure. Parts of the resin have thus been
converted from anion to cation exchangers (Figure 43).
+
(CHJl3
ow
OW
(a)
Figure 43. Conversion 0/ anion to cation exchange sites (a) New resin. All quaternary sites
available (b) Poisoned resin. Quaternary sites in tightly crosslinked regions replaced by
carboxylic sites
1t is the presence of these cation exchange regions which causes

the phenomenon of long rinse times, with correspondingly high
rinse water consumption, which is characteristic of resin poisoning.
The fixed carboxylate groups are converted to the sodium form
during regeneration of the resin, and their subsequent hydrolysis
causes unacceptable effiuent water conductivities, until the sodium
ions have all been lost.
R - COO-Na+ +H 2 0 ~ R COOH + Na+OH- .... (37)

During this long rinse period, other, unblocked ion exchange
sites are becoming exhausted by inorganic anions in the influent
105
H
water, thus reducing the operating capacity to 50-60 per cent of

the original value, a much greater extent than would be calculated
from the simple loss of active groups by poisoning.
NON-POISONING RESINS
1. Macroporous (Macroreticular)
The problems of organic poisoning manifested themselves
increasingly during the years 1950-1960, due to the more stringent
standard of water quality which were applied during that period.
Towards the end of the decade, three different resin manufacturers
had developed independently, within a few months of each other,
the first method of combating the problem. It was reasoned that, as
differential crosslinking could not be avoided, its effects must be
reduced by producing a spongelike structure, containing a complex
network of water channels through which the large ions could
travel unhindered. The webs of solid material between the channels
would be extremely thin, as compared with the diameter of a
normal bead. A high proportion of the knotted resin regions would
thus be elose to the surface of the internal water channels, thus
giving the possibility that the organie matter collecting in these
regions could be freed during regeneration, to be removed through
the channels, which become known as macropores. The two
methods of producing macropores already described were invented,
and were highly successful in producing resins essentially reversible
to organic ions, with consequent freedom from poisoning. The
first demineralizing plants using resins of this type were installed
during 1959, and have since given many years of excellent operating
service with waters known to cause intolerably rapid poisoning of
the elassical D.V.B. gel resins.
Unfortunately, these resins, which became known as macro-
porous, or macroreticular, possessed a defect which partially
counterbalanced their obvious advantages. Because of the presence
of a considerable proportion of holes in the resin, their total content
ofactive matter, and therefore their capacities, were lower than those
ofthe corresponding D.V.B. gel materials. In addition, the method
of production, whether by the over-expansion or the sintering
procedure, resulted in a structure which held the simple inorganic
ions more firmly than had been the case with the earlier resins.
As a result, it became more difficult to remove these ions during
regeneration, and a greater quantity of caustic soda was required
to achieve the same degree of removal, that is, to free the same
106
number of aetive sites for use during the next operating eyde.
Consequently, in addition to a loss of total eapacity, there was an
increase in the quantity of regenerant required to achieve a given
operating capacity. Plants containing the maeroreticular resins
thus suffered from higher capital and operating costs than those
using the earlier D.V.B. gel materials. However, the virtual
elimination of poisoning implied that the initial operating figures
were maintained over long periods, so that after several years in
service with bad waters, the macroretieular resins often retained
residual operating capacities than the dassical gel resins.
2. Isoporous
Following the diffieulties with the macroporous resins, the
opposite method of overeoming the poisoning problem was studied.
If poisoning were due to irregularities in erosslinking, it could be
prevented by making the crosslinking homogeneous, so that aIl
pores would be substantiaIly the same size, and tightly knotted
regions would no longer be present. It is impossible to achieve
this result in a crosslinked copolymer structure, by existing methods,
sinee the phenomenon of differential crosslinking is a fundamental
feature of the polymerization proeess. There is however, a weIl
known method of introducing crosslinking into anion exchange
resin struetures. It has been shown in Chapter 2 that the process
of anion resin manufacture indudes a chloromethylation stage,
which is the precursor to the addition of the active groups. During
this stage, a secondary Friedel Crafts reaction can oecur, between
a chloromethyl group and an adjaeent benzene ring
-
(38)
This reaction always takes place to some extent during chloro-
methylation, and for this reason anion exchange resins are always
107
slightly more tightly crosslinked than cation exchange materials

made from identical hydrocarbon beads. Normally, conditions are
used to minimize the side reaction, but it is possible to control it
so as to produce the whole of the crosslinking needed in the resin,
no divinylbenzene being used at all.
The methylene bridge crosslinking differs fundamentally from
copolymer crosslinking, in that its mechanism is largely random,
and does not lead to the bunching of crosslinks which is inherent in
the copolymer process. It is thus possible to produce a substantially
uniform network, free from tight regions. Resins produced in this
way have become known as 'isoporous', and they form the fifth
main type of structure. The difference between macroporous,
normal and isoporous resins is illustrated in Figure 44.
Macroporous Normal lsoporous

copolymer
Figure 44. Comparison of standard types
The isoporous resins have the same reversibility to organic

matter as the macroporous materials, removing it from the water
and releasing it on regeneration without loss of capacity or treated
water quality, and without increase in rinse requirements. They
do not, however, have the corresponding disadvantage of reduced
capacity, and in British practice at least, they have very largely
superseded the macroporous materials for demineralizing purposes.
Macroporous resins are still used for organic traps (see below) for
which their reduced demineralizing capacity is not disadvantageous.
3. Weak Base Materials

The structural considerations discussed above apply equally to
strongly and weakly basic resins ; but in the latter case, the effect
of the active group itself must also be taken into account. Any
primary or secondary amine, when reacted with chloromethylated
108
polystyrene, will produce a weakly basic ion exchange resin, and a

large number of chemically different materials are available from
different manufacturers, in contrast to the two main types of strong
base materials, which are universally supplied.
The early weak base resins were commonly manufactured by the
use of polyamines, which, by adding more than one amino group
per benzene ring in the resin skeleton, gave resins of high total
capacity, which frequently exceeded 6·0 m.equiv.fg, or 2,500
m.equiv./l. These materials had correspondingly high operating
capacities, but were somewhat slow in action, and particularly
prone to organic poisoning, probably because of high attraction
between polyamine groups and polycarboxylic ions. When
poisoned, their exchange rate diminshed further, and they thus
became highly rate sensitive. When opera ted slowly, so as to give
eyde tim es in excess of 24 h, their operating capacities were not
markedly inferior to those of new resins. At high flow rates, and
short cyde times, the reduction in capacity was serious. The usual
phenomenon of high rinse requirement was, of course, independent
of operating flow rate. These effects were not removed by placing
the same active groups on macroporous or isoporous skeletons, and
it was necessary to use an active group which was intrinsically more
rapid in action, and more similar to a quaternary ammonium
group in its general properties. The logical step was to use the
smallest possible tertiary amine, that is to say, a resin based on
dimethylamine. A number ofresin manufacturers have now adopted
this principle, and one has gone further, by introducing a propor-
tion of strong base groups to give a further increase in reaction
rate.
The tertiary amine groups, in combination with a macroporous
or isoporous structure, are not only rapid when new, but are freely
reversible to organic ions. They thus preserve their original operat-
ing characteristics almost indefinitely. Materials of this type are
Amberlite IRA-93, De-Acidite H/IP, and Lewatit MP-60.
THE PROTECTION OF MIXED BEDS
(a) Prior Demineralizing Unit

For a large demineralizing installation the most satisfactory
method ofprotecting the final mixed bed is to use a prior demineral-
izing_ pair in which the anion res in is reversible to organic ions. If
the resin used is a non-fouling strong base type (e.g. Amberlite
lRA-900 and 910, De-Acidite FF/IP and N/IP or Lewatit MP-500
109
and 600), over 90 per cent of the organic matter is removed from
most waters, and released on regeneration of the resin. If the
corresponding weakly basic resins are employed (Amberlite IRA-93,
De-Acidite H/IP or Lewatit MP-60), the removal oforganic matter
is usually slightly less complete at 75-80 per cent. Nevertheless, the
degree of protection given to the foHowing mixed bed is almost
equally as good as that given by strong base resins, since both types
selectively absorb the most strongly held fractions of the organic
matter, which have the greatest poisoning potential. Both strong
and weak base resins carry out their full normal demineralizing
function in addition to removing organic matter, so that the mixed
beds are protected with no extra capital or running cost.
(b) Trap Columns

For small installations, in which the total demineralizing duty
can be performed by a single small mixed-bed unit, the capital
cost is increased by splitting the load between three columns. In
these cases, the mixed bed can be protected by a single column
of strong-base resin in the chloride form. Either macroporous or
isoporous resins can be used for this duty, the best results being
given by exceptionally macroporous materials having very high
affinities for organic matter, the correspondingly low capacity for
inorganic ions having in this case no importance.
Examples of res ins designed primarily for trap columns are
Amberlite IRA-904 and De-Acidite K(MP). The resins are re-
generated with brine, normally made slightly alkaline with caustic
soda to ensure that the organic matter is fuHy ionized, and therefore
in its most mobile condition. Organic removal by traps is lower than
by deionizing columns, being normally 60-70 per cent, but, as in
the case of weak base columns, the action is selective towards the
most obnoxious ions, and the mixed bed protection is far greater
than would be calculated arithmetically from the degree ofremoval.
PREVENTION OF POISONING, SUMMARY

The problem of organic poisoning has been considerably reduced
with the production of substantially non-fouling resins. While it
cannot be claimed that any one combination of processes will give
complete freedom from difficulty under all circumstances, attention
to certain basic principles can now be expected to re du ce the prob-
lem to manageable levels. The key points are as folIows:
(a) Where colloidal or insoluble matter is suspected to be present,
it must be removed prior to the demineralizing process to prevent
110
PREVENTION
coating of the outside of resin beads, or blocking of channels in

macroporous materials. When the organic content of the water is
higher than 2-3 p. p.m. as carbon dioxide, measured by the 4 h
permanganate test, there is a high probability that part of the
organic matter is colloidal. Under these circumstance coagulation
is essential.
(h) Subject to the above, the use of modem non-fouling resins
of the isoporous or macroporous type in two-bed systems normally
gives no difficulty.
(e) Mixed-bed systems are inherently subject to poisoning, by the
extra mechanism discussed above and are more sensitive to it,
owing to the low conductivities involved. It is therefore essential
to protect the anion resin in the mixed bed, by removing ionizable
organic matter from the water before it reaches the unit. This can
be achieved either by a prior two-bed demineralizing system using
organic-reversible resins, or by means of an organic trap column.
(d) In attempting to estimate the poisoning power of a water,
note must be taken of the season of sampling. Sampies taken in
summer and early autumn are likely to present falsely optimistic
results.
(e) The poisoning power, which as a first approximation may be
considered directly proportional to the O.A. is also inversely
proportional to the total dissolved solids. The second relationship
sterns from the fact that the total quantity of water treated per
cyde is itself inversely proportional to the T.D.S. Thus at constant
organic content, if the T.D.S. is halved, the total weight of organic
matter taken up by the resin between regenerations is doubled, and
the probability of its becoming fixed in the structure is correspond-
ingly increased.
While no very precise figures can be quoted, the generalizations
in Table 7 may be taken as a reasonable guide.
In practice, waters in any of the groups tabulated may
give results characteristic of the category immediately above or
below, and the final decision on method can be made only as a
result of a pilot test, or of previous experience with the same water
supply. Unfortunately, the former is a laborious procedure, since
several hundred operating cydes are required to establish reliable
indications of the poisoning conditions. In the absence of previous
experience, it is therefore a sound general rule to treat all waters as
being in the category inferior to the one recorded in Table 7. In
particular for thin waters, the absolute value for O.A. given in
paragraph Ca), should be considered to override the ratio effect.
111
Table 7
OA/TDS* Satisfactory UnsatisftUtory

< 0·002 All systems, including None
unprotected mixed beds
with c1assical D.V.B. resins
2 0·002-0·015 Two-bed systems with all 'Unprotected mixed
resins. Mixed beds with beds with c1assical
non-fouling resins. D.V.B. resins
Protected mixed beds
3 0·005-0,015 Two-bed systems with Two-bed systems

non-fouling resins. wi th c1assical
Protected mixed beds, D.V.B. resins.
containing non-fouling All unprotected
resins mixed beds
4 0·015-0·03 Possibly as above, but As above

becoming unreliable
5 > 0·03 None All systems

unreliable.
Pre-coagulation
needed
• The figures refer to the 4 h 27°C test. If the Kubel or 30 min 100°C tests are used, the figures
should be multiplied by 3·0 and 1·5 respectively.
(f)Finally, in all cases where significant concentrations of

organic matter are present, i.e., Gases 2-5 of Table 6, regular
cleaning of the resin bed with alkaline brine is advisable as a
routing maintenance procedure, whether or not the operating
results appear to require it. In Gases 2 and 3, the interval between
treatments can be about 3 months, but in the borderline Gase 4,
a greater frequency, of up to once per month is preferable. In
Gase 5, the OAjTDS ratio after coagulation will be reduced, and
the pre-treated water can be reclassified in one of the first four
categories, the resin cleaning interval being selected accordingly.
While in many cases, the application of rules (a)-(e) may make
the cleaning procedure unnecessary, it is such a simple and inex-
pensive precaution that there is no object in omitting it.
112
CHAPTER7
EQUIPMENT AND SPECIAL PROCESSES
STANDARD RES IN COLUMNS

Laboratory equipment for ion exchange experiments is essentially
simple, consisting of glass tubes, with sintered dises, or plugs of
Me Neil type ~----- Brine intel

manhole
Hard water
'-----1101 - inlel
r - - -+--Brine
distributor
;'~~~__ Ion-exehange
res in
Strainer type
co llecl ing
system
Fine si
Coarse
Conerete
Figure 45. Internat arrangement of ion-exchange unit
glass wool to support the resin. The ratio of height to diameter is

large, and problems of distributing the water to ensure even flow
113
do not arise. On rare occasions, such as special industrial separation

problems (Chapter 8), industrial plant represents a simple linear
enlargement of the laboratory equipment, but for water treatment
purposes, this type of design is impracticable, since the tall narrow
columns would give unacceptably high pumping costs. The majority
of large industrial units have bed depths of 4--6 ft, irrespective of
their diameter, and the diameterJheight ratio becomes increasingly
favourable as the overall size increases, frequently being as much
as 2: l. Typical units are shown in Figures 45 and 46.
Bottom Collecting Systems

Under these circumstances, considerable care is needed in the
design of the water collecting system below the resin bed, to ensure
that the flow through the column is even. Preferential flow in one
area would, of course, lead to premature exhaustion of the resin
in that region, with apparent loss of overall capacity. Provided that
bottom collection is uniform, the problem of introducing water
into the top of the unit is oflesser importance. If violent flow varia-
tions are avoided, the above-bed space A (Figure 45) is effectively
apressure chamber which must feed water uniformly into the bed,
if it is being abstracted evenly. It is normally sufficient to introduce
the water at a number of evenly spaced points, varying from one, in
a 3 ft diameter unit, to five, in units of 10ft diameter and above.
Bottom collection systems have evolved from long-standard
practice in the design of sand filters. Water softeners normally have
a system of perforated pipes, which may be radial from a central
boss, or lateral from a central header pipe. The pipes are buried in
about 15 in of graded flint, which is sufficiently fine to prevent
loss of resin, and gives adequately even collection (Figure 45). By
either method, it is essential to place the collecting pipes themselves
elose to the bottom of the unit, to avoid the presence of stagnant
pockets in which brine can collect during regeneration, to be
removed only slowly during the subsequent rinse. A badly designed
system may work perfectly as a softener, but nevertheless give
difficulties due to bleeding of residual salt into the treated water.
For demineralizing units, exactly the same bottom collecting
systems can be used, the preferred methods using flat bottom
plates, with header and lateral pipes, which give the best contro!
over hide-out ofresidual regenerant. Increasingly, however, systems
based on flint underbeds are being replaced by designs based on
strainer buttons, which are fixed to the underside of the distribu-
tion pipes, so as to be elose to the floor of the cylinder. The main
114
BOTTOM COLLECTING SYSTEMS
header, which carries the total flow, is normally a fairly massive

pipe, often of rectangular section, made of mild steel rubber
covered inside and out. Lateral pipes, which are smaller, may be
made in stainless steel, ebonite, or plastics, The floor itself is a
flat plate, welded to the shell, and supported by filling the space
Sta inless steel

wedge wire strainer
Caustic soda
distributor
Acid inlet
cau s tic
outlet
Treated wa Bottom
collecting
outlet
system
Figure 46. Mixed bed unit
between it and the bottom dish with concrete. The strainers,

moulded in high impact polystyrene, polypropylene, or poly-
phenylene oxide, are made, to various designs by different plant
manufacturers, but have in common aseries of fine slits, normallY
about 0·01 in wide, which retain the resin particles without becom-
ing blocked. A t ypical design, shown in section in Figure 47 uses
115
EQUIPMENT AND SPECIAL PRO CES SES
crenellated openings to ensure that any fragments which do enter

the gap are immediately swept through and lost. Strainer systems
based on wire mesh are rarely successful, since square openings are
readily blocked by spherical particles. Sintered metal or ceramic
tubes, while giving excellent results when new, become clogged
by traces of suspended matter in the water, or the regenerant
solution, and thus gradually build up excessive pressure drops.
Perforated pipes covered with closely-woven Tygan or other plastic
cloth have also been used, and give satisfactory service provided
that adequate precautions are taken to avoid tearing or bursting
under pressure.
Stots O·01in
(O ·25mm)
Figure 47. Typical strainer (actual size)
The bottom collecting systems for mixed-bed units need par-

ticularly careful design, since they perform four separate functions,
service, backwash, regeneration and air mix. During normal
service, water passes at high flow rate, and sufficient total slot area
must be provided to permit this flow without excessive head loss.
The backwash stage serves the dual purpose of cleaning the bed,
as in other ion exchange units, and of separating the resins prior
to regeneration.
Separation of the majority of the resin mass is easily achieved,
with almost any type of bottom pipe system, but unless great care
116
BOTTOM COLLECTING SYSTEMS
is used in design, pockets of undisturbed resin may be left between

the buttons. Any anion exchange resin remaining at the bottom of
the unit during regeneration of the cation exchange material with
sulphuric acid becomes converted to the bisulphate form. If it is
again left undisturbed by the subsequent air mix, hydrolysis of the
bisulphate ion during subsequent service will cause bleeding of
sulphuric acid into the treated water, giving symptoms of long
rinse and poor quality which are indistinguishable from resin
poisoning, aIthough the phenomenon is in fact completely un-
connected with the fouling problem. To prevent this fauIt, the
bottom collecting system must be designed to produce during the
backwash stage powerful horizontal jets which sweep the whole
of the bottom plate. As the total backwash flow which can be used
is limited to about 2·5 gal ft- 2 min -1, while service flows may be up
to 40 gal ft- 2 min -1, it is difficult to design a slot system sufficiently
fine to give the required jet action during backwash, without
seriously restricting the service flow or increasing the pumping
pressure required. For this reason, it is increasingly common, in
cases where exceptionally high water quality is required, to use
separate absorber and regeneration units, each one designed for
its own flow requirements. The resin bed is transformed from one
unit to the other by a simple hydraulic system. For larger treatment
plants, the external regeneration system has the extra advantage
of capital economy, since one regenerator can serve several absorber
units, each of which is greatly simplified by the absence of its own
regeneration pipework.
Provided that the bottom slot system gives good bed separation,
it will normally also be capable of giving adequate remixing by
air, since the requirements of the two processes are similar. Its
effectiveness for this purpose can, however, be seriously reduced if
the bottom plate of the shell is not absolutely horizontal. A differ-
ence in height of only 0·1 in can cause maldistribution of air, which
rises preferentially from the higher buttons.
The use of a complex pipe network at the bottom of the cylinder
has obvious disadvantages, aIthough it is perfectly satisfactory when
correctly designed, and is probably the most widely used form of
bottom system. Simple laboratory apparatus uses a porous bottom
plate as the water transfer unit, and various methods of adapting
the technique to industrial scale equipment are in use. For small
units up to 3 ft in diameter, the res in supporting plate can be of
stainless steel with perforations in which strainer buttons or other
devices are fixed. The purified water then passes through the plate
117
into the compartment formed between it and the bottom dish of

the unit. This technique becomes more difficult as the shell diameter
increases. For obvious reasons, the lower compartment can no
longer be filled with concrete, to support the plate. At 30 Ibjin 2
pumping pressure, there is a total load of 100 tons on an 8 ft dia-
meter plate, which must be made very massive to withstand the
load without distortion. The bottom plate cannot be made of
stainless steel, unless the shell is cut and flanged to receive it, which
is an expensive and inelegant technique. A thick, mild steel plate
can be welded in place during the fabrication of the shell, but the
problem then arises that the whole of the shell, ineluding the lower
face of the support plate, must be rubber covered to prevent
corrosion. The lower compartment must then be large enough for a
man to get inside to carry out the rubber lining work, and the
necessary manhole must be provided. The work is carried out
under adverse conditions, and it is difficult to ensure a perfect
covering. Nevertheless, both these systems are in use.
Centre Collecting Systems

The central pipe system of a mixed bed unit, which serves separ-
ately to collect the spent regenerant from the anion resin layer, and
distribute the acid to the cation exchange material, is similar in
design to the bottom unit. Because it is in the middle of the resin
bed, there are a number of conflicting design requirements which
cannot be fully resolved, so that all industrial systems contain a
degree of compromise. To give perfect regenerant distribution, the
pipes should be elose together, but this would impede the water flow,
and render bed separation and remixing almost impossible. Gaps
of 4-6 in are therefore used. To support the various stresses imposed
by down-flow and backwash conditions, the whole unit must be
strongly made, but if the design is too massive, it will again impede
the flows, and increase the stresses which it is aimed to overcome.
There are many successful mechanical solutions to this problem, but
all of them interfere to some extent with the ideal flow patterns.
Consequently, it is normally found that a given pair ofresins operate
at slightly lower overall capacity in a mixed bed unit, than in a pair
of single units. This price has to be paid for the very high treated
water quality, which can be obtained only by the mixed bed process.
Regenerant Inlet Systems

The remarks made above about water inlets apply equally to the
regenerant inlet in a single bed unit, or the upper reagent inlet of a
118
MATERIALS OF CONSTRUCTION
mixed bed. As the solution is entering a closed water chamber, quite

simple means of entry are adequate, provided that collection at the
bottom of the bed is uniform. The regenerant can, in fact, be
brought into the unit through the top water inlet, and this system
is used by some plant manufacturers. It suffers from the disadvant-
age that the incoming solution is initially diluted by the water
present in the top space, while at the end of regenerant input, it
fills this space. Rinsing therefore tends to take place by a process of
continual dilution, and is correspondingly prolonged. It is preferable
to bring in the regenerant solution through distribution points
placed a few inches above the resin bed, and designed to avoid
vertical flow patterns. Under these conditions, a relatively still pool
forms just above the resin, with litde mixing or diffusion into the
water above. At the end of regeneration, the rinse water is brought
in at the top of the dome, displacing the remaining regenerant
piston-wise into and through the resin bed.
Materials of Construction
The materials used for fabrication of ion exchange units vary
according to the size and duty of the unit. Water softeners have only
mild corrosion conditions to resist, and are normallY manufactured
from bitumen enamelled steel, for large units, or galvanized steel, for
units up to 18 in in diameter. The latter method is increasingly
being superseded by resin-bonded fibreglass construction, but this
method is at present uneconomic for large cylinders.
For demineralizing units, which must resist acid corrosion, rubber
covered mild steel is virtually standard procedure, except for the
smallest sizes, where plastic or stainless steel construction may prove
economic. Coverings other than rubber, which are sometimes
employed, include butyl rubber, neoprene or polypropylene, but
they represent only a minority of cases.
For small units, both internal and external pipework, up to
diameters of about 2 in, are commonly assembled from standard
plastic pipes, P.V.C. and high impact polystyrene both being
suitable. FUll ranges of elbows, tees and other fittings are available
as standard from specialist manufacturers. Although polyethylene
and polypropylene have advantages, they cannot readily be
cemented, and are thus subject to leaking at joints. Plastic pipes
are available in much larger sizes, but are rarely used in diameters
over 2 in. Rubber-lined mild steel pipes are more economical in
large sizes, and are not only self-supporting, but can be used as
structural supports for valves, controllers, and other equipment,
119
whereas large plastic pipes are comparatively fragile, and need a

considerable degree of external support.
Large internal pipes may be rubber covered internally and
externally, or p.v.e. coated by dipping. Smaller internal pipes are
ebonite or p.v.e. extrusions, for plants operating at ambient
temperature. In the case ofunits operating at elevated temperatures,
up to the limit of 60-70 oe imposed by the stability of the anion
exchange resins, the smaller internal pipework is normally made of
stainless steel, since most readily extrudable polymers are subject to
slow plastic flow, and may show considerable distortion over a few
years' use. Polypropylene, which would be suitable for this duty,
has been found difficult to extrude with sufficient accuracy, but
polyphenylene oxide, which has high temperature resistance,
appears to be a promising alternative to stainless steel. Strainer
buttons present no problem, since very accurate injection mouldings
can be made in polypropylene or P.P.O., both of which resist all
conditions which are imposed on them in water treatment practice.
Although many types of valves would in principle be suitable for
use with ion exchange equipment, diaphragm valves are almost
universally preferred. The valve bodies can be rubber, plastic or
glass lined, the diaphragm normally being of rubber, occasionally
with fluorinated hydrocarbon facing, for special applications.
eOUNTERFLOW UNITS
In Chapter 4, mention was made of the problems of sodium slip at
economic regeneration levels. The extent of the slip can be reduced
in two ways. The first is to mix the entire bed, at the end of re-
generation, with an upflow of air. As the emergent water quality is
controlled by the lowest layers of res in, removing the metal-Ioaded
resin from this position, and spreading it through the bed, gives a
considerable general improvement. In Figure 48 the topmost curve
is identical with Curve B of Figure 26 (page 63). The centre curve
illustrates the effect of air mixing. An even greater effect is obtained
by carrying out the regeneration process in the counterflow direc-
tion, so that the bottom ofthe bed be comes converted predominantly
to the hydrogen form. The subsequent service cyde is shown dia-
grammatically in Figure 49. The residual sodium is then left
mainly in the upper half of the bed, any remaining at the bottom
being rapidly displaced by downflowing hydrogen ions, so that the
treated water quality is uniformly good throughout almost the
entire service cyde, as shown in the lowest curve of Figure 48. The
improvement in treated water quality makes it possible to use
120
COUNTERFLOW UNITS
lower levels of regeneration than in co-flow practice. Greater
efficiency of chemical consumption, and lower running costs,
result.
UI 80
t!l
~ 70
...ra
~ 60
<:
~ 50
'ra"
CI
40 '\
<:
'"
u
30
\
J
~
Q.
~-.current
UI
ra 20 \
~'"
CI
~ 10
t!l
40
~....J
'-....
Air m i xed
'"
cJunte~current
.........
Ij
o 20 40 60 80 100
Perclmtage of opera t ing
cycle
Figure 48. Effect of air mixing and counterflow regeneration
100 0 100 0 100 0 100
Effluent 10% <1% <1% <1% 10"J.

water (a) (b) (c) (d) (e)
'leakage'
Figure 49. Leakage during coullte~flowoperation (a) Start (b) 25% tif cycle (c) 50 % of
cycle (d) 75% of cycle (e) end
Four main methods of achieving counterflow operation are m

industrial use. These are (1) Packed beds (2) Perforated plate
process (3) 'Pressbed' process and (4) Buried top collector process.
121
I
(1) Packed Beds

The principal difficulty associated with counterflow regeneration
in columns that contain the conventional rising space above the bed
of resin, is that if either the regenerant or the water to be treated
is passed through the bed in an upward direction, there is a tendency
for the bed to expand, with resultant short circuiting. This difficulty
can be avoided by filling the column completely with resin, so that
there is no expansion space. This system has been successfully
applied to small diameter units up to 24 in (60 cm), which present
Treated water out Acid in
Regen er ation
Figure 50. Peiforated plate .rystern
only minor problems of collection and distribution at the top and

bottom of the columns, and which can be comparatively easily
serviced in the event of any accumulation inside the column, of
suspended matter derived from the raw water. Many thousands of
packed bed counterflow units are now in service in Great Britain. This
system is not however, suitable for large diameter industrial units.
(2) Perforated Plate System

This is a German system, which is illustrated in Figure 50. A
coarsely perforated pla te is inserted in the column approximately
122
COUNTERFLOW UNITS
one-third of the way up from the bottom, and there is a rising space
above the bed, corresponding to rather less than the space below
the perforated plate. Regeneration is carried out downwards, in the
conventional manner. The flow to service is upwards, the principle
of operation being that the flow is started at a velocity high enough
to ensure that the space above the perforated plate is completely
filled with resin, and is thus in effect, a 'packed bed'. Because of the
local high velocity through the perforation in the lower plate, the
Acid out
Raw water in
Polythene chips -
Free space
Filling line
/ tor bag
Resin ""'-"7"1- - - -
Pressbed
system
Treated water out Acid in

Figure 51. Pressbed system
flow can thereafter be significantly reduced, without any tendency

for the resin to fall back through the holes, and for the bed to
become 'unpacked'. This system gives adequate distribution and
collection ofthe water, but does not permit backwashing in the unit.
I t is necessary to have an extra external vessel, in which backwashing
for the removal of suspended matter can be carried out.
(3) The 'Pressbed' System *

This is illustrated in Figure 51. The vessel contains a vertically
mounted rubber bag, which can be inflated by filling it with water
• Brit. Patent 1,013,069 International Analyser Co. 1967.
123
from an external source. Above the resin there is a layer of polythene

chips, the grading of which is rather coarser than that of the resin
itself. This layer acts as a barrier to the penetration ofresin, and the
top collecting system has holes or slots of such a size that whilst it
retains the chips, small particles of suspended matter very easily
pass in either direction. In this plant regeneration is carried out
upwards. During gentle backwashing of the column, which has the
effect of expanding the bed, the rubber bag is inflated from the
external source of water. Since the volume of the inflated bag
Raw water in
Downflow water
Acid out ---i~4S~!+d
Ac id in
Treated water out
Treatment Regenerat ion
Figure 52. Buried eollee/or system
precisely corresponds to the original free space, the unit is now in

effect a 'packed' column, and regeneration can be carried out
upwards without any danger of short-circuiting of the regenerant.
(4) The Buried 'Top Collector' System (Figure 52) *

In this system a header and lateral system equipped with strainer
buttons is placed just below the top surface of the bed of resin. In
other respects, the unit is conventional, with the usual rising space
and top outlet, to permit of normal backwashing.
• Brit. Patent 806,107 Illinois Water Treatment Co. 1955.
124
CONTINUOUS ION EXCHANGE
During the upward injection of the regenerant, a downward ftow

of water is maintained from the top of the column, the downftow
water and the upward ftowing .. acid passing out together from the
top collecting system. In this way any significant expansion of the
resin bed is prevented. At the end of the acid injection, abrief
upwards rinse is given, to displace the majority of the spent regen-
erant, after which the main rinse is downftow.
CONTINUOUS ION EXCHANGE

In most chemical engineering processes, there are advantages to be
gained from continuous operation, for large scale purposes, even if
laboratory or small scale production work is most conveniently
carried out batch-wise.
The separation of organic liquids such as petroleum fractions for
example, would commonly be performed in the laboratory by
distillation through a fractionating column from a ftask large enough
to take the whole batch. A direct upscaling of this process to the
scale ofthousands oftons would lead to ridiculously large equipment.
Accordingly, on the industrial scale, the ftask is effectively elimin-
ated, and the pre-heated liquor fed directly into the fractionating
column, from various points of which the fractions are continuously
removed.
The ion exchange treatment of water, by standard fixed-bed
practice, is neither a batch process, nor a fully continuous operation.
It is continuous, in that a large volume ofwater is treated by passage
through a relatively much smaller piece of equipment for periods of
hours or days, but there is always an element of discontinuity,
due to the necessity for stopping the ftow, to regenerate the
reSIns.
In large scale practice, this criticism is somewhat academic, since
it is standard procedure to use two or more sets of columns in
parallel, calculated so that while any one line is being regenerated,
the full ftow required can be taken by the remaining lines. There is
thus an uninterrupted ftow of treated water. Nevertheless, the
principle of a truly continuous ion exchange plant, which in one
unit provides an unbroken ftow of treated water, while consuming
much smaller continuous ftows of regenerant or rinse, has always
been an attractive one to chemical engineers. Very many systems
have been disclosed in the patent literature, but none is yet suffic-
iently attractive to replace the standard techniques generally, and
only three, which will be described below, appear to have achieved
large scale industrial use.
125
ADVANTAGES OF CONfINUOUS ION EXCHANGE

Three main advantages have been claimed for continuous ion
exchange equipment for water treatment, as compared with fixed
bed procedures.
(a) More eJlicient usage of resin during absorption

This claim is valid, in principle, since in a fixed bed plant, there
is, at any one time, a considerable proportion of the resin which is
serving no purpose. During operation, the column contains three
zones. The uppermost consists of exhausted resin, which has ceased
to do useful work, and the lowest comprises regenerated resin,
which has no work to do, since the water reaching it is already fully
treated. The useful work is carried out in the central exchange
zone, which travels slowly down the bed (Figure 53(a)). In an ideal
continuous plant, the absorber section is sized to contain the
exchange zone only, and thus contains much less resin than in the
corresponding fixed bed plant. New res in is fed into the unit at a
rate which exactly balances the downwards movement of the
exchange zone, and thus maintains it stationary (Figure 53(b)). This
ideal is easily achieved, under laboratory conditions, with solutions
of fixed composition, and many devices have been used successfully
by research workers to give continuous counterflow operation of
this type.
Under industrial conditions, the problem is more difficult. It is
very rare for a water softener or demineralizer to operate at a fixed
flow rate. Flow conditions are dictated by the requirement for
treated water, and normally vary over a wide range. Moreover, raw
water composition is rarely constant, although variations are less
violent than those of water flow. An increase either of flow rate, or
of dissolved solids, causes a widening of the exchange band, and a
greater rate oftravel down a fixed bed column. Thelattereffect, in a
continuous plant, is balanced by an increase in the res in throughput
rate, which must therefore be caused to change automatically in
response to a suitable series of signals from control devices in the
system. Variations in the exchange zone width, however, can be
accommodated only by making the continuous absorber big
enough to contain the widest band which is possible. In practice, it
must be made somewhat larger still, to allow for small changes in
the exchange band position, due to imperfect response to the control
signals. Overall, the continuous absorber must be made somewhat
larger than the ideal size calculated for the average ftow rate and
mineral content of the water, and it does therefore contain an
126
ADVANTAGES OF CONTlNUOUS ION EXCHANGE
unused uppermost and a lowest zone, although these are much

smaller than in a corresponding fixed bed plant (Figure 53(c)).
Raw water
Exhausted Raw Exhausted
resin water resin
Exhausted Raw
resin water
Exchange
zone
Unused
resin Treated
water
Regenerated Treated Regenerated
resin water resin
(0) Treated (b) (cl

water
Regenerator
.-------Rinse
1111 " I Regenerant
Resin movement
(d)
Figure 53. Development qf continuous ion exchanger (a) Fixed bed unit (b) Ideal continuous
absorber (c) Practical continuous absorber (d) Practical complete unit
(b) Reduction in Total Resin Quantiry

The amount of resin in the absorber of a continuous plant must,
from the above considerations, always be less than in a fixed bed
plant carrying out the same duty. However, whereas in a fixed unit,
the process of backwash and regeneration is carried out in the same
127
column, continuous operation requires these steps to be carried out

separately. All the industrially practicable types of continuous
equipment therefore include at least two extra units, (Figure 53(d))
and some contain a fourth, in which rinsing is carried out after
regeneration. The extra units may normally be made somewhat
smaller than the absorber, but the complete continuous equipment
nevertheless, contains two to three times the quantity of resin
needed for the absorber alone. It follows that, while the total resin
requirements are less than in the corresponding fixed bed unit, the
difference is noticeably smaller than would have appeared from the
initial comparisons of Figure 53(a) and (h). It is not, of course,
legitimate to compare a continuous ion exchange plant, which is
necessarily automatically controlled, with a manually-operated
fixed bed plant which has been deliberately designed oversized, to
reduce the frequency of regeneration and the corresponding labour
costs. An automatically controlled fixed bed plant can be calculated
to give a service run of 5 h. If the quantity of resin in such a unit is
Q" then a continuous ftow of treated water is produced by two such
units in parallel, with a total resin quantity of 2Q" or by three half-
sized units (two absorbing and one on regeneration or standby, at
any one time) with a resin quantity of l·SQ,. It is extremely difficult
to design a continuous absorber unit to give a resin residence time of
under 1 h, corresponding with a resin quantity O·2Q" and an
approximately equal quantity in the backwash, regeneration and
rinse sections, giving a total of O·4Q,. In practice the figure is likely
to be somewhat higher.
Finally, there remain the questions of reliability, and provision
for routine maintenance shutdowns. In a system of three fixed bed
lines in parallel, there are always times in which one line is on
standby, after completion of regeneration and rinse. Routine
maintenance of pumps, valves etc., can be carried out during these
periods. Moreover, in the event of a breakdown in any one line, a
reduced service ftow can be maintained with the remainder, until
the fault has been rectified. In a single fully continuous plant, whose
three units are in series, maintenance of any one requires shut-down
of all three, while a breakdown involves a complete cessation of
water ftow until repairs are complete. Either of these conditions
would be unacceptable for duties such as feed-water treatment for
power production boilers, and a complete standby unit would be
needed to provide security ofwater supply. The total res in quantity
thus becomes O'8Q" contained in six units, as against 1'SQ" contained
in three parallel fixed bed units or 2Q" in two parallel units. The
128
SPECIAL PROBLEMS OF CONTINUOUS ION EXCHANGE
cost of the resin in a continuous plant is therefore less than in a

fixed bed installation, but the extra complexity ofthe equipment may
weIl offset this difference.
(c) Increased Regeneration Efficiency

All existing types of continuous ion exchange equipment opera te
on a countercurrent principle, and they therefore have the advant-
ages discussed for counterflow fixed bed units. Accordingly, con-
tinuous plants give higher water quality, and improved regenerant
consumption, as compared with fixed bed plants; but this result is
not connected with the principle of continuity itself. As the principle
of counterflow operation of fixed bed plants is now becoming
widespread, even on the largest seale, it is no longer legitimate to
claim increased chemical efficiency as a special feature of the
continuous processes.
SPECIAL PROBLEMS OF CONTINUOUS ION EXCHANGE
(a) Resin Distribution

All ion exchange systems depend fundamentallyon uniform flow
of water through the columns, to ensure that the exchange zone
remains completely horizontal, and as compact as the kinetics of
the exchange process permit. Any tilting or broadening of the zone
during absorption, beeause of uneven water flow, lead to early
breakthrough, in a fixed bed plant, or poor water quality, in a
continuous system. The corresponding faults during regeneration
lead to wastage of regenerant in both cases. It has already been
shown that uniform water velocity is fairly easy to achieve in a well
designed unit of large diameter, and no major difficulties should be
found in either type of equipment.
In a continuous plant, not only the water, but also the resin, must
flow at a uniform rate in an parts of the unit. Achievement of
laminar res in flow presents no problems in a tan narrow laboratory
column, but becomes a difficult matter in a large diameter industrial
plant. For obvious resons, the resin cannot be uniformly abstracted
over the whole area of the unit, as is water in a conventional plant,
by means of a network of pipes and small orifices. I t must be intro-
duced and removed at a comparatively small number of points,
and in practice, one point only is commonly used for each purpose.
The effect of this in the schematic system of Figure 53( c), would be
to cause major disturbance ofthe exchange zone stage (Figure 54(a»).
This distortion can effectively cause parts of the exchange zone to
129
reach the bottom of the unit, thus giving a deterioration of treated

water quality. Many hundreds of patents exist, covering methods
of overcoming this problem, the majority depending broadly on the
principle shown in Figure 54( b). Flows are reversed, so that water
flow is upward, and resin downward. At intervals, the water flow
is briefly interrupted, and a small slug of resin is allowed to flow
from the unit by gravity. Either simultaneously, or more often
alternately, fresh resin is allowed to flow into the space which has
thus been formed in the top of the unit, and as it is effectively
fluidized during its fall, it spreads out fairly evenly. The overall
resin flow is thus reasonably laminar. This type of procedure does,
Regenerated
resin
Exhausted
resin
Treated
water
Regenerated
resin
Exhausted
resin
(a) ·(b)
Figure 54. Distortion 01 exchange zone (a) Distortion (b) Principle of correction
of course, imply that the whole process is no longer fully continuous,

but the interruptions are normally so brief, and the resin slugs so
small in relation to the total volume, that the distinction is largely
academic.
(b) Process Control

In an automatie fixed bed plant, whether co-flow or counterflow,
process control is effectively perfeet, in the absence of instrument
130
SPECIAL PROBLEMS OF CONTINOUS ION EXCHANGE
failure. Treated water quality is uniform until the point of break-

through which is detected by a hardness or conductivity monitor, in
the respective cases of softening or demineralization. Feedback of
this information from the detection system to the control unit causes
immediate shutdown, and start up of another operating line. Extra
security can be obtained, ifrequired, by placing the detector system,
not in the treated water outlet, but in a pipe connected to a probe
point just above the bottom of the bed, in order to anticipate the
true breakthrough point.
In the case of a continuous system, irrespective of its design, the
problem is more complex. If a water of constant analysis is entering
the system at a uniform rate, and if the capacity of resin is known,
it is a simple arithmetical calculation to determine the rate of resin
feed into the system required to balance the input of ions, and keep
the exchange zone stationary. The actual measurement of the resin
input rate may be more difficult, since the resin stream is neither
liquid nor solid, but a suspension. Nevertheless, this problem can be
overcome. The real difficulty arises from the variability of feed-
water composition and ftow rate. In a fixed bed plant, an increase
in either of these factors merely reduces the time of the cyde, and
information feedback to the control system remains simple. In a
continuous plant, the same increase results in the exchange zone
starting to move slowly downwards as shown in Figure 54(a), or
upwards as in Figure 54(b). This effect must be matched by the
correct increase in resin ftow through the system, with the corres-
ponding changes in regenerant and rinse ftows in the other units.
For constant results under variable conditions, there must, there-
fore, be a detection system giving continuously varying feedback to a
control device capable of interpreting the information and initiating
the necessary actions. Such a system presents no difficulty in
principle, but it is essentiaHy more complex than that required to
give the same results with fixed bed operation.
(c) Resin Breakdown

Modern polystyrene bead resins are extremely sturdy, and in a
weH designed continuous plant, breakdown of resin should not be
sufficient to constitute a serious addition to the operating costs. The
continuous plant does, however, indude a number of water and
regenerant inlet and exit points in the various units, and it is
essential to ensure that they do not become blocked by the detectors,
a stoppage which can arise from even the most minor proportion of
resin breakdown. Strainer systems at these points must therefore
131
be extremely efficient, and the continuous unit must incIude a

device for the separation and rejection of resin fragments.
(d) Complexity
The principle of continuous ion exchange is completely simple.
In practice, plants as at present designed are somewhat complex.
A minimum of three separate vessels is required to replace a single
vessel of the fixed bed system. Each of these units requires a resin
feed system, and the whole installation is govemed by automatie
controls, which operate at very frequent intervals. Whereas in an
automatie fixed bed plant, a particular ftow valve, and the electric
relay controlling it, may open and shut only once every 5 h, the
corresponding valve and relay in a continuous unit may operate
twenty times every houf. Wear is correspondingly greater, and
maintenance costs may therefore be increased. As water treatment
plants in most industries are purely ancillary items, they are normally
required to run with the absolute minimum of attention. According-
ly, the main effort of continuous equipment designers is directed
towards simplification.
TYPES OF CONTlNUOUS PLANT

Of the hundreds of suggestions which have appeared in the patent
literature for continuous ion exchange devices, only three are known
to the author to have achieved industrial scale working. Even in
these cases, the number ofplants at present in operation is compara-
tively smalI. Continuous ion exchange as an industrial process, is
still in its infancy.
The first case, the Higgins contactor, was developed in the U.S.A,
largely for special separations in the nuclear industry. It is, in
principle, perfectly adaptable for water treatment, and some units
are now in use for this purpose. The second, the Porter-Arden
moving bed process, was developed exclusively for uranium re-
covery, and was first operated in 1957. It has been taken to a larger
scale than either of the other two, but is less fully continuous than
them, and would not be suitable for water treatment without
considerable simplification. This equipment is described in Chapter
8, in connection with uranium. The most recent process is
the Asahi unit, which has been used both for water treatment
and for special chemical purposes, and gives as near an
approach to truly continuous working as has yet been achieved
industrially.
132
Water
Feed , _i: ;::~::;:.1 I ' :~;;:;:;:;:;~,::l

._. • • Feed
I:::::"::;;;::~ .,. o-j
::z::
~
Waste 4 F\i.t} ':] I I W!:f~:d I I w~~ . ~ _ li;t'Ht l In ::z::

.....
0
0
.....
.- zrJl
~ t
~ ~ ::: Cl
w•• " 0
Z
o-j
Eluant
I
.'.'.'. ';:,,: ;~:: I :~:':. I l~
;..-
Cl
o-j
0
~
(0) (b) (c)
Figure 55. Principle 01 the Higgins Contactor (a) Solution pumping period (several minutes) (b) Resin movement period (3-5 s)
(c) Solution pumping period (several minutes )
The Higgins Contactor*

The earliest published version of this unit is shown in Figure 55.
The solution to be treated passes downflow through the upper
left-hand unit, followed by water, if the solution itself is not water.
The stripping solution (the eluant or regenerant) passes down the
lower unit, followed by water, (Figure 55(a)). At intervals, liquid
Backwash
outlet
y =------Jf'-- Backwash
Rinse inlet
inlet
& +--J'f'-- Hyd r au l ic

pulse
Regenerant
inlet - - - - K > ':<r.:<:K> I
{~O'-Q-<r<r<~~~ Treated water

outlet
0i-:(H}-:6-:<~+-.rr-... Raw water

intet
Spent
regenerant
outlet
Resin movement - clockwise
All liquid floWs -counter-clockwise
Figure 56. Operating version of Higgins contactor

(By conrtesy ofChemieal Separations Corporations)
flows are stopped, two resin transfer plug valves are opened, and a
double-acting piston withdraws to suck spent resin upwards from
the absorber, and force a different slug of spent resin into the
regenerator (Figure 55(b)). Finally the flows are recommenced,
resin transfer valves revert to their original setting, and the spent
* I. R. Higgins ORNL-1907 U.S.A.E.C. 1955.

134
THE HlGGINS CONTACTOR
resin which has been drawn into the upper right leg is aUowed to
tnckle down to the standby position, ready for the next piston action
(Figure 55(c)). In this form, the device is simple and ingenious,its
only obvious fault being in the resin transfer valves, which, frequently
turning in a packed resin column, are likely to be sources of attri-
tion. Upscaling of the original unit led to a considerable increase in
complication, later versions consisting of four units effectively con-
nected in closed circuit (Figure 56).
The Asahi Process
Spent
regenerant
Treated Wash
water out
Raw
water-
Resin
Regenerant
Figure 57. Principle qf the Asahi process
This unit, developed in Japan by Asahi Chemicallndustry Co Ltd., *

consists essentiaUy of three vessels,:each with its own feed chamber
(Figure 57). The comparatively squat absorber unit is foUowed by a
taU narrow regenerator, and a wash column. Although there are
differences in detail between them, the units all operate on the same
broad principle (Figure 58). During absorption, water passes through
A into a lower cone, and through aperforated baffie into the
operating cylinder, in which a high linear velocity retains the bed
*Brit. Patent 987,021, 1960.

135
againstan upper gauze cone, through which thewater passes, leaving

the unit at B. At the same time, the water pressure in the lower cone
forces resin' in it through C, into the feed hopper of the next unit.
This hopper is covered with agauze, so that water can pass freely
out, leaving the hopper full of resin. The transfer then stops.
During this stage, the feed hoppers of both units concerned in the
transfer are closed at the bottom by a floating ball D.
Resin to
succeedrng un it
(0) (b)
Figure 58. Asahi resin tranifer system (a) Service flow, and resin tranifer to feed-hoppers of
next unit (b) Resinfeedfrom hoppers into unit (serviceflow stopped)
At intervals controlled by times, magnet valves elose A, and open

the water dis charge line E, which is covered by agauze. All water
press ure in the unit is thus lost, and the bed drops, to refill the
lower cone. At the same time, the floating ball D falls, and resin
flows into the treatment vessel from the feed hopper. After a short
interval, the valves revert to their original position. A prime ad-
vantage of this scheme lies in the fact that, apart from the ball D,
which has a mild action, there are no valves opening and elosing in
pipes packed with resin. Attrition is thus kept to aminimum.
136
CONDENSATE POLISHING FOR HIGH PRESSURE BOILERS
CONDENSATE POLISHING FOR HIGH PRESSURE

BOILERS
The majority of the water which feeds boilers used for power pro-
duction consists of condensate, produced from the exhaust steam
leaving the turbines. Until about 1960, this water was regarded as
heing sufficiently pure to be re-used directly in the boilers, ion-
exchange treatment being confined to the make-up water. This
principle is no longer generally acceptable. Modern high press ure
boilers and turbines require a standard of water quality which the
returned condensate may not meet. Corrosion in the condenser
system normally gives rise to the presence ofsome iron and copper in
the condensate, the amount of which will depend largely on the
operating conditions of the turbine. If it is operating continuously,
as in the case of a base load generating station, the total of iron and
copper is normally under 0·1 p. p.m, whereas during the daily
start-up of a two-shift station, values in excess of 0·5 p.p.m. can be
obtained during the first 30 min after each start-up. In either case,
even very slight condenser leakage can result in an ingress of
mineral salts sufficient to raise the feed water conductivity to weIl
above the acceptable level of 0·1 p.Sjcm. The effect is particularly
severe when the condensers are sea-water cooled. It is now becoming
increasingly common to treat the condensate by ion exchange meth-
ods to give results similar to those specified for the make-up water.
The technique is by no means generally accepted at present and
there are clear differences of approach between electricity supply
authorities in different countries.
In many parts of Europe, including Germany and Scandinavia,
once-through boilers of the Benson type are used. In these units,
the feed water passes straight through the fire heated boiler tubes,
to emerge directly as steam. The whole of its dissolved matter must
therefore either deposit in the boiler tubes, leading eventually to
localized over-heating and failure, or pass over with the steam giving
deposition on the turbine blades which alters their shape and re-
duces efficiency. With boilers of this type, it is illogical to purify the
make-up water, which may form only 2 per cent of the total feed,
unless the returned condensate is also treated to the same standard.
In other countries, including Great Britain, the tendency is to
use drum boilers, with forced or natural circulation ofwater through
tubes, in which the heating takes place. The boiler drum gives a
reserve of water from which a proportion can be removed by blow-
down, either continuously or at intervals, thus limiting the build-up
of solids in the circulating water to a desired level. Since the drum
137
K
thus affords a method of reducing the quantity of solids passing out

with the steam, a drum boiler can tolerate a water quality frac-
tionally inferior to that required for once through boilers. Accord-
ingly, condensate polishing has only recently started to be prac-
tised in Great Britain, and even now, it is customary to treat onlya
proportion of the condensate returns. Whilst this partial treatment
will certainly reduce the amount of deposition on boiler tubes, it
cannot eliminate it, and the system offull flow condensate polishing
appears more logical.
There is no single technique which is yet generally accepted.
Broadly, two separate processes are needed, the first being filtration
using cellulose coated candle filters to remove suspended iron and
copper oxides, and the second being demineralization to remove
dissolved matter. The demineralization step is carried out in mixed
beds, which have such a low chemicalload that they can normally
operate for many days or even weeks between regenerations.
It is thus advantageous to operate at extremely high flow rates,
both to reduce the capital cost of the equipment, and to take the
maximum advantage of the filtering action of the resin bed, for any
residual suspended matter. This action improves with increasing
watervelocity. Rates up t040galft- 2 min-1 arecommonlyin use,and
for the reasons mentioned earlier in this chapter, remote regeneration
of the resins in separate units has become a standard practice.
It is difficult to define the forms in which iron and copper occur
in condensate. A proportion is normally in the form of particles
large enough to be removed by filtration. However, although the
remainder is readily removed by ion exchange down to levels of
0,003-0·005 p.p.m. it is not necessarily in true solution. There is
thus the danger that the anion resin beads in the top layers of a
mixed bed could become coated with a film of oxides, which would
be difficult to remove on regeneration. To obviate this, there has
been developed an automatie system in which, after regeneration,
a proportion of the cation exchange resin is put aside, while the
remainder is returned to the operating unit, and remixed with the
anion resin. The retained cation material is then transferred on top
of the mixed bed, where it acts as a protective layer to absorb
heavy metals before they can reach the anion resin.
Scandinavian practice commonly omits the filters completely,
relying on the resin beds to remove both dissolved and suspended
matter. The ion exchange process may consist of cation units in the
hydrogen form followed by mixed beds, or of mixed beds alone. In
the second case the cation resm layer technique is obviously
138
CONDENSATE POLISHING FOR HIGH PRESSURE BOILERS
advantageous. For base-load stations which are running continuously

such systems can be completely satisfactory. The problem is ob-
viously much more difficult under British conditions, with two-shift
stations where heavy surges of corrosion products occur once every day
at start-up. Under these conditions the omission of a filter is at present
considered unwise, although it is not necessarily impossible.
Powdex Process
An opposite technique is the omission ofthe ion exchange columns,
using only filter candles pre-coated with finely-ground ion exchange
resins. This technique, which was invented in America in 1962, has
been named the Powdex process*. It gives removal of iron and
copper equal to that obtained by classical mixed bed columns, at a
capital cost lower than the combination of candle filters and
standard ion exchange columns. In contrast, the running costs are
usually high er than those of normal ion exchange. The powdered
resins, which are comparatively expensive, cannot be regenerated
because they become clogged with suspended and colloidal matter,
and, in any case, the fine particle size precludes the possibility of any
normal system of regeneration. They must, therefore, be thrown
away after a service life of only a few days, with a correspondingly
high replacement cost. A second disadvantage is rather more impor-
tant. In a condensate polishing circuit based on normal mixed beds,
even when operating at extremely high flow rates, the total quantity
of resin in the circuit is high, and accordingly a considerable total
demineralizing capacity is available at any time. If a condenser
leakage develops, even in a sea-water cooled station, the condensate
polishing plant can be made large enough to ensure that aperiod
of 30-60 min is available before the resin columns are exhausted.
In that time the set can be shut down without damage to the boiler
or turbines. The total quantity of resin in a Powdex plant is ex-
tremely small, because like other pre-coats, the powdered resin is
used in layers only about i in deep. If a pinhole leak develops in a
sea-water cooled condenser tube, exhaustion of the resin can occur
in a matter of seconds, after which chlorides pass through to the
boiler, with a possibility of causing serious damage before there is
time to shut the set down. Nevertheless, the Powdex process does
have potential uses and takes its place as one aspect of modern ion
exchange technology.
*Duff and Levendusky. American Power Conferences 24, 739 (1962).

139
BRACKISH WATER DESALINATION BY ION EXCHANGE

In many areas of the world, such as the Middle East, and large
sections of Australia, supplies of potable water are limited or non-
existent, but considerable volumes of sea-water or brackish water
are available. In principle, demineralizing forms a potential means
of producing drinking water from either of these sources, but in
practice, the technique is limited to the treatment of waters which
are only slightly brackish, to a limit of about 2,SOO p.p.m. The
maximum practical operating capacity of polystyrene sulphonic
cation exchange resins is about l·S g.equiv./l, while that of the
polymeric weak base anion exchangers is around 1·0 g.equiv./l.
Sea-water contains about 33 g/l dissolved solids, chiefly sodium
chloride, and is thus 0·S7N. At first sight, it would appear that 1·0 1
of cation resin, and l·S 1 anion resin, a total of 2·Sl, would together
remove l·S g equivalents of salt from solution, and thus purify
1·S/0·S7, or 2·6 1 ofsea-water. In otherwords, the resin would purify
approximately its own volume of sea-water. In practice, this is not
the case. Mter regeneration of the resins, they must be rinsed, and
the absolute minimum rinse water usage which can be used is two
resin volumes. In industrial practice, it is extremely rare to consume
less than three res in volumes. If purified water is used for rinsing,
the requirement is greater than the total production, while if
untreated sea-water is used, the resin columns become exhausted
by the incoming water weIl before the regenerants have been re-
moved. No usable water therefore can be produced in either ofthese
cases.
If a brackish water containing 3·3 g/l NaCl is demineralized
under the same conditions, the calculated production of treated
water is ten res in volumes, of which three will be consumed as rinse
water, while a feed water containing 2·S g/l, or 2,SOO p.p.m. will
yield, after rinsing, around ten resin volumes ofusable water, which is
about the minimum figure on which a workable process can be based.
The running cost of such a demineralizing process is, however,
high. Assuming an acid usage of 40 per cent, a caustic soda consump-
tion of 70 per cent, and a rinse wastage of 20 per cent, a water
containing 2·S g/l NaCI would require 6·4 g H 2S04 and 2·9 g NaOH,
per litre ofwater produced. At British prices of 1·2d/lb for sulphuric
acid and 3·3d/lb for caustic soda, the cost of regenerants alone
would be 15s/1,000 gal. The use ofsodaash, orlime,forregeneration
of the anion unit would reduce this figure. In the case of lime, the
quantity required would be 2·0 g/l as CaO, and the total operating
cost of the process would be reduced to about 8s/1,000 gal. Multi-
140
THE DESAL PROCESS
stage flash distillation, operating on a large scale, pro duces drinkable

water for less than half this cost, and is accordingly the only process
at present in general use on the industrial scale for treating water
whose salinity exceeds 2,500 p.p.m.
In the case of brackish supplies whose mineral content is not
seriously above the tolerable limit of potability (500 p.p.m.),
demineralizing becomes a practical possibility, and has been used
for many years. A water containing 1,000 p.p.m. NaCI would, from
the above calculations, impose a regenerant cost of6s/1,000 gal for
the production of demineralized water, and as this can be blended
in equal quantities with the raw water, a potable supply becomes
available in principle at a cost of 3s/1 ,000 gal. In practicc, however,
many ofthe areas most needing brackish water treatment are re mo te
from industrial centres, and the cost figures given may be consider-
ably inflated by the cost of transporting chemieals to the site.
Many methods of increasing the efficiency of the ion exchange
process have been considered, of which the two most promising
appear to be the Desal Process and the Sirotherm Process.
The Desal Process

This technique, developed in the U.S.A. by Kunin and Vassiliou, *
depends on the use of an unusual weak base anion exchange resin,
Amberlite lRA-68 whose basic strength is such that it can be
regenerated at almost 100 per cent efficiency with a base as weak as
ammonia, but can nevertheless absorb bicarbonate ions from
solution. This material thus appears to be intermediate between the
classical weak base and strong base resins, and this unusual combina-
tion ofproperties is the key to the process. It is used in combination
with a carboxylic cation exchange resin, Amberlite IRC-84. The
cation exchange stage of the process is not in itself unusual, and
could apparently be carried out with other equivalent resins.
Three columns are used in series, containing respectively lRA-68
in the bicarbonate form, IRC-84 in the hydrogen form, and lRA-68
in the free base form. The process, as described by the inventors, is
carried out in the following stages.
R A.NH+.HC03- + Na+CI- + Na+HC03- (39)
~ RANH+.CI-
Rc.COO-H+ + Na+HC03- ~ RcCOO-Na+ + H 2 0 + CO 2 (40)

.... (41)
* [nd. Eng. ehern. Proc. Des. Dev. 3, 404 (1964).

141
The third column is thus converted to the bicarbonate form during

the process, and the emergent water is demineralized. The first
column, on exhaustion, is regenerated at about 100 per cent effic-
iency with ammonia or lime, and the cation resin with sulphuric
acid. During the next cyde, the three units are operated on the
reverse order.
The process as described would appear to have two possible
difficulties. The first is that the whole of the carbon dioxide must be
kept in the system, passing backwards and forwards between the
two anion columns without loss. This would appear impracticable
in itself, and it seems probable that in practice, bicarbonate con-
tained in the raw water to be treated is retained in the system by
reactions 39 and 41, thus making up for losses. The second point is
that the polyacrylic resins are known to be less efficient for the
absorption of sodium than calcium ions. It thus seems probable that
reaction might not, in practice, always proceed to completion if the
incoming brackish water is predominantly soft. However, if this is
true, it would not matter in practice, since the object is to produce
potable, not demineralized, water, and a considerable degree of
sodium slip would be perfectly acceptable. Since the regenerants
are consumed at 100 per cent efficiency, the cost of sulphuric acid
and lime supplies for the treatment of a water containing 2,500
p.p.m. NaCl would be about 4s/1,000 gal, which is just half the
figure calculated for the standard demineralizing technique using
the same regenerants. The technique thus appears promising, and
has already been operated in the U.S.A. on the industrial scale.
The Sirotherm Process*

Since the regeneration efficiency of 100 per cent, using the cheapest
available chemieals, represents a direct operating cost of 4s/1,000
gal, in the case of a water containing 2,500 p.p.m. NaCl, it is dear
that any further reduction in eost must be achieved by eliminating
the use of chemieals. Workers at C.S.I.R.O. Melbourne have in-
vented a teehnique whieh, although still only in early stages of
deve1opment, could becorne of eonsiderable irnportance in the
future for the partial purification of brackish waters. The process
depends on two observations. First, a mixture ofregenerated weakly
acidic and weakly basic resins can be used to give partial dernineral-
izing of brackish waters. Dependent on the flow rate, and on the
particle size of the res ins used, a salt eontent of 2,000 p. p.rn. rnay be
reduced to values down to 500 p.p.rn, which is a tolerable drinking
"'W~iss et al. Aust. J. ehern 19, 561 (1966).- -~ --- ._- --_. _.-._-.
142
THE SIROTHERM PROCESS
standard. The second observation is that the salts ofthese weak resins
are hydrolysed under the influence ofheat. The hydrolysis reactions
constitute auto-regeneration of the resins :
Heat
Rc-COO-Na+ + H 20 ~ R-COO-H+ + Na+OH- .... (42)
R-N(CH3h H+CI- ~ R-N(CH3)2 + H+CI- .... (43)
Thus, if alternate cold and hot streams of brackish water are passed
through the mixed resin bed, they emerge in a respectively more
dilute, and more concentrated form, and can be collected separately.
No chemicals are used, the only consumable item being heat. The
system has, however, a major difficulty. The auto-regeneration
process is far from complete, and the available resin capacity is
correspondingly small. Consequently, the volume of water which
can be purified at each pass is as low as 25 per cent of the volume of
the resin. This restriction makes it extremely difficult to prevent
physical mixing of the fractions, or exchange of he at between them.
Either of these processes would prevent the overall demineralizing
action from taking place. To overcome this problem, the Australian
workers have devised a system of introducing and collecting a large
number of small fractions, maintained at aseries of gradual temp-
erature steps. By recycling all fractions except the hottest and coldest
ones, it is possible to produce two streams of cold potable water and
hot reject brine. Heat recovery and re-use must be practised in
order to achieve economical running costs.
ELECTRODIALYSIS
In the Sirotherm process, the energy required to remove salts from
water is supplied in the form of heat. In the electrodialysis process,
electrical energy is used. It was first discussed in 1928, but practical
applications of the process were delayed until about 1950, when
industrially produced ion exchange membranes, that is ion exchange
resins in sheet form, first became available. The membranes may be
heterogeneous, consisting of finely ground standard ion exchange
resins dispersed in a polyethylene or other plastic matrix. The pro-
portion of ion exchange resin is then about 70 per cent of the total,
so that the particles are in contact, and are not separated by poly-
thene. Too low a proportion of resin leaves an insulated sheet
which is useless. Homogeneous membranes can also be made,
materials such as sulphonated polyethylene sheet being used for the
cation exchange membranes, and aminated P.V.C. for the anion.
143
Thin flexible polystyrene sheets, supported with P.V.C. mesh, and

converted into ion exchange resins by normal methods, are also
used.
An electrodialysis cell is shown schematically in Figure 59. It
consists essentially of aseries of compartments, containing the
solution to be desalted, and separated by alternate cation and anion
exchange membranes. The two end compartments contain elec-
trodes, and in them, the normal electrolytic processes take place.
Thus, in the example given, sodium hydroxide and hydrogen are
-ve +ve
N~S~ N~S~
+NaOH +H2S04
Dilute Concentrated
stream stream
Figure 59. Electrodialysis cell
produced in the cathode compartment, while sulphuric acid and

oxygen are formed at the anode. These actions are, however, of
minor importance. An electrodialysis stack normally contains
several hundred unit cells, and in all except the end ones, the process
occurring is not electrolysis, but simple transfer. The sulphate ions
in each compartment travel to the right towards the anode, until they
are halted by a cation exchange membrane through which they
cannot pass. Similarly, the sodium anions travel to the left, until
144
ELECTRODIALYSIS
stopped by an anion exchange membrane. The net result is that the

solution in one set of alternate compartments becomes denuded of
sodium sulphate, while the other alternate set becomes enriched.
If, now, the saline solution is fed into all compartments, while the
effiuents from the two sets of alternate compartments are combined
into two streams by me ans of a manifold system, the result is a
continuous supply of desalinated water in one stream, and concen-
trated reject solution of sodium sulphate in the other. By suitably
adjusting the ftow rates of the two streams, up to 90 per cent of the
input water may be recovered in purified form. The effiuent
liquors from the two electrode compartments, which form only a
trivial proportion of the total, are also rejected. The process is thus,
in principle, simple, and indeed a laboratory scale cell to reproduce
the results of Figure 59 can be constructed very easily, and gives
no difficulty in operation. In industrial practice, however, a
considerable number of serious difficulties were found, and although
each was overcome in turn, they delayed the successful exploitation
of the technique. The main problems were:
(a) Electrical resistance-The power required for electrolysis in the
end compartments is negligible, an e.m.f. of 3-5 V. being required
for electrolysis and electrode overvoltage. The main power con-
sumption is in the intercompartmental transfer process. The
amperage is directly governed by the quantity of salt to be trans-
ferred in a given time. Values of about 5 mA/cm 2 (5 A/ft 2 ) of
membrane area are normal, although currents up to three times this
figure have been successfully used. The voltage required is directly
dependent on the number of unit cells, and the resistance of each.
A unit cell consists of a desalting compartment, a ca ti on membrane,
a concentrating compartment, and an anion membrane, all in
electrical series. The resistance of the desalting compartment is by
far the highest of the four, and its value depends on the level to
which the dissolved solids are reduced. Values much below 500
p.p.m. give impractically high figures, and this value is normally
the limit to which the electrodialysis process is taken. Since the aim
is to use the maximum possible number of cells in series, the unit
resistance must be made very small. This is achieved by the use of
thin membranes, 0·2--0·5 mm being normal, placed only about
1 mm apart. Under these circumstances, a voltage drop ofabout 1 V.
per unit cell can be achieved.
As cells have been constructed to use membranes as large as
3 ft X 6 ft (90 X 180 cm), with total ftows measured in thousands
of gallons per hour, the problem of introducing water into hundreds
145
of extremely slim compartments is a difficult one. Equipment

manufacturers have arrived at various solutions, but all are based
on the same general principles. The complete stack, which may be
operated with the membranes either horizontal or vertical, is built
up in the same way as a plate and frame filter press. The spacer
frames are moulded, or stamped out from plastic sheet, so as to
form aseries of water passages right through the stack, locating
with insulated pipes passing through the electrode blocks. As
shown in Figure 60 the system ofpassages is arranged to connect into
Brackish
water
i t
Figure 60. Flow pattern in electrodia/ysis cel!
alternate compartments. To prevent membranes bowing and

touching one another in the hollow central areas of the spacers,
these areas are filled with plastic mesh, or the spacers themselves
may include, not only the outer frames, but also a complex series of
bars forming a maze pattern. The simple diagonal entry and exit
from each compartment shown in Figure 60 is adequate for fairly
small cells, up to about 12 in square, but for larger units, more
sophisticated methods are needed to ensure a completely even flow
of water through each compartment. The presence of areas in
146
ELECTRODIALYSIS
which the ftow rate is significantly less than the average, would
lead to preferential desalting, and a corresponding rise in the
e1ectrical resistance of the cello
(b) Water clariry-Because of the larger number of extremely fine
gaps, through which the water must pass, it must be filtered to a
high degree of efficiency before it can be used in the cell.
(c) Electrode effects-The example chosen was of a solution con-
taining only sodium sulphate, which presents no problems either at
the electrodes, or in the body of the cello Natural brackish waters
invariably contain considerable concentrations of chloride, resulting
in the production of chlorine in the anode compartment. The early
anion exchange membran es were readily attacked by chlorine, and
the on es next to the anode broke down comparatively rapidly.
Materials of higher stability were produced, and an anode mem-
brane life of over one year is now normal. The membranes in the
main body of the cell normally last for several years of continuous
operation.
Calcium and magnesium, also present in natural brackish
supplies, can cause difficulties in the cathode compartments, where
the alkaline conditions can cause deposition of calcium carbonate
or magnesium hydroxide in quantities sufficient to block the water
channels. This problem is overcome by feeding acid into the cathode
compartment, sufficient to maintain the pR at about 2·0. Another
useful technique is to reverse the polarity of the whole cell at
intervals of 10-15 min, so as to produce electrolytic acid at each end
in turn. The water ftows must, of course, be correspondingly changed
on each occasion. Polarity reversal does not eliminate the necessity
for acid dosing, but assists in keeping the cell free from deposit.
(d) Membrane polarization-The simple picture of sodium and
sulphate transport given in Figure 59 is substantially correct, but is
incomplete. The mobilities of the R+ and OR- ions through the
membranes are greater than those of other ions. Consequently the
water layers at the appropriate membrane surfaces become partially
denuded of these ions, and films of high and low pR respectively
form on the membrane surfaces. The effect is known as membrane
polarization. The high pR films cause localized deposition of
calcium and magnesium scales. The effect is minimized by acid
dosing the concentrated salt stream, by maintaining the voltage and
current density below the critical values at which membrane
polarization becomes noticeable in any particular cell, and by
e1iminating non-uniform ftows in individual compartments, since
these can produce localized polarization in the low-ftow areas, which
147
become denuded of salts. Polarity and water stream reversal assist in

the removal of any scale which does form, in spite of the precautions
already mentioned.
(e) Organic poisoning-Many brackish waters arise from subterran-
ean sources in arid countries which have little vegetation. The
organic content is therefore very low. Nevertheless, cases do fre-
quently occur in which electrodialysis must be applied to surface
waters with O.A. figures in the normal region of 1-2 p.p.m. If the
total dissolved solids are around 2,500 p.p.m., the O.A.jT.D.S.
ratio is very low, and the waters would be considered non-poisoning
from the viewpoint of normal ion exchange. Poisoning problems in
electrodialysis are, however, much more severe. The total quantity
of anion resin present in a cell is small, in relation to the volume of
water being treated, so that the total quantity of organic matter
coming into contact with the resin each month is very much higher
than in standard demineralizing practice. Moreover, the organic
matter, being negatively charged, is driven into the anion exchange
membran es under the influence of the e.m.f. applied, and there is
evidence that organic molecules too large to enter a particular
resin under columnar conditions be comes forced into the same
resin, when it is used in the form of a membrane in an electro-
dialytic cell. Membrane poisoning can therefore be extremely
rapid, its symptoms being a rise in the resistance ofthe cell, followed
by polarization as the voltage is raised to maintain the current
constant.
It is therefore necessary, when membrane cells are used with
surface waters, to precede them with organic trap columns of the
type described in Chapter 6. It is interesting that in the author's
laboratories the early work on the organic poisoning problem, lead-
ing to the development of the macroporous resins, was initiated
because the problem was a source of great difficulty in the experi-
mental electrodialysis programme, at a time when it had not yet
become serious in normal demineralizing practice.
(f) Saturation-Many brackish supplies contain proportions of
calcium and sulphate, and may be almost saturated solutions of
gypsum. Under these circumstances, any attempt to increase the
total concentration of salts in the receiving stream can lead to
supersaturation of gypsum, with subsequent deposition throughout
the cell. The resultant scale is extremely difficult to remove. Luckily,
the problem is somewhat reduced by the fact that the solubility of
calcium sulphate rises with increasing sodium chloride concentra-
tion, and it is possible to achieve a greater concentration factor than
148
ELECTRODIALYSIS
would be calculated from the normal solubility figure. Nevertheless,

the necessity for avoiding saturation is permanent, and the ratio of
concentratedfdiluted stream flow rates must always be set so as to
make it impossible to exceed saturation in the cel!. With some
waters, this restriction is quite severe, and only a minor proportion
of the incoming water can be converted to a potable supply.
(g) Gell re-assembly-A membrane cell consists essentially of
several hundred fairly soft plastic sheets, the membranes themselves,
separated by an equal number of plastic spacers, all of which must
be assembled together in the correct order, with exact alignment of
the ports. There is no difficulty in carrying out this task, and
operators in a factory producing membrane cells can be trained to
do the work quickly and efficiently. However, almost by definition,
the cells are used in remote areas, where any servicing must be
carried out by general fitters. The fact that modern cells have become
very reliable implies that they are stripped down for cleaning and
maintenance comparatively infrequently, and it is difficuIt for
fitters who have been trained in the work to maintain their skills.
It is perhaps for this reason that the electrodialysis technique, which
in the early 1950's appeared the most promising method for brackish
water treatment, has not fulfilled early expectations. Some fifty, or
perhaps one hundred units have been installed throughout the
world, the majority being fairly smalI, and placed in areas of the
U.S.A. where servicing is not greatly hindered by geography. A very
large pilot programme, in the Orange Free State, South Africa,
operatedjointly by the government and the goldmining companies,
and using the biggest block of cells assembled anywhere in the
world, was finally closed down because technical difficulties
rendered the technique less attractive than other methods of
dealing with the water shortage problem.
In Australia, where a reliable economical desalination method
could lead to the opening up of areas at present virtually unin-
habited, no industrial size units have ever been operated. The
electrodialysis technique has thus been disappointing, and while
work on the subject continues in many countries, it is no longer
considered to hold out the promise of its early days.
149
CHAPTER 8
INDUSTRIAL APPLICATIONS
The techniques described in this chapter are concerned with

special applications of ion exchange resins in the treatment of
industrial solutions, rather than of natural water supplies. Never-
theless, it is appropriate to discuss the subject briefly, since there
are many points of similarity with water treatment procedures.
In many cases, the object is the same, that is the production of a
pure water from a contaminated supply. In others, the methods
used are identical with those already described, although the
purpose may be different, being for example, the purification of an
organic compound such as sugar, the recovery of a valuable metal,
or the use of the resin as areagent in a manufacturing process. In
some cases, such as the chromatographic separation of similar
metals, both the techniques and their aims are completely different
from those applicable to water treatment. The number of individual
applications of resins is so large, that no attempt will be made to
catalogue them fully. Instead, the available types of processes will
be described, and typical examples given in each case. The ion
exchange literature includes hundreds of possible applications,
which are not yet necessarily in large scale use, and the examples
will be confined to those known to be generally practised.
THE TREATMENT OF WATER-SOLUBLE ORGANIC

COMPOUNDS
Demineralizing
Many natural organic compounds are now purified by ion
exchange, in preference to earlier methods, such as crystallization,
or active carbon treatment. Typical cases are those of sugar,
glucose, glycerine, and gelatine, the object in each case being the
removal of inorganic impurity by demineralizing, with simultaneous
decolorizing by rem oval of anionic colour bodies. The methods used
are identical with those of water treatment, but there are several
extra factors which require special consideration.
150
THE TREATMENT OF WATER-SOLUBLE ORGANIC COMPOUNDS
(a) The choice if demineralizing methods-In the treatment of

natural products, the choice of the demineralizing technique is
dicta ted by the degree of purification required, and by the stability
ofthe products themselves. In the production offood or photographic
grade gelatine from crude liquors, complete removal of weakly
acidic compounds is normally unnecessary, and two-bed demineral-
izing using a tertiary amine resin is the most common practice.
Although gelatine is, in general, degraded by mineral acids, the
time of contact in the demineralizing plant is insufficient for this
effect to be significant. To convert crude glycerine to pharmaceutical
grade, mixed bed demineralizing is required, and as the ash content
necessitates high capacity conditions, the mixed resin unit is pre-
ceded by a demineralizing pair including a weak base resin.
Demineralizing does not, of course, remove organic impurities
such as glycols. It is therefore inapplicable when dynamite grade
glycerine is being produced. Glucose solutions used for the produc-
tion of white syrup may be treated by single two-bed demineraliz-
ing, using weak base resins, but for the production of high quality
crystalline dextrose, the liquor must be purified to a higher standard,
organic acids present in the solution being removed by strong base
resins. In this case, mixed bed units are preferable, since contact
with the alkaline conditions of a strongly basic resin unit induces
chemical changes in the glucose which lead to brown decoloration
during later evaporation. The effect does not occur when mixed
beds are used.
The case requiring the most care is that of sugar deionizing.
Sucrose is unstable in acid conditions, becoming rapidly inverted
with the production offructose and glucose. Contact with a sulphonic
cation exchange resin in the hydrogen form for a few minutes at
75°C can cause the destruction of over 25 per cent of the sucrose.
The problem has been partially resolved, in parts of the world
where only sulphonic resins have been available, by diluting the
solution to about 10 per cent, to reduce the temperature and
viscosity, and then treating in a standard two-bed system at high
flow rate to minimize the contact time. AIthough inversion can be
kept below 2-3 per cent by this means, the method is clumsy, and
gives high evaporation costs. The method now universally pre-
ferred is mixed bed demineralizing, with a strongly basic resin in
combination with a weakly acidic material of the acrylic type.
Complete freedom from inversion is obtained.
The method has two potential problems. First, the density of the
carboxylic resins is lower than that of the sulphonic materials, and
151
is thus close to that of the anion exchange resins. Bed separation for
regeneration is correspondingly slightly more difficult. If, in any
particular case, clean separations are not obtained the effect can
normally be overcome by using a salt solution instead of water for
bed separation. The greater density of the brine accentuates the
density difference between the two resins. The second problem
arises from the large volume change of carboxylic resins, between
the hydrogen and sodium form. If, after bed separation, the cation
exchange resin is regenerated first, and if by maloperation, caustic
soda solution is allowed to enter the cation layer during regeneration
of the anion resin, the carboxylic resin may swell by as much as
80 per cent, the swelling forces being sufficient to cause serious
damage to the resin and the equipment. The danger is eliminated
by regenerating the anion exchange resin first, so that, even in the
case of faulty operation, caustic soda is in contact only with cation
exchange resin which is already exhausted.
(b) Plant calculations-An approximate calculation of plant and
resin requirements for natural product demineralizing can be
made, from a knowledge of the total salt content, by means of the
standard curves used in water treatment. The results must always
be treated with considerable caution, due to the variety ofunknown
factors, which can affect the results. It is essential, before designing
equipment for the treatment of sugar and similar products, to
carry out a programme of pilot plant work on the liquors to be
treated, to establish the precise operating results in each case.
(c) Avoidance qf dilution-The products listed above must be
treated in fairly concentrated solution, varying from about 20%
w/v, in the case of glycerine, to 65-70 per cent, for cane sugar. The
ash content, that is the mineral impurity, is normally high by ion
exchange standards, figures of 1,000-2,500 p.p.m. being common.
Accordingly in demineralizing, the total quantity of liquor which
can be treated is only 10-20 bed volumes, and unless special
precautions are taken, the solutions become significantly diluted by
water from the resin beds. The final products are normally sold as
dry solids, or as concentrated syrups, and any water added during
the ion exchange process adds to the cost ofsubsequent evaporation.
The quantity is minimized by control of 'sweetening on' and
'sweetening off', two terms which originated in the sugar industry,
in the treatment of sugar juices by bone char columns.
'Sweetening on' takes place when the freshly regenerated column
of resin has been rinsed, and is ready to accept sugar, or other,
solution. The obvious method of avoiding dilution would be to
152
Plate 3. Automatie water treatment plant at Drakelow Power Station, including sand filtration and softening of river water, deionizing of
make-up water, and eondensate polishing
Plate 4. Portable 2-bed deionizers in a hospital laboratOlY Plate 5. Small industrial automatic water softener
drain the whole of the water from the bed, and then refill upflow
with the liquor to be treated; but this technique has serious dis-
advantages. The solutions under consideration are fairly viscous,
and it is difficult to obtain the even upflow required to avoid air-
locks in the bed. The high inorganic content exhausts the lowest
layers of the bed, leading to poor quality during the subsequent
service cyde. Finally, where mixed bed demineralizing is used, the
upflow refilling separates the resins. The preferred method of
'sweetening on', therefore, is to drain the water in the unit down to
the level of the bed top, a window or a test cock being provided to
check the operation. The liquor is then pumped in, as rapidly as
possible, through the regenerant distributor set just above the
resin, so as to fill the above bed space. Finally, the liquor is pumped
in through the top entry point ofthe shell, passing down through the
bed piston-wise, and displacing the interstitial water ahead of it.
The emerging liquor is continuously checked by means of a re-
fractometer, or any other direct-indication .system for determining
dissolved solids content. The first 0·4-0·5 bed volumes consist of
displaced interstitial water, and are rejected. As the organic
compounds under consideration are all non-ionic, they are able to
permeate freely into the resin partides, the concentration of sugar,
etc. inside the beds finally becoming identical with that in the
surrounding solution. Consequently, the next bed volume of
emergent liquor has a sugar concentration rising from zero to the
input value. A proportion of this liquor can be retumed to the feed
circuit for use in dissolving more raw sugar, or for corresponding
purposes in the other cases. When the concentration reaches about
30 per cent of the input value, the flow is diverted to the finished
product stock, the total quantity of added water being about 0·5
resin volumes.
'Sweetening off', at the end of absorption is carried out by the
reverse process. The liquor remaining in the unit which is, of
course, substantially untreated, is drained to bed level, and displaced
piston-wise with water to the untreated liquor stock. When the
concentration has fallen to about 30 per cent of input value, the last
runnings are retumed to an earlier stage of the process. By careful
control, it is possible to limit the total water addition, from the
resin to the liquor, to a quantity equal to the resin volume. It is
difficult to reduce this figure without accepting some loss ofproduct.
(d) Organic poisoning-The total ionizable organic matter present
in the products is much higher than in any water supply, the worst
case heing that of cane sugar, whose solutions are almost black.
153
L
Accordingly, anion resin life is much lower than in water treatment,

and is rarely more than 1-2 years. Glycerine, glucose, gelatine and
sorbitol solutions are not normally given any pre-treatment other
than simple filtration, but raw cane sugar solutions cannot be
demineralized directly. In British practice, the imported crude
solid sugar is first affinated, that is washed in centrifuges to remove
much of the adherent molasses. It is then defecated, by treatment
with phosphoric acid and lime, or by lime followed by carbon
dioxide, to form precipitates of calcium phosphate or carbonate
which carry with them much of the colloidal matter. The addition
of minor quantities of activated carbon, immediately prior to
filtration, aids this process. In Europe, where beet sugar juice is the
predominating raw material, the affination stage is omitted, the
liquors being treated only by carbonation or phosphatation. For
reasons given above, sugar demineralizing is almost always carried
out in mixed beds, whereas the other products can be treated by
either two-bed or mixed bed systems. The usual difficulties of acid
precipitation of organic matter can therefore occur in sugar treat-
ment, and it is advantageous to separate the resins, not with upflow
water, but with a brine solution wich strips some of the organic
matter from the anion exchange resin before regeneration. Glycerine
solutions, prepared by acid or catalytic splitting of fats, contain
traces of free fatty acids which can coat the resin beads over a long
term, while gelatine solutions contain a range of amino acids of·
varying molecular weight. Glucose solutions are less poisoning to
J:"esins. Nevertheless, in all cases, a regular cleaning of the resins
vvith warm alkaline brine is essential, whether they are used in
two-bed, or in mixed bed systems. In the case of cane sugar treat-
ment, the resin cleaning may be required as often as once per week.
(e) Temperature-Both sugar and gelatine demineralizing are
carried out at elevated temperatures, up to about 75 oe. This figure
is high er than the limitation of 60 oe set by almost all ion exchange
resin manufacturers for strang base resins. The higher temperatures
can be tolerated because the resin life is dicta ted by poisoning,
rather than by resin stability. Even at 75 oe the loss of active groups
in 2 years is normally insufficient to reduce the operating capacity
by more than 25 per cent, and in spite of all precautions which can
be taken, resin poisoning is likely to limit the useful life to this
term. Nevertheless, much depends on the efficiency ofpretreatment,
in the case of sugar, or the type of feedstock, during gelatine treat-
ment. If poisoning effects are particularly weIl controIled, the resin
life may be extended to the limit imposed by chemical stability. For
154
strong base resins, the maximum value at 75°C is unlikely to

exceed 3 years, but the tertiary amine weak base resins have been
successfully operated for up to 5 years.
Decolorizing
Sucrose is sold industrially in many different grades, with
various purity specifications. While the highest quality sugar
syrups require complete demineralizing, other grades require
decolorizing only. This is achieved, after pretreatment of the
solutions as before, by a process identical in principle with the
organic trap system used in water treatment. The liquor is passed
through a chloride-form strong base resin, over 90 per cent removal
of the organic colour-bodies being attained. The resultant syrups
are quite pale, although it is unusual to obtain a completely water-
white product, such as can be produced by the demineralizing
process. An interesting point, for which no clear explanation is
known to the author, is that, while macroporous resins are normally
superior to other types for use as organic traps in water treatment,
the reverse is true in sugar decolorizing. The isoporous resins, or
the classical D.V.B. gel resins, provided they are loosely crosslinked,
both give better colour rem oval and longer life than the correspond-
ing macroporous materials. The explanation may be that the high
concentration of large organic anions occurring in sugar juices
overloads the available active groups in the macroporous resins, but
no reliable evidence on the mechanism of the process exists.
Decolorizing, although not at present commonly used in Great
Britain, is widely practised throughout Europe. Beet sugar produc-
tion and refining are carried out as one complete process, a system
of countercurrent crystallization or 'strikes' being used. The first
strike gives the saleable product, the mother liquor being reconcen-
trated to yield a second strike of darker sugar. The mother liquor
is further reconcentrated for a third strike, while the crystals are
washed and redissolved, the solution being added to the next batch of
raw juice for its own first strike. When the mother liquor from the first
strike is decolorized, the second strike crystals are equal in quality to
the first, and the necessity for a second recrystallizationis eliminated.
Softening
The process is applicable almost entirely to beet sugar pro-
duction. In many European factories, the calcium content of
the sugar juices exceeds 500 p.p.m. Consequently, during concen-
tration of the liquors before crystallization, severe scaling of the
155
evaporators can occur. The beet season is very short, and sugar
production is intensive during this period. Shutdowns to descale
the evaporators thus entail costly losses in production. Softening of
the juices by a process exactly analogous to water softening has now
become a standard process throughout Europe, and the scaling
problem has been virtually eliminated. Softening and decolorizing
can be combined, by using mixed cation and anion exchange resins
in the same column, both regenerated with salto Bed separation for
regeneration is not necessary.
The Stabilization qf Wine

A process allied to sugar softening is the prevention of precipita-
tion in wine. Most wines, as first prepared, contain potassium
hydrogen tartrate in metastable supersaturated solution which
crystallizes slowly in the bottles over aperiod of months or years,
to give the characteristic gritty, bitter tasting deposit which formerly
was found in most table wines. The first method used by the industry
to overcome this problem was to refrigerate the wine for periods of
several weeks to accelerate crystallization before filtration and
bottling. This process is successful, and widely used, but is very
expensive in capital and operating cost. Passage of the wine through
a bed of a polystyrene sulphonic acid cation exchanger in the sodium
form converts potassium hydrogen tartrate to the corresponding
sodium salt, which is more soluble. The equipment is small, a
2 ft (60 cm) diameter unit usually being sufficient for a large
winery. The volume of wine which can be treated varies according
to the potassium content, but the figures are not critical, since the
stable solubility of the potassium salt is quite appreciable, and full
removal of potassium is unnecessary. For most wines, the length of
run is 80-100 resin volumes; and the exact requirement in any case
can readily be determined, even in the absence of analytical facili-
ties, by passing an excess quantity of the wine through a small
column, collecting and refrigerating the emergent sampies. The
total quantity of wine which can be treated is indicated by the last
sampie which remains clear on standing.
The method does not alter the ftavour of the wine, since the
difference in taste between the potassium and sodium salts, at the
concentrations is which they occur, is undetectable. A completely
new resin column can reduce the organic ftavour and colour
marginally, but the effect disappears after the first use of the
column. It is overcome by steeping the new resin for a few days in
any poor grade wine, to poison and block the few abnormal active
156
RECOVERY OFWATERAND BY-PRODUCTSFROM INDUST. WASTES
sites in the resin which apparently give rise to the effects. The
potassium exchange process is now very widely applied in most
wine-producing countries.
Another process, which is less frequently encountered, is to
reduce the acidity of substandard wines, produced during seasons
with poor sunshine. Passage of the wine through a weak base resin
in the free base form removes excess acidity, producing a neutral
liquor which is then blended with untreated wine to give the required
acidity. Unfortunately, as the colour, flavour and odour-producing
bodies are frequently anionic, the characteristics of the wine can be
seriously modified by this process. Loosely crosslinked resins are
unsuitable, since they may continue to remove organic acids
indefinitely, while resins based on volatile amines such as dirn ethyl-
amine or trimethylamine are inadvisable, as fish-flavoured wine has
proved unpopular. Accordingly, the best resins to use are tightly
crosslinked polyamine materials, which are allowed to poison to the
maximum extent as rapidly as possible, after which they can be
used without reducing the flavour of the treated product. At the
same time, the polyamines do not add unwanted flavour. Never-
theless, the process must always be used with caution, and it tends
to be a rescue operation for an inferior vintage, rather than a
standard treatment procedure.
RECOVERY OF WATER AND BY-PRODUCTS FROM

1NDUSTR1AL WASTES
The metal finishing industry is a prolific consumer of water, used
chiefly for was hing metal parts after the various stages of pickling,
electroplating or anodizing. 1t is then normally discharged to sewer,
or even to river, and toxic constituents such as cyanide or chrome
must be removed before discharge. A typical plating shop, for
example in the automobile industry, may use up to 25,000 gal.
(100 m 3) fresh water per hour. The cost of purchase can be [,3 per
ho ur, with an equal cost for effiuent treatment to the required
standards, together with a considerable waste of space, if the
classical methods of precipitation, thickening and filtration are
used. Any fault in operation results in the illegal discharge of toxic
materials to drain.
The demineralization of the effiuent liquor, with recirculation of
the pure water for re-use, removes the main effiuent disposal
problem. The equipment is controlled by the standard method of
conductivity measurement, and ifby any chance any unit is allowed
to run on beyond its exhaustion point, the incompletely treated
157
liquor is not discharged to drain, but remains in the circuit, where

no harm results provided that the fault is rectified fairly quickly.
Regeneration of the resins produces small volumes of relatively
concentrated solutions of the toxic metals on the one hand, and
obnoxious anions such as chromate and cyanide on the other. These
solutions are then treated batchwise, in small scale equipment, the
treated liquors being stored until laboratory checks have proved
them to be of suitable standard for discharge.
CHROMIUM PLATING. RECOVERY OF WATER

The commonest case is that of chromium plating. In this process,
the metal parts travel successively through aseries of vats each
separated by a ftowing rinse tank or spray system, from which the
effiuents arise. The total number of steps used varies in practice,
but broadly speaking, consist of alkaline degreasing (hot caustic
soda or sodium phosphate), pickling (mineral acids), copper plating
(cuprocyanide), nickel plating (nickel chloride or sulphate solution,
often with additions such as borate) and chromium plating (chromic
acid). The several rinse liquors nearly always become mixed in the
plating shop drains, and in modern fully automatic plating machines,
the mixing takes place in the internal effiuent pipe system of the
machine itself. It is not, therefore, normally practicable to recover
nickel and chromium for re-use. The demineralizing process is
used purely for water recovery and effiuent volume reduction. In
most industrial countries water supplies and disposal facilities are
both becoming overstretched, and industrial re-use of water is
correspondingly increasing in importance. A most important
secondary advantage of the recirculation process is found in the
improvement is plating quality occurring when the inter-stage
rinsing is carried out with demineralized water. In a typical case,
a company setting itself a particularly high quality standard was
rejecting 25-30 per cent of its output because of blemishes, the
rejected parts being acid stripped and replated at considerable
expense. A demineralizing and recirculating plant, one of the first
in Great Britain, was installed for the purpose of effiuent treatment,
with the completely unexpected extra result that plating rejects
immediately fell to weIl under 1 per cent. As a result the stripping
section of the shop was abandoned.
The demineralizing process, which has become a standard method
for treating chromium plating effiuents, is, in its general principles,
identical with the techniques used in general water treatment.
There are, however, several important extra points to observe.
158
(a) Sampling diJficulties-The curves already given for resin

capacities can be used equally for plating water solutions, deter-
mination of total cations and anions having been made by standard
analytical techniques. In practice, however, it is normally impossible
to obtain a representative sampie of the effiuent at the time of
plant design. No only do the figures vary considerably from day
to day, but even more important, the effiuent sampies taken before
the demineralizing plant is installed are completely different in
type from those arising in a recirculating system. They contain, in
addition to the salts derived from washing the metals, those present
in the raw water being used, the total being higher than will be
found when the incoming rinse water is demineralized. A plant
calculated from the analysis of existing effiuent is therefore likely
to prove oversized, and unnecessarily expensive.
Three methods of predicting the future effiuent analysis can be
used. The first is to determine separately the total cations and
anions in the existing effiuent, and subtract from these values the
corresponding figures for the raw water. The method must be used
with care since if the raw water contains bicarbonate alkalinity,
while some of the constituents added are acid, carbon dioxide may
be lost in the plating circuit, and the analysis of mixed liquors
correspondingly falsified. A more reliable method requires know-
ledge of the plating process being used, and the constituents of the
various baths. If it is assumed that the quantity of liquor dragged
out by a given number of plated parts is the same for each vat,
then the determination of one characteristic ion such as nickel or
chromate can be used to calculate the quantity of drag-out, and
from a knowledge of the composition of the liquor in each tank, the
total quantity of ions to be removed can be deduced. Often the
most reliable method is to reproduce the various stages of the
plating process by hand, passing single parts through an exact
reproduction of the dipping, draining and rinsing cyde used on the
main plant, and collecting all the rinse liquors for adetermination
of their total ionic constituents. None of these methods, however,
is completely reliable, and it is advisable in practice to design
equipment at least 20 per cent oversize, as compared with the
calculated figure.
(h) Plating additives-The plating industry uses a number of
proprietary additives, which are often organic compounds of
undisdosed composition. Some of them can cause severe poisoning
of anion exchange resin, even when these are of modern type. A
particularly difficult compound is a fluorinated hydrocarbon
159
sulphonic acid, used in the chromic acid vat as a surfactant to

reduce drag-out and spray formation, and held so firmly by anion
exchange resins as to be virtually irremovable.
The effect of these additions can be minimized by the use of a
column of active carbon, placed ahead of the ion exchange units.
Most of the commonly used organic additives are adequately
removed by this procedure, the protection given to the resins being
sufficient to ensure a normal service life of about 3 years. There is
no reliable means of calculating the required quantity of carbon.
Experience has shown that a suitable column volume is 25-30 per
cent of that of one of the ion exchange units, and that the carbon
should be changed at intervals of about 6 months.
(c) Complex anions-Complex cyanides in general have very high
affinities for anion exchange resins, and are comparatively difficult
to remove. Copper is present in the plating solution in the form of
cuprocyanide, while nickelocyanide may form in the swill liquor
by interaction of nickel with excess cyanide from the copper vat.
At normal levels of regeneration, these ions are incompletely
removed and tend to build up in the anion exchange resin. Single
high-level regenerations at intervals of about 3 months reduce the
effect, and in particularly difficult cases, the resin can be decon-
taminated with a solution of sodium hypochlorite to destroy the
complexes.
(d) Precipitation-Mention has already been made of the fact that
in industrial mixed beds the uppermost layers normally consist
largely of anion exchange resin, which can on occasion give rise to
precipitation difficulties even in water treatment practice. Plating
effiuents, possibly containing 25-50 p.p.m. of nickel and iron, can
give rise to voluminous gelatinous precipitates which interfere
seriously with the operation of the units. It is, accordingly, inad-
visable to use mixed beds alone for this duty. For small installations
two-bed systems using strong base resins are suitable, the slightly
alkaline treated water which resuIts not normally being disadvan-
tageous. For large plants, it is preferable to use cation exchange
columns followed by mixed beds.
Unprotected mixed beds can be used successfully when the swill
waters contain free mineral acidity equivalent to over 20 per cent
of the total anions. This acidity rapidly exhausts the upper anion
layer, preventing precipitation. It is, of course, essential to ensure
that variations in the nature of the effiuent are never sufficient to
reduce the acidity below the critical level.
Precipitation of a different type can occur du ring the treatment
160
of eiliuents from zinc plating, which is also carried out in cyanide

solutions. The anionic zinc cyanide complex is stable only in
alkaline solution. When rinse waters containing it are deminera-
lized under standard two-bed conditions, the complex decomposes
in the cation exchange column, with precipitation of zinc cyanide
in the resin bed. To overcome this difficulty, a three-bed system
may be used. The first column, containing an anion exchange
resin in the chloride form, takes up the zinc complex, while the
following pair is used for the rem oval of other ions by normal
demineralizing. The zinc complex is removed from the first bed
by means of alkaline brine.
(e) Disposal qf regeneration eJlluents-The liquors resulting from
regeneration of the anion exchange resins, including the extra
column in cases where zinc plating occurs together with chromium,
contain sodium chromate, cyanide, and complex cyanides, together
with sulphate, chloride and excess caustic soda. The regeneration
eiliuents from the cation resins may contain zinc, nickel, iron and
tervalent chromium, the last resulting from cathodic reduction of
chromic acid. Cyanide and complex cyanides are destroyed with
excess chlorine in alkaline solution, and the liquors are then mixed
with the acidic cation regeneration eiliuent, extra acid being used
if necessary, to give an acid solution in which the chromate can be
reduced to the tervalent state with sulphur dioxide. The liquors are
again made alkaline, the resulting precipitate being filtered before
the solution is discharged to drain. The filter cake ofmixed metallic
hydroxides is disposed of as asolid waste.
(f) Temperature control-Heat production during plating may
cause a temperature rise in a recirculating system. To prevent this
happening a small evaporative cooler is inserted at some suitable
point in the circuit.
ANODIZING. RECOVERY OF WATER AND
CHROMIC ACID
Anodizing of aluminium is a single stage process commonly carried
out in chromic acid solution containing 5-8 per cent CrOa, and the
eiliuent rinse liquors are thus much simpler than those arising from
electroplating. They contain aluminium, tervalent chromium, and
traces of ferric iron as the cations, together with dichromate and
free chromic acid. Water re-use is achieved by two-bed demineral-
izing as before, regeneration of the cation exchange resin then
producing minor quantities of metallic sulphates for precipitation
and disposal. The passage of ca ustic soda through the anion exchange
161
INDUSTRIAL APPLlCATIONS
unit produces a solution of sodium chromate, which is then converted

to chromic acid by means of the hydrogen ion exchange column.
The chromic acid is returned to the original anodizing vat, and the
whole process thus becomes completely self-contained (Figure 61).
A particular feature of the process is the unusual action of the
anion exchange resin. Although regenerated with sodium hydroxide,
it is never even partially in the hydroxide form after the first cycle.
'--- -.. Waste
Figure 61. ehromic acid recovery
On exhaustion, the resin is in the dichromate form, and a quantity

of caustic soda is passed, just sufficient to convert the dichromate to
chromate, without excess. The caustic soda is thus completely
consumed, in contrast with the 40 per cent usage normally achieved
in regenerating strong base resins to the hydroxide form.
By using a 2N (8 % w/v) solution of NaOH, it is possible to

produce a 15 % w Iv solution of neutral sodium chromate, in
spite ofthe dilution caused by rinsing the resin. This solution, when
passed through the cation exchange res in in the hydrogen form, is
162
GOLD PLATING. RECOVERY OF GOLD
converted to a chromic acid solution containing about 5 %w/v CrOa,

which is re-used in the anodizing vat.
Finally, the anion exchange resin, now in the chromate form, is
retumed to service as the second unit of the demineralizing pair,
where it absorbs chromic acid just as efficiently as a hydroxide
form resin.
.. .. (45)
The whole process is thus completely self-contained, the only re-

jected material being the small quantity ofsolid sludge removed from
the cation resin regeneration waste, together with the corresponding
sodium sulphate solution which can be discharged to drain.
GOLD PLATING. RECOVERY OF GOLD

Gold plating is carried out in cyanide solution, the rinse liquors
containing valuable quantities of gold as aurocyanide, which is
powerfully absorbed by any anion exchange resin. When fully
loaded, the resin can contain up to 3 lb Au/ft 3 (50 g/l). Its gold
content is so valuable, in comparison with the cost of the resin, that
it is common practice to re cover it as metal, by incinerating the
loaded resin. The gold can, however, be removed without destroying
the resin, by means of an alkaline solution of thiocyanate, from
which the metal is recovered by electrolysis. As gold plating is
carried out on a fairly small scale, there is usually no object in
recovering the water for re-use.
Similar procedures can be applied in the case of silver plating.
PHOTOGRAPHIC SOLUTIONS. RECOVERY OF

SILVER
In the industrial processing of cinematograph film, it passes through
a developing bath, then into a fixing tank, where unexposed silver
bromide dissolves in sodium thiosulphate solution, and finally into
a rinse tank. The silver accumulating in the fixing solution in the
form of an anionic thiosulphate complex, is recovered by pumping
the contents of the tank through a closed circuit including an
electrolytic cell, in which the silver is recovered as metal. Never-
theless, as the drag-out offixing solution by the continuously moving
film is high, a great deal of silver can be lost in the rinse. It can be
recovered by the passage of the was te rinse solution through an
anion exchange resin in the thiosulphate form. The silver thiosul-
phate complex is strongly held, and the solution is completely
163
stripped. Silver is recovered from the resin by the use of a concen-

trated solution of sodium thiosulphate, which is added to the fixing
bath to replace drag-out losses, the silver finally being recovered as
metal in the electrolytic cello
REACTIVATION OF METAL FINISHING SOLUTIONS

Although sulphuric acid has been most commonly used for steel
pickling prior to painting or other finishing operations, there is an
increasing trend in the metal finishing industry to use phosphoric
acid, which, in addition to descaling the metal, gives a finish more
suitable for later painting or glass enamelling. The acid is, of course,
rapidly neutralized by dissolved oxide and metal, and its efficiency
is seriously reduced weIl before the neutral point. As phosphoric
acid is considerably more expensive than sulphuric acid, the
economy of the process depends on restoring the solution to its
original condition, by passing it through a hydrogen-form cation
exchange resin, which removes the dissolved iron, and maintains
the acid in constant condition. The success of the process depends
on the fact the phosphoric acid is comparatively weakly dissociated,
and the equilibrium with the resin strongly favours iron absorption,
even from solutions containing over 10 per cent H 3P04 •
A similar process can be applied to the chromic acid solutions used
in anodizing, to remove the tervalent chromium, iron and aluminium
which accumulate in the solution and interfere with the process.
In addition to economizing in chromic acid consumption, this process
eliminates the very serious problem of disposal of the contents of an
exhausted anodizing vat. The process can be applied to chromium
plating solutions, but the application is more difficult, as these
solutions are more highly concentrated (25-30 % wjv) than
those used for anodizing. They must be diluted to 10-25 %
(wjv) for treatment, and are subsequently reconcentrated by partial
evaporation, before the solution is returned to the vat.
RECOVERY OF METALS BY COMPLEX ANION

FORMATION
Uranium Recovery
One of the standard methods ofwinning valuable metals from low
grade ores is to grind the rock finely, and leach it with some cheap
reagent, to bring the metal into solution. Leaching systems are
rarely, if ever, specific, and the liquors normally contain other
valueless metals such as calcium, magnesium, iron and aluminium.
The more valuable the metal to be recovered, the higher the relative
164
RECOVERY OF METALS BY COMPLEX ANION FORMATION
contamination of the solution is likely to be, simply because high

value permits the treatment of low grade ores. Having brought the
metal into dilute and highly contaminated solution, it is necessary
to develop a selective process for its recovery. In some cases, such
as that of gold, which is dissolved from the rock with sodium cyanide,
and precipitated selectively as metal by the use of zinc dust, the
task is technically simple. In others, a fairly complex series of
reactions may be required to isolate the product. This was the case
for uranium, in the years 1945-1950, when a world-wide search was
being made for new sources to supplement the very few known
deposits of high grade pitchblende. Many new ore-bodies were
found, in every part of the world, but without exception they were
of low grade, the uranium content rarely being as high as 0·5 per
cent, and normally less than 0·1 per cent. Extraction of uranium
from the ground ore by means of dilute sulphuric acid was almost
universally successful, but as the reactions of uranyl salts are similar
to those of ferric iron and aluminium, recovery of the uranium in
the form of high grade solid concentrates, by the use of simple and
economical reagents, was a difficult process. Gation exchange
systems were useless, as they removed all metals from solution
almost equally, differences in selectivity being insufficient to permit
separation by any simple system. The type of industrial chromato-
graphie separation discussed below in the case of the actinides is
completely impractical for the treatment of the enormous volumes
of low-grade solution arising daily in the uranium industry. A
possible method was to add to the solution some salt, with which
the uranium alone would form an anionic complex, thus permitting
it to be specifically absorbed by an anion exchange resin. Greatly
to the surprise of the early workers, it was found that the required
anion was already present in solution. It was, in fact, sulphate,
804 2-, with which the uranyl cation U022+ forms aseries of
anionic complexes U0 2 (804)n 2- 2n , ofwhich the mostimportantis
U02 (804)34-. 8tudies of the chemistry of uranyl salts carried out
intensively from 1945 onwards had given no hint ofthe existence of
this anion, which occurs only in minute traces in solution. The
reaction governing its formation:
is displaced strongly to the left in ordinary solution. Gontact with

anion exchange resins gives the further reaction:
4R+Gl- + U02 (804)34 - ~ R4 + U02 (804)34- + 4GI- .... (47)
165
The aflinity of this quadrivalent complex for resins is so high, that

equations 46 and 47 are both displaced almost completely to the
right, uranium in solution being reduced to an undetectable level.
Resin loadings are extremely high, in spite of the high relative
concentrations of 8042 - and H804-, which are present in the
leach liquors.
The only other metals forming anionic sulphate complexes, and
found to any significant extent in uranium leach liquors, are ferric
iron which is always present, and thorium which occurs in certain
Canadian ores. The nature of these complexes has not been
established, but they are clearly of lower valency than the
125
CI)
10
.-
-
.... .....--.--~ -- ---.-.-............
..........
,,.
'- ~
/
/
0 100
:J
.2" B
.
-10
"0 •
I
C <lI I
~.c 75
'-_ I
L.,;om
<li 0 I
E <lI
<lI Cl
I
I
.!: 2 ~ Iron
V
ce 50
.2 ~ I
;0
•I
<lI
.t;a.
c I
A/
<lI
u 25
c I
0
•
I
,.,
u I
0 800 1.600 2.400

Throughput gal / ft J
Figure 62. Absorption of uranium and iron
uranyl complex, and have much lower affinities for the resin.
Accordingly, while they are absorbed, together with uranium,
during the initialloading of a new colum, they are almost completely
displaced in the later stages. The effect, which is identical in
principle with the frontal development system used in chromato-
graphie analysis, is shown in Figure 62. In practice, two or more
columns are used for absorption so that the first is completely loaded,
and the iran displaced, before uranium breakthrough from the last.
166
The high affinity of the uranium complex for anion exchange

resins might suggest that it would be difficuIt to remove. In practice,
passage of any salt solution, other than sulphate, through the resin,
causes breakdown of the complex, the uranium being removed in
cationic form
R4 + U02 (S04)34- + 4Na+ + 4NOa ;;=e 4R+ NOa- +

4Na+ + U0 2+ + 3S04 2 2- •••• (48)
Re - used eluate New eluent Water

lr--------~~~~~~~
'0.----------------------------,80
N03
'"
C& 30 6° 0
,
--------~
- I
i! I (J)
"0 "0
C C
'" \ '"
Cf
-5
20
,, I t.nB
z
,
10
, \
\
20
Bed volumes effluent

IR~;~rnl To precipitation I Store tor re-use I
reprocessing
Figure 63. Elution of uranium with molar nitrate solution ejJluent
A typical elution curve is shown in Figure 63. In practice, elution is

carried out fractionaIly, so as to reject the remaining ferric iron,
and to send a rich uranium solution for precipitation (Figure 64).
The process of precipitation was chosen so as to regenerate the
eluting solution for re-use. Thus in South Africa, where a large
explosives industry made ammonium nitrate the most convenient
eluent, the uranium was precipitated with ammonia, as a mixture of
uranyl hydroxide and ammonium diuranate of over 90 per cent
purity, the filtered ammonium nitrate solution returning to the
elution circuit. In other areas, where sodium chloride was the most
167
1st 2nd 1st 2nd 1st 2n d
PL
.·~··,::·:·:·i:::· ,::.~
[[j
LJ LtJ :'-;,Ii
w
....
~
C
U>
Stage 1 Stage 2 Stage 3 stage I. ~

w :;
..- t"'
g; 1st 2nd 1st 2nd 1st 2nd 1st 2nd ~
"C
:~ :
·:...-,
..
UlJ '
trH
ULJ t:
2
~
U>
P
80
Stage 6 Stage 7 Stage 8
PL : Pregna nt li quor w : W~t~ r tst : tst Elu ~ nt 2nd =2nd El u. nt P : Oull .t to p.. ci p , tallOn BD =8arr en discharge
Figure 64. Flow diagramfor a three-column ion-exchange uranium extraction plant

commonly used eluent, the precipitant was sodium hydroxide, the

filtrate of sodium chloride being re-acidified for re-use.
It is dear, of course, that in either case, the sulphates entering
the rich eluate by reaction 48 must remain in the solution after
recovery of uranium from it. As the concentration builds up, the
efficiency of elution decreases, due to reversal of reaction 48. The
difficulty is easily overcome by rejecting a proportion of the spent
eluate at each cyde, so as to bleed sulphate from the circuit.
Another ingenious method of overcoming the problem was first
used in the South Mrican mines. The absorption stage ofthe process
is deliberately opera ted at less than maximum efficiency, the run
being stopped before complete displacement ofiron from the leading
column, and the eluate fraction collecting being arranged so as not
to reject the ferric iron present. The precipitation process is then
arranged in two stages, the first with lime to pR 3·5, causing deposi-
tion of ferric hydroxide and an equivalent quantity of calcium
sulphate, and the second, to pR 8·0 to remove the uranium. The
recyded eluate/eluent is then maintained at a constant sulphate
concentration.
The uranium process became the largest single industrial applica-
tion of ion exchange resins in the world, the first plants, which were
fully automatie, being installed in South Africa in 1952, with others
following in every continent during the next 10 years. The early
plants all followed a common pattern, with either two or three
columns in series on the absorption cyde, while a third was under-
going fractional elution.
The last generation of plants, installed in the Blind River area
of Ontario, Canada, in 1957, was considerably more sophisticated.
The system, known as the Porter-Arden moving bed process* used
a number of banks of three 8 ft diameter absorption columns, each
completely filled with resin, and holding 450-500 ft 3 (13-14 m 3 ).
Aseparate column was provided for backwashing the resin, and a
single set of three elution columns served the whole unit. The
installation was opera ted automatically so that, as the leading
column of any one bank of three absorber columns became loaded,
flow was diverted temporarily to the two trailing columns. The
loaded resin in the first column was then transferred into the back-
wash tank, and the empty column was then refilled with fully
stripped resin from the leading column of the elution bank. The
flow system was then changed so that the new column became the
* Brit. Patent 831,206. R. R. Porter and T. V. Arden, 1956.

169
M
trail unit of its bank of three. After backwashing, the loaded resin
was transferred into a unit of the elution bank, which now became the
Pregnant
liquor
.
.
Vi
~ 'i
c: ~
~
:.
ID
.
"c:
13
~
...J
Adsorption Backwash Elution

"'c:
~ .
-c. No lset
! A ! B! C !Common
10G:l!CO! 0 !®
tank A
Cf)
!B !
I Ci)
C
t2:XI~
! Common
®
~o
No 2set ! !(1)!(2)(3)!~ @ (5) ! ! !
Figure 65. Porter-Arden moving bed process
trail column (Figure 65). The whole proeess opera ted eontinuously,
170
and in countercurrent fashion, the flow of uranium bearing

liquor being interrupted only momentarily, for valve changes, and
the resin moving in slugs throughout the circuit, from trail to
middle to lead absorber, through backwash, and then from trail to
middle to lead eluter.
These installations, which are stiIl in use, were thus the first
industrial examples of really large scale continuous ion exchange
processes. As the quantities of resin being moved at any one time
are very large, and the intervals between movements are about 3 h,
the Porter-Arden system can certainly not be considered fully
continuous by modern standards. Nevertheless, there is no funda-
mental difference in principle. Even the most modern continuous
plants are not truly continuous, since there are momentary inter-
ruptions to liquor flow, and the resin stiIl moves slugwise. The trend
is, however, to approach true continuity by reducing the size of
slugs and the interval between them.
Application to other Metals

The principle of the uranium recovery process can be applied to
any case in which the required metal forms an anionic complex,
while others do not. Thorium is obviously a possibility. The leach
liquors produced in the Blind River uranium mines, in Ontario,
Canada, contain thorium in similar quantities to uranium. During
the uranium recovery process, the thorium is absorbed by the resin,
and subsequently displaced at high concentration, in a pattern
similar to that shown for ferric ir on in Figure 62. The thorium
complex can then be absorbed from the uranium-free liquors,
using a further column of anion exchange resin. The loading is not
as high as is found for uranium, due to the lower affinity of the
thorium complex, but removal of the thorium from the column is
extremely easy, and the whole process is industrially practicable.
It was not, in fact, put into operation in the Blind River mines,
since liquid-liquid ion exchange (see below) , was found to give
somewhat better results.
Another promising case under study, but not yet in industrial
use, is that of molybdenum, which occurs in trace quantities in the
acid leach liquors at copper mines. It occurs as molybdate, which
is strongly absorbed by anion exchange resins, giving high loadings
and efficient separation from other metals.
Complex Formation in Concentrated Solutions

The formation of anonic complexes in dilute solution, as in the
171
case of uranium, is a fairly rare occurrence. Very many metals,

however, form anionic chloride or nitrate complexes in solutions
containing free acid varying from 1 to 10M. The concentration of
acid favouring maximum complex formation is different for each
metal, and it is thus possible, in favourable cases, to remove any one
metal selectively from a mixture, by adjusting the HCI concentra-
tion of the solution to the required level, and passing it through a
chloride form anion exchange resin. Outstanding work by Kraus
and his co-workers in the U.S.A. has provided information on which
large numbers of separations can be based. Many of these are used,
on a fairly small industrial scale, for such special purposes as the
separations required in the atomic energy industry. Processes of
considerable elegance have been developed, but they are outside the
scope ofthis book, and the interested reader is referred to the review
papers listed at the end of the chapter.
ELUTION CHROMATOGRAPHY
In the laboratory, elution chromatography is probably the most
widely used ion exchange process. It is applied to the separation of
extremely similar metals, such as the lanthanides, or of similar
organic ions, such as the amino acids. The principle is simple. A
tall narrow column of resin is set up, and a small sam pIe of the
mixture of ions to be separated is absorbed into the uppermost layer
of resin. A solution of some other ion, for example a mineral acid, is
then passed slowly into the column. The ions move slowly down-
wards, those with the lowest affinity for the resin travelling fastest,
and those with higher affinity being held back. They finally emerge
from the column as aseries of separate fractions. The separation
effect can often be accentuated by using as eluent a solution of a
complexing agent, such as citric acid, or E.D.T.A., whose affinities
for the various ions are different from those of the resin.
Another technique is gradient elution, in which the concentration
ofthe incoming eluent is gradually increased as the process proceeds.
By a suitable choice of column size, ftow-rate and eluting agent, it
is possible to make perfect separations of any metals, however
similar they may be. A typical case is that of the lanthanide metals
(rare earths) whose classical separation methods required a complex
and tedious series of counter-current crystallizations which required
months or even years to complete. Until a few years ago, pure
lanthanides were available commercially only on the gramme scale,
at extremely high prices.
Lanthanides are now produced industrially, on a large tonnage
172
ION EXCHANGE AS A MANUFACTURING PROCESS
scale, using a direct upscaling of the standard methods of elution

chromatography. The equipment is very large, one American plant
consisting of aseries of 175 columns, each 2 ft 6 in diameter and
20 ft taU. Separations are carried out on a similar scale in Finland,
which produces large quantities of pure lanthanides, for use as
phosphors for fluorescent lights and colour television tubes, and
for the production of special optical glasses.
The very large size of the resin columns required for separations
by elution chromatography is, of course, a disadvantage of the
process, which is thus confined to cases in which other methods of
purification are difficult or expensive. In industrial practice, the
method is at present used only for the two cases of the lanthanides
and actinides series of elements, whose large scale separation by
any other technique is virtuaUy impossible.
ION EXCHANGE AS A MANUFACTURING PROCESS

There are many cases in which ion exchange can be used as a
unit process in chemical manufacture, the following list giving
typical applications.
Streptomycin Recovery
Streptomycin is a cation with a high affinity for carboxylic
resins. The broth in which it is produced is filtered, and passed
through an acrylic type resin, which absorbs the antibiotic com-
pletely, together with some normal cations such as calcium. Re-
generation ofthe resin with acid, at 100 per cent efficiency pro duces
an almost neutral solution of streptomycin contaminated with cal-
cium chloride, etc. This solution is then demineralized by anormal
two-bedsystem, using a sulphonic resin, which absorbs simple ions, but
excludes the organic cation. A pure solution ofthe antibiotic results.
Silica Sol Production

A solution of commercial sodium silicate, diluted to the equivalent
of 3% w/v Si0 2 , is passed through a sulphonic resin in the
hydrogen form. The emergent liquor is silica sol, containing mineral
acid impurities arising from the original silicate solution. These are
removed by a weakly basic anion exchange resin, and a stable sol
results.
Manufacture of Organic Acids

Many industrially used organic acids, such as E.D.T.A. (ethylene
diamine tetracetic acid) are manufactured in the form of their
173
sodium salts, but may require to be used as the free acids. When, as
in the case of E.D.T.A, the free acid is insoluble, the conversion is
simple, consisting of mineral acid addition, followed by filtration.
When the free acid is soluble, as occurs with the various hydroxy-
modifications of E.D.T.A. used in industry, the conversion to free
acid is carried out by passing the sodium salt solution through a
hydrogen form resin.
Ion Exchange Resins as Catalysts

Very many organic compounds, e.g., esters, are manufactured
by processes using sulphuric acid, or alkali metal hydroxide cata-
lysts. Separation of the product from the catalyst normally requires
distillation, which may cause side reactions, or decomposition of
product due to increasing catalyst concentration. In these cases,
hydrogen or hydroxide form resins, used as catalysts, can be readily
separated from the reaction products by simple decantation or
filtration.
LIQUID-LIQUID ION EXCHANGE

In Chapter 2, it was shown that ion exchange is possible between
any two phases, provided that one ion can be locked into one phase.
While liquid-solid ion exchange has been the method universally
used, liquid-liquid ion exchange is possible, and is increasingly
being practised for special separations.
A liquid cation exchanger consists of a large organic molecule,
containing acidic groups associated with long chain paraffins or
other similar structures which render the whole molecule soluble in
solvents such as light kerosene and substantially insoluble in wateT.
A typical exchange compound is DNNS (dinonylnapthalene
sulphonic acid). Liquid anion exchangers are similar compounds,
containing amino groups, in place of acid groups, typical compounds
being TOA (tri-n-octylamine) and TLA (trilaurylamine). To
carry out the exchange process, the kerosene solution of the liquid
ion exchanger, and the aqueous solution containing the ion to be
exchanged are caused to ftow past each other under conditions
ensuring intimate contact. Continuous countercurrent columns
packed with Raschig rings, stirred or pulsating columns causing
fine droplet formation, or banks ofmixer-settler equipment arranged
in counterftow, are all used for this purpose.
The liquid-liquid ion exchange process is identical in principle
with the procedures described for the solid ion exchange resins. It
would thus apparently be possible to develop exchange systems
174
LIQUID-LIQUID ION EXCHANGE
suitable for softening or demineralizing water, with the great

advantage that fully continuous operation is extremely easy to
control in an all-liquid system. In practice, liquid ion exchange has
been applied only to the recovery, or separation of iairly valuable
metals, particularly in the atomic energy industry, since it has
certain limitations which militate against general use. The first is
that a given volume of kerosene solution of a liquid ion exchanger
has a lower active content than the same volume ofthe corresponding
ion exchange resin. The second, and more important disadvantage
is that the liquid ion exchange compounds, since they contain
hydrophylic groups, cannot be completely insoluble in water.
Although their partition coefficients are strongly in favour of thc
kerosene phase, there must always be a certain loss of a comparative-
ly expensive ion exchange compound into the aqueous phase.
The liquid ion exchangers are however, increasingly being used
for metal recovery processes, particularly those analogous to the
uranium recovery system using ion exchange resins. Uranium itself
is now recovered on the industrial scale both by solid and by liquid
ion exchange. The two processes are chemically almost identical,
and the choice between them is largely dependent on the concen-
tration of uranium in solution. A dilute liquor implies high solvent
losses per unit of uranium recovered, and the liquid process is
therefore less favourable than the solid. A rich liquor favours the
liquid process, by the same reasoning. The two systems complement
each other, and plants using both in conjunction have been operated
for some years.
The greatest advantage of the liquid ion exchange compounds
lies in their potentially large numbers. They are not crosslinked
polymers, of which only a limited range of types can be made, but
simple long chain molecules to which a wide variety of active groups
can be attached in many different ways. I t should therefore be
possible for compounds to be tailor-made to suit individual separa-
tion processes. Liquid exchangers are already widely used in the
atomic industry for separation and recovery purposes, and the
technique is likely to arouse increasing interest in future years.
175
BIBLIOGRAPHY
BOOKS
Water and its Treatment

1. Manual of British Water Engineering Practice. Institution of Water En-
gineers; London.
A detailed treatise on the origin, nature, examination and treatment
of water supplies, chiefty useful to waterworks chemists and engineers,
but including some notes on ion exchange methods.
2. The Examination rif Waters and Water Supplies. (Thresh, Beale and Suck-
ling) E. Windle-Taylor. J. A. Churchill; London.
All aspects ofwater analysis, with a small section on treatment.
3. Industrial Water Treatment Practice. Edited by P. Hamer, J. Jackson and
E. F. Thurston. Butterworths; London.
Full practical accounts of all aspects of water treatment, including a
chapter on ion exchange methods.
4. Water Treatment for Industrial and Other Uses. E. Nordei!. Rheinhold
Publishing Corp.; New York.
Comprehensive study including occurrence, nature of impurities, con-
ditioning and purification. Three chapters devoted to ion exchange
methods.
5. Water Treatment and Water Regime in Thermal Power Stations. M. S. Shkrob
and F. G. Prokhorov. State Power Engineering Publicity House;
Moscow.
(In Russian.) Comprehensive work on all aspects ofwater treatment for
power stations. Section on ion exchange methods includes plant dia-
grams and operating results.
6. Principles and Applications of Water Chemistry. Edited by S. D. Faust and
J. V. Hunter. John Wiley; New York.
Proceedings of the Fourth Rudolfs Research Conference at Rutgers
University, U.S.A.
Advanced papers and discussions on water chemistry.
7. Water Treatment Data. W. T. M. Boby and G. S. Solt. Hutchinson;
London.
A useful collection of tables and graphs giving information required for
water treatment calculations.
Ion Exchange. General

8. Ion Exchange Resins. J. A. Kitchener. Methuen; London.
A short and simple introduction to general theory and background,
with brief comments on applications. A good starting point for general
reading.
9. Ion Exchange Resins. L. Savidan. Dunod; Paris.
(In French.) Similar to 5.
176
BIBLIOGRAPHY
10. Ion Exchange. K. Dorfner. Gruyter & Co.; Berlin.

(In German.) Similar to 5 and 6, but rather more detailed.
11. Ion Exchange Resins. R. Kunin. Wiley; New York.
A comprehensive treatise, including theory, structure, Iaboratory
practice and industrial operation.
12. Ion Exchange. Edited by F. C. Nachod. Academic Press; New York.
Similar in type to 11, but with each section contributed by a specialist
author, and therefore giving more detail.
13. Ion Exchange. T. D. Ionescu. Editura Tehnica; Bucharest.
(In Roumanian.) A most useful general study, with detailed discussion
of special applications. A very comprehensive resin list is included.
Surprisingly easy for English readers, due to similarity of key technical
words.
14. Macromolecular Ion Exchange Compounds. K. M. Saldadze, A. B. Pashkov
and V. S. Titov. State Science Publishing House of Chemical Litera-
ture; Moscow.
(In Russian.) General textbook on resins and their uses, with a par-
ticularly wide international reference list.
15. Ion Exchange and the Exchangers. G. V. Austerweil. Gauthier-Villars;
Paris.
(In French.) General textbook of ion exchange practice, in water
treatment and industrial application.
16. Ion Exchangers and Their Use in Industry. R. Eeckelaers. Eyrolles; Paris.
(In French.) General textbook ofion exchange practice, in industry and
the laboratory.
Special Applications
17. Ion Exchangers in Organic and Biochemistry. Edited by C. Calmon and
T. R. E. Kressman. Interscience; London.
A general theoretical section, followed by aseries of specialist mono-
graphs by experts. The most complete work available in this field.
18. Ion Exchange Separation in Analytical Chemistry. O. Samuelson. John Wiley;
New York.
A necessary textbook for all analysts. Theory, practical techniques and
a wide range of examples.
19. Analytical Applications of Ion Exchange. J. Inczedy. Pergamon Press;
Oxford.
Covering the same ground as 18, but with many different examples.
20. Ion Exchange. A Laboratory Manual. J. E. Salmon and D. K. HaIe. Butter-
worths; London.
A short theoretical account, followed by descriptions of generallabora-
tory practice and details of individual experiments. Particularly useful
to students.
21. Ion Exchange in Chemistry and Food Technology. T. D. Ionescu. Editura
Tehnica; Bucharest.
(In Roumanian.) Theory and industrial practice in water treatment
and general industry, with full operating results. Particular reference to
food products such as sugar, glucose etc.
22. Ion Exchange Technology. Edited by F. C. Nachod and J. Schubert.
Academic Press; New York.
177
BIBLIOGRAPHY
Aseries of chapters by expert authors, including plant design and water

treatment, but particularly concerned with special industrial appIica-
tions of the types summarized in Chapter 8 of the present book.
Fundamental Properties of Resins

NOTE: Most of the books already listed include accounts of the struc-
ture, theory and fundamental properties of resins in their introductory
chapters. The following are devoted purely to these subjects.
23. Ion Exchange. F. Helfferich. McGraw-HiII; New York.
A detailed fundamental treatise for research workers.
24. Ion Exchange. Edited by J. Marinsky. Edward Arnold; London.
Nine advanced monographs on resin theory, structure and properties.
REVIEW PAPERS (Special Applications)

Ion Exchange Methods and their Applications to Metallurgical Problems.
C. B. Amphlett. Metall. Rev. 419 (1956).
Ion Exchange Processes in the Atomic Industry. T. V. Arden. Proc. Australas.
Inst. Min. Metall. 198, 153 (1961).
Solvent Extraction in Ore Proccssing (liquid-liquid ion exchange).
K. B. Brown and C. F. Coleman. Prog. nucl. Energy, Sero 3. 2 (1958)
Chap. 1-2. Pergamon Press.
Ion Exchange Resins as Catalysts. T. R. E. Kressman. Indust. Chemist.
36,3 (1960).
LITERATURE SURVEYS
Ion Exchange. Unit Operations Review. R. Kunin. Ind. Engng Chem. (Published
annuaIly).
A summary of published advances during each year.
Ion Exchange Survey
A list of all published papers on ion exchange, issued quarterly by
The Permutit Company Limited, Pemberton House, London Road,
Isleworth, Middlesex. Available on request.
EDUCATIONAL AIDS
Film Strip. Ion Exchange Resins. T. V. Arden and J. E. Salmon. Published
by Common Ground Ltd. for the Royal Institute of Chemistry.
Film strip and booklet giving material for three lectures.
Film. An Introduction to Ion Exchange.
16 mm, sound and colour (27 min). Available from The Permutit
Company Limited, Pemberton House, London Road, Isleworth,
Middlesex, on request.
Film. The Role of Ion Exchange.
16 mm, sound and colour (25 min). Available from Lennig Chemicals
Ltd., 26-28 Bedford Row, London, W.C.l, on request.
178
CONVERSION FACTORS
Length
1 in 0·0254 m (2·54 cm) 1m = 39·4 in
(1 inch)
1ft 0·305 m (30·5 cm) 1m 3·28 ft
Area
1 in 2 6·45 cm 2 1 cm 2 0·155 in 2
1 ft 2 0·0929 m 2 1 m2 = 10·76 ft 2
Volume
1 in3 = 16·4 cm3 11 = 61·1 in3
(0·01641)
1 ft3 = 28·3 1 11 = 0·0353 ft 3
1 ft 3 0·0283 m 3 1 m3 = 35·3 ft 3
1 gal 4·55 1 11 = 0·220 gal
1 gal 0·00455 m 3 1 m3 = 220 gal
1 U.S. gal 3·79 1 11 = 0·264 U.S. gal
1 U.S. gal 0·00379 m 3 1 m3 = 264 U.S. gal
1 gal 1·201 U.S. gal 1 U.S. gal = 0·834 gal
1 ft3 6·23 gal
1 ft3 7·48 U.S. gal
Weight
I1b 0·454 kg 1 kg 2·205 Ib
1 ton 1-016 metric ton 1 metric ton = 0·984 ton
1 short ton = 0·907 metric ton 1 metric ton = 1-102 sh. ton
(U.S.A.)
I1b = 7,000 grains (gr) (7 kilograins, or kgr)
Igr = 0·065 g 1g = 15·4 gr
Density
1 ft3 water = 62·3 Ib = 28·3 kg
1 gal water = 10·0 Ib 4·54 kg
1 U .S. gal = 8·23 Ib = 3·79 kg
water
11 = 2·205 Ib = 1·0 kg
1 m3 = 220·5 Ib = 1,000 kg
0·984 ton = 1 metric
ton
= 1· 102 short tons
Concentrations
1 grjgal = 14·3 mgjl 1 mgjl 0·0703 grjgal
(14·3 p.p.m.)
1 grj = 17·1 mgjl 1 mgjl 0·0584gr jU .S.gal
U.S. gal (17·1 p.p.m.)
179
CONVERSION FACTORS
Concentration---continued
Ilb/ft3 = 16·0 g/l 1 g/l 0·0625 Ib/ft3
1 kgr/ft3 = 2·28 g/l 1 g/l 0·438 kgr/ft3
Chemical equivalents
Ilb as 9·08 g.equiv. 1 g.equiv. 0·11 lb as
CaC03 CaC03
1 kgr as 1·3 g.equiv. 1 g.equiv. 0·77 kgr as
CaC0 3 CaC0 3
1 IbJft3 as 0·32 g.equiv./l 1 g.equiv./l 3·12 kgrJft3 as
CaC03 CaC03
1 kgr/ft3 as 0·0457 g.equiv./l 1 g.equiv./l = 21·9 kgr/ft3 as
CaCOa CaC0 3
1 gr/gal as 0·286 mg.equiv./l 1 mg. = 35·0 grJgal as
CaCOa equiv./l CaC0 3
Flow rate
1 gal ft- 2 min- 1 = 2·94 m 3 m- 2 h- 1 * 1 m 3 m-2 h-1 =
0·341 gal ft- 2 min-1
1 D.S.galft- 2 min- 1 = 2'45m3 m- 2 h- l * 1 m 3 m-2 h- 1 =
0·408 D.S. gal ft- 2 min-1
1 gal ft- 3 min- 1 9·6 m 3 m-3 h- 1 1 m 3 m-3 h- 1 =

0·104 gal ft- 1 min- 1
1 D.S. galft-3 min-1 8·0 m 3 m- 3 h- 1 1 m 3 m-3 h- 1 =
0·125 D.S. gal ft- 3 min- 1
*In an open pipe or vessel, Im 3 m- 2 h- l is a linear velocity of 1 m/h, and this term
is commonly used. In an ion exchange resin bed, the beads occupy approximately
60 per cent of the bed volume, and the average linear velocity through the 40 per
cent voids volume is correspondingly 2·5 times that in the open vessel. Nevertheless,
many papers have been published, quoting flow through a resin bed in m/h, when
the text shows that the linear flow above, and not in, the bed is intended. To avoid
confusion, the term m 3m- 2h- 1 is preferred.
180
INDEX
Absorption time, 45, 60 Calcium
Acid absorption, 39, 67, 71 phosphate, 154
Acid injection, 125 stearate,5
Acidity reduction in wine, 157 sulphate, 148
Activity coefficient, 15 Candle filters, 138
ADAMS and HOLMES, 21 Capacity correction for sodium, 53
Affination, 154 Capacity
Affinity, 17,26,35,60 1055, 52, 96
Air mix, 116, 120 polyamine resins, 68
Alkali metal competition, 52 strongly basic resins, 73
Alkaline degreasing, 158 sulphonic resins, 50, 64
Alum, 95 tertiary amine resins, 70
Aluminosilicate, 19 time relationship, 45, 50, 57, 68
Amberlite weakly acidic resins, 57
IR-120,21 Carbon columns, 160
IRA-68,141 Carbonation, 154
IRA-93, 69, 109 Carboxylic resins, 23, 35, 56, 80, 86, 151
IRA-400,23 Catalysts, 100, 174
IRA-41O, 23, 85 Cation
IRA-900, 109 leakage, 40, 51, 61
IRA-904, 110 resin layer technique, 138
IRA-910, 109 Caustic embrittlement, 9
IRC-50, 23, 56 Central Electricity Generating Board,
IRC-84, 23, 36, 56, 141 12
Aminated polyvinyl chloride, 21, 143 Centre collecting systems, 118
Amination, 22 Ceramic tubes, 116
Amino acids, 154, 172 Chain entanglement, 100
Ammonium nitrate, 167 Chemical processing, 6
Anion exchange, 36, 164 Chemical Research Laboratory
Anodizing, 161 D.S.I.R., 99
Asahi process, 133 Chloride leakage, 83
Automatic fixed bed plant, 132 Chloromethylation, 22, 107
Autoregeneration process, 143 Chromates, 158
Avoidance of dilution, 152 Citric acid, 172
Classical demineralizing, 82
Cleaning poisoned resins, 98
Backwashing, 124, 170 Coagulation, 95, 111
Base exchange softening, 49, 80 Co-flow operation, 62
Bed depths, 114 Coil boilers, 11
Bed separation, 152 Colloidal organic matter, 95
Beet sugar, 155 Combination processes, 80
Benson boilers, 137 Complex anion formation, 164
Bitumen enamelled steel, 119 Complex formation, 171
Blowdown,9, 137 Concentration gradient, 44
Boiler feed water, 7 Concrete fillings, 115
Bottlenecks, 104 Condensate polishing, 135, 138
Bottle washing, 5 Condenserleakage, 136
Bottom collecting systems, 114 Conductivity monitor, 131
Bottom plate, 118 Continuous ion exchange, 125, 171
Brackish waters, 4, 140, 142 Conversion from anion to cation
Breakthrough point, 44 exchange sites, 105
Buried top collector system, 124 Copolymerization, 21, 104
181
INDEX
Copper plating, 158 Entanglement, 100

Corrosion, 5, 8, 136 Equilibrium, 15, 26
Countercurrent crystallization, 155, 172 Excessively crosslinked regions, 104
Counterflow techniques, 49, 71, 120 Exchange rates, 42
Crosslinked polystyrene, 21 Exchange zone, 126
Crosslinking, 32, 99
Cyde times, 42, 69 Fatty acids, 154
Cyanides, 158 Ferric iron, 32
Ferric sulphate, 95
D' ALELIO, 21 Fibreglass construction, 119
Damage to resins, 98 Film diffusion, 43
De-Acidite Fixed carboxylate groups, 105
FF/IP, 23, 109 Flash distiIlation, 140
H/IP, 69, 109 Flavour ofwine, 156
K/MP,110 Flow rates, 42, 138
M/IP, 68 Fluorinated acids, 159
N/IP, 23, 85, 109 Free mineral acidity, 68
Decolorizing, 155 Friedel Crafts reaction, 107
Decreasing affinity coefficient, 29 Frontal development, 166
Deep weil waters, 92 Fulvic acids, 36, 93
Defecation, 154
Degradation of strong base resins, 74 GANS, 19
Degrees of hardness, 3 Gel filtration, 93
Demineralization of efHuent, 157 Gel structure, 25
Demineralizing, 9, 37, 61, 67, 75, 81 Gelatine, 151
Demineralizing solutions of organic Glucose, 151
compounds, 150 Glycerine, 154
Deposition, 85 Gold plating, 163
Desal process, 141 Gradient elution, 172
Diaphragm valves, 120 Green sand, 19
Dichromate, 162 Gypsum, 2, 67, 148
tests, 95 Hardness monitor, 131
Differential crosslinking, 106 Hardness slip, 51
Differential polymerization, 103 Hard water, 1
Difficulties. Due to iron, 54 Header pipes, 114
Dimethylamine, 22, 46, 109 Heterogeneous structures, 99
Dimethylethanolamine, 23, 75 Higgins contactor, 133
Dinonylnaphthalene. Sulphonic High flow rates, 138
acid, 174 High pressure boilers, 11, 135
Disentanglement, 101 Highly crosslinked sites, 104
Disposal ofregeneration efHuent, 161 Humic acids, 36, 93
Distortion of exchange/zone, 130 Hydrogen ion exchange, 32, 35, 55, 60
Divinyl benzene, 21, 99 Hydrolysis, 40, 117
Dowex Hydrosulphite,54
1,23 Hypochlorite, 98
2,23,85
SO,21 Industrial softeners, 49, 113
DUNCAN AND LISTER, 99 Industrial waters, 1
Inhomogeneous structures, 27, 99
Economic boilers, 9 Inlet systeIns, 118
E.D.T.A., 172 Interface, 78
Electrical resistance, 145 Internal arrangement of ion exchange
Electrode effects, 147 unit, 113
Electrodialysis, 143 Ion exchange membranes, 143
Electrolytic processes, 144 Ionic concentration, 60
Electroplating, 157 Ionic size, 20, 33
Elution, 167 Iron and copper, 138
chromatography, 172 Isoporous resins, 155, 107
182
INDEX
Kastel C. 100, 23, 36, 56 Organic poisoning, 90, 94, 153
Kerosene,174 Organic traps, 155
Kinetics, 41 Overheating, 7, 161
Knotted regions, 104
KRAUS, 172 Packaged boilers, 10
Kubel test, 92 Packed beds, 122
KUNIN AND VASSILIOU, 141 Partial deInineralizing, 142
Particle diffusion, 45
Laboratory test work, 47 Peaty waters, 92
Lancashire boiler, 8 Perforated plate system, 122
Lanthanides, 172 Permanent hardness, 2
Lateral pipes, 114 Peroxide catalysts, 100
Laundering, 5 Phenalformaldehyde resins, 21
Leakage, 40, 51, 61, 83 Phosphatation, 154
LEIBKNECHT, 20 Phosphoric acid, 164
Lewatit Photographic solutions, 163
C.N.O. and C.N.P., 23, 36, 56 Pickling, 158
M.500 and M.600, 23 Pitchblende, 165
MP.60,69, 109 Plastic cloth, 116
MP.500, 109 Plastic pipes, 119
MP.6oo,85 Plating additives, 159
8.100,21 Polarization, 147
Limestone, 1 Polyacrylic resins, 56
Linear polystyrene, 21 Polyacrylonitrile, 23, 56
Liquid/Liquid ion exchange, 17, 171, Polyamine resins-capacity, 68
174 Polyamines, 46
Loosely crosslinked resins, 32 Polyethylene, 119
Polymethacrylic, 56
Macroporous macroreticular resins, Polymerization, 21, 103
24, 102, 106, 155 Polypropylene, 119
Manganese dioxide, 55 Pore sizes, 104
Manufacture of organic acids, 173 Porosity, 24
Mass action law, 15, 26, 33
Porous bottom plate, 117
bivalent ions, 28 Porter-Arden process, 169
Materials of construction, 119 Potassium hydrogen tartrate, 156
McBuRNEY, 21
Powdex process, 139
Mechanism of organic poisoning, 104 Precipitation in resin beds, 160
Membranes, 14, 143 Preferential ftow, 114
Metal recovery process, 175
'Pressbed' system, 123
Meta! finishing, 6, 157 Prevention of organic poisoning, 110
Methacrylic acid, 23 Priming, 8, 11
Methylene bridge crosslinking, 108 Process control, 130
Mirror silvering, 7
Pulsating columns, 174
Misconceptions, 2, 19, 24, 58, 61 Pyrolusite, 55
Mixed beds, 75,90,97, 115
Mixer settIer equipment, 174 Quaternary ammonium resin, 23, 37,
Molybdenum, 171 71
Moving bed process, 169
Natural organic acids, 95 Reaction rate, 46, 59
Nickel plating, 158 Reactivation, 164
Non-poisoning resins, 106 Recovery of water, 158
Refractometer, 153
O.A. test, 92 Regenerant distributor, 118
Osmotic dehydration, 66 Regeneration, 26
Operating capacity, 33 level, 50, 60, 68
Operating expense, 84 mixed beds, of, 77
Order of affinities, 37 strong base resins, of, 38
Organic poisoning of membranes, 148 time, 60
183
INDEX
REICHENBERG, 99 Sulphonated coal, 20, 55
Reliability, 128 Sulphonated polythene, 21, 143
Remote regeneration, 117 Sulphonic acid resins, 22, 32, 50 64,
Resin breakdown, 59, 131 151, 159
distribution, 129 Surface waters, 92
flow, 131 Sweetening-on, 152
skeleton, 18 Sweetening-off, 153
structure-effect of, 99 Swelling, 24, 28, 59, 152
transfer, 133
Re-swelling, 101 Tannin, 7
Reversibility, 17 Temperature, 154
Rinse quantity, 52 Temporary hardness, 2
Rinse times, 105 Tertiary amine resins, 47, 70, 151, 155
Rubber lining, 119 Tervalent chromium, 161
Running costs, 65, 140 Thin and thick waters, 3
Thiosulphate, 163
THOMPSON AND SPENCE, 19
SAC-DG--SBA, 82 Thorium, 32, 166, 171
SAC-DG--SBA-MB, 84 Three dimensional network, 100
SAC-DG--WBA-SBA, 88 Toluene, 101
SAC-WBA-DG, 82 Transistor manufacture, 7
SAC-WBA-DG--MB, 84 Trap columns, 110
SAC-WBA-MB-MB,88 Treated water quality, 34, 39, 120
Salt usage efficiency, 52 Trilaurylamine, 174
Sampling difficuIties, 159 Trimethylamine, 23
Scale, 6, 53 Tri-n-octylamine, 174
Sea-water Tube failures, 7
cooling, 136 Turbine blades, 137
desalting, 140 Two shift stations, 136
softening, 53 Typical waters, 4, 55
Seasonal variation of O.A., 94
Selectivity coefficient, 28
Short circuiting, 124 Units,3
Silica, 41, 83 Uranium recovery, 164
Silica sol, 173 Uranyl sulphate complex, 165
Silver, 163
Sintered metal, 116 Vapour generators, 11
Sintered structure, 102 Vinyl polymerization, 100
Sirotherm process, 142
Size of the hydrated ion, 27 WAC-DG--MB,86
Slip, 60 WAC-Na-DG,80
Sludge,8 WAC-SAC-DG--WBA-MB,86
Sodium Wavefront, 16, 43
Cyanide, 165 Water quality, 67
Silicate, 85 Water softening, 49
slip, 120 Water soluble organic compound, 150
Soft water, 2 Weak base resins, 39
Softening cyde, 29 Weakly acidic resins, 57
Softening of sugar juices, 156 Wool scouring, 5
Stabilization of wine, 156
Starvation base exchange, 9, 56 Zeo Karb
Starvation process, 55, 81, 86 216, 23, 36, 56, 58
Static film, 43 225,21
Steam generating boilers, 7 226,23,36, 56
Strainers, 115 Zeolite, 19
Streptomycin, 173 Zinc cyanide, 161
Strongly acidic resins, 37, 42 Zinc dust, 165
Sugar, 152 Zirconium phosphate, 21
184

T. v. Arden D.SC., PH.D., F.R.I.C., C.eng., M.I.M.M., P.a.I.W.E. (Auth.) - Water Purification by Ion Exchange-Springer US (1995)

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WATER PURIFICATION BY ION EXCHANGE

Fronlispiece. Polystyrene sulphonic acid calion exchange bead (Magnijicalion 10 x, reduced

T. V. ARDEN, D.Se., Ph.D., F.R.I.C., C.Eng.,

ISBN 978-1-4684-9038-1 ISBN 978-1-4684-9036-7 (eBook)

Suggested U.D.C. No. 541.183.12:628.16

2. THE ION EXCHANGE PROCESS 13

3. EQlJILIBRIA AND KINETICS, AS APPLIED TO

4. UNIT WATER TREATMENT PROCESSES 49

6. ORGANIC POISONING OF ANION EXCHANGE

7. EQUIPMENT AND SPECIAL PROCESSES 113

8. INDUSTRIAL APPLICATIONS 150

of ion exchange resins rarely publish their exact structures, or

from other types of rock, for example gypsum, CaS04.2H20, in

ions. Where a broad indication of total dissolved solids is required,

chloride solution of concentration O·OOlN, contains 23 p.p.m. Na+

TYPICAL WATERS AND THEIR USES

Table 1. Typical Waters

Considering in turn some of the main processes for which water

down for the treatment of these waters. The methods of achieving

LAUNDERING, WOOL SCOURING, BOTTLE

CHEMICAL PROCESSING, METAL FINISHING, ETC.

demineralizing, using a weak base anion resin (see Chapter 4) followed

BOILER FEED WATER

Steam Generating Boilers

(b) Decomposition of bicarbonate, with liberation of carbon

Steam space 41 ft3

in a fairly simple manner. The boiler was large in relation to its

This process of 'blowing down', simultaneously reduced the total

type of boiler, and much depends on the conditions of use. If there

High Pressure Boilers

THE ION EXCHANGE PROCESS

Na+CI- + Ag+N03- = Na+N03- + Ag+CI- {, .... (1)

Na+CI- + Li+NO- 3 =I- Na+N0 3- + Li+CI- .... (2)

Na+ + CI- + Ag+ + N03- = Na+ + N0 3- + Ag+CI- {, ... (3)

(a) Two phases.

in an electric are, are not theoretically impossible, but have no

[Na+]R represents the concentration ofsodium ions in the right-hand

If the sodium chloride solution continues to flow, then at the

Figure 3. Breakthrough curve

therefore it has in theory no finite length. In practice, the length is

properties which will be considered later. Exactly the same pair of

This method of operating the ion exchange process is of compara-

OH- for anion exchange materials. The cation exchange resin is

surrounded by a membrane through which only anions can pass.

THE DEVELOPMENT OF ION EXCHANGE RESINS

still in use. The synthetic alumino-silicates, however, had a con-

Styrene Linear polystyrene

Crossli nked polyslyrene

Calion exchange resin

hydrogen ion exchange process impossible. In 1934 two new types

Germany, and the second was the synthetic phenolformaldehyde type

50 per cent water in their structure, but are so insoluble that,there

The sulphonic acid cation exchange resins made by different

the hydrocarbon beads. The process is shown in Figure 6. When a

Irrespective of their method of manufacture, the ion exchange

swelling is related precisely to the crosslinking. When this is at the

essentially continuous gel structures, of greater or lesser solids

EQUILIBRIA AND KINETICS, AS APPLIED TO

While the reactions of ion exchange resins are all fundamentally

GENERAL CATION EXCHANGE

the resin are always directly proportional to their concentration

• Note: This statement is a simplification. Factors additional to hydrated ion size

customary to abandon the word 'constant', and refer to it as the