TECHNICAL REPORTS SERIES No.

78

Operation and Control

Of Ion-Exchange Processes

for Treatment

of Radioactive Wastes

INTERNATIONAL ATOMIC ENERGY AGENCY,VIENNA, 1967

 OPERATION AND CONTROL
OF ION-EXCHANGE PROCESSES
FOR T R E A T M E N T
OF RADIOACTIVE WASTES
 The following States are Members of the International A t o m i c Energy Agency:

AFGHANISTAN GERMANY, FEDERAL NIGERIA

ALBANIA REPUBLIC OF NORWAY
ALGERIA GHANA PAKISTAN
ARGENTINA GREECE PANAMA
AUSTRALIA GUATEMALA PARAGUAY
AUSTRIA HAITI PERU
BELGIUM HOLY SEE PHILIPPINES
BOLIVIA HUNGARY POLAND
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SOCIALIST REPUBLIC IRAQ SIERRA LEONE
CAMBODIA ISRAEL SINGAPORE
CAMEROON ITALY SOUTH AFRICA
CANADA IVORY COAST SPAIN
CEYLON JAMAICA SUDAN
CHILE JAPAN SWEDEN
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COLOMBIA KENYA SYRIAN ARAB REPUBLIC
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CYPRUS LIBYA REPUBLIC
CZECHOSLOVAK SOCIALIST LUXEMBOURG UNION OF SOVIET SOCIALIST
REPUBLIC MADAGASCAR REPUBLICS
DENMARK MALI UNITED ARAB REPUBLIC
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ECUADOR MONACO BRITAIN AND NORTHERN IRELAND
EL SALVADOR MOROCCO UNITED STATES OF AMERICA
ETHIOPIA NETHERLANDS URUGUAY
FINLAND NEW ZEALAND VENEZUELA
FRANCE NICARAGUA VIET-NAM
GABON YUGOSLAVIA

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IAEA held at United Nations Headquarters, New York; it entered into force on 29 July 1957, The
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© IAEA, 1967

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by writing to the International A t o m i c Energy Agency, Kamtner Ring 11, A - 1 0 1 0 Vienna I, Austria.

Printed by the IAEA in Austria

D e c e m b e r 1967
 TECHNICAL REPORTS SERIES No. 78

OPERATION AND CONTROL

OF ION-EXCHANGE PROCESSES
FOR TREATMENT
OF RADIOACTIVE WASTES

INTERNATIONAL ATOMIC ENERGY AGENCY

VIENNA, 1967
OPERATION AND CONTROL OF ION-EXCHANGE PROCESSES FOR TREATMENT OF RADIOACTIVE WASTES
(Technical Reports Series, No.78)

ABSTRACT. A manual dealing with the application of ion-exchange materials to the treatment of
radioactive wastes and reviewing the facilities currently using this method. This book is one of three commissioned
by the IAEA on the three principal methods of concentrating radioactive wastes and was prepared by Mr. L . A .
Emelity.
Contents: Introduction; Historical review related to removal of radioactivity; Principles of ion exchange;
Ion-exchange materials; Limitations of ion exchangers; Application o f ion exchange to waste processing;
Operational procedures and experiences; Costs of treatment by ion exchange; Appendix I - Producers of ex-
change materials; Appendix II - Conversions; Appendix III - Regeneration data: specific gravity - concen-
tration; Appendix IV - Glossary; Tables; References; Bibliography.
Available in English only.

(147 p p . , 1 6 x 2 4 c m , paper-bound, 31 figures)

(1967) Price: U S Í 3 . 0 0 ; £1.1.2

OPERATION AND CONTROL OF ION-EXCHANGE PROCESSES

FOR TREATMENT OF RADIOACTIVE WASTES
IAEA, VIENNA, 1967
STI/DOC/10/78
 FOREWORD

When facilities are planned for handling radioactive materials, one of

the many problems that a r i s e involves the disposal of l a r g e - v o l u m e l o w -
level wastes. The problem can be tackled by either of two methods: either
to 'concentrate and contain' or to 'dilute and disperse'. The choice of method
will be guided by the physical, economical, psychological and political
environment.

The designers of most m a j o r installations in the world have chosen to

concentrate and contain the w a s t e s , and the three principal techniques of
concentration are c h e m i c a l precipitation, evaporation and ion exchange.
Though these techniques are w e l l - e s t a b l i s h e d in the c h e m i c a l p r o c e s s i n g
industry, information on their application to the treatment of radioactive
w a s t e s is not readily a v a i l a b l e .
To improve this situation and to give developing Member States some
guidance on the solution of this waste-treatment problem, the International
A t o m i c E n e r g y A g e n c y has commissioned books on the three techniques.
This particular manual deals with ion exchange and has been compiled by
M r . L . A . E m e l i t y , of L o s A l a m o s Scientific L a b o r a t o r y , U n i v e r s i t y of
California, L o s A l a m o s , New Mexico, USA.
Although it is assumed that the basic process is familiar to the reader,
history and theory are very briefly mentioned. Ion-exchange materials, their
applicationto the treatment of radioactive wastes, and a review of facilities
at present using this method are the principal topics.
 CONTENTS

I. INTRODUCTION 1

II. HISTORICAL REVIEW R E L A T E D T O R E M O V A L OF

RADIOACTIVITY 4

II—1. Reactor s y s t e m s 4
II—2. Miscellaneous radioactive wastes 5

III. P R I N C I P L E S OF ION E X C H A N G E 8

III—1. General 8
III-2. C h a r a c t e r i s t i c s of ion-exchange materials 9
III—2. 1. Ion-exchange capacity 10
I I I - 2 . 2 . Sorption equilibria 10
III—2. 2 . 1 . General 10
I I I - 2 . 2 . 2 . Donnan membrane equilibrium 11
I I I - 2 . 3 . Swelling equilibrium 12
I I I - 2 . 4 . Ion-exchange equilibrium: selectivity 13
I I I - 2 . 5 . Kinetics 15
III-3. E l e c t r o d i a l y s i s - Ion-exchange membranes 16

IV. ION-EXCHANGE MATERIALS 19

IV-1. General 19
IV-2. Structure of ion exchangers 19
I V - 2 . 1 . General 19
I V - 2 . 2. Natural inorganic and organic materials 20
I V - 2 . 3. Synthetic inorganic and organic materials 22
IV-3. Synthesis of ion exchangers 26
I V - 3 . 1 . Inorganic ion exchangers 26
I V - 3 . 2. Organic ion exchangers 27
I V - 3 . 2 . 1 . Condensation polymers 27
I V - 3 . 2. 2. Addition polymers 29
IV-3.3. Ion-exchange membranes 31

V. LIMITATIONS O F ION EXCHANGERS 32

V-l. Limitations applicable to all ion exchangers 32

V-2. Limitations applicable to natural organic exchangers 33
V-3. Limitations applicable to natural inorganic exchangers 33
V-4. Limitations applicable to synthetic organic exchangers 34
V-5. Limitations applicable to synthetic inorganic exchangers 36
V - 5 . 1 . Limitations: synthetic zeolites 36
V - 5 . 2 . Limitations: inorganic chemical compounds 36
V-6. Limitations applicable to ion-exchange membranes 37
VI. A P P L I C A T I O N O F ION E X C H A N G E T O W A S T E PROCESSING .. 38

VI-1. General 38
VI-2. P r o c e s s i n g of reactor waters 39
VI-3. P r o c e s s i n g of radioactive wastes 40
V I - 3 . 1 . General 40
V I - 3 . 2 . Treatment methods: batch operation 41
V I - 3 . 3 . Treatment methods: column operation 41
VI-4. Design considerations in treatment of reactor waters 46
VI~5. Design considerations in treatment of general laboratory
and plant wastes 55
VI~6. Shielding requirements 60

VII. O P E R A T I O N A L P R O C E D U R E S AND E X P E R I E N C E S 64

V I I - 1 . General 64
VII-2. Operational procedures and experiences: treatment of
reactor waters 64
VII-3. Experiences in treatment of general plant and laboratory
wastes 66
VII-4. Transport of radioactive materials 76

VIII. C O S T S O F T R E A T M E N T B Y ION EXCHANGE 78

VIII-1. General 78
VIII-2. Capital costs 79
VIII-3. Operating costs 80

APPENDICES I - I V

I. P R O D U C E R S OF E X C H A N G E M A T E R I A L S 85
II. CONVERSIONS 86
III. R E G E N E R A T I O N D A T A : S P E C I F I C G R A V I T Y -
CONCENTRATION 95
IV. G L O S S A R Y 97

TABLES I-XXVII

I. Main components of the radioactivity of reactor coolant

water circuits 99
II. E a r l y r e a c t o r s utilizing ion-exchange demineralization 100
III. Distribution coefficient of caesium on Decalso
as a function of sodium concentration 101
IV. Approximate ion-exchange selectivity coefficients 102
V. Relative affinities of ions for a strong-acid resin with
varying percentages of crosslinking 103
VI. Comparison of observed selectivity coefficients
with values calculated by M y e r s & Boyd 104
VII. Dependence of ion-exchange rate on experimental control .. 105
VIII. Relative ion-exchange rates 106
IX. Variation of resin capacity and moisture content with
degree of crosslinking 107
X. Synthetic cation exchangers 108
XI. Natural cation exchangers 116
XII. Synthetic anion exchangers 118
XIII. Mixed bed ion-exchange resins 125
XIV. Ion-exchange membranes 126
XV. Coolant purification in certain early USA power reactors ... 128
XVI. Ion-exchange capacity at varying régénérant l e v e l s 129
XVII. E f f e c t of feed rate and temperature on pressure drop 129
XVIII. Resin depth - Ion-exchange column 130
XIX. Principal radionuclides in general waste solutions 131
XX. Exchangers in use for separation of specific
radionuclides 132
XXI. R e s e a r c h reactors using ion-exchange water treatment 133
XXII. Ion-exchange treatment of power reactor waters 134
XXIII. Ion exchange in waste treatment at nuclear energy
establishments 135
XXIV. C l a s s i f i c a t i o n of nuclides for transport purposes 136
XXV. A v e r a g e p r i c e s of common engineering materials,
October 1966, USA 137
XXVI. Unit operating cost: waste treatment by ion exchange 138
XXVII. Annual operating costs: waste treatment by ion exchange ... 139

REFERENCES 141

BIBLIOGRAPHY 144
 I. INTRODUCTION

With the rapidly expanding study and use of nuclear energy by an in-
creasing number of nations, the problems of control of the radioactive
waste products become more acute. Technological advances adapting
nuclear physics discoveries to practical applications have followed such
d i s c o v e r i e s by only brief intervals; quantities and varieties of radioactive
wastes have increased at a rate in e x c e s s of the development of control
technology.
Under the pressure of exceedingly limited time, the m a j o r effort in
attacking the problem has been directed toward adaptation of known
techniques in chemical processing and water and wastewater treatment.
One of the more attractive methods, particularly from considerations
of efficiency and volume reduction, has been ion exchange. Radionuclides
are sorbed from waste flow streams by natural or artificial media at
decontamination factors exceeding 10 3 in some c a s e s . L a r g e v a r i e t i e s
of ion-exchange materials are available in different physical forms with
a wide range of capacities for prices varying by orders of magnitude.
Many nuclear energy installations throughout the world have included
ion-exchange techniques in their radioactive waste control programmes.
Selected advantages of materials and methods have often determined ion
exchange as the most economically feasible waste control tool.
Development of ion-exchange technology, relatively slow in its earlier
y e a r s , has almost paralleled the rapid advance of nuclear physics during
the last decade. Records indicate that the phenomenon of ion exchange,
though not recognized as such, served the e a r l i e r civilizations as f a r
back as Aristotle [1] in sand f i l t e r s used for purification of sea and
polluted waters. Little i s heard then until the writings of Sir F r a n c i s
Bacon who described purification by passage of salt water "drayned
through twenty v e s s e l s " . The clay of the pots apparently deionized the
water. Natural exchange was investigated in the early nineteenth century
by Sir Humphrey Davy, Lambuschini, Huxtable[2], Liebig [3],
Thompson [2], Graham, Esprit and Fuchs [3] . Most authorities agree,
however, that the English agriculturist Thompson [4] was the f i r s t to
actually recognize the 'base exchange' phenomenon and to publish de-
scriptions. He reported results of one of his studies to a consulting
chemist of the Royal Agricultural Society, J. Thomas Way, in 1848. The
study, in which calcium and ammonium ions were exchanged, was
thoroughly investigated by Way who reported his results to the Society
with these conclusions [5]:

(1) The exchange in soils of calcium and ammonium ions noted by

Thompson was v e r i f i e d .
(2) Exchange of ions in soils involved the exchange of equivalent quantities.
(3) Certain ions were more readily exchanged than others.
(4) The extent of the exchange increased with concentration, reaching
a 'levelling off' value.
(5) The temperature coefficient f o r the rate of exchange was lower than
that of a true chemical reaction.

1
(6) The aluminium silicates present in soils were responsible for the
exchange.
(7) Heat treatment destroyed the exchange properties of silicates.
(8) Exchange materials could be synthesized from soluble silicates and
alum.
(9) Exchange of ions differed from true physical adsorption.

Way's great contribution was investigated by many others, but it was

not until 1876 that the understanding of ion exchange was materially in-
c r e a s e d . At this time, Lemberg [6] reported on experiments which
demonstrated the stoichiometry and reversibility of the phenomenon.
Lemberg and later Wiegner [7] identified natural ion exchangers and
early efforts were made to utilize these materials in plant operations and
to synthesize similar substances.
Harm, a German chemist, attempted to employ ion exchange in 1896
for removing sodium and potassium from sugar beet juice in one of the
f i r s t commercial applications. Some y e a r s later, in 1903, Harm and
Rümpler[8] prepared the f i r s t synthetic industrial ion exchanger. Gans,
also a German, is, however, credited with the first s u c c e s s f u l l a r g e -
scale industrial application. His synthetic inorganic material, of the
Na 2 A l 2 S i 3 O 1 0 - Na+ type, was applied to water softening and sugar
treatment.
Many others in the early 1900's applied themselves to the study of
the nature of the ion-exchange properties of naturally occurring materials,
but significant advances in the understanding of the phenomena were not
made until the studies of c r y s t a l structures and the relationship of c r y s t a l
structure with ion exchange were conducted. The scientists reporting
on these aspects included Pauling [9], Bragg [10], Hendricks [ 1 1 ] ,
Grim [12], F a v e j e e [13], Bacon [14] and many others.
A serious limitation of the inorganic exchangers, sensitivity to acid,
kept r e s e a r c h e r s occupied investigating other materials. E a r l i e r work
had shown ion-exchange properties of humus and other natural organics.
Extension of these efforts led to the development of sulphonated coal
exchangers which were rugged and inexpensive.
In a m a j o r breakthrough, Adams and Holmes [15], English chemists,
noted in 1935 that certain synthetic resinous material, such as crushed
phonograph records, exhibited ion-exchange properties. Their discovery
led them to the f i r s t synthesis of stable, high-capacity sulphonic acid
cation exchangers and polyamine-type resin anion exchangers. Com-
m e r c i a l production and further improvement of synthetic resins is
credited to Holmes and I . G . Farbenindustrie of Germany.
Following World War II, development of the synthetic resins was
chiefly by companies in the United States and the United Kingdom. The
modern era might be said to have begun with the work and reports of
D ' A l e l i o , USA [16], who synthesized resins from preformed polystyrene.
These resins were the first in the great family of the high capacity,
chemically and mechanically stable polystyrene resins of today. The
science of 'tailor-making' resins of specific qualities for industrial
applications was begun and rapid expansion was inevitable. In fact,
synthesis of resins for innumerable applications progressed at a rate
greater than the advance in understanding of the phenomena. In 1950 [17],
however, with the synthesis of the ion-exchange membrane with all of its

2
possible technological applications, a clearer understanding of the kinetic
and electrochemical aspects of ion exchange was obtained.
The volume of literature regarding ion-exchange studies appearing
annually since the late I940's has increased tremendously, between 1950
and 1955 by a factor of 6 [18] . Few questions remain unanswered today.
Resins are selected for specific applications with accurately predictable
r e s u l t s . Ion exchange is now f i r m l y established as a unit chemical process,
a chemical engineering tool, on a par with such as evaporation, distil-
lation and precipitation.
This manual will attempt to acquaint the readers with the chemistry
and technology of ion exchange as it can and has been adapted for t r e a t -
ment of radioactive wastes. It is hoped that much of this goal can be
accomplished by r e f e r r a l to facilities presently in operation which utilize
ion-exchange methods. By review of the material herein it should be
possible to decide whether use of these phenomena is applicable to
problems at hand; whether sufficient space is available; whether man
power is adequately trained; and whether costs would be within the budget.
It is hoped that by careful study of the contents it might be possible to
design an ion-exchange waste processing plant for a specific need.
Subsidiary information to the main text of this manual is given in
Appendices I - I V .

3
 II. HISTORICAL REVIEW
R E L A T E D TO REMOVAL OF RADIOACTIVITY

II-1. R E A C T O R SYSTEMS

Advantages of the use of water as a reactor coolant and/or moderator

were recognized in the early phases of reactor design. These included:

Low cost
High specific heat
Low v i s c o s i t y
E a s e of pumping
Availability.

It was n e c e s s a r y , of course, that the water be of v e r y high purity -

in the order of 1 X 106 o h m - c m r e s i s t i v i t y . Impurities in coolant or
moderator would [19]:

(a) possibly become radioactive in passing through the core. Increased

l e v e l s of radioactivity in the system would reduce accessibility for
maintenance;
(b) have a deleterious effect on corrosion rates;
(c) increase radiolytic decomposition of the water;
(d) in certain reactors, tend to collect in the core or be transferred in
the steam to turbines.

To achieve and maintain the required degree of purity most economically,

demineralization by ion exchange was examined and found desirable.
Ion-exchange demineralization is applied to coolant and moderator
usually by continuous purification of a percentage of the total volume of
recirculating water. This is n e c e s s a r y for removal of corrosion and
decomposition products which are irradiated in the reactor. Table I
lists the principal nuclides of concern. There are others, of course,
when other construction materials are used.
To remove the impurities, synthetic organic resins in mixed bed
or dual bed s y s t e m s are generally provided. Exhausted resins are r e -
generated in place, transferred to separate regeneration facilities,
packaged for disposal or incinerated.
E a r l i e s t uses of ion exchange in reactor systems, as shown in
Table II, were for treatment of water in heavy and light water moderated
research r e a c t o r s .
In the flow diagram of F i g . 1 [20], typical location of ion-exchange
units in small secondary circuits is indicated. In F i g . 2 [20], use of p r e -
and post-filtration reduces problems of bed fouling and prevents release
of fine resin p a r t i c l e s . All pressurized water and boiling water re-
actors constructed through 1964 have employed ion exchange with f i l -
tration for purification of coolant water.
To eliminate the source of the problems directly related to the
resins, such as fine, soluble organic material and chloride contami-
nation, special 'nuclear grades' have been developed and are commercially

4
available. To overcome organic resin instability at high temperatures,
much work is being done to develop inorganic exchangers, such as the
zirconium derivates, for reactor coolant purification applications.

FIG.l. NRX reactor flow diagram. Use of ion-exchange purification.

BORAX - 3
REACTOR STEAM
SEPARATOR

F D--
I TURBINE I GENERATOR

'li
CIRCULATING
PUMP

FILTER COOLER
-D-fvwvwv-f - -jj—
—pi —
— ^. CONDENSER
ION
EXCHANGER
CONOENSATE
PUMP
FILTER

• MAKE-UP
FEEOWATER
TANK

t>
FIG.2. BORAX-3 flow diagram. Pre- and post-filtration at the demineralizer.

II-2. M I S C E L L A N E O U S R A D I O A C T I V E WASTES

The history of the use of ion exchange for treatment of laboratory,

processing plant and miscellaneous radioactive wastes is almost wholly

5
unrelated to its history of use for reactor coolant purification. The
problem is complicated by great variations in type of waste, by often
e x c e s s i v e solids concentrations, by pH control difficulties and by other
waste characteristics which tend to inflate the cost. One of the earliest
reports of studies of the use of ion exchange for laboratory wastes, by
A y e r s [21] in 1951, concluded that high decontamination factors could
be achieved at a reasonable cost with synthetic organic resins. This
work was closely followed by that at Argonne National Laboratory [22-24] .
Rodger, Fineman, Swope and Anderson reported on laboratory column
work and were instrumental in including ion exchange for l o w - l e v e l waste
treatment at Argonne. In this case, mixed bed strong-acid and strong-
base synthetic organic resins were used.
In 1956, a 1 - f t . diam. column containing a strong-acid cation resin
was placed in operation for removal of s 9 Sr and 90 Sr from an industrial
waste at L o s Alamos [25] . A second column with similar resin was added
shortly thereafter ( F i g . 3 ) , and in 1960, a much l a r g e r plant utilizing
identical methods replaced the older units. In 1963, a waste treatment
facility incorporating ferric hydroxide precipitation with the alternative
of further treatment by organic cation-exchange resins began processing
of wastes from additional areas at Los Alamos [26] . In all of the Los
Alamos ion-exchange experiences, resins are regenerated and spent
régénérant is chemically treated.

FIG.3. First cation resin exchange columns at Los Alamos Scientific Laboratory, Los Alamos, N . M . , USA.

Bolshakov et al.[27] reported at the Second United Nations Inter-

national Conference on the Peaceful Uses of Atomic Energy, Geneva,
1958 on the use of ion exchange following chemical treatment at a USSR

6
installation. In this case, two-stage treatment, cation exchange followed
by anion-cation-anion columns, was used. Again, resins were r e -
generated. In 1959 at Monaco, Yamamoto et al. [28] reported on the
JAERI facilities for l o w - l e v e l waste treatment. The 1956 plans for this
establishment provided two columns of strong acid-strong base synthetic
organic resins for purification of chemically treated waste. The columns
could be operated as mixed bed or two bed, in parallel or s e r i e s , and
with either column as the first unit in series operation.
In the United States of A m e r i c a , ion-exchange capacities of the
natural soils were studied at Brookhaven, Hanford, Idaho F a l l s , Oak
Ridge and Savannah River. Operating facilities relying to some extent
on this property of the soils were placed in operation with varying methods
as follows:

Hanford - crib disposal with absorption field

. Idaho F a l l s - deep wells
Oak Ridge - open pit seepage basins
Savannah R i v e r - open pit seepage basins

Dejonghe et al. [29] at the 1958 Geneva Conference reported on

studies of the use of ion-exchange properties of brown coal (lignite) in
various applications including columns, as precoat material, and as a
filtering l a y e r in a centrifuge. The brown coal has the apparent ad-
vantage of being easily incinerated upon exhaustion. At the same con-
ference, Burns and Glueckauf [30] described the Harwell system which
utilized exfoliated vermiculite for strontium and caesium ion removal
from chemical treatment plant effluent. Other natural materials such
as the clays, sawdust, peat, e t c . , have been investigated to achieve
lower costs.
At Oak Ridge, much research has been completed on the use of
phenolic carboxylic cation resin ion exchange for a l i m e - soda treatment
plant effluent [31]. At these same laboratories, the use of continuous
countercurrent solid-liquid contact units has been investigated and
recommended for certain applications in waste treatment [32] .
Newest approaches to the application of ion exchange for radioactive
waste treatment have been toward the development of synthetic inorganic
exchangers and the use of electrodialysis. Due to their stability at high
temperatures and to large doses of radiation, and their high selectivity
for cations of the alkali metals, certain salts of zirconium have been
investigated for application to waste treatment. The extensive studies
of Amphlett [33-35] and Kraus [36-38] were some of the f i r s t reported
works involving radionuclide separations with these materials.
Glueckauf and c o - w o r k e r s [39] at Harwell and Seal and Pecsok [40]
at Oak Ridge found electrodeionization to be of definite value in treat-
ment of radioactive wastes, particularly in conjunction with other methods.
Ito and Nishidoi [41] described use of a membrane electrodialyzer
following chemical treatment and preceding ion-exchange columns.
Advances in ion-exchange treatment of radioactive wastes have been
extensive. The brief history presented here does not begin to credit all
the notable work reported. Later sections of this text, however, will
attempt to indicate Other achievements.

7
 III. PRINCIPLES OF ION E X C H A N G E

III- 1. GENERAL

An attempt will be made in this section to provide a concise, consider-

ably simplified explanation of the theory and mechanism of ion exchange.
A s indicated in the foregoing discussion on the history of the phenomenon,
a wide v a r i e t y of substances have been shown to exhibit this property.
C l a y s , humus, coal, cellulose, lignin, phosphates, resins, protein and
living c e l l s are but a few of these m a t e r i a l s .
Ion exchange, as the name implies, i s m e r e l y the exchange of ions
that o c c u r s a c r o s s the boundary between a solid particle and a liquid.
When certain substances are dissolved in water, they become ionized. An
equal number of positively charged ions, cations, and negatively charged
ions, anions, are formed and the solutions conduct e l e c t r i c i t y . Such
substances are called e l e c t r o l y t e s . Dissolved e l e c t r o l y t e s , when in
contact with ion-exchanger solids, will exchange stoichiometrically
equivalent amounts of ions of the same sign. Ions from the solid migrate
from sites on the surface and even from the interior of the solid.
Materials which exchange cations with e l e c t r o l y t e s are known as cation
exchangers; those which exchange anions are called anion exchangers.
Certain substances, capable of exchanging both cations and anions, are
termed amphoteric ion exchangers. If it is assumed that R represents
the insoluble matrix of an exchanger, typical cation-exchange reactions
are:

2NaR + C a C l 2 (aq. ) S C a R 2 + 2NaCl (1)

2HR + 90 Sr(NO
3 ) 2 (aq. ) S 90 SrR
2 + 2HN0 3 (2)

T y p i c a l anion exchange reactions are:

2RC1 + Na 2 S0 4 (aq. ) S R 2 S0 4 + 2NaCl (3)

RC1 + Na 1 3 1 I (aq. ) й R 1 3 1 I + N a C l (4)

Equation (2) d e s c r i b e s the removal of 90 Sr from waste by ion exchange.

H + ions from the solid exchanger HR are replaced by 9<>Sr2+ ions from the
waste solution. Complete conversion of the HR to the ^ S r l ^ form can be
accomplished by treatment of a sufficient e x c e s s of the 90 Sr waste solution.
An exchanger in this state i s termed 'exhausted'. It can be 'regenerated',
however, to the original HR form by r e v e r s i n g the indicated reaction.
During regeneration, the concentrated 90Sr(NC>3)2 solution can be recovered
for disposal as such or for further treatment by other means.
Ion exchange i s often termed a 'sorption' p r o c e s s since in both ad- and
absorption a solute becomes attached to a solid. In true sorption, however,
e l e c t r o l y t e s and n o n - e l e c t r o l y t e s are collected with no r e l e a s e or exchange
taking place. The ion-exchange p r o c e s s i s stroichiometric. E v e r y ion

8
removed from solution is replaced by an equivalent amount of other ion of
the same sign.
To illustrate simply the phenomenon of ion exchange, a sponge may be
used as a model of an exchanger. The sponge itself represents the f r a m e -
work held together by chemical bonds of lattice energy and c a r r y i n g a
surplus positive or negative charge. To achieve the required electro -
neutrality, assume the pore spaces are filled with a sufficient number of
mobile or counter ions of charge opposite that of the framework. When
the sponge is placed into a solution, the counter ions may float out of the
pore « p a c e s . However, no counter ion may leave unless a stoichiometri-
cally equivalent number of ions of identical sign from the solution float into
the pore spaces to p r e s e r v e the electroneutrality. The number of counter
ions available for this exchange, according to this model, is termed the
ion-exchange capacity.
If the sponge is permitted to remain in the solution until all exchange
c e a s e s , a state of ion-exchange equilibrium is reached. At this time,
exchanger counter ions and solution ions will be found both in the sponge
pore spaces and in the solution. A f t e r the sponge has been placed in
various solutions, solvent in the pore spaces may cause an increase in
size of the framework, or a swelling.
When the sponge is placed in the solution, it may be noted that the
counter ions exchange more readily with certain solution ions than with
others. This ability of the exchanger to distinguish between the various
solution ions is labelled ' s e l e c t i v i t y ' and is influenced by solution ion size,
valence and other interactions with the environment.
With ion-exchange membranes, s e v e r a l other aspects must be con-
sidered. Two solutions are involved and almost any ion-exchange material
used as a separating wall between the solutions has been broadly termed
a membrane. C o m m e r c i a l materials, however, are generally strong,
durable sheets, film, foil, ribbons or discs. The membranes are
'permselective', i. e. they permit passage of one species of ion while
prohibiting passage of others. Cation-permeable membranes will pass
cations and exclude anions while anion-permeable membranes will perform
the r e v e r s e .
Ion-exchange membranes have found greatest application in electro-
chemical p r o c e s s e s where they improve efficiency by permitting migration
of cations and anions to the respective electrodes only. They also prevent
diffusion of products formed at each electrode.
This, very briefly, i s a description of ion exchange. An attempt will
be made in the following pages to elaborate on the nature of the p r o c e s s
with particular regard to use in treatment of radioactive waste.

Ill-2. C H A R A C T E R I S T I C S OF I O N - E X C H A N G E M A T E R I A L S

It has been determined to this point that ion exchangers are virtually
insoluble materials with a framework held together by chemical bonds or
lattice energy. The framework is charged by a positive or negative
electric charge and electroneutrality is maintained by counter ions of the
opposite sign. When placed in a solution of an electrolyte, the counter
ions are free to exchange positions with electrolyte ions of the same sign.
In the following paragraphs, the factors influencing this exchange will be
discussed.

9
III-2.1. Ion-exchange capacity

Elementary as the term capacity may seem, it is often misused due

to a lack of appreciation of the number of exchange values it can represent.
When capacity is stated, total exchange capacity of a material is the value
intended. However, it is often misunderstood as apparent capacity,
breakthrough or operating capacity, sorption capacity, etc. Capacity or
total exchange capacity is equal to the number of fixed ionic sites, the
magnitude of the framework charge, that can enter into an ion-exchange
reaction. This value i s a constant for a particular exchange material. On
the weight basis, it is expressed as milliequivalents per gram. This
r e f e r s to dry exchanger in the H + o r C l ~ f o r m . It is n e c e s s a r y to indicate
the reference state since the weight will vary with the nature of the ions
initially saturating the exchange sites. On a volume basis, capacity is
expressed as milliequivalents per millilitre. The total volume capacity of
resin r e f e r s to a settled bed of fully water-swollen resin in the N a + o r
С Г form for the strong-acid and strong-base and in the H + and f r e e - b a s e
form for the weakly acid and weak-base resins.
The capacities quoted in literature supplied by manufacturers of ion
exchangers are normally the total exchange capacities. However, in-
formation is also usually available on "operating or breakthrough" capa-
cities. These values are estimates based on experience and dependent
upon:

Ion to be removed from the electrolyte

Equipment design
Method of operation

N e c e s s a r y safety factor.

III-2.2. Sorption equilibria

III. 2. 2 . 1 . General
This section deals with sorption of electrolytes and non-electrolytes.
Ion exchange would normally be involved but is excluded by assuming all
electrolyte ions are identical to exchanger counter ions. Sorption is a
term used to describe a condition in which both adsorption and absorption
reactions occur. Dissolved material is concentrated both on the surface
and in the pores. Ion-exchange materials are sorbents. When in a solution
of weak or non-electrolytes, sorption by ion exchangers is s i m i l a r to that
of nonionic adsorbents. In a solution of strong e l e c t r o l y t e s with
counter ions identical to exchanger counter ions, a sorption equilibrium
results due to the reaction with the strong electrolytes of the electrostatic
f o r c e s arising from the fixed ionic groups and the counter ions of the
exchanger.
Sorption equilibria are usually represented by curves drawn by plotting
concentration of solute in the solvent as a b s c i s s a and concentration of
solute in the exchanger as ordinate under equilibrium conditions. The
data for a curve are obtained at a constant temperature. These curves
are called sorption isotherms. The ratio of the co-ordinates of any point
on a sorption isotherm, that i s , the ratio of an ordinate value to an
a b s c i s s a value, is termed the distribution coefficient. By definition,

10
therefore, the distribution coefficient, is the ratio of the concentrations
of the solute in the sorbent or exchanger and the concentration in the
solution at equilibrium.
Many f o r c e s and interactions, determined by experimental methods,
have been found to affect the sorption of non-electrolytes. Solute ions
may form complexes or chelates with the counter ions of the exchanger.
Temperature variations may not only affect the state of the solute but also
the condition of the exchanger. Molecular size of solute and degree of
с ros s linking 1 of the exchanger will serve to determine the slope of the
sorption isotherm. A number of other controls have similar e f f e c t s and
general rules must be used to predict sorption equilibria for non-
electrolytes.
Sorption equilibria for electrolytes which have counter ions identical
to exchanger counter ions are controlled in a much more complex manner.
Electrostatic f o r c e s affect the sorption and can be studied for prediction of
equilibria. The concept of the 'Donnan potential' as discussed in
section III-2. 2. 2 is the basis for much of the theory regarding electrolyte
sorption.
Several of the controlling factors are:

Exchanger capacity
Degree of crosslinking
Concentration of the solution
Ionic valences
Ionic sizes
Swelling pressure
Sieve action
Interactions between the mobile ions
Solution temperature
Interactions between mobile and fixed ions in the exchanger.

A general rule states that exchangers tend to exclude strong electro-

lytes with counter ions identical to exchanger counter ions, the degree of
exclusion being controlled by the factors stated above. Exclusion is
favoured or enhanced by high exchange capacity, low solution concentration,
high degree of crosslinking, low valence of the counter ions and high
valence of ions of sign identical to the framework sign (known as co-ions).

III-2.2.2. Donnan membrane equilibrium

Ion exchange has been described as a special case of the Donnan

membrane theory [42] . When an ion exchanger is immersed in a solution
of an electrolyte, the exchanger-solution interface may be described as a
membrane. When the product of diffusible ion concentrations on one
side of the membrane is equal to the product of the diffusible ion concen-
tration on the other side, equilibrium is attained according to the theory.
As an example, assume that the sodium form of a strong-acid ion ex-
changer i s immersed in a sodium chloride solution. A small amount of

' Degree of crosslinking = extent of interconnection of polymers in synthetic organic resin. (See
section IV for details.)

11
sodium chloride will diffuse into the exchanger, but the concentration of
sodium chloride in the exchanger will be less than that in the solution.
When equilibrium conditions are attained,

Na + (exchanger) X С Г (exchanger)

= Na + (solution) X С Г (solution)

since there is a high Na + concentration within the exchanger due to its

capacity.
When an electrolyte is sorbed from a solution by an exchanger, ions
of the same sign as the exchanger framework and ions of opposite sign,
co-ions and counter ions, are sorbed to maintain electroneutrality.
Another feature of the Donnan theory, the Donnan potential, is used to
explain control of sorption of co-ions. The Donnan potential, which is
dependent upon ionic concentrations and valences, is an electrostatic force
created by migration of ions through the membrane in both directions.
Equilibrium is eventually established in which action of the electric field
balances the tendency of ions to equalize concentration differences.
Donnan potentials are higher in the stronger, more crosslinked exchangers;
therefore, efficiency of exclusion of electrolyte from exchanger increases
with decrease in solution concentration and with increase in capacity and
degree of crosslinking.

III-2.3. Swelling equilibrium

The concept of swelling equilibrium will be reviewed to a limited

extent since an awareness of this exchanger characteristic is essential to
plant design. P r e s s u r e sufficient to burst a column develops as a resin
swells. On the other hand, shrinkage of resins can result in channelling
in a column.
When an ion exchanger is placed in a solution or solvent, aqueous or
non-aqueous, a certain amount of sorption of solvent occurs and the
exchanger expands or swells. If the exchanger is soluble in the particular
solvent, swelling continues until the exchanger is completely dissolved.
Normally, however, this is not the case and swelling continues only until
an equilibrium is attained. With resins, for example, polar and ionic
constituents tend to surround themselves with the solvent. The f r a m e -
work or matrix continues to yield and stretch until its elastic f o r c e s
balance the dissolution tendency.
The f o r c e s involved can be described as:

(1) Tendency of fixed and mobile ions to form solvation shells.

(2) Tendency of the interior of the exchanger to dilute itself. This
continues until interior and exterior osmotic f o r c e s balance. The osmotic
pressure difference or 1 swelling p r e s s u r e ' i s often large and may be
greater than 1000 atmospheres.
(3) Tendency of the framework to stretch as a result of the electrostatic
interactions between neighbouring fixed ionic groups.

12
 A large number of conditions affect the extent of the swelling of an
exchanger. B r i e f l y , swelling is favoured by the following [51 ]2:

Polar solvents
Low degree of crosslinking of the resin
High capacity of the resin
Strong solvation tendency of the fixed ionic groups
L a r g e and strongly solvated counter ions
Low valence of the counter ions
Complete dissociation in the resin
Low concentration of the external solution.

III-2.4. Ion-exchange equilibrium: selectivity

Ion-exchange reactions are true, r e v e r s i b l e equilibrium reactions.

At equilibrium, exchanger and electrolyte solution contain both the
exchanger counter ion and the electrolyte counter ion. The distribution
of these ions at equilibrium will be the same whether the reaction is
approached from either end. Assume the reactions are represented by
the following equations:

R Ex + El" 2 R E l + Ex" (anion) (5)

Ex R + E l + г E l R + E x + (cation) (6)

(R represents the ion exchanger, E l the electrolyte counter ion and Ex the
exchanger counter ion, )
Ion-exchange equilibrium can be conveniently expressed in t e r m s of
distribution coefficients as with sorption equilibrium. The s i m i l a r
definition for the distribution coefficient of a counter ion is the ratio of
concentrations of the counter ion in the exchanger and the solution at
equilibrium. Considering ions of various valences and simplifying on the
basis of trace concentrations of radioisotopes, an expression of this
equilibrium distribution coefficient, K j , may be stated as:

_ sorbed radioisotope/g of exchanger

d dissolved radioisotope/cm3 of solution

This equation is widely used in the study of mineral exchangers. In

Table III the decrease in K d for Cs on a synthetic mineral exchanger as
the sodium concentration of the solution is increased is illustrated.
F a c t o r s discussed later as affecting the selectivity coefficient also relate
directly to the distribution coefficient.
The favoured direction of either reaction (5) or (6) depends upon the
relative affinity of the ion-exchanger framework or matrix for the various
counter ions. This preference for one counter ion over the other also
results in a different concentration ratio of counter ions within the
exchanger from that in the electrolyte solution.

г From HELFFERICH, F., Ion Exchange, copyright (с) 1962. McGraw-Hill, Inc. Used by permission
of McGraw-Hill Book Co.

13
 Ion-exchange equilibrium can also be expressed in terms of a quantity as :

( (j
li'
Ex res

К -=¡- is the 1 selectivity coefficient 1 and •=T~ ) are the ratios

El irL and
üx/res
of the concentrations of counter ions in the solution (sol) and resin (res)
phases. The selectivity coefficient is not a constant but v a r i e s with
experimental conditions. Table IV provides a list of selectivity coefficients
for various ions when the resin phase contains equivalent amounts of the
two different counter ions.
Based on selectivity coefficients, Table V presents the relative
affinities of certain monovalent and divalent cations for a strong-acid
sulphonated styrene-divinylbenzene resin, Duolite C - 2 0 . The affinity for
the hydrogen ion was arbitrarily taken as one.
Selectivity coefficients can be calculated when the experimental
conditions are known. The variables involved include the swelling p r e s -
sure, the partial molar or molal volumes of ions in resins and solution
phases and the activity coefficients of the ions in the two phases. A l l of
this information is readily available or can be computed except the value
of the activity coefficient of the ions in the ion exchanger or resin phase.
This value can be determined by empirical methods as demonstrated by
Helfferich [45]. Methods used to this date, however, are not completely
satisfactory as is evidenced in Table VI. Comparison of the observed
and calculated values indicates the greatest disparity at high degrees of
crosslinking.
Determination of selectivity coefficients is an involved task and is
ordinarily not required in design of a waste treating s y s t e m . The co-
efficients can be taken from available literature, or, in most c a s e s ,
certain 'rules of thumb' which have evolved from laboratory e x e r c i s e s can
be adapted to problems at hand. These rules include [47] :

(1) At low concentrations (aqueous) and ordinary temperatures, the extent

of the exchange increases with increasing valency of the exchanging ion:

Na+ < Ca +2 < A l + 3 < Th +4

(2) At low concentrations (aqueous), ordinary temperatures and constant

valence, the extent of exchange i n c r e a s e s with increasing atomic number
of the exchanging ion:

Li < Na < К < C s ; Mg < Ca < Sr < Ba

(3) At high concentrations, the differences in the exchange 'potentials'

of ions of different valence (Na+ vs. Ca + 2 ) diminish, and, in some c a s e s ,
the ion of lower valence has the higher exchange potential.
(4) At high temperatures, in non-aqueous media, or at high concentrations,
the exchange potentials of ions of s i m i l a r valence do not increase with
increasing atomic number but are v e r y similar, or even d e c r e a s e .

14
 I
(5) The relative exchange potentials of various ions may be approximated
from their activity coefficients: the higher the activity coefficient, the
greater the exchange potential.
(6) The exchange potential of the hydrogen (hydronium, H 3 0 + ion) and
hydroxyl ions varies considerably with the nature of the functional group
and depends on the strength of the acid or base formed between the
functional group and either the hydroxyl or hydrogen ion. The stronger
the acid or base, the lower the exchange potential.
(7) Organic ions of high molecular weight and involved metallic anionic
complexes exhibit unusually high exchange potentials.
(8) As the degree of crosslinking or the fixed ion concentration of an
ion-exchange material is lowered, the exchange equilibrium constant
approaches unity.

Figure 4 graphically illustrates the variation in capacity with c r o s s -

linkage for certain Dow resins.

FIG.4. Typical resin capacities — effect of crosslinkage. (Reprinted from Dowex: Ion Exchange, with
permission of the Dow Chemical C o . , Midland, Mich., USA [48]).

III-2.5. Kinetics

When designing an ion-exchange processing system, it is desirable to

have an appreciation of the speed at which the reaction will occur.
Whether the necessary contact time is minutes or days will determine the
physical size of the plant.
The ion-exchange reaction occurring when a porous exchanger and
the solution of an electrolyte are in contact can be divided into five distinct
successive occurrences. These are: (1) diffusion of electrolyte ions to
the surface of the exchanger; (2) diffusion of the electrolyte ions through
the exchanger-solution interface or film into the structure of the exchanger;
(3) the exchange of ions; (4) diffusion of the exchanged ions from the
structure; (5) diffusion of the exchanged ions into the solution. Three of

15
these diffusional occurrences - in the solution, in the liquid interface or
film, within the structure of the solid exchanger - determine the kinetics
of ion exchange. The first process, diffusion in the solution, has little
effect on rate when the general porous exchangers and relatively dilute
solutions are considered. Solution strength, in fact, determines which of
the two remaining p r o c e s s e s will be the exchange rate controller. In very
dilute solutions, diffusion in the interface or film will control rate of
exchange. As the solution concentration is increased, both film diffusion
and diffusion in the structure determine rate. With continuing increase in
solution strength, a level is reached at which diffusion in the structure
(solid diffusion) alone is the rate-determining p r o c e s s . Though nature of
the exchanger and of the counter ions affect the concentration levels at
which the several diffusion p r o c e s s e s are rate-controlling, these levels
are generally taken as [49] :

conc < 0.00Ш (50 mg/1 as CaC0 3 ) - film diffusion

0.3N (15 000 mg/1) > conc > 0.001N - both film and solid
diffusion

conc > 0.3N - solid diffusion

Actual rates of ion exchange can v a r y from seconds to months and a

number of factors in addition to those mentioned above play important
roles. Exchanger particle size is one of these. It has been shown that
exchange rates increase with diminishing size of exchanger particle under
most conditions. Increasing temperatures have been found to increase
the rate of exchange. Table VII presents a summary of rate-controlling
factors and their e f f e c t s . Table VIII lists s e v e r a l resin exchange rates
with cations of increasing valence and crosslinkage.

III-3. E L E C T RODIA LYSIS - ION-EXCHANGE MEMBRANES

The process of electrodialysis is a combination of e l e c t r o l y s i s and

dialytic diffusion. Ion-exchange membranes are used to form the b a r r i e r s
which separate compartments containing various electrolyte solutions.
P a s s a g e of a current through the compartments at right angles to the flow
of the electrolyte causes the membranes to offer varying degrees of
resistance to passage of cations and anions. The most recently developed
membranes are permselective, e . g . cation-exchange membranes will
theoretically permit passage of cations only and anion-exchange membranes
theoretically permit passage of anions only. As ions migrate towards
cathode and anode as a result of the electric potential across a compart-
ment, they eventually encounter the membranes. If the fixed charges of
the membrane are opposite to the charge of the ion, the ion p a s s e s
through; if they are identical, the ion is repelled.
Single membrane c e l l s , either cationic or anionic, have been used to
separate certain ions to a relatively high degree, in the order of 95-99%.
In r e s e a r c h on the use of electrodialysis for waste treatment and in
desalination p r a c t i c e s , c e l l s containing a minimum of one cationic and
one anionic membrane are used in s e r i e s , in parallel and with various
recirculation s y s t e m s . Basic methods which have evolved from practice

16
include (1) series arrangement of individual cells, (2) s e r i e s arrangement
with c e l l s stacked - one set of electrodes, (3) parallel arrangement with
continuous feed, recirculation and product withdrawal, and (4) parallel
arrangement with recirculation, intermittent feed and intermittent
withdrawal of product. The perfection of the permselective membrane has
permitted use of a number of membranes, cation and anion, per cell in
alternate arrangement with one set of electrodes for the unit. Alternate
compartments are therefore brine and demineralizing p a s s a g e s .
Figure 5 is a simple illustration of a three-compartment c e l l .

CATHODE DEIONIZED ANODE

WATER

CATHOLYTE RINSE WASTE • ANOLYTE RINSE

CATION PERMEABLE MEMBRANE"1 SOLUTION - ANION PERMEABLE MEMBRANE

FIG. 5. Three-compartment electrodialysis cell.

Two unique properties of membranes are their e l e c t r i c a l conductivity

and their selectivity for ion transport. These values are used to describe
and compare c o m m e r c i a l synthetic membranes. Conductivity i s normally
stated in terms of its reciprocal, e l e c t r i c a l resistivity (ohm-cm 2 ). It is
determined in a standard test in which the membrane is immersed in a
given solution of electrolyte at a fixed distance from two electrodes.
Potential drop a c r o s s the electrodes is measured with the membrane in the
solution and with the membrane removed. The difference in potentials is
taken as the drop a c r o s s the membrane alone. Resistance is determined
by dividing the membrane potential drop by the current. Table XIV
indicates that the tests of cation-exchange membranes are
made in rather weak NaCl or KC1 solutions and that resistances v a r y , for
the membranes listed, from 1.5 to 15 ohm-cm 2 . The total resistance of
a given membrane is calculated by dividing its specific resistance
(ohm-cm 2 from the table) by the c r o s s - s e c t i o n a l area of the membrane
(cm 2 ) in a direction perpendicular to the flow of electric current. Thus a
membrane with a specific resistance of 2 o h m - c m 2 and an area of
100 cm 2 will have a total resistance of 0.02 ohm.
Membrane selectivity r e f e r s to its ability to pass ions of only one
charge. The property can be explained to some extent by the Donnan
equilibrium between the fixed ionic groups of the membrane matrix and
the mobile ionic groups of the solution wetting the membrane s u r f a c e s .
An indication of the selectivity is provided by the transport number.
This figure is defined as the ratio of the number of ions of a given sign
which pass through a membrane to the total number of ions of both signs
which are carried through. Thus, theoretically, the transport number for
a sulphonated polystyrene cation-exchange membrane should be 1.0 since
it should pass only cations. In all c a s e s , however, there is a certain
amount of leakage, and some anions will pass through cation p e r m s e l e c t i v e
membranes as will some cations pass through anion-exchange membranes.

17
 A s seen in Table XIV a, transport numbers for cation-
exchange membranes vary from 0.80 to 0.99 with most of them over 0.90.
These figures indicate that 80 to 99% of all ions passing through the
membrane, with the solutions as listed on either side, will be cations.
Feasibility of the use of electrodialysis for treatment of radioactive
waste solutions d e c r e a s e s as the conductivity (concentration of electrolyte)
of the waste solution d e c r e a s e s . Power requirements vary directly as
solution resistance. To extend the range of its use in this application,
low-conductivity problems can be overcome by filling the demineralization
(dialysate) compartments with mixed bed ion-exchange resins. The
conductivity of the dilute solution is then the conductivity of the resin
itself. A limitation is the onset of hydrolysis of the resin if exchangeable
ions are removed from it at a rate greater than their replacement by the
solution.
E l e c t r i c current densities in electrodialysis applications usually
v a r y from 6 to 20 milliamperes cm"2 for solutions containing up to
5000 ppm dissolved solids but have ranged to 80 milliamperes c m " 2
for more concentrated solutions. Without the use of the resin f i l l e r , it has
been found that electrodialysis is usually economical in those applications
where reduction of solids concentration to about 0.01N or 600 ppm NaCl
is acceptable.

18
 IV. ION-EXCHANGE MATERIALS

IV-1. GENERAL

A wide range of materials is available for the ion-exchange treatment of

wastes. Exchangers of many s i z e s , shapes and forms, of wide varying ca-
pacities, costs, and chemical, thermal and mechanical stabilities, of natural
or synthetic structure, and of inorganic or organic composition can be
obtained to meet the specifications for solution of a particular problem.
In this section, structure of various materials will be discussed; the
synthesis of many f o r m s , particularly those c o m m e r c i a l l y available,
will be outlined; and lists of exchangers, with specifications, will be
furnished. Certain materials, although c o m m e r c i a l l y available, will not
be considered. These include pharmaceutical ion-exchange gels, ion-
exchange celluloses, liquid exchangers and amphoteric exchangers.
Application of these materials to waste treatment is probably non-
existent.
•Nuclear grade 1 synthetic organic ion-exchange resins are c o m -
m e r c i a l l y available from a number of f i r m s . Developed for use in treat-
ment of reactor water, these v e r y high purity resins, low in heavy metal
and organic matter content, are specially conditioned by a combination
of cycling and solvent washing. To reduce the corrosiveness of the water,
the resins are available in various ionic f o r m s , enabling pH control. At
a certain pH value, attack of the metal surfaces in which the particular
water is in contact is minimal.

IV-2. S T R U C T U R E OF ION EXCHANGERS

IV-2.1. General

A structure s i m i l a r to the sponge model discussed in section III-1,

i . e . , a framework with surplus e l e c t r i c a l charge and mobile ions of
opposite sign sufficient to maintain electroneutrality, is possessed by
all types of ion exchangers. To have commercial value, however, the
exchanger must p o s s e s s certain additional features as [52]:

(a) A large surplus framework e l e c t r i c a l charge per unit weight or per

unit volume. This is the total exchange capacity and is expressed in
t e r m s of milliequivalents of exchangeable ion per gram of dry resin or
per m i l l i l i t r e of wet resin.
(b) The surplus framework charge must be a c c e s s i b l e to ions in solution.
This feature is an indication of the porosity of the exchanger.
(c) Exchanger pores must be of sufficient size to admit common ions
as H + , Na + , K + , Ca + , Mg + , OH", CI", NO", S0 4 = etc. in hydrated
form.
(d) The exchanger must be of material which is physically and chemically
durable over a wide range of conditions.

19
(e) The exchanger must be available in a useful f o r m . Optimum range
of particle size for the particle type of material has been found by oper-
ational use to be 0. 3 to 1 . 20 mm.

I V - 2 . 2. Natural inorganic and organic materials

An extremely large number of naturally occurring materials exhibit

the phenomenon of ion exchange. These include the following [52] :

Polysaccharides Proteins

A l g i c acid Casein
Carrageen Keratin (wool)
Cellulose Collagen
Corn starch Spongin
Flour
Paper
Pectin Humus in soil
Potato starch
Straw
Wood Lignites, coals

Minerals

Clays Zeolites

Attapulgite Analcite
Halloysite Chabazite
Kaoliriite Clinoptilolite
Illite Harmotome
Montmo rillonite Heulandite
Vermiculite Natrolite
Sodalite

Of the substances listed, only the zeolites meet most of the afore-
mentioned requirements for commercial exchangers and have been
marketed on a l a r g e s c a l e . Humus, lignites, coals, straw and wood
have been investigated thoroughly in certain areas for use in treatment of
radioactive waste. Relatively low exchange capacity is offset by low cost,
availability, and ease of incineration of spent m a t e r i a l s .
Zeolites are crystalline alumino-silicates belonging to the subclass
tektosilicate of the class silicate. The tektosilicates are silicates in
which the Si0 4 tetrahedra (arrangement of oxygen atoms at four corners
of a tetrahedron with silicon at the centre) share all corners (or oxygen
atoms) with other tetrahedra to present a three-dimensional network.
Substitution of A l + 3 for Si +4 requires the addition of other positive ions,
as Na + or C a + 2 , to p r e s e r v e electroneutrality. F o r zeolites, the ratio
( C a 0 + N a 2 0 ) : A 1 2 0 3 is always 1 : 1 and the (Al +Si) : О ratio is always 1 : 2 .
Figure 6 illustrates the typical three-dimensional network of the zeolite
silicon-oxygen tetrahedra.
The zeolite framework is open and wide-meshed with cavities
containing cations to balance the negative charge of the framework. Pore
s i z e s are v e r y uniform and rather small, providing a 'sieving' action

20
 ANGSTROM UNITS

FIG.6. Types of linkage of silicon-oxygen tetrahedra. Three-dimensional network. (Reprinted from

Berry, L.G., Mason, В., Mineralogy. Copyright © 1959 W.H. Freeman and Company, San Francisco,
Cal., USA.)

as m o b i l e ions are exchanged. L a r g e r ions a r e excluded f r o m exchange,

the m a x i m u m s i z e being dependent upon the p a r t i c u l a r z e o l i t e . The
z e o l i t e f r a m e w o r k (Si, A 1 ) 0 2 is held t o g e t h e r by strong bonds and is
v e r y r i g i d . Water m o l e c u l e s can be r e m o v e d without a f f e c t i n g the s t a b i l i t y
of the s t r u c t u r e . The name ' z e o l i t e ' , in f a c t , is derived from the Greek
and means 'to b o i l ' , r e f e r r i n g to the apparent boiling that o c c u r s when
t h e s e m i n e r a l s are heated and the water is r e l e a s e d .
Other natural i o n - e x c h a n g e m i n e r a l s are those c l a y c r y s t a l l i n e
a l u m i n o s i l i c a t e s of the s u b c l a s s ' p h y l l o s i l i c a t e s ' , f r o m the G r e e k
meaning ' l e a f ' o r ' s h e e t ' . In the lattice s t r u c t u r e of t h e s e e x c h a n g e r s ,
t h r e e o x y g e n s of each tetrahedron are shared with adjacent t e t r a h e d r a
to f o r m extended flat s h e e t s . Si: О ratio is 2 : 5 . This type structure is
common to all c l a y s and m i c a s and one of the chief c h a r a c t e r i s t i c s of the
t y p e is the p e r f e c t b a s a l c l e a v a g e p a r a l l e l to the plane of the sheet. The
sheet s t r u c t u r e is illustrated in F i g . 7. The p h y l l o s i l i c a t e s c a r r y their
m o b i l e ions between the l a y e r s of the l a t t i c e .
The ' t e t r a h e d r a l l a y e r ' , as the sheet f o r m e d by S i 0 4 t e t r a h e d r a is
c a l l e d , is c o m m o n l y joined by other s h e e t - l i k e groupings of cations
(normally aluminium, m a g n e s i u m or iron) in co-ordination with o x y g e n
and hydroxyl ions. T h e s e other s h e e t s are o c t a h e d r a l groupings of anions
around a cation centre with anions shared b y adjacent o c t a h e d r a . When
a m i n e r a l is composed of a t e t r a h e d r a l l a y e r and an o c t a h e d r a l l a y e r , it
is c l a s s i f i e d as having a t w o - l a y e r s t r u c t u r e , e . g . kaolinite, h a l l o y s i t e ,
antigorite. When an o c t a h e d r a l l a y e r is sandwiched between two t e t r a h e d r a l
l a y e r s , the structure is t e r m e d t h r e e - l a y e r , e . g . montmorillonite,
muscovite, talc, vermiculite. The p h y l l o s i l i c a t e s can s w e l l m o r e than
the t e k t o s i l i c a t e s but they are much l e s s r e s i s t a n t to m e c h a n i c a l b r e a k -
down.

21
 Many of the natural organic exchangers must be treated
chemically to improve stability before they are of much value as ion
exchangers. Treatment with solutions of certain metal salts, sodium
hydroxide or hydrochloric acid has been used to stabilize c o a l s .

7.15 д

AXIS

Ь AXIS

FIG. 7. Structure of kaolinite, Al 4 Si 4 O 10 (OH) 8 . A tetrahedtal sheet Si4Ol0 linked to octahedral A1 4 0 4 (OH) 8 .
(Reprinted from Berry. L . G . , Mason, B., Mineralogy. Copyright @ 1959 W.H. Freeman and Company,
San Francisco, Cal., USA.)

Sulphonation, however, has been found to be the most commercially i m -

portant treatment. Exchangers of sulphonated coal have been marketed
for many y e a r s . The sulphonation treatment works well with many sub-
stances, and in fact, almost any materials which will not dissolve in
sulphuric acid can be made into cation exchangers.
Tables XIa and Xlb list a number of natural exchangers with some
of their properties.

I V - 2 . 3 . Synthetic inorganic and organic materials

Among the f i r s t synthetic inorganic ion exchangers were those which

resembled the z e o l i t e s . These were improved through the y e a r s until
the present when the synthetic zeolites are exact counterparts of the
natural m i n e r a l s . Due to their ability to exclude l a r g e r molecules from
their uniform pore structures, they have been termed 'molecular s i e v e s ' .
Adjustment of pore size can to a certain extent be accomplished by
converting the exchanger to other ionic f o r m s . Some of the sieves avail-
able c o m m e r c i a l l y include:

Linde AW 400 synthetic erionite

Linde AW 500 synthetic chabazite
Linde AW 300 synthetic mordenite
Linde 13X synthetic faujasite
Linde 4A (no natural counterpart)
Norton Zeolon synthetic mordenite

22
The structure of the zeolites con-
sists of a rigid three-dimensional
framework of SiO, and AlO,
tetrahedra.

The Type A Molecular Sieve has

a framework composed of trun-
cated octahedra joined in a cubic
array.
This produces a central truncated
cube octahedron with an internal
cavity of 11 Â in diameter. Each
central cavity, termed the a
cage, is entered through 6 circu-
lar apertures formed by a nearly
regular ring of eight oxygen
atoms with a free diameter of
4.2Â. The cavities are thus ar-
ranged in a continuous three-
dimensional pattern forming a
system of unduloid-like channels
with a maximum diameter of FACE OF CUBIC ARRAY
11Â and a minimum of 4.2Â. TRUNCATED OCTAHEDRON OF TRUNCATED OCTAHEDRA
The truncated octrahedra them-
selves enclose a second set of
smaller cavities 6.6Â in internal
diameter (/3 cages) and con-
nected to the larger cavities by
means of a distorted ring oí six
oxygen atoms of 2.2Â free diam-
eter.

Model o f the s t r u c t u r e of zeolite

t y p e A based oil skeletal t e t r a h e d r a .

FIG.8. Molecular sieve structure. (From Linde Molecular Sieves brochure. Reprinted by permission of
Union Carbide Corp., Linde Div., New York, USA.)

23
 Figure 8 illustrates the structure of the Linde s i e v e s . In com-
m e r c i a l form, they are available as micro crystalline powders, as pellets
and as beads. The pellet form utilizes the m i c r o c r y s t a l s with porous
clay binder m a t e r i a l .
Many v e r y promising ion exchangers have been prepared from
zirconium phosphates. Tin, titanium and thorium compounds have shown
s i m i l a r promise. They are extremely insoluble, have high exchange
capacities and high rates of exchange. Probable structure of a zirconium
phosphate is [53] 3 :

OPOg = 0P0 3 -

I I
Zr - О - Zr - О

I I
OPOg = OPOg =

Materials of this type prepared to date have varied from granular precipi-
tates of small particle size to dried gels of much l a r g e r particle s i z e .
The largest group of exchangers available commercially today are
the synthetic organic resins. The framework of the resins is a flexible
random network of hydrocarbon chains. This framework, or matrix as it
is known, c a r r i e s fixed ionic charges, as - S O " , - C O O " in cation ex-
changers and -NH3+, in anion exchangers. The resins are made in-
soluble by crosslinks which interconnect the various hydrocarbon chains.
Degree of crosslinking determines mesh width of the framework or m a t r i x ,
swelling ability, movement of the mobile ions, hardness, and resistance to
attrition and mechanical break-down. Highly crosslinked resins are harder,
more resistant to attrition and break-down, l e s s porous and swell l e s s in
solvents. Addition polymerization in the formation of the vinyl group which
is included in many starting materials for present-day plastics can be
shown as

CH = CH2 CH

+ Peroxide
heat

Sty rene Linear polystyrene

Copolymerization with divinylbenzene (DVB) creates the crosslinked

matrix and degree of crosslinking is adjusted by varying the DVB content.

3 From HELFFERICH, F.,Ion Exchange, copyright (c) 1962 McGraw-Hill, Inc. Used by permission of

McGraw-Hill Book Co.

24
The reaction is shown as:

н е — с н 2 н с = с н 2

Styrene HC=CH2 CH - C H 9 - CH-

Divinylbenz ene

Resin
(Copolymer bead of styrene-
divinylbenz ene)

Nominal DVB content, expressed as a percentage, is used to indi-

cate degree of crosslinking. Thus a resin of 8% crosslinkage has a
nominal DVB content of 8% and a styrene and other monovinyl content
of 92%.
To create an exchanger, fixed ionic groups are introduced into
the resin by p r o c e s s e s such as sulphonation. Eight to ten - S 0 3 H groups
are added f o r every ten benzene rings. The H+ of the - S 0 3 H group then
becomes the mobile or counter ion. Neutralization by NaOH converts the
-SO3H groups to - S 0 3 N a groups with Na+ as the mobile ion.
In a much older process, resins were made by condensation r e -
actions. One of the earliest was a phenolformaldehyde-sodium sulphite
condensate which had the - C H 2 S 0 3 N a functional groups. An improved
resin was then prepared in which the -SOgH group was attached directly
to the phenol ring.
Condensation polymers, briefly, are the result of polycondensation
of p-substituted phenol with formaldehyde, addition of unsubstituted
phenol to provide a crosslinked polymer, and introduction of fixed ionic
groups. The most common condensation polymers are the strong-acid
resins with sulphonic acid (-SO3 ) groups and the weak-acid resins with
carboxylic acid ( - C O O - ) groups. Properties of the resins can be varied
widely by introducing other groups such as those of phosphonic, phos-
phinic, arsonic and selenonic acid for exchangers of other strengths.
C l o s e l y related to the synthetic organic resins are the rather recently
developed and now c o m m e r c i a l l y available ion-exchanger membranes.
The concentrated effort to develop economic desalination methods was
a primary cause for an intensive investigation of membranes. Success
in this field led to their use in waste treatment efforts, as in reduction
of total solids prior to ion exchange by standard resin columns.
A membrane is normally defined as a film or l a y e r with a v e r y large
surface area to thickness ratio. However, as applied to the ion-exchange

25
membrane, a much broader definition has been accepted. Geometrical
configuration has been deleted from the definition with the remaining
requirement being ion-exchange material which is used as a separation
wall between two solutions. Materials including cylindrical plugs, ribbons
and ion-exchange beads imbedded in binder are all used as membranes.
Ion-exchange membranes are classified as heterogeneous or homo-
geneous. The heterogeneous are those consisting of colloidal ion-
exchanger particles embedded in an inert organic such as polyethylene,
polystyrene, polyvinyl chloride, rubber, wax, etc. Homogeneous
membranes, usually in the form of discs, ribbons or sheets, are coherent
ion-exchanger gels made by condensation p r o c e s s e s . Most of the
c o m m e r c i a l membranes available are the homogeneous materials in
sheet form varying in thickness from 0.09 to 0.75 m m . Cation-exchange
membranes are usually in the Na+ form while the anion-exchange
membranes are most often in the Cl~ form.
A new membrane which seems to fit both heterogeneous and homo-
geneous classifications is the g r a f t - c o p o l y m e r type. Gamma irradiation
(cobalt-60 source) of polyethylene films impregnated with styrene or
s t y r e n e - D V B causes a grafting to the polyethylene b a s e . Sulphonation
or chloromethylation followed by amination produce strong-acid cation
exchangers or weak-base anion exchangers.
Membranes marketed by National Aluminate Corporation are termed
'interpolymer' since they are obtained by evaporation of a solution con-
taining a linear inert polymer and a linear polyelectrolyte. The film
formed is insoluble in aqueous solutions even though crosslinking has not
occurred.
The structure of miscellaneous other organic exchangers, as
celluloses, ion-exchange papers and liquid exchangers will not be d i s -
cussed due to their v e r y limited application to waste treatment.

IV-3. SYNTHESIS O F ION EXCHANGERS

The preparation or synthesis of inorganic and organic ion exchangers

will be discussed v e r y briefly since in most cases c o m m e r c i a l l y avail-
able materials would be used in a waste treatment f a c i l i t y .

I V - 3 . 1 . Inorganic ion exchangers

Many synthetic aluminosilicates have been prepared in the laboratory

by crystallization at relatively high temperatures from solutions con-
taining silica, alumina and alkali. Clinoptilolite-like materials have
been prepared from silica, alumina and lithium hydroxide with mole
ratios varying from ( S i 0 2 / A l 2 0 3 / L i 0 2 / H 2 0 ) 8/1/0. 6/8. 5 to 1 0 / 1 / 1 / 8 . 5
[54] . Temperatures ranged from 280°C to 300°C and pressures varied
from 625 to 1200 lb/in 2 . Zeolites analcite and mordenite are prepared
with Si: A l ratios of 2:1 for analcite and 6: 1 for mordenite, both at
275°C for a period of two to three days [55] . As stated previously, synthetic
zeolites of v e r y regular crystalline structure are available c o m m e r c i a l l y .
The high-capacity exchangers of the phosphate, arsenate, molybdate
and tungstate salts of zirconium, titanium, tin and thorium have been p r e -
pared by precipitation from the chloride f o r m . A ferrocyanide molybdate,

26
prepared by precipitation from a mixture of sodium molybdates (in
HC1 solution) and H 4 Fe(CN) 6 has a high selectivity for caesium [62] .
Cerium (IV) exchangers, with properties s i m i l a r to those of the
zirconium salts, were prepared from a gel formed by the mixing of
cerium (IV) in sulphuric acid and dilute phosphoric acid [56] . C o m -
m e r c i a l compounds of this type are now available from Bio-Rad
Laboratories, USA, and most recently SERAI, Belgium. A number of
these exchangers and their properties are listed in Table X.

I V - 3 . 2 . Organic ion exchangers

Strong-acid cation exchangers have for many years been prepared

by sulphonation of coals with fuming sulphuric acid. Treatment with nitric
or phosphoric acid has also been used to 'activate' the material. The coal
is 'gelified' and carboxylic acid groups are formed.
Sulphonation or phosphorylation are used to convert such unlikely
m a t e r i a l s as olive pits, nut shells and spent coffee grounds to ion
exchangers.
Sulphonated coals are available c o m m e r c i a l l y from IMACTI,
Netherlands and Jos. Crosfield, UK.
Synthesis of ion-exchange resins can be generally subdivided into
condensation polymerizations and addition polymerizations. The synthesis
must produce a three-dimensional crosslinked matrix of hydrocarbon
chains with fixed ionic groups. The fixed ionic groups can be introduced
while the polymerization is in progress or added later to the completed
matrix. The finished resin must be insoluble but capable of swelling to
a certain extent. This is controlled by establishing the degree of c r o s s -
linking. With crosslinking varying from minimum to maximum, solubility
ranges from soluble with extreme swelling to insoluble with no swelling
capability.
Condensation polymerizations are those in which molecules of
several different compounds combine to form a l a r g e r molecule, e l i m i -
nating a small molecule such as H 2 0 . The phenol-formaldehyde reaction
is an example. Addition polymerizations are those in which s e v e r a l
molecules of the same or similar compounds combine to form a large
molecule. These reactions also differ in that no small molecules are
eliminated in the addition polymerization and the total weight of the
product is the sum of the weight of all molecules used in the polymeri-
zation. The unsaturated organic compounds, those containing double or
triple bonds between carbon atoms, are polymerizable.
In the following discussion, synthesis of cation- and anion-exchange
resins by condensation and addition reactions will be covered separately.
Tables X a - c list commercially available cation-exchange resins
and Tables XIIa-d list the anion exchangers.

IV-3.2.1. Condensation polymers

Cation-exchange resins. The phenol-formaldehyde condensation

products, with the phenolic OH groups as the fixed ionic groups, have a
v e r y low acid strength. The simplest method to improve acid strength

27
is to introduce groups of higher acid strength as in sulphonation of the
phenol prior to polymerization. Phenolsulphonic acid resins are bi-
functional - both strong-acid, - S 0 3 " H + , groups and weak-acid, OH,
groups, are included.
When carboxylic groups, COOH, are the fixed ionic groups, weak-
acid resins are formed. Synthesis involves reaction of monomers as
s a l i c y l i c acid and 1, 3, 5 - r e s o r c y l i c acid. The resin has the form:

OH OH

When the fixed ionic groups are attached directly to aromatic rings,
as in the sulphonation of phenol with H 2 S 0 4 and addition of formaldehyde,
nuclear sulphonic resins were prepared. A similar resin results from
the alkaline condensation of phenolate, sodium sulphite and formaldehyde.
In the f i r s t case, the fixed ionic group is the "SOgNa while in the latter
c a s e , the fixed group is the methylene sulphonic acid, ( - C H S0 3 ~Na + ).
The C H 2 S 0 3 N a resins have a slightly weaker acidity but higher thermal
stability than the phenolsulphonic type.
As a general rule with condensation polymers, unsubstituted phenol
or materials as resorcinol are added to enhance polymerization. A
resin of the latter type is the Lewatit CNO.
Medium-acid strength condensation polymers with phosphonic acid
and arsonic acid groups have recently become available. Other v a r i -
ations include the use of the aldehyde rather than the phenolic component
as the c a r r i e r , introduction of ionic groups after polymerization, p r e -
paration of bifunctional resins (S0 3 H and COOH groups), and preparation
of condensation polymers with a silicone framework.

Anion-exchange resins. Though several minerals (apatite,

hydroxylapatite) act as anion exchangers, their use is v e r y limited due
to iow resistance to acidity. The first satisfactory materials for anion
exchange were the synthetic organic resins.
As with the cation-exchange resins, condensation polymers are
rapidly being replaced by the more stable addition polymers. Ionic groups
on the anion exchangers are l e s s stable than those in use in cation resins
and the best anion-addition polymer does not compare well with the best
cation exchanger.
Among the f i r s t anion exchangers prepared by condensation polymeri-
zation was the product of condensing phenol, formaldehyde and triethylene

28
t e t r a m i n e whose s t r u c t u r e i s :
OH

н 2 с - сс нн 22 - О - CH,
"2

Н з С - С ~ С Н з

II2C Cil,

OH
N11

C H 2 - C H 2 - NH - C H 2 - C H 2 - NH - C H 2 - C H , , - NH, ¿

The r e s i n is r e l a t i v e l y low in cost and high in c a p a c i t y . - It i s a w e a k -

b a s e e x c h a n g e r , the functional groups being the s e c o n d a r y ( - N H - ) and the
p r i m a r y ( - N H 2 ) amine groups.
Another of the e a r l y r e s i n s was prepared by a condensation reaction of
m - p h e n y l e n e d i a m i n e with f o r m a l d e h y d e . The r e l a t i v e amount of
f o r m a l d e h y d e used d e t e r m i n e s both d e g r e e of c r o s s l i n k i n g and base
strength. B a s e strength can be i n c r e a s e d b y condensing aliphatic
p o l y a m i n e s rather than the a r o m a t i c amines with aldehydes. Halo-
epoxides a r e v e r y strong condensing agents, and used with or instead
of the aldehydes, provide r e s i n s with s t r o n g - b a s e quaternary ammonium
g r o u p s . A l l such r e s i n s are polyfunctional.
Condensation p o l y m e r s have been prepared with ammonia or
ammonium s a l t s , and r e c e n t l y r e s i n s with quaternary phosphonium and
t e r t i a r y sulphonium groups, of high base strengths, have been s y n t h e s i z e d .

I V - 3 . 2. 2. Addition p o l y m e r s

Cation-exchange resins. Most of the c a t i o n - e x c h a n g e r e s i n s

c o m m o n l y used in w a s t e t r e a t m e n t are addition p o l y m e r s made by
sulphonation of a s t y r e n e - d i v i n y l b e n z e n e c o p o l y m e r . Sulphonic acid
groups are introduced a f t e r p o l y m e r i z a t i o n by heating with concentrated
sulphuric acid or chlorosulphonic acid. C o m m e r c i a l divinylbenzene
(DVB) is g e n e r a l l y used as the c r o s s l i n k i n g agent. Ratio of D V B to
s t y r e n e is e a s i l y adjusted in the reaction and t h e r e f o r e control of d e g r e e
of c r o s s l i n k i n g , which in turn d e t e r m i n e s porosity, is s i m p l e . Reproduc-
ible r e s u l t s are achieved with r e l a t i v e e a s e .
Nominal D V B content, as mentioned in m a n u f a c t u r e r s ' l i t e r a t u r e ,
r e f e r s to m o l e percent of pure divinylbenzene. C o m m o n l y used r e s i n s
contain 8 to 12% D V B , but f o r s p e c i a l p u r p o s e s , 0 . 2 5 to 25% D V B resins
have been m a d e a v a i l a b l e . I n c r e a s i n g D V B content d e c r e a s e s swelling
and p o r o s i t y and i n c r e a s e s toughness and m e c h a n i c a l s t a b i l i t y . The
opposite happens as D V B content d e c r e a s e s . Low D V B content r e s i n s
s w e l l s t r o n g l y and are soft and gelatinous. T a b l e IX d e m o n s t r a t e s
v a r i a t i o n of m o i s t u r e content and capacity with percent D V B .

29
 This type resin, with sulphonic (SOgH) or methylene sulphonic
(CH 2 S0 3 H) functional groups, is of high capacity, has relatively high
thermal, chemical and mechanical stability, a rapid rate of exchange and
a 'salt-splitting 1 ability when operating in the hydrogen c y c l e . By salt-
splitting is meant the ability of the hydrogen form of a resin to remove
cations from neutral salt solutions.
A weak-acid ion-exchange resin, with weakly ionized carboxylic
acid groups, is prepared by suspension copolymerization of acrylic or
methacrylic acid with D V B . The - C O O H groups have little or no salt-
splitting capacity but in alkaline solutions, these resins will remove
cations equivalent to the alkalinity present. The resins have a strong
affinity for Ca + + and regeneration with Na+ directly is v e r y difficult.
Intermediate-acid resins with phosphonic acid ( - P O | ~ ) , functional
groups, phosphonous acid ( - P 0 3 3 ) , phosphinic acid ( - H P 0 2 ) and arsonic
acid ( - A s O | ~ ) groups have proven of value and some, as Duolite ES-63
(phosphonic acid) are available c o m m e r c i a l l y .
New resins have been prepared with v e r y wide pores which permit
a c c e s s to the interior even when nonpolar solvents are used. P o r e s in
the spherical beads provide openings s e v e r a l hundred  units in width.
These 'macroreticular' resins are prepared by a variation of one of the
addition polymerization techniques. An organic monomer solvent which
will not affect the polymers is added to the polymerization mixture and
as the polymerization proceeds, the growing copolymer areas emit the
solvent. Rohm and Haas 'amberlyst' resins are of this type.

Anion-exchange resins. Synthesis of anion-exchange resins by the

addition reaction is v e r y similar, to a point, to preparation of the cation
exchangers. Beads formed by suspension copolymerization of styrene
and DVB are treated with chloromethyl ether catalyzed by aluminium
chloride or zinc chloride. - C H 2 C 1 groups are introduced on the benzene
rings. This product is then áminated with trimethylamine to provide a
highly ionized functional group of quaternary ammonium

CH 3
I
- C H 2 - N + — CHg
I
CH3

The resin is a strong-base anion exchanger and in the OH" form has the
basicity of NaOH. Methylstyrene, vinylanisole and other styrene deri-
vatives can be used with crosslinking agents other than DVB, such as
vinylacrylate.
Strong-base resins are c o m m e r c i a l l y available as Type I or Type II.
When the four substituents on the nitrogen atom include a polymeric
benzyl and three methyl groups, the resin is termed a T y p e - I resin.
When one of the methyl groups is replaced by another group, as the
ethanol group, the resin is termed Type II. T y p e s I and II differ slightly
in chemical stability and in affinity for the hydroxide ion relative to
other anions. The T y p e - I resins are more chemically stable, par-
ticularly in the hydroxide form, but the Type-II resins are more e f -
ficiently converted to the hydroxide f o r m .

30
 When the chloromethylated copolymer of styrene and DVB is reacted
with ammonia or with primary or secondary amines, weak-base anion
exchangers with primary, secondary, and t e r t i a r y amine functional groups
result.

I V - 3 . 3 . Ion-exchange membranes

Ion-exchange membranes are of two principal types, the. heterogeneous

and the homogeneous. The heterogeneous, though capable of being made
from almost any ion exchanger, have limitations such as lower e l e c t r i c
conductivity and higher permeability for e l e c t r o l y t e s . They are being
replaced by homogeneous membranes as physical strength problems are
resolved.
Heterogeneous membranes are prepared by dispensing colloidal or
finely ground ion-exchange m a t e r i a l s throughout a thermoplastic inert
binder such as polyethylene, polystyrene or synthetic rubber. Ion-
exchange particles must be in contact with one another within the binder
but not to the complete exclusion of the binder and loss of mechanical
strength. They therefore comprise 50 to 75% by volume of the hetero-
geneous membrane. Mixtures of resin and binder are rolled, compressed
or extruded to form thin ribbons, discs or film.
Homogeneous membranes are condensation products of sulphonated
phenol and formaldehyde or nitrogen-containing compounds and formaldehyde.
These strong-acid or strong-base condensates are laid out in thin sheets
on m e r c u r y or acid-resistant plates. They can also be prepared by
heating a precondensed, viscous reaction mixture between glass plates.
The membranes formed are translucent. If additional mechanical
strength is required, membranes are prepared by polymerization on
supporting wide-mesh plastic screen or tissue.
C o m m e r c i a l membranes have also been prepared by 'interpolymer'
and 'graft-polymerization' techniques. The interpolymer films are ob-
tained by evaporation of a solution of linear polyelectrolyte and linear
inert polymer. The membranes are insoluble in aqueous solutions though
no crosslinking has been achieved. In the graft polymerization method,
cobalt-60 gamma radiation is used to graft styrene or s t y r e n e - D V B
mixtures impregnated in polyethylene film to the polyethylene b a s e .
Sulphonation of the graft copolymer produces a strong-acid cation-
exchange membrane while chloromethylation and quaternization or
amination provide strong-base and weak-base anion-exchange membranes.
Optimum styrene content of the film ranges from 30 to 50 mole percent.
Tables XlVa and XlVb list c o m m e r c i a l l y available membranes.

31
 V. L I M I T A T I O N S OF I O N E X C H A N G E R S

V - l . LIMITATIONS A P P L I C A B L E TO A L L ION EXCHANGERS

In solving chemical processing problems, existing methods are

investigated and evaluated. The problem is normally well defined and
the processing method providing the desired product at the lowest unit
cost is selected. To evaluate the use of ion exchange for removal of
radionuclides from waste solutions, the capabilities and limitations of
the process must be recognized and understood. In this section, some
of the limitations in the use of ion exchange will be discussed.
Certain characteristics of ion-exchange materials and the process
itself limit its applicability and e f f i c i e n c y . These include:

(1) Leakage. Whether column, batch, or moving bed s y s t e m s are used,

complete removal of a specific radionuclide is not normally possible due
to leakage. In a properly designed system, leakage may be v e r y low,
but improved removals would require a considerable effort at high cost
per unit improvement. This leakage may be due to:

(a) radionuclides in colloidal size particulate form;

(b) a portion of the radionuclide concentration, though in solution,
may be in non-exchangeable or non-electrolyte form;
(c) mechanical difficulties, e . g . channelling in columnar operation,
which are difficult to detect and prevent.

In most c a s e s , the amount of leakage from a well-designed system will

be within acceptable limits.

(2) Radionuclides in the waste must be in an exchangeable, electrolyte

f o r m . Radioelements of some of the heavy metals have hydroxide forms
of low solubility. In other instances, radionuclides in solution may be
sorbed by suspended matter in the waste and thereby become non-
exchangeable.

(3) The concentration of suspended solids in the waste solution must be

v e r y low. F o r most efficient and economical operation, the exchanger
beds cannot be used for filtration as during column operation. In most
cases, prefiltration will extend the length of ion-exchange c y c l e s , extend
the life of the exchanger, permit closer control of the operation, reduce
leakage and permit more efficient backwashing and regeneration.

(4) The concentration of total solids in the waste solution must be r e l a -

tively low. A s reported in section III-2. 4, at high concentrations
exchange potentials of ions of different valences diminish. Exchange
potentials of ions of s i m i l a r valence become similar or decrease with
increasing atomic number. Competition for exchange sites is much
greater and exchange efficiency of a specific nuclide is impaired.

32
2500 m g / l is generally accepted as a maximum total solids concentration.
F o r most efficient resin use, however, total solids should be l e s s than
1000 m g / l .

(5) Certain radioelements, as ruthenium, are very difficult to remove

from solution by ion exchange because of their chemical complexity.

(6) Radionuclides which are monovalent or of low atomic number are

difficult to remove by ion exchange except when exchangers specific for
the element are used.

(7) In certain c a s e s , costs may be a limiting factor in consideration of

the ion-exchange p r o c e s s . Synthetic ion-exchange resins are relatively
expensive. The cation-exchange process is normally operated in an acid
phase, requiring the use of more costly acid-resistant piping and
equipment.

V - 2. LIMITATIONS A P P L I C A B L E T O N A T U R A L ORGANIC EXCHANGERS

This group includes lignitic and bituminous coals and anthracites,

woods, cotton, tar, nut shells, olive pits, and other materials. They are
seldom used in their natural state because of instability. They will swell
e x c e s s i v e l y , many will decompose in alkali, and many are mechanically
weak. The coals are often stabilized with metal salts and almost all
materials are sulphonated or phosphorylated to improve exchange capacity.
Limitations in the use of these materials for treatment of radioactive
wastes include:

(1) Low exchange capacities as compared to other available exchange

materials
(2) E x c e s s i v e swelling with a tendency to peptize
(3) Limited radiation stability
(4) Weak physical structures
(5) Non-uniform structure
(6) May be subject to decomposition by alkalis.

Several exchangers of this type are available commercially. They

have been 'stabilized 1 , however, and treated chemically to overcome
many of these limitations. They are normally used where close control
of the electrolyte solution can be maintained. Dusarit S (IMACTI N . V . ,
Amsterdam), a sulphonated coal, for example, is recommended for
water treatment, but is particularly suitable for purification of glucose
syrups since it has properties of activated carbon.

V-3. LIMITATIONS A P P L I C A B L E T O N A T U R A L INORGANIC

EXCHANGERS

These materials, as stated in section I, were the f i r s t to be used for

ion-exchange separations. The clay minerals and the zeolites, though
replaced to a large extent by synthetic exchangers, continue to be used
and have been applied extensively to treatment of radioactive waste
solutions. Limitations in their use include:

33
(1) Relatively low exchange capacities
(2) Relatively low abrasion resistance of the zeolites
(3) Relatively limited swelling of zeolites with restricted mobility of
the exchangeable ions
(4) C l a y minerals tend to peptize
(5) The zeolites are difficult to size mechanically
(6) These materials are partially decomposed by acids and alkalis
(7) Many of the clays and zeolites have only limited stability in solutions
of v e r y low silica or salt content.

Several of the naturally occurring inorganic exchange materials

are treated by stabilization techniques and are available commercially,
e . g . Neopermutit and Superneopermutit. With these, of course, the
treatment is designed to preserve the desirable characteristics of the
natural material and overcome limitations as listed above.

V - 4 . LIMITATIONS A P P L I C A B L E TO S Y N T H E T I C
ORGANIC EXCHANGERS

Synthetic resins are the most widely used and highly developed ex-
changers available. Research and development continue on a relatively
l a r g e scale and new materials, new applications and new capabilities
are presented at an increasing rate. Advantages in the use of resins for
applicable chemical processing problems are many. However, there are
limitations which include:

(1) Limited radiation stability. The effects of large doses of radiation

on exchange materials have been rather thoroughly investigated. In an
extensive study at Vanderbilt University, USA, Fisher and Threadgill [58]
reported capacity reductions in resins subjected to a total of 109 roentgens
(2X 106 R/min) of X - r a y s as:

Capacity loss
Resins
(%)

Strong-acid 10
Weak-acid 100
Strong-base 40
Weak-base 20

Colour, particle size and shape are also adversely affected. Similar
studies by Nater at J E N E R , K j e l l e r , Norway [59], by Hall, Streat and
a s s o c i a t e s of the Imperial College, London, UK, and by a number of
workers at Oak Ridge, USA, have agreed on the limited stability of
resins to radiation. F i g u r e s 9 and 10 illustrate several of the adverse
effects.
(2) Comparatively high c o s t . This limitation is concerned with original
capital costs of resins since attrition rates are low and little resin r e -
placement is required. A properly operated regenerated s y s t e m is r e l a -
tively long-lived. It is also concerned with the cost of régénérant
chemicals and the cost of treating the régénérant waste. Regeneration
costs must be weighed against costs of resin replacement.

34
FIG. 9. Variation in weight and capacity of strong-acid-type cation-exchange resin (Nalcite HCR) with
X-irradiation as a function of crosslinkage (°¡o DVB).

•21
X-RAY ENERGY ABSORBED <eV/GRAM*IO )
0 13.5 27.0 40.5 540

PERIOD OF RADIATION (HOURS)

FIG. 10. Variation in ion-exchange capacity of resins with X-irradiation.

(3) Limited stability to heat. Strong-acid resins are usually recommended

for use where temperatures will not exceed 120-150°C. Strong-base
polystyrene resins should not be used at temperatures exceeding 40-70°C.
Tables X-XII provide manufacturers' recommendations for the
maximum temperature at which the available exchangers can be

35
used. This limitation has restricted use of resins to treatment of
low- and intermediate-level radioactive waste. Generally, wastes of these
activity l e v e l s are at much lower temperatures or can be cooled below
the recommended limits before treatment.
(4) Increased equipment costs. Where strong-acid resins are operated
in the H + cycle, acid conditions will require use of more costly materials
of construction for tanks, piping, valves, etc.

V - 5 . LIMITATIONS A P P L I C A B L E TO S Y N T H E T I C INORGANIC
EXCHANGERS

Two groups of distinctly different materials, physically and chemically,

comprise this category. These are the synthetic zeolites and the inorganic
chemical compounds such as the exchangers prepared by combining
group-IV oxides with the more acidic oxides of groups V and VI. They
will therefore be discussed separately.

V - 5 . 1 . Limitations: synthetic zeolites

The synthetic zeolites, of which a number are c o m m e r c i a l l y available,

are highly specific sorbents rather than ion exchangers. They act as
'molecular s i e v e s ' by excluding particles l a r g e r than the openings in the
crystalline structure. The openings are adjustable for size by converting
the exchanger to other ionic f o r m s . Limitations include:

(1) Relatively high cost as compared to natural zeolites

(2) Limited chemical stability in acids and bases
(3) The presence of potassium in the waste solution seriously interferes
with caesium removals. Studies at Hanford and Brookhaven, USA [60]
demonstrated the high selectivity of the molecular sieves for caesium
and strontium and their application to particular wastes.
(4) Limited mechanical stability. The synthetic zeolites are exact
counterparts of the natural materials with some improvement in capacity
and stability.

The material Decalso (Permutit), a synthetic alumino-silicate gel

and not a molecular sieve, should be included in this classification be-
cause of the s i m i l a r chemical composition. Its limitations, other than
mechanical stability, are similar to those mentioned above.

V-5. 2. Limitations: inorganic chemical compounds

Few of these materials are presently available commercially (see

Table X) due to their rather recent development. However, their out-
standing characteristics - high capacity, insolubility, thermal and radi-
ation stability - will hasten their development and result in wide com-
m e r c i a l availability. At this stage in their acceptance, they exhibit
several limitations which include:

.(1) They lose fixed ionic groups due to hydrolysis at high pH.
(2) They are difficult to prepare in mechanically stable convenient size.

36
 The earliest reported work with these materials was from laboratories
at Oak Ridge, USA (Kraus et a l . ) and Harwell, UK (Amphlett et a l . ) . In-
vestigations at the Boris Kidric Institute, Yugoslavia (Gal and Gal) and at
the University of Strasbourg, France (Hure et a l . ) confirmed and expanded
the information on them: zirconium phosphate, tungstate, molybdate;
titanium phosphate, etc. In a v e r y recent work at SERAI, B r u s s e l s ,
Belgium, Balon et al. [61] described the use of A B E D E M T i A (a titanium
phosphate) for the separation of caesium from high-level radioactive
wastes.
A number of synthetic inorganic compounds with somewhat s i m i l a r
properties as ion exchangers, though not utilizing the group-IV oxides,
have also been studied. These include ferrocyanide molybdate as r e -
ported by Baetsle e t a l . [62], from work at Mol, Belgium; ammonium-12-
molydophosphate as described by Smit [63], Harwell, UK, and others;
potassium hexacyanocobalt II ferrate II as reported by Prout et al. [64],
Savannah River, USA, and many others. These compounds, though
highly selective and thermally stable, do not have the high capacity e x -
hibited by the exchangers of the group-IV oxides.

V - 6 . LIMITATIONS A P P L I C A B L E TO I O N - E X C H A N G E M E M B R A N E S

E l e c t r o d i a l y s i s , the use of permselective ion-exchange membranes,

is an operational process (as a pre-treatment step to conventional ion
exchange) at only one waste treatment facility, the Tokai Research E s -
tablishment, JAERI, Japan [65] . Use of the membranes for removal
of ruthenium from waste solutions, as investigated at Battelle Northwest
Laboratories, USA, has shown great promise. Limitations to the process
include:

(1) Relatively high operating costs

(2) In certain solutions, back-diffusion of ions may be e x c e s s i v e
(3) Increasing concentrations of calcium and iron ions decrease cycle
length (time that a membrane system can be used before remedial
action, as cleaning or replacement, is necessary)
(4) Limited mechanical stability
(5) Precipitation of compounds on and in the membrane reduces c y c l e
length
(6) High electric resistance at low electrolyte concentrations
(7) Osmotic and e l e c t r o - o s m o t i c water transport.

37
 VI. A P P L I C A T I O N OF ION E X C H A N G E
TO W A S T E PROCESSING

VI-1. GENERAL

With the development of new ion exchangers and the advances in ion-
exchange technology, the field of application of these materials in waste
treatment continues to grow. Alone or in conjunction with other p r o c e s s e s
as chemical precipitation, prefiltration, electrodialysis or evaporation,
ion exchange is presently in use in facilities in all parts of the world for
the removal of radioactivity. The earlier serious limitations of relatively
low thermal and radiation stabilities are being overcome by the new
synthetic inorganic materials. A temperature of 150°C (see tables of
resins) and a total of 10® R [35] will no longer r e s t r i c t exchange operations
as the synthetic groups-IV, - V and - V I oxides become commercially
available.
V e r y pure nuclear grades of organic resins are manufactured for use
in demineralization of reactor coolant or p r o c e s s water. The resins can
be regenerated by remote methods, if n e c e s s a r y , and reused a large
number of times. In many c a s e s , storage of the spent régénérant for
relatively brief periods, a matter of a few months, will permit decay of
activity to l e v e l s below ICRP (International Committee on Radiological
Protection) drinking water standards.
In many instances, the high selectivity of the inorganic exchangers,
both natural and synthetic, is adapted to the effective processing of
specific wastes. Several of these facilities successfully remove the
monovalent 1 3 7 C s from waste streams, though according to the ion-
exchange rules listed in section III-2. 4, this should be very difficult.
U s e of the natural zeolite or clay minerals in exchange applications
is possible after mechanical sizing and in some c a s e s stabilization treat-
ments, providing a relatively low-cost material. In such c a s e s , regene-
ration i s unnecessary and the exhausted exchanger is treated for disposal
as a contaminated solid.
Decontamination factors achieved in ion-exchange treatment of waste
solutions vary in accordance with the type and composition of the waste
stream, the radionuclides in the solution, type of exchanger, regeneration
methods, and operational procedures. With synthetic organic resins,
D F s have been reported as low as 2 and as high as 10 5 , with the higher
values in s y s t e m s using dual or mixed bed (monobed) multiple stage
arrangements.
Volume reduction factors (ratio of volume of solution processed to
volume of residue into which the activity has been concentrated) reported
vary with regard to the factors mentioned above as controlling the D F .
Final disposal of the resin, the spent régénérant or the spent régénérant
residues have a decided effect upon the V R F . Incineration of an exhausted
organic resin enhances the V R F while neutralization of a spent régénérant
solution and solidification of the mass with cement increases the volume
for final disposal and causes a reduced V R F . Evaporation or distillation
of the spent régénérant d e c r e a s e s the volume of waste for final disposal.

38
 In this section the application of ion exchange to the removal of
radioactivity from waters and principal considerations in the design of such
s y s t e m s will be discussed.

VI-2. PROCESSING OF R E A C T O R W A T E R S

Many of the reactors in operation today or planned for future con-

struction are water cooled or water moderated. In a number of these
instances, the water also s e r v e s as a shield. F o r the water to be of
maximum value, it must be noncorrosive toward materials it will contact
and must be f r e e of neutron absorbing ions. This latter requirement is
essential not only from the standpoint of unwanted and uncontrolled
neutron capture and removal, but also from the attitude of increasing
radioactivity of the system. The requirements are ideally suited to the
capabilities of ion exchange, both cationic and anionic, which [66]:

(1) Can provide demineralized, neutral make-up water;

(2) Can provide on-stream removal of radioactive contaminants, such as
activated corrosion products;
(3) Can remove oxygen from coolant in reactor s y s t e m s as necessary;
(4) Can control concentration of additives such as corrosion inhibitors
and neutron poisons.

Mixed bed, dual bed and s e r i e s column operation with strong-acid

and strong-base organic resins are the most common methods of applying
ion exchange to the problems. A number of the earliest research reactors
employing ion exchange for demineralization are listed in Table II. In
Table X V , some later USA power reactors and their methods of maintaining
coolant purity are presented.
Make-up water for both primary and secondary loops of the Indian
Point reactor originates from a municipal supply. To make it suitable
for use in the reactor, it is f i r s t softened by treatment through cation-
exchange resins, then treated for removal of carbon dioxide. A f t e r
realkylization with caustic soda, it is evaporated and the condensate is
demineralized in mixed bed exchangers. The product contains about
0.01 m g / l silica and <0.05 m g / l ionizable solids.
A s of 1962, seventeen USA, two Canadian, one Belgian, one German,
one Japanese, one Puerto Rican, and one Swedish power reactor utilized
ion exchange for coolant purification. In most c a s e s , treatment on a
continuous basis of only a small portion of the primary coolant of a reactor
is sufficient to maintain the level of c o r r o s i o n - f i s s i o n products within a
tolerable range. Usually this percentage can be varied within certain
limits. The fission products, from recoil nuclei or from diffusion through
or defects in the cladding, must be continually removed to maintain a
low radiation level in external components of the reactor.
The Vallecitos Boiling Water Reactor, USA, utilizes ion exchange in
the condensate return line f r o m the turbine hot well and the Canadian NRX
and NRU reactors employ mixed bed units in processing fuel rod bay
water.
Reactor installations generally produce other liquid wastes, such
as laboratory solutions, gas scrubber effluent, etc. and often provide
separate treatment f a c i l i t i e s . Of the reactors listed in Table X V , three

39
provide waste processing facilities including mixed bed ion exchangers
and the fourth, at Rowe, is designed to permit use of the coolant purifi-
cation resins for waste treatment.

VI-3. PROCESSING OF R A D I O A C T I V E W A S T E S

VI- 3 . 1 . General

When radioactive wastes are produced which are amenable to treat-

ment by ion exchange or can readily and economically be so converted,
the many diverse materials and methods of application of the p r o c e s s
must be reviewed to determine the most suitable combination. Guidelines
which emerge after a study of the exchangers available as summarized in
section IV and the limitations of the process as discussed in section V
include the following:

(1) Waste solutions to be processed by ion exchange should have a v e r y

low suspended solids concentration, l e s s than 4 ppm [68], since this
material will interfere with the p r o c e s s by coating exchanger surface and
by sorbing radionuclides. Ion exchangers are too valuable to be used as
filter media, and, in most c a s e s , it will prove economical to pretreat
the waste mechanically or chemically. Exceptions might include instances
where l o w - c o s t natural exchangers, as the zeolites or c l a y s , perform
filtration and ion exchange on a once-through or batch treatment basis.

(2) Generally, the waste solutions should contain l e s s than 2500 mg/1
total solids. Most of the dissolved solids would be ionized and would
compete with the radionuclides for the exchange sites. Length of runs
or c y c l e s before exhaustion is therefore directly, and a d v e r s e l y , affected
by increasing dissolved solids concentrations.
Non-ionic dissolved solids normally have little effect on synthetic
organic exchangers. However, with materials which adsorb rather than
exchange ions, such as the 'molecular s i e v e s ' , much of the capacity
can be wasted on solutes which would be removed more economically
by other means.
Exceptions would again include those c a s e s where cost advantage
would lie in the use of exchanger capacity rather than separate pretreat-
ment means for removing the non-active ions. In most instances, this
would involve the use of the l e s s expensive materials, such as the
natural zeolites and c l a y s .

(3) Radioactivity associated with non-electrolytes and colloids should

be v e r y low. Most active non-electrolytes would be unaffected by the
exchanger while the colloids would be filtered out, would coat the ex-
changer or would also be unaffected. In any event, they would interfere
with removal of the radioactive electrolyte. With this problem, an in-
vestigation of pretreatment by chemical means or mechanical filtration
should be made. Use of commercial or natural adsorbers or adsorbent
resins should be investigated. Colloidal activity can be separated through
use of adsorbers or by electrodialysis.

40
VI-3.2. Treatment methods: batch operation

In the event waste solutions are amenable to or can be readily con-

verted to meet these specifications, two principle techniques, with
variations, are available for contacting waste solution and exchanger
(excluding electrodialysis). These are: (1) batch operation and (2) column
operation.
The batch operation system consists of placing a given quantity of
waste solution and a predetermined amount of exchanger in a v e s s e l ,
mixing the components well, and permitting them to remain in contact
until equilibrium is reached. The solution is then filtered off. The
extent of the exchange is limited by the selectivity of the resin under the
equilibrium conditions. Therefore, unless the selectivity for the radio-
active ion is very favourable, the efficiency of removal will be low. Use
of the batch system of operation for treatment of radioactive wastes in a
currently functioning facility is unknown. An interesting application of the
batch method, to illustrate its value, is the small scale sea-water-desalting
units furnished in survival kits. The silver form of a strong-acid resin
reacts with the sea water to remove the sodium and precipitate silver
chloride, as:

RS0 3 Ag + Na" Cl" > RSO3 Na + A g C l + potable water

resin sea water resin

VI-3.3. Treatment methods: column operation

The system of column operation has a number of variations. These

include:

( 1) Single column, fixed bed

(a) Cation exchange only
(b) Anion exchange only
(c) Monobed or mixed bed

(2) S e r i e s columns, fixed bed

(a) Cation-exchange columns in s e r i e s
(b) Anion-exchange columns in s e r i e s
(c) Mixed bed columns in s e r i e s

(3) Dual columns, fixed bed

(a) Cation-exchange column followed by anion-exchange column
(b) Series columns of (a)

(4) Moving bed, continuous counter-current exchanger or pulsed bed

contactor
(a) Cation-exchange columns
(b) Anion-exchange columns

(5) Centrifuge lined with exchanger

(a) Cation exchanger
(b) Anion exchanger

41
 Column o p e r a t i o n is e s s e n t i a l l y a l a r g e n u m b e r o f b a t c h operations
in s e r i e s . It is m u c h l e s s d e p e n d e n t u p o n selectivity t h a n the b a t c h method
a n d t h e o r e t i c a l l y c a n b e effective r e g a r d l e s s of t h e selectivity coefficient
if s u f f i c i e n t r e s i n i s a v a i l a b l e . C o l u m n operation b e c o m e s m o r e practical,
h o w e v e r , a s the selectivity for the r a d i o n u c l i d e s b e c o m e s m o r e favourable.
F i g u r e 1 1 is a s i m p l e s c h e m a t i c of a f i x e d b e d column.

WASTE REGENERANT
SOLUTION

ALTERNATE

EXCHANGE

AND

REGENERATION

TREATED SPENT
WASTE REGENERANT

FIG.ll. Fixed bed ion exchange, single column.

ALKALINE REGENERANT INFLUENT

R I N S E WATER I N F L U E N T
BACKWASH WATER E F F L U E N T
RAW WATER INFLUENT

S P E N T REGENERANT E F F L U E N T
R I N S E WATER E F F L U E N T

^ -t» * i

ACID REGENERANT INFLUENT

RINSE WATER INFLUENT
BACKWASH WATER INFLUENT
DEIONIZED WATER E F F L U E N T

FIG. 12. M i x e d bed ( m o n o b e d ) i o n - e x c h a n g e c o l u m n (showing resins segregated for regeneration).

42
 In many waste solutions, the r a d i o a c t i v e ions a r e cations and a single
column or s e r i e s of columns of cation exchanger will provide sufficient
decontamination. H i g h - c a p a c i t y organic r e s i n s a r e often used because of
their good f l o w r a t e c h a r a c t e r i s t i c s , rapid rate of exchange, s t a b i l i t y
and e a s e of r e g e n e r a t i o n . Other exchange m a t e r i a l s a r e in use w h e r e
conditions dictate their p r e f e r e n c e . M i n e r a l exchange columns r e m o v e
cations where w a s t e v o l u m e s are low and it is m o r e e c o n o m i c a l to d i s -
pose of exhausted e x c h a n g e r than to r e g e n e r a t e . T h e high s e l e c t i v i t y of
the synthetic inorganic m a t e r i a l s has r e s u l t e d in t h e i r s e l e c t i o n f o r use
where w a s t e i s predominant in a s p e c i f i c nuclide.
U s e of single or s e r i e s a n i o n - e x c h a n g e columns is v e r y l i m i t e d .
A c t i v i t y must be p r e s e n t s o l e l y in anionic f o r m . Though this i s p o s s i b l e
with e l e m e n t s a s iodine, sulphur, phosphorus, e t c . , it is r e l a t i v e l y un-
usual to find w a s t e solutions with anionic a c t i v i t y in the a b s e n c e of the
cationic.
Monobed or mixed bed columns contain both the cation and anion
e x c h a n g e r s in the s a m e v e s s e l as shown in F i g . 12. Synthetic organic
r e s i n s of the s t r o n g - a c i d and s t r o n g - b a s e type a r e n o r m a l l y used, but
all combinations of s t r o n g - a c i d , w e a k - a c i d with s t r o n g - b a s e , w e a k - b a s e
r e s i n s can be found in industrial applications. U s e of m a t e r i a l s other
than synthetic r e s i n s is unknown. During operation of m i x e d bed c o l u m n s ,
cation and anion e x c h a n g e r s a r e intimately mixed to ensure that the acid
solution f o r m e d a f t e r contact with the H + - f o r m cation r e s i n i s i m m e d i a t e l y
neutralized by the O H ' - f o r m anion r e s i n . T h e w a s t e solution is t h e r e f o r e
maintained at a neutral pH and s p e c i a l m a t e r i a l s of construction a r e not
r e q u i r e d . T h i s action can be shown g r a p h i c a l l y a s in F i g . 13. The
monobed or mixed bed s y s t e m i s n o r m a l l y m o r e e c o n o m i c a l f o r d e m i n e r a l i -
zation of w a t e r s of low s o l i d s content than distillation. T h e s y s t e m y i e l d s
a product e x t r e m e l y low in s i l i c a content with a s p e c i f i c r e s i s t a n c e a s
high a s 20 000 000 ohm. (See T a b l e XIII f o r c o m m e r c i a l m i x e d bed r e s i n s . )

CATION EXCHANGER ANION EXCHANGER

FIG. 13. Equilibria in monobed or mixed bed ion exchangers.

T h e p r i n c i p a l application of the mixed bed s y s t e m in f i e l d s r e l a t e d

to the atomic e n e r g y industry is in the purification of r e a c t o r coolant a s
d i s c u s s e d p r e v i o u s l y . In many c a s e s , duplicate monobed columns a r e
provided so that one unit is a l w a y s a v a i l a b l e f o r s e r v i c e . General

43
practice is to regenerate exhausted resin, store the radioactive régénérant
to permit decay of the short-lived nuclides, and discharge the very low-
level waste with or into a non-active stream of dilution water.
Mixed bed s y s t e m s are in use for treatment of the general radioactive
waste solutions produced at atomic energy installations. In intermittent
use, they have an advantage over the multiple bed s y s t e m s in that ionic
leakage following shutdown periods is much lower. F o r treatment of
wastes containing mixed fission products, efficiencies obtained by the
mixed bed system will be higher than those obtainable with cation-exchange
resins alone due to removal of the active anions.
Dual columns, as the name implies, are merely separate columns of
cation- and anion-exchange resins which are operated in s e r i e s . They
have an advantage over the monobed system in that regeneration is much
simpler. Operation of the cation-exchange column with resin in the H+
form, however, will require use of acid-resistant materials of construction
since the effluent of the column will be a dilute acid. If the anion-exchange
resin is then in the OH" form, final effluent will be deionized water. Dual
columns are presently in use for treatment of radioactive wastes as dis-
cussed in section VII. In a number of instances, improved decontami-
nation factors are obtained by serial use of the dual units. In all c a s e s
reviewed, resins have been regenerated and reused rather than destroyed.
U s e of the moving bed, continuous counter-current exchanger or
pulsed bed contactor system for treatment of wastes on a plant-scale basis
is presently unknown. Higgins Contactors, sold by Chemical Separations
Corporation, USA, are in use, however, in the Purex and Redox s y s t e m s
at Hanford, USA, in separation of uranium ores and other industrial
applications. F i g u r e 14 shows one of the larger industrial models. Pilot
plant scale treatment of wastes by Higgins units at Oak Ridge has s u c c e s s -
f u l l y demonstrated the advantages of the moving bed system, which include:

(1) Constant effluent of uniform quality;

(2) Smaller space requirements than other ion-exchange techniques;
(3) Smaller capital investment required as compared to ion-exchange
systems of equal capacity;
(4) Lower labour requirements as compared to the other ion-exchange
systems;
(5) Capability of treating wastes of higher solids content.

In the moving bed system, the resin as well as the waste solution and
régénérant is circulated. Wastes are treated by cation exchange, the
resins are continuously regenerated and spent régénérant is continuously
withdrawn. The moving bed systems are not governed by flow rate and
pressure drop limitations to the degree that the fixed bed systems are.
F i g u r e 15 is a simple schematic diagram of the p r o c e s s .
There are at least eight variations of the continuous counter-current
system which have been developed in the USA, primarily for specific
industrial applications. A number are not actually continuous in that the
resin does not move at all times but rather at regular short fixed intervals.
The methods used to move the resin comprise one of the main areas of
difference among the present systems because they are results of one of
the most complex design problems in this operation (maintaining counter-
current flows when resin and solution densities are only slightly different).

44
APPLICATION: HYDROGEN CYCLE
WATER SOFTENING
(Removal of cations.
Input hardness 320
ppm Sodium: 141
ppm (expressed as
CaC0}). Iron: 1.6
ppm

DIMENSIONS: Overall 10* X 10* X

30'
Loading Section 84"
diameter
Regeneration Section
42" diameter
MATERIALS: Rubber lined Carbon
Steel
CAPACITY: 2850 Gallons per minute
(over 4 million gallons
per day.)

FIG. 1 4 . C h e m i c a l Separations C o r p . m o v i n g bed c o n t a c t o r . (Reprinted by p e r m i s s i o n o f C h e m i c a l

Separations C o r p . , O a k R i d g e , T e n n . , USA.)

45
 ELUANT

WASTE

FIG. 15. Continuous counter-current exchanger [ 6 9 ] .

It is l i k e l y that the many advantages of the moving bed will result in its
much wider application in radioactive waste t r e a t m e n t .
A modified fixed bed column method employing the use of a centrifuge
has been p r a c t i c e d at s e v e r a l installations. E x c h a n g e r m a t e r i a l and type
of c e n t r i f u g e v a r y , but in the c a s e s known, exhausted exchanger is r e -
moved f o r d i s p o s a l . T h e s e s y s t e m s , at H a r w e l l , UK and Mol, B e l g i u m ,
will be d i s c u s s e d at length in section VII.
Application of m e m b r a n e e l e c t r o d i a l y s i s to treatment of radioactive
w a s t e s i s a l s o in the e a r l y stage of development. It would appear f r o m
its use in desalination that it was best adapted to treatment of w a s t e s high
in d i s s o l v e d or colloidal s o l i d s . In this event, its application would
usually be a s a pretreatment method since decontamination down to
p e r m i s s i b l e l e v e l s of the lower solids waste could be a c c o m p l i s h e d by
m o r e e c o n o m i c a l m e a n s . T h e J A E R I f a c i l i t y , Japan, has such a s y s t e m
in operation. M e m b r a n e d i a l y z e r effluents at this installation are polished
to low a c t i v i t y l e v e l s by further treatment through mixed bed ion exchange.
C e r t a i n studies [30, 70] have concluded that the use of e l e c t r o d e -
ionization f o r concentration of dilute ionic constituents, as in l o w - l e v e l
w a s t e s , a p p e a r s f e a s i b l e . No such applications are known, but the method
should be considered when waste treatment s y s t e m s are contemplated.

VI-4. DESIGN CONSID ERA TIONS IN T R E A T M E N T OF RICA С TOR

WATERS

A s d i s c u s s e d in section II, r e a c t o r water used as coolant, moderator

and/or shielding m a t e r i a l must be of v e r y low ion content to m i n i m i z e
shielding p r o b l e m s f r o m induced r a d i o a c t i v i t y . It must be n o n c o r r o s i v e
to m e t a l s used in the r e a c t o r and it must deposit a minimum of s c a l e in
the s y s t e m . The method adopted almost u n i v e r s a l l y , with v a r i a t i o n s , i s

46
demineralization by mixed bed or monobed synthetic organic ion-exchange
resins. The resins used should be low in fines, with a minimum of
sodium in the cation and chloride in the anion exchangers. The content of
soluble organic matter in the resin must be at a very low level since it
will be leached out and eventually decomposed by radiation. The products
of the decomposition contribute to the attack on metal surfaces and are
therefore highly objectionable. Depending upon the metals used in the
reactor, the optimum pH of the water may be other than 7. 0 for minimum
c o r r o s i v i t y . Adjustment of the pH can be accomplished through additives
or through selection of the proper type of ion exchanger. Though sodium
is objectionable since its unstable isotopes will create shielding problems,
lithium- or ammonium-form cation exchange resins will provide basic
solutions without affecting the activity of the water. If slightly acid
conditions are required, a hydrogen-form cation-exchange column can be
operated in parallel with the hydrogen-hydroxide mixed bed. The
effluents can be blended to achieve the desired pH.
Many commercial mixed bed nuclear grade resins are available.
They are specially prepared for s e r v i c e in reactor water treatment.
They are v e r y low in fines, and are specially treated for removal of
soluble organics and inorganic impurities. The cation exchanger is
available in the hydrogen, lithium, 7 L i and ammonium forms which are
particularly low in sodium. The anion exchangers are available in the
hydroxide form and are particularly low in chloride.
In the treatment of make-up water, mixed bed columns are used alone
or in connection with other methods for ensuring a high degree of
demineralization depending upon the quality of the raw water. It is
generally advisable, in any case, to filter the exchanger influent and
effluent.
P r i m a r y coolant water is usually demineralized in a b y - p a s s stream.
Treatment of as little as 0. 2% of the total volume being recirculated is
often adequate to maintain low conductivity water. Here again, p r e - and
post-filtration through cartridge-type replaceable f i l t e r s is recommended.
In all instances, cooling of the b y - p a s s stream is n e c e s s a r y if the t e m -
peratures exceed about 60°C, the recommended maximum for synthetic
anion-exchange resins.
The ion-exchange columns can be shielded by wrapping them in lead
or locating them behind shielding b a r r i e r s and providing remote operation.
Several methods are in use for determining exhaustion or end of run.
These include column activity, decrease of decontamination factor to a
given level, and resistance or conductivity. In many c a s e s , a combi-
nation of these control methods i s n e c e s s a r y . F o r s e r v i c e in a reactor,
water must have a resistance of fifteen to twenty million ohms. Metering
devices can be installed in several parts of the system (loop water, pool
water, exchanger effluent) and resistance data can be transmitted to indi-
cators in a remote central control area. When it has been determined
that resin performance has declined to a point where f r e s h resin is
desirable or n e c e s s a r y , the operating units are valved out of s e r v i c e and
reloaded or regenerated columns function in their stead. Length of the
cycle between regeneration or resin replacement is based on the design of
the system and the accuracy of estimates of corrosion rates. Varying
the resin volume directly varies the length of the operating c y c l e .
Columns in the water purification system of the OWR Reactor at L o s
A l a m o s are regenerated every six weeks to three months.

47
 When r e s i n s are r e g e n e r a t e d , they are either treated in place or
a r e drained to a s e p a r a t e f a c i l i t y f o r this purpose. Mixed beds must be
backwashed to r e m o v e particulate m a t t e r and to separate the cation and
anion r e s i n s . C l a s s i f i c a t i o n by this means is p o s s i b l e b e c a u s e of the
d i f f e r e n c e in s p e c i f i c g r a v i t y of the r e s i n s . R é g é n é r a n t s used are dilute
m i n e r a l a c i d s for the cation e x c h a n g e r s and dilute caustic solutions for
the anion e x c h a n g e r s where r e s i n s are in the H + and OH" f o r m s . Sul-
phuric acid and sodium hydroxide a r e most commonly used in the USA.
Quantities of régénérant used determine to a l a r g e extent the r e g e n e r a t e d
c a p a c i t i e s of the r e s i n s .
In v e r y few c a s e s is any attempt made to utilize the total exchange
c a p a c i t y . A s a g e n e r a l rule, 50 to 75% of the total capacity is r e a l i z e d
based on a balance between régénérant and capital investment c o s t s .
In r e a c t o r w o r k , regeneration i s usually c a r r i e d to a further extent to
a s s u r e minimum l e a k a g e but actual utilization of capacity is lower due
to the s a m e need for minimum l e a k a g e and the d e s i r e to maintain low
column r a d i o a c t i v i t y .

REGENERATION LEVEL lb 66° Be H 2 S0„ PER ft3

FIG. 16. Leakage and capacity data fot Na-H cycle of a sulphonic cation-exchange resin.

L e a k a g e is any amount of ion in the column effluent that should have

been r e m o v e d but was not. It is a f f e c t e d by a number of conditions, but
amount of régénérant is one of the m a j o r controlling f a c t o r s . The amount
of l e a k a g e v a r i e s i n v e r s e l y as the régénérant l e v e l . T h i s is shown
g r a p h i c a l l y in the g e n e r a l c u r v e s of F i g . 16. F o r instance, at a r e g e n e -
ration l e v e l in the N a - H c y c l e of 80g acid regenerant/1 s t r o n g - a c i d r e s i n ,
the c a p a c i t y is about 39g C a C 0 3 / 1 [71]. The sodium l e a k a g e at this l e v e l
is such that 50% of the total cations in the effluent would be sodium. A t
a regeneration l e v e l of 320g/l, c a p a c i t y is 78g С а С О з / l and ieakage is
reduced to about 8% of the total cations as N a . C u r v e s such as those of
F i g . 16 must be determined f o r each set of conditions, each p a r t i c u l a r
combination of r e s i n , régénérant and solution.
T a b l e X V I l i s t s the exchange c a p a c i t i e s attainable at s e v e r a l
régénérant l e v e l s f o r a s t r o n g - a c i d and a s t r o n g - b a s e synthetic organic
resin.
It must be r e a l i z e d that spent régénérant v o l u m e s will be g r e a t e r
than the v o l u m e s of r e s i n used-and that the spent régénérant constitutes
a waste disposal p r o b l e m . In many c a s e s , the problem is minor since
most of the radionuclides are of short h a l f - l i f e . Storage alone can s u f f i c e
in these c a s e s to lower a c t i v i t y to l e v e l s at which r e l e a s e to the environ-
ment is p e r m i s s i b l e . Where l o n g e r - l i v e d nuclides are involved, c h e m i c a l

48
treatment can be used to contain the activity in a sludge which can be fixed
in cement or asphalt. The spent régénérant, in other instances, is
evaporated and the residues are insolubilized.
Since regeneration produces wastes of greater volume than the ex-
hausted resins, it has often been found more economical to dispose of
the resin rather than regenerate it. This is particularly true where the
spent régénérant will not decay to low l e v e l s in a reasonable length of
time and will, therefore, require treatment. Exhausted resins can be
drained from specially designed columns or, if originally packaged in
cartridge-type containers, can be removed and replaced as a unit. Final
disposal is effected by insolutilizing the resins in cement or asphalt and
packaging them l'or ground burial or sea disposal. Whore quantities and
activities are low, the insolubilization step may not be required. A sig-
nificant volume reduction can be achieved by incinerating the resins prior
to final disposal measures.
Before discussing design of an ion-exchange column, the theory of
column operation should be considered briefly. F o r an example, assume
that it is desired to remove 1 3 7 C s from a solution and that 1 3 7 С s is
present as the electrolyte 1 3 7 C s C l . A cation exchanger in the H + form
will be used. It would seem that the exchange could be accomplished by
batch methods by placing the solution in an adequate amount of exchanger
and permitting sufficient contact time for equilibrium to be attained. At
equilibrium, however, the 1 3 7 C s + has not been completely replaced by H .
To accomplish complete replacement, an extremely large e x c e s s of ex-
changer must be used or the solution must be permitted to attain equi-
librium repeatedly with fresh batches of exchanger. This latter alter-
native is provided in column operation. In passing through a bed of ex-
changer, the solution repeatedly contacts l a y e r s of fresh exchanger.
With proper flow rates and exchange depth, the 1 3 7 C s + of the example
would be completely replaced by H + before the solution appeared at the
column effluent.
When the solution is first fed to the column, replacement of 1 3 7 C s +
by H+ takes place with the first exchanger contacted. A small zone at
the influent end of the column will contain exchanger in the 1 3 7 С s + form.
A s more solution is applied, this zone expands or enlarges until it reaches
the effluent end. 1 3 7 С s + is then found in the column effluent and the unit
is termed 'exhausted 1 . At breakthrough of the 1 3 7 C s + , the column would
normally be regenerated to return the exchanger to the H+ form. This
breakthrough capacity of the exchanger, the amount of 1 3 7 C s ions r e -
moved from solution prior to being determined in the effluent, is not the
total capacity. The bottom zone of exchanger has not been completely
converted to the 1 3 1 C s form. The total or overall capacity is, of course,
the product of volume capacity and volume of exchanger. The ratio of
breakthrough capacity to overall capacity, termed the 'degree of utili-
zation', defines the fraction of exchanger volume which is effective. The
following conditions or factors enhance column utilization [72]:

(a) The exchanger is highly selective for the solution counter ion;
(b) The exchanger is of small and uniform particle size;
(c) The exchanger has a high volume capacity;
(d) The exchanger has a low degree of crosslinking;
(e) The solution is at an elevated temperature;

49
(f ) The solution flow rate is low;
(g) The concentration of counter ions in the feed solution is low;
(h) The ratio of column length to diameter is high.

Certain disadvantages are inherent in a number of these conditions

and they must be applied with understanding. Resins cannot withstand
v e r y high temperatures. D e c r e a s e in particle size increases resistance
to flow. Low degrees of crosslinking enhance resin swelling with proba-
bility of channelling. Increasing height to diameter ratios also result in
increasing resistance to flow.
The regeneration phase of column operation, when adsorbed ions are
eluted, must also be considered. A s the régénérant solution flows through
the column, the adsorbed ions are repeatedly released from and sorbed by
the resin. The concentration of these ions in the column effluent gradually
increases from zero to a maximum, then d e c r e a s e s to zero again in an
almost symmetrical pattern. The form of this curve, concentration of
eluted ion v s . bed volumes of spent régénérant, is a graphic representation
of regeneration conditions. Favourable conditions of flow rate and
selectivity yield a relatively short, steep curve while unfavourable
conditions yield a wide, squat representation.
The column may be considered as a stacked series of very short
columns or 'plates'. These theoretical plates may be defined as any
part of the column such that the solution leaving one end will be of the
same composition as a solution which is in equilibrium with the resin of
the other end. Theoretically, it is possible that minimum plate thickness
would amount to the diameter of the resin particles. Actual thickness,
however, due to time required to attain equilibrium, usually varies from
a few millimetres to several centimetres. A s time to attain equilibrium
is decreased, plate thickness decreases and the number of plates per unit
column length increases. Column efficiency varies directly as the number
of theoretical plates per unit length.
In the mathematical approach, the number of theoretical plates re-
quired to produce effluent of a desired quality is calculated on the basis
of the distribution coefficient of the ion to be removed and the Gaussian
curve with a maximum ordinate based on the distribution coefficient. The
number of theoretical plates is directly proportional to the column height.
With knowledge of the number of theoretical plates, therefore, column
height can be defined.
In the application of commercial synthetic resins, it is unnecessary
in most c a s e s to calculate theoretical plate thicknesses. Loading,
leakage and capacity curves are among the studies of the resins which are
available from the manufacturer. A sample calculation would be as follows:

Example (1):

Problem: Removal of all ions from 1% of the primary loop coolant water.

B a s i c data:

(a) Coolant water circulation — 15 000 litres/min.

(b) Coolant water was originally demineralized.

50
(c) Cations and anions will be accumulated in the water from corrosion of
metal s u r f a c e s . There will also be some suspended matter, such as
insoluble hydroxides. A s s u m e that cation concentration will be in
the order of 6X 10"5 equivalents per litre in a system such as this
(metals, temperatures, flow rates, pH, etc.),

(d) Temperature of loop water will exceed the maximum temperatures

recommended for synthetic organic resins.

Solution:

(a) Cool the loop b y - p a s s water to 20-25°C.

(b) F i l t e r the cooled loop b y - p a s s water removing all particles larger

than 20 цin.

(c) Provide duplicate mixed bed ion-exchange columns with one unit for
s e r v i c e and one unit for stand-by,

(d) Use strong-acid and strong-base synthetic organic resins, nuclear

grade, with approximate total capacities of:

Cation resin — 2.0 equiv/litre

Anion resin — 1.4 equiv/litre

(e) A s s u m e the columns will be regenerated and that it is planned to

utilize 85% of the total cation-resin capacity and 55% of the total
anion-resin capacity.

(f) Calculate the volume of resin required:

Volume to be treated = 1% of 15 000 l i t r e s / m i n

= 150 l i t r e s / m i n or (150X1440)
= 216 000 litres/d

Cations removed per day = 0.00006X216 000

= .12. 96 equiv

Actual exchanger capacity = 85%X2.0

= 1 . 7 equiv/litre

L i t r e s of cation resin required for one day's operation = 12. 96/1. 7 = 7 . 6

The column can be sized for any desired s e r v i c e (exhaustion) cycle.

A s s u m e a 20-day period is selected.

Total cation resin required = 20X7. 6 = 152 litres. In order that the
mixed resins contain an equivalent of hydroxide ions for each equi-
valent of hydrogen ions, the volume of anion resin required will be
1 7
, _ - - ' , , — 7 7 X 152 or 336 l i t r e s . (The cation resin has 2. 21 times
(0.55X1.4)
the capacity of the anion resin). Each column will therefore contain
152 litres cation resin and 336 litres anion resin.

51
(g) Check:

Optimum flow rate for columns is 0.27 litres per litre per minute
(flow volume per resin volume per minute) with a normal range of
0. 2 to 0. 3. In this c a s e , flow of 150 l i t r e s per minute into a column
150
containing 488 (152+ 336) litres of resin amounts to — — or
488
0. 31 litres per litre per minute. To satisfy the maximum value of
150 or 500 litres of resin would be required. It is recommended,
0. 3, -Q—g
therefore, that total resin volume, for longer contact time and i m -
proved hydraulic performance, be increased to 500 l i t r e s , with
156 l i t r e s cation resin and 344 litres of anion resin. The s e r v i c e or
exhaustion cycle will be extended to:

156 litres cation resin

7 . 6 litres cation resin req'd/day

or 20.5 days.

(h) L i f e expectancy of the resins is affected by chemical degradation,

physical degradation and fouling due to i r r e v e r s i b l e binding of certain
ions. Many contributing factors or influences are involved, some
of which can be controlled only to a limited extent. A 'rule of thumb1
value where conditions are not obviously a g g r e s s i v e is based on the
total volume of liquid which has been treated. These values are, for

Cation-exchange resins > 667 000 litres per litre of resin

Anion-exchange resins 133 400 to 266 800 l i t r e s per litre

of resin.

In the example, therefore, the cation resin should serve for pro-
cessing more than (667 OOOX 156) or 104 052 000 litres, while the
anion-exchange resin should treat (266 800X344) or 91 779 000 l i t r e s .
With the high-purity waters involved in reactor coolant service,
practice has shown that these values can. be increased by more than
a factor of 10, so that the question of regeneration must be considered.
If the capital investment required for the equipment necessary for pre-
paring and feeding régénérant chemicals and for treating the spent
régénérant solutions cannot be justified as opposed to replacing the
resin, some satisfaction may be realized in being aware that the
resins had served a number of normal lifetimes. In the example,
it will be assumed that considerations in favour of regenerating
outweighed those opposed.

(j) Consider the physical plant and operating conditions:

In addition to knowledge of the 150-litre per minute feed rate and the
resin volumes, certain other basic data must be at hand to select
column s i z e . These include (a) variation in head loss with varying
feed rate and solution temperature, (b) minimum resin depth and (c)
space required for bed expansion in backwashing.

52
 Table XVII shows variation in pressure drop per 30.48 cm of
depth in a column of the sulphonic acid cation exchanger Amberlite
IR-120 as the feed rate is increased.
P r i o r to demineralization, the primary coolant b y - p a s s will be
cooled to about 30°C. P r e s s u r e drop will be l e s s than that indicated
under 23. 9 ° C . Before selecting the feed rate, it would be advisable
to consider the effect of minimum depth recommendations.
Where a mixed bed of strong-acid and strong-base resins is used,
bed depth may be as shallow as 30 cm. Whenever one of the resins
is weakly acid or weakly basic, the bed depth must be a minimum of
60 cm or only a portion of the realizable capacity will be utilized.
Table XVIII lists possible bed depths.
Backwashing requires at least 50 - 75% freeboard for expansion
of cation-exchange resins and 75 — 100% freeboard for expansion of
anion-exchange resins. In the mixed bed systems, this amount of
expansion permits separation of the resins by difference in specific
gravity. The separation is necessary prior to regeneration. Mini-
mum difference in specific gravity of the cation and anion resins
should be 0. 1 for satisfactory separation.
Any of the columns of Table XVIII would provide satisfactory
removals with the strong acid-strong liase resins of the problem.
The 100-cm resin depth will be selected, however, on the bafeis of
a balance of feed rate per unit area (distribution problems) vs. i n -
creased depth with increased pressure drop. In some c a s e s ,
pressure drop will be the decisive factor if minimum depth is ob-
tained. In our case, referring to Table XVII and using the figures
for 23. 9 ° C , pressure drop will be approximately 51 g / c m 2 per
30.48 cm or a total of 167 g / c m 2 .
Provide e x c e s s space of 120%. Straight side height will therefore
be 100 cm plus (1. 2X100) 120 cm or a total of 220 cm. The column
will, of course, be a pressure v e s s e l with dished heads both ends.

(k) The column should be fabricated of special stainless steel, hastelloy

steel or lined boiler plate to keep corrosion products to a minimum.
Linings may be plastic or rubber of such type and quality that they will
be unaffected by the acid and alkali régénérant solutions. Piping and
valves must also be resistant to corrosion. F o r this application, the
resin bed should be supported by a screen of resistant metal, glass
or plastic rather than gravel and sand.

(i) Operation:

(1) C a r e f u l l y condition new resins as recommended by the manufacturer.

(2) Operate in the s e r v i c e or exhaustion cycle at 0. 2-0. 3 volumes
solution per volume resin (150 1/min in example).

(3) Switch operation to the stand-by column when resistance of the water
from the operating column d e c r e a s e s to 1 - 5 m e g o h m - c m .

(4) Backwash the resins with deionized water to obtain 100% bed ex-
pansion. The resins will separate with the heavier cation-exchange
resins settling to the bottom. Drain the tank till the solution level
just covers the resin.

53
, (5) Regenerate: Régénérants used will be 4% sodium hydroxide and 10%
sulphuric acid. Quantities used are based on the original decision to
obtain 85% of the total cation-exchange capacity. F r o m the manu-
facturers' literature, it is found that (0. 85X2) or 1 . 7 equiv/litre
capacity will require 240 g of 66° Bé sulphuric acid per litre of resin
or (240X152) 36.48 kg. The 0. 77 equiv/litre capacity of the
anion-exchange resin will require 160 g of sodium hydroxide per litre
of resin or (160X344) 55 kg. Total régénérant volumes are:

(i) A 10% solution of 66° Bé sulphuric acid contains approximately

111 g / l i t r e . T h e r e f o r e , a total volume of 329 litres is

required.
(ii) A 4% solution of NaOH contains 41. 8 g/1. Therefore, a total
/ 5 5 000 \ 1 0 1 c l . t . ,
I ^ g lor 1316 litres is required.

Two methods of regenerating mixed beds are in use. These are the
'two-step' method in which each type exchanger is regenerated sepa-
rately and the 'simultaneous' method in which both resins are
regenerated at the same time. The simultaneous method s a c r i f i c e s
a certain amount of close control in exchange for a saving in time.
In the two-step method, anion resin is regenerated f i r s t with the
régénérant either permitted to pass through the cation bed or diverted
through the control distributor by an upflow of deionized water through
the cation resin. Rates of flow of régénérants are critical and
should not exceed 0. 067 ml of régénérant per millilitre of resin
per minute (67 ml per litre per minute) or (67X156) 10.45 litres
per minute for the cation-exchange resin and (67X344) 23. 05 litres
per minute for the anion-exchange resin.
A point to consider in establishing the regeneration technique is
that upflow of régénérant in a column where service or exhaustion
is downflow will minimize leakage. A band of unregenerated resin
will normally be found at the downstream end of the régénérant
passage, the thickness of the band depending upon the amount of
régénérant used. Regenerating in a direction opposite service flow
places this band at the head of the column and requires any leakage
to pass through the more completely regenerated resin.

{6) Rinse: T o remove e x c e s s régénérant from the column, it is rinsed

with deionized water at a rate equal to the regeneration rate. When
the volume of displaced solution equals one-half the volume of the
resin being rinsed, the rate is doubled until one column volume of
displaced rinse water has been obtained. Following rinsing of both
resins, the column is drained to within 2-5 cm of the resin surface.

(7) A i r mixing: It is now n e c e s s a r y to remix the resins before returning

the column to s e r v i c e . L o w - p r e s s u r e air, approximately 350 g / c m 2 ,
is introduced at the bottom of the column. Mixing is continued until
thorough intermingling of cation and anion resins can be assured.
This should require about 15 minutes, though a longer period would
not be harmful. A note of caution should be injected here regarding

54
 the air. Equipment should be provided to assure air which is o i l - f r e e
ánd v e r y low in solids.
Following air mixing, the resins should be given a final brief rinse
to remove the last t r a c e s of régénérant. The column is then again
ready for s e r v i c e .

The above is one solution to the problem. There are many more.
Nuclear grade resins are relatively new and many mixed bed columns
presently in s e r v i c e have not taken advantage of them. Generally, the
problem is complicated by pH requirements, silicates, etc. and volumes
for treatment are greater. Some solutions to the problem at existing
operating facilities are described in section VII.

VI-5. DESIGN CONSIDERATIONS IN T R E A T M E N T OF G E N E R A L

L A B O R A T O R Y AND P L A N T WASTES

Application of ion exchange and adsorption to treatment of general

low- and intermediate-level radioactive waste solutions varies widely as
compared to application to demineralization of reactor waters. The
solutions involved differ considerably in chemical and physical character-
istics between sites. Though approaches to the problems may be similar,
influences such as economics, availability, site location, etc. will guide
s y s t e m designs to solutions which are different but yet best suited to the
particular installations. Where in one instance synthetic organic resins
are used, natural zeolites or clays may be found most appropriate in
another locale for somewhat similar wastes.
Two primary conditions for the successful use of ion exchange, as
discussed previously, are (1) low suspended solids and (2) low dissolved
solids. In only exceptional c a s e s would it be economical to use ion-
exchange materials as a filter since much cheaper substances are avail-
able for this purpose. Plugging by solids would also deny use of some of
the exchange capacity. Dissolved solids must be low to allow use of the
exchange capacity for removal of the t r a c e amounts of radioactive ions.
Where the exchange sites are occupied by the non-active ions of the sol-
ution, decontamination factors will be low and the use of this method may
become uneconomical. Exceptions, of course, are those c a s e s where
exchangers are readily available at low cost.
A s an illustration of the almost unlimited capacity available for treat-
ment of low- and intermediate-level wastes by strong-acid synthetic
organic cation exchangers, when no competing ions are present,
Example (2) is presented below.

Example (2):

A s s u m e a waste consisting of l X 1 0 _ 2 ^ C i / m l of 90 Sr in otherwise

demineralized water. This solution will be treated by 50 litres of a
strong-acid synthetic organic resin with a breakthrough capacity of
1. 6 meq/ml of wet resin.

Total resin capacity = 1 . 6 X 5 0 X 1 0 3

= 8 X 10 4 meq
= 80 eq
55
 ft 7 fi 9
80 eq of 9 0 Sr = 80 X — ^ = 3505 g 9 0 Sr. At 144 C i 90 Sr per g r a m , the

50 l i t r e s of resin would be capable of removing (144X3505) or 504 720 C i

of 90 Sr before exhaustion, if it had not s u f f e r e d radiation damage.
T w o important considerations indicated in Table XIX are (1) the long-
h a l f - l i f e of many of these nuclides and (2) the v e r y low p e r m i s s i b l e
drinking water t o l e r a n c e s . Due to the slow decay, t e m p o r a r y storage
of exhausted r e s i n s or régénérant solutions cannot be considered. The
collected activity i s either further concentrated by incineration of the
resin, evaporation of the spent régénérant, or chemical treatment of the
spent régénérant, or the exhausted r e s i n s are fixed in a slow-leaching
matrix. Concentrated activity f r o m the incineration, evaporation or
c h e m i c a l treatment is also insolubilized before final ground or sea
disposal.
The low p e r m i s s i b l e drinking water tolerances establish the n e c e s s i t y
for a v e r y high degree of treatment which can be provided by ion exchange
for the nuclides l i s t e d . If the waste contains only one or two or the radio-
nuclides, it is possible to use an exchanger with a high s e l e c t i v i t y f o r
them; for example, v e r m i c u l i t e has been found to have a high s p e c i f i c i t y
for c a e s i u m and strontium. In some instances, a cation exchanger alone
will provide the required decontamination factor while in others, c o m -
plexed ions will require treatment by both cation and anion exchange for
s a t i s f a c t o r y r e m o v a l . Mixed f i s s i o n product wastes of c o u r s e are most
s u c c e s s f u l l y decontaminated by dual bed or mixed bed types of treatment.
Table X X l i s t s exchangers found to be s u c c e s s f u l in r e m o v a l of s p e c i f i c
radionuclides.
Since the waste contains 10' 2 /nCi/ml or 10 mCí/1, the number
of l i t r e s treated before exhaustion is

504 720 X 1 0 6 ^ C i = 504 7 2 0 x l 0 5 l

10 AiCi/1
= 5047X107 m3

In many instances p r e - t r e a t m e n t by chemical means is justified prior

to a polishing by ion exchange. In one instance, electrodeionization by
membrane is the p r e l i m i n a r y step to final treatment by ion exchange. It
is often n e c e s s a r y to adjust the pH of the waste solution since the exchanger
may not be compatible with the acid or alkaline condition of the solution or
the capacity, rate of exchange, etc. may be optimum at a s p e c i f i c pH. The
degree of treatment n e c e s s a r y is controlled by local conditions. The d e g r e e
furnished by ion exchange can be adjusted by use of more extensive t r e a t -
ment. Single c a t i o n - o r anion-exchange columns can be used in certain
c a s e s . A higher degree of treatment is afforded if the single column is
replaced by s i m i l a r s e r i a l columns. The dual bed and mixed bed s y s t e m s
afford the l a r g e s t decontamination f a c t o r s .
T a b l e XIX l i s t s a number of the principal nuclides of concern in
g e n e r a l waste solutions.
F o r the synthetic organic r e s i n s , operating conditions a r e s i m i l a r
to those described in discussing treatment of reactor cooling w a t e r s .
Maximum t e m p e r a t u r e s and pH ranges a r e specified by the manufacturer.
F o r r e m o v a l of radionuclides by resin cation exchange, certain authorities
[86, 87] recommend operation at a pH of 2. 5 to a s s u r e that all f i s s i o n

56
products are ionized. S e r v i c e flow rates are again optimum at 0. 27
litres per litre of resin per minute, but rates five times a s great have
been used. Resin bed depth should not be l e s s than 60 c m . The r e c o m -
mended backwash rate is based on bed expansion which is dependent upon
the resin specific gravity and régénérant temperature. F o r a 50% ex-
pansion of a strong-acid polystyrene resin bed, a rate of about 4. 0 l i t r e s
per second per square metre of bed area is required. Regeneration of
resins operated in the H4 cycle is accomplished with 10% HC1, 1 - 5%
H2SO4 or 6N HNO3. Regeneration flow rates and rinse rates are as
mentioned previously. In many c a s e s , quantity of régénérant used is
decreased by saving all but the first portion of spent régénérant for use
as first régénérant in the following c y c l e .
The wastes at each installation must be examined individually and a
laboratory study of the application of ion exchange to the treatment and
disposal problems must be undertaken. It is likely that ion exchange in
some form could be a major part of any waste processing installation. It
is n e c e s s a r y to determine in which form it will be most practical and
economical. Where in one case electrodeionization may be the optimum
method of reducing solids in a waste, in another instance use of additional
ion-exchange columns or other preliminary treatment may be more
economical. Basic design computations for an ion-exchange waste treat-
ment facility are identical to those shown in Example (1). Total hardness,
however, would be used to determine volume of resin required. In the
case of general wastes, there are more instances of resin regeneration
since c y c l e s are usually of much shorter duration.
In the treatment of the general wastes, there has been a much wider
application of natural materials on a once-through basis. Capacities of the
natural materials are only a fraction of those of the synthetic organic, but
advantages in original cost prescribe use of the minerals, coals, etc.
Equipment requirements are fixed by the particular p r o c e s s selected.
If alkaline conditions will prevail, iron or steel piping, v a l v e s and tanks
will be adequate. Under acid conditions and for storage of acid régénérants,
specific materials are n e c e s s a r y as follows [88]:

(a) F r o m very dilute to 70% HNO3:

(1) 304, 316, 430 stainless steel - excellent

(2) Cobalt base superalloy — no penetration at room temperature
(3) Titanium — satisfactory
(4) Zirconium — satisfactory
(5) C F E fluorocarbon — excellent
(6) Polyvinylchloride — resistant to 10, 30 and 68% acid solutions
(7) Nitrile elastomer — excellent for solutions to 20% at room
temperature
(8) G l a s s — excellent.

(b) F r o m very dilute to 66° Bé (96%) sulphuric acid:

(1) Aluminium — satisfactory for very dilute solutions at room

temperature
(2) Carbon steels — satisfactory for solutions of 90-100% acid
provided there is no agitation
 C a s t iron (grey) — satisfactory for solutions >65% (wt) acid
C a s t iron (high silicon) — resistant to all conditions and tempera-
tures up to the boiling point
C o b a l t - b a s e superalloy — satisfactory at room temperature
Copper, copper-silicon, copper-nickel — satisfactory
Lead — resistant to 96% solution at room temperature
Phosphor bronze — satisfactory
Red brass — satisfactory
Wrought iron — satisfactory at concentrations above 85%
Zirconium — satisfactory
Chlorinated polyether — excellent to 80% to 1 2 1 ° C , do not use
for solutions > 98%
Polycarbonates — no attack to 75% solution
Styrene-acrylonitile — satisfactory to 30% concentration
Vinylidene fluoride — satisfactory
Butyl rubber — satisfactory to 50% concentration
Neoprene — satisfactory to 50% concentration
Nitrile elastomer — good to excellent for 17-56% at room
temperature to 70°C
Stoneware — excellent to 135°C
P o l y e s t e r coatings — no e f f e c t s .

(c) F r o m dilute to concentrated HC1:

(1) High silicon cast iron (chromium added) — resistant to dilute to

7 9 ° C ; to intermediate concentrations to 66°C; to high concen-
trations to 52°C
Hastelloy С — resistant to all concentrations to 49°С
Red brass — fair
Phosphor bronze — f a i r
Tantalum — good
C F E fluorocarbon — excellent
Chlorinated polyether — excellent to 50% concentration to 121 °C
Ethyl cellulose — good
Polyvinylchloride — resistant to concentrations to 35%
Reinforced epoxy — excellent in cold
Vinylid fluoride — good
Butyl rubber — excellent
Nitrile — excellent to 20% concentration at room temperature
Polysulphide rubber — good
Silicon rubber — good at dilute concentrations
G l a s s — excellent
Stoneware — resistant
G l a s s lining — excellent at room temperatures
Furane coating — no attack.

In the majority of applications of ion exchange to waste treatment,

the fixed bed v e r t i c a l column s y s t e m s are used. The columns are com-
monly operated downflow at a rate of 16 bed volumes per hour (0. 27 waste
volumes per resin volume per minute) during s e r v i c e or exhaustion. This
rate can be higher for the smaller ionic s i z e s , for operation at somewhat
elevated temperatures, for operation of columns in series or for mixed
bed s y s t e m s .

58
 Backwash is carried out upflow just prior to regeneration and at
other times as it may become n e c e s s a r y . Backwash is used to (1) remove
collected matter which may have been filtered Out during downflow, (2)
eliminate any g a s e s collected in the resin, (3) break up compressed clumps
of resin caused by resin expansion and (4) r e c l a s s i f y resin particles as
to size and position. Rate of flow during backwash must be sufficient to
expand the exchanger bed a minimum of 50%. N e c e s s a r y rates depend
upon the exchanger density. With resins, cation exchangers are more
dense than anion-exchange resins and require a higher backwash flow rate.
The proper rate should be determined by laboratory methods and checked
periodically to prevent washing resins to waste. Backwash waters are
usually taken from stored, treated wastes, which, following the washing
operation, are returned as raw waste for future treatment or are collected
separately for treatment by other means.
When resins are exhausted, regeneration will immediately follow
backwashing. In treatment of radioactive wastes, acids are normally used
to regenerate cation exchangers and alkalis are used for anion exchangers.
Optimum concentrations of régénérant solutions are obtained from the manu-
facturers of c o m m e r c i a l resins, but must be determined by laboratory
methods for the n o n - c o m m e r c i a l types. Quantity of régénérant used, as
discussed previously, determines the capacity of the resin. The value
selected i s a balance of the desired capacity and length of c y c l e s with the
cost of the régénérants. With strong-acid and strong-base resins, for
instance, a large e x c e s s over theoretical quantities is required to obtain
a high percentage of total resin capacity. Weak-acid and weak-base
resins are regenerated to hydrogen and f r e e - b a s e forms with little more
than stoichiometric quantities of régénérants. Régénérant solutions are
usually fed downflow through columns at a rate of 4 - 1 2 bed volumes per
hour (0. 06-0. 2 litres per litre of resin per minute). The lower r a t e s
provide a longer period of contact, thereby allowing more complete dif-
fusion of régénérant into the resin and migration of the l a r g e s t ions out
of the resin.

Upflow regeneration is practiced in some c a s e s and is desirable in

that leakage of strongly adsorbed ions is minimized. These ions tend to
be retained in the bottom resins during the exhaustion c y c l e . With upflow
regeneration, they are contacted first and tend to be displaced upward.
The most thoroughly regenerated portion of the bed is then at the bottom
of the column and leakage during the exhaustion c y c l e is reduced.
Use of auxiliary régénérants is sometimes necessary when organic
compounds in the waste reduce efficiency of standard regeneration tech-
niques. This is often combatted by washing cation exchangers with
alkalis prior to acid regeneration and anion exchangers with acid solutions
prior to alkaline regeneration.
Following regeneration, the ion exchangers are rinsed to remove any
e x c e s s régénérant or eluted matter. Rinsing is continued until activity
l e v e l s in the rinse water indicate that the exchangers are clean. Use of
deionized water for rinsing is preferable since no exchange capacity will
be lost to rinse water ions. However, this is not practical or economical
in many c a s e s . To compromise, a softened water can be used for
rinsing cation exchangers and a 'decationized' water can serve for the
anion exchangers. Minerals in rinse waters would form insoluble salts
when contacting e x c e s s régénérant or ions released from alkali-regenerated

59
s t r o n g - b a s e r e s i n s . Insoluble hydroxides of c a l c i u m and m a g n e s i u m , f o r
e x a m p l e , would coat the r e s i n s and reduce e f f i c i e n c y .
Rinsing is actually conducted in two c y c l e s . T h e f i r s t c y c l e at 0. 06
- 0 . 2 l i t r e s per l i t r e of exchanger per minute s e r v e s to d i s p l a c e e x c e s s
régénérant which i s drained to the spent régénérant holding v e s s e l . The
second c y c l e is conducted at a flow rate t w i c e that of the f i r s t and the
effluent rinse water is drained to waste.
Spent régénérant and f i r s t c y c l e rinse water, containing all the a c -
tivity eluted f r o m the e x c h a n g e r s , are c o l l e c t e d in a separate v e s s e l for
further t r e a t m e n t . G e n e r a l l y used treatment methods are those which
attempt to further reduce v o l u m e s . E v a p o r a t i o n p r o v i d e s m a x i m u m
volume reduction, but is the most c o s t l y . C h e m i c a l treatment is p o s s i b l e
in many c a s e s and a c t i v i t i e s a r e concentrated in sludges which amount
to 1 - 1 0 % of original régénérant v o l u m e . In either c a s e , r e s i d u e s or
sludges must usually be insolubilized b e f o r e final d i s p o s a l .

VI-6. SHIELDING REQUIREMENTS

The r a d i o a c t i v i t y c o l l e c t e d in i o n - e x c h a n g e columns c r e a t e s a hazard

to o p e r a t o r s in the a r e a . T o p e r m i t a c c e s s to control m e c h a n i s m s , the
b a s i c p r i n c i p l e s f o r radiation protection — t i m e , distance and shielding —
must be c a r e f u l l y considered in design and location of tanks, piping,
c o n t r o l s , and appurtenances. The distance principle can be employed by
locating m e t e r s , when p o s s i b l e , in s e p a r a t e rooms away f r o m the equip-
ment. F o r operating personnel, extended v a l v e handles can be used or
remote control d e v i c e s can be incorporated in the design. T h e importance
of distance cannot be o v e r e m p h a s i z e d . It is usually the most e a s i l y
applied principle and it is very e f f e c t i v e . The i n v e r s e square law g o v e r n s
radiation intensity f r o m point s o u r c e s of g a m m a radiation. T h i s law
states that radiation intensity f r o m a point v a r i e s i n v e r s e l y as the square
of the distance f r o m the s o u r c e , or:

Il_ (D2)2
=
I2 фг)2

where I i is the radiation intensity at distance D j and I 2 is the radiation

intensity at distance D2 f r o m the s o u r c e . F o r example, if g a m m a radiation
intensity were 100 R / h at 1 m, it would be only 4 R / h at 5 m.

I i d 0 0 ) _ (P2)2 (52) 25
Ч ~ (Di) ( l ) 2 ~ 1

or I 2 = 4.
Controlling e x p o s u r e t i m e is a l s o an e a s i l y applied principle in most
c a s e s . T i m e r e q u i r e m e n t s f o r operational functions can be minimized by
proper equipment s e l e c t i o n . Where work must be p e r f o r m e d in high dose
rate a r e a s , it can usually be completed by i n c r e a s i n g the number of p e r -
sonnel and limiting exposure t i m e of e a c h .
T o reduce dose r a t e s in working a r e a s , the principle of shielding is
applied. With p r o p e r shielding m a t e r i a l s , X - and g a m m a radiation are

60
attenuated to an extent that dose rates are lowered with minimum inter-
ference with equipment and procedures.
Radiation energy i s absorbed or lost in passing through material by
the photoelectric effect, the Corripton effect and/or pair production. The
decrease in the number of the photons as they are absorbed by these methods
i s governed by the energy of the radiation, the specific absorber medium
and the thickness of the material. F o r narrow beam conditions, this can
be expressed mathematically as:
-ЦХ
I= I0e

where I = radiation intensity after absorption by material of thickness x,

I 0 = intensity of incident radiation, e = natural logarithm base, x = thick-
ness of absorber transversed and ц = proportionality constant or ab-
sorption coefficient.
The formula is easily applied when pt is known, ц , which is dependent
on the particular material and the intensity of the incident radiation, must
be determined experimentally. This has been done for a wide range of

FIG. 17. Transmission of radium, cobalt-60 and caesium-137 gamma rays through concrete. (From
Radiological Health Handbook, 1960 rev. e d . , Div. of Rad. Health, US Dept. of Health, Education
and Welfare — National Bureau of Standards.)

61
materials at all radiation energies and the values are provided in tables
and graphs in many handbooks (e. g. B l i z z a r d , E . P . , Abbott, L . S . (Eds),
Reactor Handbook, Vol. Ill, P a r t B, Radiation Shielding, Interscience
Publishing Co., New York (1962)). It can be noted from the formula that
the l a r g e r the value of ц for a given thickness, the greater the reduction
in intensity. The metal lead has a high ц and is widely used as a shielding
material.
In practice, narrow beam conditions are not usually met since point
sources are not involved. B e a m s are broad and wide absorbers of con-
siderable thickness are needed. Radiation becomes scattered within the
absorber and increases in intensity. An additional coefficient or factor
must enter the equation above to provide this adjustment. This 'build-
up factor', b, is determined for specific materials, radiation energies,
source geometries and penetration depths. Values are provided in graphs
or tables in handbooks. With b inserted, the attenuation equation becomes:

One manner in which attenuation data are presented is shown in

F i g s 17 and 18. F r o m F i g . 18, for instance, it is shown that 51 cm of
concrete will permit transmission of only 0. 0017 of the initial intensity of
a 1 3 7 C s source.

FIG,IS. Transmission of radium, cobalt-60 and caesium-131 gamma rays through ion and lead (B repre-
sents fractional transmission.) (From Radiological Health Handbook, 1960 rev. e d . , Div. of Rad. Health,
US Dept. of Health, Education and Welfare — National Bureau of Standards.)

Shielding for attenuation of beta radiation is a much simpler matter

because of the short range and low penetrating power of beta particles.
Shielding is designed to absorb the beta radiation completely and the low
material requirements are presented graphically in F i g . 19.

62
 FIG. 19. Penetration ability of beta radiation. (From The industrial uses of radioactive fission products,
USAEC, Stanford Research Institute Report No.361.)

Where great intensities of beta radiation are absorbed, the electro-

magnetic bremsstrahlung radiation is produced by the deceleration of the
beta particles. The bremsstrahlung are effectively X-radiation and as
such are much more penetrating than beta radiation. Shielding must be
calculated using methods as for X - or gamma radiation.
Where only alpha emitters are involved, shielding as such is not
usually considered. Alpha particle range is v e r y limited. The expression
R „ = 0. 312 E 3 / 2 where R а = range in cm air at 1 atm and 1 5 ° C , and E =
energy in MeV demonstrates the very short range in air. Materials as
paper, sheet plastic or even a coat of paint will render alpha-contami-
nated surfaces h a r m l e s s . The greatest cause for concern is that wind
drafts over alpha-contaminated surfaces will c a r r y the particles so that
they may be inhaled. A s long as alpha contamination is controlled at
the no-swipe level, dangers are minimal.
A s applied to ion-exchange practices, shielding for protection from
gamma radiation is usually accomplished by wrapping units in lead sheet,
by providing lead b a r r i e r s or by using concrete walls of sufficient density
and thickness. The distance principle is easily employed since little
continuous surveillance is n e c e s s a r y during operation. Remotely read
meters and gauges provide adequate functional control.

63
VII. OPERATIONAL PROCEDURES AND EXPERIENCES

VII-1.' GENERAL

The many types oí ion-exchange materials and the wide variety of

s y s t e m s developed for using them have been discussed in the previous
sections. Principal effort in this section will be directed at reviewing
the known waste treatment facilities which incorporate ion exchange in
any form.
Here again, demineralization of reactor coolant and radioactivity
removal from general laboratory and plant waste solutions will be con-
sidered separately. Treatment of reactor waters is a v e r y specific
problem which has been solved in the majority of c a s e s in a very similar
manner. Laboratory and plant waste solutions differ widely and the
many problems which have been solved in whole or part by ion exchange
have utilized almost the entire range of materials and methods known.

VII-2. O P E R A T I O N A L P R O C E D U R E S AND E X P E R I E N C E S :
T R E A T M E N T OF R E A C T O R W A T E R S

The problems in the deionization of reactor waters have been faced

many times in many parts of the world. Solutions reached are the results
of laboratory appraisal of the particular problems and cannot be applied
at random to similar problems. However, there is much to be learned
from these operating facilities in regard to design criteria. Descriptions
of a number of installations follow.

(a) Consolidated Edison Thorium Reactor (CETR), Indian Point, N . Y . , USA

Type: P r e s s u r i z e d water power reactor

P r i m a r y coolant flow rate: 24X10 6 kg/h

% of total demineralized: -

Activated corrosion products: 56 Mn, 5 9 Fe, 1 8 2 Ta, 60Co, 187 W

Treatment of make-up water: Raw water is softened by cation

exchange, treated for removal of carbon dioxide, realkalized with
caustic soda, evaporated and finally demineralized through four
rubber-lined mixed bed units. The make-up water averages 0. 01 mg
silica per litre and l e s s than 0. 05 mg ionizable solids per litre.

(b) NRX and NRU Reactors, Chalk R i v e r , Ont., Canada [89]

Type: Natural uranium, heavy water moderated

Total rod bay volume: 12 000 m3

Total make-up: 850 m 3 /week

Make-up water: Deionized steam condensate

64
 Treatment of recirculating rod bay water: Filtration and deionization
through mixed bed exchangers

Type resins: Strong acid, strong base

Volume r e s i n / c o l . : 0.85 m 3
3
S e r v i c e (exhaustion) rate: 27 0 l i t r e s per min per m .
Regenerate with 6% wt H N 0 3 and 4% wt NaOH. Evaporate spent
régénérant and store residue
Controls: Conductivity maintained at 2 - 3 fimho-cm 1 ; beta activity
<5000 disintegrations per minute per millilitre

Materials of construction: 304 stainless steel

F i g u r e 20 is a schematic of the circulating system.

The operation requires approximately 2200 man-hours of s e r v i c e
annually.

FIG.20. Flow sheet of rod bay deionization system for Atomic Energy of Canada Ltd., NRX and NRU
Reactors, Chalk River, Canada.

(c) Karlsruhe R e s e a r c h Reactor F R - 2

Type: Tank type, natural uranium, heavy water moderated and cooled
r e s e a r c h reactor

Coolant mass flow rate: 397 k g / s

Make-up water: Well water is filtered and deionized

E m e r g e n c y cooling system: Settling tank, filter, ion-exchange

columns and storage tank.

65
(d) Belgium Thermal Reactor B R - 3

Type: Slightly enriched uranium, two regions, light water

moderated and cooled, pressurized water type

Coolant m a s s flow rate: 630 k g / s

P r i m a r y coolant b y - p a s s flow rate: 1360 kg/h

Treatment by mixed bed demineralization, degasification,
injection of H2 and boric acid.

Table XXI lists a number of research reactors, by country, which

use ion exchange to purify reactor coolant waters. In Table XXII,
water treatment s y s t e m s for several of the larger power reactors are
set forth.

VII-3. E X P E R I E N C E S IN T R E A T M E N T O F
G E N E R A L P L A N T AND L A B O R A T O R Y W A S T E S

Many operational facilities over the world use ion exchange in

their processing of general plant and laboratory radioactive wastes.
In most c a s e s , it is a small part of their total capability and in many,
it is merely a polishing operation. Table XXIII lists s e v e r a l of the
major laboratories of the world with some general data regarding their
utilization of ion exchange in waste processing. To cover the individual
characteristics of a number of installations, they are discussed below
under separate headings.

Hahn-Meitner-Institut für Kernforschung (HMI), Berlin,

Federal Republic of Germany [92]

For polishing of chemically treated l o w - l e v e l wastes when certain

nuclides, particularly 1 3 7 C s , have not been removed to satisfactory
levels, ion exchange is provided. The chemical waste treatment plant
effluent can be treated through cation-exchange resins, anion-exchange
resins, mixed bed resins or through the three columns in series.
Figure 21 is a schematic diagram of the plant.
Influent waste averages 250 mg/1 (as C a C 0 3 ) in total hardness and
400 to 500 mg/1 in total solids. Beta emitters are less than 5X 10~4 juCi/ml.
Exchangers used in the columns are strong-acid and strong-base
synthetic organic resins in the Na+ and NO¿ forms. The resins are
regenerated upon exhaustion and the spent régénérant is treated by
evaporation. It has been possible to treat approximately 8 m 3 of waste
with 25 litres of cation resin and obtain decontamination factors of 10 2 t o l O 3 .
Materials of construction in the s y s t e m include plexiglass (acrylic),-
polyvinylchloride and stainless steel.
In a recent innovation, columns of a natural inorganic exchanger have
been added. The columns will accept waste either prior or subsequent
to chemical treatment. The low-cost material, sold c o m m e r c i a l l y as
'Filtrolit', is highly selective for 1 3 7 C s for which it has a total capacity
of 22 meq/100 g. The material is heterogeneous, containing s e v e r a l
silicate minerals. P r i o r to use for 1 3 7 C s removal, it is given a N a C l

66
 CHEMICAL FEED

Дг
j
WASTE-
WATER
П
и v
х -

WASTE
• — SLUDGE
F . Т О CITY
" SEWERS
flrtt
,TJ j g T...
([ l« D О9
г \ / / г r>

I. GREASE TRAP 6. ION-EXCHANGE COLUMNS

2 HOLDING TANK 7 STORAGE TANK FOR ION-EXCHANGE
COLUMN RINSE WATER
1 STORAGE TANK 8. FINAL E F F L U E N T HOLDING TANK
4 CHEMICAL PRECIPITATION TANK 9. WASTE PUMP
й PRESSURE FILTER 10. SLUDGE P U M P

FIG.21. Waste treatment, Hahn-Meitner Institute, Berlin.

treatment which significantly increases its capacity. Preliminary

studies indicate that it will be possible to treat 40-50 m 3 of waste with
a column containing 25 1 of exchanger. Exhausted media will be
collected in drums for final disposal as solids.

Atomic Energy Research Establishment, Harwell, Berks, UK [94]

Ion exchange for waste treatment at Harwell is still somewhat

experimental. In one application, effluent of a chemical treatment
plant for m e d i u m - l e v e l waste is given a final polishing through v e r m i -
culite. Total dissolved solids in the feed to the exchanger vary from
500 to 200 m g / l and activity in the form of mixed fission products
averages 10-1 to 10"3 /jCi/ml.
The inorganic mineral vermiculité with a specificity for 1 3 7 C s and
90 Sr is used as a lining in a v e r t i c a l centrifuge. Figure 22 is a schematic
of the p r o c e s s and F i g . 23 shows the actual equipment being used. E x -
haustion is determined by breakthrough of radioactivity and exhausted
mineral is discharged directly into the disposal container. Decontamina-
tion factors for the exchanger are approximately 10 for alpha emitters
and 20 for beta emitters. Materials of construction for the system are
generally mild steel or rubber-lined mild steel.
In another application at Harwell, filtered m e d i u m - l e v e l radioactive
waste is demineralized in a s e r i e s of cation-anion exchange columns.
Suspended solids in the column feed are < 4 m g / l and dissolved solids
v a r y from 500 to 1500 m g / l . Activity due to mixed fission products
ranges from 1 to 10~3 juCi/ml.
Resins used in the cation-exchange columns are strong-acid
sulphonated polystyrene and resins of the anion-exchange columns are
w e a k - b a s e polystyrene. Each of the four columns contains 0.38 m 3 of

67
FIG.22. Flow diagram of centrifuge ion-exchange plant, Harwell, UK.
 FIG.23. Centrifuge ion-exchange plant, Harwell, UK.

resin. Figure 24 is a schematic diagram of the facility and Fig. 25 shows

the actual plant.
The plant is operated with an average feed rate of 97.2 litres min" 1
m" 3 through the serial cation-anion resin columns. Exhaustion is de-
termined by increase in conductivity in the effluent of the fourth column.
The first pair of columns is then regenerated and used as the second
pair in the following run. Nitric acid, 4.4N, is used to regenerate the
cation-exchange resin and 3N sodium hydroxide is used to regenerate
the anion exchanger. Two bed volumes of régénérant are used, with
the first bed volume being the second bed volume of régénérant from the
previous c y c l e . The method is very effective in reducing régénérant
volumes requiring further processing. After the used régénérant from
the previous cycle has served for the second time, it is absorbed by
exfoliated vermiculite for storage or sea disposal.
Materials of construction used include rubber-lined mild steel for
the m a j o r portion of the plant and stainless steel for those units in
contact with nitric acid.

69
L o s A l a m o s S c i e n t i f i c L a b o r a t o r y , L o s A l a m o s , N. M . , USA

T h e n o r m a l w a s t e s t r e a m at L o s A l a m o s i s p r o c e s s e d by c h e m i c a l
t r e a t m e n t m e t h o d s f o r r e m o v a l of the a l p h a e m i t t e r s p l u t o n i u m and
u r a n i u m . C e r t a i n of the w a s t e - c o n t r i b u t i n g f a c i l i t i e s , h o w e v e r , on an
i r r e g u l a r schedule, d i s c a r d solutions containing relatively l a r g e amounts
of m i x e d f i s s i o n p r o d u c t s . T h e r a d i o n u c l i d e of m a j o r c o n c e r n due to i t s
c o n c e n t r a t i o n in the w a s t e s and i t s v e r y low d r i n k i n g w a t e r t o l e r a n c e i s
90
S r . T o r e d u c e i t s l e v e l in the w a s t e , two i o n - e x c h a n g e c o l u m n s have
b e e n p r o v i d e d at the e f f l u e n t end of t h e c h e m i c a l t r e a t m e n t f a c i l i t y .
P i p i n g a r r a n g e m e n t s a r e s u c h that e i t h e r u n t r e a t e d o r c h e m i c a l l y
t r e a t e d w a s t e m a y b e fed t o t h e c o l u m n s . T h e u n i t s a r e 1.98 m in d i a m .
and c o n t a i n 4.15 m 3 of s t r o n g - a c i d p o l y s t y r e n e c a t i o n - e x c h a n g e r e s i n
e a c h . pH of the f e e d s o l u t i o n i s a d j u s t e d to 2 . 5 - 3 . 0 with n i t r i c acid
and the f e e d r a t e i s m a i n t a i n e d at 0.23 1 / m i n / l of r e s i n . E x h a u s t i o n i s
d e t e r m i n e d by 9 0 Sr b r e a k t h r o u g h .
P i p i n g at t h e c o l u m n is a r r a n g e d to p e r m i t s e r i e s o r p a r a l l e l
o p e r a t i o n e i t h e r upflow o r downflow. R e g e n e r a t i o n , h o w e v e r , i s
e s t a b l i s h e d a s downflow only. All piping, v a l v e s and t a n k s a r e
s t a i n l e s s s t e e l to t h e point of n e u t r a l i z a t i o n of t h e c o l u m n e f f l u e n t .
T h e r e s i n s a r e r e g e n e r a t e d with 6N n i t r i c a c i d upon e x h a u s t i o n
and s p e n t r é g é n é r a n t i s c o l l e c t e d in a s e p a r a t e t r e a t m e n t t a n k . C h e m i c a l
t r e a t m e n t of t h e r é g é n é r a n t s o l u t i o n with s t r o n t i u m n i t r a t e , l i m e , f e r r i c
s u l p h a t e and s o d a a s h r e s u l t s in a s l u d g e c o n t a i n i n g o v e r 99.9% of the
90
S r . T h e s l u d g e , a p p r o x i m a t e l y 15% of the r é g é n é r a n t v o l u m e , i s
d r a i n e d to a s t o r a g e tank f o r e v e n t u a l d i s p o s a l in c e m e n t - v e r m i c u l i t e
in 200-1 d r u m s . A d i a g r a m of the e n t i r e f a c i l i t y i s shown in F i g . 26.

COAGULANT AID
VACUUM
FLOCCULATOR PUMP
CLARIFIER
DEWATEREO
SLUDGE TO BURIAL

CHEMICALS- SrlNO,), .nojCO,

NaOH.CotOH^.FepfSlVj
GRIT DRUMS TO BURIAL- CEMENT 8
VERMICULITE

DRUM
TUMBLER:
; SLUDGE-
I CEMENT DRUMS
I TO BURIAL
CANYON -SPENT
-SLUDGE REGENERANT
STORAGE SLUDGE
GRIT CHAMBER 8 TREATED WASTE- TANK SPENT HOLDING TANKS
BUCKET ELEVATOR HOLDING TANKS REGENERANT-
TANK
RAW WASTE
HOLDING TANKS

FIG.26. W a s t e t r e a t m e n t f a c i l i t y , L o s A l a m o s S c i e n t i f i c L a b o r a t o r y , Los A l a m o s , N.M., USA.

BelgoNucléaire, Mol, B e l g i u m [96]

Very stringent r e q u i r e m e n t s limiting effluent activity concentration

f r o m r e s e a r c h c e n t r e s n e c e s s i t a t e the u s e of i o n - e x c h a n g e p o l i s h i n g of
chemical treatment plant effluent. The waste to the columns contains
500 to 1000 mg/1 total dissolved solids, b e t a - g a m m a activity of 10~5 ¿iCi/ml
and alpha activity of 10" 7 /uCi/ml. The v e r y soft water, hardness 12.5 mg/1,
has a pH of about 9.0.
Two columns are used in s e r i e s , both containing 1 m 3 of resin. The
dual bed system uses a strong-acid synthetic organic resin in the Na + form
in the f i r s t column and a strong-base organic resin in the C l " form in
the second. Feed to the columns is at the rate of 0.5 litres min" 1 litre
of resin. Exhaustion is determined by radioactivity and hardness b r e a k -
through. When this occurs, the resins are regenerated with 10% sodium
chloride and the spent régénérant is directed to the l o w - l e v e l radioactive
waste treatment plant. Decontamination factors achieved are 2 to 5 for
b e t a - g a m m a emitters, 10 for 9(ÎSr and 2 to 5 for alpha emitters.
With the waste maintained at a pH of about 9.0, mild steel construction
for plant equipment has proven s a t i s f a c t o r y .

Reactor Centrum Nederland, Petten, Netherlands [97]

The ion-exchange facility included in the treatment plant at RCN is

used only occasionally. When effluent of the chemical flocculation plant
has over-tolerance amounts of 1 3 7 C s , it is directed to cation-exchange
columns. The two units, operating in parallel, are 64 cm in diam. and
are constructed of hard-rubber lined mild steel. Exchangers are highly
crosslinked strong-acid synthetic organic resins in the H* form. E x -
haustion is determined by increase in column effluent beta activity.
Exhausted resins are regenerated with 8% nitric acid and the spent
régénérant is stored in plastic-lined 200-litre drums for future mixing
with cement- vermiculite and seal burial. The decontamination factor
for beta activity has averaged 100. Figure 27 is a view of the columns.

Savannah R i v e r Plant, Aiken, S . C . , USA [98]

To p r o c e s s evaporator overheads and miscellaneous wastes with

137Cs concentrations at 0.05 to 0.10 /uCi/ml, the Savannah River Plant
utilizes a synthetic chabazite, Linde AW-500. The material is highly
selective for 1 3 7 C s and has a total cation-exchange capacity of 2.2 meq/g.
Total dissolved solids in the overheads are usually l e s s than 100 mg/1
but solids in the miscellaneous wastes reach 10 000 mg/1. Feed rate to
the column v a r i e s from 0.13 to 0.16 litres m i n - 1 l i t r e " 1 of exchanger for
the miscellaneous waste.
The s t a i n l e s s - s t e e l columns contain 265 litres of exchanger which
is utilized until 1 3 7 C s activity in the effluent reaches 1500 disintegrations
per minute per millilitre. The material is then discharged to a storage
tank and the column is refilled with f r e s h zeolite. The decontamination
factor for 1 3 7 Cs is usually between 100 and 200 but a maximum of 350
has been attained. A column of exchanger will adequately treat 3000 to
10 000 bed volumes of overheads or 1000 to 1500 bed volumes of the
miscellaneous waste before breakthrough.

Tokai Research Establishment, JAERI, Tokai-Mura, Japan [99]

Wastes containing 640 mg/1 total solids, 500 mg/1 dissolved solids
and 1.8 X 1 0 " 4 ^ C i / m l radioactivity are treated by sand filtration in the

73
 FIG.27. I o n - e x c h a n g e c o l u m n s , r a d i o a c t i v e waste t r e a t m e n t f a c i l i t y , RCN, P e t t e n , Netherlands.

FLOWMETER M TO
EVAPORATOR

MEASURING TANKS

i^J—DISCHARGE

FIG.28. Flow d i a g r a m o f l o w - l e v e l w a s t e t r e a t m e n t , J A E R I , T o k a i - M u r a , Japan.

74
f i r s t step of the l o w - l e v e l waste treatment p r o c e s s . Dissolved solids
concentration is then reduced by passage through a Selemion ion-exchange
membrane of 700 l/h capacity. Membrane effluent is demineralized by
mixed bed ion-exchange resins to provide an overall decontamination
factor of 450.
The mixed bed resins are strong-acid and strong-base synthetic
organic materials operating in the H + and Cl" forms. Feed rate to
the columns is maintained at about 0.128 litres m i n " 1 litre" 1 resin.
Figure 28 is a schematic view of the installation.

FIG.29. I o n - e x c h a n g e columns (evaporator in background), JAERI, T o k a i - M u r a , Japan.

Exhaustion is indicated by an increase in resistivity to 1 X 106 ohm-cm.

Resins are regenerated with 2N HC1 for the cation and 2N NaOH for the
anion; spent régénérant solutions are collected and treated by evaporation.
The plant, as shown in Fig. 29, has removed 180 mCi of activity from
l o w - l e v e l waste in a recent s i x - y e a r period.
Rubber-lined mild steel is used where acid conditions require
additional protection.

75
VII-4. TRANSPORT OF RADIOACTIVE MATERIALS

In treatment of radioactive wastes by ion exchange, it may become

necessary to transport contaminated materials to other locations for
further processing or for final disposal. T h e s e materials might include:

Exhausted exchangers
Spent régénérant solutions
Spent régénérant sludges
Incinerated resin ash
Evaporator spent régénérant residue.

Locally and nationally established regulations for the safe transport

of these materials on land, water or in the air must be known and
complied with. Internationally, the problems involved have been taken
under consideration by Member States of the International Atomic Energy
Agency and a set of regulations has been published. The text. Safety
Series No. 6, is entitled "Regulations for the Safe Transport of Radio-
active M a t e r i a l s " . Much of what follows has been excerpted from this
text.
For purposes of control, radionuclides are c l a s s i f i e d into eight
groups. Table XXIV l i s t s groups into which the main nuclides of concern
in waste treatment are placed.
The regulations define large sources as those single packages
containing activities greater than:

Group I 20 Ci
Group II 20 Ci
Group III 200 Ci
Group IV - 200 Ci

Low specific activity material is that in which activity is uniformly

distributed and estimated per g r a m concentration does not exceed:

Group I - 0.001 mCi

Group II - 0.005 mCi
Group III - 0.3 mCi
Group IV - 0.3 mCi

Packaging design is divided into T y p e s A and B, with Type В used

for higher activity l e v e l s in certain c a s e s and also where there is danger
of submersion in water to depths to 15 m. Packages are to be coloured,
labelled and marked. Category I, white packaging, is to be used when
radiation from the package does not exceed 0.5 mR/h or equivalent at
any point on the external surface at any time during transport. Categories II,
yellow, and III, yellow, are for increasing l e v e l s of external radiation
with the maximum for Category III as 200 mR/h on the external surface
and 10 m R / h at 1 m from the centre of the package.
A large number of special regulations govern transport of f i s s i l e
materials. P a c k a g e s of these materials are further c l a s s i f i e d as
F i s s i l e C l a s s I, F i s s i l e C l a s s II and F i s s i l e C l a s s III. F i s s i l e C l a s s - I
packages are nuclearly safe in any number or arrangement; F i s s i l e

76
C l a s s II are nuclearly safe in limited number in any arrangement; and
F i s s i l e C l a s s III are nuclearly safe in special arrangements.
The regulations c l e a r l y set forth testing procedures for the various
types of packages. T e s t s listed include:

Water spray test with impact

The f r e e drop test
Compression test
Penetration test
Thermal test
Immersion test
Contents leakage test
Radiation leakage test.

The test name implies the conditions to which the package is subjected.
Packages must be designed to prevent loss or dispersal of contents
and to retain the e f f i c i e n c y of their radiation shielding properties under
varying conditions of handling.

The above summary is only of sufficient length to indicate the

complexity of transport control. The pertinent detailed regulations -
international, national and/or local - must be consulted when considering
removal of radioactive materials from one area to any other.

77
 VIII. COSTS OF T R E A T M E N T BY ION EXCHANGE

VIII-1. GENERAL

A large number of variables are involved in comparing costs of use

of ion exchange for waste treatment among various sites. In addition to
the normal variables such as differences in wage rates and costs of
materials, few facilities are identical in their manner of employing ion
exchange, the extent to which it is employed or the type of solution being
processed. In many facilities ion exchange is established as a polishing
operation to be used when effluent activities have not been reduced suf-
ficiently by other means. Separate accounting of ion-exchange costs in
a number of these instances is not maintained and figures listed are
estimates.
In this section, costs as provided by operating facilities will be
reported with an attempt made to break the costs down into components
as determined by a recent IAEA panel. B r i e f l y , the operating cost
estimate for ion exchange should include the following:

(a) Labour - Actual cost including benefits

(b) Chemicals — Cost of exchanger and régénérant chemicals
(c) Utilities, s e r v i c e s - Costs of steam, gas, electricity, plus the
costs of s e r v i c e s specifically assigned to the ion-exchange operation
(d) Current maintenance - Cost of maintaining the ion-exchange
facility in good repair
(e) Direct or operating overheads - Costs of supervisor, secretarial
and c l e r i c a l staff, insurance, travel, etc.
(f) Depreciation - The annual charge for amortization based on 20-yr
building life and 7 | - y r equipment life
(g) Total costs - The sum of the above. This total will not include
cost of general overheads or applied research.

In the case of ion exchange demineralization of reactor waters,

costs of materials, s e r v i c e s , utilities, maintenance, etc. are fairly
well defined. Total costs include the expenses involved in deminerali-
zation plus the expense of regeneration, if used. Where resins are not
regenerated, total costs will include disposal of spent resins.
In treatment of general radioactive wastes, allocation of costs is
often complicated by use of extensive pretreatment methods such as
chemical coagulation. It is questionable whether any of the pretreatment
cost should be charged against the ion-exchange facility. A question
also exists where spent régénérant is treated by evaporation in a unit
for which the régénérant is but a small fraction of its feed. In the case
of pretreatment, the argument for costing the additional process sepa-
rately may be justified due to activity removals obtained. Spent régéné-
rant treatment, however, is related directly to the ion-exchange process
and provides no additonal activity removal. Where the spent régénérant
is a m a j o r portion of the feed of an evaporator, the proportional part
of the cost of the subsequent p r o c e s s must be charged against ion exchange.

78
VIII-2. C A P I T A L COSTS

In the capital cost items are included building and equipment costs.
As a guide in the selection of construction materials for p r o c e s s equip-
ment, Table X X V presents current (October 1966, USA) costs of
some of the metals, plastics and elastomers which might be used in an
ion-exchange facility.
In Fig. 30, the comparative costs of v e r t i c a l storage tanks constructed
of a number of these materials are presented. The curves indicate the
increase in cost for increasing capacity. Though most ion-exchange
columns are pressure v e s s e l s in size ranges under 30 m 3 , the compara-
tive costs shown would be similar.

i г 3 45 ю
CAMCITY-THOUSAND GALS

1. CARBON STEEL 7. GLASS LINED

2. R U B B E R LINES 8. M0NEL
3. ALUMINUM 9. INCONEL
4. L E A D L I N E D 10 F I B E R G L A S S , ERECTED
5. 3 0 4 S T A I N L E S S I I. FIBERGLASS, J O B SITE
6. 316 S T A I N L E S S

FIG.30. Comparative costs of vertical storage tanks.

The variables are extremely numerous but mention of the range of

investments in existing ion-exchange facilities may prove of assistance
in preliminary estimating for contemplated installations.

Example (1) [92]:

The installed equipment cost of the 25-1 mineral exchanger column

at the Hahn-Meitner Institute, Berlin, was US$5 000. Equipment for the
synthetic organic resins columns, dual bed units with 25 and 50 1 of resin
in cation-anion units respectively, had an installed cost of US $6 000.

Example (2) [94]:

The dual bed columns of synthetic organic resins at Harwell, four

separate columns with0.38m 3 resin in each, had an installed cost of
£13 500 (about US$37 800). The 149-m 2 building housing the ion-exchange

79
and filtration plant cost £3200(about US $8960). Equipment for p r e -
filtration of waste solutions was obtained and installed for £2200 (about
US $6160).
To treat the chemical plant effluent with 0.051 m 3 vermiculite in
the v e r t i c a l centrifuge, building and equipment were provided at a cost
of £8000 (about US$22 400).

Example (3) [99]:

At the Tokai R e s e a r c h Establishment, JAERI, electrodialysis p r e -

treatment followed by mixed bed ion exchange with 130 litres of strong-
acid synthetic resins is accomplished in a facility for which building
and installed equipment costs totalled US $79 300.

Example (4):

Two cation-resin-exchange columns, each containing 4.15 m 3 of

strong-acid synthetic organic resin, and all appurtenant equipment were
provided at the Los Alamos Scientific Laboratory for a cost of about
US$72 000. This figure does not include any of the cost of the building
housing the ion-exchange material.

Example (5) [98]:

Cation-exchange columns at the Savannah River plant, containing

265 l i t r e s of synthetic inorganic exchanger, were provided for a total
building and installed equipment cost of US$75 000.

VIII-3. O P E R A T I N G COSTS

Among the many variables affecting the operating cost of ion-exchange

treatment per unit volume of waste is the extent of the use of the facility.
Columns at the Hahn-Meitner Institute and at the Los Alamos Scientific
Laboratory are in use l e s s than 5% of the time. It is estimated that the
Harwell vermiculite-lined centrifuge will be in operation about 15% of
the normal working hours. Many of the utility costs, service charges,
the overhead and the depreciation are charged against a facility whether
or not it i s in use. T o obtain reasonably accurate information on ope-
rating costs, large numbers of installations operating at varying percen-
tages of total capacity and utilizing the various ion-exchange methods
must provide their cost data. Existing sites using ion exchange for
general waste treatment are yet v e r y limited and in many, charges to
ion exchange are not separated from overall waste treatment expenses.
Table XXVI lists unit cost data for s e v e r a l sites which vary widely in
their application of ion exchange to waste processing.
In a paper presented at the Symposium on P r a c t i c e s in the Treatment
of Low- and Intermediate-Level Radioactive Wastes, IAEA, Vienna(1965),
B. Gaudernack and J. E . Lundby of K j e l l e r , Norway, reported a cost of
US$17/m 3 of l o w - l e v e l waste. The cost, however, ,included régénérant
evaporation and solidification. In this system, strong-acid and strong-
base resins were used to treat approximately 360 m 3 of waste per year.

80
 Table XXVII provides an itemized list of operating expenses at
s e v e r a l installations.
An engineering study by Hiester et al. [100], published in 1954,
provided calculated costs for full-time usage of ion-exchange p r o c e s s e s
in which radioactive materials are handled. Using an estimated 36%
increase to bring costs to levels of today, their paper determined costs
of US $1.07 to US $ 1 1 . 50/m3 depending upon the volume processed. This
range agrees well with the reported costs. It would be extended upward
in c a s e s of part-time usage of the facility.
In a recent article by Downing [101], an equation is presented for
calculating total operating cost. By solving the equation with a number
of assumed values for the variables, the size of an ion-exchange unit
which will provide the most economical operation can be determined.
Optimum regeneration l e v e l s and resin volumes can also be obtained by
use of the equation. The terms used, after conversion to the metric
s y s t e m , are 4 :

Ac *• Resin cost, US $/litre

Ad *• Resin depreciation cost, U S $ / y r
Ar - Resin depreciation time, y r
Av - Resin volume, litres
Ax - Resin capacity, average overall life of resin in
equivalents l i t r e - 1 c y c l e - 1
Ec *- Equipment cost, US $
Ed •- Equipment depreciation cost, US $/yr
Et •- Equipment depreciation time, y r
Ik "- Influent ion concentration, equivalents per litre
In •- Volume water treated per c y c l e , litres
Iv *- Effluent requirements, litres/day
Lc •- Labour cost, US $ / y r
Lr •- Labour rate, US $/h
ч • Labour time, h / c y c l e
N - Number of c y c l e s / y r
R1 *- Regeneration level, kg l i t r e " 1 c y c l e " !
Rc •- Regeneration cost per year, US $
- Regeneration requirements/yr, kg
r p •
Rr •- Régénérant cost, US $/kg
o c •- Total operating cost, U S $ / y r

The total cost, O c , comprises four m a j o r items — regeneration cost,

resin depreciation cost, equipment depreciation cost and labour cost.
In equation form, then:

Oc= Rc + Ad+ Ed + Lc

4 Equations and Fig. 31 reprinted with permission from Chemical Engineering,Dec. 6,1965.

Copyright (c) 1965, McGraw-Hill, Inc.

V a l u e s for each of these t e r m s are derived as f o l l o w s :

litres^ _ . f equiv \ A " (litres)

М11 Vт c ^
y c lгe ) /
x
V litre c y c l e J X Ik V l'tfequiv^
e У

T = A X A v
Ik

/lUres \ Х 365 ^ Х 1
V yr / V day ) yr j /litres\
n
\ cycle /

_ 365 I v = 365 I v

N = 365 4 h
A x Av

- ( ш ^ Г е ) X Av (Htres) X N

= R! A v N

„ _ 365 R i I v I k
Rp = rx

R c ( ^ > RP ( f ) = R p R l

(a) r = 365 R r R, I v I„
Ax

AT(lltreB)XAc(jgÍ) AyAc
(b) A¿
m - A r (yr) At

(c) E Л ® $ \ E.(US$)„ E ^
\ У r j ~ E r (yr) " E t

US$
Уг = Gssr) x (T)
Lc = NLtL,

365 Iy Ik Lt Lr
(d) L c =
A x Av

82
Thus, total cost is obtained by combining (a), (b), (c) and (d) above
to obtain:

O c = R c + A d + E d + L,с

365 R r R , I v Iw AvA r + Ер+ 3 6 5 I v Ik L t L :r

= 365 I v Ik E
X

F o r comparing installations with identical equipment, the equipment

depreciation term can be omitted and the equation is simplified to:

In many c a s e s , values for I v and I k will be known. Values for R r

L t and L r will be known or can be estimated to a fair degree of
accuracy. Through use of the formula, operating costs can then be
calculated for s e v e r a l selected values of:

R r - regeneration level

A y and A c - resin volume and resin cost

A t - assumed resin life

A x - average resin capacity

940
920

TOO,
0 2 4 6 8 10 12 14 16 1в 20 22
BED VOLUME, «Э (A tf )

FIG. 31. Operating cost vs. bed volume at various regeneration levels.
 Plotting cost vs. volume curves, with a separate curve for each
regeneration level, will yield a graphical representation of conditions
providing minimum total operating cost. T y p i c a l curves from solution
of the equation for a particular problem are shown in Fig. 31. It can
be seen that optimum volume for the unit is 6 f t 3 , regenerated at 8 l b / f t 3 .

84
 APPENDIX II

PRODUCERS O F E X C H A N G E M A T E R I A L S

American Machine & Foundry C o . , USA

Asahi Chemical Industry Co. Ltd., Japan
Asahi Glass Co. Ltd., Japan
Bio-Rad Laboratories, Richmond, Calif., USA
Chem. Fabrik Budenheim, Federal Republic of Germany
Chemické závody ustin labem, CSSR
Chemicky kombinát záluáíu mostu, CSSR
Crosfield, Jos., and Sons Ltd., London, UK
Davison Chemical Div., W.R. Grace & C o . , Baltimore, Md., USA
Diamond Alkali Company, Redwood City, Calif. , USA
Dow Chemical Company, Midland, Mich., USA
Farbenfabriken Bayer AG, Leverkusen, Federal Republic of Germany
Gosud. Institut Prikladnoi Khimii, USSR
Industrieele Maatschappij Activit N. V. (IMACTI), Amsterdam, Netherlands
Institut vysokomol. soedin. AN, USSR
Ionac Chemical Company (Division of Pfaudler Permutit, Inc.), Birmingham, N. J . , USA
Ionics Inc., Cambridge, Mass., USA
Japan Organo Co. Ltd., Tokyo, Japan
Linde Division, Union Carbide Corp., New York, N . Y . , USA
Mitsubishi Chemical Industries Ltd., Tokyo, Japan
Montecatini, Milan, Italy
Moskovsk. chem. technol. inst. im. Mendeleeva, USSR
MUKY, Budapest, Hungary
Nalco Chemical Company, Chicago, 111.. USA
Nauchno-issled. inst. plast, mass., USSR
Norton Company, Worcester, Mass., USA
Permutit Co. (Div. of Pfaudler Permutit),Paramus, N . J . , USA
Prosim, France
Rohm and Haas Company, Philadelphia, Penn., USA
Société d'études, de recherches et d'applications pour l'industrie (SERAI), Brussels, Belgium
Spolek pro chemickou a hutnf vyrobu ustf n. labem, CSSR
VEB Farbenfabrik Wolfen, German Democratic Republic
VJfzkumny ústav synthetickych pryskyfic a lakû, Pardubice, CSSR
Zerolit Ltd.. UK
 APPENDIX II

CONVERSIONS

(a) CONVERSION T A B L E S

To convert from To Multiply by

ÂngstrBm units Centimetres 1X10" 8

AngstrBm units Inches 3.937X10"9
Angstr'dm units Microns 0. 0001

Atmospheres Centimetres of Hg (0°C) 76

Atmospheres Centimetres of H 2 0 (4°C) 1033.26
Atmospheres Feet of H 2 0 (39. 2°F) 33. 8995
Atmospheres Grams per square centimetre 1033.23
Atmospheres Pounds per square inch 14. 696

Bed volumes per hour Gallons per minute per cubic foot 0.1247
Bed volumes per minute Gallons per minute per cubic foot 7.481

Centimetres Angstrbm units 1x10e

Centimetres Inches 0. 3937
Centimetres Microns 10 000
Centimetres Mils 393. 7

Centimetres per second Feet per second 0.032808

Cubic centimetres Cubic inches 0,01Л024

Cubic centimetres Gallons (Brit. ) 0.000220
Cubic centimetres Gallons (US, liq. ) 0. 000264
Cubic centimetres Millilitres 0.999972

Cubic feet Gallons (Brit. ) 6. 22884

Cubic feet Gallons (US, liq. ) 7.48052
Cubic feet Litres 28.31605

Cubic metres Cubic feet (US) 35. 3147

Cubic metres Cubic yards (US) 1. 3080
Cubic metres Gallons (Brit. ) 219.9694
Cubic metres Gallons (US, l i q . ) 264.1721
Cubic metres Litres 999.972

Curie Disintegrations per second 3.7ХЮ10

Equivalents per litre Kilograins per cubic foot as C a C 0 3 21.85

86
T o convert from To Multiply by

Feet (US) Centimetres 30.48

Feet (US) Inches 12
Feet (US) Metres 0.3048

Gallons (Brit. ) Cubic feet 0.16054

Gallons (Brit, ) Gallons (US, liq. ) 1.20095
Gallons (Brit. ) Litres 4.54596

Gallons (US, liq. ) Cubic feet 0.13368

Gallons (US, liq. ) Gallons (Brit.) 0. 83267
Gallons (US, liq. ) Litres 3. 7853

Gallons (Brit. ) per minute Cubic centimetres per second 75.76812

Gallons (US) per minute Cubic centimetres per second 63.090197

Gallons (US) per minute Cubic feet per second 0.002228
Gallons (US) per minute Litres per second 0. 063088

Gallons per minute per cubic foot Bed volumes per hour 8. 02
Gallons per minute per cubic foot Litres per hour per litre 8. 02
Gallons per minute per cubic foot Bed volumes per minute 0. 1336
Gallons per minute per cubic foot Litres per minute per litre 0. 1336

Gallons per minute per square foot Millilitres per minute per square centimetre 4. 074

Grains Grams 0. 064799

Grains Pounds (avoirdupois) 0. 0022857

Grains per cubic foot as CaCO s Equivalent per litre 4.573x10"

Grains per gallon (Brit. ) Grams per litre 0.014254

Grains per gallon (Brit.) Parts per million 14.25418

Grains per gallon (US) Grams per litre 0.017118

Grains per gallon (US) Parts per million 17.1185

Grains per gallon as C a C 0 3 Normality 3.42X10"

Grams Grains 15. 43236

Grams Pounds (avoirdupois) 0. 002205

Grams per cubic centimetre Pounds per cubic foot 42.42796

Grams per cubic centimetrc Pounds per gallon (Brit. ) 10. 02241
Grams per cubic ccntiinctre Pounds per gallon (US) 8. 34540

87
T o convert from To Multiply by

Grams per litre Grains per gallon (US) 58.41620

Grams per litre Parts per million 1000
Grams per litre Pounds per cubic foot 0.06243

Grams per square centimetre Centimetres of Hg (°0C) 0.07356

Grams per square centimetre Centimetres of H г О (4°C) 1.00003
Grams per square centimetre Feet of H 2 0 (60°F) 0.03284
Grams per square centimetre Inches of Hg (32°F) 0.02896
Grams per square centimetre Pounds per square foot 2.04816
Grams per square centimetre Pounds per square inch 0.01422

Inches (US) Centimetres 2.54

Inches (US) Feet 0.08333
Inches (US) Mils 1000

Kilograins per cubic foot as C a C 0 3 Equivalents/litre 0.0458

Kilograms Grains 15432. 35Í

Kilograms Grams 1000
Kilograms Ounces (avoirdupois) 35.27396
Kilograms Pounds (avoirdupois) 2.20462

Kilograms per cubic metre Gram per cubic centimetre 0.001

Kilograms per cubic metre Pounds per cubic foot 0. 06243
Kilograms per cubic metre Pounds per gallon (US, l i q . ) 0.008345

Kilograms per square centimetre Atmospheres 0.96784

Kilograms per square centimetre Centimetres of Hg (0°C) 73.5559
Kilograms per square centimetre Pounds per square foot 2048.161'

Kilolitres Cubic feet 35.31566

Kilolitres Cubic inches 61.02545
Kilolitres Cubic yards 1.30799
Kilolitres Gallons (Brit.) 219.9755
Kilolitres Gallons (US, liq. ) 264.1794

Litres Cubic centimetres 1000.028

Litres Cubic feet 0.03532
Litres Cubic inches 61.02545
Litres Gallons (Brit. ) 0.21998
Litres Gallons (US, l i q . ) 0.26418

Litres per hour Gallons (US) per hour 0.26418

Litres pet hour per litre Gallons per minute per cubic foot 0.1247

litres per minute Cubic feet per minute 0.03532

Litres per minute Gallons (US, liq. ) per minute 0.26418

88
To convert from To Multiply by

Litres per minute per litre Gallons per minute per cubic foot 7.481

Metres Ângstrûm units 1X1010

Metres Feet 3.28084
Metres Inches 39. 37008
Metres Microns
6
I X 10
Metres Mils 39370.079

Microns Angstrom units 10 000

Microns Centimetres 0.0001
Microns Inches 3.937008 X10" 5
Microns Metres IX 10"6

Milliequivalents per millilitre Grains per cubic foot 21 850

Milliequivalents per millilitre Kilograins per cubic foot 21. 85

Milligrams Grains 0.01543

Milligrams Pounds (avoirdupois) 2.2 046 x 106

Milligrams per litre Grains per gallon (US) 0.05842

Milligrams per litre Grams per litre 0.001
Milligrams per litre Parts per million 1.0
Milligrams per litre Pounds per cubic foot 6.24262

Milligrams per litre as СаСОз Equivalents per litre 2X10"

Mils Centimetres 0.00254

Mils Inches 0.001
Mils Microns 25.4

Millilitres per hour per millilitre Gallons per minute per cubic foot 7.481

Millilitres per minute per millilitre Gallons per minute per cubic foot 0.1247

Normality Grains per gallon (US) as CaCO a 2923.2

Ounces (avoirdupois) Grains 437.5

Ounces (avoirdupois) Grams 28. 34952
Ounces (avoirdupois) Pounds (avoirdupois) 0.0625

Ounces (Brit, fluid) Cubic centimetres 28. 41305

Ouiiocs (Brit, fluid) Cubic inches 1.73387
Ounces (Brit, fluid) Litres 0.02H41
Ounces (Brit, fluid) Ounces (US, fluid) 0. 96076

89
To concert from To Multiply by

Ounces (US fluid) Cubic centimetres 29. 57373

Ounces (US fluid) Cubic inches 1.80469
Ounces (US fluid) Gallons (US, liq. ) 0.00781
Ounces (US fluid) Litres 0.02957
Ounces (US fluid) Ounces (Brit, fluid) 1. 04084

Parts per million Grains per gallon (Brit. ) 0.07015

Parts per million Grains per gallon (US) 0. 05842
Parts per million Milligrams per litre 1.0
Parts per million Parts per million as CaCO s 50/equiv. wt.
Parts per million Pounds per million gallons (US) 8.34517

Pounds (avoirdupois) Grains 7000

Pounds (avoirdupois) Grams 453.59237
Pounds (avoirdupois) Ounces (avoirdupois) 16

Pounds per cubic foot Grams per cubic centimetres 0.01602

Pounds per cubic foot Grams per litre 16.01891
Pounds per cubic foot Pounds per gallon (US, liq.) 0.13368

Pounds per gallon (Brit. ) Kilograms per cubic foot 2. 82535

Pounds per gallon (Brit. ) Kilograms per kilolitre 99.77923

Pounds per gallon (US, liq.) Grams per cubic centimetre 0.11983
Pounds per gallon (US, l i q . ) Kilograms per cubic foot 3.39311
Pounds per gallon (US, liq. ) Kilograms per kilolitre 119.8298

Pounds per square inch Atmospheres 0.06805

Pounds per square inch Centimetres of Hg (0°C) 5.17149
Pounds per square inch Centimetres of H 2 0 (4°C) 70.3089
Pounds per square inch Feet of H 2 0 (32°F) 2.30894
Pounds per square inch Kilograms per square centimetre 0.07031

Square centimetres Square feet 0. 00108

Square centimetres Square inches 0.15500

Square feet Square centimetres 929.0304

Square feet Square inches 144
Square feet Square metres 0. 09290

Square inches Square centimetres 6.4516

Square inches Square feet 0. 00694

90
( b) D O L L A R E Q U I V A L E N T S : Local currency approximately equivalent
to one US dollar ($1.00) (early 1966)

Australia 8 shillings, 11 pence (0.46 pounds)

Austria 25. 86 schillings
Belgium 49.62 francs
Bolivia 11. 88 pesos
Brazil 1850 cruzeiros (free rate)
Bulgaria 1 . 1 7 levas (official rate)
Burma 4 . 8 0 0 kyats
Cambodia 35.00 riels (1955)
Canada «1.083 (fluctuates daily)
Chile 3 . 8 4 escudos (official exchange rate)
China, Republic of 40.10 NT dollars
Columbia 19. 5 pesos
Czechoslovak Socialist Republic 14.36 koruna (official)
Denmark 6 . 9 4 kroner
Ecuador 18.18 sucres (official selling rate)
Finland 3 . 2 2 markka
France 4. 90 francs
German Democratic Republic 2 . 2 2 MDN (official)
Germany, Federal Republic of 4 . 0 0 Deutsche Mark
Greece 30 drachmae
Guatemala I . 00 quetzals
Hungary I I . 74 forints (official)
India 4.795 rupees
Indonesia 315-349 rupiahs (prin. export rate 1963)
Iran 75. 75 rials
Iraq 0.3571 dinars
Israel 3 pounds
Italy 624.76 liras
Japan 362 yens
Jordan 0.3571 dinars
Korea, Republic of 271 wons
Lebanon 3 . 0 6 pounds
Mexico 12. 5 pesos
Morocco 5.060 dirhams
Netherlands 3 . 6 0 guilders
New Zealand 0.3627 pounds
Nicaragua 7.05 córdobas
Norway 7.16 kroner
Pakistan 4.802 rupees
Panama 1. 00 balboas
Paraguay 126.00 guaranis
Peru 26. 82 sols
Philippines 3 . 9 1 pesos
Poland 4 . 0 0 zlotys (official)
Portugal 28. 94 escudos
Romania 6 . 0 0 lei (official)
Saudi Arabia 4 . 5 0 riyals
South Africa 0.7189 rands
Spain 60.01 pesetas
Sweden 5.178 kronor
Switzerland 4 . 3 3 4 francs
Syrian Arab Republic 3 . 8 2 pounds
Thailand 20. 83 bahts
Turkey 9 . 0 8 liras
Union of Soviet Socialist Republics 0 . 9 0 rubles (official)
United Arab Republic 0.4348 pounds

91
United Kingdom of Great Britain
and Northern Ireland - 7 shillings, 2 pence (0.357 pounds)
United States of America - 11.00
Uruguay - 24. 00 pesos
Venezuela - 4 . 5 0 bolivars
Vietnam - 60. 00 piastres
Yugoslavia - 750 dinars

92
S I E V E SYSTEMS

US Standard British Standard Tyler Standard German DIN

Sieve Opening Opening

Meshes/in. Meshes/in. ^ ^ SieVe Mesh/cm 2
no. (mm) (mm) (mm) no. (mm)

5 4.00 5 3.353 5 3.962 1 1 6.000

6 3.36 6 2.812 6 3.327 2 4 3. 000
7 2.83 7 2.411 7 2 . 794 2i 5.25 2.400
8 2.38 8 2.057 8 2.362 3 9 2. 000
10 2.00 10 1.676 9 1.981 4 16 1.500
12 1.68 12 1.405 10 1.651 5 25 1.200
14 1.41 14 1.204 12 1.397 6 36 1.020
16 1.19 16 1.003 14 1.168 8 64 0. 750
18 1.00 18 0. 853 16 0.991 10 100 0. 600
20 0.84 22 0.699 20 0. 833 11 121 0.540
25 0. 71 25 1 0.599 24 0. 701 12 144 0.490
30 0.59 30 0.500 28 0.589 14 196 0.430
35 0.50 36 0.422 32 0.495 16 256 0.385
40 0.42 44 0.353 35 0.417 20 400 0.300
45 0.35 52 0.295 42 0. 351 24 576 0.250
50 0.297 60 0. 251 48 0.295 30 900 0. 200
60 0.250 72 0.211 60 0.246 40 1600 0.150
70 0.210 85 0.178 65 0.208 50 2500 0.120
80 0.177 - - 80 0.175 60 3600 0.102
100 0.149 100 0.152 100 0.147 70 4900 0.088
200 0.074 200 0.076 200 0.074 80 6400 0. 075
325 0.044 240 0.066 325 0.043 100 10 000 0.060
400 0.037 300 0.053 400 0.038
(d) S P E C I F I C CONDUCTANCE - RESISTANCE

Sp. cond. resist Approximate electrolyte content (ppm)

microtnhos 111 °hmS NaCl HC1 NaOH

0. 1 10 000 000 0. 04 0. 01 - -

0. 2 5 000 000 0. 08 0. 02 0..03 -

1 1000 000 0. 4 0. 13 0.,2 0.,8

2 500 000 0. 8 0. 26 0. 4 2..5
4 250000 1. 6 0. 55 0. 8 9.,5
6 166 000 2. 5 0. 9 1.,0 20
8 125 000 3. 2 1. 2 1.,5 40
10 100 000 4. 0 1. 5 2. 0 70
20 50 000 8. 0 2. 0 4.,0 320
30 ' 33 333 14. 0 3. 0 5.,0 730
40 25000 19. 0 4. 0 6.,0 1400
50 20000 24. 0 4. 5 7.,0 2200
60 16 666 28. 0 5. 5 - -

70 14286 33. 0 6. 5 - -

80 12 500 38. 0 7. 5 11.,0 -

90 11111 43. 0 8. 0 - -

100 10000 50. 0 9. 0 14.,0 -

200 5 000 100. 0 18. 0 27.,0 -

94
 APPENDIX Ш

REGENERATION DATA: SPECIFIC GRAVITY - CONCENTRATION

A. Sulphuric acid

Grams Specific
%H,SO, ,, „ _ „. Normality . Baume
2 4 H2S04/litre ' gravity

1 10.05 0.205 1.0051 0.7

2 20.24 0.413 1.0118 1.7
3 30.55 0.623 1.0184 2.6
4 41.00 0. 836 1.0250 3.5
5 51.59 1.05 1.0317 4.5
6 62.31 1. 27 1.0385 5.4
8 84.18 1.72 1.0522 7.2
10 106.6 2.17 1.0661 9.0
12 129.6 2.64 1.0802 10.8
15 165.3 3.37 1.1020 13.4
20 227.9 4.65 1.1394 17.7
50 697.6 14.2 1.3951 41.1
96 1762.0 35.9 1. 8355 66.0
100 1831.0 37.3 1.8305 65.8

B. Hydrochloric acid
Grams „ ,. Specific „_
№ C 1 HC1/litre NOrmaUty gravity B a u m e

1 10.03 0.275 1.0032 0.5

2 20.16 0.553 1.0082 1.2
4 40.72 1.12 1.0181 2.6
6 61.67 1.69 1. 0279 3.9
8 83.01 2.28 1.0376 5.3
10 104.7 2 . 87 1.0474 6.6
12 126.9 3.48 1.0574 7.9
16 172.4 4.73 1.0776 10.4
20 219.6 6.02 1. 0980 12.9
30 344.8 9.46 1.1492 18.8
40 479.2 13.1 1.1980 24.0

С. Nitric acid
Grams ,. Specific „„
№ N ° 3 HNO3 /litre NOtmaUty gravity B a U m e

1 10.0 0.159 1.0054 0.8

2 20.2 0.320 1.0109 1.6
4 40.8 0. 647 1.0219 3.1
6 61.9 0.982 1.0329 4.6
8 83.4 1.324 1.0446 6.2
10 105.4 1. 673 1. 0563 7.7
12 127.9 2 . 030 1.0681 9.2
16 174.4 2 . 768 1.0921 12.2
20 223.0 3.538 1.1169 15.2
30 354.0 5.618 1.1822 22.3
40 498.6 7.911 1.2486 28.9
D. Ammonia

Grams vt Specific
70NH3 „„, ... Normality r Baume
NH 3 /litre gravity

1 9.94 0. 58 0.9939 10.9

2 19.79 1.16 0.9895 11.5
4 39.24 2.31 0.9811 12.7
6 58.38 3.43 0.9730 13.9
8 77.21 4.53 0.9651 15.1
10 95. 75 5.62 0.9575 16.2
12 114.0 6.70 0.9501 17.3
16 149.8 8. 79 0. 9362 19.5
20 184.6 10. 8 0. 9229 21.7
30 267.6 17.0 0. 8920 27.0

E. Sodium chloride

Grams Specific
%NaCl Normality "Baume
NaCl/litre gravity

1 10.05 0.17 1.0053 0.8

2 20.25 0.35 1. 0125 1.8
4 41.07 0. 70 1.0268 3.8
6 62.48 1.07 1.0413 5.8
8 84.47 1.45 1.0559 7.7
10 107.1 1. 83 1.0707 9.6
12 130.3 2.23 1.0857 11.5
16 178. 6 3 . 06 1.1162 15.1
20 229.6 3.93 1.1478 18.7
26 311.3 5.33 1.1972 23.9

F. Sodium hydroxide

Grams Specific
%NaOH Normality 'Baumé
NaOH/litre gravity

1 10.11 0. 25 1.012 1.72

2 20.44 0. 51 1.023 3.26
3 30.99 0. 77 1.034 4.77
4 41. 77 1.04 1.045 6.25
5 52. 77 1.32 1.056 7.69
6 63.99 1.62 1.067 9.10
8 87.10 2.18 1. 090 11.97
10 111.1 2. 78 1.112 14.60
12 135. 9 3.40 1.134 17.13
Hi 188. 4 4. 71 1.178 21.91
•20 244. :i 6.11 1.223 26.45
50 764. 5 19.11 1.530 50.23

96
 APPENDIX IV

GLOSSARY

Anion A negatively charged ion.

Cation A positively charged ion.

Co-ion Any ion, whether in the exchanger or in the solution being treated,
which has the same sign as the exchanger framework.

Counter-i от Any ion, whether in the exchanger or in the solution being treated,
which has a charge sign opposite to that of the exchanger framework.

Curie (Ci) An amount of radioactive isotope undergoing 3. 7 x 1 0 disintegrations

per second.

Decontamination factor (DF) The ratio of the radioactivities in a solution prior to and following
treatment.

Distribution coefficient Referred to a counter ion, the distribution coefficient is the ratio
of the concentrations of the counter ion in the exchanger and in
the solution.

Divinylbenzene (DVB) Organic monomer containing two double bonds: CH = CH,

CH = CH,

Electcodialysis A process in which an electrical potential difference applied between

two solutions causes a migration of ions through a membrane or
diaphragm separating the solutions.

Electrolyte A substance which, when added to water, will provide a solution

which will conduct electricity. Most inorganic acids, bases and
salts are electrolytes, whereas most organic compounds are
non-electrolytes.

Exchange capacity (total)
A constant which represents the number of inorganic groups per
specific weight of exchanger when the material is completely converted
to the H + o r C l " form, a s m e q / g , or the number of inorganic groups in a
specified volume ofa fully water-swollenpacked bed of exchangerusually
when the materialis completely converted to the H + o r C l " f o r m , in
terms of m e q / m l . The counter-ion content of an exchanger.

Ion exchange A stoichiometric, reversible reaction in which mobile ions of a

solid (generally) exchange with the mobile ions of a solution of
an electrolyte when the solution contacts the solid.

97
Macroreticular resins Highly porous resins. (From 'macro' meaning 'large* and
'reticular* meaning 'netlike* or 'sievelike*).

Molecular sieves Materials with rigid, uniform pore structure which can sorb small
molecules but completely exclude molecules larger than the structure
pore openings.

MPC The maximum permissible concentration. This refers to maximum

levels of radioactivity in water or in air as established by national
or international commissions.

Nuclide A species of atom characterized by its nucleus.

Permselectivity From permeable-selective. Refers to that property of a membrane

which permits certain species of ions to pass through the membrane
while excluding other species.

Radioactivity The spontaneous disintegration of an unstable nuclide with emission

of a particle or photon to form a different nuclide.

Regeneration With reference to ion-exchange materials, regeneration is defined

as the process of removing those counter ions from the exchanger
which had been absorbed during treatment of a solution and re-
placing them with an appropriate ionic form for subsequent treat-
ment of additional solution.

Roentgen An exposure dose of X - or gamma radiation such that associated

corpuscular emission per 0 . 0 0 1 2 9 3 g of air produces in air ions
carrying one electrostatic unit (esu) of quantity of electricity of
either sign.

Selectivity (ion exchange) The preference of an exchanger for one species of counter ion
over another.

A general term which includes absorption, an engulfing, and

adsorption, an interface or surface attraction.

Volume reduction factor. The ratio of the volumes of radioactive

waste prior to and following treatment. In concentration processes,
the VRF > 1 ; in dilution systems, the VRF <1.

98
T A B L E I. MAIN C O M P O N E N T S O F T H E R A D I O A C T I V I T Y O F
R E A C T O R C O O L A N T W A T E R C I R C U I T S [19] a

Source Nuclear Radioactive

Half-life
reaction product

A
Short-lived species 16 О (n.p) 16 N 7.4 s

"О (n.p) 17 N 4.1 s

IB0
(n.p) "F 1,87 h

В
Important long-lived 5 °Cr (n.y) "Cr 27.8 d
species in a stainless
steel system 54 Fe (n.p) 54мп 290 d

s8 ní (n.p) 58 Co 71 d

59 Co (n.y) 60 Co 5 . 2 4 yr

60 Ni (n.p) «Со 5 . 2 4 yr

58 Fe (n.y) 59 Fe 45 d

"Ni (n.ot) 59 Fe 45 d

С
Species arising from "Al (n.Ot) 24 Na 15 h
other materials
«Zr (n,y) « Zr 65 d

"As (n.y) 76 As 26.5 h

I21 Sb (n,y) 122 Sb 2.8 d

123 Sb (n.y) 124 Sb 60 d

ITS
1T4
Hf (n,y)
H f
70 d

18
°Hf
181 Hf 46 d
(n.y)

181Ta 182 T a 115 d

(n.y)

a From DAWSON, J . K . , SOWDEN, R . G . , Chemical Aspects of Nuclear Reactors 2, Water-Cooled

Reactors, Butterworths, London (1963). Used by permission of Butterworths, London.

99
S T A B L E II. E A R L Y R E A C T O R S U T I L I Z I N G I O N - E X C H A N G E D E M I N E R A L I Z A T I O N [20]
о

Reactor Nominal Ion exchange

Designation Location Moderator
critical power {°h treated )

NRX Chalk River, O n t . , Heavy water Jul. 1947 50 MW 20

Canada

EL-1 (ZOE) Châtillon, Fontenay- Heavy water D e c . 1948 150 kW 2.1

-aux-Roses, France

LITR Oak Ridge, T e n n . , Light water Feb. 1950 3 MW 3 1/3

USA

BSR-1 Oak Ridge, T e n n . , Light water D e c . 1950 1 MW

USA

sura Los Alamos, N . M . , Light water in (as HYPO, 25 kW

USA He solution 1944)
Mar. 1951

JEEP Kjeller, Norway Heavy water Jun. 1951 4 5 0 kW

MTR Idaho Falls, Idaho, Light water Mar. 1952 4 0 MW

USA

EL-2 Saclay, France Heavy water O c t . 1952 2 MW

SP Aiken, S . C . , USA Light water Jul. 1953 10 kW

CP-5 Argonne, 111., USA Heavy water Feb. 1954 5 MW

WWR-C Moscow, USSR Light water 1954 2 MW

R-l Stockholm, Sweden Heavy water Jul. 1954 6 0 0 kW

BORAX-3 Idaho Falls, Idaho, Light water Jun. 1955 12 MW

USA
T A B L E III. a DISTRIBUTION COEFFICIENT OF CAESIUM ON
DECALSO b A S A FUNCTION OF SODIUM CONCENTRATION
(0. 2 g of Decalso per 10 ml of solution, pH 12. 7, Cs conc. 10 mg/1,
16 h contact at 25°C, sodium as NaNO s )

Distribution
Na c o n c , M
coefficient

0.2 430

1.0 170

2.0 85

2.8 49

4.0 22

6.0 13

8.0 8

9.0 6.7

a From LEWIS, R . E . , BUTLER, T . A . , LAMB, E . , Recovery of 137 Cs from fission-product wastes

and transport by an aluminosilicate ion exchanger, ORNL-3765 (May 1 9 6 5 ) .

k Decalso = synthetic alumino-silicate gel having a 6 : 1 silica to alumina ratio manufactured by

Permutit, N . Y . , USA.

101
T A B L E IV. A P P R O X I M A T E ION-EXCHANGE S E L E C T I V I T Y
C O E F F I C I E N T S [43] a

Ion Ion к *
Ion-exchange material Ex
Ex El
(50% sat'd)

Cation Sulphonated styrene- h Li 0.8

divinylbenzene (DVB)
h Na 2.0
(8%)
h к 3

h nh4 3

h Ag 18

h Tl. 24

Na к 1.8

h Ca 42

Ni Ca 2.5

Sulph. styrene-DVB (5%) h Na 1.4

Sulph. styrene-DVB (25%) h Na 2.5

Chabazite Na к 14.4

Sodalite Na к 0.06

Anion Quaternary ammonium Cl F 0.1

(strongly basic,
Cl Br 2.5
styrene-DVB)
Cl I 18

Cl N0 3 3

Cl ОН 0.5

C10 4 SCN 0.6

a
From KUNIN, R . , Elements of Ion Exchange. Reinhold Publishing Corporation, New York,
1 9 6 0 . Used by permission of Reinhold Publishing Corporation, New York.

102
TABLE V. R E L A T I V E A F F I N I T I E S O F IONS F O R A S T R O N G - A C I D
R E S I N WITH V A R Y I N G P E R C E N T A G E S O F C R O S S L I N K I N G [44] a

Monovalent cations X-4b X-8 X-12 X-16

H 1.0 1.0 1.0 1.0

Li 0.90 0.85 0.81 0.74

Na 1.3 1.5 1.7 1.9

Rb 1.9 2.6 3.1 3.4

Cs 2.0 2.7 3.2 3.45

Ag 6.0 7.6 12 17

Divalent cations

Mn 2.2 2.35 3.5 2.7

Zn 2.6 2.7 2.8 3.0

Co 2.65 2.8 2.9 3.05

Cd 2.8 2.95 3.3 3.95

• Ni 2.85 3.0 3.1 3.25

Ca 3.4 3.9 4.6 5.8

Sr 3.85 4.95 6.25 8.1

Hg 5.1 7.2 9.7 14

Pb 5.4 7.5 10.1 14.5

Ba 6.15 8.7 11.6 16.5

a
Reproduced by permission o f D u o l i t e Resins, Diamond A l k a l i C o m p a n y , Western
D i v i s i o n , Redwood C i t y , C a l i f .

b X - n o . = degree o f crosslinking in °¡o DVB, as X-4 - DVB.

103
T A B L E VI.a COMPARISON O F O B S E R V E D S E L E C T I V I T Y
C O E F F I C I E N T S WITH V A L U E S C A L C U L A T E D
B Y M Y E R S & B O Y D [46]

Degree of Ionic Selectivity coefficient

Ion
crosslinking composition
exchange Ь
№ DVB) {<% Na + ) calculated observed

Na+/Li+ 2 0 1.25 1.12 i 0.03

50 1.24 1.10 ± 0.03

100 1.21 1.08 i 0.02

0 2.00 1.72 à 0.03

Na+/Li+ 8 50 1.88 1.80 ± 0.04

100 1.72 1.89 ± 0.04

0 3.34 3.25 ± 0 . 0 7

24 50 2.92 2.40±0.05

100 2.80 1.80 ± 0.04

0 0.99 1.02 i 0.02

2 50 1.08 1.07 ± 0.02

100 1.25 1.12 ± 0.03

0 1.35 1.38 i 0.03

Na+/H+ ' 8 50 1.66 1.52 i 0.03

100 2.24 1.20 ± 0.03

0 9.36 6.38 t 0.13

24 50 3.79 2.32 ± 0.05

100 3.06 0.69 ± 0.02

a Reprinted from Journal of Physical Chemistry 60 (1956) 5 2 1 , by permission of American

Chemical Society, Easton, P a . , USA.

''ion exchangers: sulphonated polystyrenes of various degrees of crosslinking.

104
T A B L E VII. D E P E N D E N C E O F I O N - E X C H A N G E R A T E ON E X -
PERIMENTAL CONTROL [50]a

Solid diffusion F i l m diffusion

control control

Counter-ion mobility

In solid phase oc D No e f f e c t

In aqueous phase No e f f e c t D

Co-ion mobility No e f f e c t No e f f e c t

P a r t i c l e size cc 1 / r 2 oc 1 / r
о о
C a p a c i t y o f ion e x c h a n g e r No e f f e c t cc 1 / x

Nature o f fixed i o n i c groups Slow when fixed No e f f e c t

i o n i c groups
a s s o c i a t e with
m o b i l e ions

D e g r e e of crosslinking D e c r e a s e s with No e f f e c t
increasing
crosslinking

S e l e c t i v i t y o f ion e x c h a n g e r Preferred counter ion is t a k e n up at a higher

r a t e and r e l e a s e d at a lower r a t e , e x c e p t
under c e r t a i n s p e c i a l (boundary) conditions

C o n c e n t r a t i o n o f solution No e f f e c t ocC

Solution v o l u m e D e c r e a s e s with increasing solution v o l u m e

Temperature Increases with Increases with

temperature, temperature,
approx. 4 - 8 % / d e g С approx. 3-37o/deg С

Rate of a g i t a t i o n or flow N o effect Increases with

agitation rate

D = interdiffusion c o e f f i c i e n t in the i o n e x c h a n g e r .

D = interdiffusion c o e f f i c i e n t in the f i l m .

r 0 = b e a d radius.

x = c o n c e n t r a t i o n o f fixed i o n i c groups.

a F r o m HELFFERICH, F . , Ion E x c h a n g e , M c G r a w - H i l l . I n c . , New York ( 1 9 6 2 ) . Used by

permission of M c G r a w - H i l l Book C o .

105
T A B L E VIII. R E L A T I V E ION-EXCHANGE R A T E S [49]a

Time
Resin (50% equilibrium attainment)
(hydrogen form of resin)

Sulphonated polystyrene- DVB (8%)

Na + 1 . 5 min
++
Ba 3 . 0 min
+++
Al 5 . 5 min
Th, ++++ 6 0 . 0 min

Organic dyes Days-months

Sulphonated polystyrene- DVB (20%)

+
Na 5 min

a
From KUNIN, R . , Elements of Ion Exchange, Reinhold Publishing Corporation, New York,
1 9 6 0 . Used by permission of Reinhold Publishing Corporation, New York.

106
T A B L E IX. V A R I A T I O N O F R E S I N C A P A C I T Y AND M O I S T U R E
C O N T E N T WITH D E G R E E O F C R O S S L I N K I N G [ 5 7 ] a

Capacity

Resin "¡o DVB % Moisture (meq/g) (meq/ml)

A 4.0 62.6 4.81 1.27

В 8.5 48.6 4.79 1.87

С 10.0 43.1 5.07 2.30

D 12.5 40.8 5.12 2.47

E 15.0 35.4 4.81 2.65

a
From KUNIN, R . , Elements of Ion Exchange, Reinhold Publishing Corporation,
New York, 1 9 6 0 . Used by permission of Reinhold Publishing Corporation, New York.
о TABLE X. SYNTHETIC CATION E X C H A N G E R S
oo
a. Polystyrene base, bead form addition polymers

Exchange capacity Physical characteristics Operational controls

Functional
Trade name Manufacturer a Ion form (meq/g) (meq/ml) Moisture Size Max.oper. pH Remarks
group
(dry) (wet) (wt.») (mm) temp. ("С) range

Allasion CS Prosim, France -so;ь 0.3-0.6 110 1-14

Amberlite IRN- 77 Rohm & Haas C o . , -so; H 4.7 55 0.3-1.2 Nuclear grade
XE-100 USA -SOj" Na 4.5 1.5 56-60 120 0-14 ~57° DVB
IRN-163 distributed by -so; Li 4.6 55 0.3-1.2 150 Nuclear grade
IRN-169 MalUnckrodt, USA -so; NH< 4.4 55 0.3-1.2 150 Nuclear grade
IRN-218 and -so; Li 4.6 55 0.3-1.2 150 Nuclear grade
IR-120 Tokyo Organic -so; Na 4.3-5 1.9 44-48 0.3-1.2 120 0-14 ~ 8% DVB
IR-122 Chemical Industry -so; Na 4.3-5 2.1 39-43 0.3-1.2 120 0-14 ~ 107° DVB
IR-124 Ltd., Japan -so; Na 4.3-5 2.2 37-41 0.3-1.2 120 0-14 ~ 12% DVB
200 -so; Na 4.3 1.75 46-51 0.3-1.2 120 0 - 14 'Macroreticular' resins
200C -so; Na 4.3 1.75 46-51 120 0-14 'Macroreticular' resins

Amberlyst 15 -so; 4.9 1.2 60-66 120 0-14 'Macroreticular' resins

(Amberlyst resins are designed for non-aqueous applications)

Diaion SK 1A Mitsubishi Chemical -so; Na - 1.9 43-50 0.3-1.2 120 0-14 ~ 87° DVB
SK IB Industries Ltd., -so; Na - 1.9 43-50 0.3-1.2 120 0-14 ~ 8% DVB
SK-102 Japan -SOi Na - 0.6 7 2 - 82 0.3-1.2 120 0-14 ~ 27» DVB
SK-103 -SOi Na - 0.9 64-74 0.3-1.2 120 0-14 ~ 3% DVB
SK-104 -so; Na - 1.2 57-67 0.3-1.2 120 0 - 14 ~ 47" DVB
SK-106 -so; Na - 1.6 47-57 0.3-1.2 120 0 - 14 ~ 6% DVB
SK-110 -so; Na - 2.0 35-45 0.3-1.2 120 0 - 14 ~ 107> DVB
SK-112 -sos Na - 2.1 32-42 0.3-1.2 120 0-14 ~ 121o DVB
SK-116 -so; Na 2.1 27-37 0.3-1.2 120 0-14 ~ 167° DVB

Dowex 5 0 - X 8 Dow Chemical C o . , -so; H 5.0 1.7 53 0.3-0.8 150 ~ 87° DVB
50W -X4 USA -so; H 5.0 1.7 53 0.3-0.8 150 ~ 47° DVB; replace Dowex
marketed by 50 resins
50W-X8 Nalco Chemical C o . , -so; Na 4.8 1.9 42-48 0.3-0.8 150 ~ 87) DVB
50W-X10 USA -so; H - 1.9 46-52 0.3-0.8 150 ~ 10% DVB
50W-X12 -so; H - 2.1 42-48 0.3-0.8 150 ~ 127° DVB
50W-X16 -so; H - 2.3 36-42 0.3-0.8 150 ~ 167° DVB
MPC-1 -so; H 4.5-4.9 1.6-1.8 0.4-1.2 300 Macro porous
 Duolire C - 2 0 Diamond Alkali -so; Na 5.1 2.2 4 5 - •51 0 . 3 - 1.2 ISO ~ 8% DVB
C-25 -so', Na 5.1 1.7 5 5 - 62 0 . 3 - 1.2 120 Porous resin ~ DVB
ES-63 -Po; H 6.6 3.3 0 . 3 - 1.2 100 4 - 14 Intermediate acid

Imac C - 1 2 IMACTI, Netherlands -so; Na 2.0 0 . 3 - 1.2 120 0 - 14

" C-16P -so; Na - 2.1 0.3- 1.2 120 0 - 14

Ionac C - 2 4 0 Permutit Q, marketed by Ionac C o . , USA

Kastel C-300 Montecatini, Italy -so; Na 4.25 - 45 0 . 3 - 1.2 120 0 - 14 ~ 87» DVB
" C - 3 0 0 AGR -so; Na 4.5-4.7 - 45 0.3- 1.2 120 0 - 14 ~ 12% DVB
" C-300 P -so; Na - 1.7 53 0 . 3 - 1.2 120 0 - 14 Highly porous

KF-1 NIIP, USSR -pop - 5.0 - - Intermediate acid

KF-2 -CH,PO|" 7.0 - - Intermediate acid

& -POf-

KU-2-8 -so; Na, H 4.7 - 60 0.3- 1.5 120 ~ 87» DVB; 2 , 8 , 1 2 , 167»
also available

KU-2-8-CHS .. -so; H 4.7 4 5 - 65 0 . 4 - 1.5 - Special purity

Lewatit S-100 Farbenfabriken -so; - 4.75 2.5 4 0 - 45 0.5- 1.0 120 0 - 14 ~8ToDVB
S-115 Bayer A . G . , -so; 4.6 2.4 4 0 - 45 0.3- 2.0 120 0 - 14 Higher resistance to oxidizing
Fed. Rep. of Germany agents
" SP-100 -so; - 4.75 1.3 0 . 3 - 1.4 120 0 - 14 Macroporous

Mykion PS MUKY, Hungary -so; 4.0 1.57 - - -

PSM -so; 4.0 1.0 -

Nalcite HCR Dowex 5 0 - X 8 marketed by Nalco Chemical C o . , USA

HGR " 50-X10 .. „
HDR " 50-X12

Permutit Q Permutir Co. , -so; Na, H 4.6 1.9 45- 55 0.3- 1.2 120 0 - 13 - 107o DVB
~ QB USA -so; Na, H 5.0-4.6 2 . 1 - 1.9 45- 55 0.3- 1.2 120 0 - 13 ~ 12% DVB
" QC -so; Na 5.0 2.1 45- 55 0.3- 1.2 120 0 - 13 ~ 157» DVB
QR -so; Na 3.9 1.7 45- 55 0.3- 1.2 120 1 - 14 High stability to oxidizing
conditions
NQ (H, NH,, Li) -so; H, NHj. Li 4.6 1.8 4 5 - 55 0 . 3 - 1.2 120 0 - 13 Nuclear grade
NQ 'Li -so; 'Li 4.6 1.8 4 5 - 55 0 . 3 - 1.2 150 - Nuclear grade

а See Appendix I for full паше of manufacturers.

О ^ - S O j group resins are strong-acid resins.
CO
T A B L E X. (cont.)

Exchange capacity Physical characteristics Operational controls

Functional
Trade паше Manufacturer a Ion form (meq/g) (meq/ml) Moisture Size Max. oper. pH Remarks
group
(dry) (wet) (wc.%) (mm) temp.('C) range

b
Permutit RS Permutit A. G . , -so; Na 5.2 2.2 - 0.3-1.2 150 - Nuclear grade
Fed. Rep. of Germany

Resex P Jos. Crosfield, UK -so; Na 4.8 2.0 - 0.3-1.2 120 -

S-katex VyzkumnJ iistav -so; H 4.9 0.5 0.3-1.2 120 0 - 14

synthetick^ch
pryskyfic a 1акб,
Pardubice, CSSR

SDV Moskovsk Chem. -so; - 4.2 - - 0.3-1.4 - - Fine ground

Technol. Inst., USSR

Wolfatit KPS VEB Farbenfabrik -so; Na 4.5 1.8 45-53 0.3-1.2 115 3-14
R ( H , L, K, N) Wolfen, German -so; H, Li, К 1.8 0.3-1.2 115 3-14 Nuclear grade
Democratic Rep. and NH4

Zerolit 225 Zerolit Ltd., UK -so; Na 4.8 2.1 45-50 0.3-1.2 120 0 - 14 Standard resin 8% DVB* also
available with 1, 2 , 4 . 5 , 12
& 20?o DVB

b. Vinyl addition polymers (acrylic, methacrylic)

Exchange capacity Physical characteristics Operational controls

Type of Functional Ion
Trade name Manufacturer a (meq/g) (meq/ml) Moisture Size Max. oper. pH Remarks
acid group form
(dry) (wet) (wt.%) (mm) temp.('C) range

Amber lite IRC-50 Weak Rohm & Haas C o . , -coo" H 10.0-10.2 3.5 43-53 0.3-1.2 120 5-14 Capacities - in alkaline
IRC-84 USA -COO" H 10.0 3.5 43-50 0.3-1.2 150 4-14 médiat spherical beads

CFB-P Strong Chem. Fabrik -oso; - - 100

Budenheim,
Fed. Rep. of Germany

Duolite C S - 1 0 1 Weak Diamond Alkali C o . , -COO" H 10.0 3.5 0 . 3 - 1.2 100 ~ l0<7o DVB; beads
USA
Ionac С - 2 7 0 Permutit H-70 marketed by Ionac C o . , USA

Imac Z5 Weak 1МАСП, Netherlands -COO" 3.0 - 0.3-1.2 100 4 - 14 Beads

Kastel C - 1 0 0 Weak Montecatini, Italy -COO" 3.0 45-50 0 . 3 - 1.2 110 0-14 Beads; ~ 10% DVB

Karboxylovy Weak Spolek pro chemlckou -COO" 10.0 3.5 - 0.3-1.2 120 5 - 14 Beads
vyrobu, CSSR

KB-1 Weak NIIP, USSR -COO" 10.0 - - 0.3-1.5 Beads

KB-2 -coo" 10-11 - - 0.3-1.0 Beads
KB-3 -COO" 6-7 - - 0.3-1.5 Beads; acrylonitrlle- DVB
KB-4P-2 -coo" 9.5 - 0.25-1.0 Beads

Kn Weak Moskovsk Chem. -COO" 6.0 - - 0.25-1.5 Fine ground

Technol. Inst., USSR

KF-3 Intermed. NIIP, USSR -PO, 3.5

KF-4 Intermed. CH¡POÍ" 5. 5

KU-3 Strong -soi 5.5 - - - Fine ground

Mykion KMK Weak MUKY, Hungary -coo" 8.6 1.2

- CP 8.0 2.8
-COO" •
Petmutit С Weak Permutit A . G . , H 10.0 4.0 100 6 -14 Beads
Fed. Rep. of Germany -coo"
H-70 Permurit C o . , USA H 6.5 2.4 4 0 - 50 0.3-1.2 120 5 - 14 Beads
-COO"
Wolfatit CP VEB Farbenfabrik Na 10.0 3.5 43-53 0.5-2.0 100 7 ~ ffb DVB, beads
Wolfen, German -coo"
Democratic Republic

Zerolit Ltd., UK 10.0 3.5 - 0.3-1.2 100 - Beads; 2 . 5 & 4.5% DVB
available

a See Appendix I for full name of manufacturers.

Ь -SOs group resins are strong-acid resins.
T A B L E X. (cont.)

с. Phenolic resins

Exchange capacity Physical characteristics Operational controls

Type of Functional Ion
Trade паше Manufacturer (meq/g) (meq/ m 1) Moisture Size Max.oper. pH Remarks
acid group form
(dry) (wet) (wt.Vo) (mm) temp.fC) range

Dorolit FK-22 Strong MUKT. Hungary - S O 3 , OH" - 2.7 0.6 - - Fine ground

Dowex CCR-1 Weak Dow Chemical C o . , -COO" H - 1.4 0.3-0.8 100 Marketed by Nalco Chem.
USA -OH C o . , USA, granular

Duolite C - 3 Strong Diamond Alkali -so; H 2.9 1.2 0.3-2.0 60 0-9 Beads; -CH z SO¿ groups
C o . , USA
" C-10 -so; H 2.9 0.6 0.3-2.0 40 0-9 Beads; -CH2SO3 groups

Lewatit KSN Strong Farbenfabriken -so; - 4.0 1.6 45-50 0 . 3 - 1.5 30 0-8 Granular
Bayer A. G . . Fed.
Rep. of Germany
CNS Strong П -SOS. - 5.0 2.5 36-43 0.3-1.6 40 0 - 10 Granular
& weak -coo" H
CNO Weak " -coo" - 4.0 2.4 3 0 - 35 0 . 3 - 1.6 40 0 - 10 Granular

MSF-3 Weak Moskovsk Chem, -so;. - 4.3 - 0.3-2.0 - Fine ground

T e c h . Inst., USSR -OH

Mykion FG Strong MUKY, Hungary -CH¡SO¡,-OH - 2.8 0.9 - -

« »
P -OH - 2.2 0.65 - -

NSF Strong Moskovsk Chem. -so; - 3.0 - 0.3-1.5 - Fine ground

Tech. Inst., USSR

Permutit H Weak Permutit C o . , USA -coo" 5.0 1.9 - 65 Granular

Permutit A . G . , -coo" 4.0 - - 40 Granular
Fed. Rep. oí Germany

Resex W Weak Jos. Crosfield, UK -coo" - 2. 5 - 3.0 - - - Granular

RF Intermed. Moskovsk Chem. -PO|" 4.3 - - -

Tech. Inst., USSR

 Strong Institut vysokomol. -so;. 5.2 - - 0.3-1.5 Fine ground
USSR •OH

SNF Strong -so;, -OH 5.2 - - 0.3-1.5 Fine ground

FN-katex Strong Chemicky kombinat -so; 0.54 - 0.3-1.5 1-9.5 Beads, fine ground
záluZT, CSSR

KB-5 Weak -ch 2 coo",oh 7.5 - - 0.25-1.5

KU-I Strong -so;, -он 4.0 - 50 0.3-3.0 Dark brown grains

KU-1G Strong -SOj", -OH 4.5 - 50 0.3-2.0 Beads, black or brown

KRFU Weak Institut vysokomol., -coo" 4.0 - - 0.25-1.5 Fine ground

USSR

KU-5 Strong NIIP, USSR -so; 5.0 - - 0.3-2.0 Beads, fine ground
KU-6 Strong -SQ>", 5.5
& weak -coo"
KU-6F -coo" 5. 6
KU-7 -COO" 5. 5
KU-8 -sc5 ,-coo" 6. 0
KU-9 Strong -s05.-0h 6.0 . . . Fine ground
KU-21 -so; 5.5 Fine ground

Staionit F-extra Strong Chemicky kombinát -ch 2 so; 0.2 - 0.5-2.5 1 - 9.5 Fine ground
záluZT, CSSR -он

Strong veb Farbenfabrik •so," 2.9 - - 0.3-1.5 50 - Granular

Wolfen, German
Democratic Republic
P -so; Na 1.9 - - 0.3-1.5 50 - Granular
C\' -coo" Na 2.0 - - 0.3-1.5 30 - Granular
CV -coo" 4.0 l.C 40-50 0 . 3 - 1.5 40 0- 8 Granular

Zerolit 215 Strong Zerolit Ltd., UK -SO,, OH Na 0.92 - 0.3-1.2 40 0-9 Granular
" 216 Weak -COO", OH h 2.5 1.1 - 0.3-1.2 30 0- 9 Granular
£ T A B L E X. (cont.)

d. Inorganic e x c h a n g e r s (synthetic zeolites)

Exchange capacity Operational controls

Chemical or Functional
Matrix Manufacturer (meq/g) (meq/ml) Max. oper. pH Physical form Remarks
trade name group
(dry) (wet) temp.('C) range

Alum inosilicates Decalso Permutit C o . , USA AlOjNa 1.4 0.53 40 6.9-8.0 Granules Na form; intermediate capacity

Doucil Jos. Crosfield, UK - 1.2 - - Granules

Molecular Davison Chemical Div., - - 590 - Powder, pellets,

sieve ЗА W.R. Grace C o . , USA granules

Molecular - - 590 - Powder, pellets,

sieve 4A granules

Molecular - - 590 - Powder, pellets,

sieve 5 A granules

Molecular Powder, pellets

H
sieve 10 A - - 590 - granules

Molecular Linde C o . , USA - 5.3 400 - Pellets Synthetic zeolites; nominal

sieve 4A pore diameter 4 Д

Molecular - - 400 - Pellets Synthetic zeolites; nominal

sieve 5A pore diameter 5 Â

Molecular - 4.8 400 - Pellets Synthetic zeolites; nominal

sieve 13X pore diameter 10 A

AW300 - 1.7 - - Nominal pore diameter 4 A

AW400 - 2.0 - -
AW500 2.0 - - Nominal pore diameter 5 A

Zeolon Norton, USA - 1.9 538 Pellets or . Synthetic mordenite

(Na form) powder

Ammonium-molybdoarsenate Kd (Cs) = 400 to 4000 (method of prep. )

Ammonium-12-molybdophosphate Bio-Rad AMP-1 Bio-Rad Labs, USA 0 . 7 (Cs) K d (Cs) = 6000

Ammonium-tungstophosphate K(] (Cs) = 3300 to 3500 (method of prep.)

 Exchange capacity
Matrix Chemical or trade name Manufacturer Remarks
(ftieq/g) (dry)

Arsenates Ferric arsenate At pH 3 . 5 5 - 1 0 . 9 5 : 1 . 1 8 - 5 . 7 3 (Sr)

Zirconium arsenate At pH 3 . 1 2 - 1 0 . 6 8 : 2 . 87 - 6 . 1 5 (Sr)

Cerium (IV) compounds Ceric phosphate, H*form; eerie At pH 0 . 1 0 - 1 1 . 7 : 0.07-3.24 Na + ion-exchange capacity
phosphate, NH4 form; ceric oxide.
AH not available commercially

Ferrocyanide-molybdate Not available commercially

FEM

Hydrous oxides Not ávailable commercially

CO (OH) s At pH 7 - 1 0 : 0 . 2 5 - 0 . 7 8 Blue particles
Sn(OH) 4 At pH 4 - 11: 0 . 7 3 - 1 . 7 8 White particles
Al (OH) s At pH 7 - 1 0 : 0 . 1 0 - 1 . 2 4 White particles
Ni (OH)s At pH 6 . 5 - 10: 0 . 0 2 - 2 . 2 5 Green particles
Fe(OH) 3 At pH 6 - 1 0 : 0 . 1 1 - 2 . 1 9 (Sr)
Lead sulphate (tribasic) At pH 1 - 6 . 7 : 8 . 5 - 0 . 8 (anion exch.)
At pH 7 . 2 - 1 2 . 5 : 0 . 1 - 7 . 5 (cation exch.)

Phosphates ABEDEM Sn SERAI, Belgium 3.70 (H)

ABEDEM TiA 7.50 (H)
ABEDEM TiB 9.50 (H)
ABEDEM Zr 5.20 (H)

Potassium hexacyanocobalt (II) ferrate (III) Not available commercially 6 . 0 (Cs)

Quinoline- moly bdophosphate K d (Cs) = 1500 m l / q

Silicates АЬОз-Х Si02

S N 0 2 • X SiOj
AnO • X S i 0 2
(X = varying number of silicates)

Thorium-base Thorium phosphate At pH 3 . 0 - 1 1 . 0 : 0.30-1.1

Titanium-base Titanium phosphate At pH 2 . 5 - 3 . 1 . 5 : 0.20-3.5

Zirconium-base Zirconium arsenate At pH 2 . 5 - 1 , 3 0 : 0 . 3 0 - 3 . 0

Zirconium oxide
Zirconium phosphate (ZP) At pH 3 , 5 - 1 1 . 5 : 0.10-5.5
Zirconium phosphate with citrate (Z CP)
Zirconium tungstate At pH 2 . 5 - 1 2 . 0 : 0.3-1.5
Bio-Rad ZP-1 Bio-Rad Labs, USA
ZT-1 1.0
ZM-1
T A B L E XI. NATURAL CATION EXCHANGERS

a. Organic

Exchange capacity Operational controls

Mineral or Functional Physical
Matrix Manufacturer (meq/g) (meq/ml) Max. oper. pH Remarks
trade name group form
(dry) (wet) temp.('C) range

Coals Dusarit S M ACTI, Netherlands -S03 0 . 7 (strong) 80 0 - 14 Granules Polyfunctional

-COONa 0 . 3 5 (weak)

Imac С 19 " -so; 0 . 3 (strong) 80 4-14 Granules Polyfunctional

-COOH 1.0 (weak)

Soucol los. Crosfield, UK -so; 1.8 0.6 30 Granules

Zeokarb-H Permutit C o . , USA -so; 1.6 0.56 70 0 - 8.5 Granules Intermediate

-COOH acidity

Brown coal Local - Mol, Belgium -COOH 0.45

(lignite) Idaho, USA At pH 4 . 1 : 0 . 0 2 - 1 . 0 8

Peat Local - Poland 0.05-0.4

b. Inorganic

Greensand Zero lit Zerolit Ltd., UK

(stabilized)

Greensand Zeodur Permutit C o . , USA AlOjNa 0.11 0.14 60 6 . 2 - 8.0 Granules Na form
(stabilized)
Clay minerals Kaolinite 0.03-0.15
(natural) Halloysite 2Н г О 0.05-0.10
Halloysite 4H2 О 0.40-0.50
Montmorillonite 0. 8 0 - 1 . 5 0
Illite 0.10-0.40
Vermiculite 1.00-1.50
Chlorite 0.10-0.40
Sepiolite- attapulgite 0.20-0.30
Palygorskite
Analcite 4.50

Zeolite minerals Clinoptilolite 1.5 2.8 - 3.2 Granules

(natural) 1.61 ±0.01 Granules
1.7 Granules
At pH 4 . 1 : 0.35 Granules
Cancrinite 10.9
Erionite .2.2
Heulandite 3.30
Mordenite 1.40
Natrolite 5.3
Phillipsite 2.3
Sodalite 9.2
Ultramarine 8.3

Pyroclastic rocks Andesitic tuff 0 . 1 0 - 0.40

Rhyolitic tuff 0.0-0.30
Rhyodacitic tuff 0.80-1.30
Basaltic tuff 0 . 3 0 - 0.80
Tefritic & fonolitic tuff 0.20-0.80
Tuffites 0.0-0.50
T A B L E XII. S Y N T H E T I C ANION EXCHANGERS

a. Strong base polystyrene addition polymers

Type I [functional group - N ( C H 3) 3]

Exchange capacity Physical characteristics Operational controls

Trade name Manufacturer Ion form (meq/g) (meq/ml) Moisture Size Max.oper. pH Remarks
(dry) (wet) (wt.%) (mm) temp. CC) range

Amberllte IRA-400 Rohm & Haas C o . , USA CI 3.7 1.4 42-• 88 0.. 3 - 0 . 0 8 60 (OH) 0-14 Beads, c a . 8% DVB: avail, in larger particle
distributed by size as 400 С
IRA-401 Tokyo Organic Chemical CI 3.5 1.0 53-•58 0.. 3 - 0. 8 60 (OH) 0-14 Beads, porous
IRA-401S Industry Ltd., CI 3.4 0.8 59-•65 0.. 3 - 0. 8 60 (OH) 0-14 Beads, porous
ЮА-402 Japan CI 4.4 1.25 50-•57 0., 3 - 1 . 2 80 (CI) 0 - 14 Beads, porous
бо(он)
IRA-900 CI 4.4 1.0 6 0 -•64 0,. 3 - 1 . 2 60 (OH) 0-14 Beads, porous, mean pore size 250 'A*
IRA-904 CI 2.6 0.7 56-•62 0,, 3 - 1 . 2 60 (OH) 0-14 Beads, porous, mean pore size 645 'A'
IRN-78 OH 3.5 - 60 0,. 3 - 1 . 2 60 (OH) - Reactor grade

AV-15 NIIP, USSR - 3.0 - - - Beads

AV-17-6 CI 4.3 - 4 0 -•60 0. 3 5 - 1 . 2 50 - Beads; 6% DVB
AV-17-8 CI 3.8-4.5 - 4 0 - •60 0. 3 5 - 1 . 2 50 - Beads; 8% DVB
AV-17-8 - 3.4 - 0. 4 - 1 . 2 - - Beads, special porosity

Diaion SA 10A Mitsubishi Chemical CI - 1.2 4 3 - •47 0. 3 - 1 . 2 60 (OH) 0 - 12 Beads; 8% DVB

" SA 101 Industries Ltd., CI - 0.85 5 0 - 65 0. . 3 - 1 . 2 60 (OH) 0-12 Beads, porous, low crosslinking
" SA 11A Japan CI - 0.85 55-•65 0. 3 - 1 . 2 60 (OH) 0-12 Beads, porous, 4°¡o DVB
" SA 100 CI - 1.0-1.3 50-•60 0. 0 7 - 0 . 1 5 - 0-12 Beads, analytical uses

Dowex 1 Dow Chemical CI 3.5 1.33 43 0. 3 - 0 . 8 50 0-14 Beads, c a . 8% DVB: 1, 2 , 4 t % DVB

C o . , USA also available
" 21K CI 4.5 1.25 57 0. 3 - 0 . 8 50 0-14 Beads; improved mech. stability
" 11 CI 4.0 1.24 57 0. 3 - 0 . 8 50 0-14 Beads: uranium recovery

Duolite A-101D Diamond Alkali CI 4.2 1.4 5 0 - 55 0. 3 - 1 . 2 60 (OH) 0-14 Beads

" ES-111 C o . , USA CI 4.7 1.0 4 5 - •50 0. 3 - 1 . 2 40 (OH) 0-14 Limited quantities; beads

Imac S 5 - 4 0 1MACTI, Netherlands CI - 1.0 55 0. 4 - 0 . 8 5 50 (OH) 0-14 Beads

" S 5 - 50 CI - 1.2 0. 4 - 0 . 8 5 50 (OH) 0-14 Beads

Ionac A-540 (Permutit S - l , marketed by Ionac C o . , USA)

 Kastel A-500 Montecatini, Italy CI 3.0 0 . 3 - 1.0 60 (OH) 0 - 14 Beads
A-500P CI 3.3 0 . 3 - 1.0 60 (OH) 0 - 14 Beads, porous

Lewatit M-500 Farbenfabriken CI 4.0 1.6 0.3- 1.2 70 0 - 14 Beads

" MP-500 Bayer A. G . , CI 4.0 1.2 0.3- 1.6 70 0- 14 Beads, porous
" M-600 Fed. Rep. of Germany 3.7 1.6 0.3- 1.2 40 0- 14 Beads, porous
MP- 600 3.7 1.1 0.3- 1.5 40 0 - 14 Beads, porous

Nalcite SBR (Dowex 1, marketed by Nalco Chemical Co . . USA)

SBR-P Porous

Permutir ESB Permutit A. G. , CI 3.2 1.2 70 Beads

ESB-26 Fed. Rep. of Germany CI 3.3 1.3 - 70 Beads

Permutit s - 1 Permutit C o . , CI 3.6 1.0 5 0 - 60 0 . 3 - 1.2 100 0 - 14 Beads

NSI USA OH 3.5 1.0 5 0 -• 60 0 . 3 - 1.2 60 0 - 14 Beads, nuclear grade

Resenex HBL Jos, Crosfield, 3.5 1.5 60 Beads

HBT UK - 3.5 - 60 Beads

3 - S - T M anex Vyzkumny ústav CI 3.45 1.35 0.3- 0.8 40 (OH) 0 - 12

synthetickych
pryskyrïc a lakb.
Pardubice, CSSR

Wolfatit ES VEB Farbenfabrik CI 3.5 0.5 65-•75 0.5- 2.0 60 (OH) 2- 10

SBT Wolfen, CI 3.0 0.9 53-• 63 0.6- 2.0 - 0- 14 Uranium recovery, beads
SBW German Democratic Rep. CI 3.5 0.9 5 8 -• 68 0.3- 1.5 60 0- 11 Beads
RO OH 0.9 0.3- 1.5 60 0- 14 Beads, nuclear grade

Zerolit FF-1P Zerolit Ltd., CI 4.0 1.2 0 . 3 - 1.2 60 Beads, 7 - 9% DVB

K-MP UK CI - - - Beads, macro porous

b. Strong base polystyrène addition polymers

Type II [functional group - N(CH 2 OH) ( C H 3 ) J

Amberlite IRA-410 Rohm & Haas C o . , USA Cl 3.3 1.40 40-45 0.3-0.8 40 (OH) 0 -14 Approx. 8% DVB, beads
IRA-910 distributed by Cl 1.10 55-60 0.3-0.8 40 (OH) 0-14 Beads; macroreticular
IRA-911 Tokyo Organic Chem. Cl 2.7 0.9 42-44 0. 3 - 1 . 2 40 (OH) 0-14 Beads; macroreticular
Ind, Ltd., Japan

Diaion SA 20A Mitsubishi Chemical Cl 1.3 40-45 0.3-1.2 40 (OH) 0 -12 Bead s
- SA 21A Ind. Ltd., Japan Cl 0.8 55-65 0.3-1.2 40 (OH) 0-12 Beads, porous
^ T A B L E XII. (cont.)
to
о
Exchange capacity Physical characteristics Operational controls

Tradename Manufacturer Ion form (meq/g) (meq/ml) Moisture Size Max.oper. pH Remarks
(dry) (wet) (wt.%) (mm) temp. (°C) range

Dowex 2 Dow Chemical C o . , USA Cl 3.5 1.33 30 (OH) 0 -14 Beads, c a . 8% DVB; 4% DVB also available

Duolite A-102D Diamond Alkali Cl 4.2 1.4 4 5 - 50 0 . 3 - 1.2 40 (OH)

C o . , USA

Imac S5-52 IMACTI, Netherlands Cl 1.2 0 - 14 Beads

40 (OH)

Ionac A-550 (Permutit S - 2 . marketed by Ionac C o . , USA)

Kastel A-300 Montecatini, Italy Cl 3.2 0 -16 Beads

40 (OH)

Nalcite SAR (Dowex 2 , marketed by Nalco Chemical C o . , USA)

Permutit ES Permutit A . G . , Cl 3.2 1.2 40 Beads

ES-26 Fed. Rep. of Germany Cl 3.3 1.3 40 Beads

Permutit S - 2 Permutit C o . , USA Cl, 3 . 5 (Cl) 45-55 0 . 3 - 1.2 100 (Cl)

0 - 14 Beads
OH, SO, 3 . 5 (OH, SOj) 60 (OH, SO3 )

Vyzkumny ústav 40 (OH)

0 -12 Beads
synthetickych
pryskyric a lakfi,
Pardubice, CSSR

VEB Farbenfabrik 35 - 45 0.3-1.5 40 (OH) 0-10.5 Beads, 6 - 8 % DVB

Wolfen, German
Democratic Republic

Zerolit N-1P Zerolit Ltd., Cl 1.10 0 . 3 - 1.2 40 0-14 Beads; isoporous

" P-1P UK Cl 1.14 0.3-1.2 40 0-14 Beads; isoporous
с. M e d i u m and weak base polystyrene addition polymers

Exchange capacity Physical characteristics Operational controls

Functional
Trade name Manufacturer Ion form (meq/g) (meq/ml) Moisture Size Max.oper. pH Remarks
group
(dry) (wet) (wt.%) (mm) temp.(eC) range

Amberllte IR-45 Rohm & Haas C o . , USA Weak base Freebase 5.0 1.9 40-45 0.3-0.84 100 (OH) 0 -9 Beads
IR-68 -ЩЮг - - 1.60 57-63 0.3-1.2 60 0 -9 Acrylic resin - beads
1R-93 4.8 1.4 46-54 0.3-1.2 100 (OH) 0 -9 Beads; macroreticular

AN-18-6 NIIP, USSR Amino groups CI 3.5 - 40-60 0.35-1.2 - Beads

AN-23 CI 5.0 - 30 0.25-1.0 - Beads
AN-25 „ CI 5.0 - 30 0.25-1.0 - Beads
AV-20 " Pyridine base CI 3.5 - 60 0.25-1.0 130 Beads
AV-23 CI 3.5 60 0.25-1.0 130 Beads

Dowex 3 Dow Chemical Weak base OH 5.5 2.5 35 0.3-0.84 65 Beads

C o . . USA amino groups

Duolite A-14 Diamond Alkali Weak base OH 8.0 2.5 - 0.3-1.2 - - Beads
C o . . USA amino groups

Imac A20 IMACTI, Weak base OH - - 0.4-0.85 100 0- 8 Beads; p r i m . . sec. &
Netherlands amino groups tertiary aminos
" A21 OH - 0.4-0.85 100 0- 8 Beads; tertiary amino groups only

lonac A-315 (Permutit W, marketed by Ionac C o . , USA)

Lewatit MP-60 Farbenfabriken Weak base - 6.3 2.2 40-50 0.3-1.5 100 0 -14 Beads; macroporous
Bayer A . G . , amino groups
Fed.Rep.of Germany

Nalcite WBR (Dowex 3, marketed by Nalco Chemical Co. . USA)

Permutit W Permutit Co. , Weak base CI 4.5 1.3 45 - 55 0.3-2.0 95 - Beads

USA amino groups

Wolfatit Y13 VEB Farbenfabrik Weak base OH - 1.25 - 0.3-1.2 - 0 - 14 Beads

Wolfen, German amino groups
Democratic Rep.

Zerolit G Zerolit Ltd., UK Amino groups Ci 3.5 1.6 0 . 3 - 1.2 100 - - N ( C 2 H S ) 2 groups only; beads
M 0 . 3 - 1.2 60 Beads
H ..
"
Weak & strong
Cl
-
5.5
3.8
1.9
1.28 0.3-1.2 10
-
- Beads: ¡soporous
base groups
£ T A B L E XII. (cont.)
isa
d. Condensation polymers

Exchange capacity Physical characteristics Operational controls

Type of Functional
Trade name Manufacturer Matrix ion form (meq/g) (meq/ml) Moisture Size Max.oper. pH Remarks
base group
(dry) (wet) (wt.%) (mm) temp.('C) range

AN-1 Weak NIIP, USSR Amino groups SO, 4.2 50 0.3 - 2.0 40 _ Fine particles
AN-2FN Weak - - Cl 9.0 15 0.3 -2.0 50 Fine particles
AN-9 Weak - - 4.5 - - 0.3 -2.0 - Beads
AV-16G Strong
„ - Cl 9.8-10.5 - 60 0.4 -2.0 60 Beads
AN-31 Weak Cl 9.0 - 15 0.3 -2.0 Irregular grains

Dowex WGR Intermed. Dow Chemical C o . , Epoxy-amine Free - - 50-54 0.4 - 0.8 93 0- 7 Marketed by
USA amine Nalco C o . , USA

Duolite A-2 Weak Diamond Alkali Sec. amine Phenolic SO, 8.4 2.3 58-64 0.3 - 1.2 40 0 -4 Granules, porous
C o . , USA
A-6 Weak » Tert. amine Phenolic Cl 7.6 2.4 4 8 - 54 0.3 -1.2 60 0 -5 Granules, porous
A-7 Weak Sec. amine Phenolic S04 9.1 2.4 55-62 0.3 - 1.2 40 0 -4 Granules, porous
ES-15 Weak Tert. amine Aliphatic Salt 6.2 2.4 38-42 0.3 - 1.2 80 0 - 5 Beads
Intermed. H Tert. amine OH 8.7 2.6 58-62 0.3 - 1.2 80 0 - 9 Beads, high
А-ЗОВ Epoxy-
Quat. NHj polyamine stability
ES-57 Intermed. " Tert. amine Epoxy- Salt 9.2 2.2 60-66 0.3 - 1.2 80 0- 9 Beads, porous
Quat. NH3 polyamine stability

EDE-LOP Strong NIIP, USSR Quat. NH 3 , sec. - Cl, OH 9 - 10 (Cl) - 10 0 . 4 - 1. 8 (Cl) OH form is of
& weak & tert. amine 8 (OH) - 0 . 5 - 2 . 0 (OH) special purity

Imac A-27 Strong IMACTI, Amino groups Poly- Free- - - 0.3 - 2 . 0 35 0- 8 Beads,
& weak Netherlands alky lene base polyfunctional

lonac A-300 (Peimutit A, marketed by Ionac C o . ,, USA)

Kastel A-100 latermed. Montecatini, Quat. NH4 Epoxy-amine Cl 7.5-8.0 - 60 0.3 - 1.25 4.5 0- 5
Italy & amino (partial)

о
L-anex - Chemické závody =N - SO, 2.6 0.8 - 0.5 - 1.5 50 (OH) 0 - 12 Beads
usti n. labem,
CSSR
Lewatit MIH 59 Weak Farbenfabriken Amino 6.0 2.4 4 0 - 50 0 . 3 - 1.2 30 0 - 14 Granular
" MN Strong Bayer A . G . , -N (alky 1)| 2.3 0.9 46-54 0.3-2.0 30 0 - 14 Granular
Fed. Rep. o f Germany

Moskovsk Chem. = NH, S N 4.1 0.3-2.0 Fine particles

Technol. Inst., USSR

Mykion G MUKY, Hungary 4.6 1.25 Guanidine,

formaldehyde

N Weak Moskovsk Chem. = NH, = N 4.1 0.3-2.0 Fine particles

NO Weak T e c h n o l . Inst.. USSR = NH,=N,-NR3 4.1 0.3-2.5 Fine particles

РЕК Strong Gosud. Institut sNH2,=N 6.0 0.3-1.0 Fine particles

& weak Prikl. K . . USSR

Permutit E - 3 Weak Permutit A . G . , Amino groups 6.0 0.3-1.0 Granules, - N R 2

Fed.Rep. of groups only
E-7P Weak Germany 6.0 - 40 Granules, highly
porous

Permutit A Intermed. Permutit C o . , USA NR 3 , NR4 Aliphatic CI-SO4 5.5 1.8 1-5 0 . 3 - 1.2 40 0 - 12 Granules
polyamine
NRJ, NR 4 CI-S04 5.5 1.8 1-5 0.3- 1.2 40 0-12 Beads
CCG NR 3 Phenolic C1-S04 5.5 1.6 2-7 0 . 3 - 1.2 60 0 - 12 Granules
Deacidite Weak NHR 2 , NR 3 Aliphatic CI-SO4 5.5 1.8 1-5 0.3-1.2 40 0 - 12 Granules
polyamine

Resanex Weak Jos. Crosfield, UK Amino groups 9.0 3.0 80 0-9 Granules

Wolfatit N Weak VEB Farbenfabrik Amino groups '4.3 0.3-1.5 30 Granules

Wolfen, German
Democratic Rep.

Zerolit E Medium Zerolit L t d . , UK Amino groups Phenol Free- Granules

formaldehyde base
T A B L E XIII. M I X E D B E D ION-EXCHANGE RESINS

Cation Anion Approx. v o l . ratios „ ,

Trade name Manufacturer , , . Remarks
e x c h a n g e resin e x c h a n g e resin c a t i o n : anion

Amber lite M B - 1 Rohm & Haas C o . , USA IR-120 IRA 4 0 0 or 4 0 1 1.5

MB-2 IR-120 IRA 4 1 0 1.5
MB-3 IR-120 IRA 4 1 0 1.5 Exhaustion colour i n d i c a t o r
MB-4 IR-120 IR-45 1
MB-5 IRC-50 IRA 4 1 0 1.5
MB-6 IRC-50 IR-45 N u c l e a r grade
IRN-217 IRN-218 ( 7 L i ) + IRN-78 N u c l e a r grade
IRN-150 IRN-77 ( H + ) IRN-78 N u c l e a r grade
IRN-154 IRN-163 ( U + ) IRN-78 N u c l e a r grade
IRN-170 IRN-169 (NH+) IRN-78 Nuclear grade

Bio-Deminrolit Z e r o l i t L t d . , UK Zerolit 225 Zerolit FF-IP Also a v a i l a b l e with i n d i c a t o r

Nalcite MR-1 Dow C h e m i c a l C o . , USA HCR-W S BR T e c h n i c a l grade; indicator

" MR-2 distributed by HCR SBR N u c l e a r grade
" MR-3 N a l c o C h e m i c a l C o . , USA HCR-W SBR N u c l e a r grade
" MR-5 HCR-W ( K + ) SBR N u c l e a r grade
" MR-6 HCR-W ( L i + ) SBR N u c l e a r grade
" MR-7 HCR-W ( N H j ) SBR N u c l e a r grade

W o l f a t i t MBW KPS SBW

ROH RH RO N u c l e a r grade
ROL RK RO N u c l e a r grade (LiOH)
ROK RK RO N u c l e a r grade (KOH)
RON RN RO N u c l e a r grade (NH 4 OH)
 T A B L E XIV. ION-EXCHANGE MEMBRANES
О!
a. Cation exchangers

Exchange Electric
Moisture
Functional capacity Transport number Thickness resistance
Trade name Manufacturer Matrix content Remarks
groups (meq/g) dry (solution used) (mm) (ohm-cm2)
(wt.io)
membrane (ion form)

AMF ion С - 6 0 American Machine Polyethylene- -so; 1.510.3 0.92 10.03 35 0.28-0.33 5 1 2 (K) 9 1 . 5 and 112 cm
(Series 60) &. Foundry, USA styrene ( 0 . 2 N / 0 . 1 N KC1) wide roll
copolymers
AMF ion С - 1 0 0 " -so; 1.310.3 0.9810.1 15 0.20 7 1 2 (K) Roll
(Series 100) ( 0 . 2 N / 0 . IN KC1)
AMF ion C - 3 1 0 Polymeric -so; 0.610.2 0.8610.5 - 0.28 4.542 Roll
fluorocarbon ( 0 . 5 N / 1 . ON KC1)
AMF ion C - 3 1 3 -so". 0.610.2 0.9010.003 12 0.17 4 . 5 1 2 (K) 112 cm wide roll
(Series 300) ( 0 . 2 N / 0 . 1 N KC1)

CK-1 Asahi Chem. Industry Polystyrene -so; 2.6 0.99 36 0.23 4.2
Co. Ltd., Japan (0.5N NaCl)

MC-3142 Permutit C o . , USA, • - 1.06 0.941 - 0.15 3.4 Heterogeneous

distributed by (0.5N/1N NaCl) (1.0N NaCl)
MC-3235 Ionac Chemical C o . , - - 1.26 0.953 - 0.30 11 Heterogeneous
USA ( 0 . 5 N / 1 N NaCl) (1.0N NaCl)
MC-3470 XL - - 1.05 0.962 - 0.30 4.8 Heterogeneous
( 0 . 5 N / 1 N NaCl) (1.0N NaCl)

MK-40N NIIP, USSR Polystyrene 2.3 0.93 41 0.7-0.8 Spec, resist. Heterogeneous,
(KU-2) -so; ( 0 . 0 1 N / 0 . 2 N NaCl) 250 ohm-cm 500 X500 mm sheets

Nal film 1 Nalco Chem. C o . , USA -so; 0.91 20 0.09 10 - 1 5 (K) 9 6 . 5 cm wide
(0.15N KC1)

Nepton CR-61 Ionics I n c . , USA Polystyrene -so; 2.8 0.9-0.95 45-50 0.58 5 . 3 (Na) Porous;
( 0 . 5 N NaCl) Dynel reinforced

Scrion C - 1 0 0 Japan Organo Co. - -so; - 0.9 - 0.20-0.22 4-5 90 c m wide roll
Ltd., Japan ( 0 . S N / 2 . 5 N NaCl) * (0.5N NaCl)

Selemion CMG-10 Asahi Glass Co. - -so; 1.05 0.91 - 0.20-0.25 5 . 5 - 8 . 5 (Na) 9 8 x 9 8 cm
Ltd., Japan (0.5N NaCl)
CMG-20 - - 0.80 - 0 . 2 3 - 0.25 1 . 5 (Na) 9 8 x 9 8 c m , porous
( 0 . 5 N / 1 . 0 N NaCl) ( 0 . 5 N NaCl)
 CMV-10 -SO", 0.91 6.0-8.0 f x98 c m
( 0 . 5 N / 1 . 0 N NaCl) ( 0 . 5 N NaCl)
CSG 0.92 10 - 14 (Na) ¡ x98 cm
-so", ( 0 . 5 N NaCl)
( 0 . 5 N / 1 . 0 N NaCl)
Zerolit L t d . , UK 1 0 . 3 (K) 1 5 2 X 1 5 2 mm to
-so", 0.94
( 1 . ON NaCl) ( 0 . IN KC1) 7 6 0 X 3 0 4 mm

b. Anion exchangers

AMF ion A - 6 0 American Machine Polyethylene -NR, 0 . 93 ± 0 . 0 3 2215 0.31 6 1 2 (CI) 9 1 . 5 X 1 1 2 c m wide roll
& Foundry C o . , USA & styrene ( 0 . 2 N / 0 . IN KC1) ( 0 . 6 N KC1)
" A-104B graft- -NR. 0.9810.01 1513 0.15 9 1 3 (CI) 5 1 x 112 c m wide
copolymer ( 0 . 2 N / 0 . IN KC1) ( 0 . 6 N KC1) roll*, high selectivity

MA-3148 Permutit C o . , USA 0.96 0.899 0.30 1.7 Density 1 9 6 g / m 1

distributed by ( 0 . 5 N / 1 . 0 N NaCl) (1, ON NaCl) heterogeneous
MA-3236 Ionac C h e m i c a l 0.765 0.933 0.30 20 Density 3 5 8 g / m 2
C o . , USA ( 0 , 5 N / 1 . ON NaCl) ( 1 . ON NaCl) heterogeneous
MA-3475XL 0.743 0.941 0.30 5.3 Density 3 5 8 g / m 2
MA-40N NIIP, USSR Heterogeneous- Amino 3.0 0.84 38 0 , 7 - 0. S p e c , resist. 1500 x 500 mm sheets
EDE- OP resin groups
( 0 . 0 1 N / 1 0 . 2 N NaCl)
Nalco C h e m i c a l C o . 0.10 2 0 - 2 5 (CI)
Polystyrene -NRj
USA 0.96 ( 0 . 1 5 N KC1)
( 0 . 2 N / 0 . IN KC1)

Nepton A R - l l l - A Ionics I n c . . USA Polystyrene -NR3 0.90-0.95 0.58 5 . 9 (CI) Dynel hacking-,
( 0 . 6 N NaCl) ( 0 . 5 N NaCl) porous

Permutit C o . 0.93 0.75 8 . 1 (CI)

Polystyrene -NR3
L t d . , UK ( 0 . I N KC1)
( I N NaCl)

Serion A - 1 0 0 Japan Organo C o . -NR, 0.10-0.12 4 - 6 (CI) 90 c m wide

>0.9
L t d . , Japan ( 0 . 5 N NaCl)

Selemion A M T - 1 0 Asahi Glass C o . , 1.25 ( 0 . 5 N / 2 . 5 N NaCl) 0.18-0.2 2 . 0 - 4 . 0 (CI) 9 8 x 98 c m

L t d . , Japan 0.92 ( 0 . 5 N NaCl)
AMT-20 -NRj ( 0 . 5 N / 1 . 0 N NaCl) 0 . 3 4 - 0 . 36 2 . 4 (CI) 98 x98 cm
0.78 ( 0 . 5 N NaCl)
AST ( 0 . 5 N / 1 . 0 N NaCl) 0.21-0.23 6 . 0 - ~ 9 . 0 (CI) 98 x98 c m
0.95 ( 0 . 5 N NaCl)
DMT weakly ( 0 . 5 N / 1 . 0 N NaCl) 0.10-0.12 1 . 5 (CI) 88 x 88 c m
basic 0.93~ ( 0 . 5 N NaCl)

Zerolit L t d . , UK -NR, ( 0 . 5 N / 1 . 0 N NaCl) 0.75 8 . 1 (CI) 1 5 2 X 1 5 2 mm to

( 0 . 1 N KC1) 760 X 3 0 4 mm
(0I.N
9 3 NaCl)
T A B L E XV. COOLANT P U R I F I C A T I O N IN C E R T A I N E A R L Y USA P O W E R R E A C T O R S [67]

Shipping-Port Rowe Indian Point Dresden

Status Full p o w e r Critical late Critical Critical

Dec. 1957 1960 early 1 9 6 1 Oct. 1959

Type Pressurized w a t e r Pressurized w a t e r Pressurized water Boiling w a t e r

N e t electric capacity 60 M W electric 134 M W electric 255 M W electric 180 M W electric

Coolant Light w a t e r Light w a t e r Light water Light w a t e r

Additives to coolant Morphaline, N a O H and

during operation s o d i u m phosphate

Additives to coolant Soluble boron Soluble boron

during cold shutdown

C o o l a n t purification Full pressure b y - Low pressure b y - Low pressure by-pass By-pass d e m i n e r a l i z a t i o n

pass filtration pass ion e x c h a n g e filtration, ion e x c h a n g e , (primary f e e d gets full-flow
a n d ion e x c h a n g e ; degasification, c a t i o n , demineralization)
mixed bed mixed bed, dual bed
columns columns
T A B L E XVI. ION-EXCHANGE CAPACITY
AT VARYING REGENERANT L E V E L S

Régénérant Strong-base anion Strong-acid cation

level exchanger - hydroxide cycle exchanger - hydrogen cycle
(kg/m3) (meq/ml) (meq/ml)

80 0.64 0.87

160 0.82 1.38

240 0.96 1.56

T A B L E XVII. E F F E C T OF F E E D RATE AND T E M P E R A T U R E

ON PRESSURE DROP [73] a

Pressure drop per 3 0 . 4 ÍÎ c m ( g / c m 2 )

Feed rate, litres/m 2 /min 10°C 21.1°C 32.2°C

81.4 13.3 10.2 7.9

162.8 27.9 21.1 16.9

244.2 49.0 33.0 26.0

325.6 56.5 44,3 34.8

407.0 73.8 56.2 43.6

a From Amberlite Ж-120 technical notes. Used by permission of Rohm and Haas
Company, Philadelphia, Pa.

129
T A B L E XVIII. RESIN D E P T H - ION-EXCHANGE COLUMN
500 l i t r e s r e s i n , 150 l i t r e s / m i n feed

Resin . , Col. „ ,
. . Surface area Feed rate
depth , 2. diam. , ,, . .
(cm) <Ш > (cm) (litres/m / m i n )

30 1.67 146 90.4

50 1.00 113 150

75 0.67 92 224

100 0.50 80 300

125 0.40 71 375

150 0.33 62 465

130
T A B L E XIX. P R I N C I P A L RADIONUCLIDES IN G E N E R A L W A S T E SOLUTIONS

M a x i m a l permissible 1 5
Radionuclide Half-lifea a e У c o n c e n t r a t i o n in
waste ( j J c / c m 3 )

144 Ce, 144 Pr 285 d - 0.3 0.134 io- 4

I37 Cs, 137 Ba 3 0 yr - 0. 5 1 ( 9 2 % ) 0.66 4X10"4

1.17 ( Щ

13 lj 8.06 d - 0 . 6 1 (87%) 0.36 2 X10"5

0.34 (9%)

32p 14.3 d - 1.70 - 2 XlO"4

239 Pu 2 . 4 4 X 1 0 4 yr 5.1 - 0.053 5 X10"5

226 R a , 1 daughter 1 6 2 2 yr 4.78 - 0.186 10"7

106 Ru, 106 Rh 1 . 0 1 yr - 0. 0 4 - 10-4

90 Sr, 90 Y 2 8 . 6 yr - 0.61 • - 10" 6

235 y 231 X h
7 . 1 3 Х 1 0 8 yr 4.40 - 0.184 3X10-4

238ц 4 . 5 1 X 1 0 9 yr 4.21 - 0.05 4X10'4

a For parent nuclides o n l y ,

k Continuous exposure ( 1 6 8 - h w e e k ) .
TABLE XX. EXCHANGERS IN USE F O R S E P A R A T I O N O F
S P E C I F I C RADIONUCLIDES

Radionuclide Exchanger Total capacity Remarks

137 Cs, 137 Ba Clinoptilolite 1.5-1.7 meq/g [74-76]

Potassium h e x a c y a n o - 6.0 meq/g [77]
c o b a l t (II) ferrate II

Vermiculite 1 . 0 0 - 1 . 5 0 meq/g [64,78,79]

Strong a c i d - A c i d - 2 . 5 meq/ml [80] Cols.

weak base synthetic
resins Base 1 . 9 m e q / m l Operated in series

Filtrolit 0.25 meq/ml [81] Commercial silicate

mineral

Synthetic zeolites 1 . 0 - 2 . 0 meq/g [82]

Phenolic-carbaxylic 1 . 2 - 2 . 4 meq/ml [70]

c a t i o n resins

T i t a n i u m phosphate 7.5 meq/g [61, 83]

(Abeden T i - A )

Ammonium molybdo- 0.7 meq/g [63]

phosphate

Tuff 36-132 meq/100 g [84]

M i x e d fission S y n t h e t i c resins; See Tables X a - c , [85]

products strong and weak c a t i o n ХПа-d
and anion

°Sr, M Y S y n t h e t i c strong a c i d See Tables X a - c [25, 8 5 ]

c a t i o n - e x c h a n g e resins

Synthetic zeolites 1 . 0 - 2 . 0 meq/g [82]

Clinoptilolite [74, 7 5 ]

132
T A B L E XXI. RESEARCH REACTORS USING ION-EXCHANGE W A T E R T R E A T M E N T [20]

Nominal
Water treatment
power

MOATA Australia (Lucas Heights) 10 kW MB&10 |im filter

BR-2 Belgium (Mol) 50 MW Demineralizer

11SNR Belgium (Ghent) 150 kW MB

IRT-Sofia Bulgaria (Sofia) 2 MW Ion exchange

NRU Canada (Chalk River) 200 MW MB, filters

NRX Canada (Chalk River) 40 MW MB, filters

WWR-C-Prague CSSR (Rez) 2 MW

DR-1 Denmark (Risif) 500 MW

DR-1 Denmark (Risii) 5 MW

Aquilon France (Saclay) 1-100 W Ion exchange

EL-1 (ZOE) France (Fontenay-aux-Roses) 150 kW Ion exchange

FR-2 Federal Republic of Germany (Karlsruhe) 12 MW Ion exchange, filters

FRM Federal Republic of Germany (Munich) 1 MW

GRR Greece (Athens) 1 MW

WWR-C-Budapest Hungary (Budapest) 2 MW MB

APS ARA India (Trombay) 1 MW Ion exchange

ZERLINA India (Trombaу) 100 W Ion exchange, filter

IRR Israel (Rehovot) 5 MW

AVOGADRO. RSI Italy (Sáluggia) 2 MW

ISPRA-1 Italy (Ispra) 5 MW

UTRR Iran (Teheran) 1 MW

JRR-1 Japan (Tokai-Mura) 50 kW

HFR Netherlands (Petten) 20 MW Cation exchange, MB, i

HOR Netherlands (Delft) 100 kW

JEEP Norway (Kjeller) 450 kW Ion exchange, filters

NORA Norway (Kjeller) 100 W

PARR Pakistan (Rawalpindi) 5 MW

PRR-1 Philippines (Diliman) 1 MW

WWR-C-Warsaw Poland (Swierk) 2 MW

JEN Portugal (Lisbon) 1 MW

WWR-C-Bucharest Romania (Bucharest) 2 MW

SAFARI South Africa (Pelindaba) 20 MW Demineralizer, filters

R-O Sweden (Studsvik) 50 W

R-l Sweden (Stockholm) 600 kW MB

DIORIT Switzerland (Wiirenlingen) 20 MW MB, filters

SAPHIR Switzerland (Würenlingen) 1 MW

TRR-1 Thailand (Bangkok) 1 MW MB, filters

TR-1 Turkey (K. Cekmece) 1 MW

WWR-C-Cairo UAR (Inshas) 2 MW

MERLIN UK (Aldermaston) 5 MW MB, filters

DIDO UK (Harwell) 15 MW Ion exchange

OWR USA (Los Alamos) 5 MW MB, filters

HFIR USA (Oak Ridge) 100 MW Demineralizer, filters

ЮТ USSR (Moscow) 2 MW Ion exchange

WWR-M USSR (Leningrad) 10 MW Ion exchange, filter

Notes: MB = mixed bed ion exchanger; Demin. = demineralizer.

133
T A B L E XXII. ION-EXCHANGE T R E A T M E N T OF
P O W E R R E A C T O R W A T E R S [90, 9 1 ]

Gross heat
Name Location Water treatment
output (MW)

CANDU Canada (Douglas Point) 693 Filters a n d ion exchangers

NPD Canada (Des Joachims) 3 litres/s to one of two

m i x e d bed ion exchangers
KAHL/MAIN Federal Republic of Germany 60 Mixed bed demineralizers in
(Kahl/Main) by-pass lines

JPDR Japan ( T o k a i - M u r a ) 45 Purification by condensate

demineralizer and c l e a n - u p
demineralizer

R-3/ADAM Sweden (Stockholm) 65 4 k g / s through 3 mixed bed

exchangers

EBWR USA (Argonne) 100 Prefilters, afterfilters, a n i o n -

e x c h a n g e columns, mixed bed
units (one with borate ions)

DRESDEN USA (Grundy County, 111.) 626 Mixed bed ion exchangers

134
TABLE XXIII. ION E X C H A N G E IN W A S T E T R E A T M E N T A T N U C L E A R E N E R G Y E S T A B L I S H M E N T S [ 9 3 ]

Volume
Regen, Decon.
Waste Type reduction
Site Nation Type of waste T y p e of system or factor
nuclides exchanger factor
disposal (DF)
(VRF)

Argonne USA laboratory MFP Single column, cation Syn. org. R 30-10 .
Argonne USA Laboratory MFP One c a t i o n , one mixed bed Syn. org. R -

Hahn-Meitner Federal Republic of Germany Laboratory Cs

131 Single column, cation Nat. inorg. D 10 5 1600
Hahn-Meitner Federal Republic of Germany Laboratory MFP C a t i o n , anion & mixed bed column Syn. org. R - •

Harwell UK General MFP Lining of centrifuge Vermiculite D 10-20

Harwell UK General MFP Cols: C a t i o n - * A n i o n - » C a t i o n - A n i o n Syn. org. R 100-500

Idaho Falls USA Chemical 90 Sr and Four parallel columns of Nat. inorg. D 9 °Sr-200 800
processing 137 Cs 2 cols in series

JEN Spain General MFP Cation, anion columns Syn. org. R - -

Kjeller Norway General MFP C a t i o n , anion columns Syn. org. R 103 20-100

Lawrence USA General MFP Columns - vary Syn. org. D - -

Los Alamos USA General M Sr 2 cation cols in series Syn. org. R 30-60 10 s

Mol Belgium General MFP Cation, anion col Syn. org. R 2-10 -

Mol Belgium General MFP Lining of centrifuge Syn. org. D -

Moscow USSR General MFP S e r i a l c a t i o n , anion cols Syn. Org. R - • -

Pelindaba South Africa General MFP Mixed bed column Syn. org. D - • -

Pelindaba South Africa General MFP Mixed bed column Syn. org. - -

Fetten Netherlands General mC$ 2 cation cols R 100 -

Savannah River USA Evaporator 137 Cs , C a t i o n - e x c h a n g e column Syn. zeolites D 200 ( ot CJ) 4000
overheads
Savannah River USA Reactor tube MFP Mixed bed column Syn. org. R - -
Disassembly
basin
Takai-Mura Japan General MFP Membrane - * mixed bed column Syn. org. R 450 -

Notes: M F P = mixed fission products; Syn. org. = synthetic organic resins; Nat. inorg. - natural inorganic resins.
T A B L E XXIV. CLASSIFICATION O F NUCLIDES F O R
TRANSPORT PURPOSES

Nuclide Group Nuclide Group

144 ш 239
Ce and Рг IV Pu I

137 Z2
Cs IV fca I

131 j 106
Ш Ru III

90
M i x e d fission products II Si 11

32p 238ц
IV III

90y
IV

136
T A B L E XXV. AVERAGE PRICES OF COMMON ENGINEERING
MATERIALS, OCTOBER 1966, USA

Material C o s t / k g (US J )

Acrylic 1. 01
Aluminium 1.01
A l u m i n i u m alloys 0.62
Austinitic stainless 0.84 - 1.32
Butadiene - a c r y l i c rubber 1.01 - 1.50
Butadiene - styrene rubber 0.31 - 0.77
Butyl rubber 0.51 - 0.66
Carbon s t e e l 0. 084
CFE-fluorocarbon 1 5 . 40 - 1 8 . 70
Chromium 2 . 88
C o m m e r c i a l bronze 1.21
Epoxy, liquid resins 1.06
Epoxy, solid resins 1.17
F e r r i t i c stainless 0 . 68 - 0 . 9 0
Hastelloy F 7.43
Hastelloy X 7.43
High-density p o l y e t h y l e n e 0. 55
K e l F rubber 3 5 . 20
Lead 0 . 33
Low-density p o l y e t h y l e n e 0 . 35 - 0 . 4 8
Manganese bronze 1.28
M a r t e n s i t i c stainless 0 . 59 - 0 . 7 9
Natural rubber 0. 5 3 - 0 . 5 7
Neoprene rubber 0. 81 - 1 . 6 5
Nickel 1.69
Pig iron 0 . 066
Polypropylene 0 . 53
Polystyrene 0.32
Polysulphide rubber 1 . 3 2 - 2.75
Polyvinyl chloride 0 . 5 5 - 0.68
S i l i c o n e bronze 1.36
Silicone plastic 5.06 - 7.81
S i l i c o n e rubber 5.50 - 8.80
TFE-fluorocarbon 7 . 1 5 -11.00
Urethane rubber 2 . 5 3 -• 3 . 6 3
Vinyls 0.53 - 1.01
Viton rubber 22 •28.60
Zinc 0. 31

137
T A B L E XXVI. UNIT OPERATING COST:
WASTE TREATMENT B Y ION EXCHANGE

°\o of t i m e V o l . treated Operating cost

in use annually ( m 3 ) per m 3 (US S)

Savannah River 90 15140 0.79a

3 785 2.12

Harwell 100 8 597 4.61

15 600 7.93

JAERI 20 400 36.50

a Does not i n c l u d e d e p r e c i a t i o n .

138
T A B L E XXVII. ANNUAL O P E R A T I N G COSTS: W A S T E T R E A T M E N T B Y ION E X C H A N G E

Harwell Savannah R i v e r 3 JAERI

Columns Centrifuge Overheads Miscellaneous T o k a i -Mura

(US$) (uss) (US 8) (US 8 ) (US 8 )

C h e m i c a l s and 4368.00 146.00 7 000.00 10 0 0 0 . 0 0 830.00

supplies

Labour 16 6 1 0 . 0 0 420.00 500.00 800.00 1460.00

Maintenance 1588.00 1120.00 500.00 800.00 140.00

Overhead 10 2 9 6 . 0 0 260.00 2 000.00 2 000.00 560.00

Utilities 462.00 - - - -

Depreciation 6 294.00 - - - -

T o t a l costs 39 6 1 8 . 00 4760.00 11 000. o o b 14000.00 14600.00

V o l . treated 8 597 m3 600 m 3 15140 m3 3 785 m3 400 m 3

a S a m e e x c h a n g e columns for 2 m a i n uses,

k Does not include d e p r e c i a t i o n .
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[72] HELFFERICH, F . , Ion Exchange, McGraw-Hill Book C o . , New York (1962) 427.
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[83] LOP EZ-M ENCUERO, E., "Research and development work on the treatment of low- and medium-level
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[87] ROHDE, K . , Argonne National Laboratory, ANL-4820 (1952) 118.
[88] MATER. DES. ENGNG, Materials Selector Issue (1966).
[89] MAWSON, C . A . , personal communication, 15 Aug. 1966.
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[91] INTERNATIONAL ATOMIC ENERGY AGENCY. Operating Experience with Power Reactors 1. (1963).
[92] LEVI, H.W., personal communications, 16 Aug. 1966 and 30 Sept. 1966.
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Level Radioactive Wastes (Proc. Conf. Vienna, 1965) IAEA, Vienna (1966).
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IDO-14657 (1965).
[96] VANDEVOORDE, N., personal communication, 31 July 1966.
[97] VERKERK, В . , SMEETS, L., personal communication, Aug. 1966.
[98] GIRDLER, R . M . , personal communication, 26 Sept.1966.
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