IAEA-TECDOC-365

ION EXCHANGE TECHNOLOGY

IN THE
NUCLEAR FUEL CYCLE

A TECHNICAL DOCUMENT ISSUED BY THE

INTERNATIONAL ATOMIC ENERGY AGENCY, VIENNA, 1986
ION EXCHANGE TECHNOLOGY IN THE NUCLEAR FUEL CYCLE
IAEA, VIENNA, 1986
IAEA-TECDOC-365

Printed by the IAEA in Austria

February 1986
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 FOREWORD

Since the dawn of the nuclear energy development, the ion

exchange process has been used as a key technology for the production of
nuclear materials. Nuclear grade uranium and ultra-pure water required
in the nuclear industry have become technically available by use of ion
exchange technology. The application of ion exchange has recently been
expanded to various parts of the nuclear fuel cycle. Major applications
are:

- in uranium production facilities; concentration of uranium from leach

solution, refining of uranium, recovery of uranium from various sources,
etc.

- in nuclear power plants; chemical controls of coolant water, e.g.

controls of pH and boron concentration, condensate polishing, quality
control of water in spent fuel storage pools etc.

in spent fuel reprocessing and waste treatment; separation of uranium

and plutonium and their purificaton, separation of transplutonium,
removal of actinides and specific isotopes from radioactive wastes etc.

Furthermore, application to isotope separation has been under

development. Special enrichment technology applicable only for the
production of commercial-purpose uranium fuel has been intensively
studied by using ion exchange resins, and recently regarded as quite
promising. The enrichment of B, which is used as the neutron
absorption material, is another promising field of ion exchange
application.

The ion exchange process is well established for water treatment

and incorporated in most industrial plants using pure water. Efforts
have constantly continued to expand its application to various fields in
the separation and controlling of chemical substances. Numerous
technical papers have been reported on scientific and engineering aspects
of ion exchange. A number of scientific books on the general uses of ion
exchange have been published in different languages. Information on the
nuclear application of ion exchange has been dispersed among these
numerous publications. For the recent needs of the information of this
kind, this technical document was planned to describe state-of-the-art of
the ion exchange technology applied to the processes in the nuclear fuel
cycle. It is hoped that this document would be useful not only for the
specialists who are working in the field of ion exchange or nuclear
chemical engineering, but also those who are concerned with various
fields of the nuclear industry.

The Agency wishes to thank all the authors who contributed to

this document: Ms. S. Fisher (USA), Mr. F. X. McGarvey (USA), Mr. A.
Himsley (USA), Mr. J. D. Navratil (USA), Mr. I. Dobrevsky (Bulgaria),
Mr. B. Czeglédi (Hungary) and Messrs. Y. Fujii, M. Okamoto and
M. Kakihana (Japan). Special thanks are due to the ion exchange resin
manufacturers listed in Appendix 2 for providing their resin data.

The officer of the Agency responsible for editing and finalizing

the document was M. Ugajin of the Division of Nuclear Fuel Cycle. His
predecessor, Mr. Y. Fujii, one of the authors of this document, began
this task by organizing the initial series of Consultant Meetings.

EDITORIAL NOTE
In preparing this material for the press, staff of the International Atomic Energy Agency
have mounted and paginated the original manuscripts as submitted by the authors and given
some attention to the presentation.
The views expressed in the papers, the statements made and the general style adopted are
the responsibility of the named authors. The views do not necessarily reflect those of the govern-
ments of the Member States or organizations under whose auspices the manuscripts were produced.
The use in this book of particular designations of countries or territories does not imply any
Judgement by the publisher, the IAEA, as to the legal status of such countries or territories, of
their authorities and institutions or of the delimitation of their boundaries.
The mention of specific companies or of their products or brand names does not imply any
endorsement or recommendation on the part of the IAEA.
Authors are themselves responsible for obtaining the necessary permission to reproduce
copyright material from other sources.
 CONTENTS

Introduction .................................................................................................................... 7

Chapter 1
Ion exchange materials used in nuclear technology .............................................................. 9
S. Fisher, F.X. McGarvey

Chapter 2
Application of ion exchange to uranium recovery ............................................................ 53
A. Himsley

Chapter 3
Uranium production by ion-exchange methods ................................................................ 85
B. Czeglédi

Chapter 4
Ion-exchange systems and ion-exchange materials in nuclear power plants ........................ 131
I.D. Dobrevski

Chapter 5

Ion exchange technology in spent fuel reprocessing ............................................................ 177

J.D. Navra til

Chapter 6
Miscellaneous uses of ion exchange in the nuclear fuel cycle ............................................ 197
Y. Fufii, M. Okamoto, M. Kakihana

APPENDIX 1 .................................................................................................................... 223

Glossary
APPENDIX 2 .................................................................................................................... 231
Compilation of resin data
 INTRODUCTION

Ion exchange is the reversible exchange of ions between a solid

and a liquid in which there is no change in the structure of the ion
exchange material.

Ion exchange technology has been widely applied to numerous

processes used in the nuclear fuel cycle. Ion exchange has been used for:

1) Concentration and purification processes in uranium mills

and refining facilities.
2) Fuel fabricatiopn scrap recycle.
3) Spent fuel reprocessing operations.
4) Treatment of radioactive wastes.
5) Coolant purification and pH control and boron control in
reactors, and many others including stable isotope
separation.

Application and development of ion exchange technology has

constantly continued in the field. Furthermore, significant improvements
are being made of its use in the separation of materials and in various
process operations.

There have been a number of scientific publications on

fundamental aspects of ion exchange processes and the specific
applications of ion exchange in uranium production and other nuclear fuel
cycle steps, many of which are either too academic or too specialized for
general use. A general book on ion exchange processes applied to the
nuclear fuel cycle has not previously been published. It is hoped that
this technical document will fill that gap and assist a larger group of
people dealing with the nuclear fuel cycle to better understand the
processes. The expected users of this document include:

- experts on specific ion exchange processes in the nuclear

fuel cycle;
 - industrial engineers dealing with the general ion exchange
processes;

- ion exchange resin manufacturers;

- students of nuclear chemistry and chemical engineering;

- nuclear development and nuclear fuel facilities planners.

The technical document is designed to be a guidebook or source

book for ready reference containing the following scientific and
engineering topics:

- implemented ion exchange processes in the nuclear fuel cycle;

- recent developments in the field;

- general scientific descriptions on ion exchange resins and ion

exchange reactions;

- general engineering descriptions on ion exchange equipment;

- glossary of relevant technical terms;

- tables and specifications of ion exchange resins commercially

available;

- necessary descriptions of uranium chemistry.

The chapters cover each major nuclear fuel cycle step, e.g.
uranium milling, reactors and reprocessing. Analytical application of
ion exchange is also important for the producition of nuclear fuel.
Unfortunately there are many forms of analytical application and because
of its vastness this subject is not included in this publication.
 CHAPTER 1

ION EXCHANGE MATERIALS

USED IN NUCLEAR TECHNOLOGY

S. FISHER
Puricons, Inc.,
Berwyn, Pennsylvania
F.X. McGARVEY
Sybron Chemical, Inc.,
Birmingham, New Jersey
United States of America

Abstract

Ion exchange materials make a dual and vital contribution to nuclear

technology. From the beginning, ion exchange materials, both bead-form and
liquid, played major roles in the recovery of high purity uranium from complex
uranium-bearing deposits. Subsequently the development of nuclear power systems
expanded the need for ion exchange processes to purify and repurify water
for both steam generation and cooling and to provide a concentration process
for radioactive waste from aqueous systems. As a result, a broad spectrum
of resin types are now used in some aspect of nuclear technology. Indeed,
without ion exchange materials power generation via nuclear technology would
be impossible.

The majority of cation resins used in nuclear applications are sulfonated

styrene-divinyl benzene polymers generally called nuclear sulfonic acid
resins. However, méthylène sulfonic acid resins are used in the treatment
of some radioactive waste streams and carboxylic acid polymers based on
either crosslinked methacrylic or acrylic acid polymers are used in some
specialized applications in the nuclear industry.
 SULFONATED STYRENE-DIVINYLBENZENE POLYMERS

Sulfonated styrene-divinylbenzene copolymers used in the nuclear

industry are normally split into two broad catagories: gels and macroporous.
The distinction between the two is based on the structure of the copolymer
bead rather than the functionality. Both types of resins have as their
exchange functionality a sulfonic group substituted directly on a six-
membered unsaturated ring as an appendage to or a crosslink between two
linear saturated méthylène chains. This produces a three-dimensional network
of the following structure:

CM CM,

(r
—CM,—CH—CH,—Cil-Cil. CII -CM.—Oil—CIIr-OH—.

»MI WMl "S('V MM?

-OU--CII--OM, CI! CM--CM CM,-CH •-

—oit-CHj-cM -CM,— en— cir,—CH— cu,-

SOJl 8O,H SO.H

The differences in the two polymer types arise from the solutions
of monomers assembled for the bead making process. Gel structures are
usually produced following the teaching of d'Alelio (1,2) wherein a mixture
containing only styrène, divinylbenzene and a catalyst is suspended as
droplets in a medium in which it is not soluble and heated to form solid
copolymer beads.
Macroporous beads are formed when a component that does not enter
into the polymerization 1s added to the styrène and divinylbenzene prior
to the formation of the suspension of droplets. Usually a third component
is chosen that is miscible with the monomers but not a solvent or swelling
agent for the polymer. This process forms a finished bead, aptly described
by Corte and Meyer (3) as 'sponge-like', consisting of highly crossl inked

10
microgel polymer containing large macropores filled with the non-polymerizable
third component. This component is sometimes described as having been
squeezed out of the polymer as it formed but in actuality the polymer precipitates
from it.
Patents have been issued covering a number of variations of the macroporous
process. Those of Millar (4), Werotte and Grammont (5), Mindick and Svarz
(6) and Meitzner and Oline (7) represent a sampling using a variety of
starting combinations. By varying the third component, its ratio to the
polymerizing monomers and their ratio to each other almost an infinite
range of physical properties in the sulfonated polymer is possible. However,
the basic chemical structure is the same as that of the gel polymers. Further,
the polymer itself is a gel with the same characteristics as a bead prepared
at an equivalent degree of crosslinking. It differs from the so-called gel
bead primarily because the solution being treated permeates" the macropores so
that the ratio of surface to polymer is substantially larger.

GEL SULFONIC ACID RESINS

Nuclear sulfonic acid gel resins that are fully sulfonated differ from
each other in their degree of crosslinking. This is primarily a function
of the ratio of divinylbenzene to other monomers, such as styrène and ethyl-
vinylbenzene, in the original monomer mixture. Other factors such as the
amount of catalyst used, rate of polymerization,the thermal pattern during
the polymerization, all modify the properties of the final polymer slightly.
The type of sulfonating agent and the sulfonation temperature also have
some effect. But these changes usually produce differences smaller than
those encountered in routine replication of a given monomer ratio in commençai
production of these resins.
For the user, the water retention capacity of the finished polymer
in a known ionic form is the most convenient parameter for estimating the
crosslinking of a gel sulfonic acid resin. Standard methodology for measuring
this parameter has been developed in the United States in the ASTM system (8).

11
This methodology produces numbers which correlate so well with those published
by manufacturers in other countries for materials described as having the
same degree of crosslinking, that one must conclude similar methodology
is universally used.
Although polymers prepared under research conditions will show a
slightly higher capacity at low degrees of crosslinking, commercial polymers
used in the nuclear industry all have a dry weight capacity in the hydrogen
form very close to 5.0 milliequivalents per dry gram. All of their other
properties: volume capacity, hydrated bead density, selectivity, stability,
are functions of the degree of crosslinking in the polymer.

Variation of Properties with Crosslinkage

Many, many workers have published articles relating the properties of sulfonated
styrene-divinyl benzene polymers with the divinyl benzene content. In some cases
major differences exist between the values reported. These differences often
reflect the fact that one or both investigators were working with commercial
polymers and, hence, did not really know what the true divinylbenzene contents
of their materials were. In other instances the polymers used were not fully
sulfonated or may have been decrosslinked in the sulfonation process. Even more
often the difficulties of producing a pure ionic form were not clearly understood
and, hence, measurements were made on polymers only partially in the intended
ionic form. These uncertainties are compounded by the fact that the methods
of producing and analyzing divinylbenzene have improved markedly in the last
forty years. A true 10% divinylbenzene copolymer prepared today contains a different
spectrum of monomers than one produced in the middle 1940's.
However, the correlation of resin properties with crosslinkage in the sulfonic
system is a very useful approach to predicting their performance. More reliable,
perhaps, than using their nominal divinylbenzene content, which is difficult
to measure in the final product, is the use of the water retention capacity in
a known form. This parameter can be easily and reproducibly measured (8).

12
 The correlation of selected properties with nominal divinylbenzene content
and water retention is given in Table 1. Volume capacities assume that an equivalent
bead size distribution has been produced at each level of crosslinkage. It will
be noted that the implied precision of the numbers given is much less than those
normally seen in the literature. The variation in normal commercial production
of a polymer at any given nominal divinylbenzene content will produce a ±5% variation
in the values selected.

Table 1
Effect of Crosslinkage on the Properties of
Sulfonated Styrene-Divinylbenzene Copolymers
in the Hydrogen Form (a)
Nominal % % ^0 Volume Capacity(b) Hydrated Bead
Divinylbenzene Retained(b) meq/ml Density'0)
2 80 0.7 1.09
4 68 1.1 1.13
6 57 1.6 1.16
8 53 1.8 1.19
10 47 2.0 1.22
12 44 2.1 1.24
16 39 2.3 1.28

(a) A composite of data by Reichenberg, Pepper, McCauley and Hale

(9, 10); Glueckauf (11) and data from commercial materials accumulated
by the author
(b) ASTM Method D2187 (8)
(c) Method of Kunin and Fisher (12)

This variation is illustrated by the data in Table 2. Here data from polymers
of the two most commonly encountered crosslinkages from United States suppliers
have been tabulated. These data are not production control data but the results
of analyses of lots shipped to plant sites. The data were collected over a three
year period and represent a minimum of 10 shipments from each source. As may
be seen, not only are resins claiming the same nominal percentage divinylbenzene
different when procured from different sources but the variation from a single
source may in some cases be even greater. The nominal DVB content is based
on calculated charge values so that part of the difference is due to the precision
of material measurement.

13
 Table 2
Comparison of the Properties of New Sulfonic Cation Resins
from Different Producers (13)
8% Gel Type ____10% Gel Type_____
Source A B F G H
Water Retention, % U)
Sodium Form
High 48.90 48.40 40.60 45.58 40.76
Low 45.77 44.83 39.44 40.72 39.86
Average 47.13 46.99 40.41 42.40 40.33

Hydrogen Form
High 56.73 56.32 48.45 51.82 46.95
Low 52.69 52.58 46.15 48.07 46.03
Average 54.30 53.80 47.32 49.49 46.73
Exchange Capcity, H-form (a)
meq/g dry
High 5.10 5.11 5.16 5.10 4.95
Low 5.04 4.87 5.04 4.79 4.77
meq/ml
High 1.88 1.87 2.12 2.06 2.09
Low 1.70 1.55 2.01 1.75 1.97
Average 1.81 1.72 2.08 1.91 2.00

(a) ASTM Method D2187 (8)

All of the properties in Table 1 are also a function of ionic form. The
dependence of just one of them, water retention capacity, is shown in the data
in Table 3. That the measured water retention capacity changes dramatically
when one ion is substituted for another emphasizes the necessity for knowing
the ionic form wher. polymer properties are measured.

Other properties are similarly dependent on ionic form. Bead density,

for example, increases as water retention decreases. The exchange capacity per
gram decreases as heavier ions are substituted into the polymer.
If the water content is calculated in a more fundamental manner as millimoles
of water per milliequivalent of capacity, the water content of ionic forms from
potassium down becomes a constant for a given crosslinkage. The higher values
for the lighter elements indicate that the polymer matrix swells when converted,
say, from the potassium to the hydrogen form. This swelling results in a decrease
in the volume capacity during the transition.

14
 Table 3
Effect of Ionic Form on the Water Retention Capacity
of Sulfonic Cation Exchange Resins

Exchange Capacity
meq/g dry % Water Retained^) Mi'11 impies HpO/Mi 11 l'équivalent
Nominal % DVB 4 8 16 4 8 16
Ionic Form
Lithium 4.85 67.0 50.7 38.8 23. 2 11.8 7.2
Hydrogen 5.00 68. 3 50.0 40. 5 23.9 11.1 7.6
Sodium 4. 50 62.8 45.2 33. 7 20.8 10.2 6.2
Ammonium 4. 60 52. 4 44.1 32. 7 20.0 9.5 6.1
Potassium 4. 20 58. 9 40.6 31. 7 18. 9 9.0 6.1
Rubidium 3. 50 54.6 35.9 27. 2 18.9 8.8 5.8
Cesium 3. 00 50. 7 32.4 23. 5 18. 9 8.8 5.7

(a) Calculated from data of Bonner (14). % HgO Retained = g H?0

g hydrated polymer

Selectivity as a Function of Crosslinkage

Many elegant papers have been published on the measurement of selectivity
coefficents of sulfonated styrene-divinyl benzene polymers. Taken as a whole,
the magnitude of the numbers reported have little or no value in the designing
of a water treatment plant. When used as computer feed, as they now frequently
are, they sometimes generate operational fantasies which cannot be converted
into operational reality. However these values are useful in cases where no
column data are available.
Most of the problem arises in trying to take data derived in serene equilibrium
conditions in the laboratory with two ionic species and convert it to the tumultuous
multi-component, multi-variable, high flowrate atmosphere in a nuclear water
treatment plant. There the concentration relationships in both phases are constantly
shifting. That is not to say, however, that selectivity data is not of value
in orienting one's choice of parameters for a nuclear system particularly with
regard to selection of the resin phase.

15
 The choice between materials of different selectivities in a specific exchange
reaction depends first upon what the process to be operated is. In a primary
loop where the resin is to be used once, a resin with high selectivity for the
ions to be removed, other properties being satisfactory, is a clear choice.
In once used systems the frequently quoted data of Bonner, et. al. sumrrarized
in Table 4, is still used. Here removal of radioactive nucleides is the primary
job of the ion exchange system. Rubidium and cesium are the ions most likely
to be found on the cation sites. Bonner's data have been partially recalculated
here to permit comparison of hydrogen and ammonium forms with the original lithium
form presentation since all three forms are used in this service. On the basis
of selectivity alone, the lithium form is to be prefered over the other two forms.
If diffusion problems are ignored, these data also suggest an advantage in using
as high a crosslinked resin as possible.

Table 4
Monovalent Selectivity Data of Sulfonated
Styrene-Divinyl Benzene Cation Exchange Resins (15)

Compared to H* Compared to NHa* Compared to Li+

% DVB 4 8 16 4 8 16 4 8 16
Cation
Li* 0.77 0.79 0.69 0.57 0.45 0.33 1.00 1.00 1.00
H+ + 1.00 1.00 1.00 0.74 0.57 0.47 1.30 1.26 1.45
Na 1.15 1.49 1.54 0.85 0.85 0.73 1.49 1.88 2.23
NH4+ 1.35 1.76 2.11 1.00 1.00 1.00 1.75 2.22 3.07
K+ 1.60 2.08 2.86 1.19 1.18 1.35 2.09 2.63 4.15
Rb+ 1.71 2.29 2.89 • 1.21 1.30 1.36 2.22 2.89 4.19
Cs+ 1.82 2.30 2.86 1.35 1.31 1.35 2.37 2.91 4.15

The continued use of these data after so many years reflects not so much
confidence in their numerical correctness but rather the fact that they properly
depict the trends seen in operating plants both with regard to ions and cross!inkage.
They also predict some vital differences between the performance of condensate
polishing systems in the hydrogen and ammonium forms. These systems are normally
operated as regenerable, multicycle beds where the selectivity is a double-edged
sword. Since high selectivity may also cause difficulty in regeneration, the
reverse reaction must also be considered if the beds are to be regenerated.

16
 In these systems, the ability of polishing beds to remove any sodium that
might enter the system as a result of condenser leakage is of primary importance.
These data leave no question that this removal is more favorable if cation resin
in the hydrogen form is present in the system. This is particularly true if
medium to high crosslinked cation resin is used. However, it also predicts
that if the cation resin is decrosslinked in service its ability to remove sodium
diminishes. Such decrosslinking does occur in condensate systems where oxygen
removal is not complete and is frequently encountered in makeup démineraiizer
systems due to the presence of chlorine or other oxidants in the raw water supply.
Measurements of divalent-monovalent exchange using the same techniques
were reported by Bonner at a later date (16). These values, calculated with
lithium as a reference, are shown in Table 5. Of major interest are the relative
differences between magnesium and calcium and the marked increase in calcium
selectivity with increasing crosslinkage. Both of these are important considerations
in designing make-up demineralizer systems. However, application of these data
to engineering design is not an easy task as was shown by Frisch and McGarvey
(17).

Table 5
Divalent Selectivity of Sulfonated
Styrene-Dinvinylbenzene Copolymers
as a Function of Crosslinkage (16)

Ion Selectivity Relative to Li+= 1.00

4% DVB 8% DVB 16% DVB
2.36 2.45 3.34
2.95 3.29 3.51
3.13 3.47 3.78
Co++ 3.23 3.74 3.81
Cu++ 3.29 3.85 4.46
3.37 3.88 4.95
3.45 3.93 4.06
4.15 5.16 7.27
4.70 6.51 10.1
7.47 11.5 20.8

17
 The major emphasis on the selectivity for divalent ions in the makeup water
system is not the removal of these ions from solution but the problems of restoring
the resin phase back to the hydrogen form for another cycle. A wealth of data
on monovalent-divalent equilibria does exist in the technical literature published
by resin manufacturers in many countries. An example of this, recalculated into
terms more readily understood internationally, is the lonac Chemical Company data
in Figure 1. These data compare an Q% and a 10% nominal divinyl benzene polymer
for operating capacity in the hydrogen cycle on the same influent water when
various amounts of acids are used in the regeneration cycle. The water used
here contained 6milliequivalents per liter total ions. Half of the cation equivalency
was due to sodium and the remainder to calcium and magnesium in a ratio of two

1.2

1.1

1.0

/ HC/

0.9
u

0.8

0.7

0.6 ^ 8% DVB
D 10% DVB
0.5

1.00 1.80 2.60 3.4

Equivalents Acid per Liter Resin

Figure 1. Effect of Cross-linkage on Resin Performance (18, 19. 20)

18
calcium to one magnesium. On the anion side, since the anion population does
influence uptake of cations, half of the equivalency was carbonate and the remainder
chloride and sulfate in a ratio of two equivalents of chloride to one of sulfate.
Operating conditions so far as flow rate and temperature were the same at all
regeneration levels.
The data in Figure 1 show that when both the forward and reverse reactions
are taken into account the differences in selectivity due to crosslinking are
so small that for practical purposes the data from the two polymers can be represented
by a single line. The marked difference between the regeneration with hydrochloric
acid and sulfuric acid is well known. It accounts for at least part of the differences
in performance between the démineraiizing systems in the United States where
sulfuric acid is widely used and those in Europe where hydrochloric acid is the
standard régénérant.
However, the difference in the selectivity between calcium and magnesium
does influence the performance of the system. Here again, the technical literature
published by the manufacturers contains very useful information. One interesting

0.9

0.8

0.7

0.6

0.5

20 40 60 80
Percent Na In Water

Figure 2. Variation of Operating Capacity of a Nominal 8% Divinyl benzene

Sulfonic Acid Resin with the Ratio of Influent Ions (18)
Regenerated with 1.5 equivalents H2SO^/Liter Resin

19
mode of presentation of such data is illustrated in Figure 2. This is one of
a family of curves developed to define performance in the three component system
of sodium-calcium-magnesium. Unlike the data in Figure 1, it represents the
performance of a single polymer, in this case a nominal 8% divinyl benzene sulfonic
resin, at a single acid regeneration level. The variable here is the ratio of
cations in the influent water.
Figure 2 shows the marked affect of changing the ratio of calcium to magnesium
in waters containing only divalent ions. All other parameters are held constant.
On the other hand, if calcium-sodium or magnesium-sodium waters are deionized
the presence of the monovalent ion exerts no influence until it is present at
approximately a two-to-one equivalency ratio. And even there, in the case of
sodium-magnesium the effect on the operating capacity of the system is small.
Curves like those in Figure 2, when supplemented by data on the effect of
the total equivalents in the influent water, the effect of the accompanying anions,
the flowrate, the concentration of régénérant and temperature serve as Programming
data for computers. These programs, when given supplied with appropriate leakage
limits, permit the performance of a given system for a specific water supply
to be forecast. Thus it may be seen that overall performance depends on many
variables some of which assume more importance than the selectivity of the resin
for ions being exchanged.

Kinetics as a Function of the Cross!inkage

Data such as that presented in Figures 1 and 2 reflect the kinetics of

the ion exchange process as well as the selectivity of the resin itself. It
is generally believed that the cation resin reaction in sulfonic acid resins
is extremely rapid once the ion to be exchanged reaches the exchange site. Indeed,
it is very difficult to set up experiments to measure the exchange rate alone.
Many elegant theoretical papers have been published developing the equations
for the overall ion exchange reaction including the diffusion of ions in and
out of the particles. Experimentally, much of the work on the kinetics of
the cation reaction dates back to the studies done in the 1940's and early 1950's

20
in connection with the development of the separation of the lanthanides. Although
much of this work was done with sulfonic resins no longer commercially available
the simple conclusions drawn are applicable to present day resins.
For example, the observation by Boyd, et al_ (21) that "the magnitude of
the internal diffusion constants are from five to ten-fold smaller than the
diffusion constants for the same ions in solution" has stood the test of time.
This paper also contains data confirming the inverse relationship between the
square of the particle radii and the fraction of sites used per unit contact
time.
Another interesting and instructive set of data, this time on modern resins,
is that of Soldano (22) shown in Figure 3. These data, for example, measure
the exchange of sodium in solution with sodium in the resin by the use of radioactive
sodium in one of the starting phases. Not only is the effect of selectivity
for practical purposes eliminated but the fact that the exchange reaction is
dynamic is clearly demonstrated. There are, to be sure, exchange reactions
where the selectivity of the anionic group of the resin is so great that once
the cation approaches it the probability of it moving away spontaneously is
very small. The behavior of barium in a sulfonic resin is a classic example

10-*-

ijio-'
S
o

I
o
to-«
«J
o
o

l IQ-»
'•o
«J
1/1
.0"

5 10 15 20
Degree of crosslinking, percent OVB

Figure 3. The Self-Diffusion Coefficients of Sulfonated Styrene-Divinyl benzene

Polymers as a Function of Cross!inkage and Temperature as Determined

by Soldano (22)

21
of such behavior. But a given sodium ion may be visualized as moving from site-to-site,
sometimes deeper into the bead and sometimes back into the free liquid to attach
itself eventually on a neighboring bead.
These data have added value in that they show that diffusion is faster
as the temperature rises. That is not a startling finding but it must be remembered
that it refers to movement both in and out of the bead. If, as many believe,
exchange in a high flow rate polisher takes place primarily at the readily available
surface sites, the dynamic nature of exchange reaction indicates that there
will be an increased tendency for the sodium, for example, to return to solution
if the temperature is raised. Although the existance of a sodium shell in these
sulfonic systems has never been demonstrated experimentally, corresponding data
with the much slower carboxylic resins has been obtained by Schmuckler (23)
to show that an exchange gradient from surface to core is reality.
While there are many ion exchange systems where the cation kinetics are
limiting, in nuclear systems cation kinetics are most important in the condensate
polishing operations where ammonium is used for pH control. This is particularly
true if the system is monitored by sodium leakage. In these high flow rate systems,
reaching in the United States as high as 50 gallons/minute/ft2 (2 meters/min) of bed
surface, the residence time of an increment of water in a bed can be as little
as 20 seconds. The fact that when these beds are run to a conductivity endpoint all
of the available hydrogen capacity is seldom utilized suggests kinetic limitations
as well as selectivity problems. When run to a sodium breakthrough 7-10% bed
loading with sodium is normal. Sodium exchanged at the surface certainly has
a higher probability of returning to solution than diffusing into the still
available groups. Certainly this low degree of bed utilization is accentuated
by the large size of the beads popularly used in these applications.

Stability Toward Radiation

A discussion of radiation stability is probably considered a standard

portion of the properties of resins for the nuclear industry. However, only
in situations where resin is reused such as in the separation, concentration,

22
and recovery of radioactive isotopes or in cases where the resin is to be used
for the long term storage of radioactive wastes is the matter of the radiation
stability of a sulfonic acid resin of primary importance in resin selection.
However, the effect of radiation is an intriguing thing to study and many
workers in many countries have done so. A comprehensive review of the work
done prior to 1977 is available in the report by Gangwer, ert al_ (24). This
report clearly illustrates the problems inherent in evaluating data from publications
where the resins are identified only by trade names.
Despite the conclusions of Gangwer that "the fundamental processes involved
in radiation damage to ion exchange materials are not understood", the practical
results in gel sulfonic resins are well established. Exposure of sulfonic acid
cation to radiation can result in three different types of attack on the polymer
structure. It is likely that all of these mechanisms occur to some degree simultan-
eously. Hence no significance should be attached to the order in which they
are discussed here.
Loss of Exchange Capacity. Since these are functional polymers, the first
change that one tends to think of is the possibility of the loss of functional
groups. Such a loss does occur at high dosage levels as is shown by the data
assembled by Simon (25) in Figure 4. These data indicate that once the critical
dosage level is reached, neither the degree of crosslinking nor the ionic form
of polymer make significant differences in the rate of capacity loss. However,
inspection of some of the data from which Figure 5 is drawn (29) does show that
fully hydrated polymers are slightly more suspectable to loss of capacity than
those that have been dried.
Formation of Gases. A second possible result of exposure of sulfonic
acid ion exchange resins to radiation involves the formation of gaseous materials.
The most commonly measured gases from the sulfonic resin have been sulfur dioxide,
carbon dioxide, carbon monoxide and hydrogen. The work of Mohorcic and Kramer
(34) provides insight into the relative amounts of these gases formed from the
lithium and hydrogen forms of the sulfonic acid resin in different degrees of
hydration. These forms are the most commonly used in primary loop water purification.

23
 100 i i

90 + + + +

-o 80- -f 4- 4- 4- -f 4- 4-
O)
c

7CU + 4 - 4 - 4 - 4 - 4 -
o:
>>
o
to
60 4- + -f 4- -f 4- -f
Q.
ni
«J
50
4 5 6 7 8 10 11
Accumulated Dosage, Rads

Figure 4 - Capacity Loss as a Function of Radiation Dosage for Styrene-Divinylbenzene

Sulfonic Resins. Data from references 26 to 33 integrated by Simon (25)

o =2% DVB, Na+ form

• =6% DVB, Na+ form
• =8% DVB, Na+ form
A =8% DVB, H+ form

2.5
• H'lwm(DRY)
'V Li* lorn (DRY)
CM • Li* form (SWOLLEN)
O
1.875-
It-
CD

1.25

O)
"0 0.625

0-5 1.0 1.5 2.0

Integrated Dosage, Rads

Figure 5 -Sulfur Dioxide Formation as a Function of Radiation Dosage

(34) 10% DVB Sulfonic Resin

24
These results obtained, redrawn by Gangwer (24), are shown in.Figures
5 through 8.
It will be noted first that the evolution of gas in measurable quantities
begins at the same cumulative dosage as the loss of exchange capacity shown
in Figure 4. Although sulfur dioxide was measured in the highest yield (Figure
5), its rate of formation is approximately one-tenth of the rate of capacity
loss suggesting that the majority of the sulfur lost from the polymer is not
liberated as a gas. Indeed, it should be noted that liberation of sulfur dioxide
from dry resin greatly exceeds that from swollen resin and that the hydrogen
form in this case is more liable to attack than the salt form.
Formation of hydrogen (Figure 6) could indicate the formation of unsaturation
in the polymer chains. However, the fact that resins in water are a source
of markedly larger amounts of hydrogen than dry or moist resins suggests a mechanism
involving the water molecule. This may not involve the formation of unsatuation

10.0

O)

CT • H* FORM. DRY
CM • LI* FORM, DRY
• H* FORM. SWOLLEN
5.C. V LI* FORM, SWOLLEN
• H* FORM. UNOER WATER
CM (nolt unll»)
I
O « LI* FORM. UNDERWATER

* 2.5
i

0.5 1.0 1.5

Integrated Dosage, Rads

Figure 6 - Hydrogen Formation as a Function of Radiation Dosage (34)

10% DVB Sulfonic Resin
H+ form under water = Millimoles x 10"*

25
but rather an oxidative reaction. Such reactions usually involve the carbon
on the polymer chain alpha to the benzene ring. If a peroxide is involved,
as is likely here, a hydroxyl group is added to the chain and hydrogen liberated.
This is usually the first step in reactions which break the polymer chain. It
should be noted that the hydrogen form of the resin is more susceptible to this
type of attack than the lithium form. This follows the same pattern as susceptibility
to damage by chemical oxidants.
At a given dosage rate, the amount of carbon dioxide liberated is approximately
a hundreth of the amount of sulfur dioxide as may be seen in Figure 7. Again
water obviously is a partner in the process with the dry resins being substantially

• H* FORM,onr
• Li* FOAM. DAY
• Vf FORM. SWOLLEN
<D A LI* FOAM, SWOLLEN
• H* FORM. ÜN06R WATER (»<*• unlit)
• LI FORM. UNOCR WATER
CO
O 18.0
n
i
o
13.5

0.5 i.o 1.5

Integral Dose, 108 Rads

Figure 7 - Carbon Dioxide Formation as a Function of Radiation Dosage (34)

10% DVB Sulfonic Resin; Broken line Millimoles x 10'2

lower in gas formation than the wet which are in turn lower than those evaluated
in water. Again the relative instability of the hydrogen form compared with
the lithium form is shown. Carbon monoxide is formed at about half the rate
of carbon dioxide (Figure 8).

26
 H* FOHM. DRY
LI* FORM. DRY
H* FORM, SWOLLEN
7.C-
LI* FORM. SWOLLEN

tu
en
5.E-
O

0.5 1.0 1.5

Integral Dose, Rads

Figure 8 - Carbon Monoxide Formation as a Function of Radiation Dosage (34)

10% DVB Sulfonic Resin

Decrosslinking. When the resin is attacked by radiation at high dosage

levels, the polymer chains are broken and it effectively assumes the characteristics
of lower crosslinked polymers. This change is shown in Table 6. Regrettably
these data are for the sodium form of the resin since it was not appreciated
at the time they were obtained that the hydrogen form would be much more liable
to this mode of attack. However, they do show that the presence of water is
a factor in chain breakage and it is generally believed that the mechanism involves
formation of peroxides in the water. (35)
While decrosslinking of this sort is not a factor in nuclear water treatment
plants, it is of importance if the resins from such units are to be stored with
the nuclides on them. The decrosslinking reaction may eventually proceed to
a point where sufficient bonds have been broken so that the beads become water
dispersable. Decrosslinking is also a factor to be considered when solutions
of highly radioactive species are being processed on a cation exchange resin.

27
 Table 6

Effect of Radiation on the Water Retention

Capacity of Styrene-Divinyl benzene
Sulfonic Acid Resins (29)
All Sodium Form
Percent Water Retained
Nominal % DVB
State During Exposure Dry Wet Dry Wet
Total Dosage (Rads)(a)
None 65.8 65.8 43.9 43.9
106 65.3 76.0 44.6 44.6
10? 69.5 76.4 44.9 45.3
108 74.7 80.5 48.8 52.2

(a) Conversion to rads approximate

Table 7
Isotope Loading on Typical Spent Mixed Bed
From a BWR Plant (36)

Nuclide Specific Activity g xlO-9 Nuclide meq Nuclide

g dry resin(a) Ci/g nuclide g dry resin g dry resin
54
Mn 0.87 7.98xl03 0.11 4xlO-6

60Co 7.3 1.13xl03 8.2 2.6x10-4

65Zn 6.3 8.20xl03 0.77 2.3xlO-4

134Cs 2.4 1.30xl03 1.8 1.3x10-4

137fr 7.3 87 84 0.61x10-3

Bonding of these materials in a discrete zone on the resin column can subject
a small portion of the resin to high radiation dosages. Such decrosslinking
has been a contributing factor to at least one accident involving reprocessing
on a sulfonic acid exchange cation resin.
That radiation stability plays such a small role in the choice of resin
in the nuclear water systems reflects the fact that all experimental data shows
that radiation damage is a function of the cumulative dose of radiation encountered

28
by the resin. Even when the resins are used in the primary loop in a BWR plant
the amount of radioactive species accumulated by the resin before leakage reaches
the point where its removal from service is mandated is small. This is shown
in the data in Table 7 which is typical for spent once-use resin in such an
application.
The exhaustion data for radioactive systems is usually given in terms
of the radioactivity of the isotopes on the resin. In Table 7 these data have
been translated into milliequivalents of the various entities since these numbers
will be more meaningful to those whose primary experience is in resin technology.
As may readily be seen, the extent of cationic exhaustion so far as radioactive
species is concerned, is very small indeed. This particular set of data does
not include radiation from potentially anionic Carbon 14 which has been reported
present in other systems. In actuality, rubidium and cesium are probably the
principal radioactive isotopes that are exchanged with the cation resin
since most divalent metal activity appears to be associated with the crud filtered
out by the resin bed.

Chemical Stability as a Function of Crosslinkage

In the beginning, people believed that sulfonated styrene-divinyl benzene
cation exchange resins were so stable that their operating life could be measured
in decades. Situations do exist where this dream has become a reality. However,
it is now well recognized that oxidizing agents augmented by high temperatures
do rupture the polymer chain. The result, no matter what the specific oxidant,
is generally termed decrosslinking because the resins so attacked assume all
of the characteristics of polymers made at lower nominal divinylbenzene contents.
It should be noted that the observable result, an increase in water retention
capacity, is the same whether the chain breaks between two former styrène monomers
or between a former styrène and a former divinylbenzene.
The rate of decrosslinking by any oxidant is dependent upon its concentration
and the ionic form of the polymer. The hydrogen form of a sulfonic acid polymer
is markedly more susceptible to decrosslinking than any of the salt forms. Since
this is the form most commonly used in large scale installations both in nuclear

29
and in fossil plants, it is the form that has been studied most extensively
in recent years although early results were all sodium form (37).
The damage in terms of chains ruptured per unit oxidizing agent has never
been established experimentally. Many papers have been written showing the
qualitative effect of a specific amount of oxldant on resins of various degrees
of cross!inkage. Typical data for uncatalyzed peroxide attack at two temperatures,
are presented in Figures 9 and 10. These data, which were all obtained at the
same ratios of dry resin to peroxide using the hydrogen form of the resin, are
of interest not only because they compare the increase in hydration as a function
of crosslinkage but more so for the dramatic temperature effect. Degradation
that requires 20 days at 25°C is matched in less than 2 hours at 45°C under
otherwise similar conditions.

20 40 60 80 100
Time, Days

Figure 9 - Comparative Degradation of Sulfonic Acid Polymers in 3% Hydrogen

Peroxide (38). Temperature = 25°C

30
 10

Figure 10 - Comparative Degradation of Sulfonic Acid Polymers in 3% Hydrogen

Peroxide (38). Temperature = 45°C

These data do not take into account the catalytic effect on the rate of
decrosslinking by such metals as iron, copper and manganese. The effect of
iron precipitated in the polymer is shown by the data of Downing and Kunin (38)
which is presented in Figure 11. This catalytic effect is important not only
in makeup demineralizers but in condensate polishers as well.
Results such as those shown in Figures 9 to 11 have generated a belief that
high cross!inked sulfonic resins are less suspectable to attack by oxidants than
low cross!inked. This thinking is actually in error. The number of chain bonds
broken by a given amount of oxidant in any sulfonated styrene-divinyl benzene polymer
is probably statistically identical. However, the effect of breaking a specific
number of bonds in a given weight of polymer is greater in a polymer with less

31
 50

40
50 100 150 200
ppm Fe in Resin Phase

Figure 11 - Effect of Iron on the Rate of Decrosslinking of Sulfonic Acid Resins

in Hydrogen Peroxide. Data of Downing and Kunin (39). Recalculated
and Redrawn.

divinyl benzene since it represents the rupture of a larger percentage of the cells
present. Further, the method of following this breakage involves monitoring either
the increase in swelling or in water retention, both of which increase logarithmically
as the mole percent effective crosslinkage decreases.
Indeed, the effective life of a resin that starts with a high percentage
of cross!inking is longer in a given set of oxidizing conditions than one that
has fewer bonds initially. This is shown clearly in the data of Downing and Kunin
(38). Resin life is an important consideration in both makeup demineralizers,
which sometimes are subjected to severe oxidative conditions, and in condensate
polishers where the operating temperature is higher.
Resin life is often estimated in terms relative to that of the 8% nominal
divinyl benzene polymer. To make this estimate it is assumed that the resin in
a typical condensate polisher is a candidate for replacement when the water retention
of the hydrogen form has reached 56%. Beyond that point changes in the bead density
may effect the separability of cation from the anion resin.
In makeup demineralizers the value for replacement is usually 60% water
retention in the hydrogen form. Data based on this assumption is shown in Figure 12,

32
 Life Relative to Life of an 8 Mole Percent DVB Polymer

Figure 12 - Approximate Resin Life in Makeup Demineralizer Compared with

8 Mole Percent DVB Calculated from Data in Figures 9 and 10 (38) and
Assumptions in Text.

k l 1

25

20

o 15 *
o
^

O10
•®
O)
E
5 # _

c-
I

5D 60 70 80 90
°' /O 'H
'oO v
f.

Figure 13 - Sloughage of Organic Carbon from the Hydrogen F.orm

of Decrosslinked Sulfonic Cation Resins (39)

33
This value is chosen there because the decrosslinking process is accompanied by
an increased sloughage of organic material from the cation resin (40). This sloughage
is a serious foulant for the strong base anion resin in these systems. It increases
rapidly at hydrogen form water retention capacities greater than 60% as shown
in Figure 13.

Physical Stability on Sulfonic Cation Exchange Resins

Concern for the physical stability of the cation resins in nuclear water
treatment systems arose with the development of continuous deionization processes
in the late 1950's. Bead breakage in these systems was usually attributed -to
mechanical shock. Tests such as rolling the resin with steel balls in a ball
mill jar were advocated (12) to simulate it.
As condensate polishing systems developed, it has been generally believed
that the bead breakage occurring in the cation resin is a combination of mechanical
and osmotic shock. Early testing for osmotic damage involved cycling with relatively
high concentrations of acid and base as described by Kunin, ^ al_ (41). The
recognization that the bead breakage was a function of the swelling between
forms prompted the development of a simple test where swelling was caused by
drying followed by rapid rehydration (37,38). Data obtained by the latter methods
are reproduced in Figure 14. The intent is not to show the differences in stability
between the three types of resin since gel resins of far better stability are
IWW
0.
' 'r
I6/ÎO

FIGURES DENOTE
to - x
/ V U.S. SIEVE SIZE.

o to
< t 3/ to

4O .
\
/
^ 2 )/ 0

a
<

20 - \ ^ 30/40
/
^ JO/40

/
t\
'/ ^
Ü
/ rvl iy?o

10% 8% Macroporous
Gel Gel

Figure 14 - Relative Physical Stability of Sulfonic Acid Cation Beads

of Various Types and Sizes (37)

34
now produced, but rather to present testimony concerning the effect of bead
size on physical stability of cation resins. That the larger the beads are,
no matter what the polymer structure, the greater the tendency for physical
breakage is, is an inportant property to remember.
Interest in bead stability was greatly accelerated by the appearance of
the Chatillon test procedure in the General Electric specifications in the early
1970's (42). This is a purely physical test wherein a single bead is squeezed
between two parallel plates by a known applied force until it breaks. Many
manufacturers have modified their production methods, particularly of anion
resins, to produce materials which give high values in this test although correlation
of the results with field performance has yet to be established.
Recently a new test method utilizing a column of resin subjected to both
mechanical and osmotic shock has been described by Skriba, et il (43). While
this procedure was developed primarily for anion resins used in uranium recovery,
it is currently being applied in modified form to cation resins as well. It
has the advantage of mimicking the conditions in a packed bed under plant operating
pressures and temperature and permits the use of whatever reagents are being
used in the specific plant system. Results are normally evaluated by measuring
the percentage of broken beads after specified numbers of cycles. Correlation
with cation resin breakage in condensate systems where a portion of the cation
resin may contact sodium hydroxide are following plant performance.

The Importance of Bead Size

The effect of bead size on the kinetics of the system has already been
brought to attention. Further, in the preceding section its influence on bead
stability is shown. Controlling the size of the beads has received increased
attention as the operating flowrates in condensate polishers have increased.
In general, an increase in average bead size has followed this development.
As it happens, correction of one problem in an ion exchange system frequently
generates others since all of the properties of the bead, both chemical and
physical, work together to govern the overall properties of the system. Bead

35
size is particularly important in understanding the hydraulics of the system
and the separability of mixed beds. A discussion of its effect on these properties
is a fundamental part of a discussion of the properties of the resin itself.

The factors related to pressure drop has been correlated in a recent paper
(44). Over a considerable range, the pressure drop can be calculated by the
following equation:

150 U0L
(Dp)2 g £3
Where P = pressure difference, Pa/m
U0 = flow velocity, m/min
L = bed height, m
u = viscosity of the liquid at the operating temperature, poise
£ = void fraction
g = gravitational constant
Dp = geometric average particle diameter, m

The relationship between particle size, flow rate and pressure drop implied
in the above equation is illustrated graphically in Figure 15. Here pressure
drop is plotted as a function of particle size at three different linear flow
rates. The effect of high flow rate operation on pressure drop is clearly shown.
In counteracting this by an increase in bead size, the loss in kinetic efficiency
must not be neglected particularly where very low leakage is desired.

Bed Expansion. Bed expansion is an important step in the operation of

a nuclear water system, both in freeing the beds from accumulated particulate
material and in separating the components of a mixed bed for regeneration. If
a bed expands too much, resin losses occur. If the bed does not expand sufficiently
the accumulation of particulate material causes pressure drop problems and mixed
bed separations will be inadequate.

36
 32

Effect of Bead Size and Flow Rate

on Pressure Drop (44)

450 550 650 750 650 950

Bead diameter, microns

——— FLOW RATE, METERS/HOUR'

2.45 49 7.35 9.8 12.2514.7017151960

ioo%-

70« f
z
o
</>
<
ü.
X
LU
Q

O
1-
UJ
Ü
K

Figure 16 -

Effect of Temperature on Bed Expansion

0 1
1 2 3 4 5 6 8% Nominal DVB Sulfonic Resin
1___ BACKWASH FLOW RATE. U.S. gpm/tq. Hydrogen-Form (18)

37
 The amount of expansion of an ion exchange material when water is passed
upward through it depends upon the hydrated density of the bead itself, the
size of the bead, the rate of flow of the water and the water temperature. A
surprising number of systems fail to appreciate the effect of the latter. This
is shown in Figure 16 with data from an 8% sulfonic acid resin (18).

The effect of bead size is shown in Figure 17. Polymer characteristics

are eliminated here since all of these data were obtained on a single lot of
nominal 8% divinyl benzene sulfonic acid resin in the hydrogen form. Technical
grade material was selected so that a full particle size range was available.

20 -

15 20 25
Backwash Flow Rate m'/mVhr 0 20°C

Figure 17 - Backwash Expansion of Different Particle Sizes From a Single Batch

of 8% DVB Sulfonic Acid Polymer (45). Hydrogen Form. See Table
7 for Screen Analysis

The backwash expansion was first determined on the bead population as originally
sold. Sieve analysis in Table 7 confirms that it did indeed have a full range
of particle sizes. Next, a portion of the lot was backwashed vigorously and
the fine material gradually removed until some particles retained on 40 mesh

38
appeared in the backwash water. The bed expansion was then redetermined on
the residual population whose sieve analysis is shown also in Table 7.
At the end of the backwashing, this column of material was allowed to
settle by gravity and divided as nearly as possible into a top portion and a
bottom portion. Backwash expansion characteristics were then determined on
each of these. Subsequently both of these fractions were wet sieved (Table 7).
Most backwash data published were determined on what is considered here to be
the normal particle size range. When bead sizes either larger than or smaller
than this are employed, hydraulic data should fit the bead size that is to be
used.

Table 7
Screen Analysis of 8% Divinylbenzene Sulfonic Acid Resin
Used in Bed Expansion Tests
Hydrogen Form (45)

Original Fines Top Bottom

Removed 'a/
% of Total Population 100 94.4 47.1 47.3
On 16 mesh 2.4 2.5 0 5.0
Thru 16 on 20 40.7 42.9 5.8 78.0
Thru 20 on 30 45.6 48.2 81.8 16.6
Thru 30 on 40 5.5 5.2 9.9 0.4
Thru 40 on 50 4.7 1.0 2.4 0
Thru 50 1.0 <0.1 0.1 0
Effective Size, mm 0.54 0.62 0.53 0.80
Uniformity Coeff. 1.59 1.42 1.34 1.25

(a) Removed by backwashing

Separability of Hixed Beds. The development of the three-layered beds

is a recognization that both the size and the density of the cation polymer
is a critical factor in the separability of mixed beds. Data such as that shown
in Figure 17 make this clear. Such sharp boundaries in the three-layered beds
reflect use of cation resin whose bead size is very closely controlled and,
hence, whose expansion can be precisely predicted.

39
 Problems arise, however, when material made to operate in newly designed
high flow rate units with proper attention to the hydraulic properties of the
larger beads are put into older units without suitable modification of the backwash
rates. It is not unusual in such cases to find that the bottom of the bed does
not expand at all resulting in the complete exhaustion of anion resin, left
in the bottom unseparated, with acid.

MACROPOROUS SULFONIC CATION EXCHANGE RESINS

Chemically, the resins that are termed macroporous are the same as the
gel resins. The difference between the two classes is in the physical structure
within the bead. In the case of resins termed gel, an individual bead is an
essentially homogeneous polymeric spheroid. In the polymers called macroporous,
this sphere contains artifically generated holes in the polymer mass which permit
the external liquid phase to penetrate the sphere. Thus the effective surface
area of the polymer is increased.
Chemical Properties of Macroporous Sulfom'c Resins
A review of the patent literature covering the preparation of sulfonated
macropolymers (3 to 7) will reveal that they are prepared using a vast variety
of ternary mixtures of styrène, divinyl benzene and solvent. Each solvent, each
ratio of that solvent to a given ratio of styrène and divinylbenzene, and each
ratio of styrène to divinylbenzene produces a change in the final product. This
vast collection of possibilities makes it impossible to correlate the properties
of macroporous sulfonic resins in some orderly fashion that is possible in the
pure gel resins unless one has full knowledge of the manufacturing processes.
It is doubtful that two commercial products are made from identical ratios of
the same starting materials. None the less, the two most widely used commercial
products of this type are strikingly similar in chemical properties (Table 8).
These data were collected on the same terms as those for gel resins in Table 2.

Chemically, the ratio of styrène to divinylbenzene governs the properties

of the polymer itself just as it does in the gel resins. The water retention,
true polymer density, selectivity, diffusion kinetics into the polymer itself,

40
 Table 8
Comparison of the Properties of New Macroporous
Sulfonic Cation Resins from Different Producers (13)
Source A Source B
Hater Retention, %
Sodium Form
High 49.15 48.27
Low 46.86 46.92
Average 47.87 47.39
Hydrogen Form
High 53.92 52.55
Low 50.91 51.84
Average 52.54 52.48
Exchange Capacity, Na-form
meq/g dry
High 4.34 4.37
Low 4.20 4.27
meq/ml
High 1.80 1.89
Low 1.77 1.72
Average 1.79 1.81

and the resistance to oxidation are all governed by this ratio as they are in
the gel system. The amount of artificial holes in the bead govern the surface
available for the ingress of the external solution and the hydrated bead density.
They also have a marked effect on the physical properties of the final bead.
If the ratio of holes to polymer becomes too high the physical stability of
the resultant bead will diminish.
The problem in characterizing macroporous polymers is. that water retention
capacity does not provide the key to the overall composition of the system that
it does in gel sulfonic resins. In the macroporous system, water retention
capacity is the sum of the water held in the pores plus the water retained in
the polymer itself. A producer of these materials usually controls the pore

volume by solvent sorption before the polymers are sulfonated. Drying curves
do provide a means of characterizing these material since the water held in
the macropores is lost very rapidly compared with the water in the tight polymer
network. However, these are not routine measurements, since the process must
be carefully controlled. For practical purposes, a simple measurement of pore

41
volume is more readily obtained by measuring the displacement volume when the
water in a small column of resin is displaced with a non-exchanging solution
of electrolyte. The difference between the measured displacement volume and
the theoretical interbead void volume calculated following the method of Delia
Valle (46) is a an approximate estimation of the volume of the pores within
the beads.

Since macroporous sulfonic acid resins are made with a higher divinylbenzene
content than gel resins, Bonner's data (16) in Table 5 predict that they should
have a very high selectivity for calcium, as compared with an 855 gel resin,
but only a slightly higher selectivity for either sodium or magnesium. In
Figure 18 performance curves obtained under exactly the same conditions as

i.o

0.9

0.8

0.7

Na-Mg

0.6

Na -Ca/Mg

0.5 Na-Ca

20 40 60 80 100
Percent Na in Water

Figure 18 - Variation of Operating Capacity of a Typical Macroporous

Sulfonic Acid Resin with the Ratio of Influent Ions
Regenerated with 1.5 Equivalents HgSO^Liter Resin (47)

42
 Table 9
Comparison of the Operating Capacity^3)
of a Gel and macroporous Resin

Capacity, Equivalents/liter
Ions in Influent Water Nominal
b
8% Macroporous^0)
Gel( )
100% Na 0.87 0.80
50% Na-50% Ca 0.59 0.53
100 Ca 0.56 0.52
50% Ca-50% Mg 0.64 0.59
100% Mg 0.73 0.72
50% Mg-50% Na 0.74 0.72
(a) Both resins regenerated with 1.50 Equivalents f^SCWLiter. Influent water
of zero alkalinitity.

(b) Data taken from Figure 2

(c) Data taken from Figure 18

Table 10
Comparison of the Bead Densities and Surface Areas of
Gel and Macroporous Sulfonic Acid Resins

Hydrated Bead Density'5) Surface Area

H"*" Form Na"*" Form m2/g dry
8% DVB Gel 1.19 1.27 <1
10% DVB Gel 1.22 1.31 <1
Macroporous 1.19 1.26 35-42.5 (36,48)

(a) Data accumulated by the authors from commercial materials.

the data for a gel sulfonic (Figure 2) are shown. Selection of a few points
at different ratios of influent ions in Table 9 confirms the fact that the
major difference in performance between the two types of polymers is in waters
where calcium is a major component of the influent population. That the macroporous
polymer is more selective for calcium manifests itself in a lower operating
capacity since the reverse reaction of hydrogen replacing calcium is less efficient.
Despite the differences in their structure, the bead densities of commercial
macroporous resins are essentially identical with those of a nominal 8% divinylbenzene
gel resin (Table 10). The difference between the two types of polymers is
shown primarily in surface area measurements.

43
 The similarity in hydrated bead density of the macroporous resin and the
nominal 85! gel indicates that if both are made in the same particle size range
their hydraulic properties, and particularly their backwash expansion rates,
should be so similar that they can be used interchangeably in a given unit
without adjustment of flow rates.

Stability of Macroporous Sulfonic Resins

In the nuclear system, macroporous resins are most often utilized in condensate
polishing systems to obtain the better chemical and physical stability of
a higher cross! inked resin while avoiding the serious kinetic problems shown
in the work of Soldano (Figure 3), by increasing the effective surface. Various
papers have been published attesting to their superior physical and chemical
stability, of which the data in Figures 14 and 19 taken from early work (36,
38) are typical. Like most commercial products, macroporous sulfonic resins

2.5 5 7-5 10 12.5

Throughput, «i'/m1 * 1C|5

Figure 19 - Comparison of the Decrosslinking of Gel and Macroporous

Sulfonic Resins in Field Tests (38)

44
presently sold represent a compromise in properties and the material s made now
are not identical to those first marketed under similar trade names. The chemical
stability toward oxidants of these polymers will, however, follow the curves
in Figures 9 and 10. Such measurements actually provide a means of estimating
what the divinylbenzene content of a given polymer is.
Although data on the subject are scarce (49), the stability of these high
crosslinked materials to radiation should be superior to that of gel resins
with respect to the tendency to decrosslink. Otherwise their radiation stability
should depend only on dosage as has been shown above. The accessibility of
their groups to large ions and colloids has promoted their use in radwaste
treatment.

METHYLENE SULFONIC ACID CATION RESINS

Méthylène sulfonic acid cation resins are of greater historical than current
interest in the nuclear industry. Since styrene-divinyl benzene based sulfonic
resins were not available until the mid-1940's, much of the earlier work was
done with méthylène sulfonic acid resins. Their preparation, which involves
a condensation reaction of phenol, formaldehyde and sodium sulfite is described
in patents by Holmes and others (50, 51). In general, their structure
is represented as follows:
o-Nii* o-NV- O-NU+
.. ,. r,,> iiico • ' '

The properties of these materials are described by Kressman and Kitchener

(52). They were a marked improvement over the earlier nuclear sulfonic acid
resins formed by sulfonation of phenol-formaldehyde polymers which could only
be used in the hydrogen form at temperatures below 40°C. Higher sulfonic capacities
of the styrene-based materials (Table 11) and the ease with which bead-form
polymers could be made in that system resulted in the rapid displacement of
the méthylène sulfonic polymers in industrial applications.

45
 Table 11

Comparison of the Chemical Properties of a

Méthylène Sulfonic Acid Polymer
With a Typical Sulfonated Styrene-Divinylbenzene Polymer
Before and After Radiation Exposure (28)
All Values for Sodium Form
8% Nominal
Méthylène Sulfonic Styrène - DVB
Before AfterU) Before After\a)

% H20 Retained 60.8 63.5 43.9 52.2

Total Cation Capacity
meq/g dry 5.38 4.53 4.90 (b)
Sulfonic Capacity
meq/g dry 1.69 1.60 4.40 4.43
Sulfate in Leach
Millimoles/10 g 0.12 1.12 0.09 5.34
(a) Approximately 108 Rads
(b) No data given

However, numerous workers (28, 29, 53-56) have reported that méthylène
sulfonic materials have superior resistance to high levels of radiation compared
with the nuclear sulfonic resins. This, plus their excellent selectivity for
the heavy isotopes, means that they still find use in some special radwaste
systems.

CARBOXYLIC CATION EXCHANGE RESINS

Although the original patents of D'Alelio (1, 57) describe the production
of cation exchange resins with carboxylic acid functionality made from many
monomers, those commercially available are either methacrylic acid cross!inked
with divinylbenzene or acrylic acid crosslinked with divinylbenzene. The structure
of the methacrylic acid polymer is represented as follows:

CH, OH, Cn,

~ C— CH; -C—CHS—CH-- CH=—C—CH, -
COOH COOH A. COO M

CH, CI I, \/
- C: -011: - C- CH--C11 CH- -
coon coon

46
The acrylic acid polymer is of similar structure with the methyl group on the
carbon alpha to the carboxyl group replaced by a hydrogen. Both types of polymers
may be made as gels or as macroporous structures (58). Generally similar macroporous
materials of both acid types and gel acrylic resins comprise the available commercial
spectrum (Table 12) encountered in nuclear applications.

Table 12
Typical Properties of Commercially Available
Types of Carboxylic Acid Resins (59-63)
Acid Methacrylic Acryl ic
Polymer Type Macroporous Macroporous Gel
Standard Porous
% HoO Retained
H* Form 48 47 44 52
Na+ Form 73 73 62 72

Total Cation Capacity

meq/g dry,+ H+ form 10.6 10 12 13
meq/ml , H + form 3.5 3.0-3.8 4.0 4.4
meq/ml , Na form 1.7 2.1 2.3 2.2

Hydrated Bead Density

H+ form 1.25 1.13 1.19 1.1
% Volume +Increase
a 100 85 50-70 70-100

The properties of carboxylic acid polymers are far more dependent upon
cross!inkage than those of sulfonated styrene-divinyl benzene polymers. The
total weight capacity, for example, is an inverse function of the mole percent
crosslinking agents since only the acrylic monomers contribute functionality.
Many workers have published on the effect of crosslinking on both the acidity
and the physical properties of these resins (64-67). From the standpoint of
the nuclear industry, however, these properties are academic since only a limited
number of carboxylic polymers are used. Except for certain limitations on bead
size, these are materials which have been made commercially available for other
applications. These include one macroporous methacrylic acid type, gel acrylic
resins which can be roughly separated into porous and standard classifications,
and a macroporous acrylic type. The basic properties of these materials are
summarized in Table 12.

47
 In nuclear applications, carboxylic acid resins are used in some makeup
démineraiizer systems where the water has a high sodium bicarbonate alkalinity.
Their advantage here, of course, is that they are easily and completely regenerated
with acid which frequently can be the excess acid used to regenrate the styrene-
divinyl benzene sulfonic acid resin that follows them. The standard gel acrylic
or the macroporous acrylic are the resins most frequently seen in this service.
The application more specific to the nuclear industry is the use of the
acrylic macroporous resin as a carrier in the recycle of Uranium-233 (68-70).
The carboxylic polymer, which has a very high affinity for the uranyl (UU2+2)
ion is loaded with uranium from a nitrate solution. The loaded resin particles
are subsequently dried and carbonized to form kernels for use in fuel rods.
The chemical properties of the resin used in this application are similar to
those of resins used for water treatment but the physical properties of the
beads with regard to both size and shape are carefully controlled. The fact
that the carboxylic polymers have poor radiation stability (29) is not a factor
here since the residence time on the resin before carbonization is short.
A somewhat related use of carboxylic polymers in uranium metallurgy is
disclosed in a patent application by Kunin (71). This too depends on the high
capacity of the carboxylic polymers for uranyl ion which permits its uptake
by the resin as a cation from carbonate 1 cachâtes. The excellent regeneration
efficiency of these resins with acid permits recovery from dilute feed at high
concentration factors.

REFERENCES

1. D'Alelio, G.F., U.S. Patent 2,340,110 (1944).

2. D'Alelio, G.F., U.S. Patent 2,366,007 (1944).
3. Corte, H. and Meyer, A., German Patent 1.045,102 (1958); also U.S. Patent
3,586,646 (1971).
4. Millar, J., British Patent 849,122 (1960).
5. Werotte, L. and Grammont, P., U.S. Patent 3,418,262 (1968).

48
6. Mindick, M. and Svarz, J., U.S. Patent 3,549,562 (1970).
7. Meitzner, E. and Oline, J., U.S. Patent 4,224, 415 (1980).
8. Annual Book of ASTM Standards, Part 11.02, ASTM, 1916 Race Street, Philadelphia,
PA. (1983) (Note: A revised update of these methods is published annually.)
9. Reichenberg, D., Pepper, K.W., and McCauley, D.J., J. Chem. Soc. 1951 493.
10. Pepper, K.W., Reichenberg, D., and Hale, O.K., J. Chem. Soc. 1952. 3929.
11. Glueckauf, E., Proc. of Roy. Soc. (London) A214. 207 (1952).
12. Kunin, R. and Fisher, S., Chapter XVII in "Analytical Chemistry of Polymers"
(G. Kline, editor) Interscience Publishers, New York (1959)
13. Fisher, S.A. and Otten, G., Proceedings of the 43rd International Water
Conference, 393, Eng. Soc. of Western PA, Pittsburgh, PA (1982).
14. Bonner, 0., J. of Phy. Chem., 59 719 (1955).
15. Argensingers, W., Davidson, A. and Bonner, 0., Trans. Kansas Acad. Sei.,
j>3_, 404 (1950).

16. Bonner, O.D. and Smith, L.L., J. Phy. Chem., 6U 326, (1957).
17. Frisch, N.W. and McGarvey, F.X., Chem. Eng. Prog., j>5, 51, (1959)

18. Technical Bulletin lonac C267, Sybron Chemical Division, Birmingham, NJ

(1983).
19. Technical Bulletin lonac C250, Sybron Chemical Division, Birmingham, NJ
(1983)
20. Technical Bulletin lonac C267 - HC1, Sybron Chemical Division, Birmingham,
NJ (1983)
21. Boyd, G.A., Adamson, A.W., and Myers, L.S., J. Am. Chem. Soc., 69. 2836,
(1947).
22. Soldano, B.A., Ann. N.Y. Acad. Sei., 57^, 116, (1953).
23. Schmuckler, G., Nativ, M., and Goldstein, S., Proceedings of the 1976 Cambridge
Conference on Ion Exchange; Paper 17, Soc. of Chem. Ind., London (1976).
24. Gangwer, T.E., Goldstein, M. and Pillay, K.K.S., BNL 50781, U.S. Dept. of
Energy, Wash. DC (1977).
25. Simon G.P. Chapter 5 in "Ion Exchange for Pollution Control", Calmon, C.
and Gold, H. (Eds), CRC Press, Boca Raton, FL (1979).

49
26. Nikashima, V.A., et jjl_ Trudy 2-90 Vsesoyuznogo Soveshchaniya po Radiatsionnoi
Khimii, 596, (1962).
27. Nater, K.A., Proc. of 2nd Ann Conf. on Peaceful Uses of Atomic Energy,
United Nations, Geneva (1958).
28. Higgins, I.R., Nuci. Sei. Abstr. H_, 8538, (1957).
29. Fisher, S.A., RMO-2528, US Atomic Energy Commission, Wash., DC (1954).
30. Kuzin, I.A. and Shemushin, A.M., Zh. Prekt. Khim. J4_, 1710, (1961).
31. Kiseleva, E.D. Trudy Taskenlskoi Ronf. po Mirnomu Ispolzovaniyu Atomni
Energii Tashkent, Vol. 1, 313, (1961).
32. Semushin, A.M. and Kuzin, I.A., Tr. Lenings. Inst, im Lensoneta 55, 67,
(1961).
33. Semushin, A.M. and Kuzin, I.A., Zh. Prikl. Khim., j!3,_ 2323, (1960).
34. Mohreic, G. and Kramer, V., J. Polymer Sic., Part C No. 15, 4185, (1968).
35. McGarvey, F.X. and Fisher, S.A., AICh.E. Meeting, Boston, Mass. (Sept. 1975)
36. Clark, W., Addendum to ORNL-4792, Oak Ridge Natl. Lab., Oak Ridge, Tenn.
(1978).
37. Kunin R., Meitzner, E.F., Oline, J., Fisher, S.A., and Frisch, N.
I.& E.C., Prod. Res., 1, 140, (1962).
38. Fisher, S.A., Previously unpublished data.
39. Downing, D. and Kunin, R., Proc. of the 21st Ann. Water Conf., Eng. Soc.
of W. PA., Pittsburgh, PA (1960).
40. Fisher, S.A. and Otten, G., Proc. of the 41st Int. Water Conf., Eng. Soc.
of W. PA, Pittsburgh, PA (1981).
41. Kunin, R., Frisch, N.W. and McGarvey, F.X., Proc. of the 19th Ann. Water
Conf., Eng. Soc. of W. PA., Pittsburgh, PA (1958).
42. Specification A50A306-S2, General Electric Co., Schenectady, NY (1971).
43. Skriba, M., Alvino, W.M. and Kunin, R., I.& E.C., Prod. Div. 19. 624,
(1980).
44. McGarvey, F.X., AICh.E. Sym. Series 219, 78, 74, (1982).
45. Fisher, S.A., and Otten, G., Proc. of the 43rd Int., Water Conf. of W.
PA, Pittsburgh, PA (1983)

50
46. Delia Valle, J.M., "Micrometrics - The Technology of Fine Particles" Pitman
Pub. Co., New York, (1943).

47. Technical Bulletin, CFP-110, Hydrogen Cycle, lonac/Sybron, Birmingham, NJ

(1982).

48. T.D. Index 180.01, Dow Chemical Co., Midland, Michigan (1976).
49. Kubota, M., Konani, Y., Nakamura, H. and Amano, H., Radio Anal. Chem,,
45, 73, (1978).
50. Holmes, E.L., U.S. Patent 2,191,853 (1940).
51. Lyndberg, L.A., American Cyanamide, Brit. Patent, 648,281 (1952) (Also
U.S. Patent 2,610,170)
52. Kressman, T.R.E. and Kitchener, J.A., J. Chem. Soc., 1949. 1193
53. Shigematsu, T. and Oshio, T., Bull. Inst. Chem., Res., Kyoto Univ., jtf
349, (1959).
54. Tulupor, E.D., Chmutor, H.M. and Kleintovskaya, M.M., RUSS. J. Phy. Chem.
(English trans.) 42(11), 1518 (1968).
55. Kiseleva, E.D., Chmutov, H.H., and Kleintovskaya, M.M., Russ. 0. Phy. Chem.,
(English trans.) 39(3). 406, (1965).
56. Kiseleva, E.D., Chmutov, H.M., and Krupnova, V.N., Russ.. J. Phy. Chem.,
(English trans.) 36(11), 1331, (1962).
57. D'Alelio, G.F., U.S. Patent 2,340,111 (1944).
58. Oline, J., U.S. Patent 3,367,889 (1968).
59. Technical Bulletin IE-241/78/81, Rohm and Haas Co., Phila. PA (1983).
60. Technical Bulletin DS-FC7-404-5M, Diamond Shamrock Functional Polymers
Div., Redwood City, CA (undated).
61. Dow Chemical Co., publication in press
62. Technical Bulletin 9-77, lonac/Sybron, Birmingham, NJ (1977).
63. Technical Bulletin 2-7500, Bayer, Leverkusen, W. Ger. (1981).
64. Fisher, S.A. and Kunin, R., J. Phy. Chem. j60, 1030, (1956).
65. Kunin, R. and Barry, R., Ind. & Eng. Chem., ^1_, 1269 (1949).
66. Gregor, H.P., Hamilton, M.J., Becker, J. and Bernstein, M., J. Phy. Chem.,
59, 874, (1955)

51
67. Bregman, J.L., Ann. N.Y. Acad. of Sei., 57^, 125, (1953).
68. Haas, P.A., ORNL/TM 3817, Oak Ridge Nat'1 Lab, Oak Ridge, Tenn (1972).
69. Shaffer, Ü.M. and Greene, C.W., ORNL/TM-6611, Oak Ridge Nat'1 Lab., Oak
Ridge, Tenn (1978).

70. Shaffer, J.M. and Green, C.W., ORNL/TM-6631, Oak Ridge Nat'1. Lab., Oak
Ridge, Tenn (1979).
71. Kunin, R., U.K. Patent Application 2,084, 126 (Sept. 1981).

52
 CHAPTER 2

APPLICATION OF ION EXCHANGE

TO URANIUM RECOVERY

A. HIMSLEY
Himsley Engineering Ltd,
Toronto, Ontario,
Canada

Abstract

The a p p l i c a t i o n of ion e x c h a n g e to u r a n i u m recovery i n v o l v e s

the study of s o r p t i o n and é l u t ion p r o c e s s e s and the e f f e c t of
c o m p e t i n g ions upon the l o a d i n g of u r a n i u m on the resin.
The e q u i l i b r i u m l o a d i n g d e p e n d s s o l e l y upon the concentrations
of the v a r i o u s i o n s in the s o l u t i o n to be treated. The rate
at w h i c h the resin reaches the e q u i l i b r i u m l o a d i n g d e p e n d s u p o n
the c o m p e t i t i o n from o t h e r unwanted ions, the concentration of
ions and the ratio of v o l u m e t r i c flow rate to r e s i n v o l u m e as
w e l l as the r e s i n s t r u c t u r e , p a r t i c l e size and the temperature
of operation.
E f f i c i e n c y of e l u t i o n depends upon the type and amount of
e l u a n t used a n d t h e c o n t a c t t i m e o r r a t e a t w h i c h t h e e l u a n t
is p a s s e d t h r o u g h the bed of resin. It is also d e p e n d e n t upon
the resin structure, p a r t i c l e size and the t e m p e r a t u r e of the
eluant. The water retention of the resin b e a d s , w h i c h is a measure
of c r o s s l i n k i n g and porosity a l s o has a m a r k e d effect u p o n the
rate of exchange both on sorption and e l u t i o n .

URANIUM PROCESSING CONDITIONS

Sorption of U r a n i u m
When solutions of u r a n i u m c o n t a i n i n g an excess of free s u l p h u r i c
acid are passed t h r o u g h a c o l u m n of s t r o n g base ion e x c h a n g e
r e s i n the u r a n i u m is sorbed by the resin. The u r a n i u m on the
resin could be any of the f o l l o w i n g forms:

U s u a l l y it is the first form, uranyl tri sulphate, that is

encountered with most a c i d i c leach s o l u t i o n s . The second form
is u s u a l l y e n c o u n t e r e d w h e n the pH is h i g h - in the region of
pH2 - and when the sulphate is low. The third form is expected
to be f o u n d in s o l u t i u o n s w h e r e the c o n c e n t r a t i o n of u r a n i u m
is h i g h . It w i l l be noted t h a t t w i c e as m u c h u r a n i u m can be
taken up by the resin when the u r a n i u m is in either the second
or the third form.
Resin h a v i n g a capacity of 1.25 e q u i v a l e n t s per l i t r e would
have a m a x i m u m capacity for the t e t r a v a l e n t ion in the r e g i o n
of 80 g/1 as U3Û8. H o w e v e r , the p r e s e n c e of other ions that
can be taken up by the resin often reduces this sorption to values
which are somewhat below this figure.

53
 The ions g e n e r a l l y competing with u r a n i u m for s i t e s on the
r e s i n a r e t h e b i s u l p h a t e i o n w h i c h i s d e p e n d e n t upon p H , t h e
sulphate ion and the ferric ion.
F e r r i c ion also forms an a n i o n i c complex with sulphate and
this c a n b e a s e r i o u s c o m p e t i t o r p a r t i c u l a r l y w h e n t h e m o l a r
ratio of the ferric iron to u r a n i u m is in excess of 1 5 : 1 . C h l o r i d e
and nitrate also compete but they o n l y become n o t i c e a b l y r e s t r i c t i v e
at l e v e l s above 1 to 2 g/1.
W h i l s t t h e u r a n i u m c o m p l e x i s more s t r o n g l y h e l d than t h e
iron complex the m e c h a n i s m of l o a d i n g results in the resin b e i n g
brought to e q u i l i b r i u m first with the barren s o l u t i o n w h i c h c o n t a i n s
ferric iron and b i s u l p h a t e . This has then to be e l u t e d off the
resin by the pregnant l i q u o r and the more iron there is the more
time is required for the resin to come to e q u i l i b r i u m w i t h the
u r a n i u m c o n t e n t of the feed l i q u o r . When the resin is f i n a l l y
in e q u i l i b r i u m , some of the ion e x c h a n g e s i t e s w o u l d s t i l l be
o c c u p i e d w i t h t h e i r o n c o m p l e x a n d t h e s u l p h a t e ions d e p e n d i n g
upon their relative concentrations and selectivities.
The formation of the ferric iron s u l p h a t e c o m p l e x is favoured
at h i g h e r pH v a l u e s and consequently the c o m p e t i t i o n from i r o n
b e c o m e s n o t i c e a b l y stronger at pH v a l u e s above 2. It has been
found that when ferric iron is present in s i g n i f i c a n t q u a n t i t i e s
the o p t i m a l pH for operation is a r o u n d 1.5. If the pH is much
lower than this there is a reduction in u r a n i u m l o a d i n g due to
competition from the b i s u l p h a t e iron.
O t h e r c o m p o n e n t s such a s s i l i c a , p o l y t h i o n a t e s a n d some
o t h e r m e t a l a n i o n i c c o m p l e x e s a s m e n t i o n e d e a r l i e r m a y cause
resin f o u l i n g resulting i n decreased r e s i n c a p a c i t y . T h i s h a s
to be r e m e d i e d by s p e c i a l r e g e n e r a t i o n treatment of the resin
at certain i n t e r v a l s .
Contact Time
One of the most inmportant parameters in any mass transfer
process such as ion exchange is the r e l a t i o n s h i p of v o l u m e t r i c
l i q u i d flow t o r e s i n v o l u m e . T h i s i s s o m e t i m e s expressed i n
terms of c o n t a c t t i m e w h i c h is the c a l c u l a t e d r e s i d e n c e t i m e
of the l i q u i d as it flows through the resin bed. The estimated
v o i d v o l u m e of the bed d i v i d e d by the flow rate through the bed
g i v e s the contact or retention time. This however, is not considered
to be the best way of expressing contact time because not a l w a y s
is the v o i d a g e known and in any event the rate of ion exchange
is m a i n l y governed by the volume of resin and not the voids.
The m o s t c o n v e n i e n t m a n n e r is to e x p r e s s the l i q u i d flow
in e q u i v a l e n t resin bed volumes per hour which obviates the need
to a s s u m e a v o i d a g e in the resin bed. The resin bed v o l u m e is
the v o l u m e occupied by the wet s e t t l e d resin and i n c l u d e s the
resin beads and the voids.
The rate at which the resin is eluted may also be expressed
in terms of bed v o l u m e s per hour. The n u m b e r of bed v o l u m e s
of e l u a n t r e q u i r e d may be e s t i m a t e d based on existing data or
a l t e r n a t i v e l y some tests c a r r i e d out to d e t e r m i n e t h i s v a l u e .
Safety factors must be a p p l i e d to a l l o w for any fall-off in the
k i n e t i c s of sorption or e l u t i o n .

E qui l i b r i u m L o a d i n g of R e s i n
The e q u i l i b r i u m l o a d i n g for u r a n i u m can e a s i l y be e s t a b l i s h e d
by p a s s i n g the s o l u t i o n to be t r e a t e d t h r o u g h a s m a l l bed of
resin in a 25 mm dia. tube at a flow rate of 4 to 6 bed volumes
per hour u n t i l the effluent concentration of the ion of interest

54
is e q u a l to the i n f l u e n t concentration. The resin can then be
stripped completely using perchlorate or an excessive amount
of a c i d and the a m o u n t of u r a n i u m in the e l u a t e d e t e r m i n e d .
The amount in grams d i v i d e d by the volume of resin in the tube
in litres w i l l give the e q u i l i b r i u m loading in grams per litre.
Rate of U r a n i u m L o a d i n g
The rate at which resin w i l l load with u r a n i u m can be determined
by p a s s i n g pregnant solution through a bed of r e s i n a b o u t 1200
mm deep in a tube 25 mm or l a r g e r in diameter at a rate of 6
to 7 bed volumes per hour. S a m p l e s of the e f f l u e n t s h o u l d be
t a k e n from time to time until the effluent concentration is the
same concentration as the i n f l u e n t . The p l o t of such data is
known as a breakthrough curve.
The s l o p e of the curve is a function of the rate at which
u r a n i u m is being taken up by the resin. If the ratio of volumetric
f l o w rate to r e s i n volume is increased, the slope of the curve
decreases, i.e., the c u r v e becomes l o n g e r . L i k e w i s e , if the
concentration of u r a n i u m in the feed is increased w h i l s t m a i n t a i n i n g
the same flow rate, the l e n g t h of the c u r v e becomes l o n g e r .
In all cases however, the rate at which u r a n i u m is taken up by
the resin increases m a r k e d l y up to a concentration around
l g U308/1 and then it begins to tail off.
An important piece of information to be obtained from such
a c u r v e is the ratio of the time when the resin is e s s e n t i a l l y
in e q u i l i b r i u m with the feed and the time at which b r e a k t h r o u g h
occurs. This ratio has a strong bearing upon the size of e q u i p m e n t
required to satisfactorily treat the pregnant liquor. Different
r e s i n s may g i v e d i f f e r e n t r a t i o s and it is d e s i r a b l e to use a
resin which gives a low ratio.
If a r e s i n c o l u m n were e l u t e d when breakthrough occurred,
the amount of u r a n i u m so e l u t e d w o u l d o b v i o u s l y be l e s s t h a n
if the resin had been a l l o w e d to reach its e q u i l i b r i u m or saturation
l o a d i n g . It is therefore d e s i r a b l e to h a v e two r e s i n c o l u m n s
in series so t h a t the l e a k a g e from the first c o l u m n (between
breakthrough and saturation) can be taken up by the second column.
This demands that the aforementioned ratio be at least 2.
Rate of Uranium Stripping
H a v i n g loaded the resin it is necessary to strip the resin
to determine the amount of u r a n i u m sorbed by the resin and a l s o
the rate at w h i c h it can be e l u t e d . It m u s t a l s o be decided
which type of eluant w i l l be most satisfactory from the s t a n d p o i n t
of cost, a v a i l a b i l i t y , effectiveness and e n v i r o n m e n t a l constraints.
The v a r i o u s eluants that can be used have a l r e a d y been discussed.
The rate at w h i c h the u r a n i u m is s t r i p p e d off the r e s i n
is m a i n l y controlled by the laws of diffusion. Time is therefore
an e s s e n t i a l r e q u i r e m e n t for good e l u t i o n and p r o v i d e d adequate
time is allowed the amount of e l u a n t required to elute the resin
can be kept to a m i n i m u m .
I n c r e a s i n g the f l o w rate of e l u a n t r e d u c e s the t i m e for
e l u t i o n but the total v o l u m e of e l u a n t used i n c r e a s e s t h e r e b y
i n c r e a s i n g cost and decreasing the strength of eluate.
The rate of e l u t i o n can be increased by r a i s i n g the temperature
at w h i c h it is carried out but it must be recognized that d e g r a d a t i o n
of the resin is more rapid at the higher temperature; also the
corrosive properties of the solution are u s u a l l y increased thereby
d e m a n d i n g superior m a t e r i a l s of construction.

55
E l u t Ion Curve
H a v i n g d e c i d e d w h i c h type of e l u a n t to use a l o n g with the
technique to be adopted, some e l u t i o n tests s h o u l d be m a d e to
o b t a i n the d e s i g n data. The loaded resin c o l u m n used for o b t a i n i n g
the sorption curve should now be used for o b t a i n i n g the e l u t i o n
c u r v e . E l u a n t s h o u l d be passed down the c o l u m n at a flow rate
g e n e r a l l y between 0.5 to 2 BV's/hr and samples taken at i n t e r v a l s
so t h a t a n a l y s e s for U^QQ can be made for p l o t t i n g the elution
curve. The eluate is b u l k e d and its v o l u m e measured.
When the eluate is at a level of 0.1 g u^Os/l the r e s i d u a l
u r a n i u m on the resin is a b o u t l g U 3 0 3 /1 w h i c h is considered
stripped to a degree that s h o u l d ensure a barren of 0.001 g u^Os/l
from the sorption column.
The p l o t t i n g of the e l u t i o n curve w i l l show the number of
bed v o l u m e s of eluant to strip the resin and a l s o the rate at
w h i c h the resin is stripped. The b u l k e d eluate is then a n a l y s e d
for U3Û8 and knowing the v o l u m e , the total amount of 1)303 stripped
from the resin can be determined.
E l u a n t Recycl e
T h e o p e r a t i n g cost o f i o n e x c h a n g e i s s t r o n g l y dependent
upon the e f f i c i e n c y of e l u t i o n and the costs of the c h e m i c a l s
i n v o l v e d and therefore the design of any system must reduce the
amount of e l u a n t used to an absolute m i n i m u m .
In the case of c h l o r i d e and n i t r a t e , the a m o u n t l e f t on
the resin after e l u t i o n (approx. 40 g/1 and 70 g/1 of resin re-
s p e c t i v e l y ) goes out and is lost in the barren solution. However,
when s u l p h u r i c a c i d i s used f o r e l u t i o n , t h e b i s u l p h a t e l e f t
on the resin after elution w i l l form s u l p h u r i c a c i d when barren
solution is passed through it and it can therefore be recovered
by r e t u r n i n g it to leach or u s i n g it for filter w a s h i n g .
To recover the u r a n i u m from the e l u a t e an a l k a l i s u c h as
a m m o n i a , c a u s t i c soda or m a g n e s i a is u s e d to p r e c i p i t a t e the
u r a n i u m as y e l l o w c a k e . It is therefore d e s i r a b l e to use the
m i n i m u m a m o u n t of acid in the e l u a n t and also to reduce the v o l u m e
of e l u a n t used to a m i n i m u m . By so d o i n g not o n l y is the c o n s u m p t i o n
of e l u a n t reduced but also the a m o u n t of a l k a l i and c o n s e q u e n t l y
the cost of p r e c i p i t a t i o n can be k e p t l o w . One way of d o i n g
this is to recycle part of the eluate.
It may be o b s e r v e d from the e l u t i o n curve that the second
half of the eluate c o n t a i n s much less u r a n i u m than the first
h a l f . There is a l s o a l a r g e amount of e l u a n t a v a i l a b l e in this
second h a l f and consequently this may be stored and used as the
f i r s t h a l f of the n e x t e l u t i o n . In t h i s way the c o n s u m p t i o n
of e l u a n t is r e d u c e d r e s u l t i n g in an i n c r e a s e in s t r e n g t h of
el ua te .
COLUMN OPERATIONS
Design of Fixed Bed U n i t s
T h e i n f o r m a t i o n o b t a i n e d from t h e a d s o r p t i o n a n d e l u t i o n
curves may be adjusted for d e s i g n p u r p o s e s d e p e n d i n g u p o n the
c o n d i t i o n s of testing and the type of pregnant l i q u o r . If there
is l i k e l y to be any resin f o u l i n g from c o n t a m i n a n t s in the feed
l i q u o r then due a l l o w a n c e m u s t be m a d e in the design capacity
to o b v i a t e any problems in the m a i n p l a n t .
As p r e v i o u s l y indicated the volume of resin in the sorption
column must be such that the time required for it to reach saturation
at the d e s i g n flow and concentration of pregnant l i q u o r is longer
than the time required to elute a column of resin.

56
 In a d d i t i o n , some time must be a l l o w e d for the b a c k w a s h i n g
and r i n s i n g of the resin (which could take 90 m i n s , or so) and
a l s o some s t a n d b y t i m e w h i c h p r e f e r a b l y should be 20% or more
of the total adsorption time in order to take care of any surges
in flow or increases in feed concentration.
The time required for satisfactory e l u t i o n is u s u a l l y the
c o n t r o l l i n g factor in the design of fixed bed columns and a c c o r d i n g l y
the flow of feed solutions to the sorption columns must be such
that b r e a k t h r o u g h on the second column on sorption does not occur
before a freshly eluted column is a v a i l a b l e to be placed on l i n e .
It w i l l be a p p r e c i a t e d that for a constant feed flow rate
in m 3 / h the s m a l l e r the flow rate in BV's/h the larger is the
v o l u m e of resin in each column.
Fixed Bed Systems
The f i r s t a p p l i c a t i o n of ion exchange f o r u r a n i u m r e c o v e r y
was in South A f r i c a in the e a r l y 1950's. T h e t y p e o f s y s t e m
c o m p r i s e d three c o l u m n s p i p e d a n d v a l v e d in such m a n n e r as to
e n a b l e any two columns to be operated in s e r i e s o n s o r p t i o n w h i l s t
the third i s b e i n g e l u t e d . The The dd eettaaii ll ss o f this p r o c e s s i s f u l l y
described e l s e w h e r e [1]. T h i s h a s been r e f e r r e d t o a s t h e " M e r r y -
go-round" system and is shown d i a g r a m m a t i c a l l y in Figure 1.
These s y s t e m s h a v e b e e n i n s t a l l e d i n S o u t h A f r i c a , A u s t r a l i a
and elsewhere, and i n C a n a d a a l o n e o v e r 5 0 such t h r e e - c o l u m n
sets were i n s t a l l e d d u r i n g the l a t e 1 9 5 0 ' s . T h e s e w e r e d e s i g n e d
to treat c l a r i f i e d acid l e a c h l i q u o r s c o n t a i n i n g 0 . 6 t o 1 . 0 g
1)303/1 some of w h i c h are s t i l l in o p e r a t i o n in 1 9 8 4 . The e l u t i o n
is carried out a u t o m a t i c a l l y e m p l o y i n g electro-mechanical e q u i p m e n t
c o m p r i s i n g timers and v o l u m e t r i c counters.

T '
t —\ J——^ X
i L-C^s-
6.
r
t
i
————»—.4 » I (

O u t l e t to
Precipitation

FIG. 1: THREE COLUMN SET FOR URANIUM EXTRACTION

57
M o v i n g Bed Systems
F o l l o w i n g upon the d e s i g n of the fixed bed units already
d e s c r i b e d in w h i c h the e l u t i o n of the r e s i n is c a r r i e d out in
the same c o l u m n as the s o r p t i o n , a n o t h e r approach was made to
increase the efficiency of o p e r a t i o n . This is known as the Porter-
A r d e n m o v i n g bed system and is used at Denison Mines in E l l i o t
Lake, C a n a d a .
The p r i n c i p a l d e p a r t u r e s of this system from the usual fixed
bed a p p r o a c h are:
1. Three c o l u m n s are used in series-sorption
a l l o w i n g for h i g h e r specific flow rates to be
empl oyed .
2. Three columns are used in series-elution re-
s u l t i n g in lower e l u a n t consumption and a shorter
time between eluted columns becoming a v a i l a b l e .
3. A separate c o l u m n for b a c k w a s h i n g the resin and
acting as a h o l d i n g tank between resin transfers
from the sorption sets to the e l u t i o n set.
The system comprises two sets of 3 sorption c o l u m n s l i n k e d
to one b a c k w a s h c o l u m n and one set of 3 elution columns. The
columns i n t h e sorption a n d e l u t i o n sets a r e p i p e d a n d v a l v e d
in s u c h m a n n e r as the "Merry-go-round" concept and is shown in
F i g u r e 2.
W h e n the r e s i n in the l e a d i n g sorption column is saturated
it is transferred to the b a c k w a s h c o l u m n . The e m p t y s o r p t i o n
c o l u m n i s t h e n i m m e d i a t e l y f i l l e d w i t h e l u t e d r e s i n from t h e
l e a d i n g c o l u m n o f t h e e l u t i o n s e t a n d then b e c o m e s t h e t h i r d
o r t r a i l i n g c o l u m n o n s o r p t i o n . T h i s t y p e o f system e n a b l e s
the ion e x c h a n g e zone to extend over two sorption columns thereby
a l l o w i n g the c o l u m n s to be operated at higher l i n e a r v e l o c i t i e s
of l i q u i d flow.
After the l o a d e d resin is b a c k w a s h e d , it is transferred
to the empty e l u t i o n column w h i c h then becomes the t r a i l i n g c o l u m n
on e l u t i o n . This e n a b l e s the v o l u m e of e l u a n t to be applied
in three e q u a l amounts instead of two (as p r a c t i s e d w i t h f i x e d
bed c o l u m n s e m p l o y i n g recycled e l u a n t ) which increases the strength
of e l u a t e and a l s o e n a b l e s a c o l u m n to be m a d e a v a i l a b l e for
sorption in a shorter space of time.
The sorption and e l u t i o n c o l u m n s are a l m o s t f u l l of r e s i n
as t h e y do not r e q u i r e any freeboard for b a c k w a s h i n g the resin.
Also there a r e fewer c o n t r o l s r e q u i r e d t h a n a r e c u s t o m a r y o n
f i x e d bed systems where each set must h a v e flow c o n t r o l l e r s for
sorption, backwash and e l u t i o n .
T h e r e are s e v e r a l of these resin movement plants i n s t a l l e d
in E l l i o t Lake, C a n a d a in the late 1950's u s i n g 2450 mm d i a . (8'
-0") pressure vessels for c o n t a i n i n g the resin.
It t a k e s a b o u t 20 m i n u t e s to transfer a p p r o x i m a t e l y 13 m3
r e s i n at a l i q u i d flow of 22 m^/h. At the end of that time it
has been found t h a t a b o u t 30 to 60 l i t r e s of resin r e m a i n at
the bottom of the unit. This is of no consequence in the backwash
and e l u t i o n c o l u m n s but it is m o s t u n d e s i r a b l e in the case of
the sorption c o l u m n s . The l o a d e d resin left b e h i n d is i m m e d i a t e l y
covered with eluted resin from the e l u t i o n set and the c o l u m n
is placed in the t r a i l i n g p o s i t i o n on sorption. The "Royal Barren"
effect so produced necessitates r e c y c l i n g back to l e a c h a l a r g e
p e r c e n t a g e of the b a r r e n . The r e c y c l i n g of 20 - 25% was not
uncommon but e v e n so the a v e r a g e b a r r e n e f f l u e n t to t a i l i n g s

58
 FIG. 2: PORTER-ARDEN MOVING BED SYSTEM

was often in excess of 0.005 UßOg as compared with less than

0.001 g L^OS/I f r o m f i x e d bed s y s t e m s in the s a m e a r e a .
These s y s t e m s were automated so that all the resin transfers
and e l u t i o n s were c o n d u c t e d a u t o m a t i c a l l y . A more c o m p l e t e des-
cription is given elsewhere [ 2 ] .

Resin Attrition

I n a n y i o n e x c h a n g e s y s t e m t h e r e i s some r e p l a c e m e n t o f
resin r e q u i r e d from time to time. The l i f e of resin depends
upon m a n y f a c t o r s , t h e p r i n c i p l e ones b e i n g : -

1. the m a t e r i a l from w h i c h the r e s i n is m a d e .

2. the p h y s i c a l f o r c e s to which it is subjected

in u s e .

59
 3. the s w e l l i n g and s h r i n k i n g which may occur when
g o i n g from one i o n i c form to another.
M o s t r e s i n s in use today are based on a co-polymer styrène
and the m e t h o d s used by the major r e s i n m a n u f a c t u r e r s r e s u l t
in a f a i r l y r o b u s t m a t e r i a l . Nevertheless, it is important to
m i n i m i z e the rate of a t t r i t i o n by t a k i n g s u i t a b l e p r e c a u t i o n s
in the design of systems.
D u r i n g the f o r m a t i o n of the resin beads there are u s u a l l y
some i n t e r n a l stresses which result in c r a c k s a p p e a r i n g in the
finished m a t e r i a l . These show up q u i t e c l e a r l y under a microscope
and it is these beads w h i c h w i l l break down most q u i c k l y in use.
W h e n a new b a t c h of resin is p l a c e d in o p e r a t i o n therefore the
first 30 to 50 c y c l e s s h o u l d see m o s t of these c r a c k e d b e a d s
b r o k e n down and removed d u r i n g normal b a c k w a s h i n g as resin fines.
Thereafter the rate of a t t r i t i o n s h o u l d f a l l to a s t e a d y l e v e l
e s t a b l i s h e d by m e c h a n i c a l and c h e m i c a l effects. The fixed bed
systems in E l l i o t Lake are reported to h a v e a r e s i n m a k e - u p of
2 1/2% per a n n u m a l t h o u g h there are no firm records to substantiate
this. The m o v i n g bed systems h a v e b e e n shown to h a v e a r e s i n
m a k e - u p of about 10% per a n n u m .
The m e c h a n i c a l forces w h i c h affect a t t r i t i o n are such t h i n g s
as h i g h présure losses across the resin bed. This c o u l d be the
result of e x c e s s i v e l y h i g h flow rates or an a c c u m u l a t i o n of dirt
or slimes on the resin. The resin b e i n g a polyelectrol y te acts
as a very effective f i l t e r and a dense mat of such arrested i m p u r i t i e s
can r e a d i l y form on the surface of a p a c k e d bed of r e s i n and
cause a c o n s i d e r a b l e resistance to flow. Sometimes resin fines,
if not backwashed from the bed, w i l l t h e m s e l v e s cause a c o n s i d e r a b l e
increase in pressure loss. This is because these smaller p a r t i c l e s
of resin in the bed w i l l reduce the v o i d a g e . The pressure l o s s
t h r o u g h the bed is g r e a t l y affected by v o i d a g e since it v a r i e s
i n v e r s e l y as the third power of the v o i d a g e .
It also must be recognized that the resin beads can be deformed
under pressure and this decreases the void volume. For e x a m p l e
a bed of p o l y s t y r e n e b e a d r e s i n 1000 mm deep may be compacted
by 40 mm when subjected to a s u p e r f i c i a l f l o w of 180 m/h (75
U.S. gpm/ft 2 ). if we assume an i n i t i a l v o i d a g e of 0.4 then this
is reduced to 0.375 and the p r e s s u r e d r o p i n c r e a s e s by 18%.
H o w e v e r , any traces of suspended matter at such flow rates w i l l
increase this loss d r a m a t i c a l l y .
A p o i n t of i n t e r e s t here w h i c h is worthy of further study
is the observation by G o l d i n g & I r v i n g [3] that the p r e d i c t e d
i n c r e a s e in p r e s s u r e loss t h r o u g h a compacted bed is somewhat
greater than that a c t u a l l y found i n p r a c t i c e . A n e x p l a n a t i o n
they offer is t h a t o n l y part of the v o l u m e change is due to a
reduction in v o i d a g e . The r e m a i n i n g v o l u m e c h a n g e m u s t be by
s q u e e z i n g water out of the b e a d s t h u s d e c r e a s i n g t h e i r size.
This c o u l d a d v e r s e l y affect t h e k i n e t i c s o f e x c h a n g e t h e r e b y
r e q u i r i n g longer contact times.
In E l l i o t Lake the fixed bed systems are o p e r a t i n g at flow
rates in the region of 10 m/h s u p e r f i c i a l v e l o c i t y (4 U.S. gpm/ft2).
In South Africa it is usual for fixed beds to operate at l o w e r
rates in the region of 4 to 7 m/h due to the lower rate of ion
exchange caused by competition from other i o n s and b l o c k a g e of
resin pores with s i l i c a .
The l a r g e r the d i a m e t e r of the r e s i n bead the s m a l l e r is
the pressure d r o p t h r o u g h the b e d . H o w e v e r , the rate of ion
exchange with coarse beads is slower because there is less surface
area of the b e a d s per u n i t v o l u m e of wet settled r e s i n since
this v a r i e s i n v e r s e l y with the diameter of the beads.

60
 The é l u t i on or r e g e n e r a t i o n of the r e s i n m u s t be done so
as to m i n i m i z e the c h a n g e in v o l u m e w h e n g o i n g from one form
of the resin to another. The s u d d e n c o n t r a c t i o n of a resin bead
brought into contact with a strong e l e c t r o l y t e c r e a t e s stresses
on the resin which can shatter the outer shell and this may then
peel o f f l i k e a n o n i o n s k i n . T h i s t y p e o f f a i l u r e g e n e r a l l y
referred to as osmotic shock, is more common when the resin is
in its most swollen form, i.e. the h y d r o x y l form and is b r o u g h t
into contact with a strong a c i d in the r e g i o n of 20% - 30% ^$04.
Treatment of Eluate
As m e n t i o n e d e a r l i e r the u r a n i u m is p r e c i p i t a t e d from the
eluate as yellow cake and this i n v o l v e s r a i s i n g the pH by a d d i n g
a n a l k a l i such a s c a u s t i c s o d a , m a g n e s i a o r a m m o n i a . A m m o n i a
is most frequently used but e n v i r o n m e n t a l r e g u l a t i o n s are c a u s i n g
u r a n i u m producers to look toward l i m e and m a g n e s i a . Iron being
less strongly held by the r e s i n is e l u t e d off f i r s t so t h a t a
separate cut can be made if the iron is of a s i g n i f i c a n t amount.
Sometimes the first two bed v o l u m e s or so c o n t a i n i n g the i r o n
and some u r a n i u m are returned to l e a c h .
A two stage precipition of the e l u a t e is g e n e r a l l y employed,
in the first of which a s m a l l amount of l i m e is added along with
a m m o n i a (or other a l k a l i ) to raise the pH to a r o u n d 3.5. T h i s
c a u s e s the p r e c i p i t a t i o n of g y p s u m for r e d u c t i o n of s u l p h a t e
and the ferric iron. By a d d i n g more a l k a l i the u r a n i u m is p r e -
c i p i t a t e d around pH 6.5 w h i c h is used to make up fresh eluant.
This barren eluate contains s u l p h a t e that has been e l u t e d
off the r e s i n w i t h the u r a n i u m and this should not be a l l o w e d
to b u i l d up to more than about 30 g/1 when nitrate is used for
e l u t i o n . C h l o r i d e c a n e l u t e s a t i s f a c t o r i l y a t somewhat h i g h e r
l e v e l s but the gypsum p r e c i p i t a t i o n can c o n v e n i e n t l y keep the
sulphate under control.
El uex
W h e n s u l p h u r i c a c i d is used as an e l u a n t , the a m o u n t of
free acid in the e l u a t e is g e n e r a l l y s u c h t h a t some r e c o v e r y
system is required to reduce the cost of o p e r a t i o n . It is usual
for fixed bed systems to send the strong e l u a t e to a s o l v e n t
e x t r a c t i o n p l a n t to extract and further concentrate the u r a n i u m
and r e t u r n the a c i d r a f f i n a t e for f u r t h e r use as an e l u a n t .
The s o l v e n t used a l s o m a k e s a s a t i s f a c t o r y s e p a r a t i o n of any
ferric iron and other i m p u r i t i e s t h a t may h a v e been taken up
by the r e s i n thus o b v i a t i n g the need for the precipitation of
iron. This treatment of eluate by solvent extraction is referred
to as an E l u e x system in North America and as Bufflex in South
Africa.
Royal Barren
W h e n the resin is e l u t e d the majority of its a c t i v e sites
are occupied by the ions that have d i s p l a c e d the u r a n i u m . However,
t h e r e w i l l s t i l l be some u r a n i u m left on the resin as it would
require an excessive amount of e l u a n t to strip off all the u r a n i u m .
The amount u s u a l l y left on the r e s i n is about l g 11303/1 or below
w h i c h is the level at which b a r r e n e f f l u e n t s in the r e g i o n of
0.001 g/1 or less can be a c h i e v e d .
The eluted column of resin is p l a c e d in the t r a i l i n g p o s i t i o n
of the sorption c o l u m n s so it receives barren s o l u t i o n from the
p r e c e d i n g c o l u m n . The e x c h a n g e a b l e a n i o n s in the a c i d i c barren

61
s o l u t i o n d i s p l a c e s t h e e l u t i n g I o n from t h e r e s i n a n d d e p e n d i n g
upon the t y p e of ion u s e d for e l u t i o n w i l l form h y d r o c h l o r i c ,
n i t r i c o r s u l p h u r i c a c i d until a l l t h e e l u t i n g ions h a v e t h e m s e l v e s
been e l u t e d . T h i s w a v e of a c i d p a s s i n g through the bed along
with any residual eluant l e f t in the r e s i n bed w i l l s t r i p off
some of the few remaining uranium ions on the resin and result
i n w h a t i s termed a " R o y a l B a r r e n " . B e c a u s e o f t h e u r a n i u m c o n t e n t
the f i r s t few bed volumes are u s u a l l y returned to the leach c i r c u i t .
It w i l l be perceived that this w i l l a l s o i n t r o d u c e c h l o r i d e or
nitrate ions in the l e a c h liquor. S i n c e chloride and nitrate
ions compete with uranium for s i t e s on the r e s i n the b u i l d - u p
in the l e a c h c i r c u i t of such ions must not be a l l o w e d to reach
such l e v e l s as to reduce the l o a d i n g of u r a n i u m to any s e r i o u s
degree .
The c o n c e n t r a t i o n o f n i t r a t e i n t h e R o y a l B a r r e n c a n r a n g e
f r o m 10 to 15 g N O ß / l r e s u l t i n g in the u r a n i u m c o n t e n t b e i n g
a r o u n d 0 . 0 5 to 0.1 g UßOß/l • W h e n t h i s is r e t u r n e d to the l e a c h
c i r c u i t the n i t r a t e content in the pregnant liquor may f l u c t u a t e
b e t w e e n 0.7 to 1 .0 g

Sorption from A l k a l i n e Solutions

The sorption from a l k a l i n e leaches depends upon the concentration
of u r a n i u m , carbonate and b i c a r b o n a t e in m u c h the same way as
i n a c i d l e a c h i n g where i t i s d e p e n d e n t u p o n u r a n i u m s u l p h a t e
and b i s u l p h a t e . High concentrations of carbonate or b i c a r b o n a t e
result in low u r a n i u m l o a d i n g s on the resin. At ambient temperatures
the best uranium l o a d i n g s are obtained around pH 10 and above.
I n t e r f e r e n c e in the l o a d i n g of u r a n i u m is also experienced
from sulphate, c h l o r i d e and nitrate ions but for a g i v e n concentration
t h e y d e p r e s s the u r a n i u m l o a d i n g to a g r e a t e r degree than in
the acid l e a c h i n g process. This reduces the p o s s i b i l i t y of re-
c i r c u l a t i n g any " R o y a l B a r r e n " to the l e a c h c i r c u i t since the
b u i l d - u p of c h l o r i d e s , nitrates or s u l p h a t e c o u l d s e r i o u s l y affect
the l o a d i n g of u r a n i u m .
Anionic complexes of phosphate, a l u m i n a t e and molybdate
are m u c h less strongly held than the u r a n y l tricarbonate complex
so t h a t a f a i r l y good s e p a r a t i o n is effected by ion exchange
from such solutions.
The competition from v a n a d i u m in a l k a l i n e solutions depends
upon the pH of the solution and when v a n a d i u m is p r e s e n t it is
p r e f e r a b l e to o p e r a t e in the r e g i o n of pH 11 or so. At pH 9
v a n a d i u m can d i s p l a c e the uranyl tricarbonate ion quite e f f e c t i v e l y
and as suggested e a r l i e r , it presents an i n t e r e s t i n g p o s s i b i l i t y
for the recovery of u r a n i u m and v a n a d i u m in separate fractions.
E l u t i o n of U r a n y l Tricarbonate
A s a l r e a d y known, c h l o r i d e , nitrate a n d s u l p h a t e w i l l d i s p l a c e
u r a n y l tricarbonate ions and the lowest cost a n i o n of these is
c h l o r i d e . As a result, sodium c h l o r i d e is often used as an e l u a n t
but s u i t a b l e care m u s t be t a k e n to p r e v e n t the c o n c e n t r a t i o n
of c h l o r i d e s b u i l d i n g up to such l e v e l s in the l e a c h circuit
that it interferes with u r a n i u m l o a d i n g . A m m o n i u m c h l o r i d e with
some carbonate is another type of e l u a n t in use.
In much the same way as acid is added to the e l u t i n g agents
of u r a n y l t r i s u l p h a t e so is it found d e s i r a b l e to add some b i c a r b o n a t e
to the c h l o r i d e s o l u t i o n for most e f f e c t i v e l y e l u t i n g u r a n y l
tri carbonate.
C h l o r i d e e l u a n t s u s u a l l y are between 1 ,to 1.5 m o l a r and
the a m o u n t of b i c a r b o n a t e to i n s u r e good s t r i p p i n g is in the
region of 0.2 to 0.5 molar.

62
 A m m o n i a can a l s o be used for é l u t i o n a l o n g w i t h CO 2 f° r
the formation of bicarbonate. Such a technique e n a b l e s recovery
of a m m o n i a from the e l u a t e to be o b t a i n e d for r e c y c l i n g . It
also o v e r c o m e s the p r o b l e m of c o n t a m i n a t i n g the l e a c h l i q u o r
with c o m p e t i n g anions.
Types of Resin in Use
The most c o m m o n resins used for u r a n i u m recovery in North
America and South Africa are the gel type strong base polystyrene
b e a d r e s i n s e x a m p l e s of w h i c h are R o h m & H a a s IRA 400, Dowex
21K, D u o l i t e A101D and lonac 641.
There has been some a p p l i c a t i o n of m a c r o r e t i c u l a r weak base
resins with the i n t e n t i o n of o b t a i n i n g a better s e p a r a t i o n of
i r o n and u r a n i u m . However, such resins are r e l a t i v e l y slow in
sorption and e l u t i o n rates and the u r a n i u m l o a d i n g of the r e s i n
has been found to be somewhat less than for strong base resins;
l e v e l s of 30 - 35 g UßOß/l are not uncommon when treating a 1
g/1 p r e g n a n t solution. B e i n g a m a c r o p o r o u s r e s i n , it is prone
to b l o c k a g e w i t h s i l i c a w h i c h contributes to its slow exchange
rates. B e c a u s e of its tertiary ion exchange groups it can m a k e
a b e t t e r i r o n s e p a r a t i o n on the a v e r a g e l e a c h l i q u o r than the
q u a t e r n a r y groups of the strong base resins and it can be eluted
w i t h a l o w e r v o l u m e of e l u a n t . H o w e v e r , the weak base resins
presently a v a i l a b l e d o n o t a p p e a r s u f f i c i e n t l y a t t r a c t i v e f o r
use in u r a n i u m extraction at this time.
The p a r t i c l e size of the resin must be c h o s e n to s u i t the
p a r t i c u l a r a p p l i c a t i o n for which it is intended. The smaller
the p a r t i c l e size, the more r a p i d are the e x c h a n g e rates but
the pressure loss through a packed bed of s m a l l resin beads becomes
s i g n i f i c a n t l y greater at any g i v e n flow rate as it v a r i e s i n v e r s e l y
w i t h the square of the diameteer of the bead.
If the resin is to be used in a f l u i d i z e d b e d , t h e n some
c o n s i d e r a t i o n m u s t b e g i v e n t o i t s d e n s i t y a n d p a r t i c l e size
from the s t a n d p o i n t of its f l u i d i z a t i o n properties. For d i l u t e
s o l u t i o n s , a large bead resin with its slower exchange k i n e t i c s
may e n a b l e u r a n i u m to be extracted at a faster rate t h a n u s i n g
a s m a l l e r b e a d for w h i c h the f l o w rate m u s t be restricted to
prevent e l u t r i a t i o n of the resin from the column.
The s e t t l i n g rate of the resin becomes more i m p o r t a n t when
d e a l i n g with l e a c h l i q u o r s c o n t a i n i n g large amounts of suspended
m a t t e r . L e a c h p u l p s c o n t a i n i n g 7% to 10% s o l i d s have not only
a h i g h e r apparent density but also the viscosity may be affected
by the nature of the solids in suspension.
R e c o g n i z i n g this fact,there h a s b e e n some a t t e n t i o n g i v e n
o v e r r e c e n t y e a r s to the d e v e l o p m e n t of an ion exchange resin
h a v i n g a g r e a t e r d e n s i t y t h a n those p r e s e n t l y a v a i l a b l e . I n
recent y e a r s S e n t r a c h e m L i m i t e d in South Africa have d e v e l o p e d
a heavy resin named Senbrix but no commercial experience is a v a i l a b l e
at this time.
Resin-in-Pulp
F o r m a n y years c o n s i d e r a b l e a t t e n t i o n h a s been g i v e n t o
methods whereby ion exchange resin beads can be loaded with u r a n i u m
without first h a v i n g to c l a r i f y the p r e g n a n t s o l u t i o n thus s a v i n g
space, c a p i t a l and operating costs [4].
E a r l y a t t e m p t s were made employing stainless steel baskets
m o v i n g up and down in tanks arranged to operate in a counter-current
fashion [5]. At the Anaconda Company's Blue Water p l a n t 14 tanks
5' x 6' x 50' long were installed in series each of w h i c h contained
ten 4' c u b i c l e baskets. W h e n the resin in the first tank is

63
saturated, the tank is d r a i n e d and rinsed and a new tank c o n t a i n i n g
eluted resin is added at the end of the series. The tank c o n t a i n i n g
the loaded resin is then a d d e d to the series of t a n k s f o r m i n g
the e l u t i o n section in which it becomes the last tank on l i n e .
When the resin is completely eluted it is rinsed and made a v a i l a b l e
for use in the sorption section. These i n s t a l l a t i o n s were very
cumbersome and the resin a t t r i t i o n was f o u n d to be e x c e s s i v e .
The h i g h m a i n t e n a n c e costs for the baskets and associated m e c h a n i s m
led to the abandonment of the process and in 1983 there c o u l d
have been o n l y one of those i n s t a l l a t i o n s in service.
A different approach was made by Homestake M i n i n g in treating
a l a r g e v o l u m e of m i n e water from a d r a i n a g e ditch. Downflow
operation was unsuccessful because the slimes b l i n d e d the r e s i n
bed. T h e y used two 14' d i a . x 8' deep t a n k s e a c h c o n t a i n i n g
400 cu. ft. of resin. U p f l o w o p e r a t i o n in s e r i e s was c a r r i e d
out and w h e n the first c o l u m n was loaded the resin was removed
and taken by truck to the m i l l 16 m i l e s away for e l u t i o n [6].
O t h e r f l u i d i z e d systems h a v e b e e n i n s t a l l e d f o r treating
acid l e a c h l i q u o r s c o m p r i s i n g a s e r i e s of t a n k s t h r o u g h w h i c h
the s l u r r y and resin passed in counter-current d i r e c t i o n . A g i t a t o r s
in each tank keep t h e r e s i n m i x e d w i t h t h e s l u r r y a n d a n a i r
l i f t or a p u m p is used to take the r e s i n from one chamber to
the next. The tanks are at different e l e v a t i o n s to obtain g r a v i t y
l i q u i d flow but the resin is carried up by an air l i f t (or p u m p )
to some s t a i n l e s s steel Sweco screens w h i c h s e p a r a t e the r e s i n
from the s l u r r y . The s l u r r y is t r a n s f e r r e d downstream to the
next tank and the resin is transferred u p f l o w to the p r e c e d i n g
t a n k . A t y p i c a l s c r e e n - m i x r e s i n - i n - p u l p system is shown in
Figure 3 [7]. Western N u c l e a r i n s t a l l e d e i g h t sorption v e s s e l s
13' d i a . x 14' h i g h o p e r a t i n g at 3.75 gpm/sq.ft. and l o a d i n g s
of 2.5 I b s . 11308/cu. ft are r e p o r t e d . There are fifteen 7'
dia x 8' deep e l u t i o n vessels operating at 1.25 gpm/sq.ft. p r o d u c i n g
a strong eluate of around 12 g U^QQ/I .
Other i n s t a l l a t i o n s of e q u i p m e n t e m p l o y i n g a number of tanks
with air l i f t s i m i l a r to Western N u c l e a r are A t l a s M i n e r a l s Cor-
p o r a t i o n , Moab M i l l , Federal A m e r i c a n P a r t n e r s ' M i l l a n d U n i o n
C a r b i d e Corporation Gas H i l l ' s plant. The latter has six stages

Air lift

Splitter

Slii^e slurry
f r o m unit 3
Surre slurry —, |
from unit 2 • • '

To unit

Air ociicred
mix Tonfc

Unit 4
r>-A„

FIG. 3: SCREEN-MIX RESIN-IN-PULP SYSTEM (Two Unto Shown)

64
on sorption and ten on élut ion and the a v e r a g e l o a d i n g of the
resin is 3 l b s / c u . ft. These systems have been well described
and illustrated by Merritt [8].
Most of these m i l l s are in the United States in areas where
the slimes are very d i f f i c u l t to separate as c o m p a r e d to the
E l l i o t L a k e area where s e p a r a t i o n is somewhat s i m p l e r due to
the structure of the ore.
A d v a n t a g e of F l u i d i z e d Beds
There are some distinct advantages in using a l i q u i d fluidized
bed of ion exchange resin instead of a packed b e d , a m o n g w h i c h
are :
1. Low pressure drop - approximately equal to
the weight of the suspended particles per
u n i t area of bed.
2. Suspended solids can pass straight through
the bed - thus a v o i d i n g the need for prior
f i l t r a t i o n when solids removal is not
mandatory for other reasons.
3. Any change in volume of resin resulting
from mass transfer can easily be accommodated.
This avoids possible crushing of resin in
those cases where the resin expands in v o l u m e
d u r i n g its loading cycle.

Continuous Ion Exchange

For m a n y years there has been an interest in ion exchange
systems which can operate continuously instead of the batch type
process characterized by fixed bed systems. Continuous ion exchange
processes offer economic a d v a n t a g e s in those cases where l a r g e
a m o u n t s of i o n s are required to be exchanged per day. This is
because the resin inventory in a continuous system would be m u c h
less than that required by a well designed fixed bed system for
the same recovery process. Such systems therefore are p a r t i c u l a r l y
s u i t e d to h y d r o m e t a l 1 u r g i c a l processes or any other a p p l i c a t i o n
where the product of flow and ionic concentration is h i g h .
The f l u i d i z e d bed systems d e s c r i b e d e a r l i e r e m p l o y i n g a
number of tanks arranged horizontally in series could, when automated,
be c o n s i d e r e d as a c o n t i n u o u s ion e x c h a n g e system. However,
the amount of space taken up by the tanks a l o n g with the p r o v i s i o n
of screens for separating slimes from the resin with the consequent
maintenance of those screens and the number of pumps or consumption
of air for resin transfer r e s u l t e d in a t t e m p t s b e i n g made at
h a v i n g one tall column containing f l u i d i z e d resin.
It is known that when the d e n s i t y d i f f e r e n c e between the
fluid and particles is small, the entire bed e x p a n d s u n i f o r m l y
and p a r t i c u l a t e f l u i d i z a t i o n is a c h i e v e d . Any differences in
settling v e l o c i t i e s of p a r t i c l e s due to size or d e n s i t y l e a d
to s e g r e g a t i o n or c l a s s i f i c a t i o n and when d y n a m i c e q u i l i b r i u m
conditions are achieved the larger p a r t i c l e s are below. There
is no gross m i x i n g other than the d i s t u r b a n c e s created within
the f l u i d stream lines and the small amount caused by the coarser
particles passing through the bed during the segregation.
The moving and fluidized particles create a "choke " effect
upon the rising l i q u i d and a steady state turbulence is achieved.

65
This is local and much less circulation of particles occurs than
is g e n e r a l l y o b s e r v e d with gas fluidized beds. If there is no
excessive disturbance apparent on the surface then it is an i n d i c a t i o n
that good flow distribution is achieved.
In 1951 a process was investigated in w h i c h a vertical fluidized
bed ion e x c h a n g e c o l u m n c o n t a i n i n g a strongly a c i d i c bead type
c a t i o n resin was used for the extraction of copper [9], It was
o b s e r v e d t h a t the d e g r e e of l o n g i t u d i n a l m i x i n g of the resin
is i n f l u e n c e d by differences in diameter or density of the particles
in the bed. From the p r i n c i p l e s of e l u t r i a t i o n a bed is c l a s s i f i e d
with the largest beads at the bottom Such c l a s s i f i c a t i o n is
u n d e s i r a b l e in a continuous system and it is therefore necessary
that resin particles of nearly uniform diameter should be used.
H o w e v e r , in a c o n t i n u o u s ion e x c h a n g e system it is necessary
that the resin be moved around from the sorption section to the
é l u t ion section and therefore some r e s i n attrition must occur
which w i l l destroy any i n i t i a l uniformity of resin p a r t i c l e size.
O v e r the y e a r s a n u m b e r of systems have been proposed and
many patents taken out of v a r i o u s designs. These h a v e i n c l u d e d
systems in which the resin bed is compacted as well as m a n y systems
where the resin is f l u i d i z e d .
M a n y of these h a v e been r e v i e w e d by Slater [10] but o n l y
a few have been used in f u l l s c a l e c o m m e r c i a l p l a n t s . It is
proposed to mention only those which are presently being a p p l i e d
to recovery of u r a n i u m from leach l i q u o r s .
Higgins Column
The first of these is a packed bed system which was invented
around 1950 by I. H i g g i n sa t O a k R i d g e N a t i o n a l L a b o r a t o r y . l t
was d e v e l o p e d by Chemical Separations in Tennessee and has been
used for w a t e r s o f t e n i n g and c h e m i c a l r e c o v e r y systems. T h e
d e s c r i p t i o n of the process has b e e n g i v e n by H i g g i n s [11] and
it is depicted by Figure 4.

Overflow to resm
ond recycle tonk

R i n s e liquor
pulse
control

-T~l Conductivity controller

Waste —c£j
E I ua nt
E Iuate
or
product

FIG. HIGGINS COLUMN

66
 It c o m p r i s e s a l o o p a r o u n d w h i c h resin is moved in slugs.
The resin moves upwards in the Contacting Section where sorption
t a k e s p l a c e and the flow of l i q u i d is c o u n t e r - c u r r e n t to the
flow of resin. At the same time e l u a n t is p a s s i n g t h r o u g h the
e l u t i n g section of the loop a g a i n in a counter-current direction.
The sorption and elution sections c o n t a i n h o r i z o n t a l flow d i s -
t r i b u t o r s and c o l l e c t o r s of the J o h n s o n W e l l Screen type and
are u s u a l l y made of 316 stainless steel wedgewire with s u i t a b l e
rei nforcement.
The feed and e l u a n t flows are i n t e r r u p t e d after s e v e r a l
minutes of o p e r a t i o n to a l l o w e l u t e d r e s i n to be p u l s e d into
the bottom of the contacting section. The period of the sorption
cycle may be from 5 to 20 m i n u t e s or more d e p e n d i n g u p o n the
feed f l o w rate and c o n c e n t r a t i o n . D u r i n g this time v a l v e s A,
B, C and D are c l o s e d and e l u t i o n is p r o c e e d i n g . At the end
of the s o r p t i o n c y c l e v a l v e s A, B and C are opened and water
under pressure from an h y d r a u l i c accumulator is i n t r o d u c e d into
the P u l s e S e c t i o n through v a l v e 7 w h i c h forces resin to move
smartly around the loop. V a l v e s A, B and C are then closed and
the feed s o l u t i o n and e l u a n t s o l u t i o n flows are resumed. The
time for movement of resin is u s u a l l y less than a minute so that
the ratio of sorption time to resin movement time is large.
When t h e r e s i n i s p u l s e d a r o u n d t h e l o o p , t h e l i q u i d i n
t h e e l u a n t l o o p i s a l s o d i s p l a c e d w i t h r e s i n . T h i s requires
a flow of rinse water to enter through v a l v e 3 u n t i l the eluant
is restored to its proper position as indicated by the c o n d u c t i v i t y
controller. The e l u t i n g solution d i s p l a c e s the pulse water through
the waste v a l v e 5 w h i c h then closes and v a l v e 8 opens to a l l o w
product or strong e l u a t e to be r e c o v e r e d . T h i s d i s p l a c e m e n t
is also c o n t r o l l e d by a c o n d u c t i v i t y probe.
The resin that was d i s p l a c e d from the C o n t a c t i n g Section
goes to the R e s i n Storage area in which it is backwashed by opening
v a l v e 6. The w a s h e d r e s i n is a l l o w e d to f a l l i n t e r m i t t e n t l y
by g r a v i t y i n t o the p u l s e section by o p e n i n g and c l o s i n g v a l v e
D. When the p u l s e c o n t r o l l e r senses that the correct v o l u m e
of r e s i n has settled in the Pulse Section the c y c l i n g of v a l v e
D ceases and the resin is ready for transfer on the next r e s i n
movement cycle.
As the r e s i n is in a p a c k e d form, the f l o w rates can be
somewhat h i g h e r than are achieved in systems w h i c h e m p l o y f l u i d i z e d
b e d s of r e s i n . H o w e v e r , the p r e s s u r e l o s s a c r o s s the bed at
very h i g h flow rates can result in short resin life. Also, the
pressure required to d r i v e the resin around the c i r c u i t , through
b u t t e r f l y v a l v e s and c o n v e r g i n g cones and around the flow distributors
and c o l l e c t o r s can be v e r y h i g h . T h i s is u s u a l l y between 400
to 550 k i l o p a s c a l s (60 to 80 p s i ) and i n d i c a t e s the h i g h frictional
forces in the loop. The butterfly v a l v e s operate in the resin
stream and these open and close r a p i d l y on the resin which m u s t
be extremely tough if the resin attrition is to be low. Nevertheless,
there are some s i t u a t i o n s where such a system has been shown
to h a v e m e r i t and these are u s u a l l y when the flow rate and the
frequency of p u l s e s are low and the l i q u i d g o i n g t h r o u g h the
system contains very l i t t l e suspended matter.
Two 2400 mm dia (8'-0") u n i t s for u r a n i u m recovery were
i n s t a l l e d in 1977 for W y o m i n g M i n e r a l s C o r p o r a t i o n to extract
u r a n i u m from copper leach solutions at the B i n g h a m C a n y o n M i n e
of K e n n e c o t t C o p p e r C o r p o r a t i o n [12], These were designed to
treat a flow of 7600 U.S. gpm (1727 m 3 /h) c o n t a i n i n g about 6
to 7 ppm UßOg which shows a specific flow rate of 67 U.S. gpm/ft^
or 163 m/h. It was found that the h i g h flow rate r e s u l t e d in
e x c e s s i v e p r e s s u r e losses w h i c h r e s u l t e d in c r u s h i n g the gel

67
type resin. To correct this the l e n g t h of the sorber s e c t i o n
was r e d u c e d f r o m 8'- 0" ( 2 4 4 0 mm) to 5 ' - 0 " ( 1 5 2 5 mm) and an a d d i t i o n a l
unit was a d d e d w h i c h brought the f l o w rate down to 45 U . S . g p m / f t 2
(110 m / h ) . A l s o the gel resin was replaced with m a c r o r e t i c u l ar
or m a c r o p o r o u s r e s i n . The r e s i n is r e g e n e r a t e d w i t h 3 N H2$04
and p r o d u c e s an e l u a t e of 0.5 to 1 .0 g U^QQ/] w h i c h is s u b s e q u e n t l y
u p g r a d e d b y s o l v e n t e x t r a c t i o n ( E l u e x ) t o a r o u n d 3 5 g 1)303/1.
The b a r r e n e f f l u e n t is u s u a l l y around 0.5 mg U30fl/l . R e s i n re-
placement due to attrition and l o s s of k i n e t i c s is r e p o r t e d to
be a b o u t 70% of the i n v e n t o r y per annum.

U.S. B u r e a u of Mines Column

In the 1 9 6 0 ' s two s y s t e m s were d e v e l o p e d in w h i c h a v e r t i c a l

c o l u m n i s d i v i d e d into s e p a r a t e c o m p a r t m e n t s b y h o r i z o n t a l p e r f o r a t e d
b a f f l e p l a t e s . O n e o f these u n i t s a s d e v e l o p e d b y t h e U . S . b u r e a u
of M i n e s is shown in Fiqure 5 [ 1 3 , 1 4 ] .

Barren
solution-

(l-inch
on 4-inch
ûboul 5'6 pcf
orid'ce a r e a )

Feed solution

FIG. 5: Multiple compartment

ion exchange column,
Resin outlet U.S. BUREAU OF MINES

The perforations in the b a f f l e plates, d i v i d i n g the compartments

represent about 5% of the cross-sectional area of the column.
Each of the compartments contains resin and the upward flow
of l i q u i d prevents the resin from f a l l i n g t h r o u g h the h o l e s in
the baffle plates.
When breakthrough occurs at the top of the column, the flow
is stopped and a reverse flow enables loaded resin to be removed
from the bottom of the column to be eluted. At the same time,
resin falls down the column from one chamber to another and eluted
resin is fed into the top.

68
 The l o a d e d resin is fed into the top of a tall elution column
of s i m i l a r d e s i g n to the sorption c o l u m n where it meets an upward
f l o w of e l u a n t . The strong e l u a t e passes from the top of the
c o l u m n w h i l s t the e l u t e d r e s i n is d r a w n from the base of the
column.
D e t a i l e d descriptions give performance data on v a r i o u s solutions
r a n g i n g from 0.009 g U^ÛQ/I to 0.74 g U308/ 1 • Resin l o a d i n g s
from 37 g/1 to 76 g/1 are reported and s t r o n g e l u a t e s of 23.8
9 U30«/l were obtained when e l u t i n g resin c o n t a i n i n g 72 g u^Oa/l • 2
On d i l u t e s o l u t i o n s {9 ppm 1)303) flow rates up to 19.5 gpm/ft
were a c h i e v e d with a 98% recovery of U^OQ when l o a d i n g the resin
up to 46 g U3Û8/1 •
M e s s r s George and R o s e n b a u m [14] state that "an essential
requirement for the successful operation of the m u l t i p l e compartment
c o l u m n is a resin of uniform p a r t i c l e size... Resins of conventional
mesh size 0.3 to 0.8 m i l l i m e t e r s diameter (20 to 50 mesh) cannot
be used b e c a u s e the r e s i n p a r t i c l e s c l a s s i f y according to size
and the finer particles either accumulate on the upper sections
or overflow". The accumulation of s m a l l , p a r t i a l l y loaded resin
particles in the upper sections m i l i t a t e s a g a i n s t o b t a i n i n g low
b a r r e n v a l u e s . A d u r a b l e and c l o s e l y sized resin is therefore
d e s i r a b l e for use in this system.
Systems of this type are in operation in v a r i o u s locations
of the U n i t e d States. O p e r a t i o n a l d a t a has been p u b l i s h e d by
George [13].
Cloete-Streat Column
A somewhat s i m i l a r column was developed in E n g l a n d at Imperial
College by Cloete and Streat [15,16].
The s o r p t i o n c o l u m n is d i v i d e d into a number of sections
by horizontal perforated plates. Two p e r f o r a t e d b a f f l e p l a t e s
for e a c h c o m p a r t m e n t are placed f a i r l y close together with the
open holes offset. The purpose of this is to ensure t h a t when
flow stops the resin does not all f a l l through the perforated
plates and settle at the bottom of the c o l u m n . L i q u i d enters
the bottom of the c o l u m n and eluted resin is fed into the top
of the column. See Figure 6.
W h e n s o l u t i o n is f l o w i n g up through the adsorption column
each compartment w i l l be f i l l e d to the full depth by the expanded
resin bed. If the flow increases the excess resin moves up into
the next compartment whilst if the flow decreases the compartment
w i l l be only partly f i l l e d by the fluidized resin bed.
P e r i o d i c a l l y the resin is r e m o v e d from the bottom of the
c o l u m n and fed into the top of an elution column. To move the
resin from the sorption column the l i q u i d flow is first stopped
to a l l o w the resin to settle in each compartment. A v a l v e is
then opened at the bottom of the c o l u m n and the l i q u i d flows
down the column thereby a l l o w i n g the resin to flow from the bottom
of the column and at the same time c a u s i n g resin to go downward
in the c o l u m n and through the baffle plates separating the com-
partments. This downward flow is timed to a l l o w only a portion
- say 20% to 25% - of the resin from each chamber to pass down
the column.
The resin from the bottom of the column is slurried to the
top of an elution column and the c a r r y i n g l i q u i d is s e p a r a t e d
over a screen at the top of the c o l u m n . The resin is eluted
by an upward flow of an eluant and operates in a s i m i l a r manner
to the s o r p t i o n c o l u m n . P e r i o d i c a l l y resin is discharged from
the bottom of the e l u t i o n c o l u m n , washed and sent to the top
of the sorption column.

69
 BARREN RESIN
LIQUOR FEED

DISTRIBUTOR
TRAYS

COMPRESSED
AIRLINE

PREGNANT
FEED

{XJ———

LOADED WATER
RESIN EJECTOR
PRODUCT

FIG. 6: SCHEMATIC DIAGRAM OF THE CLOETE-STREAT

COLUMN AT IMPERIAL COLLEGE

T h i s d e s i g n h a s been a d o p t e d w i t h m i n o r m o d i f i c a t i o n s b y
Davey Power-Gas [17] and the N a t i o n a l I n s t i t u t e of M e t a l l u r g y
of South A f r i c a . An i n s t a l l a t i o n by D.P.G. is in operation in
South Africa at the R a n d f o n t e i n M i l l s i t e P l a n t and a n o t h e r at
their Cooke Plant. A d i a g r a m m a t i c arrangement of the D.P.G. system
which is typical for all systems based on the Cloete-Streat d e s i g n
is shown in Figure 7.
National Institute of M e t a l l u r g y Column (NIM) South Africa
A fluidized bed system based on the d e s i g n of Cl oete-Streat
has been developed in South Africa to recover u r a n i u m from u n c l a r i f i e d
leach liquors. A stainless steel sorption column 2.5 m diameter
(8'-0") was i n s t a l l e d as a demonstration p l a n t at B l y v o o r u i t z i c h t
Gold M i n i n g C o m p a n y L i m i t e d c o m p l e t e w i t h f i b e r g l a s s é l u t i o n
column. The baffle plates between the stages have smaller holes
- around 12 mm d i a m e t e r - and the total free area is between
1% and 2% as a g a i n s t 5% or so on other systems. No precautions
are taken to p r e v e n t resin f a l l i n g t h r o u g h the p l a t e s d u r i n g
shut down but as the holes are small the rate of resin discharge
would be fairly slow.
A t t h e d e s i g n flow, t h e resin a l m o s t f i l l s a l l c h a m b e r s
except the top chamber. There is a small free space at the top
of each bed due to the upper particles of resin being swept up

70
 Elution/Regeneration ,
Storage

Eluate

^ i———Cx}-> Spill Back

_ r^ (T*)" Ammonium Nitrate

_ Wash Water

Wash Column

Eluted Resin
Transfer Vessel

Ammonia

Solution Flow

Resin Flow

Water

FIG- 7= DIAGRAMMATIC ARRANGEMENT OF CLOETE-STR EAJ

SYSTEM - DAVY POWER GAS LIMITED

Into the chamber above by the Increased v e l o c i t y as the l i q u i d

approaches the perforations in the d i v i d i n g plates.
When it is required to move resin from the c o l u m n , the flow
is s t o p p e d and a v a l v e at the bottom of the c o l u m n is opened
which a l l o w s a reverse flow of l i q u o r to occur. T h i s c a u s e s
r e s i n to be c a r r i e d down from c h a m b e r to chamber. The bottom
chamber has a restricted outlet for the resin so that the r e s i n
is t r a n s f e r r e d between the u p p e r c h a m b e r s at a faster rate.
This is done to ensure that when forward flow starts a g a i n there
is more resin on each stage than can be contained in the fluidized
state and this excess of resin per stage is r e d i s t r i b u t e d o v e r
the c o l u m n l e n g t h when forward flow is r e s u m e d . T h i s causes
some degree of resin and l i q u i d b a c k m i x i n g but it is p r e f e r a b l e
to h a v i n g unequal batches of resin in each chamber which is what
would h a p p e n without the restricted outlet on the bottom chamber.
The results of the 2.5 m demonstration p l a n t were s u f f i c i e n t l y
e n c o u r a g i n g for two 4.25 m d i a . u n i t s to be i n s t a l l e d at
SI y v o o r u i t z i c h t and these have been in o p e r a t i o n since the latter
part of 1977.
There has been some data [18,19] p r o v i d e d on the performance
of the 2.5 m diameter demonstration unit. The c o n c l u s i o n s were
t h a t such systems a r e m e c h a n i c a l l y a n d m e t a l l u r g i c a l l y sound
and they can h a n d l e suspended matter with a low resin a t t r i t i o n
l o s s of o n l y 3% per a n n u m . O p e r a t i o n a l d e t a i l s of the 4.25 m
diameter system are g i v e n in a paper by D.W. B o y d e l l [20].

71
 The top section of the sorption and e l u t i o n c o l u m n s of the
U.S. Bureau of Mines and those based on the Cloete-Streat design
are a b o u t 50% l a r g e r in d i a m e t e r than the m a i n body, This is
so that the s u p e r f i c i a l v e l o c i t y at the top of the c o l u m n i s
reduced thereby preventing loss of resin by e l u t r i a t i o n p a r t i c u l a r l y
when resin is being added to the top of the c o l u m n .
Porter F l u i d i z e d Bed System
A n o t h e r type of c o n t i n u o u s system has been patented [21]
an arrangement of which is shown in Figure 8. This is somewhat
s i m i l a r to the systems d e s c r i b e d e a r l i e r for Federal American
Partners, Union Carbide and Western N u c l e a r w i t h the exception
that there are no screens for separating the resin and p u l p in
transferring from one c h a m b e r to the next. The p a t e n t states
that the resin in the first vessel of the series may be removed
in a batch operation which may involve the entire volume of resin
in the one chamber at one time or, which is more to be preferred,
there may be a continuous w i t h d r a w a l of ion e x c h a n g e m a t e r i a l
therefrom by m e a n s of an air l i f t over a period of time. This
method of resin transfer results in b a c k m i x i n g of l i q u i d .
/-Air lifts Resm flow
Soluion fl
/-Absorption vessels ————— OU.U..UH °"
/ — — — Air flow

11 1
! I—————t
1 1
3 1 1 1
1 4 1 1

r* iff zzz 1 5 1

— »(ZZZZ 1
— * iw W w ^

Eluate In
. Rinse HjO and
Transfer H20 In
Treated solution Out-

—CX3—»Eluate Our

£*Q—»Rmse Out

—[X}-»Oroin Out
Raw solution In ______
Cycle

FIG. 8: PORTER FLUIDIZED-BED ION EXCHANGE SYSTEM

This system is i n s t a l l e d on the large uranium extraction

plant i n N a m i b i a o f R o s s i n g Uranium. The e l u t i o n s y s t e m there
e m p l o y s three c o l u m n s in s e r i e s to o b t a i n a s t r o n g eluate in
the same manner described earlier for the Porter-Arden resin
movement plant.

72
Hfmsley Column
A more recent d e s i g n of c o n t i n u o u s ion exchange commenced
operations In June, 1977 at Agnew Lake Mines in E s p a n o l a , Ontario.
This system was piloted at the Quirke M i n e of Rio A l g o m in E l l i o t
Lake and a d e s c r i p t i o n of t h i s work is g i v e n e l s e w h e r e [22].
Operating performance of systems are also a v a i l a b l e [23].
The d i s t i n g u i s h i n g features of t h i s system is t h a t there
is no i n t e r r u p t i o n of the feed l i q u o r when transferring resin
from the l o a d i n g column and elution is carried out downflow through
s e v e r a l b a t c h e s of p a c k e d resin. The a d s o r p t i o n is therefore
truly continuous.
A t y p i c a l a r r a n g e m e n t of the system is shown in Figure 9
and comprises a sorption column, a resin m e a s u r i n g c h a m b e r , an
elution column and a rinse chamber.

Barren
Liquor

Eluant Inlet

Absorption Liquid ,
Column Inlet/Outlet

Elution Column

Rinse
•0 Chamber

Liquid
Inlet/Outlet

Packed
Resin
Bed

Liquid
>0 Inlet/Outlet

Measuring
Chamber

Liquid
Inlet/Outlet

\A/ .J
Eluate

Typical arrangement of Hlmsley Continuous

Ion Exchange System
Fig 9

73
 T h e s o r p t i o n c o l u m n i s d i v i d e d b y c o n e s a n d baffles into
several chambers c o n t a i n i n g resin t h r o u g h w h i c h a n u p w a r d f l o w
of l i q u i d f l u i d i z e s the resin w i t h i n each chamber. D u r i n g normal
o p e r a t i o n all of the c h a m b e r s contain resin except the one i m m e d i a t e l y
below the top chamber. The number of such chambers and the v o l u m e
of resin in each chamber depends upon the rate laws of ion exchange
g o v e r n i n g the p a r t i c u l a r system.
The élut ion column contains several batches of resin in
a p a c k e d bed c o n f i g u r a t i o n . L o a d e d r e s i n in i n t r o d u c e d into
the bottom of the column and is eluted by the downflow of e l u a n t
through the packed bed of resin. This o b v i a t e s the b a c k - m i x i n g
effect often encountered with dense eluates and resin b a c k - m i x i n g
is also a v o i d e d because of the packed bed c o n f i g u r a t i o n . H i g h
s t r e n g t h s of e l u a t e are o b t a i n e d w i t h t h i s process because of
the m u l t i - s t a g e downflow counter-current e l u t i o n technique.
Each resin batch proceeds upwards through the e l u t i o n c o l u m n
at each e l u t i o n cycle and by the time it reaches the top of the
c o l u m n , it has been contacted with enough e l u a n t to s t r i p e s s e n t i a l l y
all of the u r a n i u m from the resin.
The R i n s e C h a m b e r e n a b l e s the r e s i n to be rinsed free of
e l u a n t before returning it to the sorption column. It a l s o may
be used to change the ionic form of the resin e.g. from nitrate
to s u l p h a t e as practised for n i t r i c a c i d recovery or to treat
the resin for removal of s i l i c a or polythionates.
The transfer of resin t h r o u g h o u t the system is done in a
f l u i d i z e d m a n n e r r e q u i r i n g very l i t t l e pressure. There are no
valves which close on the resin and no pumps t h r o u g h w h i c h the
resin is passed and in this way resin attrition is m i n i m i z e d .
When breakthrough occurs at the top of the c o l u m n the resin
in the lowest c h a m b e r is close to e q u i l i b r i u m l o a d i n g with the
feed solution.
At t h i s time the r e s i n in the top c h a m b e r is transferred
to the empty chamber below and freshly eluted resin is immedi ate!y
transferred to the top chamber of the sorption column, The resin
from the lowest chamber of the sorption c o l u m n is then transferred
to the m e a s u r i n g c h a m b e r w h i c h is f u l l of feed l i q u o r . This
is is done by d i r e c t i n g the l i q u i d flow as shown in F i g u r e 10
without interrupting the flow of feed through the sorption column.

FIG 10- RESIN TRANSFER FROM ABSORPTION COLUMN Ta MEASURING CHAMBER

74
 The m a i n function of the M e a s u r i n g C h a m b e r is to p r o v i d e
p o s i t i v e control over the batch size of resin passed around the
system so that the resin in each compartment of the l o a d i n g column
is the same. It may a l s o be u t i l i z e d for resin pretreatment,
e.g. an iron scrub prior to elution. E s p e c i a l l y when p r e g n a n t
s o l u t i o n w i t h h i g h s o l i d s content is treated, the resin may be
cleaned by backwashing and if necessary an air scour can be a p p l i e d .
All of the resin in chamber B is then transferred in f l u i d i z e d
fashion to chamber A. When chamber 8 is empty, it receives all
of the r e s i n from c h a m b e r C. The transfer of resin continues
from chamber to chamber until all the chambers but one are empty.
These resin transfers are done by directing l i q u i d flow as shown
in Figure 11.

RecircuUting Pump

FIG 11: RESIN TRANSFER FROM CHAMBER C TO B

S t r a i n e r s are provided to prevent the e n t r a i n m e n t of resin

p a r t i c l e s with the l i q u i d drawn from the c h a m b e r s d u r i n g r e s i n
transfer. Each strainer has flow going through it in one direction
for 3 m i n u t e s or so and then in the opposite d i r e c t i o n for the
same l e n g t h o f t i m e w h i c h keeps t h e s t r a i n e r s c l e a n . D u r i n g
the remainder of the operating cycle, the s t r a i n e r s are not in
use. There is no strainer on the outlet at the top of the column
and therefore a free d i s c h a r g e is a v a i l a b l e for any s u s p e n d e d
m a t t e r or r e s i n fines. Also the diameter of the c o l u m n is the
same throughout which obviates the p o s s i b i l i t y of p a r t i a l l y loaded
fine resin p a r t i c l e s a c c u m u l a t i n g at the top and r a i s i n g the
e q u i l i b r i u m concentration of the barren effluent which can occur
with an upper flared section.

75
R e q u i r e m e n t s of F l u i d i z e d Resin Systems
Any system e m p l o y i n g a s e r i e s of f l u i d i z e d beds in t a n k s
or chambers arranged either h o r i z o n t a l l y or in a v e r t i c a l c o l u m n
can o n l y operate at m a x i m u m e f f i c i e n c y if the r e s i n t r a n s f e r
is done in a counter-current direction to the l i q u i d flow. Also
the transfer of resin frome one chamber to the next must be essen-
t i a l l y complete before it receives resin from its a d j o i n i n g chamber.
Any r e s i n left b e h i n d in a c h a m b e r w i l l not o n l y affect
the degree of extraction from that chamber but also w i l l create
uneven resin batches in the various chambers. Such unequal dis-
t r i b u t i o n of resin can not only lead to poor extraction and high
c o n c e n t r a t i o n s of the ion of i n t e r e s t in the b a r r e n e f f l u e n t
but a l s o it can r e s u l t in e l u t r i a t i o n of resin from a chamber
which contains an excessive amount of resin.
The c h a m b e r s or tanks m u s t be deep enough to contain the
resin when fluidized at the design flow so that small p a r t i c l e s
of p a r t i a l l y loaded resin are not c a r r i e d . a l o n g with the l i q u i d
flow into the next tank.
A further consideration in design p e r t a i n i n g m a i n l y to vertical
c o l u m n s of f l u i d i z e d resin beds is the s u p e r f i c i a l v e l o c i t y .
It is r e c o g n i z e d that resins may c h a n g e t h e i r d e n s i t y as the
ion e x c h a n g e process takes p l a c e e.g. a strong base resin in
tne s u l p h a t e form may be f l u i d i z e d to a v o i d a g e of 0.7 at 15
m / h s u p e r f i c i a l v e l o c i t y w h e r e a s when l o a d e d w i t h i r o n a n d / o r
u r a n i u m the v e l o c i t y may be i n c r e a s e d to 19 m/h or so w h i l s t
still m a i n t a i n i n g the same voidage. As it is not p r a c t i c a l on
a large scale to make the column conical to change the s u p e r f i c i a l
velocity a compromise is made by m a k i n g the c o l u m n c y l i n d r i c a l
and a l l o w i n g for a difference in the degree of f l u i d i z a t i o n as
the l i q u i d passes up the column.
Some c o l u m n s p r o v i d e for a larger diameter section at the
top of the column so that the superficial velocity is lower because
it is at the top where the resin is lightest, h a v i n g been stripped
of u r a n i u m . W h i l s t this reduces the p o s s i b i l i t y of e l u t r i a t i o n
of r e s i n it does however lead to a concentration of fine resin
beads, p a r t i a l l y loaded with u r a n i u m , r e m a i n i n g in the top section
of the column v i r t u a l l y all the time. T h i s affects the e q u i l i b r i u m
of the r e s i n m a s s in the top c h a m b e r and can c a u s e e x c e s s i v e
loss of the ion of interest in the barren effluent.
R e s i n t r a n s f e r s m u s t be m a d e as a slurry so as to reduce
resin attrition and the velocity in pipes should not exceed
2 m/ s.
Pumps and ejectors should preferably be avoided for transferring
resin as the h i g h velocities incurred w i l l lead to resin breakage
and eventual loss.
V a l v e s should not close on resin p a r t i c l e s if resin attrition
is to be m i n i m i z e d and the pressure loss in m o v i n g resin should
not exceed 175 kPa. This latter figure also a p p l i e s to pressure
losses in fixed beds of resin to e n s u r e that resin b e a d s are
not fractured.
Basis of Design
Any c o n t i n u o u s ion exchange system makes use of a constant
width ion exchange zone for f a v o u r a b l e ion e x c h a n g e processes.
T h i s has been a m p l i f i e d by Michaels [24] wherein he considered
fixed beds and showed that the exchange zone moves down t h r o u g h
the column at a certain velocity depending upon the feed concentration
and the flow rate.
By t h i s c o n c e p t , the total resin inventory in a fixed bed
system is the volume of resin contained in the ion exchange zone

76
p l u s the a m o u n t of r e s i n needed to c a r r y on the exchange for
several h o u r s or w h a t e v e r l e n g t h of time is a l l o w a b l e before
breakthrough occurs and the resin is eluted.
In a f l u i d i z e d resin c o l u m n the l i q u i d m o v e s u p w a r d s and
the e x c h a n g e zone a l s o tends to move u p w a r d s . H o w e v e r , when
the zone starts to l e a v e the top chamber as detected by analyzing
the s a m p l e from the stream l e a v i n g the top chamber, the resin
is immediately moved down the c o l u m n and its p l a c e taken by a
b a t c h of freshly eluted resin. The resin in the lowest chamber
is then taken away to be eluted.
In t h i s w a y , the u p w a r d m o v e m e n t of the exchange zone is
l i m i t e d to the distance of one chamber after which the e x c h a n g e
zone is brought back by m o v i n g the resin downwards and is thereby
contained w i t h i n the column. It is this w h i c h accounts for the
efficient u t i l i z a t i o n of resin in continuous columns as compared
to fixed bed columns.
It is p o s s i b l e to d e s i g n systems regardless of size based
on tests with s m a l l laboratory columns such that comparable per-
f o r m a n c e can be expected provided that the ratio of the volume
of wet settled resin to volumetric l i q u i d feed rate is the same
as the test work.
F l u i d i z a t i o n of Resin
The first b a s i c requirement in d e s i g n i n g any f l u i d i z e d bed
is to see t h a t all c o n d i t i o n s p r e v a i l to p r o d u c e a d e s i r a b l e
degree of fl u i d i z a t i on. In order to a c h i e v e good m i x i n g and
m a s s t r a n s f e r it is u s u a l to k e e p the v o i d a g e between 0.6 and
0.8.
The f l u i d i z a t i o n of strong b a s e r e s i n s used for u r a n i u m
extraction v a r i e s d e p e n d i n g upon t h e l o a d i n g o f u r a n i u m . W h e n
in the s u l p h a t e form the r e s i n has a d e n s i t y a r o u n d 1 . 1 5 but
when loaded with u r a n i u m it can be as m u c h as 1.3 or so. Also,
when the resin l o a d s with iron its density increases but not
as much as w i t h uranium.
It is known that the rate of ion exchange varies inversely
with the diameter of resin particles w h i l s t the f l u i d i z i n g velocity
v a r i e s d i r e c t l y w i t h i n c r e a s i n g diameter of particles. As the
required rate of ion exchange is the product of flow and concentration
it f o l l o w s t h a t coarse bead resin can be more effectively used
with d i l u t e s o l u t i o n s than concentrated solutions. The l i m i t i n g
factor when using small resin beads for treating d i l u t e solutions
is u s u a l l y the specific flow rate at w h i c h the r e s i n w o u l d be
elutriated from the system rather than the rate of ion exchange.
Because of this, the s m a l l e r size resin beads are g e n e r a l l y favoured
when treating concentrated solutions.
The f l u i d i z a t i o n c h a r a c t e r i s t i c s of r e s i n s are i n d i c a t e d
by Figure 12 which shows the expansion of two resins h a v i n g uniform
sizes of 0.5 mm and 0.7 mm r e s p e c t i v e l y . A l s o , the affect of
r e s i n d e n s i t y is illustrated for the two resins h a v i n g specific
g r a v i t i e s of 1.17 and 1.25 respectively.
From this it w i l l be seen:
1. Increasing the resin particle density from
1.17 mm to 1.25 mm allows a 40% increase in
flow for the same bed expansion of 100%.
2. If the bed expansion in aqueous solution is
100% at 15°C then it will expand to approximately
125% at 5°C or 75% at 30°C.

77
 n: 30

ü BED EXPANSION 100%

o PARTICLE DIA. 0.7 MM
tu 25
RESIN DENSITY 1.25
O

20
10° 20° 30°

125
2 RESIN 0.7 MM DIA. RESIN DENSITY 1.25
g UPFLOW25M/HR.
t/>
2 100
RESIN 0.5 MM DIA.-
X
LU UPFLOW 14.4 M/HR.
O
75

10° 20° 30°

125
2 -RESIN 0.7 MM DIA. RESIN DENSITY 1.17
O
UPFLOW 18 M/HR.
2 100
J
RESIN 0.5 MM DIA;
x
LU UPFLOW 10.8 M/HR.
O

75

I l
0.015 poise 10°C O.Ollpoiie 20°C 0.009 poise 30°C

AFFECT OF VISCOSITY, DENSITY AND PARTICLE SIZE ON RESIN

FLUIDIZATION IN AQUEOUS SOLUTION OF DENSITY 1.02
FIG. 12
(M/HR. x 0.41 = U.S.gpra./ft.2)

3. Increasing the resin bead diameter from

0.5 mm to 0.7 mm allows the flow to be increased
to 170% for the same bed expansion of 100%.
The rate of ion exchange, however, would decrease
by about 30$.
Moving Packed Bed Ion Exchange
A m o d i f i c a t i o n of the Himsley continuous ion exchange system
is made when t r e a t i n g l i q u i d s with low s u s p e n d e d s o l i d s such
as heap leach solutions and mine waters.

78
 The a r r a n g e m e n t of the system is shown d i a g r a m m a t i c a l l y
in F i g u r e 13 and consists of the f o l l o w i n g major components:
1. Sorption Column
2. R e s i n M e a s u r i n g Chamber
3. E l u t i o n Column
4. R e s i n Rinse Chamber
The s o r p t i o n c o l u m n o p e r a t e s in a somewhat s i m i l a r manner
to the e l u t i o n column as p r e v i o u s l y d e s c r i b e d . It c o n t a i n s a
bed of resin deep enough to contain the ion exchange zone length
at the proposed m a x i m u m operating flow.

RINSE
OUTLET

FIG. 13 TYPICAL ARRANGEMENT OF MOVING PACKED BED ION EXCHANGE SYSTEM

The water to be treated enters the top of the sorption column

and passes down through the bed of resin and the treated water
is d r a w n off from the bottom. After a g i v e n volume of feed has
been treated a batch of resin is drawn off the top of the sorption
column and d i s c h a r g e d into the measuring chamber as a slurry.
The frequency of transfers depends upon the flow rate, feed
concentration and the size of the resin batch. Because the resin
is transferred from the top of the unit f a i r l y frequently, t h i s
system is m u c h l e s s s u s c e p t i b l e to b e i n g f o u l e d by suspended
matter in the feed than a conventional fixed bed unit.
The r e s i n in the m e a s u r i n g c h a m b e r can be air scoured if
necessary and backwashed to remove any suspended solids entrapped
by the r e s i n . The l i q u i d is then d r a i n e d from the measuring
chamber after which it is filled with eluate. The resin is then
transferred as a slurry to the bottom of the elution column using
el uate.
This column is of sufficient volume to contain several batches
of resin - the number being m a i n l y dependent upon the temperature
and the frequency of resin batches entering the column and also
the required concentration of the eluate.
W h e n the r e s i n enters the elution column it lifts the bed
of resin already in the column as a solid plug which avoids m i x i n g
of the previous batches of resin.
When the batch of loaded resin has been completely transferred
to the bottom of the column the plug of resin is allowed' to drop
and form a compact bed of resin thus d i s p l a c i n g the excess f l u i d i z i n g
l i q u o r (eluate) to the eluate tank from which it came.

79
 The resin is eluted by the downward flow of a measured volume
of eluant through the packed bed of resin. Because of the multi-stage
d o w n f l o w counter-current elution technique the volume of eluate
produced each cycle is much lower than that produced by a conventional
column and this results in an eluate of high concentration.
The batch of eluted resin at the top of the column is then
transferred in a fluidi/ed manner to the rinse column for rinsing
or backwashing away any resin fines. The r i n s i n g is done w i t h
b a r r e n e f f l u e n t from the sorption column after which the resin
is r e t u r n e d to the bottom of the sorption column in a s i m i l a r
manner to that used for transferring resin to the e l u t i o n column.
The first commercial i n s t a l l a t i o n of t h i s type was c o m m i s s i o n e d
in J a n u a r y , 1983 for treating m i n e water from the Schwartzwalder
M i n e of Cotter Corporation in Golden, Colorado, U.S.A. The ore
body contains u r a n i u m and the mine water has between 2 to 5 mg
U/l at a pH around 8.4.
B e c a u s e t h i s m i n e water d i s c h a r g e s i n t o a creek f l o w i n g
to a d r i n k i n g water storage reservoi r, di scussi ons with the Department
of H e a l t h r e s u l t e d in the m i n e m a n a g e m e n t d e c i d i n g to i n s t a l l
equipment to reduce the effluent to less than 10 g U/l.
Once the e q u i p m e n t reached steady state c o n d i t i o n s it produced
an eluate c o n t a i n i n g 15 g U/l from a feed concentration averaging
3.9 mg U/l over a two week p e r i o d which shows a concentration
factor of a p p r o x i m a t e l y 4000. The eluate is trucked to the m i l l
250 kilometers away for direct p r e c i p i t a t i o n of the y e l l o w cake.
A detailed d e s c r i p t i o n of the i n s t a l l a t i o n is g i v e n e l s e w h e r e
[25].
Sulphate E l u t i o n
In recent y e a r s there has been some concern expressed by
environmental authorities about the use of nitrate as an eluting
agent. This is because the nitrate ion left on the resin after
elution is displaced by sulphate and goes out in the t a i l i n g s .
The loss of n i t r a t e can be r e d u c e d by using s u l p h u r i c acid to
strip off the n i t r a t e when the resin is in the r i n s e c h a m b e r
as p r e v i o u s l y m e n t i o n e d resulting in about 50% to 70% recovery
of nitrates on the r e s i n as n i t r i c a c i d . N e v e r t h e l e s s , some
risk exists of c o n t a m i n a t i n g the effluent with nitrate and as
a result, the industry is being encouraged to turn towards the
use of sulphuric acid as an elutant.
S u l p h u r i c a c i d is not as e f f i c i e n t and é l û t e s m u c h more
s l o w l y t h a n n i t r a t e . A c t u a l l y it is the b i s u l p h a t e ion that
élûtes the uranium from the resin and consequently, the strength
of acid g e n e r a l l y used is between 100 to 125 g HpSO/j/l at which
concentration the b i s u l p h a t e ion is almost c o m p l e t e l y dissociated.
W h e n f i x e d beds are employed l o a d i n g resin to 50 g U30ß/l
the s u l p h u r i c acid consumption (assuming 50% recycle eluant)
w o u l d be in the region of 15 grams H2SÛ4 per gram 0303« It is
o b v i o u s l y uneconomical to consume a l k a l i to neutralize this large
amount of acid and consequently recovery of the acid is necessary.
As mentioned earlier this has been achieved in the past by passing
the e l u a t e through a solvent extraction p l a n t and this produces
h i g h grade yellow cake because c o n t a m i n a n t s in the e l u a t e such
as iron are removed and go out in the raffinate with the recovered
sulphuric acid.
However, the solvent extraction process requires a r e l a t i v e l y
large area along with special fire prevention e q u i p m e n t and u s u a l l y
a s e p a r a t e b u i l d i n g . It a l s o d e m a n d s a c l e a r feed l i q u o r to
p r e v e n t d i f f i c u l t i e s in phase s e p a r a t i o n resulting in solvent
losses w h i c h c o n t a m i n a t e the e f f l u e n t . T h e s e c o n s t r a i n t s of

80
t h e E l u e x process m u s t t h e r e f o r e b e r e c o g n i z e d a n d e v a l u a t e d
a g a i n s t other a v a i l a b l e methods.
From the s t a n d p o i n t of acid recovery it has been shown that
the m u l t i - s t a g e counter-current élut ion results in less than
a t h i r d of the a c i d r e q u i r e d by a f i x e d bed system e m p l o y i n g
50% recycle eluant. At typical resin l o a d i n g s the acid consumption
of t h i s m u l t i - s t a g e e l u t i o n column is in the region of 3 to 5
grams H2S04 per gram t^Og which is acceptable because the n e u t r a l i -
zation of this amount of acid is l e s s c o s t l y t h a n the e a r l i e r
processes using nitrate elution. It follows that l e s s s u l p h a t e
in the form of g y p s u m must be removed thus l i g h t e n i n g the load
on the filters.
The n e u t r a l i z a t i o n w o u l d be done in two stages, the first
of which at pH a p p r o x i m a t e l y 3.5 would precipitate the s u l p h a t e
a l o n g w i t h iron and some other c o n t a m i n a n t s to e n a b l e a good
q u a l i t y yellow cake to be obtained from the second stage precipitation
carried out at pH 7.
There is, h o w e v e r , a more recent process known as H I M I X
developed for those cases where e x c e s s i v e c o n t a m i n t i o n of the
feed l i q u o r e x i s t s a n d e l u t i o n i s w i t h s u l p h u r i c a c i d . This
process [26] e n a b l e s a pure e l u a t e to be p r o d u c e d in one ion
e x c h a n g e step at a low cost. It was developed for use when 100
to 125 g H2SÜ4/1 is e m p l o y e d as an eluant in conjunction with
the Himsley continuous ion exchange system. At m o d e s t cost it
r e s u l t s in better p u r i f i c a t i o n of the eluate than is obtained
by the acid scrub and iron and sulphate p r e c i p i t a t i o n referred
to earlier. Acid consumption in the region of 3 to 5 kg H2SU4/kg
p r o d u c e d can be a c h i e v e d by this process when using 120
g H2S04/1 as an eluant. A full description has been given elsewhere
[271.
M a t e r i a l s of Construction
The g r e a t e s t care that m u s t be t a k e n in the selection of
materials and components is when acid leach circuits are used.
In cases where chlorides are low 316 L stainless steel can
be used with reasonable success. H o w e v e r , s t a i n l e s s steel is
not s u i t a b l e under reducing conditions and consequently if poly-
thionate p o i s o n i n g of the resin is l i k e l y then m a t e r i a l s in contact
w i t h the e l u a t e s h o u l d be of p l a s t i c or other m a t e r i a l which
is inert under such conditions.
R u b b e r - l i n e d carbon steel is used e x t e n s i v e l y in acid leach
c i r c u i t s but care m u s t be t a k e n to t h o r o u g h l y s p a r k - t e s t the
l i n i n g before p l a c i n g it into service. Today there is a tendency
for p i p i n g to be either stainless steel or fiberglass.
In cases where an Eluex circuit is used to recover s u l p h u r i c
acid there is always some organic that is returned with the a c i d
w h i c h w i l l a t t a c k n o r m a l r u b b e r l i n i n g . I n such cases carbon
steel should be l i n e d with Buna N or F.R.P. It m u s t a l s o be
recognized that the solvents from an E l u e x p l a n t can attack some
plastic m a t e r i a l s and c o n s e q u e n t l y a study of the p a r t i c u l a r
o p e r a t i n g c o n d i t i o n s m u s t b e made before f i n a l l y d e c i d i n g upon
the materi als.
The returned acid from an E l u e x p l a n t may c o n t a i n c h l o r i d e s
and nitrates which appear as h y d r o c h l o r i c and n i t r i c a c i d s re-
spectively in the eluant. The c h l o r i d e s w i l l attack 316 stainless
steel w h i l s t the nitrates w i l l attack Buna N rubber. This l e a v e s
f i b e r g l a s s as being the most s u i t a b l e m a t e r i a l for use in cases
where Eluex circuits are e m p l o y e d u n l e s s the c h l o r i d e s can be
kept low enough to e n a b l e stainless steel to be used.

81
 The flow meters and controllers r e q u i r e the u s u a l care 1n
s e l e c t i o n d e p e n d i n g upon the duty, bearing in mind the comments
p r e v i o u s l y made c o n c e r n i n g the n a t u r e of s o l u t i o n s with w h i c h
they may be in contact.

REFERENCES

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2. The M i l l Staff, "Uranium Oxide Recovery at C o n s o l i d a t e d

Denison", Can. Min. & M e t . B u l l e t i n , March (1962) 175.

3. G o l d i n g , L.S. and Irving, J., "Resin Structure - Mechanical

Strength", Soc. Chem. Ind. Conf. on "The Theory and Practice
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4. Slater, M.J., "Continuous Counter-Current Ion Exchange in the

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8. Merritt, R.C., "The Extractive Metallurgy of Uranium",

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9. Selke, W.A. and Bliss, H., "Continuous Counter-Current Ion

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10. Slater, M.J., "A Review of Continous Counter-Current

Contactors for Liquids and Particulate Solids", Brit. Chem,,
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11. Higgins, I.R. and Chopra, R.C., "Chem-Seps Continuous Ion

Exchange Contactor and its Application to Demineralization
Processes", Soc. Chem. Ind., Int. Conf. on "Ion Exchange in
the Process Industries", London, England, July, (1969).

12. Brooke, J.N., "Uranium Recovery from Copper Leaching

Solutions", Min. Congress Jour., August (1977) 38.

82
13. George D.R. and Ross J.R., "Recovery of Uranium from
uranium Mine Water and Copper Mine Waste Dump Leaching
Solutions", I.A.E.A., Vienna, June (1966), U.S. Bureau of
Mines, Salt Lake City Metallurgy Research Centre.

14. George, D.R. and Rosenbaum, J.B., "New Developments and

A p p l i c a t i o n s of Ion Exchange Techniques for the Mineral
Industry", Soc. Chem. Ind. Conf. on "Ion E x c h a n g e in the
Process Industries", London, England, July (1976).

15. Streat, M.S. and Qassim, R.Y., "Recovery of Uranium from

Unclarified Liquors by Ion Exchange", Dept. Chem. Eng.,
Imperial College, London, England.

16. Cloete, F.L.D. and Streat, M., U.S. Patent 3,551,118, (1970).

17. Naden, D., Willey, G. and Newrick, G.M., "The Use of Fluid
Bed Ion Exchange to Reduce Uranium Costs", Annual Mtg.,
A.I.M.E., Las Vegas, February (1976).

18. Craig, W.M. et al., "The Design and Operation of a

Continuous Ion Exchange Demonstration Plant for the Recovery
of Uranium", S. Afr. Inst. Min. & Met., Orange Free State
Colloquium, November (1977).

19. Haines, A.K., "The South African Programme on the Development

of Continuous Fluidized Bed Ion Exchange with Specific
Reference to its Application to the Recovery of Uranium",
Ibid.

20. Boydell, D.W. et al., "The New Uranium Recovery Circuit at

B lyvooruitzieht", Proc. 8th. Annual Hydromet allurgical Mtg.
- Uranium, Atomic Energy Board, South Africa.

21. Porter, R.R. and Rossing Uranium Ltd., U.K. Patent 1,382,450
(1975).

22. Himsley, A. and Farkas, E.J., "Operating and Design Details

of a Truly Continuous Ion Exchange System", Soc. Chem. Ind.
Conf. on "The Theory and Practice of Ion Exchange",
Cambridge, England, July (1976).

23. Himsley, A., "Performance of Himsley Continuous Ion Exchange

System", Soc. Chem. Ind. Symp. Hydrometal lurgy (1981).

24. Michaels, A.S., Ind. Eng. Chem. 44^ (1952) 1922.

83
25. Himsley, A. and Bennett, J.A., "A New Continuous Packed Bed
Ion Exchange System Applied to Treatment of Mine Water", Soc
Chem. Ind., Int. Conference on Ion Exchange Technology
Cambridge, July (1984).

26. U.S. Patent 4,427,639 (1984).

27. Himsley, A., "Production of Pure Yellow Cake by Ion Exchange

Processes Employing S u l p h a t e Elution, (Proc. Advis. Group
Mtg. Paris, 1980) I.A.E.A. Vienna (1980) 51.

84
 CHAPTER 3

URANIUM PRODUCTION7 BY ION-EXCHANGE METHODS

B. CZEGLÉDI
Magyar Tadomanyos Akadémia,
Pecs. Hungary

Abstract
Application of ion exchange methods is described for the recovery
of uranium mainly from ores. Ion exchange processing of uranium-ore
leach solution using anion and cation exchangers is explained in terms of
selection of suitable ion exchanger, behaviour of uranium sorotion and
elution, and poisoning of ion-exchange resins. Leaching chemistry using
sulfuric acid and carbonates is reviewed.

The uranium required for the nuclear energy production is

y i e l d e d first of all from its ores. Besides t h i s , uraniurr, in a s m a l l e r

q u a n t i L y is gained by reprocessing of the used fuels as w e l l , which is

returnee! to the production of fuel elements.

Hereinafter we review development: of the uranium production

u n t i l now and the raw material d e p o s i t s for the production.

The uranium production has continuously increased since the

1940s to the beginning of the 60s, when the quantity of U..C)0 exceeded
j O

30 thousand tons. Afterwards the production declined by 15-18 thousand

tons U,0„/year but in the second halt of the 70s the peak production

values of. the 60s were exceeded. The production in 1980 was approxi-

mately 50 thousand tons U,00 . [ 1 ""'

J O '

Tn the course of time the share of different countries in

the production has significantly changed. The degree of this change is

shown on Figure I.[2]

85
oo
ON Table 1. Exploration, production, resources and production capability

Country First First Total US /00/kgU US )Jl30/lcgU US i/60/kgU \I3 j<130/kgU Attainable Year Qualitativ«
exploration production production Reasonably lieasonably Estimated Estimated •axiaiui maxi«u» potential
to I960 Assured Assured Additional Additional production production
/1 000 /100U /1 000 /1000 capability capability
tonnes U/ tonne» U/ tonnes U/ tonnes U/ reached

Algeria Before 1961 0 28 28 0 6 Moderate/high

Argentina 1968 - 750 23 28 4 9 700 1903 high
Australia 1947 1954 9 600 292+ 301 127*- 53 20 000 1990 very high
Alia tria - _ 0 2 2 0 0 moderate
Bolivia Late 1960s - 0 0 0 0 <1 •oderate
Botswana Late 19608 - 0 0 0 0 uoderate/high
Br-zil 3952 1979 100 74 74 90 go 1 000 1963 high/very high
Canada t 1942 1938 131 500 230 259 381 770 15 500 1990 very high
Centr.Afr.hep. 1947 1982 0 18 16 0 0 1 000 1962 moderate
Chile 1950 - 0 0 0 5 5 low
Denmark
/Greenland/ 1955 - 0 0 27 0 16 BOderute/high
K&/p\, - - 0 0 5
Finland lyS9 1958 <100 0 3 0 <1 uoderate
France 1945 1949 29 600 38 54 26 46 4 500 1986 uoderate/high
Uabon 1948 1969 9 700 36 35 0 0 1 500 1982 moderate/high
Germany , Fed. Kep.1953 1975 200 4 5 7 8 200 1984 low
India 1953 - 30 30 1 24 200 1979 high
Italy 1954 1981 0 0 1 0 2 <100 1961 •oderate
Japan 1954 1970 <100 8 B 0 0 <100 1979 low
horeu/liep. of/ - - 0 4 0 0 low
Madagascar 1946 1955 4 000 0 0 0 2 •oderate
Mexico 1957 - < 100 6 6 2 2 90 1979 •oderate/high
Namibia 1966 1977 9 400 113 122 30 53 5 000 1985 high
Niger 1954 1967 13 000 157 157 53 53 12 000 1986 high
1'hilippinea 1953 - 0 <1 <. i 0 0 < 100 1981 low
I'ortuol 1945 1945 2 200 7 8 3 3 300 1984 •oderate
^ioualia 1955 - 0 0 7 0 3 •oderata
Uouth Africa Hid 1950s 1952 88 000 242 386 54 139 10 700 1966 high/very high
iipain 1952 1958 1 200 10 10 9 9 1 300 1985 high
Sweden Mid 1950s - 200 0 301 0 3 400 1963 •oderate/high
Turkey 1956 _ 0 2 4 0 0 •oderate
United Kin^dou* 1945 - < 100 0 0 0 7 •oderate
Un j ted States* 1945 1942 272 300 496 673 773 1 158 44 200 1990 very high
Yugoslavia 3965 - 0 5 7 5 20 400 1990 •oderate
Zaire 1920s 1940s 25 600 2 2 2 2 high

Kxcept where noted, data on resources are fro« UraniuM Resources, Production and De»and /December 1979/, adjusted for 1979 production and updated to 1 Jan. 1980.
« Tot.tl production fro« 1645 for glass and ceraaic colouring and radiua; 200 tonnes.
< Source: US l)epjrt«ent of Energy /US figures fro» DOE/ÜJO-100/00/. January 1980/.
j Uranium In Canada - 1979 assessnent of supply and requirements - at a price of US /130/keU and US j<20u/kgU.
 Uranium production

70 i

50 -

30

10 -

80 85 90

Fig. 1. P r o b a b l e change of r a t i o of u r a n i u m p r o d u c t i o n in 80s,

URANIUM PRODUCTION
(Tonnes U)

Country Pre-1977 1977 1978 1979 1980 1981 1982 19831

Argentina 339 98 109 134 187 123 155 200

Australia 8,159 356 516 705 1,561 2,860 4,453 3,700
Belgium 0 0 0 0 20 40 40 40
Brazil 0 0 0 0 0 4 290 300
Canada 112, 0803 5,790 6,800 6,820 7,150 7,720 8,080 7,500
Finland 30 0 0 0 0 0 0 0
France 23,133 2,097 2,183 2,362 2,634 2,553 2,859 3,200
Gabon 8,464 907 1 ,022 1,100 1,033 1,022 970 1,042
Germany, Federal Republic of 151^ 15 35 25 34 36 34 40
Japan 38 3 2 2 5 3 5 7
Namibia 594 2,340 2,697 3,840 4,042 3,971 3,776 3 , 8005
Niger 6,108 1,609 2,060 3,620 4,100 4.3606 4,25g6 n. a.
Portugal 1,932 95 98 114 82 102 113 100
South Africa 75,332 3,360 3,961 4,797 6,146 6,131 5,816 5,800
Spain 476 177 191 190 190 178 150 150
Sweden 200 0 0 0 0 0 0 0
United States of America 209,800 1 1 , 500 14,200 14,408 16,804 14,793 tO, 331 7,900
Zaire 25,6003 0 0 0 0 0 0 0
TOTAL 472,436 28,347 33,874 38,117 43,988 43,892 41,331 38,000
1. Estimated. 4. Plus 120 tonnes uranium of foreign origin.
2. Uranium from imported phosphates. 5. Secretariat Estimate
3. Pre-1938 data not available. 6. CEA - Rapport Annuel (1981, 1982).
7. Production in the US in 1983 is expected to fall
between 7,500 and 8,300 tonnes.
* Supplement to Figure 1. Cited from: Uranium Resources, Production and Demand OECD-NEA/IAEA
(December 1983).

87
 Certainly there were several reasons which contributed to

the change of the production and its volumes but we will not deal with

them here.

Deposits of uranium production which are nowadays at our

disposal can be divided into two categories as shown in Table 1. The

first category contains ore deposits from which recovery of uranium is

economical under the value 66 $/kg U_0_ and to the second category belong

deposits for which this value is between 66-110 $/kg U-O». In the first

category these uranium deposits occur in 317» in sand stones and in

vein form respectively, 22% of them in primary conglomerates, usually

accompanied by other metals (gold, thorium, etc.), 11% of deposits are to

be found in pegmatite gneisses, 2% in calcicrits, 1% in oil shales and 2%

in quarries of other types. Distribution of the lower grade ores being in

the second category is as follows: 30% of them occurs in sand stones,

25% in veins, 15% in conglomerates, 22% in oil shales, 6% in pegmatite

gneisses and 2% in clacicrits.[4]

Besides the abovementioned categories there are several

deposits containing a lot of uranium, but their concentration is very low

/<0.03%/, therefore exploitation of them is not economical taking into

consideration present prices. These deposits contain uranium mainly in

granites, syenits and phosphorites. Enormous deposits can be found in the

sea water as well, but we have no technology by which uranium can be

obtained from sea water economically, so it is unlikely uranium will be

extracted from sea water in the near future.

Nowadays and in the near future the uranium containing ores of

the first and second categories can be considered as the raw material of

the uranium production. However, in recent years the spot price for

uranium has significantly decreased and at minimum point reached the value

of 17 $/lb = 37.48 $/kg U_0 . [3] As a consequence production in several

88
mines and ore processing plants was interrupted and the proportion of the

exploitation of the ores with lower uranium concentration decreased.

In spite of this during the following years and until the turn of the

century in all probability, the raw materials belonging to the above-

mentioned categories will be processed and for this mainly the current

methods will be used.

Other raw materials of the uranium are not of great importance

today, though e.g. the waters of world seas can be an inexhaustible

source for the uranium production.

During the mining and processing of the uranium some solutions

and mine waters appear as byproducts, the uranium content of which is

significant. It is necessary to process them in interest of environment

protection as well, but in some places even economical uranium production

is guaranteed. Ion-exchange processes are applied for recovery of uranium

from such solutions, but these processes are similar to the methods already

in existence.

3.1. Main methods of uranium ore processing

Today mainly the sulfuric acidic leaching is used for uranium

production, but the carbonate leach is also important.[27, 29]

In some places physical enrichment methods are applied

depending on the mineral-rock characteristics and physical state of the

ores: radiometric classification, heavy-media process and sometimes

flotation.

The uranium ore and concentrate respectively is prepared

usually by wet milling and the pulp of suitable grain-size is led to the

leaching process. The processing methods applied nowadays as further

89
steps for uranium ores can be classified as follows:

(a) Process using sulfuric acid:

- Leaching by sulfuric acid, processing of pulps with

filtration, and by counter-current precipitation

respectively, and extraction from pure solutions;

- Leaching by sulfuric acid, processing of pulps with

filtration, and by counter-current precipitation

respectively, and ion-exchange from pure solutions;

- Leaching by sulfuric acid, ion-exchange from pulp.

(b) Process using carbonates:

- Leaching by using carbonates, processing of pulps

with filtration and by counter-current precipitation

respectively, and precipitation of uranium;

- Leaching by using carbonates, processing of pulps

with filtration and by counter-current precipitation

respectively, and ion-exchange from pure solutions";

- Leaching by using carbonates, ion-exchange from pulp.

(c) Combined and other technologies.

Hereinafter we shall review only processes which require

application of ion-exchange methods.

3.1.1. Leaching by sulfuric acid

Greater part of the uranium ores and raw materials containing

uranium can be leached by sulfuric acid. This method can be limited only

by degree of consumption of sulfuric acid. If the stone is rich of acid

consuming components /CaCCL, MgCO_, etc./ it will become uneconomical,

because of high acid consumption.

90
 From its pretreated ores the hexavalent uranium is dissolved

by leaching with sulfuric acid as follows:

As uranium occurs in its minerals in tetravalent form as well

which cannot be dissolved in sulfuric acid, during the leaching tetra-

valent uranium must be oxidized. In practice the oxidation is guaranteed

by Fe ions which are present in the leaching solution:

U02 -r 2Pe3+ ^=^ UO|+ + 2Pe2+ (2)

For the continuous oxidation of ferrous ions pyrolusite

/MnO / , sodium chlorate /NaC10~/, etc. are used:

2Pe2+ + :Jn02 + 4H+ =^ Z?e3+ + ^n2+ + 2H20 (3)

and

+ 6H+ s=s 6?e3+ + Cl~ + 3H0 (4)

respectively.

The uranyl ions being formed during the leaching enter into

reaction with the sulfuric acid and the result is complex uranyl di- and

trisulfate ions:[5, 6]

U02+ 4- n S02~

The equilibrium is always dependent on uranium and sulfate

concentration:

p-
K]

91
 Formation constants of complexes [6]:

n = l ß-L = 50
n = 2 p2 = 350
n = 3 = 2500.

The uranium is present in leaching solutions of uranium ores,

containing sulfuric acid, in form of uranyl cation U0„ , unionized uranyl

2_
sulfate UO-SO, , divalent uranyl disulfate [UO„/SO,/„] and tetravalent

uranyl trisulfate anion complex [UCL/SO/.,]

If uranyl ions are step by step sorbed from leaching solution

by an ion-exchanger, the quantity of uranyl complexes will decrease, they

change into uranyl ions and vice versa. By increasing the quantity of

sulfates the formation of uranyl complexes will be promoted and by

decreasing their quantity the formation of uranyl cations and neutral

uranyl sulfate molecules, respectively.

During the leaching by sulfuric acid besides the uranium

other components will be leached as well which remain in the solution in

different forms. Especially at higher temperature the sulfuric acid

partially recovers the quartz as well (about 17o) .

H^SO.
c 4
Si02 + H20 » HgSiO-j (6)

The produced silicic acid remains in the solution in colloidal

state. 2-6% of aluminium is solved from the ore during the leaching by

sulfuric acid:

(7)

Trivalent iron oxide /Fe„0,/ of siliceous uranium ores hardly

dissolves in diluted sulfuric acid solution /4-8%/:

(8)

92
 Divalent iron oxide or other compounds of iron are more e a s i l y

dissolved /40-507»/:

PeO +

However, in presence of an oxidant (oxygen of the air or

pyrolusite) the iron is oxidized into trivalent form according to the

equations (3) and (4).

At suitable pH value trivalent iron hydrolyses:

Fe 2 /S0 4 / 3 + 6H20 = Pe/OK/ 3 + 3^0^ (10)

and at s u i t a b l e s u l f a t e ion c o n c e n t r a t i o n anion complexes w i l l be f o r m e d :

Fe 2 /S0 4 / 3 + SO"" = 2Fe/S04/~ } ( i l )

and

+ 3SO. = aPe/SO./r ,r r e s p e c t i v e l y . ( 1 2 )
- - r ^ 4 4 J

Calcium and magnesium carbonates /CaCO , MgCO , CaCO_.MgCO„/

react entirely with sulfuric acid and calcium and magnesium sulfate

respectively will be formed:

CaC03 + H2S04 = CaS0

4 + H
2° + C0
2' (13)

+ H20 + C02. (14)

Solubility of calcium sulfate is about 2 g/1 in dilute

sulfuric acid leaching solutions, but magnesium sulfate can be totally

dissolved in practice. At the beginning of the leach the leaching

solution becomes supersaturated with calcium sulfate. In further stage

of leaching a precipitate of gypsum is suddenly formed, which contains

besides calcium and magnesium sulfate, uranium in a rather significant

quantity [5]. This makes loss of uranium at the leaching.

93
 Vanadium and phosphorus content of the ore dissolves in dilute

sulfuric acid liquor to a great extent /70-80%/. Vanadium usually occurs

in carnotite form which dissolves according to the following equation:

(15)

In aqueous solutions vanadium besides vanadil anions occurs

in form of ortho-, pyro- and metavanadil acid /H VO, , H,V 0 and HVO-j/.

In the uranium ores the phosphorus can be found either in secondary

uranium phosphate minerals: otunite, torbernite, parsonsite, etc.,

or in original apatite Ca.F/PO,/,,, phosphorite Ca„/PO,/„ form. In all

cases during the reaction with sulfuric acid phosphoric acid will be

formed:

Further impurities /Cu, Cr, Ni, Ti, SB, As, Mo, etc./ can be

found only in a small quantity in the siliceous uranium ores, so their

solved quantity will be small as well.

If the uranium occurs in complex ores the composition of the

leach solution will be significantly different from the above-mentioned;

for its processing a technology must be worked out in each case

separately. The situation is similar to the processing of uranium

containing phosphorites.

At a given uranium concentration the ratio of uranyl ions and

complex forms depends on the concentration of sulfate ions. At a small

sulfate ion concentration the uranyl cation and neutral uranium complexes

dominate, while at a greater concentration the quantity of anionic

complexes is more significant.

94
 Depending on the circumstances of the leaching by sulfuric

acid at the plant the following solutions are formed during the leaching

of sandstone ores of low uranium content:

U 0,3 - 2,0 g/l

Pe/III/ 2 - 10 g/l
Fe/II/ 0,05- 0,1 g/l
Al 0,1 - 6 g/l
K 0,1 - 0,3 g/l
Na 0,5 - 1,5 g/l
Ca 0,1 - 0,2 g/l
Mg 1 , 0 - 6 g/l
S0~ 30 - 100 g/l
PO^ 0,01 - 0,1 g/l
Cl 0,1 - 2,0 g/l

As contaminating ions even copper, nickel, chrome, manganese,

titanium, antimony, molybdenum, vanadium, scandium and other ions occur

in the solution in various concentrations, depending on the composition

of the ore, will depend on the applied technology. The free sulfuric acid

content of the solutions also depends on the applied technology, it usually

changes between values 2-15 g/1.

Solutions similar to the above mentioned composition will be

formed during underground leaching of the uranium ores by sulfuric acid,

and at different percolation leaching processes, where sometimes bacterial

oxidation is applied as well. But, there are two important characteristics

in which they differ from the above solutions: first, the total salt

content of these solutions - included uranyl sulfates as well - is smaller

than that of liquors arising at intensive plant leaching by sulfuric acid

using for example pachucas. The other difference is that the solutions

from the percolation leaching are pure, almost quite free from suspended

solids.

95
3.1.2. Leaching by carbonates

Uraninite and nasturanium content of primary uranium ores can

be hardly leached by carbonates, but uranium minerals of secondary ores

are easily recovered by them. However, an oxidant must be added to the

leaching for the oxidation of tetravelent uranium. Soda is usually used

for the leaching, but ammonium carbonate is a good leachant as well:

U03 + 3Na2C03 + H20 = Ha, ruOp/CO./,! + 2îïaOH, (17)

^ T/ 02CO,3 + H200 = /ÏÏH./,

4 4 LU02'0 /CO-j/i
3 3J + 21IE.OK
4 v( i s )
'

In presence of tetravalent uranium an oxidant must be used

at the leaching. Oxidation of uranium by oxygen takes place according

to the following reaction:

+
U00 + 3Ha0CO, + ioo + H00 = ITa, fUOo/COVil 2HaOH ( 1 9 )

In order to avoid becoming alkaline during the leaching and

formation of diuranate precipitate (loss of metal) which is the

accompanying event,

C03 + 3H20; (20)

it is necessary to neutralize continuously the hydroxyl ions which form.

For this purpose sodium bicarbonate is also added to the leach liquor:

HCO- + OH' = CO^" + K20. (21)

Other minerals being present also react with sodium; the

gypsum and the magnesium sulfate dissolve to a great extent, therefore

96
they are unwanted components of the uranium ores:

CaSO. + Ua2CO., = CaCO., + Ha2SO. ( 2 2 )

and

MgSO. + ïJapCO-ï = MgCO, + Ha^SO. (23)

respectively.

The sodium sulfate being formed causes on the one hand loss

of soda and on the other hand unwanted rise of salt concentration which

may disturb the sorption of uranium in case of recirculation.

To some extent the sulfides present in the ores also enter

into reaction during the sodium leaching. The degree of reaction depends

on the temperature, pressure and duration of the leaching:

0 = 2Pe/OH/3 (24)

The bicarbonate so formed neutralizes hydroxyl ions which

form at the dissolution of uranium, that is why the presence of sulfides

is advantageous to a certain extent. But, sulfide content of the ore

above 2-4% gives rise to a signficant loss of soda, therefore it increases

the cost of sodium leaching.

Even at higher temperature the quartz is leached only to a

small extent during the sodium leaching, so its concentration in the leach

solution rarely exceeds the value 0.2-0.4 g/1. The reaction of soda with

aluminium and iron minerals is insignificant as well. Concentration of

iron and aluminium in the sodium leaching solution is between 0.1 and

0.01 g/1. Calcium and magnesium carbonates do not enter into reaction

with soda, that is why sodium leaching is applied on the ores of high

carbonate content.

97
 Vanadium and phosphorus pentoxides dissolve well during the

sodium leaching forming vanadates and phosphates:

and

If molybdenum and arsenic are found in form of oxides in the

ores they will be also recovered to a great extent.

The composition of the leaching solutions formed during plant

sodium leaching of the uranium ores can be characterized by the following

values (g/1):
U,0o 0,3-4,0 Sqo— 0,1-5,0
Pe
V205 0,01-4,0 2°3 0,05-0,1
P205 0,05-0,3 A1203 0,06-0,6
Ha2C03 2,0-10,0 Si02 0,05-0,5
NaHCQ3 2,0-5,0 CaO+MgO 0,05-0,1

Ionic composition of the solutions depends on the original

composition of the ore and the leaching conditions, i.e. the composition

of leach solution. Uranium mainly occurs in form of uranyl tricarbonate

complex [U0„/C0_/ ] , however at a lower carbonate ion concentration

2- 2—
/C0_ / uranyl dicarbonate complexes [UO /CO„/9/H90/„] can be found as

well. In the sodium leach solution vanadium can be found in form of

3 - 2 -
vanadate - VO,, phosphate - PO/i silicate - SiO„ , aluminate - A10„ and

iron of ferric tricarbonate - [Fe/CO,/_] anions.

Composition of the carbonate-containing solutions, obtained

by heap leaching is essentially the same as above. But, these solutions

are pure, usually free from suspended solids, which is why they can be

easily processed by any kind of ion-exchange method.

98
3.1.3. Leaching by other reagents

For the leaching of the uranium ores other strong mineral acids

/HC1, HNO-/ can be used as well. These acids can dissolve the uranium even

from ores, which are difficult to leach but in spite of this they are not

widely applied, because their price is much higher than that of sulfuric

acid, and what is more they would cause many technological problems at the

processing plants.

Uranium ores can be leached by non-aqueous solutions as well.

In this case the leaching reagent (sulfuric, hydrochloric or nitric acid)

is fed in a mixture of organic and solid phases, and by agitation the

solution of the uranium takes place.

For example, mono- or diisooctyl phosphoric acid, dissolved

in isopropylether, has been used, to which the sulfuric acid was separately

fed. As regards the carnotite-containing ores on Colorado the metal

recovery was around 90%, but the organic phase loss .remained 2-8 1/t after

the aqueous washing of the solid phase. Industrial application of these

methods has not been extensively used.

Ion-exchange accomplished simultaneously with the leaching

also guarantees the good equilibrium condition of the leaching of uranium.

Continuous sorption of the uranium ions, entering into solution, removes

the equilibrium in direction of promoting the solving process. In spite

of this their industrial application has not been widely adopted because

of relatively high demand in leaching reagent.

3.2. Ion-exchange processing of leaching solutions

Introduction

In processing technology of the uranium ores the uranium,

passing into the solution during the leaching, can be recovered by different

methods. In this paper we review the methods, based on the application of

ion-exchange processes.

99
 To select the most suitable ion-exchange process the conditions

must be examined from two points of view. On one hand the physical and

chemical characteristics of the products being formed after the leaching

(solution and solid residue) must be determined in detail, on the other

hand properties of the ion-exchange resins must be known.

After due consideration of these two points of view optimal

conditions and methods of ion-exchange can be chosen including the ion-

exchange material.

There is insufficient knowledge to determine theoretically the

equilibria and kinetics governing the ion-exchange process when applied

to multi-component systems such as leach liquors. It is therefore necessary

to conduct experiments using a typical leach solution and apply ones

theoretical knowledge and experience in determining the required design

parameters. Occasionally one may be able to use some data from an existing

installation.

To recover uranium from its leach solution by ion-exchange, it

is first necessary to choose the sorption process followed by selection of

the type of eluant and finally it is advisable to study the mutual influence

of the two processes (recirculation of mother lye, etc.).

3. 2.1. Sorption

In the equilibrium examination of ion-exchange at sorption the

apparent equilibrium constant /K/, distribution quotient /D/, separation

factor 1*11, i.e. as it is more frequently called selectivity coefficient,

are determined.

The given ion-exchange process can be followed by graphical

interpretation of equilibrium of the ion-exchange (see Fig. 2). By graphic

representation of equilibrium isotherms of the uranium and different

100
 " 90 -

10 -i

SO 70 90

Me* content in solution , eq. %

? a

10 10

10 30 10 30 50 70 90
Me** content In solution Multivalent ion content in solution , eq. %

FIG. 2 b PI'
Graphical performance of equilibrium NH4R + Me — V» 1,2,3,4
1-BaCI 2 ; 2 - S r C I 2 ; 3 - C a C I 2 ; 4-MgCI 2 , ZnCI 2 ;
5-BeS0 4 i 6 - C a C I 2

Fi
S- 2. Experimental isotherms on phenol acetic acid condensation

resin of ammonium form.

101
contaminating ions, the selectivity of ion-exchange can be extended to

the examined ions, and the rank of selectivity in the process for the

given ions [22].

One has to see that the selectivity ranks - otherwise determined

for diluted solutions - are not always proved for the heavy physico-chemical

environment of uranium technologies. They must be specified by experiments.

Selectivity coefficient data from diluted solution are known for different

resins [9].

On the strong-acid sulfo-cat ion-exchanger the ions with greater

valency are sorbed earlier:

Order of priority of sorption of monovalent ions on the same

resin is the following:

Li + <H + < Na + < NH^<K + <Rb" f <Cs" i "

of divalent metal ions:

+
< Ca2+ < Sr2+ < Ba2+ ;

and of trivalent ions:

With resins containing weakly acidic carboxyl-, amidoacetate-

and phosphate active groups, there is an important difference among the

ranks which will be formed. With carboxyl resin for example the rank is

reversed:

H+ > Ca 24 > l^2+> Li"1" > rTa+ > K+ > Rb+ > Cs+.

The selectivity ranks on amidoacetate resins are as follows:

U02+ >Cu 2 + > Pb 2 + > Ni 2 +>Cd 2 + > Zn 2 + > C o 2 + > P e 2 + > LIn 2+ > Ca 2+
^ ° + >Ir 2 - f ->Li + *> ^

102
 The latter ranks differ from the previous ones because of

complexes formed between some cations and ions, sorbed on the ion-exchanger.

On the strong-base anion-exchangers, containing quaternary

ammonia-groups the selectivity ranks are as follows:

P < OH <C1 < H O g < C i r <3r < Î T 0 3 < H S 0 4 < I < SCSI <C10 4 ;

and

and

P0^_3- <AsO^3—< tartarate < citrate.

Concerning the weak-base resins (di and triamines) the

selectivity ranks are the same as above with the exception of OK ions.

The reason is the poor dissociation of weak-base resins and the strong

sorption of OH ions.

3.2.1.1. Cation-exchange recovery of uranium from leaching

solutions, obtained by using sulfuric acid

Because of the complicated salt- and ion composition of the

sulfate-containing leaching solutions the cation-exchange recovery of

uranium is possible only under certain circumstances.

In leaching solutions the greater part of cations /VO ,

Fe3+, Fe2+, A13+, Mn2+, Cu2+, Ni2+, CQ2+, Cu2+, Mg2+, H+, Na+, etc./

occur in such concentration, alongside the uranyl ions that they are

sorbed to a great extent on strongly acidic cation-exchangers.

Consequently, there is no possibility for recovery of uranium from such

leach solutions by ion-exchange due to lack of selectivity.

From sulfuric acid leach solutions the uranium could be

recovered by cation-exchange with acceptable selectivity only by using

weakly acidic cation resin (e.g. of acryl- or metacryl base)[8].

103
 But the uranium-containing solution must be of properly high

ionic strength. The good result can be explained by the fact that as a

consequence of low dissociation of the cation-exchanger the conditions of

ion-exchange are worse, so the metal ions are sorbed only to a small extent.

But, the uranium is sorbed well, because it forms complexes on the resin.

Weakly acidic methacrylic resin SzG-1 begins to sorb the

uranium in important quantity between pH values 1.7-1.9. Highest loading

capacity of cation-exchanger for uranium is at pH values 2.8-3.5, when the

selectivity is the greatest as well. With further increasing of pH,

dissociation of ion-exchanger and the loading capacity at the same time

rise, but simultaneously selectivity for uranium decreases.

Elution of cation-exchanger SzG-1 loaded with uranium is made

by dilute sulfuric acid solution. The volume of eluent needed for elution

equals with 0.8-1.0 of the bed-volume, so 90-95% of uranium passes into

eluating solution.

Uranium sorption of resin SzG-1 from complicated and concentrated

solutions is advantageous, because the price of the resin is relatively low,

its loading capacity is high, its mechanical and chemical resistance is good

and requires a cheap eluent.

In the literature there is not any other important reference

to uranium-industrial application of cation-exchange.

3.2.1.2. Recovery of uranium from sulfate-containing

solutions by anion-exchange sorption

From sulfate-containing leach solutions the uranium is sorbed

on strong-base anion-exchangers according to the following reactions:

~; (27)

104
and

+ S0?~. (28)
4
As in technological solutions the neutral uranyl sulfate

complexes can be mainly found and besides them ions with negative charge

occur only at higher sulfate concentration, the following reaction plays

a role at anion-exchange sorption:

_^ Y1* l "r-rs^ / I«N A / I

(29)

The experimental data which prove decrease of uranium sorption

and not increase simultaneously with the rise of sulfate concentration of

the solution - since the condition promotes the formation of uranium

complexes - indicate the fact that in practice rather the neutral uranium

complexes should be sorbed on strong-base anion-exchangers. However, at

high acid content bisulfate ion is also sorbed on strong-base anion-

exchanger to a great extent.

If the solution is more concentrated for uranium (some g/1)

2-
LU^O./SO,/„J anions will appear as well which also will be sorbed on

the anion-exchangers.

The strong-base anion-exchangers sorb other anions as well

from the solution. As the trivalent iron forms sulfate complexes, it will

be also sorbed on anion-exchangers, but the degree of the sorption can

be decreased by increasing the acid content of the solution without an

important change in sorption of uranium (see Fig. 3). At high pK values

and sulfate concentration some other metal ions (scandium, strontium, etc.)

will probably be sorbed by ion-exchange on strong-base anion-exchangers

besides uranium, but its degree can be neglected and it will not cause

any technical problems. That is why in the above situation the uranium

can be yielded from its sulfate-containing solutions, with high selectivity.

105
 60
•00
E

40
u
I
I 20

30 40
«2804 concentration , g/l

Fig. 3. Change of sorption of uranium and ferric iron depending

on acid concentration on anion-exchange resin of AN-2F

type.

Other anions being present in leaching solutions /Cl , N0~ ,

- 2- 2-
SO,, S,0, , MoO, and ions, polymerized in acid medium, etc./ will be

sorbed on strong-base anion-exchangers under processing circumstances of

the uranium ores. In spite of this anion-exchange for uranium is a

more selective process than cation-exchange.

Active groups of strong acid cation-exchangers dissociate well

in acid medium too, therefore they are not selective at uranium sorption.

However, in sulfate-containing solution only anions of some metals occur,

and of those only the sulfate complex of iron is present in any appreciable

amount. The disturbing effect of iron's sorption can be overcome as well

during anion-exchange sorption of the uranium.

Application of weak-base anion-exchangers is advisable first

of all for ion-exchange from leach solutions of high acid content.

But they sorb uranium preferentially from solutions of high phosphate

content or from solutions containing anions which can be well sorbed by

strong-base resins such as iron.

106
 By increasing the acid content of the solution the sorption of

uranium decreases on weak-base anion-exchangers to a smaller extent than

strong-base anion-exchangers under the same conditions (see Fig. 4), and

simultaneously decreases sorption of the iron as well. From sulfate-

containing solutions with phosphoric acid the selectivity of weak- and

medium-base anion-exchangers is also good.

Ofl
—•»
06
300

u
a
CL
03
U

.1 200
IB
t.

100

so

0,3 0,5 0,7 0,9

concentration , mol/l

Fig. 4. Effect of free acid concentration on uranium sorption

capacity of different ion-exchange resins /V = 0.5 g/1/.

3.2.1.3. Ion-exchange recovery of uranium from carbonate-

containing leaching solutions

If the uranium content of the leach solution formed for recovery

of uranium from carbonate ores is smaller than 2-2.5 g U/l, the precipitation

by lye will not be economical. It is therefore advisable to recover

uranium from weak leach solutions by anion-exchange first and then to

produce the required uranium product by eluting the uranium from the resin

into aqueous solution.

107
 Sorption of uranium from carbonate solutions on anion-

exchangers is very similar to the ion-exchange from sulfate-containing

solutions.

The uranyl carbonate complex is sorbed on strong-base anion-

exchangers of chloride form as follows:

4RC1 -i- [ïï02/C03/3]4- 5= R4|JJ02/C03/3~| + 4C1". (30)

For purposes of ion-exchange it is better to use strong-base

resins than medium- or weak-base ones (see Fig. 5). Uranium sorption

capacity of the anion-exchanger depends on the pH value of the solution

to a great extent (Fig. 6); if pK decreases, i.e. the solution becomes

acidic, the uranium loading capacity will decrease as well.

ç 50-

40 -

30 -

0,8
solution U,g/l

* strong-base (Varion AT ) soda cone. 0,2 mol/dm3

0
medium-base ( Varion AP )
* weak-base (Varion A D A ;

Fig. 5. Uranium sorption capacity of anion-exchange resins with

different base in carbonate solutions.

108
 60 -
CHCOj] + CC0 3 3 = 0,4 eqv/dm 3

50 -

40 -

9 10 pH

Fig. 6. Change of uranium Sorption capacity of anion-exchange resin

in carbonate medium depending on pH value of solution

(type of resin: VARION AP).

Composition of carbonate leach solutions exerts a considerable

influence on the sorption of uranium on anion-exchangers - As it is widely

4- —
known these solutions contain besides anion [UO-/CO-/. ] , anions VO.,,
3_ _ 2- - 2- - - - 2-
PO , Cl , SO , HCO , CO , maybe MnO , NO CIO , SeO , etc. and basic

iron carbonate anion complexes, respectively. From the mentioned anions

the sorption of uranium is signficantly decreased by Cl , and by NO.,, if

present. These two are sorbed first on anion-exchange resin from a

carbonate leach liquor. The priority order of sorption is as follows:

•an-'"" -^ [?e/OH//C0 ]4-

ra« /nu / /nn / / 14—
3 3 >V0 3 > [U02/C03/J

Contaminating anions, sorbed on the resin: phosphates,

vanadates, aluminates and silicates are pushed away from the resin to a

109
small extent under the influence of the uranium being sorbed later, but

as a final consequence the sorption of these impurities decreases the

sorption of uranium. But, luckily, only a small quantity of interfering

ions, excluding vanadium, occurs in carbonate-containing leaching

solutions, so their disturbing effect for sorption is moderate as well.

If the uranium ore contains vanadium in significant quantity

the carbonate leach solution will contain both uranium and vanadium.

Using fixed-column sorption for example both metals will be sorbed

initially on the ion-exchange resin, as it is shown on Fig. 7. Because

the selectivity of the resin for vanadium is greater than for uranium,

the uranium is displaced by the vanadium until the column is loaded

mainly with vanadium.

200
e
•** O

IÏ

o <=
M .2

J 15 120
c =: <=
03 —

6 8
Quantity of collected fractions of output
solution (as per 100ml )

Fig. 7. Sorption of uranyl tricarbonate, vanadate and phosphate ions

from solutions on ion-exchange resin of Amberlit IRA-400 type.

110
 Carbonate leach solutions of vanadium and uranium content can

be processed for its useful products in alternative way by an ion-exchanger:

- the resin is loaded until the breakthrough of uranium,

then the loaded resin is selectively regenerated for

uranium and vanadium;

- the column is loaded until the breakthrough of vanadium,

when the uranium is sorbed in another column; vanadium

and uranium can be eluted separately.

From carbonate leach solutions the aluminate /AlO / ions are

not sorbed in practice on strong-base anion-exchangers.

3.2.1.4. Recovery of uranium from other solutions (mine waters,

waste solutions, etc.) by ion-exchange

Waters of the earth's crust always contain dissolved salts

which can be considered as leaching reagents if they contact uranium

mineralization. From this point of view the carbonate-hardness of the

waters is especially of great importance: for this reason mine waters

of high hardness usually contain a significant amount of uranium.

Mine waters must be purified for several reasons: from the

point of view of environment protection the waters of high radioactivity

cannot be led into natural water streams, sometimes these waters are

needed for irrigation or for other purposes, and last but not least the

uranium cannot be neglected as it can reduce operating costs.

Recovery of uranium from mine waters should be made on strong-

base anion-exchange resin. The chemical process is almost the same as

uranium sorption from the carbonate leach solutions. Selection of a

suitable ion-exchange technique is influenced by the fact whether in

neighbourhood there is a chemical processing unit or not. If there is

111
not the Sorption and elution are often carried out in one column by the

method well-known from water-softening technologies. The uranium is

precipitated from the eluate by lye, and the product of high uranium

content, obtained in such a way, is forwarded to a mill for further

purificat ion.

In neighbourhood of chemical plants the resin, loaded by

uranium, is eluted in these plants, where the uranium is processed as

well. Serni-continuous ion-exchange equipment is often selected, where

almost a quasi-counter-current process is carried out by frequent removal

of small quantities of loaded resin from the sorption columns.

3.2.2. Elution

Ion-exchange resins, loaded in sorption processes, will be

subjected to elution. Elution is the reverse process of sorption by

which the uranium goes from the ion-exchange resin into aqueous phase

again. It means that from chemical point of view equilibria discussed

at sorption will be moved into direction of left side.

During elution almost the total quantity of uranium must be

stripped from the resin, because during sorption the uranium content of

the eluted resin (as a result of the equilibrium processes) determines

the uranium content of the effluent or in other words, the metal loss

of the sorption process. In practice the value of 0.5-1.0 gU/1 is allowed

on the eluted resin in order to produce a barren solution containing less

than l mg U/1.

During elution the ion-exchange resin usually regains the

form in which it was at entering into the sorption process. However, in

practice it sometimes happens that some unwanted material is not removed

from the resin by the normal eluant and it may build up and reduce the

capacity of the resin. In such cases a separate process is used to clean

112
or regenerate the resin. This build up of unwanted material is called

resin poisoning and this will be discussed later. For uranium elution of

ion-exchange resins, several methods can be applied, depending on the

quality of the ion-exchanger, the state of loading and further steps of

the uranium processing.

3.2.2.1. Elution of cation-exchange resins

As it is known U0„ ions are sorbed on cation-exchange resin,

e.g. of sodium type, according to the following equation:

^=^ U00R -t- 2Ha+. (31)

This equation can be reversed and the elution of cation-

exchangers, loaded with uranium, is based just on this. If the ion-

exchange resin is treated by solution containing a high Na or H

concentration, the uranium will be transferred into solution.

The characteristics of elution of cation-exchange resin

SzG-1 , loaded by uranium, are shown on Fig. 8.

3-2.2.2. Elution of anion-exchange resin

Uranium extraction from acid or carbonate leach liquors is

generally carried out using strong-base anion resins. Ion-exchangers.

loaded in such a way, can be eluted by different methods-

3.2.2.2.1. Elution of anion-exchange resins in the sulfate form

When eluting anion-exchange resins loaded from a sulfuric

acid leach liquor, besides uranium, mainly iron, vanadium and some other

contaminating rnetals and sulfate anions are found. Eluting these resins

the following reactions take place:

/3 -i- 42T = 4RS + U0^+ + 3So|"; (32)

113
 -C 14

10

\
6 8 10
Eluent of bed-volume

Fig. 8- Elution of uranium from ion-exchange resin of AN-2F type

by nitrate-containing solution.

2X~ ^—— 2RX + + 2S04~; (33)

(34)

',-. T, <ü.
ov~ T• IT"*"
il -•—_». .3+ 'î (35)

+ H" RI + HS04; (36)

-r 21" 2ES + SO|"; (37)

- - 2-
Where X = NO , Cl or ^SO^ and

R = the resin.

Elution is also an equilibrium process, so all the conditions

are valid for this which have already been mentioned.

114
 Elution may be carried out by sodium-, ammonium or magnesium

nitrate of 1.0-1.2 moles acidified for pH = 1 and are chosen depending on

what will be used for separation of uranium from the elute, ammonia,

sodium hydroxide or magnesium oxide,

Eluting by nitrates, the anionic metallic complexes and other

anions sorbed on the resin are exchanged by nitrate ions, so the quantity

is determined by the total capacity of the resin.

After precipitation of uranium the nitrate loss from the

solution is made up, the pH value is adjusted and the solution is fed

back to elution. The loss is caused first of all by the quantity of NO.,,

sorbed on the resin and the quantity of reagent in the solution which

adheres mechanically on resin. Also by the quantity of reagent sorbed

by the precipitate during precipitation of uranium and iron by hydroxide.

As the elution is the main operating cost of the ion exchange

process it is very important to decrease the consumption of reagent to the

minimum value. Elution is promoted by increasing the nitrate concentration,

but nitrate losses become larger. That is why in practice the nitrate

solution of 1.0-1.2 moles acidified by HNO for value of 1.0-0.8 pH is

considered optimal.

Chloride ions are proved to be a good eluant for anion-

exchange resins. In practice the chloride concentration of 1.0-1.2 moles

is optimal as well at pH = 1.0-0.8 adjusted by sulfuric or hydrochloric

acid. Here the rise of chloride concentration to a small extent also

improves the concentration of elution, but in operation it proportionally

increases its loss as well, similarly to elution by nitrate. But by

increasing chloride concentration above 2 moles, the effectiveness of

2_
elution begins to decrease. At higher chloride concentration UCLC1,

complexes will be formed which are strongly sorbed on anion-exchangers.

115
The sorbed iron behaves in similar way, therefore elution with concentrated

chloride, only sulfates w i l l be removed from the resin; uranium and iron

will remain on the resin partially or totally.

In (ho chloride cluatc of the saturated sulfatic anion-

exchanger a significant sulfate concentration could build up, especially

if the mother lye of uranium precipitation is recirculated to the elution.

At concentrations occurring in elut.ing solutions the sulfates from HSO,

2-
and SO. ions, which can be also sorbed on anion-exchangers during elution

and may take the role of nn eluant. But the increase ol sulfate

concentration to a great extent leads to the decrease of elution -

presumably because of the improvement of forming conditions of uranyl

sulfate complexes; therefore sulfates must be continuously removed from

the recirculating solution.

Uranium can be effectively stripped from anion-exchangers by

chlor ide-con! ri iriing élut ing solutions, in q u a n t i t y of 2.5-3.5 bed-volumes.

Such solutions contain mainly 5-16 g/1 of uranium, 5-15 g/1 of iron,

40-90 g/1 of sulfates and cations in a corresponding quantity. First of

all the unwanted iron and sulfate ions in the eluatc are separated by milk

of lime solution; being neutralized to the value of pH 3.5, CaSO will

p r e c i p i t a t e which, after i i l t r a t i o n , is fed back to the leach circuit

because of its small uranium content. The uranium is then precipitated

from the filtrate by sodium- or ammonium hydroxide, and lime milk

solution, respectively at pH 6.5 to 7.5.

Elution by sulfuric acid of anion-exchangers loaded with

uranium is based on the principle that HSO, anions might show a greater

affinity for anion-exchangers, than the ions of uranium and iron sulfate

respectively. So, by a stronger sulfuric acid solution (when the quantity

of HSO, ions is great enough) the loaded resin can be eluted.

116
 However, the Glution by sulfuric acid is less effective than

chloride or nitrate. Therefore in practice it is applied as a combined

method, or in a special case, where relatively high uranium content of

mother lye, getting away at sorption, is not lost, does not cause metal

loss and environment p o l l u t i o n , respectively.

Instead of élut ing by sulfuric acid, Na„SO, and /NH,/„SO, resp.

is applied and only the pH value of the solution is adjusted by sulfuric

acid. In practice a sulfate concentration of 1.0-1.2 moles and a

sulfuric acid concentration of 0.1-0.2 moles are generally adequate.

After elution by sulfuric acid there is no possibility of

decreasing the iron content of the recovered product by neutralization

using lime, therefore this content must be limited even on the ion-

exchanger by prewashirig of the resin before the elution. An ion complexes

of the iron, being sorbed more wedk.lv than anion complexes of uranium,

will bo removed first from the resin.

From the sulfuric' acid eluate. the uranium is precipitated by

neutralization using NaOK or Nli.OH solution. The separated precipitate

is filtered, dried and taken away for further processing. From the mother

lye a sulfuric acid t? luting solution is made again.

Compared with the elution using chloride and n i t r a t e , the

advantage of using sulfuric acid is on the one hand that the eluted resin

returns to the sulfate form, and does not cause any nitrate or chloride

ion contamination in the barren liquor. On the other hand in case of

recirculcît. ion of wastes (waters of pulp reservoirs) they should not

accumulate hindering the uranium to be sorbed on the resin.

Elution can be carried out by Na„CO„ and NaHCCL solutions

as well. It is proved [10~\ that C0_ gas should not arise at elution of

117
loaded resin in sulfate-containing solution, if in the first step the

resin was treated with a rather concentrated Na.CO. solution, when only

the following reaction could take place:

^, (38;

and not the following:

. (39)

As HCO_ ions are able to elute uranium fron resin, treated

in such a way, the uranium can be eluted by a solution of NaHCG-.

l N Na^CO., solution of 1 bed-volume and l N bicarbonate solution of

2-4 bed-volumes are suitable for this process.

The advantage of the process that unwanted N0_ and Cl ions

from the resin at the commencement of sorption should not pass into solution,

but as the eluted resin is in the HCO,, form nevertheless there will be gas

release during the sorption on contacting the resin with the acid solution

which can affect the mechanical stability of the ion-exchange column.

3.2.2.2.2. Elution of anion-exchange resins in carbonate form

Mainly uranium anion complexes are sorbed on anion-exchangers

of carbonate form arising at processing of uranium ores by using

carbonates. If carnot ite-containing ores are processed, vanadium anion

complexes also will be well sorbed on anion-exchangers. Other metal, and

other anions may be sorbed on the resin depending on the character of the

ore; however these are not typical cases of the sorption by using

carbonates .

For elution of loaded resins of carbonate type several reagents

can be used. Elution effect of different salts, acids is shown on Fig. 9-

118
 400 600 800 1000
Volume of regenerating agent , ml

I - 2 , 0 m NaCI ; l l - 1 , 0 m NaCI ; III - 0,5 m NaCI ; I V - 0 , 2 5 m NaCI ;

V - 1 , O m NaNOj; VI-0,5m NaNOj ; V I I - 0 , 5 m H2S04; VIII-0,25 m H2S04

Fig. 9. Desorption of uranium from ion-exchange resin; Amberlit

IRA-400 type by different solutions.

As it is proved by the Figure, NaNO_ and NaCI can be considered as the

most 'effective eluants. Efficiency of sulfuric acid and different

sulfates is much smaller. The sodium elution of loaded anion-exchangers

of carbonate form is also possible, but its efficiency is small, too.

In practice usually nitrate or chloride containing solutions

of 0.8-1.0 moles, containing 0.1 moles soda are used for elution of

carbon anion-exchange resins. It is possible to feed acid instead of

soda to the solution, but in this case the uranyl carbonate complex

decomposes and the uranium changes into a compound of sulfate form.

119
At the same time decomposition of the carbonates is accompanied by

release of CO- gas of a great quantity which exerts unfavourable

influence for the resin.

For regeneration of loaded anion-exchangers in carbonate

leach solutions a loaded solution of ammonium-carbonate form is applied.

Mixing the ion-exchanger with such a solution the uranium will be eluted

and will form /NH, / ,UCL/CO_/ crystals with the solution as third phase.

After the separation of crystals the solution is loaded again with

/NH,/„CO„ and fed back to elution.

The crystals /NH./.UO„/C00/0 formed are heated, where U_0 0 is

4- H- Z J J JO

gained. The released gases are regenerated, so only a small quantity of

reagent for compensation is necessary at elution.

3.3. Poisons of resin

Ion-exchange resins often sorb materials from the leaching

solutions which cannot be removed from the resin during the usual elution.

So, these materials can disturb ion-exchange processes even in a small

quantity, because they accumulate on the resin if sorption-elution cycles

are repeated. This reduces the useful capacity of the ion-exchanger and

it will become eventually unsuitable for uranium production.

Poisons of resin can exert their influence through either

physical or chemical effects.[11-15]

Polythianate ions are poisons of resin of a strong chemical

effect. In practice we can meet them at leaching of ores, containing

sulfides, by using sulfuric acid or when processing cyanized wastes for

uranium. They arise at leaching of sulfide-containing ores by sulfuric

acid, if there are strong oxidants present /MnO / and the leaching

solution contains sulfuric acid only in a small quantity.

120
 Oxidation of pyrite in alkaline /NaOH/ solution results in

ferric hydroxide or sodium sulfide» but the latest quickly changes first

into thiosulfate, then into sulfate. At oxidation of pyrite in neutral

and acid solutions sulfuric acid and ferrous sulfate and f.erric sulfate

will be formed. It is found /10/ polythionates /S 0,1 poison the resin;

where n = 2-6, arising from pyrite at acid leaching, pH being 1.

Thiosulfate arising from sulfide enters into reaction with pyrolusite

as follows:

+ H,0 (40)

Tet rathionate , sorbod on ani on-exchangers , is a very radical

poison of resin, it cannot be removed by the usual olufion. Theoretically

more than one reaction would be able to regenerate the resin, poisoned by

tct rathianate :

- by sulfides:
S4o|~ + S2" ———222^~ * S;

- by cyanides:
S 44 of~ + ClT + H20 ——— SO2" + CITS' + 3202- + 2H + ; (42)
- by thiosulfite:

by mercuric chloride:
2S 2— +, 3H
-stT~m
C1 + . 4H
AÏS ri _— Un-m otTrr«: j. oc; j. /im"~ + (44)
2°6~ S 2 2° —— KgCl2.2HgS + 2S
+ 4S02/" + SH"*";

and ( 4 5 )

2S20^" + 3HgCl2 + 2H20 —— HgCl2.2HgS + 4C1~ + 2S02" +

- by hydroxides:

2S40?" + 60H" ——— 3S2°3~ + 2S0

3" + 3H
2°*

121
 In practice, however, the last reaction is applied for

regeneration of the resin. In first step the tetrathianates bound on

the resin are decomposed by lye to trith?.anates :

4S4Og" + 60H" ——— 5S2°3" +

^^l" + 3H
2°* (47)

The trithianate and thiosulfate being formed mainly remain

on the resin, because OK ions are sorbed on the resin not so strongly.

Then trithianate and thiosulfate ions may be eluted by chlorides.

Rhodanide ions are poisons of anion-exchange resins of

chemical effect. Their effect is met only at plants where the uranium

ores to be processed are pretreated by cyanide-containing solution for

example in order to recover gold. Cyanide ions form with sulfides

rhodanide ions. and with uranium being present uranium cyanide complexes.

From such solutions besides [UO«/SO,/„] complexes uranium rhodanide

complexes, and rhodanide and sulfate ions are sorbed as well on anion-

exchangers as it is shown on Fig. 10. Anion complexes of uranyl rhodanide

may be present in sulfate-containing solution in the following forms:

On the free ion exchange sites of the same quantity of anion-

exchangers more uranyl rhodanide complexes of low negative charge /1-3/

can be sorbed. in which 1-1 uranyl ion is present, than uranyl trisulfate

anion complexes which also contains only one uranyl ion. So, the resin

shows a greater total capacity than the theoretical one in sulfate-

containing solution at sorption, accomplished in the presence of rhodanide

ion contamination for [U0„/S0./ ] than in the absence of it. So, during

the first cycle the rhodanide ions could effect advantageously for the

sorption. But, in reality this advantage would not appear, because

122
 100

80
K
thiocyonate
60
X

40

20

uranium v

-20
500 1500 2500
Quantity of passed through solution , ml

Fig. 10. Sorption of uranium and thiocyanate on ion-exchange resin

of Deacidit FF type.

disadvantages of the following deleterious effects are much greater and

cover up the previous advantage:

1- Strong-base anion-exchangers show greater affinity for

rhodanide complexes than for uranyl trisulfate complex,

therefore because of sorption of the previous ones the

capacity of resin for uranium decreases.

2. Uranyl rhodanide anion-complexes are sorbed on anion-

exchangers more strongly than uranyl sulfate anion complexes,

therefore the latter cannot be removed from resin by the

usual elution, so it makes the useful capacity of resin

decrease.

3. Rhodanide salts are sorbed very strongly on strong-base

anion-exchangers, therefore after the total elution of the

uranium (uranyl trisulfate and uranyl rhodanide ions) there

will be some salts on the resin decreasing its useful capacity.

123
 As the rhodanide ions in practice cannot be totally removed

from anion-exchangers even by elution using nitrate, they will accumulate

dangerously in ion-exchange cycle. In nitrate-containing medium of

elution the rhodanide ions can be decomposed and as a consequnce of this

elementary sulfur can be separated.

In order to avoid poisoning effect of rhodanides it is

advisable to wash out the ore with water thoroughly and to apply acid

concentration as high as possible in the first stage of the leaching to

decompose cyanides to a great extent.

The resin, already poisoned by rhodanide ions (and by

elementary sulfur) must be given a special regeneration.

The silicon dioxide poisons the resin in a physical manner.

Sulfuric acid leaching solutions always contain silicium in different forms

and quantities. In sulfuric acid solution the solved silicium occurs in

mono- or dimer i.e. low polymer form (AMP form - reacting with ammonium

molybdate) which is soluble, or in colloidal polysilicic acid of higher

polymerization degree. If concentration of soluble silicon dioxide of

AMP form is above 2 g/1, then - one part of it - relatively quickly changes

into silicon dioxide of colloidal form - about to the value of l g/l SiO„.

This means that in practice, during the sorption, the increase of SiO.

content of the resin is in direct relation with the SiO„ content of AMP

form of the solution and not with total SiO~ content (see Fig. 11).

Silicium is sorbed from the solution on the resin in mono- and dimer, and

low polymer form, respectively.

On strong-base resin the silicium is not sorbed in ionic form.

This is proved even by the fact that at sorption of silicon dioxide counter

ion should not appear in the solution /e.g. Cl or N0_/. According to our

124
 .= 100

BO

60

40

20

4 8 12 16
Cycles of sorption

1- solution I, total qty Si02 3,0 g/l, AMP 1,8 g/l

2-solution U, total qty Si02 2,4 g/l, AMP 0,8 g/l
3 - solution III, total qty Si02 1,3 g/l, AMP 0,7 g/l

Fig. 11. Sorption of silica on ion-exchangers of DeacidiC FF type

from leaching solutions.

present knowledge the sorption of silicium on anion-exchangers takes place

similarly to the mechanism of water diffusion. The explanation is that

silicic acid should not dissociate in practice under the circumstances of

the sorption (high salt contents pH = 1.5-1.8). Then silicium, getting

into resin by diffusion, quickly polymerizes which is promoted by water

washing of the resin, i.e. by increase of pH of surrounding solution.

Non-polymerized quartz is removed from strong-base resin by

normal elution; but the polymerized one does not leave, it fills up the

pores of the resin, makes the kinetics of sorption and elution slow down

and reduces the capacity due to filling up the pore volume. Only alkaline

treatment can be effectively applied for removal of such poisons. In such

a case the poisoned resin is regenerated either in its original place

(from elution) or by a separate regenerating process.

125
 Poisoning of ion-exchangers by elemental sulfur takes place as

a secondary process of sorption of rhodanide and polythionate ions,

discussed previously. In contrast with poisoning effect of chemical

character of these two processes, the elementary sulfur is a poison of

resin of physical nature. Fine aggregated sulfur, arising as a result of

decomposition of polythionates and rhodanide ions, mechanically closes the

free channels and the active groups of ion-exchangers, by hindering or

preventing diffusion and consequently the ion-exchange. Such elemental

sulfur can be removed from the resin only by NaOH solution. By an alkaline

treatment the sulfur being on the resin can be transformed into sulfide-

and polysulfide sulfur respectively which can then be easily removed from

the resin by common salt. Applying this method the sulfur can be totally

removed from the anion-exchangers.

Molybdenum and some other elements can also play the role as

a poison of resin for extracting uranium. If the ore contains molybdenite,

it can be dissolved during leaching by using sulfuric acid. In the

solution the molybdenite cations /Mod,, /, being present because of

amphoteric characteristics of molybdenum, form anionic complexes which

are similar to uranyl sulfate anions and they are sorbed on strong-base

anion-exchangers.

Molybdenum does not cause decrease of resin capacity even after

several cycles when elution of resin by nitrate is employed but it does

when elution is by chloride. This may be explained by the fact that in

nitrate-containing medium the molybdenum should be polymerized and leave

the resin. Molybdenum can be easily removed from the resin by lye.

In sulfate-containing solution titanium also forms an anionic-

complex. But it can easily precipitate if the pH of the solution increases.

Titanium precipitation may occur on anion-exchange resin for example during

126
washing which causes physical poisoning of resin. The separated titanium

precipitate can be dissolved by sulfuric acid containing ammonium bifluoride

solution.

Zirconium also forms sulfate complexes; but in the presence of

phosphorus it can be sorbed on the resin in ZrOHPO, form as well. It can

be eluted from the resin by strong sulfuric acid.

Thorium also can be accumulated in a small quantity on the anion-

exchangers at sorption of sulfuric acid containing solution. It can be

removed by elution using sulfuric acid.

Different groups of organic materials being solved from the

ores may behave as poisons of resin', for example, humic acids, some

sulfonic acids, etc. Organic molecules can be sorbed on anion-exchange

resin either by sorption or by ion-exchange. First of all the resins of

gel-type are susceptible for poisoning. The poisoned ion-exchanger can

be regenerated by sodium hydroxide solution.

References

1. DARMAYAN, Ph., The economics of uranium supply and demand.

HANSEN, M.V., World uranium resources. IAEA Bulletin 1981.

Vol. 23. No. 2.

2. EKLUND, S., The development of nuclear power - tasks for the 1980s,

IAEA Bulletin 1981. Vol. 23. No. 3.

3. METAL Bulletin, issues of 1982.

4. Uranium. Changing sources of supply. Ibid., 1976.

v. 287, N 7350, p. 6.

127
 5. SZABO, L., BAKOS, L., CZEGLEDI, B., FODOR, M. and MULLER, P.,

Recent results in the processing of Hungarian uranium ores.

Third United Nat. International Conference on the Peaceful Uses

of Atomic Energy. 1964. A/CONF.28/P/450. Hungary.

6. AHRLAND, S., On the Complex Chemistry of the Uranyl Ion V.

The Complexity of Uranyl Sulfate. Acta Chemica Scand.

5, 1151-1167. 1951.

7. CZEGLEDI, B., Dissertation, 1961.

8. LASKORIN, B.N., Atomnaia energia, 1960. t. 9, vip. 4. str. 286.

9. Separation on ion-exchange resins, "MIR", Moscow (1967)

430 pages with illustrations.

10. BROWN, E.A., et al., Some Variations of Uranium Ore Treatment

Procedures. Second United Nations Int. Conf. on the Peaceful Uses

of Atomic Energy, UN, Geneva, 1958. Nr. 227/58.

11. EVEREST, D.A. et al., Resin Poisons in Ion Exchange Processes.

Second United Nations Int. Conf. on the Peaceful Uses of Atomic

Energy, UN, Geneva, 1958. Nr. 101/58.

12. Uranium in the South Africa. 1946-1956. v. II. Johannesburg, 1957.

13. CARMAN E.H.D.J., South Africa Inst. of Min. and Met., v. 60. Nr. 12.

14. NUGET, E.A., South Afr. Ind. Chem., v. 10. Nr. 11. 1956.

15. AGRES, D.E.R., WESTWOOD, R.J., J. South Afr. Inst, of Min. and M e t - ,

v. 57. Nr. 7. 1957.

16. GRINSTEAD, R.R., ELLIS, D.A., OLSON, R.S., Recovery of Uranium

Suifuric Acid and Carbonate Leach Liquors by Anion Exchange.

128
 First United Nations Int. Conf. on the Peaceful Uses of Atomic Energy,

UN, Geneva, 1955. Nr. P/522. USA.

17. PREUSS, A., KUNIN, R., A General Survey of Types and Characteristics

of Ion Exchange Resins Used in uranium Recovery. First United Nations

Int. Conf. on the Peaceful Uses of Atomic Energy, UN, Geneva, 1955.

Nr. P/527. USA.

18. STEPHENS, F.M., MACDONALD, Fr. and R.D., Alkaline Leaching of Uranium

Ores. First United Nations Int. Conf. on the Peaceful Uses of Atomic

Energy, UN, Geneva, 1955. Nr. P/520. USA.

19. McCLAINE, L.A., BULLWINKEL, E.P., HUGGINS, J.C., The Carbonate

Chemistry of Uranium. Theory and Applications. First United Nations

Int. Conf. on the Peaceful Uses of Atomic Energy, UN, Geneva, 1955.

Nr. P/525. USA.

20. SHANKAR, J., BRATNAGAR and MURTHY, T.K.S., An Ion Exchange Process

for the Recovery of Uranium from Carbonate Leach Solutions.

First United Nations Int. Conf. on the Peaceful Uses of Atomic Energy,

UN, Geneva, 1955. Nr. P/871. India.

21. KRESSMAN, T.R.E., KITCHENER, J.A., J. Chem. Soc., 1949, 1196, 1202.

22. PLASKIN, I.N., TEHTARU, S.A., Hydrometallurgy using ion-exchange

resins, "Metallurgy" publication, Moscow (1964).

23. SZABO, E., Bevezetés az urân kémiai technologiejâba.

Tankönyvkiado, Budapest, 1962.

(Introduction to the chemical technology of uranium)

24. LEBEDEV, K.B. et. al., Ion-exchange resins in non-ferrous metallurgy,

"Metallurgy" publication, Moscow (1975).

129
25. HABASHI, F., Principles of extractive metallurgy.

Volume 2. Hydrometallurgy. Gordon and Breach. New York, London,

Paris.

26. VELIKNAN, A.M. et. al., The theory of hydrometallurgical processes,

"Metallurgy" publication, Moscow (1975),

27. GRIESSBACH, R., Austauschadsorption in Teorie und Praxis.

Akademie - Verlag, Berlin, 1957.

28. SKOROVAROV, D.I., Hydrometallurgical processing of uranium ore,

Atomizdat, Moscow (1979).

130
 CHAPTER 4

ION-EXCHANGE SYSTEMS
AND ION-EXCHANGE MATERIALS
IN NUCLEAR POWER PLANTS

I.D. DOBREVSKI
University of Chemical Technology,
Bourgas, Bulgaria

Abstract

Specific technological solutions for ion-exchange plants

used in NPP are explained: Water treatment (make up) plants;Ion-

exchange water treatment plants in NPP with PWRs ( Condensate

polishing systems in secondary circuit;Plants for clean-up of
blowdown water from steam generators); Ion-exchange systems in
the reactor circuit of PWRs (Chemical and Volume Control Systeas-
bypas instalation for reactor water purification;Ion-exchange
systems for control of EL30, concentration in reactor water);
Ion-exchange water trcrtment plants in NPP with BWRs reactor
clean-up systems and turbine condensate(feed water) polishing
systems.
The ion-exchange units in typical radioactive liquid waste
systems and the cleaning up of fuel storage pools in NPP are
also explained.
An attempt to evaluate the efficiency of technological
behaiviour of the ion-exchange systems cited above was made.
The evaluation is based on the data of units running in NPP in
UK,Bulgaria,Japan,Belgium,Soviet Union,Sweden,India,USA,Canada etc,

131
4.1 ION-EXCHANGE UNITS IN NUCLEAR POWER PLANTS.WATER
TREATMENT PLANTS

In the NPP with BWRs and PWRs the necessary desalinated

water to make up the unavoidable water losses is usually pro-
duced by ion-exchange demineralization of fresh water (from
rivers,lakes,reservoirs,under ground sources etc).In most cases
the demineralized water must meet the following requirements:
- chlorides content: max 20* (100) M g/l;
- silicates content: max 20* (50 )/Hg/l;
- specific electrical conductivity:below 0.5 (1.OVtfS.cm
In order that the desalinated water meets these require-
ments it is necessary to resort in all cases to ion-exchange
processes.
Depending on the quality of the raw water,the ion-exchange
part of the water treatment plants comprises units for:

1. H-removal with strongly acidic cation exchangers.(in

the case of high alkalinity units for H-removal with weakly-
acidic cation exchangers can be preconnected):
2. OH-removal with weakly anion exchangers.(usually,macro-
porous weakly basic anion exchangers are used thus quaranteeing
the effective protection of the postconnected strongly basic
anion exchangers threatend by contamination with organic matter
contained in the water (1,3).

* These data are characteristic of the water treatment plant

at Kozlodui NPP (l ).

132
 A - Raw water inlet
B - Distribution grid
C - Air outlet
D - Inspection window
E Manhole
- Strainer fioor « i i l i i;o/7les
- Treated w a l r r outlet an:! b.
wacci and rei'eneianl i n l e f
H - /mionic resin
I - Iriei'î resin
J - C'arioiur icsin
K - kc;;ci.ei.ir.t ourlet
I. - Régénérant inlet j'.'i.l
M - Diain.ißc aiul

Fig. 1 Type of equipment used, for triouod s:yi;t;e:n (2).

3. OH-roaoval with strong3.y basic ariior exchangers,

(usually stron^y basic anion exchangers type I with gel
structure.When treating surface waters,strongly contaminated
with organic substances,macroporous or isoporous strongly basic
anion exchangers are recommended):
4. Déminéralisation through niixed bed (with internal or
external regeneration) loaded with strongly acidic cation
exchanger and strongly basic anion exchanger usually in a 1:2
ratio by volume.
In order to achieve a higher degree of water deTiineraliza-

tion arid to use more effectively the reagents for regeneration

mixed beds of the"trio-bed" type have also been recommended in
recent years ( 2 ) . Fig. 1.

133
 In order to limit to the possible minimum the chloride
ions concentration in high purity water the regeneration of the
strongly acidic cation exchangers in mixed bed is done usually
with sulfuric acid instead of hydrochloric acid.
The introducing of systems for counter-current regenera-
tion (for the H-cation exchanger units) and of conjugated
regeneration for the units loaded with strongly basic and weakly
"basic anion exchangers makes possible a 30-40;« cut of the costs
for acids and respectively 20-30$ cut of the costs for the
hydroxides as compared with the ordinary (once-through) ion-
exchange method (3).
At normal service cycle of the individual ion-exchange
units (over 18-20 hours) the annual losses of ion-exchange re-
sines do not exceed.
1 % for the cation exchangers and

2J/o for the anion exchangers (\'?<> in the case of macro-

porous anion exchangers).

The usual total life of the ion exchangers is over 10
years.This life is also valid for the gel type strongly basic
anion exchangers if the ion exchangers units,loaded with this
type of ion exchanger,are preceeded by units with macroporous
weakly basic anion exchangers.
(Any irreversable contamination of the anion exchangers
with orginic substances or ions of heavy metals might result
in shortening this life to 1 or 2 years.)
Some authors (4) recommend to avoid water from survace
sources in the water treatment plants of KPP because this water
contains organic substances some of which pass directly through
the water treatment plant,its ion exchange units included.

134
 The eventual degradation of these organic substances at
elevated temperatures may cause an increase of water corrosion
of the steam produced from it (5).
Practice at Kozlodui NPP shows (6) that if macroporous
weakly basic anion exchangers are used in the water treatment
plant and the post-connected strongly basic anion exchangers
are macroporous or isoporous and if they are followed by HBP
loaded with strongly acidic cation exchanger and strongly basic
anion exchanger type I with a gel structure then the highly de-
mineralized water is practically free from organic substances,
irrespective of the fact that water from the Danube,considerably
contaminated with organic substances,is desalinated.
In conclusion it can be pointed out that the methods and

ion-exchange resins used for water treatment in the conventio-

nal thermal power plants can be applied in the ion-exchange

water déminéralisation units in H PP, cert a inly under considera-
tion of the qualities of the respective water sourse.The right
choice of the reagents for ion exchangers regeneration might help
meet the stringent requirement that demineralized water in NPP
has an exceptionally low concentration of chloridesd ).

4.1.1. ION-EXCHANGE WATER TREATMENT PLANTS IN NPP WITH PWRs

4.1.1 .1 .ION-EXCHANGE PLANTS IN THE SECONDARY CIRCUIT.COKDENSATE
POLISHING SYSTEMS
Irrespective of the initial view that condensate polishing

is not a typical technological solution in a NPP with Pvfö,

practice shows that the clean-up of the whole amount of
condensate in the secondary circuit of NPP with PWR is
necessary not only in the cases of high salt content in

135
turbine condensers cooling water (7,8) but also of medium

salt content of this water (9,10) and especially so when

the steam generators tubes are made of stainless steel ( 7 , 1 1 , 1 2 ) .
The clean-up of the whole amount of condensate in the con-
densate polishing system (CPS) makes possible a considerable
reducing of blowdown water amount of the steam generators.
Thus,heat losses are reduced and in the case of HPP with WSR-400
conditions are created to increase unit's capacity by about

> (11 ).

.. -t
Condensare

Mixed. Bed Polisher

I/ \l I/ \

H.S. 3 . S . ?..S. • R.3.

NaCK-

Anion

Cation

r.Ci-

Resin Transportation line

S.S.——--Resin Strainer

Pig. 2 Condensate polishing system for PWR (8),

The ion-exchange units are indispensable from CPS in the

secondary circuits of NPP with PWR.CPS in the Japanese NPP of
this type are as those presented in Pig. 2 (8),ie CPS consists
only of MHF loaded with strongly basic anion exchanger and

136
 strongly-acidic cation exchanger in OH- and H- form,respectively.
The effectiveness of this system is evident from data presen-
ted in pig. 3 (8).

Polisher ir.flueat
70.
Ü.
Conductivity ; k.25 vS cm"1 -25°C /Fixed A
a.
; 0.50 ppm
VThroueput/-
x
——— *=t^/
NH3
N 2 n't ; 2.07 DDIU

0.1 ppb
0.01 rcb
0

C.C6 US ca"1 -25 C

50 r

- = 2

Ac tuai "=^0 10 -12 15

Polisher i_ j____ '
Test <=C>0 50 100 L50
Column
Water Production (t)

3 Over-production test of a codensate polisher exceeding

the fixed throughput (8).

The technology of GPS in the secondary circuit of

Leuschner NPP,aDR (WER~400) is similar (7).This CPS consists
of 5 MEP dia 2 000 mm with external regeneration.Each mixed

bed contains 4.5 nr ion-exchange mixture: 3 m^ Wofatit SBW-MB

and 1.5 m3 Wofatit KPS-MB.Each mixed bed is designed for flow-

rate 180-250 m3/h at filtration rate 60-80 m/h.The ion-

exchange resins are regenerated with 5% NaOH,respectively 5/e
polished condensate has always a specific electrical

137
conductivity below 0,1 AfS.cm"' .Rest content ofchlorides in the
polisksd condensate is below 20 ppb (even when,due to leakages
in the condensers,chlorides content in the turbine condensate
is 1 ppm ) (7).
Alkalyzing reagents are not added into the water in the
secondary circuit for which reason each MET treats about
•*
900 000 m condensate between two regenerations.However,under
such conditions the degree of corrosion products removal from
the turbine condensate is comparatively low-307^ of the iron and
60/£ of the copper corrosion products are removed (7).
Unlike Bruno Leuschner NPP,in PWR Doel, Belgium (9,10)
volatile alkalyzing reagents (ammonia and hydrazine) are added
in the water of the secondary circuit (in the turbine condensa-te),
This is reflected in the OPS scheme adopted,Fig.4 (10).

BAFFLE PLATE ,
CA.TIOH
EX CHANGE HLXEP BED
FILTER rrL,xER .
FILTER

*-<£HX!-j pJL-Tun I pj j
r^j'^°~^ri~°°ra~^'"in_ri~i
' LP n^pM j r-, s i
HOT- VELL LJ LJ Ll J j
POST- {
FILTERS !

Pig. 4 Doel full flow condensate polishing system (10).

The condensate polishing system consists of:

a) precoat filter of inert material (removes the suspended

corrosion products from the turbine condensate);

138
 b) filter with strongly-acidic cation exchanger in H-form-
Duolite C26C (removes the ammonia from the condensate);
c) MBF loaded with strongly-acidic cation exchanger in H-
form (Duolite C26G and strongly-basic anion exchanger in OH-form-
Duolite A161C).
The cation bed filter operates at a rate of 90 m/h, and MBF
at 100 m/h.Each MBF is followed by a precoat filter of powdered
ion exchangers (Powdex filter).This filter reduces sodium ions
concentration in the condensate after MBF.(However, the main
reason is the insufficient elution of the ion exchangers in
MHP after regeneration. The ion exchangers in MBP are regenerated
in the filter).Later,MBF were reconstructed in triobed filters,
Fig. 1,To this end,inert material - Duolite S3-TR (bed height
20 cm),is insertd between the cation exchanger Duolite C26C and
the anion exchanger Duolite A1610.The triobed filters consist
of 6000 1 Duolite A161C, 1000 1 Duolite S3-TR and 4800 1 Duolite
C26C.Regeneration is done with H2SO, and NaOH.
According to (2),sodium ions concentration in the polished
condensate has been about 1 ppb when using MBP but has dropped
about 20 times - up to 50 ppm - after implementing the triobed
filters.The specific electrical conductivity of the polished
4
condensate is 0.08-0.10 US.cm
In CPS of Kozlodui KPP,Bulgaria ( 1 2 ) , (reactor type WER-440)
are envisaged 5 MBP with external regeneration loaded with macro-
porous strongly-acidic cation exchangers and strongly-basic anion
exchanger of the macroporous type.The reasons for the selection
of this type of ion-exchange resins are:
a) to prevent the irreversable contamination of the ion-
exchange resins (anion exchanger) with organic matter (leaked in
the turbine condensate through the turbine condensers).
139
 b) to limit the mechanical degradation of the ion exchangers
in view of the greater mechanical loading during the transporta-
tion operations of the external regeneration of MBP and at the hl-gh
filtration rates,80-100 m/h.
In conclusion it can be summarized that the ion-exchange
resins in CPS in the secondary circuits of NPP with PWR does not
have to be "nuclear grade" but a class C is recommended
(for condensâte-polishing systems) particularly when external
regeneration of MHP is applied.Usually,these are macroporous
resins,characterized by a higher chemomechanic and mechanic
stability.

The triobed filters are to be preferred,especially in

the cases when the ion exchangers are regenerated in MBF and
the possibility of good separation of the cation and anion
exchangers is limited.

4.1.1.2. PLANTS FOR CLEM-UP OP SLOWDOWN WATER PROM THE STEM

GENERATORS

All plants for the clean-up of blowdown water from the

steam generators comprise ion-exchange demineralization units
strongly-acidic cation exchanger in H-form and strongly-basic
anion exchanger in OH-form,put in different filters or mixed
in MHP.
In the absence of condensate polishing in the secondary
circuit the amount of blowdown water from the steam generators can
reach up to £7° of feedwater consumption. (This is necessary so
that the clean-up of blowdown water from the steam generators
could affect more actively the eventual increase of admixtures
in the feedwater as the result,in the majority of cases,of leak-
ages in the turbine condensers).

140
 In Stade NPP (PWR), PRO- the plant for clean-up of blow-
down water from the steam generators comprises MHP preceded "by
an electromagnetic filter which retains the main portion of the
suspended cruds.This filter prevents the mechanical contamination
of the ion-exchange beads with crud contained in the blowdown
water.
In Kozlodui KPP, Bulgaria the plant for clean-up of blow-
down water from the steam generators comprises an electromag-
netic filter (13),but the strongly-acidic cation and the
strongly-basic anion exchangers are in separate filters.(The
ion exchangers used are Wofatit RH and Wofatit RO - nuclear).
The ion exchangers are subjected periodically to regeneration
with potassium hydroxide and nitric acid.
In some NPP with WER-440 the systems for clean-up of
blowdown water consist only of ion-exchange filters,the one with
strongly-acidic cation exchanger also taking up the functions
of the mechanical filter.
In the last case,regeneration and upwards rinse in order
to remove the crude from the strongly-acidic cation exchanger is
neede more often in comparisson to the case when using an electro-
magnetic filter.The advantages of the pre-connected electromag-
netic filter are apparent,taking into consideration the saving
of water for upwards rinse and re générâtion:as known,this water
cannot be released before being treated in special water purifi-
cation installations.
Bayer ( 1 4 ) markets the macroporous ion-exchangers Lewatit
SP112MB (strongly-acidic cation exchanger)and Lewatit MP500MB
(strongly-basic anion exchanger)for MBP in the plants for clean-
up of blowdown water from the steam generators.These ion-exchan.

141
gers are not only more stable to osmotic shock and mechanical
wear-out but are characterized by the easier elution (during
regeneration and washing)due to their real porosity which
guarantees better conditions for the diffusion processes.

4 . 1 . 1 . 3 . ION-EXCHANGE SYSTEMS IN THE REACTOR CIRCUIT.

4 . 1 . 1 . 3 . 1 . SYSTEMS FOR PURIFICATION AND CONTROL OF REACTOR

CO OLANT COMPOSITION.

Two main types of light water PWRs are currently used in NPP.
a) light water PWRs (type VYER-440) designed in the USSR,
already installed in many NPP in the Soviet Uni on, Finland, GDR,
Bulgaria,CSSR and Hungary;
b) light water PWRs designed by Westinghouse Co.Babckock &
Wilcox Co,Kraftwerkunion etc.»delivered to NPP in the USA,FRG,
Franc e,Italy,Brasil,Swed en,Japan,Spain,etc.
The main differences between them are as follows (15):
-the TVER-440 reactors are equipped with horizontal steam
generators with stainless-steel straight tubes while the other
reactors have vertical steam generators with U-shaped tubes made
of Inconel-600 and mainly Incaloy-800;
- the sheating of the fuel elements in WER-440 consists of
zirkonium-niobium alloy H-1 containing \°/o niobium while that in
the other reactors consists mainly of Zircaloy-4;

- operating temperature and pressure as well as thermal

loading in WER-440 are lower;
- the by-pass systems for reactor coolant purification and
composition control in TVER-440 operate at the pressure of the
primary circuit ( 1 2 . 5 MPa) while pressure in the other reactor is
lower ( 1 . 5 - 2.5 MPa).

142
 A characteristic feature of water chemistry in PWRe is that
boric acid* is added to the coolant -water.Physical aspects (opera-
tion and degree of fuel burn-up in the core) determine the range
of boron concentration changes from 0 to 2500 ppm,Boric acid
reduces the pH of the pure water for which reason alkalyzing
agents to correct pH are needed.
According to the concept of the Moscow Institute for Atomic
Energy (16) on water chemistry of reactors,the best solution of
the problem of reactor water alkalyzation is the use of potassium
hydroxide and ammonia as alkalyzing agents.Currently,all reactois
of the WER-440 type use KOH and NH, to alkalyze the reactor wate-
(15).The other types of PWRs use lithium base (LiOîl) as alkalyzing
agent.
One of the basic problems of water chemistry in reactors is
the determination of the optimum range of pH values in reactor
water at the operating temperatures (260-320 C) because corrosion
rate of the construction materials,crude solubility,respectively
crude transportation in the reactor circuit depend on pH at
operating t emperatures (17-19).
The concept of the Moscow Institute for Atomic Energy (16)
allows for rather small changes of reactor water pH,viz. PH2600=
7.1 to 7.3 which corresponds to pH2,-0= 9.9 to 10.1
Water chemistry of PWfis of Westinghouse Co (17) allows for
pH changes in the reactor water in a wider range,viz. pËL™ = 4.2~
9.5 or pH30QO = 5.4 to 7.6.

* H^BO^ is added as moderator to control reactivity of the

nuclear reactors.

143
 The above-mentioned differences in the concepts of WER-440
and the Westinghouse-type reactors are reflected in the technolo-
gies adopted in their systems for reactor water purification and
control of its composition.
In PWRs of the Westinghouse type the basic units in the by-
pass system for reactor water purification,called chemical and
volumetric control system (CVCS),include:mechanical filter,
cation-exchange filter and mixed bed filter,Fig. 5 (17).

FL3ter

CATION HEU ±——— —1

"11
COMPONENT j s^~\
0
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COOLING W A T C H \ » | MIXED BED
J> DEMINERALIZERS

. HfAT
l
^•J ^^

V
FROM T H E H M 4 1
f < E G E N £ N A T ( O N 'jViTTM

' r~ii^i
_ j
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TT^ l

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i XCHANtjCK
TOTHERMAL
REGENERATION SYSTEM
D-^-
MEACTort
/Öl AMT t TO BORON RECYCLE SYSTEM
«FACTOR LLTDOrtN OR WASTE PROCESSING SYSTEM
COOl AMT
KEY
RCS - REACTOR COOLANT SYSTEM
COMI'ONFNT BRS - BORON RECYCLE SYSTEM
COOLING WPS - WASTE PROCESSING SYSTEM
IVAILR )
S - SAFETY INJECTION ACTUATION
: A ö
t SIGNAL
l - VENT READER

—inSEAL RMW
-
-
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SAMPLING SYSTEM
COMPONENT COOLING WATER
REACTOR MAKEUP WATER
WATfcfl SEAL WATÉH
HEAT
IXCHANGER
FROM DEMINERALIZED MAKEUP WATER SUPPLY

-
r FROM BORON PROCESSING SYSTEM

BATCHING TANK
AGITATOR

POSITIVE
DISPLACEMCNT
CHARGING PUMP

STEAM

Pig. 5. Chemical and Volume Control System (17).

144
 Tlie coolant by-pass purification systemsin Biblis NPP ( 1 8 )
comprise two MBFs only.(Usually,one is operated on-line while
the other is operated periodically in order to reduce lithium
*
ion concentration in the reactor water; .

A? !S—h ri
O

77

Pig. 6. Scheme of the bypass Installation for reactor

water purification in a WER-440 unit in
Kozlodui NPP ( 1 9 ) .
1 - Steam generator; 2 - Main circulation pump1 ;
3 - Reactor; 4 - Regenerative heat exchanger;
5 - Heat exchanger - cooler; 6 - Cation exchan-
ger filter in H-form; 8 - Mixed bed filter;
9 - Deaerator; 10 - Pump; 11 - Drainage tank.

The coolant by-pass purification system in Kozlodui NPP

(type WER-440) (19) consists of 3 ion-exchange filters,Pig. 6

operated under a pressure of 12.5 MPa,viz.

a) filter with catian exchanger in H-form (item 6);
b) filter with anion exchanger in OH-form (item 7);
c) mixed bed filter with cation exchanger in K-NH, form
and anion exchanger in BO, form (item 8).

* The cation exchanger in the first filter is in Li-form and in

the second filter is in H - form.

145
 Normally,the mixed bed filter only is operating conti-
nually.
The anion filter is operated periodically in order to
a) reduce chloride ions concentration in the reactor
water (if necessary),and
b) reduce boric acid concentration in the reactor water
when BUBO, content in the reactor water is below 1.0-1.2 g/1.
Upon exhaustion the ion exchanger is regenerated with KOH.
The cation filter is operated periodically in order to
a) reduce potassium,lithium and eventually ammonium ions

in the reactor water to prevent pH increase above the permissible

limits,and

b) reduce the concentration of all cations in the reactor

water before it enters the anion filter in the cases when the
latter is used to reduce chloride concentration in the reactor
water.
Upon exhaustion the cation exchanger filter is regenerated
with nitric acid.
In some NPPs with TVER-440 the cation exchanger filter in
CVCS is substituted by a mixed bed filter (20).
According to available information,irrespective of the type
of CVCS they have practically the same effectiveness.
The decontamination factor in relation to the total acti-
vity is in the range 50-100 (it depends on the total activity of
reactor water),(17-19).
The unique technology for reactor water clean-up and
control,adopted in the Soviet PVIR type WER-1000 (20) deserves
mentioning.Two parallel plante for reactor water treatment are

146
provided:
a) Plant 1 - It consists of 3 MBFs operated at the water

pressure in the reactor circuit. These filters contain the

strongly-acidic cation exchanger KY-2-8 and the strongly-basic
anion exchanger AB-17-8 (volumetric ratio 1:1).(This plant is
run at stationary operating conditions of the reactor).
b) Plant 2 - Consists of 2 lines,each one comprising 3
filters dia 1000 mm.(One of the lines is in operation while the
other is a stand-by or is being regenerated).Operating pressure
is 2 MPa.
Two of the filters in each line are with the strongly
acidic cation exchanger KY-2-8 ,one in H-form and the other in

NH* (K+-ftH+) - form.The third filter is with the strongly-

basic anion exchanger AB-17-8 in OH-form.
The ion-exchange resins in plant 1 are not regenerated.
The ion-exchange resins in plant 2 will be regenerated.
Their life is between 2 and 3 years.
Considering the insufficient thermal stability of the
anion exchange resins the treated water temperature is limited
to a maximum 50 (60) C in all ion-exchange plants for reactor

water clean-up.
The ion-exchange resins in MBF are normally not regenerated.
After one year,when their total >"" -activity becomes 500-1 OOOCi/6r
resin,they are replaced with fresh ion-exchange resins.

4 . 1 . 1 . 3 . 2 ION-EXCHANGE SYSTEMS FOR CONTROL OP BORIC ACID

CONCENTRATION IN REACTOR WATER

There are technologies which make possible H,BO, concentra-

tion in the reactor water to be controlled using ion-exchange

147
 g ft 140
x
- - ^_ _ _ ^ 9.J
20'
/
H 120 / tt
>X ,r§r i
A

*<* ^
r
°*^- 100
3cT so y ïx

X ,X t
tK -
Strf ^® i
to to An
V—"
•***^
^,.
H
01 2 3 4 5 6 7 8 9 10 fl
H,BO» concentration, g/1

Fig. 7 Boric acid sorbtion capacity of strongly basic anion

exchanger at 20°C and 80°C (25).

filters with strongly-basic anion exchanger in BO, form been

found out that the strongly basic anion exchangers have different
sorption capacities toward BLBO, at different temperatures (21-24).
At higher temperatures (60-80°C) sorption capacity is
lower than at 20°(10°)C, Pig. 7 , ( 2 5 ) .
This makes possible,by changing the temperature of the
water stream in the ion-exchange filter,to reduce H,BO, concen-
tration in the water flow by sorption of H,BO, by the ion-
exchanger (when lowering the temperature to 10-20°C),or to
effect desorption of H^BO^ by the ion-exchange filter,respective-
ly to increase H,30, concentration in the water flow (when raising
water flow temperature to 60-80°C).

A scheme of such ion-exchange plant for H-JBO, concentration

control in the reactor water,using the so-called thermal regene-
ration process is shown in Pig.8.A plant of this type is already
in operation in Ringhals NPP,Sweden.
The technological potentialities of this process can be
judged from the data about the sorption-desorption capacity to

148
 to r « fi r t. or

1-Reganerative heat o::olianger, 2-Mixed bed n i t e r s , 3 , ^ , 5 - E e a t excli&ngers

E- Cooling circx-ite, 7-Ajnion excliange filters for HBO sorbtion/cesorbtion
Z- Volume ooVitEOl tank, 9-Feed pump

Fig. 8 Flow Diagram of System for ion-exchange Thermal

Regulation of Boric acid concentration (type Westing-
house C o . ) ( 2 1 ) .

EU ECU of the strongly-basic anion exchangers used to this end

at different temperatures, Fig. 7.
The data in Fig. 7 ( 25) reveal that the amount of E,BCu
which can absorb 1.0 1 of the strongly-basic anion exchanger
type I Wofatit RO at 80 °C is by about 20 g less than the amount
of ELK)., which this anion exchanger can absorb at 20°C. It is
evident also that this difference in the anion exchanger's
absorption capacity, depending on temperature, remains practically
constant at H^flO, concentrations in the water in contact with the
anion exchanger in the range 2-10g/l H^BO^. Evidently, without
using reagents, only by changing the reactor water temperature
through a filter with strongly -basic anion exchanger type I,
each 1.0 1 of this ion exchanger can desorb 20g HBO

149
(at 80 C) and sorb 20 g H,30^ during the next temperature de-
crease to 20°C.
It is noteworthy that the strongly-basic anion exchanger
Wofatit RO in B0,-form is stable at 80°C and that the anion
exchanger retains its capability to desorb-sorb reversely EL BO,

even after 20 cycles of thermal desorption-sorption.This stabi-

lity has been confirmed by the treatment of the reactor water
in the WER-440 unit in Kozlodui NPP (25).
In Ringhals NPP whose system for ion-exchange control of
EzBO, concentration has been designed by Westinghouse Co the
operating temperatures are
60°C (desorption of H,B0 5 ),and
10°C (sorption of H,BO X )»respectively.
j

4.1.2. ION-EXCHANGE SYSTEMS IN NPP WITH BWRs

4.1.2.1. ION-EXCHANGE SYSTEMS FOR REACTOR WATER CLEAN-UP AND
TURBINE CONDENSATE (FEEDWATER) POLISHING

Normally,two systems for water streams clean-up are needed

in order to meet the requirements for a high degree of purity
of feedwater and reactor water in NPP with BWRs,Table 1,Fig.9,
viz:
a) System for feedwater (turbine condensate) purification);
b) System for reactor water clean-up.
In the Winfrith SGHWR (26) the same system (Powdex-filters)
is used to clean up both the feedwater and the reactor water,

Pig. 10.(interesting in this case is that the turbine condensate

after the LP heaters is being treated only).

150
 TABLE 1. BWR VATER CHEMISTRY (27).

Ccnc '.-.;:• .u:.:."5 - ?_r:s par Billion (pi/'s Conductivity

Iron Ihloridc umho/cm at 25'C ?H at 25"C

".5 to 3C to 5 ^ 20 < 20

H:Ti-.ar.t l '-o 15 -' 0.2 20 to 50 ^^ 7

5 -.o 15 ~ 0.2 20 to 50

Reactor -vawr
1. Normal CperuTion 10 to 50 < 20 < 20 100 to 300 0.2 t ~7
2. Shutdown <20 <1
3. Hat Sr.incby <20 <1
<20 8,000 <2 6 to 6.5

Steam 10,000 to 30,000 —0.1

Ccr.'jol RJCÎ Dnvo

tool.nr *".scur 50 :c 500 < 20 <3,000

C o nd P n_Sfl1f
oraqe .
T.infc

Fig. 9 BWR water cycle ( 2 6 ) .

Although it poses operating limitations,the experience with

this unique system is of undouted interest:

... "The SGIÏWR feedwater and coolant clean-up plant ( 2 6 )

consists of two Powdex filters (type Gr-aver) opera ting at 110-116°C
coated with powdered ion-exchange resins.(Cation /anion exchangers
ratio is 2 : 1 ) .

151
 CONDENStR
70/:0 MASS
90/10 C»/NI
7O/X> C«/NI

Fig. 10 Simplified Peedwater / Coolant Cycle for WSCHWR (26).

The system deals with the full feed-water flow 550

plus 20-25 nr/h reactor coolant which is mixed with the feed-
water. Operating period of each filter is about 2 weeks and
normally one unit is recoated every 7 days. Weight of resin per
recoat cycle is 81 kg dry resin. Therefore, one unit treates
about 96 000 nr water between recoats.i.e. resin consumption
•*
is 0.85 g Per 1 nr of water treated." ...
..."Total activity removal efficiency is about 85>° for
a total activity of water before the Powdex filter 0.05 Ci/1.
(it deserves mentioning that coolant activity has been reduced
25 times because this water has been diluted in 25 times larger

amount of feed water)." ...

..."That comparatively high removal efficiency is due to
the fact that at total activity of water up to 0.05 Ci/1 the

152
activity is caused mainly by the cations of the Fe,Cr,Zn,Mg
isotopes etc" ...
..."When total activity of treated water is about 1 Ci/1,
i.e. when the main nuclides are predominantly in anionic forir
(iodides or iodates of ^ I; ^1 etc),plant 1 s efficiency is lower.
In the begining of the cycle removal efficiency is up to 75/e and
at the end it is barely 30^. (This is due to the thermal degra-
dation of the anion exchanger in the Powdex filter.With time,
at a temperature of 110°G,the anion exchanger looses its
strongly-basic active groups)." ...
..."At 110°C the plant cannot remove the silica from the
water treated.(if necessary,the temperature should be reduced
to 5 5 ° C ) . . . " ( 2 6 ) .
The individual systems for coolant clean-up are usually
designed to treat the coolant taken from the bypasses.The nor-
mal clean-up flow (nr/h)is 2-/o of the feedwater flow at 100/a
reactor power.(However,in some NPP with BWR the amount of by-
pass treated coolant is larger, e.g. in Tsuruga the plant for
coolant clean-up has a capacity 6,7> of the feedwater
stream (28).
The coolant clean-up plants operate at pressures 20-30/°

higher than in the core.Treated water temperature is reduced

to 30-60°C.The demineralization units are loaded with a mix of
cation-exchange resin in H-form and anion-exchange resin in OH-
form in a ration 1:1 to 2:1.
Removal efficiency of impurities from treated coolant is
about 90?» when the plant comprises only ion-exchange deminerali-
zers of the mixed-bed filter type (29).

153
 Hakala and Hinttala report that coolant clean-up in Fin-
land's NPP TVO-I/II (34),using a radial flow MEF.is highly
effective toward the radioactive impurities (99/S). Silvennoinen
(39) adds that this system is very effective also for corrosion
products removal:Pe content in condensate is 50 ppb before MBP
and 1 ppb after it.
Data are available (29) that the mechanical filters (Pre-
coat type),installed before MHF,remove between 96 and 99i?£ of

the corrosion products,above 0.45 Ms®- in size,from the coolant.

An. idea about the demineralization potentialities of the
ion-exchange demineralizers,type MÏÏF (installed after the mecha-
nical filters in the coolant clean-up system)give data in
Table 2 referring to Tarapur UPP (29).

TABLE 2. Decontamination factors in the ion-exchange units of the coolant

clean-up plant at Tarapur ( 2 9 ) .

Nuclides Initial phase of End of

operating cycle cycle*

8 000 16
132.,- 3.1x1044 2.6x10 3
133-j. 5.2x10 3
239NP 7.U10* 670
99
Tc 6.5x103
137Cs 5.8x103 1.2x102
134CS 5.3x103 1.4x10 2
600o over 1.5x102 1.7
103
Ru 5.9
95zr 1.52

* Ihis cycle ranges between 8 and 12 months,

154
 TABLE 3. Effect of Tsuruga NPP coolant clean-up plants (28).

Removal
Inlet Outlet efficiency
Impurities, nuolideo Unit inlet concentr.
mechanical filter mixed bed
demineraH zer outlet concentr.

Conductivity at 25 °C ^S/cn, 0.1O-0.16 '0;05

Chlorides ppb 20 20

Iron: a/ > 0.45 ^tua ppb 6.3 0.02 -315

• b/ < 0.45 .^ m ppb o.o4 0.01 **
Copper: a/ > 0.45 ^m ppb 0.1 0.001 10
D/ ^ O«'i~5 yi^ni ppb 0.32 0.005 64
Nickel: a/ > 0.45^ m Ppb. 0.02 -0.005 . 4
b/ < O.45 m Ppb 0.05 O.OO? 7
Cobalt: a/ ;> 0.45^0 ppb 1.0 0.1 10
b/ £ 0.45 >^-(n ppb 8.3 1.0 8
-3
8
1-131 -Ci/na 2.5x10"^ 2.7x10~ 9360 = DF

ii 5 7
1-133 3.5xlo" 5.2x10" 6730'= DF

n 7 7
Cß-137 9.0x10~ 1.1x10~ 8.2 = DF
5
Co-60 u 3.6x10~ 4.6X10-6 9 = DF

For comparison purposes,Ta"ble 3 illustrates the overall

effect of clean-up at Tsuruga NPP (28) whose coolant clean-up
consists of:

- Unit for mechanical filtration: precoated filter with

Solcafloc;
- Unit for ion-exchange demineralization,type M3F.
The system for coolant clean-up in the Leningrad NPP is
similar, Fig. 11 ( 3 0 ) .
The coolant bypass purification system consists of precoat
filters with Perlite powder as filter aid and mixed-bed filters
with nuclear-grade cation exchanger KY-2-8 and anion exchanger
AB-17-8 (Cat : An = 1 :1 ).

155
 Fig. 11. Flow diagram of bypass reactor water purification
system in RBMK* <30).
1 - Reactor; 2 - Steam generator; J - Main
circulation ppump; 4 - Regenerative heat
exchanger; 5 - Post-cooler; 6 — Precoat filter;
7,8 - Mixed-bed ion-exchange filters; 9 - Filter
trap; 10 - Pulp vessel.

* Reactor type RBMK-1000: Boiling-water channel-type uranium

graphite reactor.

The protection against any drain system failure is provi-

ded by a mesh filter trap installed after the ion-exchange
filters.The water for purification (200 ar/h is taken from
the pressure header of the main circulation pumps of both
reactor circuits and is cooled down to 180°C in the regene-
rative heat exchanger and then to 50°C in the post-cooler.
The purified water is returned through the regenerative heat
exchanger to the reactor circulation circuit.The equipment
operates under the pressure of the circuit; when the main
circulation pumps are out of operation the purification water is
delivered by shut-down circuit pumps.Heat exchangers/post-
coolers are used in the shut-down reactor cooling system as
well.
Down the ion-exchange filters the impurity concentrations
were as follows:hardness salts - not detected,chlorides - less

156
than 5 pp"b,iron - 5-10 ppb, copper - less than 10 ppb.The pH
value was 6.8 - 7.0.
The blow-down water DF equal to 100 (i.e log DP = 2 ) is
reached by passing 800 000 m3 water per 5 nr3 ion-exchange resin
charge, i.e the coolant specific rate equals 160 000 nr of water
per 1 nr of ion exchange resin, Fig. 12.

I
4

3
g "
o
H
£••

-4-

2 a3 4 5 6 7
10
Volume» oT puaalii<7 coolant

Pig. 12. Change of Decontamination Factor (DF) of

mixed bed purification system (30).
x - first,A - second, o - third charge of ion exchangers

•The ion-exchange resins in coolant clean-up systems are

not regenerated.Instead, fresh resin is loaded.
The efficiency of the coolant clean-up systems consisting
of Powdex filters only is usually higher than that with i-LdF.Nor-
mally, life of the Powdex filters is about a month.
Normally,the powdered ion-exchange resins used to clean
up the coolant are changed in the following cases:
a) hydraulic resistance of the filtering layer ion-exchange

resin abnormally high;

b) increased silica concentration in the filtrate;

157
 c) specific electrical conductivity of filtrate above
0.2 MS/cm.
Usually,total ^-activity of the exhausted powdered ion-
exchange resin is about 50 Ci/nr.
In the condensate polishing systems of NPP with B¥R,ion-
exchange déminéralisation and removal of corrosion products
from the turbine condensate (dissolved or suspended in it) is
done with:
a) Mixed bed filters of strongly-acidic cation exchanger
in H-form and strongly-basic anion exchanger in OH-form.(For
example the condensate polishing system of the Leningrad NPP,
USSR (30),Tsuruga NPP,Japan (28),Dresden NPP,USA ( 3 1 ) .
b) Powdex filters - pre-coated with a mixture of powdered
strongly-acidic cation exchanger in H-form and strongly-basic
anion exchanger in OH-form.(For example the condensate polishing

systems in Ttfttrgassen NPP,PEG (32)»MUhleberg NPP,Switzerland (33),

WO-I/II NPP,Finland (34),VBrmont Yankee NPP,USA (35).Comparatr

ly rare is the case of the BWR in Ringhals NPP,Sweden with its
two possibilities for condensate polishing:
- ion-exchange filters pre-coated with powdered ion-
exchange resins (Powdex filters),
- ion-exchange filters type MBF.
Under normal operating conditions,only the first Powdex
plant is in operation while MBF is operated only in case of
considerable leakages from the turbine condensers (increased
electrical conductivity of turbine condensate).
Schröder (36) points out that the main advantage of the
condensate-polishing systems with Powdex filters is that they
remove over 90?<> of the corrosion products contained in the con-

158
 densate treated, th.e respective figure in the case of MBP being
about 60>.

However, as evidenced from data in Table 4, (28) about the

*
condensate-polishing system of Tsuruga &PP ,the efficiency of
corrosion products removal using MHF is also around

TABLE 4. Effect of condensate polishing system in

NPP (28).

Inlet Outlet Removal efficiency:

Unit inlet concentr.
Indicator Condensate polishing system outlet concentr.

Conductivity at 25 °C *^S/cra 0.07 O.o6 _

Iron (> 0.^5 s«* m ppb 26.6 1.6 17
< O.*f5 /*, m) ppb 0.7 O.it 1.8
Copper ( x> 0.45 ^ m ppb 1.56 0.03 52
^ 0 f*? / f i > ppb 0.50 0.03 17
Nickel ( ^^ 0 ^t ^î A ^ ppb 0.03 O.OO't 7 .5
< O.'t5 /•"> ppb 0.05 0.007 7 .1
Chromium (j?0.'t5 ^ ra ppb 0.05 0.00't 13
<0.ij5 > m ) ppb O.OCA 0.002 2
Cobalt ( * 0.^5 ppb 2.6 0.3 8 .7
0
< O.'tf
A"
1 1) ppb 12.1

8.1x10"6
0.9
1.1x10"8
13
736 = DF
1-131
5
1-133 . ~ Ci/ml 8.5x10~ 1.3x10"7 DF
Co-60 ^ci/na 1.1x10~8 1.3X10- 10
85 = DF

It should be also mentioned that the ion-exchange resins

in the condensate-polishing systems with MHF are often strongly
contaminated with corrosion products which results in shorter
life of the filters,increased consumption of water and chemicals
for regeneration and increase of radioactive waters volume.

* The system comprises 5 MBS each holding 5.1 nr mixture of strong

ly-acidic cation exchanger and strongly-basic anion exchanger
(ratio by volume 1.7:1).Filtration rate of condensate through MBP
is 90 m/h, (28).

159
 As practice in Dresden 2 and 3 NPP shows (37) the negative
phenomena in the operation of condensate polishing systems with
MBP can fee considerably avoided if adopting ultrasonic cleaning
of resins for condensate purification mixed bed filters (38),
Pig. 13.

Fig.13. Ultrasonic cleaning system of deep-bed resins

for condensate déminéralisation systems (38).
1 - Input of deep-bed ion-exchange resins; 2 -
Recirculation line; 3 - Cleaned ion-exchange resin;
4 - To the filters of the condensate-polishing
system; 5,8 - Deionized water; 6 - Line for
transportation of the ion-exchange resin cleaned
ultrasonically; 7,9 - Control board; 10 - Power
supply board; 11 - Column for ultrasonic clean-up;
12 - Pulp and waste water vessel; 13 - Air breader;
14 - Transportation line for the water ion-exchange
resin mixture transportation; 15 - Ion-exchange
resin vessel; 16. Clean-up region.

<^

Ultrasonic treatment (0.5 ¥/cm ) makes possible to remove

over QQfi of the corrosion products stuck to the ion-exchange
without causing any mechanical destruction of the resin beads.

It has been established that when using periodically (once per

10-20 days) ultrasonic cleaning of the ion-exchange resins of

160
 MBF in Dresden 2 and 3 NPP the ion-exchange resins must be
chemically regenerated once per 120 days.As a result,MBF regene-
ration costs have been cut five-fold (38).

The turbine condensate in the Leningrad NPP is polished by

running it consecutively through a H-cation exchanger filter

(serving as a pre-filter) and MBF.In the latter filters external
regeneration in special vessels is provided (items 4 and 5 in
Fig. 14).

Fig. 14. Turbine condensate purification system (30).

1 - cation exchange prefilter, 2 - mixed bed filter, 3 - filter-trap, 4 - cation

exchanger regeneration tank, 5 - mixed bed resins regénérâtionen tank, 6 - rinse
water pump, 7 - 5 $ HNCU, 8 - return water, 9-4$ KOH, 10 - discharge for re-
processing.

Filtration rate of turbine condensate through the ion-

exchange filters is 80 m/h.When pressure loss in the H-filters
reaches 0.25 HP3- they are shut down and the ion-ex change resin
is washed with demineralized water,Usually,this operation takes
place once per 10 days.

161
 In MBP the cation exchanger and the anion exchanger are
in a ratio of 1:2.The increase of sodium ions leakage leads to
MBP shutdown.
Operating time of MBP is about 4 months.The anion exchanger
is regenerated with 4>i NaOH,and the cation exchanger with 5;£
HNCU.
The qualities of the polished condensate are as follows:
PH - 6.9-7.1 6.8-7.2
conductivity A'fS/cm 0.4 0.4
total hardness g-eg/kg 1 1
chloride Ppb 1 1
oxygen ppb 10-30 5-40
iron ppb 1-4 1-4
copper ppb 0.2 0.2
According to Ryan (37)»the condensate polishing systems
with Powdex filters in NPP with BWR have certain advantages as
compared to MBP:
... " ...Pig. 15 presents a comparison of total operating
costs for one full power year for the three systems.The costs
include installed capital costs converted to an annual cost "by
use of a 13->0 factor. The comparison shown on Fig. 15 demonstrates
several intersting points.
Por the range of service periods for each alternate,the
radwaste costs are a significant part of the total for the two
systems utilizing deep beds of "bead ion-exchange resins. The
powdered ion-exchange system costs are affected to a similar
degree by radwaste considérations.Por powdered resins the
radwasteassociated costs represent only 6.8# of the total costs
at a 20-day run length and 10/î at a 10-day run length.

162
 POWDEX ® DEEP BEDS DEEP BEDS
600
ULTRASONIC ULTRASONIC
CLEANING CLEANING

X
THROW AWAY CHEMICAL
BEDS REGENERATION

fe "°°
0
"STOTAL
z " \s^
§
EVALUATED
^TOTAL
TOTAL

0
O RADWASTE
»^DISPOSAL
RADWASTE
- DISPOSAL
RADWASTE - ***'«*••„
DISPOSAL
1 t 1 l l 1
RUN 10 15 20 6 9 12 60 9O 120
LGTH
DAYS MONTHS DAYS

Pig. 15. Comparison of total operating costs for one

full power year (37).

For the deep-bed system,using ultrasonic cleaning and

periodic regenerations,there is little additional total cost
reduction achieved by extending periods between regeneration
beyond 60 days.At 60 days,the cost of régénérante and their
disposal have been reduced to about \^% of the total cost.
By using the narrow range in cost for the ultrasonic
cleaning plus regeneration system as a base the run length for
the powdered ion-exchange resin system must be in the range of
12 to 15 days to be equivalent.For the throwsway bed system,
the beds must last at least 12 months to be equivalent.Thus,
even allowing for the approximate nature of the cost estimates,

an order-of-raagnitude comparison is available comparing actual

or anticipated performanes."(37)
Experience in JtfPPs with BWR shows the technological
effectiveness of the powdered resins (32,34):In Wrgassen NPP
(32) by using of the powdered resins the quality of the conden-

163
sate polishing unit effluent is as follows:
total iron not detectaole
total copper 1 pp"b
chloride not detectable
Si02 4 ppb
conductivity (at 20°C) 0.05 /US/cm
The similar results have been obtained in TVO I/II foPP,
Finland (34) where the condensâte polishing is processed in the
full flow pre-coat filter (filter-demineralizer) system designed
by ASEA-ATOM.The system consists of 7 filters with vertical rod-
shaped filter elements coated with powèered ion-exchange resin.
-~>
One of the filters is in stand-by.The filter area is 73 m .
The operating temperature of the filter is 65°C.The ion-
exchange resin is a mixture of anion-exchange and cation-exchange
resins.
As a characteristic information about the powdered ion-
exchange resins consumption for condensate polishing by Powdex
filters in NPP with BWR can be used data for Mühleberg NPP,
Switzerland(33).The run length of the powdered ion-exchange
resins are about 1 month while powdered ion-exchange resin con^.
sumption is 0.25 g per 1 nr polished condensate.Usually,the
exhausted powdered ion-exchange resin from condensate polishing
units in NPP with BWR has total /"-activity 1-5 Ci/m^.

4.1.3 ION-EXCHANGE UNITS IN TYPICAL RADIOACTIVE LIQUID WASTE

SYSTEM AND IM CLEAN-UP OP FUEL STORAGE POOLS IN PWR

AND BttR STATIONS

Ion-exchange processes find application in liquid

(aqueous) radwaste treatment in nuclear power plants.

164
 f Hier demin«r«lij« (Powder)

IIQUIOWASJES

1. Hvdrog*|naierJ (primary)
Primoiy coolant let down Oisrharje
Primary «itnonwnt drmm

7. Aerated (service)
Lab. and sampling drains
Floor drams
Oeminrraltfft dr»-m

liundry ind ihow)i drams

I__ Rev«,

Pig.16 Typical radioactive liquid waste systems for a

pressurized water reactor (PWR) (40).

LIQUID WASTES Ion exchange

Precoiil tiller
1. Low conductivity
Equipment dtains
Clean up and fuel pond system

7. High cnnductivity
Floor dfnins
Samijling and tab. drains
n<-r}C'iC'On(s and ducontnminalipn

Lntirulrv und <huwor drnins

Fig. 17 Typical radioactive liquid waste systems for a boiling

water reactor (BWE) (40).

Usually,they are used for decontamination of water flows

with total dissolved solids content of less than 500 (1000) mg/kg.
For that reason,as evident from Fig. 16 and Fig. 1? ( 4 0 )
the ion-exchange processes are used mainly to decontaminate
water flows with limited salt content and condensâtes produced
in evaporators when treating liquid radwaste with considerable
concentrations of dissolved and suspended matter.

165
 The ion-exchange units used in these cases are either
individual cation-exchange and anion exchange filters or mixed
bed filters.(in more rare cases precoat filters are used).
Most frequently,strongly-acidic resins and strongly-basic
resins of the macroreticular type are used.
The normally exhausted ion-exchange resins are regenerated,
i.e. they are used many times.
The decontamination factors found with the ion-exchange

units with respect to the various nuclides depend on the type of

the treated water and the ion-exci;ange system used. This is best
illustrated in Table 5.

TABLE 5. Decontamination factors for BWR and PWR liquid waste

treatment systems (ion-exchange units) (40).

Treatment system Decontamination factor

Demineralizers Anion Cs.Rb Other

nuclides

BWR
High purity -waste (mixed bed) 10 2 (10) 6 10(10) 10 2 (10)
Low purity waste
mixed bed 10 2 (10) 2(10) 10 2 (10)
cation exchanger bed 1(1) 10(10) 10 2 (10)
anion exchanger bed 10 2 (10) 1 (1) 1 (1)
PWR

Radwaste (TT+/OH~~-ion exehaneer 10 2 (10) 2(10) 10 2 (10)

filters

Evaporator condensate polishing 10 10 10

Boron recycle system feed

),) 10 10

166
 The ion-exchange systems for fuel storage basins (pools)
are designed for decontamination and clarification of the pool
•water. In view of the fact that pool water* contains both soluble
and insoluble impurities it is often filtered (Precoat-filter)
followed by mixed-bed ion-exchange unit.
In some cases,when Cs isotopes prevail in the pool water,
inorganic ion-exchangers are preferred because of their higher
selectivity toward these ions.
Lin ( 4 2 ) describes such a system for pool water clean-up.

The system consists of a filter containing Zeolon-900 (inorganic

_2
ion-exchanger).For Cs content in pool water 4 x 10 Ci/ml

this filter treats approximately 40 000 bed volumes of pool

water before breakthrough of 1 -"Cs.The
^7 ion-exchanger used is
regenerated with ammonium sulfate solution (42).

As evident from the above text,the operation of nuclear

power plants is accompanied by the producing of some amounts of
ion-exchange resins,mostly containing nuclides, Table 6 (41 ).
The problems of their storage pose a separate technological
problem which will not be discussed here because recently IAEA
published a detailed account on this subject (41 ) which reflects
the experience,the state of the art and the future trends in
this field.
We will point out here only a recently studied perspective
possibility to lower the total activity of spent resins with
electrodialysis partial decontamination of spent ion-exchange
resins(43).It concerns spent ion-exchange resins decontamination

* Fuel storage basins of KPP provide storage facilities before

irradiated fuel elements are sent for reprocessing.

167
00
TABLE 6. Spent ion-exchange resin waste arising from
operating nuclear power plants (41).

Reactor Power îype of Specific

îype out put i on-exchange Quantity Activity
C ount iy MWfe) resins Ci/T. 3 Remarks

Jerrr-ar^y, FKR 1300 bead resins 3 102 - 5.102 1 General date (a'v-erage)
^* BWR 1300 powdered resins 115 a.io^-io"1 ) condensât» cleaning
of*, •• M 10 I-"1 0 reactor water cleaning

BXR 240 " " 35 '*•' 10-20 ^ Cumulative for 9 years

(Lingen)

BWR 237 " " 4.5 400 reactor coolant

( Gundrenucingen)
n it 2 70 liquid effluents
H n 0.5 10 fuel storage pond

FrfR 640 " " 10 1 condensate cleaning

(Wurgassen)
n « 1 50 reactor coolant

bead resins 4 2 licuid effluents

PVTR 622 » " 0 *4 reactor coolant cleaning

(Stade)
0.65 100-200 reactor coolant treatment

0.5 fuel storage pond

PWR 1200 " " f+* 2

(Biblis)
 TABLE 6. (continued).

Pov:er type of Spec: fie

Reactor output ion-exchange Quantity Activity
Country Tvoe T.n-,'(e) resins ft'V.vr Ci/ftJ Per.arks

USA BWR
(Nine Mile Point) 620 "bead resins 500 ft3 0.1-1 Ci/ft - condensate demineralizes
- fuel storage pcnd
- waste collector
- Rx cleanup
powdex and /or solka floe 1,582 ft 3

FrfR
(Oyster Creek) 670 "bead resins 500 ft3 0.2-3 Ci/ft 3 " " " •'

powdex and /or solka floe 2,625 ft 3

\o
from CMDU-PHT purification columns (mixed bed ion-exchange
resins in Li+/OD~ forms). The principle of the process-termed

EDRD (Electro-Dialysis Resin Decontamination) is illustrated

in Pig. 18.

A - Anton Seicttvc Membront

C * Cation Selective Memörone

l(a) Kb)

Fig. 18 Principle of the Electro-Dialytic Resin Decontamina-

tion (EDRD) Process (43).

..."The process involves passage of a dc electric current

through a bed of the spent ion-exchange resin in a specially
designed electro-dialytic- cell consisting of alternate cation
and anion selective ion exchange membranes.Fig.18(a) shows the

service run of a fresh Li+/<DD~ form mixed bed resin during

which radioactive Cs" f (fission product) in the PHT fluid is
exchanged for Li"*" on the cation resin component.Fig. 18 (b)
shows the decontamination process.Under the influence of an

applied dc electric potential,electric current passes through

the Cs + form resin,in preference to the Li + form resin,thus

preferentially removing Cs+ ions from the resin bed and transpor-
ting them through the cation selective membrane.Dilute LiOD
(r-^0.01 M) solution is circulated through the cell as shown in

170
the figure.Any exchange sites vacated by Cs+ ions will be
occupied by Li4" ions provided by the solution thus improving
further passage of electric current through the Cs+ sites on
the resin.A dilute LiOD effluent stream from the cell,containing
small amounts of Cs+ is passed through a Cs selective sorbent
which selectively removes Cs+ from the stream,and the LiOD
solution exiting the sorbent column is returned to the electro-
dialytic cell.

The EDRD process appears to be economically attractive.

Annual cost saving of about 110 000 Canadian dollars are esti-
mated for EBRD processing of Ontario Hydro's spent PUT resins.
Although the EBRD process was developed primary for decontamina-
tion volume reduction of spent PHT resins,the process can be
effectively applied to in-line purification in the PHT circuits
of CANDU reactors to directly minimize the volume of ion exchange
resin usage.11 ... (43)

REFERENCES
(1.) Dobrevsky,I., D.fiazsukanov,N.Tilov, H.Georgiev, N.Cherva-
shidze, Papers of 2nd National Conference of Water treatment,
Water chemistry and Corrosion in Power Stations and Nuclear
Power Stations, Varna (Bulgaria) May 11,13 (1971 ) ,214-219.
(2.) Triobed: Improving the efficiency of mixed bed of ion
exchange resins DIA-PROSIM (Paris) INF.N 77001 A,Sept. 1977.
(3.) Dobrevsky I., Teploenergetika 70 9 (1979).
(4.) Schröder H.I., "Wasserchemie im kernkraftwerk mit Leichtwasser,

reactor "-Jahrbuch "Vom Wasser',' 4J_ (1973) Verlag chemie,

Weinheim /BRD/,(1974).

171
 (5.) Bohnsack G., Phosphorsäure im Dampf, VGB Speisewassertaguhg-
1969, Essen (BRD), Vortrage,s.41-47.
j

( 6 . ) Dobrevsky I., V.Tchankov, M.Georgiev, Sb.dokladov III

Symposium po teme "Vodni regim,vodopodgotovka i problemi
KGO na AES" »Neubrandenburg (DDR),2. (1976).
( 7 . ) Langeker K., B.Tille, B.Shltch, Sb.dokladov Hl r Symposium
"Vodni regim,vodopodgotovKa i problemi KGO na AES", Neubran-
denburg (DDR) 2 (1976).
(8.) Doi M., T.Hattori, Secondary water chemistry of PWR nuclear
power plant, Water chemistry 11,MES (1980) 17.
( 9 , ) Rootham M . W . , R.Philippe, Full flow condensate polisher
experience in the secondary water chemistry control of PWR
plant, Water Chemistry of Nuclear Reactor System,BNES (1978)43.
(10.) Roothhooft R., "Chemische Betriebserfohrubgen in den

begischen Kerukraftwerken Doel und Tigange"-VGB Speisewasser-

ta gong, 1978, Essen ( BRD ), Vorträge, 36.

( 1 1 . ) Margulova T., Martinova 0., "Vodnie regimi teplovich i
atomnich electrostancii (Water regimes of Power and Nuclear
power stations)»Moscow,publ. "Vichaia Shkola",1981.
( 1 2 . ) Condensate purification system of secondary curcuit of NPS
"Kozlodui" Archif of NIPPIES "Energo project",Sofia (1975).
(13.) Dobrevsky I., G.Litovska,Z.Kalpatchiev, G.Konova, Yearbook
of NIPPIES "Energoproekt",Sofia,1982 /in press/.
( 1 4 . ) Lewatit - Mischbettfilter fttr die Ab schlämmen t salzung in

Kernkraftwerken mit Druckwasserreactoren-Bayer-Ieverkussen

(1978) (Best. H-OC-1-20368)

172
(15.) Dobrevsky I., Evaluation of Water Chemistry Specification in
Nuclear Power Reactors, Chapter I in IAEA Technical Reports
Series N...»Vienna, (1983) /in press/.
(16.) Alekseev B.A., B.A.Ermacov, B.F.Kozlov,E.C.Chernorotov - Sb.
dokladov "2nd National Conference of Water treatment,Water
Chemistry and Corrosion in Power and Nuclear Power Stations",
Varna ( Bulgaria ),11-13 May ,(1971) 175-194.
(17.) Pincone L.F., Westinghouse PWR Systems with Operation
Experience,Presented at Course on Reactor Chemistry,Studsvik
Sweden,September 12/14 (1973).
(18.) Schroeder H., Dorr A.»Pattrath G.. Chemie in Kernkraftwerk
Biblis. V.G.B.-Speis ewassertanung-1979,Essen,Sonderheft.S.
35-47 (1979).
(19.) Dobrevsky I., Zankov V. Experience in Water-Coolant Chemistry
in P¥R Primery Circuit of Nuclear Power Station-Kozlodui
(Bulgaria)-IAEA Specialist meeting on "Influence of Power
Reactor Water Chemistry on Fuel Clodding Reliability"-San
Milano (Italy),Oct. 12-1 6 (1981 ).

(20.) Kulski L.A., E.B.Strahov, A.M. Voloshilova, V.A.Bliznjakova,

"Ochistka vod atonioh electrostanchii " Kiev,publ t Naukova
dumka,(1979).
( 2 1 . ) Westinghouse Electric Corp.(USA),US Patent 4017358,12.04.1977.
(22.) Laborelek, Section 5, Essaiis de deboration et de regeneration
thermique sur résine echangense d'ions,1971.
(23.) Laborelek, Section 5 "Deboration et reboration de circuit
primaire par modification de température d'échange de resins
fortment basic (1978).
(24.) Dobrevsky I., J.Seikova-Sorbtion and Desorbtion of Boric Acid

with Strong Basic Anion Exchangers, Papers of 2nd National

173
 Conference of Water Treatment,Water Chemistry and Corrosion
in Power and Nuclear Power Stations,Varna (Bulgaria),May
11-13,(1971).
(25.) Dobrevsky I., Konova G-., Termoenergetika (Moscow)S^ 10 (1977).
(26.) Perret D.J. Experience with the Decontamination of Zircoloy
Fuel Clusters in the Winfrith SGHWR.IAEA Specialist Meeting
on"Influence of Power Reactor Water Chemistry on Fuel
Clodding Reliability,San Miniato (Italy),Oct.12-16 (1981).
(27.) Fizzoti C., L.Castoldelli. Corrosion of Some Zirconium
Alloys in BWR Reactors, IAEA Specialist Meeting on "Influence
of Power Reactor Water Chemistry on Fuel Clodding Reliability"
IWRPPT/11,Vienna,June (1982) 74.
(28.) Yoshinori Merguro. Primery System Corrosion Product and
Radiatin Control at Tsuruga (BWR)-IAEA Specialist meeting
on "Influence of Power Reactor Water Chemistry on Fuel
Clodding Reliability",San Miniato (Italy),Oct. 12-15 (1981).
(29.) Ibid. - Answers to Questionnaire-Tarapur Atomic Power Station,
India ( t 9 8 1 ) .

(30.) Rybalchenko I.L., V.M.Sedov, K.D.Rogov, T.S.Shavlova,V.A.

Bochkov, V. Chavatov - Experience of Maintaining the
Chemical Conditions of Water and Operating the Coolant
Purification System at the Leningrad Nuclear Power Station.
Paper presented in the International Symposium on Water
Chemistry and Corrosion Problems of Nuclear Reactor Systems and
Components, Vienna,(Austria) Nov.22-26 (1982).
(31.) "Dresden Station Units 1,2 and 3 Semiannual Report Jan.1
(1972 to June 30,1972"; U.S. Atomic Energy Commis ion. Dock et
N 50-10,50-237 and 50-249 (1972).

174
(32.) Grunewald D.»Kallenberg k. "Startup of Condensate Polishing
at Vtlrgassen Atomic Power Plant",Techn.Bull. Basel,Switzerland
Theodor Christ,AG- n.d.
(33.) IAEA Consultant meeting on "Investigation of Fuel Element
Clodding Interaction with Water Coolant in Power Reactors".-
Answers to questionnare - NPS Mtihl eberg,(Switzerland)1981.

(34.) Hakala J., Hinttala J.,Some Corelations between Water

Chemistry and Crud Formation on Fuel in BWR, IAEA Specialist
meeting on "Influence of Power Reactor Water Chemistry on Fuel
Clodding Reliability, San Miniato (Italy),Oct. 12-16 (1981).
(35.) "Vermont Yankee Nuclear Power Station",Report of Radioactive
Effluent,Summary of Results,July, 1972 to 31 Dec. 1972. U.S.
Atomic Energy Commision Docket N 50-271-1973.
(36.) Schröder H., Wasserchemie im Kernkraftwerk mit Leichtwasser-
reactor-Vom Wasser,B. 41 (1973).
(37.) Ryan J., "The Impact of Powered Ion-exchange Resins for water
Treatment on BWR Operations"»Proceedings of the American
Power Conference, 3_£ (1973) 864.

(38.) Holloway J.H. and Hollifield P.J. "Ultrasonic Cleaning of

Deepbed Resins for Condensate DenrLneralizers Systems, (Proc.
Amer. Power Confr., 1971 ) 33 (1971) 812-22.
(39.) Silvennoinen S.,"Water Chemistry Experience of BWRs in Olki-
luoto (Finland)-Int.Syrnp. on Water Chemistry and Corrosion
Problems of Nuclear Reactor Systems and Components,Vienna,
Austria 22-26 Nov. (1982).
(40.) International Atomic Energy Agency- "Guide to the State
Handling of Radioactive Waste in Nuclear Power Plants"
Technical Reports Series N 198,Vienna (1980).

175
(41 . ) "Menagment of Spent Ion-exchange Resins from Nuclear Power
Plants "(IAEA-TECDOC 258,Vienna,1981).
(42.) Lin K.H.»"Performance of Ion-exchange Resin Systems at Nuclear
Power Plants. American Int. of Chemical Engineers (AIChE)
Symposium series 152,Volume 71(1975) 224.
(43.) Nott B.R.»"Electrodialitic Decontamination of Spent Ion
exchange Resins from Candu-PHT Purification Circuits'.1,Int.
Symp. on Water Chemistry and Corrosion Problems of Nuclear
Systems and Components,Vienna,Austria,22-26 Nov. (1982).

176
 CHAPTER 5

ION EXCHANGE TECHNOLOGY IN

SPENT FUEL REPROCESSING

J.D. NAVRATIL
Rockwell International,
Golden, Colorado,
United States of America

Abstract

Solvent extraction is the major unit operation

employed in spent nuclear fuel reprocessing. The
operation yields three streams: fission product
waste, uranium product and plutonium product. Ion
exchange is primarily used in reprocessing as a tail-
end method to concentrate and isolate the plutonium
product stream. This chapter will describe the de-
tails of plutonium recovery and purification by both
cation and anion exchange processing. A brief over-
view of miscellaneous uses of ion exchange employed
in reprocessing will 'also be given.

INTRODUCTION

Irradiated or spent fuel discharged from

nuclear reactors contains fission products, urani-
um and plutonium. Reprocessing technology is used
to recover fissile values for reuse as nuclear fuel.
The major reprocessing steps are outlined in Figure 1.

177
 SPENT FUEL
STORAGE

* •

DISASSEMBLY ———————»- CLADDING

NITRIC ACID
DISSOLUTION

FEED
ADJUSTMENT

*
PIRQT P Y PI F ^. WASTE
PUREX

Pu + U
i'

SECOND CYCLE U URANIUM

PUREX PURIFICATION

Pu

PLUTONIUM
PURIFICATION

FIGURE 1. Simplified flowsheet for spent fuel

reprocessing.

After storage and disassembly, the spent fuel

is dissolved in nitric acid. The nitric acid con-
centration of the dissolver solution is then ad-
justed and the plutonium(IV) oxidation state is
stabilized by addition of sodium nitrite prior to
tri-n-butyl phosphate (TBP) extraction (designated
Purex solvent extraction process). The process is
used to separate uranium and plutonium from fission
products .

The first extraction cycle of the Purex process

co-extracts both plutonium and uranium into TBP
leaving the fission products, the actinides (nep-
tunium, americium and curium), and small amounts of
plutonium and uranium in the raffinate or waste

178
stream. The second cycle is used to partition
or separate the uranium from the plutonium; this
is done by scrubbing the loaded TBP with dilute
nitric acid containing a reducing agent to reduce
plutonium to the non-extractable III oxidation
state. The uranium is then stripped from the TBP
with water. The separate uranium and plutonium
streams are purified further by another cycle of
the Purex process. Final purification of the
uranium stream is accomplished by either another
cycle of the Purex process or more commonly by
silica-gel adsorption. Purex, cation exchange and
anion exchange have been used as the tail-end
plutonium purification step for plutonium.

This chapter will discuss in detail both the

cation and anion exchange processes for the concen-
tration and isolation of plutonium. Furthermore, a
brief overview of the recovery and purification of
uranium and other actinides and isotopes will be
given.

PLUTONIUM RECOVERY AND PURIFICATION

All nuclear fuel reprocessing operations include

recovery and purification of plutonium, free of uran-
ium, fission products and other impurities. Methods
such as evaporation, precipitation, solvent extract-
ion and ion exchange have been proposed to accomplish
the concentration and isolation of plutonium. Evap-

179
 oration does not provide any decontamination whatso-
ever, and even concentrates impurities. Precipitation
yields high losses of plutonium and poor decontami-
nation. Both solvent extraction and ion exchange have
been used successfully, but the latter method has ad-
vantages of less equipment, simpler operation and less
waste generation.
f- rj

Both cation-exchange and anion exchange can be

used to separate plutonium from fission products,
uranium and other impurities. However, anion exchange
is more efficient and provides pure product solution
readily handled in subsequent processing steps. A
combination of cation and anion exchange processing
has also been used .

History

In the early days of the Manhattan Project,

ion exchange was considered as an alternative to
the bismuth phosphate precipitation process used
at Hanford for fuel reprocessing. In 19^3 a flow-
sheet was developed using deep beds of newly
developed organic cation exchange resins contain-
3
ing sulfonic acid groups . The process consisted
of loading plutonium(IV) from a nitric acid solution
onto the resin while uranyl nitrate and fission pro-
ducts passed through the column. The column was then
washed free of residual uranium and fission products
with dilute sulfuric acid and oxalic acid, respect-
ively. Thereafter, the plutonium was eluted with 0.4

180
M oxalic acid or 1.25 M sodium hydrogen sulfate.
The newly developed organic cation exchangers were
not adopted for primary fuel reprocessing because of
low decontamination factors for fission products and
satisfactory operation of the bismuth phosphate pro-
cess. Later the bismuth phosphate precipitation
process was replaced by solvent extraction, and im-
proved cation exchange resins with higher capacities
did provide an alternative process for concentration
and isolation of plutonium from dilute product
streams in solvent extraction processes.
o
In 1953, Durham and Mills showed that
plutonium(IV) could be sorbed on Dowex 1 anion
exchange resins from 7-8 M nitric acid. Based on
7
this work, Ryan and Wheelwright evaluated process
variables and various resins which provided oper-
ating conditions for subsequent utilization of anion
2 Q
exchange at Hanford and other sites ' .

Cation Exchange

Cation exchange has been applied for the con-

centration and recovery of plutonium from the dilute
•3 C
product stream of the Purex process * . In the
process (Figure 2), sulfamic acid is usually added
to the dilute nitric acid solution containing plu-
tonium to prevent the oxidation of plutonium(III) to
(IV); such oxidation can cause gas bubbles of nitrogen
oxides to form in the ion exchange column and create

181
 Pu & U ABSORPTION CYCLE U ELUTION CYCLE Pu ELUTION CYCLE
Basis: 350 gm Pu/8 hours
Purex Flowsheet

PUREX ILBP STREAM j r

0.05 M
1790 Liters/8 hours NH,OH % HjSO„ Vol HNO, NH ; SO,H Pu Pu Pu
0.2 gram Pu/liter 0 25 M H, SO 4 Liters M 9/1 gm %
0.3 M HNO, 25 Volumn Changes 0.05 005
44 03 022
0.05 MNHjOH • ViH 2 S0 4 109 Liters 70 48 03 50 350 90.
15 ml/min/cm; 2 ml/min/cm"' 44 07 0.1 0.5 2 05
35
1 1 r Residual Pu on Resin 10

RESIN COLUMN SPECIFICATIONS T V

Resin: Dowex 50,50-100 mesh, 12% cross linkage
Resin Bed Volume: 8.72 Liters
Excess Resin- 300%
Column Diameter: 17.80 cm (7 inch)
Cross-Sectional Area of Column: 249cm 2
Depth of Resin Bed: 35 2 cm
J_-1--1
f
Pu PRODUCT ELUTRAINT

Vol
HNO, M NH,SO,H W
It BPW STREAM 109 liters 0 25 M H, SO., (Liters)

10' Pu ü cts/mm/ml 57 03
1790 Liters/8 hours 70
99% of U m E BP 88 0 1 01
0.3 M HNO,
005MNH2OH y2H,S 0 2 ml/min/cnv (total elution
10' Pu a cts/min/ml -»- To Waste time 5 3 hours)

FIGURE 2. Flowsheet for concentration of

plutonium nitrate solution by cation
exchange.
From r é f . 5.

channeling of the solution and resultant inefficient

elution. The distribution coefficients (g Pu/g resin
per g Pu/g solution) for plutonium(IV) and plutonium
h -3
( I I I ) are 3 x 10 and 4 x 10 , respectively. Although

plutonium(IV) has higher distribution c o e f f i c i e n t s ,

loading p l u t o n i u m ( I I I ) takes less resin and com-
plexes less with sulfate ion, thus lowering pluton-
ium losses during uranium elution.

The feed solution is passed through the column

and p l u t o n i u m ( I I I ) sorbs onto the resin. Anionic
and most of the monovalent and divalent cationic

182
impurities report to the effluent stream. Uranium
is washed from the resin with dilute sulfuric acid.

The plutonium is eluted from the resin with

strong nitric acid yielding a plutonium concentration
of 40-60 g/1 in 5-6 M nitric acid. As mentioned above,
cation exchange does not yield good decontamination
5
of some elements , and fission product decontamination
factors are low. During loading, about 40 percent of
the rutherium reports to the effluent. The wash solu-
tion removes only small amounts of ruthenium and rare
earths along with the uranium. Beta and gamma decon-
tamination of plutonium have been reported as 3 and 6,
respectively.

The primary benefit of cation exchange is pro-

duct concentration. However, the high nitric acid
concentration requires lowering to provide feed
adaptable to liquid-to-solid conversion processes,
such as peroxide, trifluoride, or oxalate precipi-
tation. The eluate solution is readily acceptable
as feed to anion exchange and thus a combination
process using both cation and anion exchange is ad-
vantageous.

Dowex 50-X12, 50-100 mesh resins have been

utilized in most cases. Dowex 50 is a microretic-
ular or gel type resin with 12 percent crosslinkage.
Recently new macroreticular or macroporous (porous
gel resins) cation exchange resins (20-50 mesh) have

183
 been evaluated for plutonium loading and elution
kinetics . Dowex MSC-1 was found to have much faster
plutonium elution kinetics and better decontamination
properties than Dowex 50.

In the United States, cation exchange is used

routinely at Savannah River for concentration of the
plutonium . Since anion exchange provides better
product decontamination than cation exchange, it has
2
been more commonly used since introduced in 1959 •

Anion Exchange

In the anion exchange process, plutonium

is sorbed on anion exchange resin from a strong
nitric solution. Strong and very dilute nitric
acid is used to wash impurities from the resin and
to elute the plutonium, respectively. Details of
the process chemistry follow.

In strong nitric acid solutions, plutonium

forms a hexanitrato anionic complex which sorbs on
the resin according to the following equation:

P u ( N O )g~ + 2 ( r e s i n ) N O f£ ( r e s i n ) 2 P u ( N O )g +
2NO~ (1)

The maximum distribution coefficient for

plutonium is obtained at about 7 M nitric acid
(Figure 3). As the nitric acid concentration in-
creases between 6 and 10M, acid species of the

184
 10s
T l l T

o
X

u.
UJ
O
O

oc
I-
O 10

10J l l l
3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0

NITRATE MOLARITY

FIGURE 3. Plutonium(IV) distribution coef-

ficient as a function of nitrate
molarity.
Prom réf. ?.

plutonium complex are formed

H Pu(N030)7b (2)

H Pu(NO_)7 + H z=> H0Pu(N00),- (3)

3 o 2 3 o
2-
which are not sorted as strongly as the Pu (NO ),-
species. Furthermore, nitrate ions also compete
with the plutonium complexes for resin sites.
Both of these effects decrease the plutonium dis-
tribution ratios at high acidities. Adding metal

185
 nitrates, such as calcium nitrate to low nitric acid
feeds overcomes these effects and significantly in-

creases the distribution coefficient for plutonium

(Figure 3).

Plutonium sorption is more strongly influenced

by kinetics (which demands higher temperatures) than
by equilibrium (which demands lower temperatures).
The large size of the plutonium hexanitrato complex
presumably causes the ion exchange process to be slow.
The loading kinetics can be increased by adjusting
o
the temperature of the feed solutions to 60-70 C.
(Figure 4)

i i i nun—i—i mm ~ nm~
Feed: 1.0g.Pu/1. 7.2 M HNO.
320
z 70 C
CO
280

a-
O
240
UJ

<

t 200

CE
Q
160

120

Z
o 80

40

1.0 10 100 1000

TIME (minutes)

FIGURE 1. Plutonium(IV) sorption kinetics

versus feed temperature.
Prom réf. 7-

186
 Typically gel or mlcroreticular anion exchange
resins such as Dowex l-x4 or Perrautit SK have been
used. However, new macroreticular or macroporous
resins have shown to have better loading and elution
kinetics (Table 1). Notwithstanding, the large bead

(20-50 mesh) macroporous resins still do not out-

perform small bead (50-100 m e s h ) Dowex l-x4.

TABLE 1. The e f f e c t of resin properties on

plutonium breakthrough capacity
and elution.
Prom J. D. Navratil and L. L. Mar-
tella, Nucl. Technol., 46, 106 (1979)

Breakthrough Capacity1"

Resin Resin 500 mg/8 Feed 10 mg/8 Feed Elution

(20 to SO mesh) Properties' (3.5 ml/min-cm 2 ) (29ml/min-cm 3 ) Volume«

Amberlite IRA-938 M-S-P 20 0.5 4

Dowex MSA-I M-S-P 9 0.4 6
Amberlite IRA-900 M-S-P 7 0.3 14
Amberlite IRA-910 M-S-P 5 0.2 6
Amberlite XE-299 M-W-P 10 0.4 4
Amberlite IRA-93 M-W-P 4 0.3 5
Duolite ES-561 M-W-Ph <1 --- 23
Dowex 1 1 (A) G-S-P 12 0.5 29
lonac ASB-1 G-S-P 10 0.2 33
Dowex 1 1 (B) G-S-P 9 0.4 60
Dowex 1-X4 G-S-P 8 0.5 72
Amberlite IRA-402 G-S-P 7 0.4 68
Duolile A-101D G-S-P 6 ___ 30
Amberlite IRA-4 10 G-S-P"1 4 0.2 15
Amberlite IRA-458 G-S-A 7 0.2 7
lonac A-SS1 G-S-Pd <l 4
Amberlite IRA-68 G-W-A <1 --- 13
Duolile A-30B G-W-E <I --- 27
*AI1 values have an estimated accuracy of ±10%. Based on triplicate runs with four different resins.
"G = gel or M = macroreticular resin; S = strong or W = weak base; P = polyslyrene-divinylbenzene, Ph = phenolic, A = acrylic,
Pd = pyridinium, or E = epoxy-amine.
b
Breakthrough capacity is the milligrams of plutonium passed per millilitre of resin when the ratio of plutonium concentration
in the effluent to the plutonium concentration in feed reached O.I.
c
Millililres of 0.35 M HN03 to elute 90% of the plutonium from 1.0 ml of resin. Flow rate = 3.5 ml/min-cm j .
A f-N - (CHjfel
Amberlite IRA^lIO is a Type II resin I ~ I ; all other strong-base resins are Type I [+N_(CH 3 ) 3 J.

The plutonium can be eluted from the resin with

dilute nitric acid because the anionic plutonium
nitrate complex is destroyed. Usually 0.35 M nitric

187
 acid is used; lower acid concentrations are avoided
to prevent hydrolysis and plutonium polymer formation.
Eluent solutions containing reducing agents can im-
prove elution kinetics by forming plutonium(III).
Some reducing agents can add impurities, such as iron
and sulfate, but the use of hydroxylamine nitrate
sometimes coupled with hydrazine will not add impur-
ities. The use of ascorbic acid can cause precipitate
formation from the products of the reductant. Reduc-
ing agents can cause gassing problems in the column
resulting in channeling of solution and resultant in-
efficient elution.

Plutonium product concentrations of 50-60 g/1

can be attained in 2-3 M nitric acid, readily adap-
table for liquid-to-solid conversion processes such
as oxalate precipitation.

The anion exchange process offers excellent

product decontamination since few metal ions form
anions in 7 M nitric acid. Neptunium(IV) also forms
a hexanitrato complex which can load on the resin.
The nitrato complexes of the tetravalent actinides
have stability constants much higher than the hexa-
valent actinides. The stability constants for tri-
valent and pentavalent actinide nitrate complexes
are very small. Fission products do not form anionic
complexes in nitric acid (except for some Sorption
of Ce(IV), technetium and certain ruthenium complexes).

188
Li Be B

nr fr
N Q
_ U
th -{
——L

No/ ds N0 Ads. No Ads.

33 No Ads.— No adsorption from 1-14 M HNOi -i
SI. Ads.— Slight adsorption —————
1
Na Mg 5
1 AI ! Si 1 P s
0° m ! i
Z
4
No Ads. No Ads W olarity HN 0, NOAdS. No Ads.

=-U _L
Fn
4i
Ca Se V C 1 • Mn Fe Ni Cu Zn Ga Ge As Se i

m m\ n m n n -f ir ni m
No f ds. No Ads. No Ads No Ads. No Ads.
Z
No Ads. No Ads.
HF
No Ads. fj No /i ds. NoAds. No A ds.
ï Ne Ads. No Ads.
! Z
No A ds.
l T III 1 "[_
Rb Sr y Zr Nb Mo Te Ru Rh Pd Cd l Sn Sb Te
m m ZC 5
m 11
4-tl M 1 it pz Z TV !

4
"t"
No Ads Nof ds. No Ads , 1 S Ads. S . A ds k No Ads No Ads. No Ads. ds. No A ds No Ads.
—i- SI /

Tl T r" T T
- *-,
T ^~- N ~ "
Cs Ba Ra Hf
5 | Ta W Re O Ir Pt Au 1 Hg Pb ! Bi Pô

No. Ads NoAds.

I
SI. A ds
,.

4
!
3ZH
i:
N D. Ads.
P
Pari iy i
m\ n TTi i
•SI Ads.'
SI.A ds. /-
m
~s

Fr
—J — T
\
Si T •n - Ad 'T' ^v
N ni 1 N

Nd

SI. Ads, No Ads

rr
7 izl "
?=t
±
FIGURE 5. Removal of elements from solution in 1-1 Jj M nitric acid with
strongly basic anion exchange resin.
From R. F. Buchanan and J. P. Paris, in Radioisotopes in the
Physical Sciences and Industry, IAEA, Vienna,I960.

Figure 5 shows the distribution ratio of most

elements sorbed onto anion exchange resin from 1-14
M nitric acid. Table 2 lists the classification of
elements by degree of sorption on Dowex l-x4 resin
from a nitrate media. The elements that show no
sorption can be easily washed from the resin with only
one or two column volumes of 7 M nitric acid. Most of
the weekly sorbed elements are removed with several
more column volumes of wash solution. Elements such
as Hg2 + , Ce 3+ , UOp2+ and Bi 3+ require much more wash,
even as much as 20 column volumes. The strongly sorbed
platinum metals can be separated from plutonium

189
 TABLE ?. C l a a s J fJ cnl : on o!' e ! erii^nt:; by vief.
cf coi'pl '.()!: on D»WV.»X 1. x - !'(;»Lr.
riiut'tt..: irioc; i a .
i:;an, l'.:. ; . A. !•',.('. H - ; p t . L / \ - j : ; - > ; , :,

ELEMENTS

NO SORPTION WEAK SORPTION STRONG SORPTION

Distribution Coefficient Distribution Coefficient Distribution Coclficorit
-o <4 >5

Mg Sc Pd
A! As Ir
Ti Se F't
V Zr Au
Cr Nb Th
Mn Mo
Fe Ru
Co Ag
Ni Cd
Cu La
Zn Hf
Ga W
"^Go_^" Ro
Y Os ~
-----
In
Sn Pb
----- -B(~
Sb
Ta Co
TI Rare Earths
U
Am
Rfi

because they will not elute with dilute nitric

acid. Thus, under the proper conditions, pluto-
nium can be separated from all elements except
thorium and neptunium by anion exchange.

From a safety standpoint, the most important

consideration in the ion-exchange process is the
prevention of over-pressurization and elevated tem-
peratures in the columns. Anion exchange resins
loaded with the plutonium nitrate complex contain
up to three nitrate ions per exchange site compared

190
to nitrate form resin with only one nitrate ion per
site. If the column is not vented and elevated
temperatures are attained, an exothermic and auto-
catalytic reaction can be initiated and a rapid
chemical excursion can take place. Furthermore, if
the resin loaded with plutonium is permitted to dry out,
the situation is aggravated. To insure that this
circumstance never occurs, precautions are taken.
Whenever the anion exchange is shut down for any
period of time exceeding 8 hours, the resin bed is
left saturated with dilute nitric acid. As an
additional safety measure, the resin bed is never
left loaded with plutonium for more than 8 hours at
one time. Further, the columns should be fitted
with rupture disks to prevent overpressurization.

Anion exchange has been used routinely for the

third cycle of plutonium purification following
Purex solvent extraction . Furthermore, plutonium
has been concentrated and purified effectively from
irradiated fuel solutions. Gamma decontamination
4
factors for plutonium were 2 x 10 in a single cycle
•7
and 4 x 10 in two cycles; niobium was the limiting
activity. The same process is used for recovery of
Pu and -Np in the production of 2^ Pu for iso-
topic heat sources .

One-cycle of Purex was eliminated at Hanford by

utilizing anion exchange purification of plutonium 53 6
The process was operated continuously using a Higgins
contactor (Figure 6). The loading and elution sec-

191
 Hydraulic
"Pull"

Feed
Wash Water ———[Xj——

Feed

Hydraulic Push
(Pulse Water In

Loading
Section

Waste

Eluant Wash

Eluant
Elution Section

Product

FIGURE 6. Mode of operation of a Higgins quasi-

continuous ion-exchange contactor.
From J . T . Roberts, U . S . A . E . G . Rept.
ORNL-2504, Oak Ridge National Labor-
atory, 1958.

tions are both 13 cm in diameter and 2.1 m high. The

resin is loaded to a plutonium concentration of 30-

50 g Pu/1 resin. The effluent contained 0.5 percent

of the plutonium feed, but this stream is recycled
to prevent any loss. The process was operated for
more than two years with an e f f i c i e n c y of about 95
percent. It provided good decontamination of uranium
e g h
(10 - 10 ), fission product impurities (10 for
c
ruthenium and 10 for zirconium-niobium), and
other impurities.

192
 Anion exchange has been used for recovery of
4
plutonium from oxalate solutions , however nitric
acid concentration of 9 M is needed to prevent
interference from oxalate. Interference of fluoride
ion in anion exchange processing can be overcome by
adding aluminum nitrate to complex the fluoride ion.

MISCELLANEOUS USES OP ION EXCHANGE

Although the most important use of ion ex-

change in fuel reprocessing is the tail-end puri-
fication and concentration of plutonium following
Purex processing, ion exchange has been utilized
for uranium purification, separation and recovery
of individual actinide elements and isotopes, and
treatment Of low-level wastes.

Excellent reviews of ion exchange in the Atomic

Energy Industry have been written by Jenkins ;
he has summarized ion exchange studies dealing with
the following topics: thorium, protactinium and
uranium; neptunium and plutonium; americium, curium
and actinide-lanthanide separations; the higher ac-
tinides, Cm, Bk, Cf, Es, and Fm; and fission product
separation (mainly cesium and strontium). Also,
recent books contain various chapters on actinide
IV ~\ $
separation, recovery and purification '

Uranium

Although the most common tail-end process for

1|
uranium purification is silica-gel adsorption ,

193
 where the uranium nitrate solution is passed through
the silica-gel column which removes gamma-emitting
impurities by a factor of approximately 20, ion
exchange has been utilized somewhat.

Uranium has been decontaminated of ruthenium

i|
by a factor of 10 or greater by ion exchange . Uranyl
o
nitrate solution is first heated at 90 C for 1/2 hr.
after adding 2 g thiourea/1 solution. This solution
is then passed through a bed of carboxylic acid resin
which sorbs the ruthenium. The ruthenium can be
stripped from the resin with 6 M nitric acid.

Uranium has also been concentrated from dilute

solution by sorption on sulfonic type cation exchange
resins .

Neptunium

Neptunium(IV) can be separated from uranium,

plutonium and other common metallic impurities by
sorption on anion exchangers from a 6 M nitric acid
solution containing a reducing agent such as ferrous
sulfamate to maintain Pu(III) and Np(IV)13. The
impurities are washed from the column with 6 M nitric
acid. The sorption and elution behavior of nep-
tunium is similar to plutonium.

Other Elements

Cation exchange, usually in conjunction with

other separation processes, has been used to sep-
arate and purify cesium, strontium, promethium and

194
other rare earth fission product elements, and
americium and higher actinides 2-5J 19 . Technetium
4
has been recovered by anion exchange processing .
Applications of ion exchange in nuclear fuel re-
processing, including low-level waste treatment,
continue to grow '

REFERENCES

1. W. W. Schulz and J. D. Navratil (Eds.), Science

and Technology of Tributy1 Phosphate, Vol. I,
Synthesis, Properties, Reactions and Analysis,
CRC Press, Boca Raton, PL, 1984.

2. R. G. Wymer and B. L. Vondra (Eds.), Light Water

Reactor Nuclear Fuel Cycle, CRC Press, Boca Raton,
PL, 1981.

3. C. E. Stevenson, E. A. Mason, and A. T. Gresky

(Eds.), Progress in Nuclear Energy, Series III,
Process Chemistry, Vol. W, Pergamon Press, New
York, 1970.

J. T. Long, Engineering for Nuclear FuejL Repro-

cessing, Gordon and Breach Science Publishers,
Inc., New York, 1967-

5- S. M. Stoller and R. B. Richards (Eds.), Reactor

Handbook, Vol. 2, Fuel Reprocessing, 2nd ed.,
Interscience, New York, 1961.

6. Proceedings of the Second International Conference

on the Peaceful Uses of Atomic Energy, Geneva,
1958, Vol. 17, United Nations, New York, 1959-

7. J. L. Ryan and E. J. Wheelwright, Ind. Eng. Chem.,

51, 60, 1959.

8. R. W. Durham and R. Mills, Atomic Energy of

Canada Limited, Report CEI-62, Chalk River,
Ontario, 1953.

195
 9- J. D. Navratil and W. W. Schulz ( E d s . ) s Trans-
plutonium Elements - Production and Recovery,
American Chemical Society, Washington, D . C . ,
1981.

10. R. A. Suva ani J. D. Navratil, Solv. E x t . Ion

E x c h . , 1, (1983).

11. L. W. Gray and J. H. Radke in Actlnide Recovery

From Waste and Low Grade Sources, J. D. Navratil
and W. W . S c h u l z ( E d s . ) , Harwood Academic Pub-
lishers, I n c . , New York, 1982, p. 3.

12. J. M. Cleveland, The Chemistry of Plutonium,

Gordon and Breach, New York, 1970.

13- W. W. Schulz and G. E. Benedict, Neptunium-237

Production and Recovery, U . S . Atomic Energy Com-
mission, Washington, D . C . , 1972.

14. I. L. Jenkins and A. G. Wain, Rept. Prog. A p p .

C h e m . , 57, 308 ( 1 9 7 2 ) .

15. I. L. Jenkins, Hydrometall., 5, 1 (1979).

16. I. L. Jenkins, Sol. E x t . Ion E x c h . , 2, 1 (1984)

17. E. L. Christensen, L. W. Gray, J. D. Navratil and

W. W. Schulz, in Plutonium Chemistry, W. T. Car-
nail and G. R. Choppin ( E d s . ) , American Chemical
Society, Washington, D . C . , 1983, p. 3 4 9 -

18. J. D. Navratil and W. W. Schulz ( E d s . ) , Actinide

Separations, American Chemical Society, Washing-
ton, B . C . , 1980.

19. W. W. Schulz, The Chemistry of Americium, U . S .

Energy Research and Development Administration,
Washington, D . C . , 1976

20. W. W. Schulz, E . J . Wheelwright, H. Godbee,

C. W. Mallory, G. A. Burney, and R. M. Wallace,
U.S. DOE Rept. DP-MS-83-109, Dupont C o . ,
Savannah River, N . C . , 1983.

196
 CHAPTER 6

MISCELLANEOUS USES OF ION EXCHANGE

IN THE NUCLEAR FUEL CYCLE

Y. FUJII, M. OKAMOTO, M. KAKIHANA

Research Laboratory for Nuclear Reactors,
Tokyo Institute of Technology,
Tokyo,Japan

Abstract

Miscellaneous uses of ion exchange technology are described for

isotope separation of light elements (lithium, boron and nitrogen),
separaten of uranium isotopes and other actinide elements, and for the
recovery of uranium from phosphoric acid solutions. Application of ion
exchange membrane is also indicated for the electrolytic reduction of
uranium and for the decomposition of ammonium ion in the alpha-bearing
liquid wastes.

•5-1 - ISOTOPE SEPARATION OF LIGHT ELEMENTS

6-1-1. LITHIUM ISOTOPES

The first experiments on the lithium isotope separation were
carried out by T.I. Taylor and H.C. Urey using a zeolite inorganic
ion exchanger contained in a stainless steel pipe (35 ft long
and 3/4 inch diameter).[ 1 ]. The experiments initially aimed to
separate lithium isotopes by extraction. Lithium bromide was
extracted with methylamyl alcohol from an aqueous solution reducing
the concentration finally 1000 to 1. The residue showed no differ-
ence in the isotopic composition of lithium isotopes. During
the experimental work, however, they found the fact that the com-
mercial lithium compounds have different isotopic ratios. It
appered that somewhere in the process of the manufacture, an appre-
ciable separation of lithium isotopes had occurred. They set
up the column packed with zeolite which had been used in the manu-
facturing process to extract lithium from aluminum silicate ores,
and obtained successful results from the experiments.
D.A. Lee, G.M. Begun and J.S. Drury studied the isotope ef-
fects in ion exchange processes of lithium ion using synthetic

197
organic ion exchangers of Dowex 50.[2-5]. They determined the
single stage separation factors for the systems consisting of
ion exchange resins and aqueous.solutions. The single stage iso-
tope separation factor is defined as,
<X = (6fZ}(7Li) / (7Ll)(6Li) (!)
where "~" denotes isotopes in resin phase. In their experiments
the single stage separation factor was found to depend on the
structure of resins, compositions of the outer solution, and exper-
imental temperatures. Some results from the work are shown in
Fig. 1.
The isotope effects in this process are attributed to the
difference in the hydration of lithium ion between two phases.
Lithium ion is fully hydrated with around seven water molecules
in a diluted aqueous solution. Dehydration occurs when lithium
ions enter into ion exchange resins. The lighter isotope Li
gathers in the dehydrated state, i.e. lithium ions in resin, and
the heavier Li is fractionated in the hydrated state in the aque-
ous solution. The degree of hydration of cations in ion exchange
resins decreases with increase of the crosslinking of the resins.
Larger isotope separation factors are expected in the systems
using higher crosslinking resins accordingly.
Ion exchange resin is theoretically regarded as a kind of a
highly concentrated aqueous solution. The ion exchange selectivity
depends on the concentration of the outer solution, as a general
rule. When concentrated solutions are used as eluents, the chemi-
cal states of both phases (resin and solution) become close each
other, which results in the small selectivities of the resin for
the ionic species involved. Since isotope separation factors
depend also on the ion exchange selectivity, It is reasonable
that the lithium isotope separation factors were observed to de-
crease with increase of the concentration of eluents.
As predicted from theoretical treatments, isotope effects
based on the molecular vibration depend on temperature[6]. The net
isotope effect, separation factor - 1 , is expected to be linearly
proportional to (1/T) as a first approximation, where T indicates
absolute temperature.

198
 3. 4 _ Fig. 1. Isotope effects
(a) O of lithium in cation ex-
3. 2 O
o change chromatography.
o 3. 0 -
X
->
0
2. 8 O Effects of experimental
c Resin: Dowex X-16
•—*
2. 6 /^"*\
w conditions on the isotope
*—' Eluent: 0.25 M HC1
1 ! 1 1 I separation factor a .
3.0 3.2 3.4 3.6 3.8 (a) Temperature.
Temperature , 10 /T
(b) Concentration of
eluent.
(c) Crosslinking of
resin.
3.0 ( D)
O

A O
2.0 O

ö
c
DowexSO X-12
1.0 O HC1 O
• NH4(COO) U

Zeo Karb
A HC1
0.3 0.5 0.7 1.0 2.0 3.0
Concentration of Eluent / (mol/dm )

( C )

3.0

2.0
•
o O
n
Resin : Dowex 50
1.0
Eluent: O HC1 0.3 M
9 N H ^ C l 0.25 M

4 8 12 16 20 24
Crosslinking of Resin , DVB / %

199
 6-1-2. BORON ISOTOPES
In the era of the Manhattan Project, boron isotope separation
was also investigated. Adduct compounds of Lewis acids, e.g.
BF_0(CH.,), were discovered to have large isotope effects in the
evaporation processes. Anisole complex <jCD)>-COCH.,BF., shows an
isotope separation factor of 1.039 at 2 °C.
On the other hand ion exchange processes have relatively
smaller isotope separation factors of 1.01 - 1.03. S. Makishima et
al.[7] first applied ion exchange chromatography to the separation
of boron isotopes. They used strong base anion exchange resin
Amberlite CG-400-1, 100 - 200 mesh. The anion exchange resin
packed in a column ( 120 cm long ) was initially converted to
the OH~ form. Then a boric acid solution or a boric acid plus
glycerol solution was fed into the column, resulting in a strong
adsorption of boric acid ions in the anion exchange resin. The
Chromatographie operations were conducted in a displacement break-
through manner. The effluent fractions of the boric acid solution

50

Migration Length
9m
18 m
25 m
Resin: Dowex 1, X-8
Eluent: 0.1 M CH3COOH

30

Original isotopic composition

20

10

10 20 30 £)0 50 60 70 80
Band Length / cm
Fig. 2. Boron isotooe separation by anion exchange
Chromatography. Ref.()

200
were analysed and it was found that the heavier isotope B was
enriched at the front boundary of the boric acid zone. The observ-
ed isotopic separation factors were 1.011 and 1.016 for the system
of a boric acid solution and for the system of a boric acid plus
glycerol solution, respectively.
M.M. Urgell et al.[8] extended this system using Dowex 1x8 and
Dowex 2x8, 200 - 400 mesh. In their experiments the adsorption
bands of boric acid were displaced by acetic acid solutions, and
boron 10 was enriched at the rear boundary. The profile of isotope
distribution in a boric acid band is shown in Fig. 2. The
resin used in this process is regenerated by alkali solutions
which usually contain C0_ . When the resin is treated with acids
in elution, the adsorbed CO.,2- ions cause a problem of evolution
of carbon dioxide gas.
H. Kakihana et al. [9] developed a weak anion exchange resin
system for the boron isotope separation . They found a weak
base anion exchange resin, Diaion WA 21, absorbs boric acid ions
when charged with a pure boric acid solution, and releases the
boric acid ions when treated with pure water. No gas evolution
was observed in long migration experiments up to 256 m.

6-1-3. NITROGEN ISOTOPES

F.H. Spedding et al.[10] conducted the experimental studies on
nitrogen isotopes using a cation exchange resin Dowex SOW X12.
The cation exchange resin packed in a column was first converted
to H ion form, then ammonium ions were loaded on the resin bed.
The ammonium band was finnaly eluted in a displacement manner
by a 0.1 M (mol/dm ) NaOH solution. After the Chromatographie
operation it was found that the heavier isotope N was enriched
in the resin phase and accumulated at the rear boundary of the
ammonium adsorption band. The single stage isotope separation
factor was determined as 1.025. The isotope separation factor
corresponds to the equilibrium constant of the following isotope
exchange reaction,
14 15 15 14
NH4-R + NH4OH ———— NH4-R + NH4OH . (2)
Since NH4* ions are in the resin phase and NH4OH molecules are
in the solution phase, the experimental results indicate that
N isotope is preferentially fractionated in NH.+ions and the
14
lighter N is in NH.OH molecules which are partially dissociating
into Nu., and H_O molecules in an aqueous solution. The isotope

201
effect between NH.+ and NH, is theoretically calculated as 1.035
at 25 *C as indicated in Table I. Such a large isotope effect
for the NH, - NH,+ system
t e
is attributed to the structual difference
" a
between these molecules: amraoia molecule takes a triangle pyramidal
structure, while ammonium ion forms a tetrahedral structure.

TABLE I. THE STANDARD ELECTRODE POTENTIALS OF REDOX REACTIONS.

Redox Reactions S. E. P. ( V )

2H+ + 2e~ = H2 0.000

+ +
Ti02+ + 2H + e~ = Ti + H20 0.099
Co(NH3 )63+ + e- — Co(NH3)62+ 0.108
2e- — Sn2+ 0.15
Cu2+ + e •= Cu 0.155
AgCl + e~ = Ag + Cl~ 0.222
uo2 + 4H + 2e •= U'4 + + 2K20
2+ +
0.330
V02+ + 2H+ + e~ = V3"1" + H20 0.359
3
Fe(CN) ~ + e" — Fe(CN)64~ 0.36
Mn042- + 2H2O + 2e~ -=== Mn02 + 4OH~ 0.60
e- = Fe2+ 0.771
2" + 14H + + 6e~ — 2Cr3+ + 7H20 1 .33

The ammonium adsorption band migrates through the column

displacing the preceding hydrogen ions, simultaneously being dis-
placed by the following sodium ions. At the band boundaries,
front and rear, the ion exchange reactions proceed to completion,
owing to the large equilibrium constants of the reactions: at
the front boundary,
H+-R + NH4OH ——— NH4*-R + H2O ( K = 109 ) (3)

and at the rear boundary,

+
NH. -R + NaOH ——— Na+-R + NH.OH ( K = 105 ) . (4)
4 4
The nitrogen isotope enrichment obtained by M. Urgelletal. [8] using
the above-mentioned system is shown in Fig. 3.

202
 25-

20-

15-

VI
O 10-
o.
3
O
O

o
CL
o
t-
o 5-
in

•-:vV--
1,0-

0,8-

0,6-

0,4- 24m.

0.2

i————r
125 ISO 175 200 225
BAND LENGTH (cm)
Fig. 3. ISOTOPIC COMPOSITION OF A NH+ BAND AFTER A DISPLACE-
MENT OF 24 AND 61 m.
Ref. (8)

6-2. SEPARATION OF URANIUI1 ISOTOPES

6-2-1 . CHEMICAL SYSTEMS

For many years research and development work has been con-
ducted on the uranium enrichment process for peceful use of nuclear power.
The chemical exchange process is regarded as one of the promising
methods. A number of chemical systems studied for the uranium
enrichment by chemical exchange are classified into two chief
chategories: 1. iigand exchange systems, and 2. electron exchange
systems.

203
 The ligand exchange systems involve complex formation of
uranium ions with organic and inorganic ligands, e.g. F~ ion,
organic acids with carboxyl groups. The observed separation coef-
ficients (= single stage separation factor) for uranyl complex
formation systems are in the range of approx. 1.0001 - 1.0002.
The observed separation coefficients for uranous complex systems
are smaller than those for uranyl complexes. In spite of the
relatively smaller values of the separation coefficients, the
ligand exchange systems have the feature of the simple experimental
procedure. The investigations on the ligand exchange systems
have been still actively continued to elucidae the mechanism of
the isotope separation processes employing ion exchange chromato-
graphy.
The electron exchange systems include two possible processes
of the U(III) - U(IV) exchange system and the U(IV) - U(VI) ex-
change system. The former was developed by French CEA and quoted
as giving a comparatively large isotope separation coefficient
of approx. 1.003, The enrichment process based on this system
has been realized by employing solvent extraction [IS]. The
latter, U(IV) - U(VI) system, has been studied by several groups
of investigators [11-15]; a test plant has been constructed by
Asahi Chem. Co. in Japan. The experimentally observed separation
coefficients for this process are in the range of 1.0007 - 1.0014..
The feasibility of the enrichment process largely depends on
the magunitude of the separation coefficient, and the efficiency
of multiplication stages. The U(III) - U(IV) exchange system
is characterized as having a large separation coefficient, and
the U(IV) - U(VI) system has the advantage of the small HETP {
height equivalent to a theoretical plate ) accomplished by implemen-
tation of ion exchange chromatography. The following sub-sections
briefly describe major technological points which should be con-
sidered in the development of the enrichment process based on
the U(IV) - U(VI) exchange system.

6-2-2. REDOX REAGENTS

Table I lists the standard electrode potentials of several
redox reactions. The U(IV) - U(VI) system has the standard poten-
tial of 0.33 V. This indicates the fact that U(VI) ion is reduced
by Cu(I), Sn(II), Ti(III) ions etc., while U(IV) is oxidized by
Mn(VI), Fe(III).

204
 The standard potentials of the reductants are required to
be lower enough than that of uranium so that the reduction can
proceed to completion, but not so low as the potential of H+/H_
*3
system to avoid the generation of H^ gas. Titanium (III), Ti
ions, is chosen as the most appropriate reductant for this purpose.
In a similar manner, ferric ion, Fe(III), is chosen as the oxi-
dant: its standard potential is high enough to oxidize U(IV) ion,
but not so high as to oxidize the organic materials of the medium.
More detailed considerations on the concentrations of ions involved
in the redox reaction are given by the Nernst's equation,
E = E M/o + (RT/nF)ln(Mox)/(Mred), (5 )
where E is the potential of a solution, E the standard electrode
potential of M, R the gas constant, T temperature, n the number
of electrons transferred in the reaction, F the Faraday constant,
(Mox ) and {Mred,) are concentrations of ions in the oxidized and
reduced state, respectively. When n of the oxidant or reductant
is unity, the concentration ratio of U(IV) and U(VI) is given
as,
LU(VI)J/[U(IV); = (fMox]/[MredJ)2 exp[2F(EM/o - E^o)/RTj. (6^

6-2-3. ION EXCHANGE SELECTIVITY

Uranium displacement chromatography is achieved by using
either cation exchange resins or anion exchange resins. Uranium
ion is adsorbed on cation exchange resins and on anion exchange
resins as well due to its complex formation with anion ligands.
In either case of exchangers Ti(III) and Fe(III) are used as
a reductant and an oxidant, respectively.

Cation Exchange Chromatography. The form of U(IV) is U in aqueous

+
solutions and the form of U(VI) is UO2 . U(IV) ion has a actually
higher valency, and therefore shows a stronger adsorption select-
ivity on cation exchange resins than U(VI) does. A similar tendency
is found in the system of a pair of ions of Ti(III) and Ti(IV).
Ti(IV) forms TiO + in aqueous solutions and has lower selectivity
on a cation exchange resins than Ti(III) does. The selectivities
of a cation exchange resin for some relating cations are listed
in Table II.
Based on the selectivities shown in Table III, that is, Fe(III)
»Fe(II), U(IV) » U(VI) & Fe(II), and Ti(III) » Ti(IV) & Fe(II),
the redox cation exchange system is set up for uranium displacement
chromatography. The cation exchange resins packed in a column

205
TABLE II. DISTRIBUTION COEFFICIENTS, X,, OF SELECTED IONS FOR
CATION EXCHANGE RESIN.

Concentration of HC1
3 3
0.2 mol/dm 1 mol/dm

u4+ 2.xl04 800

+
uo/ 860 19.2
Ti(IV) 297 11.9
3+
Fe 3400 35. A
Fe2+ 370 19.8
Ti3+ ca. 104 ça. 102

K [M] / [M],
d =

TABLE III. TYPICAL DESIGN CHARACTERISTICS FOR ENRICHMENT PLANT

WITH THE CAPACITY OF 500 te 3% ( U - 2 3 5 ) URANIUM/YEAR

Plant capacity P 500 t/y

Product enrichment Rp 0.03
Feed isotope abundance R0 0.0072
o
Uranium adsorption capacity q 0.23 t/m
Separation coefficient e 0.001
Cycles of operation N 500 cycle/y
Reain bed efficiency $ 0.33
/ *3
Required resin volume V A.2x10 m
Unit production capacity P/V 12 kg/m3y ( 3% U-235 )

are first completely converted to the form of Ti(III), then U(VI)

is introduced to make an appropriate width of a uranium adsorption
band. The U(VI) ions are reduced to U(IV) and adsorbed on the
cation exchange resins replacing titanium ions. In order to elute
uranium ions, a Fe(III) solution is fed into the column. The
adsorbed U(IV) ions are oxidized to U(VI) by Fe(III) ions and
released from the resin. The released U(VI) ions pass through
the column repeating isotope exchange reactions with adsorbed
U(VI) ions, and reach at the frontal boundary of the uranium band.
The U(VI) ions at the front boundary are reduced by Ti(III) and
re-adsorbed on the resins as previously mentioned.

206
 The redox reactions involved in this system are:
at the front boundary, 2Ti(III)K. w + U(VI) S
—^U(IV)_I\. H 2Ti(IV)s,
at the rear boundary, U(IV)J\ D + 2Fe(III)S —>2Fe(II)X\ D U(VI)
s'
where subscripts R and S refer to the phases of resin and solution,
respectively. The F e ( I I ) ions adsorbed on the resin are easily
eluted out by the succeeding F e ( I I I ) ions, and flow down in the
column without adsorption, according to the selectivities shown
above.

Anion Exchange Chromatography. Chloride ions makes complexes with

a number of cations, including uranium ions. The adsorption of
concerned uranium, titanium, iron ions from hydrochloric acid
solutions on an ion exchange resin is presented in Fig.4.[l8], Figure 4
shows that the sorption depends on the concentration of chloride
ions. If suitable concentration of HC1 is chosen, the following
sequences of ion exchange selectivities can be acieved.
Fe(III) » Fe(II), U(VI) > U(IV) & Ti(III).

Ti

VI IV III si. ads.

8 12 8 12 12
3
HC1 Concentration / M ( mol/dm }
Fig. fj. Anion exchange selectivities of complex cations.
Kg- = [Ml / fflgoi ot very low concentration of M ions.
Ref. (n).

Based on these selectivities, anion exchange redox chromatography

is realized by using concentrated HC1 solutions as the medium for
the moving phase. Apparently the tendency of the selectivities
for U(IV) and U(VI) in the anion exchange system is reverse to that
of the cation exchange system. The redox reagents are arranged
in the reverse sequence in anion exchange system against the cation
exchange system.
Anion exchange resins packed in a column is first conditioned
to the form of Fe(III)-Cl complex. Then U{IV) is introduced, and
oxidized to U(VI) by Fe(III). The generated U(VI) is adsorbed
on the resin, making chloride complexes. The U(VI) in resin is

207
reduced to U ( I V ) by T i ( I I I ) in the eluent. The redox reactions
in anion exchange chromatography are as follows.
At the front boundary,
2Fe(III) R U(VI) Fe(II)
at the rear boundary,
U(VI)R + 2Ti(III)s + nCl~ —> nCl~R + U(IV)g + 2Ti(IV),s .
U(IV) and Ti(IV) ions in the latter reaction have very small ad-
sorbabilities toward the anion exchange resins. The vacant sites
caused by the release of uranium ions are filled with Cl ions,
instead of Ti(IV) ions.
The models of chromatography are shematically shown for both
cation and anion exchange systems in Fig. 5.

( b)
Eluent

( Resin (Sol. ) ( Resin ) (Sol. )

Reducing Oxidizing
Agent Agent

U(VI) U(IV) U(IV) U(VI)

uo2cin 2-n UC C' U"+ U022+

Oxidizing
—t- Reducing
Agent Agent

Selectivity: Selectivity:
U(VI) > U(IV) U(IV) > U(VI)
Fig. 5, Chromatographie systems for uranium isotooe
separation based on UdV)-U(VI) exchange
reaction,
(a) a system using anion exchange resin,
(b) a system using cation exchange resin,

Electron Exchange Reactions. The isotope exchange reaction between

U(IV) and U(VI) ions gives the most fundamental base for the isotope
separation system.
U ( IV ) + 238r,/T,-rX _
235r238rT/.rTT1
U(VIJ (7 )
The rate of this reaction is governed by the electron exchange
between U(IV) and U(VI). The rate equation is expressed by using a
second order rate constant.
Rate = kexlu(Ivß[u(Vlf) (8 )

208
The constant kG jC depends on the concentration of H ions in the medium.
E. Rona [18! observed that the kG Ä values decrease with increase of
E+ concentration in the pH region. K. Gonda et al. [19-20] found that the
rate constant in a HC1 solution increases again with increase of
the H+ concentration above 4 M, giving the minimum values at ca. 3 M.
They reported also that the exchange reaction has a large activation
energy of 25 kcal/mol. From the view point of kinetics, both high
pH regions and high HC1 concentration regions are preferable conditions
for Chromatographie operations. Due to the large activation energy
the operation temperature should be elevated as high as possible,
and the employment of a catalyst would be of great use for production
of enriched uranium. E.Tomiyasu [21] found that U(IV) - U(VI) electron
exchange reaction is catalyzed by Fe(II)/Fe(III) ions.

Ion Exchange Reactions. To attain the isotopic equilibrium at any

cross-section in the uranium adsorption band, the ions U{IV) and
U(VI) must be exchanged at sufficiently fast rate between the two
phases of resin and solution. This process is governed by ion ex-«
change properties. Both U(IV) and U(VI) ions are contained in both
phases of resin and solution as either a major component or a minor
component. The exchange reactions take place among all these ions
in two phases. These reactions are depicted in Fig. 6 . Figure 6
indicates that three of the four steps must be fast to attain the
equilibrium in a short time, while one step is allowed to be slow.
It means thatat least one of two ion exchange processes of U(IV)
and U(VI) should be fast.

Ion Exchange Solution

Resin l( IV
\J \ [ LL * uuv;
à L tt
EX r EXS
>IX
^ VI ^
U(V ) •*—————> U ( V I )

Fig. 6 . Kinetic processes in uranium

ion exchange chromatography:
IX IV : ion exchange of U(IV), U(VI),
EX : electron exchange in resin and
solution phase, respectively.

209
6-2-4. REACTION RATES
In addition to above-mentioned factors on equilibrium, another
important factor is the kinetics of the chemical reactions involved
in the process. There are three different types of reactions of
which reaction rates should be considered in the system of uranium
enrichment by ion exchange chromatography.
Uranium redox reactions at uranium band boundaries.
U(IV) - U(VI) electron exchange reactions.
U(IV), U(VI) ion exchange rates.
Uranium Redox Reactions. In the redox reaction of uranium ions,
two electrons are transferred between the pair of ions of U(IV)
and U(VI). Two-electron reactions have, as a rule, slow reaction
rates compaired with one-electron reactions. For example the
reduction of U(VI) by Sn(II) is possible in respect to the thermo-
dynamic aspect, however the reaction rate of this redox system
is so slow that the system is not applicable for the
redox chromatography. In the cases of Fe(III) and Ti(III) used
as redox reagents, on the other hand, the redox reactions show
fairly rapid reaction rates. The reason for this would be given
by the mechanism that U(IV), and U(VI) can be oxidized or reduced
through the U(V) state in the redox reactions by Fe(III) or Ti(III)
ions. In either case of cation or anion exchange chromatography,
the redox reactions take place very rapidly. As far as the uranium
redox reactions with Fe(III) and Ti(III) ions concerned, the reac-
tion rates are sufficiently fast. This fact is confirmed from
the development of very sharp boundaries at the ends of a uranium
band. The solutions containing those ions of iron, titanium and
uranium show different colors: Fe(II) light blue, Fe(III) light
brown, Ti(III) purple, Ti(IV) transparent, U(IV) dark green, and
U(VI) yellow. During the migration the formation of uranium band
boundaries can be visibly checked through the glass wall of the
column.

The rate of isotopic ion exchange processes are indicated

in terms of the self-diffusion coefficients of given ions. As
a rule polyvalent ions have small self-diffusion coefficients.
Examples of self-diffusion coefficients are shown in Fig. 7 .(23)
It is well known that the rate of ion exchange is contralled
by the diffusion processes, and two concepts are proposed for
the determining step in the diffusion: the film diffusion and
the particle diffusion. A simple criterion is given to identify

210
 10
-6

10 -7

-8
10

-9
10

-10
10

0 5 10 15 20 25
DVB / %

Fig. 7. Self-diffusion constants

in sulfonic acid cation exchange r e s i n .
Ref. ( 2 3 ) .

the rate ditermining step: ( 2 2 )

0.13
-- particle diffusion control, I
f
"R R 'S S o
L 0.1 3 -- film diffusion control, J
where subscripts R and S refer to resin and solution, respectively,
C is the concentration of concerned ion, D is the self-diffusion
coefficient, S is a film thickness, and r is a bead radius.
For the cases of uranium ion exchange, the values of the terms
in the criterion are estimated approximately as (C /Cq) = 10,
(D£\D/D_)
O
= 10~2, (s/r O ) = 10~1. Then the particle diffusion is
estimated to be the rate determining step of the ion exchange.
If the self-diffusion coefficients are improved by one order in the
resin phase, and very fine resins are used, the rate determining
step would be changed to the intermediate or the film diffusion.
From the view point of ion exchange kinetics, the low valent
ions are preferable to be used in the chromatography . It is
possible to reduce the actual valency of uranium ions by using
appropriate complex ligands. In such case, however, the ion
exchange selectivities for uranium ions decrease, because of the
reduced valencies of ions, and the chromatography would not be
realized with the low selectivities of ion exchange resins. The
optimum conditions could be chosen considering all those factors
above-mentioned in this paper.

211
6-2-5. CAPACITY OF PRODUCTION
In terms of the cascade theory the Chromatographie process
is regarded as the square cascade for the isotope separation.
The design factors of an enrichment plant can be calculated
by using the cascade theory, in principle. Here it is shown that
a simple equation derived to determine the separation coefficient
of Chromatographie isotope separation processes can be used for
the estimation of the separation power of the plant employing
ion exchange chromatography.

P = £ qR Q (1 - R Q ) V N $ /(R - RQ), ( 1 0 )
where P = production capacity, £= separation coefficient (= l n ; X ) ,
q = isotope adsorption capacity per unit volume,
V = total volume of resin packed in the column,
$ = ratio of uranium band length to total bed length for one cycle
operation, N = cycle of operarion per unit time, e.g. year,
RO = isotope abundance ratio of feed,
Rp = isotope abundance ratio of product
The capacity of the production for the uranium enrichment
system is estimated by using this equation. The Chromatographie
operation conditions and resulting data are presented in Table
III. The flow diagram of a uranium enrichment plant designed by
Asahi Chemical Industry is shown in Fig. 8 .

Fig. 8. Flow diagram of uranium enrichment plant.

Ref. (13).

212
 Experiments have been reported on U(IV) - U(VI) exchange
systems uing both cation and anion exchange chromatographies [11-
18]. An example of the experimental work is shown in Fig.9 [24].
The experimental conditions of Fig. 9 may be far from the
required conditions for industrial plants, however the results
clearly shows the importance of the consideration given in this
paper.

5 -

Effluent Volume dm
Fig. 9. Uranium isotope seoaratlon by using an I on exchange resin
Migration length 22 in, Experimental temperature 70 °c,
lief. (24).

6-3. SEPARATION OF ACTINIDE ELEMENTS

Since the actinide elements involve long-lived a-emitters,
of which emission lasts over thousands years, the contamination
with actinide elements raise serious problems in handling and
storage of nuclear wastes. There have been continuing efforts
to develop technical measures which ascertain the highly safe
containments of the ot-emitters in the waste during the long-term
storage. The most direct and effective measure for this purpose
is to decrease the level of the contamination of the actinide
elements in the wastes, and this is accomplished by the implemen-
tation of separation and recovery of actinide elements from the
wastes. So far the experiences in this subject field have been
essentially in the laboratory work level. The potential meaning
of the actinide separation, however, would be enormous to continue
the expansion of the peaceful uses of nuclear energy. The follow-
ings are some basic experiments and laboratory experiences on the
separation of actinide elements.

213
Group Separation. The lighter actinides of uranium, neptunium and
plutonium are strongly adsorbed on strongly basic anion exchange
resins from a concentrated HC1 solution, whereas transplutonium
elements show much smaller adsorbability at the concentrated HC1
solutions. This tendency is essentially true in the system of
the anion exchange resin and concentrated HNO., solutions.
In the work carried out at JAERI ( Japan Atomic Energy Re-
search Institute ) [25] the irradiated fuel sample was solved in
HC1 solutions and adsorbed on the anion exchange resin Dowex 1X8.
The groups of elements were eluted out from the resin by succès--
sively charging the different solutions in the operational mode
as follows.
(i) At the first step fission products and heavier actinides Am
and Cm were eluted by a 9M KC1 - 0.1 M HNO, solution.
(ii) Zr was then eluted by a 9 M HC1 - 0.1 M HNO., - 0.01 M HF
solution.
(iii) Thirdly, Pu and Np was eluted by a 4 M HC1 solution,
(iv) Finally U was eluted by a 0.1 M HC1 solution.

Mutual Separation of Actinides. In the above-mentioned process

Pu and Np coexist in the effluents of the third step. To separate
Pu and Np these elements were loaded on the anion exchange resin,
Dowex 1X8, then Pu was reduced from tetra-valent to tri-valent by
adding NH2OH. The Pu(III) in the resin was eluted by a 9 M HC1
solition containing 0.1 M HI. The remaining Np was eluted by a
low concentration HC1 solution.
The mutual separation of transplutonium elements is achieved
by cation exchange chromatography. By using this technique deci-
gram quantities of transplutonium elements were separated at ORNL
( Oak Ridge National Laboratory ). In this work[ 26]cation exchange
resin Dowex 50 W-X8 (28 - 70 m ) was packed in stainless columns
and converted to ammonium form by 0.3 M NH.NO,. The column system
consisted of two columns: one short (14 mm I.D. and 0.2 m long,
packed with 56 - 70 m resin ) for loading, and the other long
(13.4 mm I.D. and 1.2 m long packed with 28 - 56 m resin ) for
separation. The tri-valent actinides were loaded on the short
column, and eluted with an eluent containing a complex forming
reagent alpha-hydroxyisobutyrate (AHIB) 0.25 M, adjusted to pH
3.9. The effluent from the column was then charged to a longer
column. The elution of the actinides adsorbed in the longer column
was carried out by changing the pH values and the concentrations
of AHIB in the eluents. Fermium, einsteinium and californium were

214
eluted with the eluent 0.25 M AHIP pH 4.2, thereafter berkelium
was eluted by 0.25 M AHIP pH 4.6, americium and curium were eluted
by 0.5 M AHIB pK 4.8. The effluent of this separation was collected
in fractions and subjected to alpha counting to detect the actinides.
The separated transplutonium elements by this process at ORNL
TCT 74Q ?S"?
were totally, 4.6 g of Cf, 0.5 g of Bk, 19 mg of Es and
oc 7
1 0 pg of Fm (estimated). After the operation, the radiation
damage to the ion exchange resin was found to be serious, especial-
ly, in the short loading column.
Plutonium Recovery. At the LASC (Los Alamos Scientific Laboratory)
plutonium was recovered from plutonium-bearing residues created
in the many research and development programmes [27]. The plutonium
waste treatment at the facility comprises a number of process lines
designed to recover and purify the plutonium in the residues. For
example, the plutonium is removed from non-combustibles in pickl-
ing operation with an HNO., leach. The process rags are burned
in an incinerator at a low temperature to produce an ash which is
then dissolved in HNO^-CaF-. These HNO, solutions and various
other types of processing solutions are transferred to an anion
exchange system to remove plutonium. The flow of the waste treat-
ment at the facility is illustrated in Fig. 10.
Organics
Noncornpalable
Nonconbuslibles WuhHNOj
MgO & CoO Solutions Organics
Gosling Crucibles & Miscellaneous V/,ihNo HCI CNonde Computable
Melol & Oxide R Reduction Residues Combuslibt* SoWs Halogens Solutions Residues WrttiHNOj

Various Nitrate Anion Exchange System

Fig. 10. Flow of material in the plutonium recovery

plant in Los Alamos Scientific Laboratory. Re. 27.

215
 In the anion exchange system, HNO.- solutions containing Pu
are charged into Dowex 1X4 resin columns. The adsorbed resin is
washed with a 7 M HNO, solution, then conditioned with 1 M HN03.
Thereafter plutonium is eluted with a 0.3 M HNO., solution contain-
ing the reducing agent NH-OH. More detailed process conditions
are presented in Fig. 11.

FEED
choice of route
dependent upon VALENCE STABL1ZED
<3M H + NH, OH-HNO,-NaNCL
Pu 02* +conlent method i ~z
HNO j to 7M

SORBEO
Effluent— Discarded
on Oowex 1X4 flow rate of Ito4
mi /min /cm2

7 M HN0 3 WASHED
volume based on impurity present • Discard
flow rate of 3mJ/mm/cm 2

IM HNO, CONDITIONED Wash

flow rate of 3 ml/min/cm2 Recycled

ELUTED Resin . Recycled through

NH2OH-HN03
flow rote of ImJL/min/cm2 IM ash 8
Then, if needed, IO£ of 7M HNO
O-3M NH 2 OH-HN0 3 - j Eluote
regeneration
0.5M
To Osolate Precipitation

Fig. 11. The operation of the ion exchange system for

plutonium recovery from waste stream.

6-4. RECOVERY OF URANIUM FROM PHOSPHORIC ACID SOLUTIONS

Uranium is found in phosphate rock ( phosphorite ) at the
concentration ranging between 50 and 130 ppm U. Uranium reserves
in phosphate rock in the world is estimated to amount to approxi-
mately 15 million tonnes [28]. The regional distribution of
uranium reserves in phosphate rock is shown in Table IV. As is
conceived, the large amount of uranium is carried in the products
from the phosphate rock, mainely in the phosphoric acid ferilizer.
The theoretical amounts of uranium contained in the pnosphoric
acid products are presented in Table V.
Several plants have been constracted in the USA to produce
uranium from phosphoric acid solutions. All of these plants are
employing the solvent extraction process. In this case of uranium

216
 TABLE IV. DISTRIBUTION OF URANIUM IN MARINE PHOSPATE DEPOSITS.

Area Uranium/ million tonnes U

Africa 8.5
USA 3.0
Near East and Asia 1 .6
Australia 0.8
Pacific Islands 0.015

Total 15.0 ( rounded )

Ref. 28 .

TABLE V. PHOSPHORIC ACID PRODUCTION CAPACITIES AND THEORETICAL

URANIUM CONTENTS ( 1981 ).

Continent tonnes P-O^/a tonnes U

Western Eurooe 2,725,000 680
Eastern Europe 6,505,000 1 ,620
North America 9,197,000 2,290
Latain America 1 ,001 ,000 250
Africa 3,167,000 790
Near East 1 ,993,000 500
South East Asia 829,000 200

Total 25,417,000 6,330

For plants larger than 150,000 te P2C5 /a .

** Assuming 32.5 % P2O5 ^-nt^ie PnosPhate rock; 10 % wet-process
losses; 0.009 % avarage grade of uranium in the rock.
Ref. 28 .

production ion exchange is a promissing alternative and the R and

D work for this purpose has been conducted in various institutes.
S. Gonzalez-Luque and M. Streat [29] reported that the amino-
phosphonic group ion exchange resin Duolite ES 467 showed excel-
lent adsorption of uranium from phosphoric acid in the concentration
range 1 - 6 M. It was found in this work that impurities of Ca2+,
Fe ions in the feed solutions did not seriously affect the ad-

217
sorption of uranium on the resin from the phosporic acid feed
solutions, while the presence of Fe + ions caused the reduced
adsorption of the uranium. In phosporic acid solutions ferrous
ions can reduce uranium (VI) to U(IV) which has less adsorbability
toward the amino phosphonic type resin. The uranium adsorbed on
the resin was eluted with 3 M H^P04 containing 0.3 M Fe *, accor-
dingly. An ammonium carbonate solution, also, was found as the
excellent eluting agent, and the elution of the adsorbed uranium
was carried out with 1 M (NH. ) ->CO,. The adsorption of uranium

*°
R-CH_-NH-CH0-P-0 2.
2 2 \ Na + UO "^
2 n
O
O Na CH-P-0 Na
/ \
. =^ R-CH -NB' O' + Na+ (11)
* \ +/
U0
2
on the aminophosphric acid resin is expressed as Eq. 11

The research work on the uranium recovery from phosphoric

acid has been conducted at Ben Gurion University [30] . In this
work several special ion exchangers were developed. A synergistic
mixture of two extractants, diethylhexyl phosphoric acid (DEHPA)
and trioctylphosphine oxide (TOPO), was immobilized in a polymer
matrix (stylene and methyl methacrylate, crosslinked by divinyl-
benzene); the crosslinkings of these resins are 15 % and 30 % DVB.
It was found that the uranium capacity of the resin increases with
increase in the contents of extractants DEHPA and TOPO in the
resin. The column operation tests were carried out on the resins,
which showed good performances in the preliminary tests, changing
the coditions of solutions. The column operation of the best case
in the experiments is as follows.
The resin containing the synergistic mixture of DEKPA and
TOPO was packed in a column (bed height 125 cm, 2 cm I.D.). The
column was fed with a 4.5 M technical grade phosphoric acid solu-
tion containing uranium at the concentration of 160 mg U/dm .
The uranium adsorbed on the resin was eluted with 6 M phosphoric
acid containing Fe + (20g/dn ). The average uranium concentration
in the effluent was found as 17 g U/dm , and the capacity of uranium
uptaken in the resin as 3.5 g U/ kg resin.
Phosphoric group is a well known ligand for uranyl ions. The
phosphoric type ion exchange resins would be useful not only for
the recovery of uranium from phosphoric acid solution but also for

218
other types of uranium recovery from various solutions, such as
mining waste water, mineral leaching solutions, liquid wastes in
reprocessing facilities.

6-5. APPLICATION OF ION EXCHANGE MEMBRANE

The first successful application of the ion exchange membrane
to the major process in the nuclear fuel cycle would be the electro-
lytic reduction of uranium in the uranium processing pilot plant
at Ningyo-Toge. The Ningyo-Toge works comprises the test plants
for the up-stream processes in the nuclear fuel cycle, specifically
uranium mining, milling, leaching, refining, conversion and enrich-
ment. The electrolytic reduction process,in which ion exchange
membranes are used, is incorporated in the conversion stage to
produce tetravalent uranium, U(IV), from refined uranium in the
form of U0_ + ions. Thereafter U(IV) solutions are added with
fluoride ions resuling in the precipitates of UF. [ 31] . This is
a very efficient route to reach UF^. By using ion exchange mem-
brane as the barrier between the cathode and anode electrolytic
compartments, the reduction of uranium was acieved: the reported
data [31] are the reduction rate of 99.5 % and the average current
efficiency of 82.3 %.
This technique was applied also to the decomposition of
ammonium ion in the alpha-bearing liquid wastes discharged from
the processes in the plutonium fuel facility [32] . The ammonium
decomposition process consists of two steps: the electrolytic
reduction of NH^NO, to NH.NO^ and the thermal decomposition of
NH.NO- to N_ and H-O. By the implementation of the above-mentioned
process, much effective volume reduction was achieved in the waste
treatment of HNO, solutions by nutralizing with NH.OH instead of
conventional NaOH. The illustrates of the electrolyzer and the
process flow are shown in Fig. 12 (a) and (b).
The cation exchange membrane used as the barrier in the
electrolyzer plays a key role in this technology. The special
cation exchange membrane of the fluorocarbon polymer type was
developed for this purpose, and the membrane showed excellent
durability and performance. The current efficiency of almost 80 %
was achieved at the conditions of lower temperature than 40 °C and
higher pH than 9 of the electrolyte solution in the cathode com-
partment.

219
 ( a ) HN03. H20
byproduct
NO.NH4OH)

NH 4 N0 3 «H 2 O

C a t i o n Exchange Membrane

( b ;
)

B 3
02
i i
jJ
f
-~x
i
Ekctrolystr
,-—
Anolytc Catholy
L™ Tank

Fig. 12. Illustrates of ammonium decomposition process.

(a) Electrolyzer . ( above )
(b) Process flov; . ( below )

REFERENCES
[1] TAYLOR,T.H.,UREY,H.C.,J. Chem. Phys. 5. (1937) 597.
[2] LEE.D.A., BEGUN,G.M., J. Am. Chem. Soc. 8J[ (1559) 2332.
[3] LEE.D.A., J. Phys. Chem. 61 (1960) 187.
[A] LEE.D.A., J. Am. Chem. Soc. 83_ (1961) 1801.
[5] LEE.D.A., DRURY.J.S., J. Inorg. Nucl. Chem., 27_ (1965) 1405.
[6] BIGELEISEN.J., MAYER.M.G., J. Chem. Phys. 15 (1947) 261.
[7] YONEDA.Y., UCHIJIMA.T., MAKISHIMA.S., J. Phys. Chem. 63 (1959) 2075.
[8] URGELL.M.M., et al., Peaceful Uses of Atomic Energy (3rd Int. Conf. Geneva,
1969) A/CONF.28/P/491.
[9] SAKUMA.Y., et al., Bull. Chem. Soc. Jpn. 53 (1980) 1860.

220
[10] SPEDDING.F.H., POWEL.J.E., SVEC.H.J., J.Am. chem. Soc. 77 (1955) 6125.
[11] SHIMOKAWA.J., KOBAYASHI, F., Isotopenpraxis 6. (1970) 170.
[12] FUJII.Y., FUKUDA.J., KAKIHANA.H., J. Nucl. Sei. Technol., _51_(1978) 745.
[13] SEKO.M., MIYAKE,T., INADA.K., Nucl. Technol.50 (1980) 178.
[14] CALUSARU.A., MURGULESCU,S., naturwissenshaften 63 (1976) 578.
[15] FLORENCE,T.M., et al., J. Inorg. Nucl. Chem. 37 (1975) 1961.
[16] DELVALLE.P., French Patent, Demande 7306881.
[17] KRAUS,K.A., NELSON,F., Peaceful Uses of Atomic Energy (Proc. Int. Conf.
Geneva, 1955) Vol.7, UN, New York (1956) 113.
[18] RONA.E., J. Am. Chem. Soc. 72 (1950) 4399.
[19] GONDA.K., Thesis, Tokyo Institute of Technology (1969).
[20] ïCAXIHAi\*A,ïï., et al., Proc. Symp. Exchange Reaction, IAEA, (1965) 121.
[21] TOMIYASU.H., FUKUTOMI.H., Bull. Chem. Soc. Jpn. ^8 (1975) 13.
[22] HELFFERICH.F., "Ion Exchange" McGraw-Hill, New York (1962) pp 250 - 322.
[23] SOLDANO.B., Ann. N. Y. Acad. Sei., _57 (1953) 116.
[24] RIKUDA.J., FUJII.Y., OKAMOTO.M., Z. Natureforsch. 38 (1983) 1072.
[25] ISHIMORI, T., " Actinide Separation " ( NAVRATIL, J. D., SCHALZ, W. W. ,
Eds ) ACS Symp. Series 117, Am. Chem. Soc., Washington D. C. (1980) 333.
[26] BERKER, D. E.,et al., " Transplutonium Elements " ( NAVRATIL, J. P.,
SCHALZ, W.W., Eds ) ACS Symp. Series 161, Am. Chem. Soc., Washington
D. C. (1981) 161.
[27] CHRISTENSEN, E. L., " Management of Alpha-Contaminated Wastes " ( Proc.
Symp. organized by IAEA and CEC, Vienna, 1980 ) IAEA, Vienna (1981) 75.
[28] Report of INFCE, WG 1, IAEA, Vienna (1980) 159.
[29] GONZALEZ-LUQUE, S., STREAT, M., "Ion Exchange Technology " ( NADEN, D.,
STREAT, M., Eds ) Ellis Horwood Ltd., Chichester (1984) 679.
[30] BELFER, S., KORNGOLD, E., EGOZY, Y., " Ion Exhange Technology " (NADEN, D.,
STREAT, M., Eds ) Ellis Horwood Ltd., Chichester (1984) 736.
[31] TAKENAKA, S., KAWATE, H., " Uranium Ore Processing " ( Proc. Advisory
Group, Washington D. C., 1975 ) IAEA, Vienna (1976) 55.
[32] KOMORI, R., OGAWA, N., et al., " Management of Alpha-Contaminated Wastes "
( Proc. Symp. organized by IAEA and CEC, Vienna, 1980 ) IAEA, Vienna
(1981) 133.

221
 APPENDIX 1

GLOSSARY
(Drafted by J.D. Navratil and supplemented by A. Himsley and Y. Fujii)

Amine Type Resin: An anion exchange resin which involves amine as the
fixed functional group.

Anion: A negatively charged ion.

Anion Exchange Resin: A synthetic ion exchanger which can adsorb

and exchange anionic substances. Cationic functional groups are
fixed in the resin.

Amphoteric Ion Exchange Resin: An ion exchange resin which has the
properties of both acid and base. For example, the resin contains
aminoacids ( NH -R-COOH ) as the fixed functional groups.

Adsorption: Adhesion of gaseous molecules or dissolving substances

in liquids to the surface of solids. This term is used to
specifically express the stoichiometric sorption of ionic species
into ion exchangers in order to distinguish from the
non-stoichiometric sorption of solvents.

Amine: A group of compounds derived from ammonia by substituting organic

radicals for the hydrogens; primary amine is H NR, secondary
HNR , tertiary NR , quarternary NRf. The basicity increases
£ *J *T

in this sequence.

Attrition: The breakage and wear of resin particles.

Backwashing: Upward flow of solution through an ion-exchange resin bed

to reduce compaction of the bed and cleanse it of foreign material.

Base Exchange: Exchange of cations between solution and a cation-exchange

material.

223
Batch Operation: Method of using ion-exchange material in which the
material and the solution are mixed in a vessel and, after
equilibrium is attained, the liquid is decanted or filtered off.

Bed Depth: Depth of the ion-exchange material in a column.

Bed Expansion: Separation and rise of ion-exchange materials in a

column during an upward fluidizing flow.

Bed Volume: The total volume of wet settled resin in an ion exchange
column.

Breakthrough: The point where the concentration of the exchanging ion

in the effluent begins to increas« significantly.

Breakthrough Curve: The curve or isotherm which shows the effluent

concentration of an operating ion exchanger with respect to the
number of unit volumes (usually Bed Volumes) of liquid passed through
the exchanger until the effluent concentration is 90% or more of the
influent concentration.

Cation: A positively charged ion.

Cation Exchange Resin: A synthetic ion exchanger which can adsorb

and exchange cationic substances. Anionic functional groups are
fixed in the resin.

Carboxylic Acid Type Resin: A cation exchange resin of which fixed

functional groups are carboxylic acid.

Channeling: Creation of isolated paths of less resistance in the

ion-exchange material bed caused by the introduction of dirt, air
pockets, and other factors which cause uneven pressure gradients in
the bed. Channeling prevents the solution being processed from
uniformly contacting the entire resin bed.

Chemical Stability: Ability of an ion-exchange material to resist

changes in its properties when in contact with aggressive chemical
solutions such as oxidizing agents or ionizing radiation.

224
Chelate Type Resin: Chelating reagents, capable of forming rings
with metal ions by one or two coordinated bondings, are embeded in
the ion exchange resin as the fixed functional groups.

Chromatography: A technique by which separation in a mixture is achieved

by virtue of the differences in migration of the mixed components in
a packed column or, more generally, in a separating medium.

Co-ion: Any ion, whether in the exchanger or in the solution being

treated, which has the same sign as the exchanger framework.

Color Throw: The impartation of color from an ion-exchange material to

a solution.

Column Operation: Most common method for employing ion exchange in

which the solution to be treated passes through a bed of ion-exchange
material.

Counter-ion: Any ion, whether in the exchanger or in the solution being

treated, which has a charge sign opposite to that of the exchanger
framework.

Crosslinkage: Binding of the linear polymer chains in the matrix of

an ion-exchange material with a crosslinking agent which produces a
three-dimensional, insoluble copolymer.

Decontaminaition Factor (DF): The ratio of the radioactivities in a

solution prior to and following treatment.

Deionization: Removal of ionizable constituents from a solution by

ion-exchange processing.

Distribution Coefficient: Referred to a counter ion, the distribution

coefficient is the ratio of the concentrations of the counbter ion in
the exchanger and in the solution.

Displacement: A chemical exchange in which one element, molecule

or ionic species is replaced by another element, molecule or ionic
species.

225
Divinylbenzene (DVB): Organic monomer containing two double bonds.

Effluent: The treated solution which emerges from an ion-exchange

column.

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 not.

Eluant: The solution used to remove the sorbed ions from the resin.

Eluate: The concentrated solution of ions stripped from the resin by

the eluant.

Elution: Stripping of sorbed ions from an ion-exchange material by

passing through the material an eluant solution of such composition
that it will change the distribution coefficient of the sorbed ion
with respect to the ions in the eluant.

Elution Curve: The curve showing the concentration of the ion of interest
in the eluate with respect to the number of bed volumes of eluant
passed through the column until the concentration of the ion in the
eluate is sufficiently low as to indicate the resin is almost
completely stripped.

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 or Cl form, as meq/g, or the
number of inorganic groups in a specified volume of a fully
water-swollen packed bed of exchanger usually when the material is
J. »
completely converted to the H or Cl form, in terms of meq/ml.
The counter-ion content of an exchanger.

Exchanger: Ion exchange materials or resins which are insoluble acids

or bases.

Exhaustion: The point in an ion-exchange cycle in which the ion

exchanger can no longer remove the ions of interest from the
solution being processed.

226
Fixed Bed Process: The solid phase ( ion exchanger ) is fixed in a
separation column, forming a packed bed. Regeneration is made in a
batchwise manner.

Fluidized Bed Process: The solid ion exchanger is handled, in many

respects, like a fluid in an operational vessel under the up-stream
of feed solution.

Freeboard: Space provided above the resin bed in the column to

accommodate the expansion of the resin material during backwashing.

Head Loss: Loss in liquid pressure resulting from the passage of the
solution through the bed of ion-exchange material.

Hydraulic Classification: Tendency of small resin particles to rise to

the top of, and large resin particles to settle to the bottom of,
the column during a backwash operation.

Hydrogen Cycle: Cation-exchange material operation in which the

regenerated ionic form of the material is the hydrogen ion.

Influent: Solution entering an ion-exchange material bed.

Ion Exchange: A stoichiometric, reversible reaction in which mobile ions

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

Ion Exchange Zone: That space existing in a resin bed above which the
resin is in equilibrium with the influent and below which it is in
equilibrium with the eluant i.e. regenerated or unused. It is
within this zone chat the ion exchange is occurring.

Leakage: Appearance in the effluent from an ion-exchange column of

ions which are desired to be removed from the liquid being processed.

Macroreticular Resins: Highly porous resins. (From "macro" meaning

"large" and "reticular" meaning "netlike" or "sievelike".)

Mixed Bed: An ion exchange bed consisting of cation and anion

exchange resins packed with 1:1 equivalent ratio.

227
Molecular Sieve: Materials with porous adsorbing properties which
chemically lock molecules or ionic species into their pores.

Moving Bed Process: The ion exchange separation process in which the
solution is continuously fed and the resin is continuously or
send-continuously recycled through the regeneration process.

Operating Capacity: Portion of the total exchange capacity of an

ion-exchange material for the removal of a particular ion which is
utilized in a practical ion-exchange operation. This is less than
the total capacity due to the incompleteness of regeneration of the
resin and competition of other ions in the influent.

Physical Stability: Ability of an ion-exchange material to resist

breakage caused by physical manipulation or by volume changes.

Porosity: Term to describe that property of an ion-exchange material

which allows solutes to diffuse in and out of the resin particle.

Régénérant: Solution used to convert an ion-exchange material to the

desired ionic form for reuse.

Regeneration: Displacement from the ion-exchange material of the ions

removed from the process solution or influent.

Regeneration Level: Amount of régénérant used per unit volume of resin.

Resin Fines: Extremely small particles of an ion-exchange material

usually resulting from breakdown of resin in course of use. They
increase the pressure loss through the bed and are therefore
undesirable.

Rinse: Passage of water through the ion-exchange material to flush

out excess régénérant.

R.I.P. Process: Resin in pulp process where large-mesh ion

exchange resins loosely contained in stainless steel screen baskets
move up and down in the mineral leaching liquor in order to avoid
the preliminary filtration of finely grounded ore slurry.

228
Salt Splitting: Conversion of salts to their corresponding acids or
bases by passage through strong-acid or strong-base ion-exchange
materials.

Selectivity (Ion Exchange): The preference of an ion exchange resin

for one species of counter ion over another.

Sorption: A general term which includes absorption, an engulfing, and

adsorption, an interface or surface attraction. This term is
frequently used to specify the non-stoichiometric uptaking of
solutes (electrolytes or non-electrolytes ) from the solution.

Sphericity: Unbroken spherical state of ion-exchange resin beads.

Void Volume: The space occupied by a settled volume of resin minus

the actual volume of the resin particles. This is usually expressed
as a percentage and for spheres of roughly the same size is
generally around 0.35 to 0.4 or 35% to 40%.

Wet-settled Resin: The volume of resin in a column when immersed in

the liquid to be treated (usually abbreviated to wsr).

229
 APPENDIX 2

COMPILATION OF RESIN DATA

(Compiled by Y. Fujii)

231
Notes and abbreviations of the terms used in the tables.

Column Term

Type of acid, SA strong acid

base, or
exchange
WA weak acid
SB strong base
WB weak base
S/W "strong" + "weak"

Functional -MR alkyl amines, n = 4, 3, 2 and 1.

group
-MR-, .-> 1 the mixture of tertiary, secondary and primary amines.
0 ,£ , I
(I) quarternary ammonium group type I, -OHLNfCH.,).,.
(II) quarternary ammonium group type II, -CHJMfCH-, ) ~ ( C-H .OH ).

Ion The charge signs "+" and "-" are omitted.

form FB free base form

Matrix & PS polystyrene

porosity MAc methacrylic polymer
Ac acrylic polymer
EA epoxy-amine polymer
P porous
HP high porous
VHP very high porous
MP macroporous (macroreticular resin)

Closslinking mat. material

mat. DVB divinylbenzene

Others max. maximum

temp. temperature
var. variable

232
Table 1. Cation Exchange Resins
Trade name Type Functional Ion Exchange capacity Matrix Cross- Moisture Particle Operating Remarks
of group form dry wet & linking size max. temp. pH
acid (meq/g) (meq/ml) porosity mat.(%) (mm) (°C) range
Amber li te
>V *
IR-1 1 6 SA -so3" Na 4.5 0.3 PS Gel DVB 1 90 0.3-1 .2 120 0-14 *approx.
n * *
IR-118(H) II
H 4.4 1.3 II
" 4.5 60 It
" " values
It n II ti * II „
IR-120PLUS Na/H 4.4 1 .9 " 8* 45
II n It n * II II II
IR-1 22 Na 4.4 2.1 " 10* 40
M tt II n * * II II II
IR-1 24 Na 4.4 2.2 " 12 39
IR-1 30C II n Na/H 4.4 1.9 M n _ 46* 0.35-1.2 tt M

II n tl
* II II
200 Na 4.3 1.75 MP DVB 20* 48 0.3-1.2
II it M
TV * It tl
200C Na/H 4.3 1 .75 MP DVB 20 48 0.35-1.2
It n II
TV * II M
252 Na 4.4 1.75 MP DVB 12 49 0.3-1.2
IRC-50 WA -cor H 10.0 3.0 MAc MP DVB 48* n 120 5-14
DP-1 n " Na 8.1 2.5 MAc MP DVB 73* n II M

IRC-84 n it H 10.0 3.5 Ac Gel DVB 43* ti 4-14

Diaion
SK 1B SA -so3~ Na - 1.9 PS Gel DVB 8 43-50 0.3-1.2* 1 20 0-1 4 *ef f ective
SK 102 n It n - 0.6 II M 11
2 72-82 II ti ,i size=0.4-0.6
n mm
SK 104 n II
- 1.2 M tt " 4 57-67 II n M
SK 106 n tt K 1.6 M ii 11
6 47-57 II tt n
SK 110 n II n - 2.0 II n " 10 35-45 tl u n
SK 112 n tt n - 2.1 " M 11
12 32-42 tt n ti
SK 116 n tl n - 2.1 n II
" 16 27-37 II n n
PK 208 SA -SO3~ Na - 1.2 PS P DVB 4 58-68 0.3-1.2* 1 20 0-1 4 *ef f ective
PK 212 n II tl _ n tl ,, „ size=0.4-0.55
1.5 "
" 6 52-58 mm
PK 216 n II It - 1.75 n M 11
8 46-52 (1 n it
PK 220 it II It
- 1.9 n II II n n
" 10 41-47
PK 228 u II II -- 2.05 u II 11
14 37-43 11 n n
Table 1 (cont.)

Trade name Type Functional Ion Exchange capacity Matrix Cross- Moisture Particle Operating Remarks
of group form dry wet & linking size max. temp. pH
acid (meq/g) (meq/ml) porosity mat.(%) (mm) (°C) range
Diaion ( continued )
WK 10 WA -C00~ H _ 2.5 MAc , ? DVB 50-56 0.3-1 .2 150 5-14
WK 11 ii rr rr
- 2.9 M ir M
45-52 tl M II

WK 20 n ti n
- 3.5 AC, HP M
40-46 tl
120 4-14

Dowex
HCR-S SA -so3~ Na - 2.0* PS, Gel DVB 8 44-48 0.3-1 .2 150 0-14 *mimimum
H 1.8* 50-56
HCR-W2 n " Na _ 2.0* ri ff n
44-48 0.4-1.2 If M

H 1 .8* 50-55
HGR n u Na _ 2.2* it II
DVB 10 42-46 0.3-1 .2 tl II

H 2.0* 46-51
HGR-W2 M n Na _ 2.2* M II tl
38-43 0.4-1 .2 M M

H 2.0* 46-49
MSC-1 II n Na - 1.7* PS, MP DVB 44-50 II II M

H 1.6* 50-56
CCR-2 WA -coo~ H 3.8* Ac, Gel DVB 48-54 0.3-1.2 120 5-14
tl II II II It
MWC-1 - 4.0* Ac, MP 44-50 " 4-14

Duolite
C-20 SA -so3" Na 4.6 2.0 PS, Gel DVB 8 45-50 0.3-1.2 120 0-14
C-225 M II M II II M n II II
0.4-1.3 =Zeolit225
C-204F II II II M M 90
4.6 1.5 DVB 2-8 50-65 var.
C-206A II II II tl II 100 ii
4.6 1.6 DVB 6 55-61 0.4-1 .2
II II
C-255 II
4.5 2.0
II M
DVB 10 40-45 0.4-1.3 1 40 " =Zeolit525
C-26 II II II
4.5 PS, MP DVB 12 47-52 0.3-1.2 n n
1.85
C-264 II II II II n DVB high M II
4.6 2.3 38-43 0.4-1.2
C-265 II II II II M n 35-40 M II II
4.3 2.0
 Table 1 (cont.)

Trade name Type Functional Ion Exchange capacity Matrix Cross- Moisture Particle Operating Remaries
of group form dry wet & linking size max. temp. , pH
acid (meq/g) (meq/ml) porosity mat.(%) (mm) ("C) range
Duolite (continued)
C 433 WA -COO" H 9.5 4.2 Ac, Gel 43-47 0.3-1.1 120 5-10
C 436 n 11
" 9.0 3.7 n M
50-55 0.3-1.2 100 "
C. 464 it n 11
8.8 2.7 52-58 120 5-14
Ac, MP 0.3-1.1
ES-468 M M n n n tt n n
9.0 1.9 62-67
Imac
C 12 SA -so3~ Na 4.8 2.0 PS, Gel DVB 8 48 0.3-1.2* 120 0-14 *90 %
C 12A ti tt n n n n II
4.8 1.9 50 II II

C 8P n It n 4.5 It
1.8 PS, MP DVB 12 55 11 It

C 16P it tl ti II It
4.3 2.1 DVB 16 48 tl II

25 WA -000 H 9. 3.5 Ac, Gel 50 II II tl

TMR S/W -so3~, -s~ H 1 .3 PS, MP DVB 55 tl

60 0-14
GT 73 WA weak acid H 1 .4 PS, MP DVB 53 It
55 0-14
lonac
C-240 SA -so3~ Na 4.6 1.9 PS, Gel DVB 8 45-48 0.4-1 .2 140 0-14
C-242 It n H n It n n n tl
0.3-1.2 120
C-249 tt n " II n ti n It
Na 0.5-1.2 140 "
C-253 tl n It n It n n n tt n n
0.6-1 .2
C-250 II ti It
5.0 n it n
2.1 " DVB 10 38-43 0.3-1.2
C-255 M n tt II n n ti ti II n it
35-38
C-257 tl 11 n
H 4.6 1.9 " DVB 8 45-48 0.6-1.2 120
C-258 It M
Na 5.0 2.1 tt it ti 38-43 0.4-1.2 140
C-267 tl It
H 4.9 1.9 n n n 49-55 0.35-1.2 120
w C-298C-H II II II
4.9 2.1 M n n it n
52-58 0.4-1.2
CF It II
Na 5.5 2.3 tt n n 43-49 0.3-1.2 140
 Table 1 (cont.)
Os

Trade name Type Functional Ion Exchange capacity Matrix Cross- Moisture Particle Operating Remarks
of group form dry wet & linking (%) size max. temp. pH
acid (meq/g) (meg/ml) porosity mat.(%) (mm) (°-C) range
Icnac (continued)
CF S SA -so3" H 5.0 2.2 PS, MP DVB 45-50 0.3-1.2 120 0-14
n II ir ff M
CF Z
M tl
5.1 2.4 M II
40-42
II II II 11 It
CFP-1 10 II M
5.0 2.2 II
40-46
ii II 11
CC WA -cocf H 9.5 3.5-3.7 Ac, MP DVB 46-53
|
| It " 3.9-4.1 n n n 51-56 M M M
CNN 10.0
 Table 2. Anion Exchange Resins

Trade name Type Functional Ion Exchange capacity Matrix Cross- Moisture Particle Operating Remaries
of group form dry wet & linking (%) size max. temp, pH
base (meq/g) (meg/ml) porosity mat.(%) (mm) CC) range
Amberlite
IRA-400 SB NR4,(I) Cl/OH 3.7 1 .4 PS, Gel DVB 45* 0 .3-1. 2 60 ,8(1 0-14 *approx.
IRA-400C n u Cl It It tt n it 47* 0 .35-1 p M It n values
IRA-401 S ti n it 3.2 0.8 It n n 62* u II It n
IRA-402 n it n 4.2 1.2 M ti n 54* 0 .3-1. 2 " n
IRA-410 NR4,(II)
n 3.4 1.3 tt n n 42* 0 .3-0. 8 " " ti
IRA-420C n 1 .2 II n n 54* 0 .42-1 .2 " M
NR4/(D
IRA-430 II M n 3.9 1.1 II n n 50* 0 .84-1 .41 " ti
IRA-458 II II ii 4.4 1 .2 Ac, Gel " 60* 0 .3-1. 2 38 80 M
It
IRA- 9 3 WB NR, FB 4.6 1.2 PS, MP " 58* 100 0-9
IRA-94 it n II II II tl n n 60* II II II

n ti II
4.7 It n n II II
IRA-99 1 .2 58* / o. 5-1.2 "
II
IRA-45 NR3 2 1 5.2 1 .9 PS, Gel DVB 43* 0 .3-0. 84 100 0-7
tt II
IRA-68 NR 3 ' 5.6 1 .6 Ac, Gel " 60* 0 .3-1. 2 60
IRA-900 SB NR4,(I) Cl 4.2 1.0 PS, MP DVB 60* tt
60011 80e1 0-14
IRA-900C n n Cl/OH tl ti It n n 63* 0 .35-1 _ 2 ii it n
IRA-904 n n Cl 2.6 0.7 It n n H
57* 0 .3-1. 2 " "
IRA-910 NR4,(II) It
3.7 1 .0 It n n 55* II ti n n
IRA-938 Cl/OH 3.7 0.5 tl n n 0 .3-0. 84 n
NR4,(D 73* " "
IRA-958 n n 4.1 0.8 o n n n
Cl Ac, MP DVB 69* 0 .3-1.

to
 Table 2 (cont.)
oo

Trade name Type Functional Ion Exchange capacity Matrix Cross- Moisture Particle Operating Remarks
of group form dry wet & linking (%) size max. temp. pH
base (meq/g) (meq/ml) porosity mat.(%) (mm) ("O range
Dia ion OH Cl
SA10A SB NR4/(I) Cl 1.3 PS, Gel DVB 43-47 0.3-1 •2 60 80 0-14
SA 1 1 A n M It u ii II
0.85 55-65 M tt tl It

SA20A ti M M 1, U
NR4/(II) 1 .3 39-44 II
40 60
SA21A n II
" II n ti n
0.8 I I I I

55-65 It

PA306 SB NR4,(I) Cl 0.8 PS, P DVB 3 66-76 0.3-1 . 2 60 ,80 0-14

II tl II II II tt tl tl M
PA308 1.0 DVB 4 57-67
II M M II II [1 tl It tt
PA312 1.2 DVB 6 49-55
It II II II tt II II It tl
PA316 1 .3 DVB 8 44-50
II M M II II
PA318 1 .3 DVB 9 42-48 11 tt It M

PA406 M
NR4,(II)
II
0.7 It It
DVB 3 61-71 ti 40 60
PA408 II II II
0.9 II II
DVB 4 54-64 M M ti n

PA412 II 11 II
1.1 II II
DVB 6 46-52 II n ti ti

PA416 II II II
1 .3 II 11
DVB 8 40-46 II n M n

PA418 II tl II
1.3 II II
DVB 9 38-44 11 n ti ti
II
WA10 WB NR - FB 1.2 Ac, Gel DVB 50-56 60 0-9
WA11 it n n 1.4 ii n ti
45-52 II n u
WA20 n M n II
NR2 2.5 PS, P 40-46 100
WA21 u tl II tt II tt tl
2.0 PS, HP 63-69
WA30 n II n n ti tt It II
NR-. 1.5 57-63
 Table 2 (cont.)

Trade name Type Functional Ion Exchange capacity Matrix Cross- Moisture Particle Operating Remarks
of group form dry wet & linking ( % ) size max. temp. pH
base (meq/g) (meq/ml) porosity mat.(%) (mm) (*C) range
Dowex (continued)
SBR SB MR . , ( I ) Cl 1 .4 PS, Gel DVB 43-48 0 .3-1. 2 50 ,100 0-14
n u n ^ II It n II n n 0 .35-0 A3 II II tl

n n n OH 1 .1 n II
" max60 n M 11 M

n n K II It n II
55-65 0 .3-1 . 2 tl M II

11 II II
SBR-P " " Cl 1 .2 PS, P 53-60 0 .3-1 . 2
tl It It M n 11 II
50-67 0 .35-0 .!3 11 M tt

tl tl It 11 It It II II
OH 1 .0 M
60-70
II It M M
11 II M
Cl 1 .1 It
55-60 0 .3-1. 2
11 11 11 II II
MSA-1 1 .0 PS, MP 56-64
11 It II II It II M II 11 3 II 11 H
0 .35-0 .(
21K " 1 .2 PS, P 50-58 0 .8-1 .2 It tt tt

Particle size 0. 6-1 .2 / and 0.4-0.8 are available.

II M II tl
XFS-43116 " 1 .4 PS, Gel 43-48 0 .4-0. 8
SAR " NR4,(II) tl
1 .4 M M
38-45 0 .3-1 .2 35 77
11
MSA-2 tt
1 .0 PS, MP 53-60 0 .3-1 .2 II II M

1 .2 II n 0 .3-1. 3
MWA-1 WB NR3 FB 4.5 " 50-60 '100 0-9
WGR " NR-, " 5.0 1 .5 EA _ 50 0 .4-1. 2 93

to
OJ
Table 2 (cont.)

Trade name Type Functional Ion Exchange capacity Matrix Cross- Moisture Particle Operating Remaries
of group form dry wet & linking (%) size max. temp. PH
base (meq/g) (meq/ml) porosity raat.(%) (mm ) range
("C)
Duolite
A 101 SB Cl 3.7 1.3 PS, HP DVB 50-55 0.3-1.2
OH
60 ,100
a 0-14
NR4,(I)
A 102 n NR4,(II) II
3.5 1.3 n 11 n 45-50 n 35 , 75 It
A 109 n NR4,(I) II
3.5 1 .4 PS, Gel n 43-48 0.4-1.1 60 ,100 II

A 113 n n It
3.6 1.3 M It n 48-55 0.3-1.1 II II tl

A 116 n NR4,(II) 11
2.2 1 .4 II II n 45-50 0.3-1.2 35 75 M

A 161 n NR4,(I) M
3.8 1.1 PS, MP n 51-56 II
60 100 II

A 162 n NR4,(II) 11
3.3 1.1 It II n 48-53 It
35 75 If

A 132 n NR4 It
4.0 1.25 Ac, Gel n 51-57 0.3-1.1 35 70 11

ES 137 n 11
3.2 1.4 PS, Gel M 40-50 var. 60 100 It
NR4,(D
A 30 B WB NR
3 FB 6.0 1.9 EA, Gel - 58-63 0.3-1.2 25 40 0-9
II It
A 303 MR, 4.0 1.3 PS, MP - 45-55 0.3-1.0 60 100 0-7
A 368 II n II
4.0 1 .7 n tl
- 45-52 0.3-1.1 II tl It

A 378 It n f1
4.1 1.3 n 11
- II M tl
52-58 = A368PR
A 369 M n II
4.1 1 .1 n tl
- 56-62 tl tl ft n
tl It II
A 374 PFA 7.3 2.3 Ac, Gel - 47-51 35 70 " *polyfunct-
A 375 It
NR3 II
4.7 1.6 it 11
- 52-60 II tl II
0-9 ional amine
II
A 561 NR3 tl
7.5 1 .7 Ph, MP - 50-55 0.3-1.2 50 0-6
A 7 tl
NR2 II
9.0 2.0 Ph, VHP - 53-60 It
40 n
Imac-Asmit
256 P SB NR4,(I) Cl - - PS, MP DVB 63 0.5-1.2 90 0-14
Imac
S 540 SB NR4,(I) Cl 3.8 1 .2 PS, P DVB 53 0.3-1.2 60 100 0-14
S 550 n n " 3.8 PS, MP 11
55 n II tt 11
1 .1
n ii «
S 542 NR4,(II) 3.5 1.3 PS, P It
48 35 75 II
Table 2 (cont.)

Trade name Type Functional Ion Exchange capacity Matrix Cross- Moisture ParticleOperating Remaries
of group form dry wet & linking (%) size max . temp . pH
base (meq/g) (meg/ml) porosity mat.(%) (mmcc)) range
Imac (continued) OH Cl
A 20 S WB NR, FB 4 .1 1 .4 PS, MP DVB 57 0.3-1.2 60 100 0-7
A 20 SU " " 4.1 1.1 tt It ti 60 It
70 " u
A 20 R 4 .1 1 .7 M M n 55 It it n it
A 24 4 .0 1 .7 M It ti 57 M
80 "
A 24 F II II It II it 46 It
60 " M

*
II
A 327 " NR- " 6 1 .9 PA, Gel — 60 30 - " *Polyamide
-5/4

lonac
A-540 SB NR4,(D Cl 3 .6 1.0 PS, Gel Ac 48-60 0.4-1.2 60 0-14
A-550 " NR , (II) 3-3.3 1.3 PS, Gel Ac 43-47 u 40 100 H
*
A-641 " NR4,(D 3 .9 1.15 PS, MP DVB 54-58 0.3-1.2 70 " " *Second ge-
A-642 3.9 1 .1 II n n 57-62 0.4-1 .2 it ti ,t neration
II 11 n
type.
II
A-651 " NR4,(II) 3 .5 1 .15 49-52 0.3-1.2 60 "
ASB-1 " NR4,(I) " 3 .7 1.4 PS, Gel H 43-49 II u D " =A-430
ASB-1 P " " " 4.3 1.3-1.4 II it n 51-57 II n ii =A-440
ASB-1 PC-OH " " " 4 .3 1.35 It it n 50-55 It it n It

ASB-2 " NR4,(II) 3 .5-3.7 1.5-1.6 II n ti 38-42 II

40 77 =A-450
A-305 WB NR,, FB 1 2.0 3.5 EA, MP - 59-67 0.4-2.0 40 II
£ f \
* M
A-328 " NR3 4.5 1 .85 PS, MP DVB 46-52 0.3-1 .2 100
AFP-329 " " " 4.0 1.5 ti It n II
44-52 60 " =AFP-329K
A-365 " NR, 1 9.5 3.8 Ac, Gel DVB 54-59 " n II
 Table 3. Nuclear Grade Ion Exchange resins
to
Trade name Type Functional Ion Exchange capacity Matrix Cross- Moisture Particle Operating Remarks
of group form dry wet & linking (%) size max. temp. pH
exchange, (meq/g) (meq/ml) porosity mat.(%) (mm) (°C) range
Amberlite
IRN-77 Cation, SA, SO" H PS,
1.7 5 Gel DVB 55 0.3-1.2 120 0-14
IRN-1 63 Li
IRN-169 NH.
IRN-218 Li-7
IRA-78 Anion, SB, (I) OH 1 .2 PS, Gel DVB 60 0.3-1.2 60 0-14

Bio Rex
50W-X8 Cation, SA, S0~ H PS, Gel DVB 8 20-50 mesh
NH
Li
Li-7
RG 1-x8 Anion, SB, (I) OH 20-50
II
mesh
II
RG 2-x8 (ID
Dia ion
SKN 1 Cation, SA, S0~ H 4.7 PS, Gel DVB 8 0.4-1.2
SKN 3 Li-7 4.6
SAN 1 Anion, SB, (I) OH 3.7 PS, Gel DVB 8 0.4-1.2
Dowex
HCR-S Cation, SA, so" Li 1.8 PS, Gel DVB 8 55max 0.3-1.2 150 0-14 H form is
NH, 2.0 42-46 in Table 1
 Table 3 (cont.)

Trade name Type Functional Ion Exchange capacity Matrix Cross- Moisture Particle Operating Remarks
of group form dry wet & linking (%) size max. temp. pH
exchange (meq/g) (meq/ml) porosity mat.(%) (mm) (*C) range
Duolite
ARC 9351 Cation, SA, -S0~ H 4.9 1 .8 PS, Gel DVB 8 0.3-1.2 120 Parent =
ARC 9353 ti n n -3 Li-7 4.8 1 .75 It n n 11
" Duolite C20
ARC 9359 " ",-CH9SO~ H 3.0 1 .1 Ph, 0.4-1.2 60 =C 3
ARC 9359Na .- Na 2 .8 1 .1 "
ARC 9360 n n u Li-7 2.9 1 .1 Ph "
ARA 9366 Anion,SB,NR.(I) OH 4.0 1 .0 PS, Gel 0.3-1.0 60OH , . = A 101
ARA 9366B n n 4 If H (1 n If
0.3-1.2 " lOO00^6
ARA 9371 MB,NR3 FB 6 .0 1 .8 polyalky lamine " 50 = A 30B

lonac
NC-10 Cation, SA, SO~> H 1 .9 PS, Gel DVB z. 55 0.4-1.2 120 0-14
NC 11 n - 11
2.0 It """ 11
130
NA-30 Anion, SB, (I) OH 1 .0 PS, Gel Ac ^ 60 0.4-1.2 60 0-14
n M n 11 n n n
MA- 38 1 .4 " DVB ~"

to
*.
OJ
Table 4. Mixed Bed Ion Exchange Resins

Trade name Mixed resins Mixing Functional Ion Capacity Moisture Particle Operating Remaries
Cation / Anion ratio (C: A) group form (meq/ml) (%) size(mm) max. temp. (°C)
Amberlite
IRN-217 IRN-21 8/IRA-78 Li-7/OH 0.55 60 0.3-1 .2 nuclear grade
IRN-1 50 ERN-77 /IRA-78 H/OH n n M n
IRN-1 54 IRN-1 63/IRA-78 Li/OH n n II n
IRN-1 70 IRN-1 69/IRA-78 NHd/OH n n II n
IRN-277 AMB.200/IRA-938 H/'OH 0.25 " II n
IRN-300 IRN-77 /IRA-60 H/ OH 0.86 50 M n
MB-1 IR-1 20/IRA-400 1:1.5 0.55 55 60
MB-3 IR-120/IRA-410 1:1.5 0.55 55 40
Bio-Rex
RG 501 -X8 RG~~50W-X8/RG 1-X8 1:1 H/OH 20-50mesh nuclear grade
Other available ionic forms are Li/OH, Li-7/OH, NH./OH .
RG 502-X8 RG 50W-X8/RG 2-X8 1:1 H/OH 20-50mesh nuclear grade
Diaion
SMN 1 SNK 1 /SAN 1 1:1 H/OH 0.4-1 .2 nuclear
11
grade
II
SMN 3 SNK 3/SAN 1 1 :1 Li-7/OH

Duolite
ARM 9381 C 20/A 101 H/OH 0.3-1.2 60 Nuclear
1
grade
ARM 9381 D C 225/A 113 H/OH n n
ARM 9381 S C 3/A 101 H/OH n n i
ARM 9383 C 20/A 101 Li/OH n n t
ARM 9386 C 20/A 101 Li-7/OH M It t
ARM 9386S C 3/A 101 Li-7/OH M II i
ARM 9386T C 20/A 101 Li-7/OH II II t
ARM 9390 C 20/A 30B H/OH 50 i
lonac
NM-40 -S0,~, NR.(I) H/OH 1.9°, 1.0A 60 0.4-1.2 60 Ultrapure grade
11 J
" * H/OH 2.1 ,1.0 " M it it
NM 49 II M
NM-60 H/OH 1.9 , 1.4 " Nuclear applic.
H/OH 1.9 , 1.4 " It II n
NM-65 it
It II
NM-75 H/OH 1.9 , 1.4
The contributors of the compiled resin data.

Amberlite Rohm and Haas (UK) Ltd.

Lennig House, 2, Mason's Avenue, Croydon, CR9 3NB England U.K.
Japan Organo Co., Ltd.
5-16, Hongo 5-chome, Bunkyo-ku, Tokyo Japan

Bio-Rad The Dow chemical Company

and
Larkin Laboratory, 1691 N. Swede Rd. Midland Michigan
Dowex
48640 U.S.A.

Diaion Mitsubishi Chemical Industries Ltd.

5-2 Marunouchi 2-chome, Chiyoda-ku, Tokyo 100 Japan

Duolite Duolite International, SA / Diamond Shamrock

and
107,rue Edith Cavell, BP8 94400 Vitry sur Seine, France
Imac-Asmit

lonac Sybron Corporation, Chemical Division

P.O.Box 66 Birmingham, N.J. 08011 U.S.A.

245
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