SM

Effects of Oxidants on
Ion Exchangers

Oxidizing agents present in water in small amounts

have varied effects on ion exchange materials. Cation
exchange resins are oxidized by chlorine; in addition
to limiting the operating usefulness of the cation
resins in demineralizers, this can result in serious
fouling of strongly basic anion resins, as well as contamination of demineralized water. By elimination
of chlorine with Na2SO3 or SO2, the life of cation exchange resins is extended materially, and difficulties
such as anion resin fouling and poor water quality
are reduced or eliminated. While the water supply is
a primary source of organic contaminants and
adequate pretreatment for organic removal is necessary, fouling of anion resins by organics present as
raw water contaminants is probably not the most
serious.
Replacement of anion resin to correct a poor water
quality condition should not be made without first
examining operating conditions of the demineralizer
and the condition of the cation exchange resin. Influent and effluent tests for chlorine should be made to
determine the quantity of chlorine and extent of
reduction. Samples of cation exchange beds should
be taken representing the top 6 inches, as well as
lower levels. For a mixed bed, samples of the separated cation resin should be obtained. Evaluation of
these samples will indicate if the cation resin is contributing to the difficulty and, further, if replacement
is necessary to avoid rapidly contaminating the new
anion exchange resin.
While chlorine present in water to be demineralized
is primarily responsible for cation resin degradation,
nitrates have also been suspected. At the present time,
the authors are not aware of any problem caused by
an oxidant that cannot be corrected through the
use of a reducing agent. All styrene-type cation
exchangers commonly commercially available are
affected by chlorine when operated in the hydrogen

cycle, regardless of cross linkage or method of manufacture. Warm waters are more likely to cause difficulty than cold waters. Highly mineralized waters,
and the presence of heavy metals that may act as
catalysts, are known to increase the rate of attack.
When sodium cycle cation exchangers follow hot process lime treatment operating at temperatures ranging from 210 to 290F, small amounts of oxygen can
cause a breakdown of cross linkage of styrene-type
resins. Deaeration and catalyzed Na2SO3 feed have
been very effective in promoting long resin life, with
plants on record having operated at temperatures as
high as 290F for at least 5 years with very little
change in water content and exchange capacity. Physical degradation of conventional resins usually takes
place after extended periods of use; however, the
strain-free products currently available have minimized this condition. Care should be taken to reduce
oxygen to less than 0.1 ppm to assure reasonable resin
life. A 10% cross linked resin will assure maximum
resin life while maintaining good operating salt
efficiency.

FIELD OBSERVATIONS
Within the last year, several problems occurring with
old demineralizers were studied. In one case, a
process utilizing demineralized water was affected
periodically, and the cause of difficulty was traced to
a degraded cation exchange resin that was contributing breakdown products into the effluent. This
contaminant was passing through the weakly basic
anion resin into the demineralized water.
In another case, fresh, strongly basic anion resin was
placed in two units of a large demineralizer as
part of a systematic replacement procedure
that has been carried out for several years.

Reprinted from INDUSTRIAL AND ENGINEERING CHEMISTRY, Vol. 53, page 639.

Reprint R-111

Chlorine attack can be prevented by using a reducing agent

Under this arrangement, old anion resins, which in

this case were Type II, were being operated in parallel and on the same cation effluent as new Type II
resins. The new beds were installed about a month
apart. The first to be installed became irreversibly
fouled to the extent that replacement was necessary
in a few months time.

ized water. A considerable quantity of breakdown

product must be present to be detectable by this
method.
Cation exchanger beds that have undergone considerable degradation will show a greater change in the
upper portion of the bed than in the lower
portion. This is due to contact by larger amounts of
chlorine in the upper bed levels, since some of the
chlorine is removed by the resin as it passes down
through the bed. The rate of attack by chlorine is said
to be influenced by heavy metals present in the
water. This is neither confirmed nor denied at this
writing, since the work was done with no heavy metals present in the water. The only metals present
would be those that are in the resins through initial
processing. In the case of study using field samples,
heavy metals may have been present in the resin in
varying amounts, depending on the water supplies
on which the resins were operated.

Prior to replacement, a thorough evaluation of the

situation at the point of operation revealed several
interesting and enlightening factors. The cation
exchangers had undergone severe degradation
through chlorine attack. These resins were several
years old at the time the difficulty occurred. Sodium
sulfite feed for removal of chlorine improved cation
resin operation. Although these degraded cation beds
were not replaced at the time, further degradation
was stopped and the second anion bed continued
operation without further fouling. Type II anion resins that have undergone a large change in the salt
splitting capacity (basicity) i.e., where salt splitting capacity is approximately 50% of total capacity
apparently have little affinity for the breakdown
products of the cation exchanger.

In evaluating cation exchange resins, total capacities (on dry weight and wet volume bases) and water
content are important. For several years, water content has been a guide to early indication of cation
resin degradation. This may be misleading when
evaluating certain highly cross linked products. Dry
weight and wet volume capacity measurements then
reflect more accurately the true condition of the resin.
In the case of conventional resins, as water content
increases, the wet volume capacity decreases usually
without a change in the dry weight capacity. A change
in dry weight capacity becomes extremely meaningful, since this can be caused by introduction of chlorine into the resin through attack by excess chlorine.
Dry weight capacity loss through desulfonation is
small, although this is a factor that becomes more
important when degradation is taking place at higher
temperatures in the hydrogen cycle.

ANALYTICAL TECHNIQUES
In evaluating these problems, some analytical
techniques not commonly used in routine water evaluation have been employed. Surface tension measurements taken at various points throughout the
demineralizer have been helpful. For example, in one
case, the surface tension of a raw water supply was
68 dynes but dropped to below 60 dynes when measured on the effluent from a degrading cation resin.
Surface tension increased to 70 dynes on the effluent
of a new Type II strongly basic anion exchanger. The
drop from 68 to 60 dynes indicates the presence of a
surfactant contributed by the cation exchanger, while
the increase from 60 to 70 dynes indicates the sorption of the surfactant by the anion exchanger.

Breakdown products of cation resins that cause fouling of the strongly basic anion resins, or poor water
quality in cases where the resins are fouled and can
no longer retain this contaminant, appear to be styrene sulfonic acid polymer units that behave like anionic detergents. All of the commercially and commonly available styrene resins studied are affected
by chlorine, and all such resins contained chlorine at
the conclusion of testing. The rate of attack is essentially the same on all products, as measured by
chlorine content of the resins after testing.

Another helpful test is the methyl green anionic

detergent test5. This test has been used to show
either the presence or absence of a sulfonate-type
product through the development of a colored complex with methyl green. In one case studied, the raw
water supply was positive, but the cation effluent
yielded a considerably stronger color than the raw
water. The effluent from new Type II resin was negative, equal to a blank produced from a water known
to be free of sulfonate.

EXPERIMENTAL DATA

In severe cases, it is also possible to detect breakdown products by fluorescence of the water under
ultraviolet light. Ion exchange resins are known to
fluoresce and when operated under favorable conditions fluorescence cannot be detected in demineral-

Since the problem of organic fouling of anion exchangers was recognized some 10 years ago, considerable efforts have been made to determine the
2

nature of foulants found in natural waters. In most

of the reports on organic fouling1,3,4,6, the emphasis
has been on water-borne organics, such as humic acid,
tannins, lignins, and other products from plant
decay. Undoubtedly these are the most common
foulants. Removal of organic material by pretreatment has become increasingly more important, because of the demand for higher quality water and
longer resin life. Several procedures for clean-up of
fouled resins have been suggested1,3.
The authors have suspected for some time that the
products of cation resin degradation, being organic
substances of large molecular size, could also affect
the operation of an anion resin. Other investigators4
have also suggested that the cation resin could be a
source of foulant. In a series of recent field investigations, this situation has definitely been found to exist.

New

8
7

Used

6
5
4

15
10

Effluent pH

Effluent conductance, micromhos

New

5
Used
6
8 10 12 14 16 18 20
2
4
Totalized feed, kg/cu ft, anions as CaCO3

Figure 1 pH and conductivity values from Type II

anion resins during first cycle of demineralizing test
water produced by degraded cation resin. New resin
is quickly fouled; used resin does not remove
contaminant.

In normal plant operation, it is difficult to determine

the actual amount of organic material present in the
feedwater. It is even more difficult to distinguish
between the substances resulting from breakdown of
the cation exchanger and the organics originally
present in the water. To avoid this difficulty, these
studies were conducted on filtered Chicago tap
water, which contains only trace amounts of organics.

The old Type II material, on the other hand, exhibits

a low pH immediately, indicating the failure of this
material to sorb the high molecular weight organic
acids. In successive cycles, low pH and high conductivity were experienced with both resins throughout
the run. When the undiluted test water was used,
fouling was so rapid that the low pH and high conductivity of the effluent water were experienced from
the very beginning of the run. Once the new resin
had become fouled, the quality of the water produced
by the resin in successive cycles was poorer than that
produced by a used resin which had lost 50% of its
salt splitting capacity. This is typical of fouled resins.
When the usual clean-up procedures for organic fouled
anion exchangers are employed in the field, only about
two cycles of good quality water are obtained.

A solution was prepared by recirculating 30 gallons

of acidified demineralized water through a degraded
polystyrene-type cation resin at temperatures of 110
to 112F for a period of 8 days. During this time,
approximately 1.3 pounds of free chlorine were added
per cubic foot of resin. The chlorine content in the
cation influent was kept at an average of approximately 115 ppm; the maximum chlorine content was
kept below 35 ppm. Although no metallic cations were
added to the system, the cation exchanger was
regenerated regularly during the recirculation period
to ensure complete decationization of the water in
the polyethylene tank.

When fouling of fresh anion resins by degrading

cation resins has been experienced, severe flow
sensitivity is evident. Figure 2 shows the difference
in flow sensitivity of fouled fresh resin and an old
Type II resin.

At the end of the recirculation period, the water was

pumped through the cation exchanger and discharged
into a second tank for use in operation of the anion
columns. Final analysis of the recirculated water
showed an acidity of 430 ppm as CaCO3, consisting
primarily of SO4 and Cl, plus a small amount of a
weak acid. The methyl green test indicated the
presence of 4.4 ppm of sulfonates, as sodium lauryl
sulfate. Conductivity was approximately 3600
micromhos. A portion of this water was diluted by a
factor of 5, but the original total acidity was maintained by addition of HCl and H2SO4. Figure 1 illustrates the rapid fouling of a fresh Type II anion
exchange resin in its first cycle of operation on this
diluted supply.

Figure 3 illustrates the titration curve of the effluent

collected during demineralization tests of this solution with new and used Type II resins. Although the
solution contained no sulfates or chlorides, it exhibited the high conductivity and low pH characteristic
for the anion effluent. The solution was concentrated
by a factor of 5 by slow evaporation before titration.
Approximately two thirds of the total acidity was due
to a fairly strong acid having a pK of approximately

Effluent conductance, micromhos

Table 1 Analyses of Cation Resins Used for Breakdown Studies

50

2.65

2.0

Used
material

40

Resin

Total Capacity*
Meq./ Meq./
Gram
Ml.

Water
Content,*
%

Cl,
%

S,
%

30
Flow rates, gpm/cu ft

50

2.05 1.35
2.05
2.6

1.0

1.35

Standard cross linked

Resin A

New
material

40

Before
After

30

Resin B
Before
After

6
8 10 12 14 16 18 20
2
4
Totalized feed, kg/cu ft, anions as CaCO3

5.00
4.42

1.90
1.59

53.4
57.2

0
6.3

13.7
13.2

4.75
4.31

1.78
1.41

54
57.6

0
7.2

14.5
12.5

1.74
1.49

54
53.2

0
7.3

14.7
12.4

Highly cross linked

Figure 2 Lower conductivity curve shows flow
sensitivity developed by new Type II anion resins in
three cycles on test water containing cation resin
degradation products. Upper conductivity curve
indicates used resin is not flow sensitive.

Resin C
Before
After

4.54
3.84

*Hydrogen form

Three jacketed columns were prepared for recirculation of chlorinated water through samples of standard cross linked and highly cross linked styrene-type
cation exchangers. Each resin was prepared especially
for this cycling operation by treatment with ethyl
alcohol, hot HCl, and hot water rinses. The treatment
was continued until no organic material, as determined by color throw, was leached from the resin upon
prolonged contact with ethyl alcohol; 50-ml tapped
samples of each resin were placed in the jacketed
columns.

10
9

Solution pH

8
7
6
5
4
3
1

3
7
4
8
2
5
6
Titration volume, ml N/50 NaOH

A 5-gallon container of demineralized water, acidified with 85 ppm of HCl and 85 ppm of HNO3, both as
CaCO3, was connected to each of the three columns.
Chlorine was added to each container at the start and
during the test to maintain an average of 15 ppm
chlorine, but not more than 35 ppm. The columns were
operated on the chlorinated, acidified supplies, collecting each effluent in a reservoir which, when filled,
was used for repeating the cycle. The recirculated
water was tested periodically, and when free chlorine
was depleted to zero, samples of the recirculated
liquor were collected for analytical tests.

10

Figure 3 Titration curve of cation effluent test

solution after removal of mineral acids shows strong
(pK = 3.5) and weak (pK = 6.5) organic acids

3.5. The remaining acidity was caused by a weak acid

having a pH of 6.5. It should be emphasized that the
acidity was caused entirely by organic acids, since no
mineral acid was present.

The batchwise recirculation was carried out for

approximately 19 passes. Each unit was then put on
a continuous recirculation basis. Total contact was
30 days for each column. During this time, chlorine
additions amounted to 3.92, 4.72, and 4.92 pounds
per cubic foot of resin, respectively, for standard cross
linked resins A and B, and for highly cross linked
resin C. Table 1 lists the characteristics of each of the
three resins tested before and after chlorination. The

Since all the preceding tests were conducted on

foulants obtained from a field-degraded cation resin,
it was decided to degrade three styrene-type resins
commonly available commercially by chlorination of
fresh resins and to use the water containing the degradation products for operation of the anion columns.

Table 2 Analyses of Water Recirculated through Cation Resins

Recirculation,
Days
Constituents
0

SO4*
Cl*

21

Present in Highly
Cross Linked, ppm
Resin C

0.0
75.5

0.0
75.5

0.0
75.5

SO1*
Cl*
Sulfonate as Na
lauryl sulfate

13.8
103

18.7
103

17.2
105

SO4*
Cl*
Sulfonate as Na
lauryl sulfate

31.2
276

SO *
Cl4
Sulfonate as Na
lauryl sulfate

30

Present in Standard
Cross Linked, ppm
Resin A Resin B

0.25

0.20

0.15

35
302

30
325

2.4

1.4

1.05

33.5
358

39.3
387

38.6
415

4.9

4.9

3.5

*As CaCO3

Effluent conductance, micromhos

BAC

The recirculated waters then were deionized by new

Type II anion resins. The results of the first cycle on
each resin are shown in Figure 4. Again, there is an
indication that organic acid discharge from the
degrading cation resins rapidly fouls the anion
resins. It should be noted that these accelerated
aging tests are not necessarily a true indication of
relative stability of the cation resins.

PROBABLE DEGRADATION
MECHANISM

7
6

C
B

30
20
10

Effluent pH

characteristics of the recirculated waters, analyzed

periodically during the recycling operation, are
reported in Table 2.

A
B
C
6
8 10 12 14 16 18 20
2
4
Totalized feed, kg/cu ft, anions as CaCO3

No attempt was made to study the fundamentals of

this degradation process. However, from the early
work of Schmidt and others2, the following facts can
be pointed out:

Figure 4 pH and conductivity values from new Type

II anion resins show fouling during first cycle of
demineralizing test waters produced by degraded
cation resins A and B (standard cross linkage) and C
(high cross linkage)

The polystyrene chains have a number of weak

links because of peroxide bridges, tail-to-tail additions, and chain transfers.

It is reasonable to assume that after a certain number of chain scissions, portions of the cation exchange
resin consisting of styrene sulfonic acid polymer units
become soluble and are leached from the resin. These
soluble units undoubtedly contain chlorine and weak
acid groups. These observations should be helpful in
preparing ion exchange resins of greater stability.

The CC links next to a carbon with a double bond

are weak points.
Chlorine degrades polystyrene, and the degradation products contain chlorine.
The tertiary hydrogen is the most, and quaternary
carbon the least, vulnerable site of attack (Figure
5). In the presence of oxygen, the tertiary hydrocarbon is transformed first to the hydroperoxide
and then to the ketone, resulting in chain scission.
5

ACKNOWLEDGEMENT
Cation resins
H
CH2 C CH2

CH3
CH2 C CH2

The most
vulnerable

The least
vulnerable

quaternary C

tert-H
O OH
CH2 CH CH2

The assistance of Alfred W. Oberhofer in the experimental work is acknowledged.

CH2 C CH2

+ OO

REFERENCES

CH2 C CH2

C CH2

1. Bacon, H. E., Lewis, W. J., Combustion 32, No. 1,

37 (1960).

+ CH2

+ OH

2. Boundy, R. H., Boyer, R. F., Styrene, Its Polymers,

Copolymers and Derivatives, Chap. 13, Reinhold,
New York, 1952.

Chain scission

Anion resins
CH2
HC
CH2

R1

3. Frisch, N. W., Kunin, R., Ind. Eng. Chem., 49, 1365

(1957).

R1

R1
CH2 N R1

O2

R2 N
R1

Non-basic
Products

4. Frisch, N. W., Kunin, R., J. Am. Water Works Assoc.

52, 875 (1960).

Figure 5 Probable Degradation Mechanism

5. Moore, W. A., Kobelson, R. A., Anal. Chem. 28, 161

(1956).

The degradation of anion exchange resins is shown

in the lower portion of the reaction diagram
(Figure 5). Although they have the same backbone as
the cation exchange resins, the most vulnerable point
of attack is at the nitrogen. The quaternary nitrogen
is progressively transformed to tertiary, secondary,
and primary nitrogen and finally degraded to a
nonbasic product. This has been the subject of
several reports in recent years.3,4

6. Wilson, A. L., J. Appl. Chem. 9, 352 (1959).

7. Wirth, L. F., Proc. Am. Power Conf. 16, 626 (1954).

NALCO

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ONE NALCO CENTER

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