Technical

Paper

Factors Affecting Counterflow

Ion Exchange Effluent Quality
Authors: W.S. Miller and M.B. Yeligar, Permutit Co.
18th Annual Liberty Bell Corrosion Course 4 - 1980

Introduction
Review of the available literature on the counterflow ion exchange operation reveals that there are
many factors that affect the performance.1 These
factors can be classified into two groups. They are:

Equipment Parameters - directly related to the

engineering design of the system, such as
maintaining a compact bed and proper
regenerant distribution.

Operational and/or Process Parameters directly related to the operational characteristics and the process expectation. These include
quality of water used for acid dilution, displacement rinse, service endpoint, regenerant
recovery, etc.

The following presentation will detail our findings as

to the effect of each of the above factors on the
quality of water produced by the counter-flow system. Much of the data was generated from tests
started in 1974 and performed in our 48 inch
diameter pilot unit, employing upflow regeneration
with a water block flow technique. We feel the data
presented here would be valid for any other method
employed in achieving the basic principle, i.e. Water
Block, Air Hold Down, Packed Bed, Split-Flow and
other engineering modifications.

Definition and General Principles

In the water treatment industry, with reference to
ion exchange applications, Counterflow is defined
as service flow in the opposite direction of re-

generation flow. In the conventional ion exchange

unit operation, the service flow is carried out in the
same direction as that of the regeneration flow and
is commonly referred to as co-flow unit operation.
During regeneration of a co-flow cation unit,
hydrogen ions displace cations such as calcium,
magnesium and sodium ions in the same direction
as that of the service flow. At the normal 5-l0 lb/ft3
H2SO4 dosages used during regeneration, a small
portion of unregenerated resin is left at the bottom
of the unit. Since the ion exchange process is
reversible, the hydrogen ions produced in the top
portion of the bed during service displace the
residual cations from the unregenerated portion of
the resin present at the outlet end of the unit. This
results in what is commonly termed as leakage. In
the demineralization process, the leakage is mostly
due to sodium because of its lower selectivity for a
strong acid exchange resin compared to magnesium and calcium ions. Consequently, it is this
sodium leakage that results in high anion conductivity (sodium hydroxide) during a 2-step co-flow
demineralization process.
In the counterflow operated unit, whether it is
upflow regeneration - downflow service or upflow
service - downflow regeneration, the resin at the
outlet end of the service flow is substantially regenerated to the hydrogen form. In other words, there
should not be any partially regenerated resin, which
can contribute to the leakage during subsequent
service cycle contrary to the co-flow operated unit.
Therefore, at comparable regenerant dosages,
leakage is significantly lower in the counterflow operated unit resulting in improved quality of demineralized water produced compared to a co-flow
operated unit.
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TP1049EN.doc Jun-09

Equipment Parameters

Table 1: Effect of Proper Distribution of Regenerant in

Counterfiow Systems

Compact Bed
In the counterflow operated ion exchange unit
operation, the effective resin bed must be maintained compacted at all times during regeneration
and preferably also during service. In our developmental work, we observed that by deliberately fluidizing a well operated cation counterflow unit during
regeneration, under the exact operating conditions,
the sodium leakages from the fluidized unit were at
least three times higher than those of well compacted beds. Further, such a disturbance in the bed
will not only result in poor quality effluent for that
particular cycle but also will continue to produce
poor quality effluent for several cycles. We do want
to point out, however, that keeping the bed compacted has some definitive vessel and process design requirements but is not as difficult a problem
as one might be led to believe.
Proper Regenerant Distribution
The regenerant introduced should come in contact
with the entire volume of resin under consideration.
The performance of the counterflow operated unit
depends on how well the resin is regenerated and
maintained at near complete conversion to the
regenerated form at the outlet end of the service. If
in an upflow regenerated unit, for example, the
regenerant is not well distributed at the very bottom
of the unit, a substantial degradation in performance will be observed immediately.
The effects of improperly distributing the regenerant are shown in Table 1.
Runs A and B were performed in the 48 inch
diameter test vessel which had a hub lateral under
drain. Runs C and D were duplicate tests with the
only exception being the addition of a distribution
media to disperse the regenerant so that it could
effectively contact the resin at the outlet end of the
service cycle. The sodium leakage data clearly indicates that for successful operation of the counterflow cation units the regenerant must be distributed
properly throughout the entire bed.

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Operational Parameters
Dilution and Rinse Water Quality Requirements
In order to succeed in producing the highest quality
water possible from a 2-step counterflow system, it
is imperative that the regenerant dilution water and
displacement rinse water be of product water quality. Thus, anion product water is used for caustic
dilution and displacement while either cation effluent or anion effluent can be used for acid dilution
and displacement. The effects of using slightly contaminated regenerant dilution water for a counterflow cation regeneration is shown in Figure 1. The
use of dilution water containing just 8 mg/l of
sodium as CaCO3 to dilute the concentrated sulfuric
acid regenerant to 2% strength results in a 3 fold
increase in the average leakage on the very next
service cycle even if deionized water is used for displacement. While admittedly the quality is still
excellent compared to co-flow performance, for
an equipment manufacturer who has guaranteed
less than 0.2 ppm (mg/L) Na as CaCO3 leakage, it is
quite unacceptable.

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was noted on the first overrun cycle, no such

capacity increase was observed for the next 3
cycles which were terminated at the pre-overrun
endpoint. In fact, capacity was actually less and
leakage much higher than before the attempt to
overrun. Even after a total of 8 cycles, pre-overrun
equilibrium had not yet been established. This work
was performed in 8 inch and 48 inch (20 cm to 123
cm) diameter units. Figure 3 shows test results from
the in 8 inch and 48 inch (20 cm to 123 cm) diameter units, indicating the number of cycles required
to re-establish equilibrium conditions after a service
cycle overrun of a counterflow regenerated cation unit.

Figure 2: Effect of Counterflow Cation Overrun

Figure 1: Effect of Sodium in Dilution Water

Effect of Overrunning the Cation Unit

Unlike co-flow regenerated cation units, which are
often rated for capacity based on an endpoint considerably above the average leakage during the run
(e.g. 10 mg/l above lowest leakage), counterflow
regenerated cation units should never be operated
to an endpoint leakage substantially above the
leakage experienced during the service cycle.
Despite some technical literature references indicating positive capacity corrections for operating to
higher sodium endpoints, we and others2 have
found by experimentation that very inconsistent
results are obtained regarding both leakage and
capacity in subsequent service cycles.
For example, Figure 2 shows the effects of overrunning a counterflow regenerated cation unit to a 5
mg/l sodium as Na endpoint following four runs
terminated on a volume throughput basis where
the endpoint leakage did not exceed 0.7 mg/l
sodium. Whereas, a substantial increase in capacity
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Figure 3: Cycles Producing Inferior Quality Water After

Overrun of Counterflow Cation

Effect of Overrunning the Anion Unit

Results similar to overrun counterflow cation units
are obtained with counterflow regenerated anion
units which are allowed to operate to a substantial
silica endpoint leakage. Figure 4 illustrates the
erratic behavior obtained when trying to run a
counterflow regenerated anion column to a definite
silica endpoint. In this case, we tried for a 200-400
ppb Si02 endpoint. Review of the data shows that
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capacity and average silica leakage vary from

cycle to cycle.
The results of substantially overrunning the counterflow anion unit is depicted in Figure 5. The
extended service cycle represents an overrun of
25% beyond the pre-established volume endpoint
at which a minimum of 4 cycles were completed. As
can be seen from the graph, it takes six additional
non-overrun cycles before silica leakages return to
pre-overrun conditions. Note that these results
were obtained with a regenerant dosage of only 2lb
NaOH/ft3. It is quite possible that less than 6 cycles
would be necessary if the regeneration dosage was
3lb or 4lb/ft3 but such higher dosages are not
required for the 2.5% silica test water used in this
particular experiment which was conducted in an 8
inch diameter column.

Figure 5: Effect of Counterflow Anion Overrun

Regenerant Recovery in Counterflow Systems

In co-flow regenerated 2-step demineralization
systems where relatively high dosages of regenerant chemicals are used to obtain acceptable leakages, reclamation of a portion of the excess
regenerants is sometimes possible. However, two
factors adversely affect regenerant recovery in
counterflow systems:
1. At the relatively low regenerant dosages
employed in counter-flow systems, there is not
much excess regenerant available to recover.
2. The elution characteristics of counterflow
regenerant systems are such that sodium and
silica are present in the latter portion of the
regenerant effluents.
Figure 4: Effect of Operating to a Substantial Silica
Leakage Endpoint

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To illustrate these points, counterflow regenerated

cation and anion elution curves are shown in
Figures 6, 7 and 8.

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Figure 8: Counterflow Anion Elution Curve 8 Diameter

Unit Type 1 Strong Base Resin

Figure 6: Counterflow Cation Elution Curve 48

Diameter Unit

The elution curves shown in Figures 6 and 7 were

obtained from a 48-inch (1.2 m) diameter strong
acid cation unit counterflow regenerated with 4lb
and 6lb/ft3 H2SO4. Quite notable is the elution of calcium and magnesium before sodium. At the 4lb
acid
regeneration level, any attempts at acid reclaim
would result in acid substantially contaminated
with both sodium and hardness ions while, at the
6lb level, substantial sodium contamination of the
reclaimable acid is still prevalent in counterflow
regenerated systems.
The elution curve shown in Figure 8 was obtained
from an 8 inch (20 cm) diameter strong base (Type I)
anion unit counterflow regenerated with 3lb/ft3
NaOH. In this case, sulfates and chlorides appear in
the effluent first, with silica peaking last, thus posing
a serious technical problem for any caustic reclaim
system to be used for counterflow regenerated
anion units.

Quality of Demineralized Water

Figure 7: Counterflow Cation Elution Curve 48
Diameter Unit

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There is no doubt of the ability of 2-step counterflow systems to produce, at reasonable regeneration dosages, excellent quality water from influents
up to 500 ppm (mg/L) TDS containing very high
sodium and low alkalinity values. The question
remains, What is excellent quality water? We
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would like to suggest that excellent quality water

from a 2-step counterflow system is water of less
than 3 micromhos conductivity. Indeed, some specifications are being written requesting 1mho guarantees from 2-step systems. However, conductivity
determinations alone do not adequately
describe water quality since such measurements do
not indicate the specific type and quantity of ions
leaking from the individual units.

from the anion unit during the service

cycle will often exceed the sodium leakage from a
non-overrun counterflow cation unit as shown in
Figure 9. Indications are that the difference in leakage between the anion and cation effluent will vary
depending on such factors as structure and age of
the anion resin and the regeneration techniques
employed (e.g. hot or cold caustic), but we do not
have sufficient data to present such items at this time.

Figure 9: System: Counterflow Cation Co-Flow Anion

Counterflow Cation and Co-Flow Anion

2-Step Systems
A very common 2-step demineralizing system
today is the one in which the cation unit is counterflow regenerated while the anion unit is
regenerated in a co-flow mode. In such a system,
reasonably low cation regenerant dosages
(3-5lb/ft3 H2SO4) can be used to produce very low
sodium leakage cation effluent which then requires
only a standard co-flow regenerated anion unit to
produce water of 3 mho or better. In such systems,
however, we have found that the sodium leakage
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Figure 10: System: Counterflow Cation Co-Flow Anion

Slight Overrun Condition 5th Cycle

Figure 10 is another set of runs made by operating

the cation unit under a very slight overrun condition. In this case after 75% of the run, the cation
effluent sodium actually exceeds the anion sodium
effluent, giving indications that the anion resin, at
times, may even remove some sodium from the
cation effluent during the latter portion of the service cycle after adding sodium during the first
60% to 70% of the service cycle. We have observed
this phenomenon many times during our counterTP1049EN

flow studies, but the differences are not great

enough to overcome possible analytical precision
errors. The overall effect is that the average sodium
leakage measured from the anion effluent almost
always exceeds the average sodium leakage
measured from the cation effluent in 2-step counterflow cation, co-flow anion systems. Anion effluent conductivity generally is 2 to 3 mho and rarely
reaches 1 mho under normal operating conditions.
Counterfiow Cation and Counterfiow Anion
2-Step Systems
A 2-step system where both the cation and anion
units are regenerated counterflow has the potential
for producing 1 mho product water, if that is an
objective. However, one must critically evaluate the
projected end use of the water to determine if
indeed 1 mho water is really better than the 2-3
mho water obtainable from a 2-step system where
only the cation unit is counterflow regenerated.
The real advantage of employing a counterflow
anion unit is the potential savings in caustic for
regeneration since Type II strong base anion resins
can be used to give comparable silica leakages to
Type I units which are co-flow regenerated. Indeed,
where 2.5-5 times stoichiometric caustic dosages
are often required to obtain 20 ppb silica or less
from Type I anion resins co-flow regenerated, similar effluent quality can be obtained at 1.5-2.5 times
stoichiometric caustic dosage from counterflow
regenerated Type II strong base resins. We emphasize that the preceding sentence is a generalized
statement and is subject to many variables, which
could alter the resin selection and stoichiometry in
the final design. Such variables include the percentage of silica in the influent to the anion unit, inlet
water temperature, neutral waste requirements,
and whether or not mixed bed polishing will be provided.
The effluent quality obtainable from counterflow
regenerated anion resins are presented in Figure
11. As shown, the two resins tested have slightly
different effluent conductivities which are mainly
the result of slightly different sodium leakages from
each resin despite both having an influent cation
sodium leakage of less than 10 ppb as Na.

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Figure 11: System: Counterflow Cation Counterflow

Anion

You may notice that the effluent conductivities are

somewhat higher than the rule of thumb 5 mho
conductivity per 1 mg/l Na as CaCO3 leakage for a
2-step demineralizing system. This has been a consistent finding in all our counterflow test work. The
only significant point that we would like to make
about this is that you cannot apply the same rule of
thumb guidelines to predicting the effluent conductivity from a low sodium leakage counterflow
regenerated 2-step demineralizing system as reliably as from the higher sodium leakage co-flow
systems. Examples of actual measured vs. rule of
thumb conductivities are summarized in Table 2 below:

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Table 2: Actual measured vs. rule of thumb

conductivities

Similar findings of effluent conductivity from 2-step

counterflow systems being higher than that predicted solely from sodium leakage can be seen by
examining data presented elsewhere for operating
2-step counterflow systems.3 This anion test work
was carried out in an 8 inch (20 cm) diameter unit
which was fed by a 16 inch (41 cm) diameter counterflow regenerated cation unit. All conductivity
measurements were by in-line probe while sodium
analysis was by atomic adsorption. The following
section discusses operating data obtained from fullscale installations.

Operating Data
Case I: Paper Industry in Gulf States
The demineralization system consists of three
trains: counterflow regenerated cation units, one
degasifier and co-flow operated anion units. The
system was designed to operate at a normal flow of
400 gpm (1.5 m3/h), maximum 600 gpm (2.3 m3/h).
The cation units are 7' (2 m) diameter and contain
270 ft3 (7.7 m3) of resin. The cation resin is regenerated with 4% sulfuric acid at 6 lbs./cu.ft. dosage.
The following is the raw water analysis:

Table 3: Raw Water Analysis

The demineralization system is operated at the

designed flow of 400 gpm (1.5 m3/h). During the
service run, the Na leakage from the cation unit
was monitored and found to be 0.17 to 0.20 ppm
(mg/L) as CaCO3. The corresponding anion effluent
conductivity was 0.7 to 1.0 mho/cm. The service
cycle is terminated on the basis of gallonage of
decationized water produced and the system has
been running satisfactorily since February of 1979.
Case II: Electronic Industry - South Eastern Region
The demineralization system consists of two trains.
The strong acid cation is operated counterflow and
a weak base anion is operated co-flow. Each train is
designed to operate at an average flow of 200 gpm
(0.8 m3/h). The system treats variable raw water
containing 500 to 700 ppm (mg/L) TDS as CaCO3
with 90% sodium and 45% alkalinity. During the
service cycle, the sodium leakage in the cation
effluent were monitored and found to be 60-70ppb
as CaCO3. The cation unit is regenerated with sulfuric acid at 5.5 lbs./cu.ft. This installation has been
running satisfactorily for the past 8 months.
Case III: Refinery in Gulf States
The demineralization system consists of four trains:
counterflow operated strong cation unit, co-flow
operated weak base, strong base and conventional
mixed bed polisher. Each train is designed to operate at a normal flow of 750 gpm (2.8 m3/h) and a
maximum flow of 1000 gpm (3.8 m3/h).

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The cation unit is 12'6" (4 m) in diameter whereas

the weak base and strong base units are 12' (3.6 m)
diameter. The cation unit contains 950 cu.ft. of resin
and is regenerated with 2% and 4% sulfuric acid at
4 lbs./cu.ft. dosage. The demineralization system
treats clarified and filtered Mississippi River water
with the analysis shown in Table 4.
Table 4: Demineralization System Treats Clarified and
Filtered Mississippi River Water Analysis

Summary
In consideration of the foregoing discussion, it is
clear that for successful operation of the counterflow ion exchange system there are certain rules
one must follow. These are: compacted bed, proper
distribution of regenerant, product water quality for
regenerant make-up and displacement rinse, termination of service cycle based on predetermined
volume throughput, and deep beds. With the counterflow system, the recovery of uncontaminated
regenerants is difficult to achieve. However, the
superior quality of water produced by utilizing fresh
regenerants at considerably lower chemical dosages than co-flow requirements will likely negate
the cost savings of reclaim regenerant systems. The
quality of demineralized water produced by the
counterflow system cannot be equated solely to the
sodium leakage for the cation unit. There are several factors that affect final effluent quality
including sodium throw from the anion unit,
which may vary with resin type, age, and regeneration procedure.

References
The demineralization system has been in operation
for 8 months and has been producing an effluent
quality of 0.6 to 0.8 mho prior to mixed bed polishing. Samples analyzed for sodium leakage during
the latter part of the service cycle from the strong
base anion unit are shown in Table 5.
Table 5: Samples Analyzed for Sodium Leakage During
the Latter Part of the Service Cycle from the
Strong Base Anion Unit

1. Abrams, I. M., Counter-Current Ion Exchange

with Fixed Beds, 10th Annual Liberty Bell Corrosion Course, 1972.
2. Jackson, E. W. and Smith, J. H., Make-up
Treatment-Counter Current Regeneration Experience in the United Kingdom, 38th International Water Conference, Pittsburgh, Pa.
3. Howard, J. R. and Morgan, V. G., Countercurrent
Demineralizer at Ohio Edison Sammis
Station, Proc. 37th International Water Conference, p. 191, 1976

The system has been operating very satisfactorily in

producing both the guaranteed effluent quality and
quantity of demineralized water.

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