Demineralizers and Ion

Exchangers
Ivelisse Ortiz-Hernandez, PhD.

Objectives
1.1 LIST the three reasons for removing impurities from water
prior to use in reactor systems.
1.2 DEFINE the following terms:
a. Ion exchange
e. Polymer
b. Demineralize
f. Mixed-bed demineralizer
c. Cation
g. Affinity
d. Anion
h. Decontamination factor
1.3 DESCRIBE the following:
a. Resin bead
b. Cation resin
c. Anion resin
1.4 DISCUSS the following factors of ion exchange:
a. Relative affinity
b. Decontamination factor
2

Objectives
1.5 WRITE the reaction for removal of NaCl and CaSO4 by a mixed-bed ion
exchanger such
as one containing HOH resin.
1.6 EXPLAIN the three basic methods used to remove dissolved gases from water.
1.7 LIST five filtration mediums used to remove suspended solids from water.
1.8 EXPLAIN how mixed-bed ion exchangers may be used to control pH.
1.9 DISCUSS resin malfunctions, including the following:
a. Channeling
b. Breakthrough
c. Exhaustion
1.10 LIST the maximum conductivity and approximate concentration of electrolyte
for each level of purity for makeup water.

LIST the three reasons for removing

impurities from water
To minimize corrosion, which is enhanced by impurities.
To minimize radiation levels in a reactor facility.
Some of the natural impurities and most of the corrosion
products become highly radioactive after exposure to the
neutron flux in the core region.

To minimize fouling of heat transfer surfaces.

Corrosion products and other impurities may deposit on core
surfaces and other heat transfer regions, which result in
decreased heat transfer capabilities by fouling surfaces or
blockage of critical flow channels.
Fouling is defined as the accumulation of unwanted material on
a surface.

STATE the purpose of ion

exchange.
It is the main process used to control
the purity and pH of the reactor
coolant.
Many plants also use this process for
feedwater chemistry control and
water pretreatment.

DEFINE ion exchange

Any process which results in the reversible
exchange of ions contained in a fluid with
those contained on a solid without a
permanent change in the solid structure.
Water is treated with an ion exchange
resin.
These resins will replace undesirable ions
with those which are more acceptable
within an aqueous process stream under a
specific set of operating conditions.
6

DESCRIBE the two general types

of demineralizer resins
Ion exchange demineralizers use microscopic resin beads
composed of an insoluble inert structural matrix and a
chemically active functional group.
The functional groups are molecules with exchangeable ions
such as H+ or OH-, that can be safely released into the system.
Cation resins exchange positively charged functional
groups, for undesirable positive ions.
With their functional groups in the hydrogen form, R H, R
represents the exchange resin and H represents the attached
hydrogen ion.

Anion resins exchange negatively charged functional groups

for any undesirable negative ion.
The hydroxyl ion, OH- (ROH) is commonly used as the functional
group in an anion resin.
7

DESCRIBE a typical ion exchange

reaction
NaCl H 2O Na Cl
When NaCl is dissolved in water it dissociates to

form sodium ions and chloride ions.

The ions released by the demineralizing resin combine
to form water :
H OH H 2O
This is a reversible reaction as indicated by the arrow.
The net reaction is as follows :
R - H R OH Na Cl R - Na R Cl H OH
The net result is that the ions in the resin are exchanged
by the ions in solution. As a result we form fresh water.
8

DESCRIBE a typical ion

exchange reaction
The cation resin has a higher affinity for Na + than for
H+ and releases the H+ in the exchange reaction.
The anion resin has a higher affinity for the Cl - than
for the OH-, and releases the OH- in the exchange
reaction.
The reactions in the previous slide shows a typical
demineralizer reaction.
In reality, some of the water will leak through the
resin allowing some untreated water to reach the
reactor system.
The greater the ionic charge the greater the
affinity of the ion for the resin.
Larger ions have a greater affinity than smaller ions.
9

DESCRIBE pH control utilizing the

ion exchange process.
pH is the measure of the relative acidity (or alkalinity) of a
solution.
If a lithium form cation resin is used with a hydroxyl form
ion, the effluent will have a high pH and will be strongly
basic, due to the exchange of lithium ions (Li +) for cation
impurities and hydroxyl ions (OH -) for anion impurities.
Cation exchange resins are classified as:
Strong acid
Intermediate acid
Weak Acid

Anion exchange resins are classified as:

Strong Base
Intermediate base

If you have sodium chloride, after the cation is exchanged we

have HCl acid remaining in solution. (strong acid)
If the cation in solution is magnesium and chloride ions are
removed the result is magnesium hydroxide which is a weak base.
10

STATE the purpose of a

demineralizer
Demineralization is the removal of
essentially all inorganic salts. In ion
exchange demineralization hydrogen
cation exchange converts dissolved salts
to their corresponding acids, and basic
anion exchange removes these acids.
Purpose
Removal of ionic substances
Reduction of conductivity
Control of pH
11

Basic Definitions
Regeneration is the treatment of the
resin bed (chemical) to replace impure
cations and anions.
The spent regenerant containing the
undesirable ions is then discarded to the
plant wastewater system.
Leakage is the very small, almost
undetectable amounts of undesirable ions
that continuously pass through the
demineralizer without being exchanged.
12

Describe the principles of

demineralizer operation
The demineralizer system consists of one
or more ion exchange resin columns,
including a strong cation unit and a strong
anion unit. The cation resins exchange
hydrogen for raw water cations as shown
below:

13

Describe the principles of

demineralizer operation

The anion resins exchange hydroxyl for raw water anions.

In the example, the acids resulting from the cation

exchange process react with the anion exchange resin. As a
result we form water and the anions are embedded into the
resin.

Other weak acids are also removed because the resin is

strongly basic.

14

Describe the principles of

demineralizer operation
This reactions are equilibrium. Not all
ions will be removed by the demineralizer.
The leakage will vary according to the
demineralizer system used, the raw water
mineral composition and the
demineralizer regenerant level (the
amount of acid and caustic used for
regeneration).
To minimize leakage the resins must be
regenerated with reverse flow.
15

16

17

18

Describe the effect of

demineralizer operation on
water conduction

Conductivity of the water decreases by removing

the salts from solution and replacing them with
protons and hydroxide ions.
Variables monitored to check the performance of
the demineralizer include:
Silica concentration and water conductivity

Demineralizers that must remove silica use strong

base anion resins, and both the silica content and
conductivity are important water quality criteria
in determining the effectiveness of resin.
Both silica content and conductivity increase at
the end of the service run.
19

DESCRIBE why silica is

monitored.

Demineralizers that must remove silica use strong base

anion resins, and both the silica content and conductivity
are important water quality criteria in determining the
effectiveness of resin.
The silica level, nearly constant during the entire service
run, increases sharply at the end; conductivity, also nearly
constant during the service run, drops briefly at the end
and then rises as shown below:

20

 During the normal service run, most of the

effluent conductivity is attributed to the
small level of sodium hydroxide produced
in the anion exchanger (a small amount of
sodium always leaks through the resin).
When the capacity of the anion resin is
exhausted, silica leakage converts the
sodium leakage to sodium silicate, a
material less conductive than NaOH.
A typical mixed bed demineralizer will
rinse down to low conductivity and silica
values after regeneration.
21

Three types of demineralizers

are commonly used:
Anion demineralizers, containing
anion resin
Cation demineralizers, containing
cation resin
Mixed bed demineralizers containing
both cation and anion resins. Used at
the end of the water treatment chain
as a water polisher.
22

STATE the two basic types of

solutions used during resin
regeneration.

The cation exchange resin is regenerated

with acid, typically hydrochloric or sulfuric
acid.
The anion exchange resin is regenerated
with an alkaline solution. Sodium
hydroxide (caustic soda) is the most
common anion regenerant.

23

Regenerating a Mixed Bed

Resin
When regenerating a mixed bed resin, regenerant
must not flow through the wrong resin. This can
destroy a resin's ion exchange capability. One
method of preventing a regenerant passing
through the wrong resin is to transfer resins from
the demineralizer to separate regeneration tanks.
Once the resin has been regenerated for a
specified time, it is ready for rinsing. In the rinsing
step, resin is flushed with pure water to remove
any residual regenerant and any insoluble
materials which may have broken loose during the
regeneration step.
In a mixed bed resin, the resins must be remixed.
24

The resins are separated in two

different regeneration tanks.

25

26

STATE the two basic types of

filter
demineralizer construction.

The deep-bed and the powdered resin filter

demineralizer.
Deep Bed

water enters at the top and then passes through the

depth of mixed resin, through strainers which shouldnt
pass the resin beads, and exits at the outlet.
As the water passes through the resin mixture, ion
exchange takes place and mechanical filtration of
suspended solids occurs.
The effective length of time that a batch of resin can be
used is called the operating cycle.

Powder Resin Filter Demineralizer

These demineralizers use a filter element pre-coated with
ground up mixed-bed resins.
27

STATE the advantages and

disadvantages of both deep-bed and
powdered resin demineralizers.

The main advantage of a deep-bed demineralizer is the

large ionic capacity which will allow time for an orderly
plant shutdown if a significant condenser tube leak occurs.

Two disadvantages of a deep-bed demineralizer concern

chemical regeneration and channeling.
The chemical regeneration of the resin requires large volumes
of regenerate solutions. Large amounts of water are needed to
rinse and transfer the waste.
Since water will take the path of least resistance through the
resin bed, the overall flow distribution is uneven. This uneven
distribution can deteriorate to the point where a channel or
channels form in the resin bed. Filtration capability decreases
over time.

Excessive pressure drop due to the build up of solids will

also be a problem (decreasing the operating cycle).

28

STATE the advantages and

disadvantages of both deep-bed and
powdered resin demineralizers.
Powdered Resin Filter Demineralizers
Advantages:
Radwaste requirements are lower. The powdered resin is
not cleaned or regenerated. Filter is just disposed of.
More efficient mechanical filtering device.

There are two major disadvantages to the

Powdered Resin Demins:
Lower ionic capacityexhausts resins rapidly and allow
leakage of ions.
Sloughing Potential for internal mechanical failure
allowing water to pass through the demineralizer
without ion exchange.

29

30

Limitations of Ion
Exchangers
1)
2)
3)
4)

Exhaustion,
Differential pressure
Temperature
Radiation Exposure

31

Resin Exhaustion
When a resin has reached the limit of its ability to
undergo exchange, some of the impurity ions will
pass through the resin without exchanging.
This will result in an increase in conductivity of
the effluent (in the case of a demineralizer).
If an ion exchanger is used instead, conductivity
will not be greatly affected.
The demineralization factor is determined.
Specific conductivity in mhos, radioactivity in
c/ml, and concentration of impurities in ppm are
common parameters checked.
32

STATE the reason for sampling both

the inlet and outlet conductivity of a
demineralizer.
To check for the conductivity and the
demineralization factor (to determine
if the demineralizer is operating
correctly).
Specific conductivity in mhos,
radioactivity in c/ml, and
concentration of impurities in ppm
are common parameters checked.
33

DEFINE the term demineralization

factor (DF) as it applies to a
demineralizer
DF is a direct measure of
demineralizer efficiency. Exhaustion
of demineralizer resins can be
predicted using a concentration
history curve which is a plot of the
DF versus time.
Initial Conductivity
DF
Final Conductivity

34

Initial Conductivity
DF
Final Conductivity
Lets assume that the initial conductivity is 100. Using the equation for DF :
Initial Conductivity
DF
Final Conductivity
100
25
100 - x
where x represents the amount of conductivity removed
from the water.
25100 x 100
x 96
96% of the impurities where removed.

35

Question from NRC testing

The ion exchange efficiency of a
condensate demineralizer is determined
by performing a calculation using the...
A. change in conductivity at the outlet of the
demineralizer over a period of time.
B. change in pH at the outlet of the demineralizer over
a period
of time.
C. demineralizer inlet and outlet conductivity.
D. demineralizer inlet and outlet pH.
36

Procedure: Use the DF to calculate the percentage of impurities removed.

100 percentage removed = percentage of the initial conductivity
remaining
Fraction of conductivity remaining times the initial conductivity will
give the final conductivity.

37

38

DESCRIBE the effect of excess

differential pressure on demineralizer
performance.

The pressure drop across the demineralizer is a function of

flow rate. Excess differential pressure results in an
increased decay in the performance of the resin.

As the demineralizer acts similar to a filter, a definite

pressure drop (and flow rate) is desired.

As corrosion products and suspended solids are

accumulated over the service run, the flow resistance and
therefore the P, increases until eventually the filter
performance is compromised.
Filter is not able to remove unwanted ions as well.
As velocity increases pressure
decreases.
The smaller the area the greater
the velocity.
39

 Monitoring the P provides useful

information on demineralizer performance.
Higher than normal P may indicate the bed
is clogged due to buildup of corrosion products
and suspended solids, or may indicate high
flow through the demineralizer.
Lower than normal P indicates the
demineralizer is operating at reduced
efficiency.

40

DESCRIBE the effect of excess

differential pressure on demineralizer
performance.
High differential pressure can be
caused by resin overheating, crud
buildup, and high flowrate through
the resin.
If excess solids are accumulated the
rate of unwanted ion removal
decreases.

41

STATE the purpose for a

demineralizer differential pressure
gauge.

To determine the pressure drop in the

demineralizer. As the amount of solids in
the filter increases area for the water to
flow will decrease and the velocity will
increase.
As velocity increases the differential
pressure will increase.

As velocity increases pressure

decreases.
The smaller the area the greater
the velocity.
42

DESCRIBE the reason for

demineralizer flow limitations.
Excessive flow can result in several adverse effects:
May reduce the rate of ion exchange due to insufficient
time for exchange to take place.
Resin beads may be forced through the lower retention
element into the demineralizer effluent.
High flow can physically bread down resin beads into
fines which will also pass through the retention element.
High flow can result in channeling of the bed, which
decreases mechanical filtration and results in very little
exchange occurring.

43

DESCRIBE the effects of

channeling in a demineralizer.
decreases mechanical filtration and
results in very little exchange
occurring.

44
http://www.lakos.com/downloads/literature/LS-brochures-English/LS-827_TechPaper_SandMediaFilterPrefiltration.pdf

DESCRIBE the reason for

demineralizer temperature
limitations.
Inert resin bead structure is stable up
to ~ 300F
Anion resin begins to decompose
slowly at ~ 140F, and rapid
decomposition begins at ~180F.
Cation resin is stable up to 250F.

45

Checking your knowledge

46

DESCRIBE the reason for

demineralizer temperature
limitations.

The alcohol formed has no exchange capability.

The amine has a lower exchange capability.
47

DESCRIBE the reason for

demineralizer temperature
limitations.

48

DESCRIBE the demineralizer

characteristics that can cause a
change in boron concentration.
The hydroxide ions of the anion resin have a very
high affinity for borate ions. When a new resin is
placed in service, the hydroxide ions of the anion
resin are readily replaced by the borate ions.
If the new bed is not boron saturated, when placed
in service, the bed will remove borate ions from the
RCS water until the resins become saturated.
As the bed becomes boron saturated, it loses the
high affinity for borate ions and the affinity for
chloride and iodide ions is greater than that for the
borate ions.

H 3 BO3 3ROH R3 BO3 3H 2O

49

 Increasing temperature can affect the

boron affinity for the resin
At lower temperature, the borate ion
bonding to the exchange site contains three
boron atoms.
At higher temperatures, the borate ion
contains only one boron atom.

At low temperature Boron is more

effectively removed than at high
temperatures.
50

STATE the reason for

bypassing
demineralizers.
In systems where it is possible to
subject the demineralizer resins to
high temperature (CVCS), the
demineralizers have automatic
features that bypass the
demineralizers on high temperatures
to protect the resins.

51

STATE the reason for using mixed

bed demineralizers to process
primary water.

Mixed bed and cation ion exchangers

are installed in the primary system to
provide purification of primary water.
1) filter out suspended crud particles,
2) remove soluble ions by exchange
3) assist in the maintenance of pH of
the primary water, reducing the rate
of corrosion.

52

DESCRIBE plant evolutions which

can cause crud bursts.

Reactor trips
Rapid heat up or cool down
Reactor coolant pump starts
Chemical shock of the primary
system

53

STATE the definition of boron

saturated as it relates to a
demineralizer
The hydroxide ions of the anion resin have a very high
affinity for borate ions. When a new resin is placed in
service, the hydroxide ions of the anion resin are readily
replaced by the borate ions.
As the bed becomes boron saturated, it loses the high
affinity for borate ions and the affinity for chloride and
iodide ions is greater than that for the borate ions.
If the new bed is not boron saturated, when placed in
service, the bed will remove borate ions from the RCS
water until the resins become saturated.

54

STATE the definition of lithium

saturated as it relates to a
demineralizer

A lithium saturated resin is used in the

same way as the boron saturated
resin.
If the resin is not saturated it will
remove lithium from the water instead
of adding it.
pH can be raised by placing a lithium
saturated mixed bed in service rather
than a chemical addition.
55

DESCRIBE the effect of

temperature on saturated ion
exchangers.

The boron affinity of a resin bed is affected by the

temperature of the coolant passed through the
bed.
At lower temperature, the borate ion bonding to the
exchange site contains three boron atoms.
At higher temperatures, the borate ion contains only one
boron atom.

At lower temperatures, the resins are more

efficient at removing boron from the coolant than
at high temperatures.
A boron saturated resin bed will actually
release boron as temperature is increased.
56

Characteristics of the Mixed

Bed Demineralizer used in the
plant
The mixed bed demineralizers contain 30 ft of mixed resin.
3

The cation resin used is 99.7% Lithium-7 based and the anion
resin is OH- based resin.
This resin is purchased in the LiOH form or lithiated in the system.
Enriched lithium is used to convert the resin to the lithium form so
the production of tritium is minimized.
The anion fraction of the mixed bed is converted to the borate
form when the bed is initially placed in service.
The bed is designed to contain equal number of anion and cation
exchange sites so it is loaded with 1/3 cation resin and 2/3 anion
resin.
Each mixed bed demineralizer is designed for up to 120-gpm
letdown flow.
Used only for one fuel cycle.
57

 Each bed is designed to provide a decontamination

factor (DF) of 10 even with 1% failed fuel. This
designed DF specification is for isotopes subject to
ionic exchange excluding Rb-86, Mo-99, Cs-134, Cs137.
The cation bed is placed in service as needed to control
these isotopes.
The cation demineralizer is loaded with 20 ft 3 of
hydrogen form cation resin. It is placed in service as
necessary to remove lithium and also to control Rb, Cs,
and Mo as previously stated. It must also control Cs137 to less than 1.0 ci/gm even with 1% failed fuel.
Maximum flow through the cation demineralizer is 60 gpm.
Used only for one cycle
58

Decontamination Factor
% Eff. = ((DF-1)/DF) * 100
When the contaminants are mostly soluble, the resin should perform
normally. When the contaminants are mostly insoluble, the resin ion
exchange capability will have little effect on the particles and the bed
will only remove them by mechanical filtration. This can cause DF
values to decrease.

59

D/P Cell
Diaphragm or bellows connected
between 2 points in a system that
can be used to measure:
Flow
Pressure
level
60

OVERTRAVEL
MOVEABLE
STOP
WALL
D/P
H
L
LINK
TO
POINTER

OVERTRAVEL
STOP

SPRING BELLOWS
LOW
PRESSURE
CONNECTION

SEALING
BELLOWS
HIGH PRESSURE
CONNECTION

EQUALIZING
VALVE
61

 Low press. Inside bellows exerts a

force on the movable wall
Hi press. Outside the bellows exerts a
force on the opposite side of the wall
Greater the press. On hi side, the
more the wall will compress the
bellows against the spring
Bellows type d/p cells have large
movements over a full range of
pressures
Stronger/weaker springs can change
the range
62

 Measure the difference between

applied pressures across the bellows
D/P cells have an equalizing valve for
removing the instrument from service
Prevents overloading measuring
element by exposure to high pressure
on one side only
Follow procedure when placing D/P
cells on service
63

OE22585, Unanticipated Boration

When Placing A Mixed Bed
Demineralizer In Service (Farley, April
7, 2006 )

At the beginning of an outage, it is necessary to

ensure low lithium concentration in the RCS as part
of the crud burst and chemical cleanup process.
The 1A demineralizer was scheduled to be replaced
a week prior to the shutdown to remove lithium.
The new resin is a lithiated resin that must be
flushed to decrease the release of lithium.
The new resin was not prepared until the day of the
shutdown and the lithium output after performing
two 1000 gallon flushes the lithium output was to
high and they did not have time for more flushes
(concentration of 1.12 ppm).

64

 They decided to place the 1B demineralizer in

service which has been used during the previous
shutdown. This will release a low concentration
of lithium and should be able to decrease its
concentration.
Problem: The demineralizer contained large amounts of
boron and needed to be rinsed. They rinsed it once with
1000 gallons and the boron concentration was found to
be 5.54ppm. The existing RCS boron content was 9ppm
so they concluded that it was ok.
When the demineralizer was put into operation it was
found that 15 minutes later the temperature started to
decrease. The operator informed the shift supervisor.
The operator was instructed to bypass the demineralizer
and it was later found that a sudden increase in the
boron concentration caused the problem.
65

 Cause:
The 1A demineralizer was scheduled to be replaced
but proper procedures and scheduling was not set
into place.
By not replacing the demineralizer with enough
time, they did not have enough time to flush the
unit and prepare it for the outage.
Due to lack of time, 1A could not be used and they
decided to use 1B which was highly borated.
They did not know the impact of using a borated
column and did not know the concentration of
solids.
Self checking was not applied.
66

About Boron
During the reactor operation the concentration of
lithium and boron is controlled to keep the pH
between 7 and 7.3.
Boron is used to control reactivity
Boron concentration is decreased as the fuel is depleted.
The boron on the surface of the fuel pellet allows the
core to have more reactivity designed into it.
Due to the proximity of the boron to the uranium, the
boron-10 is converted to boron-11 which has a very low
cross section for neutron absorption.
The RCS boron concentration must be increased to
make-up for this burn up until all of the boron-10 on the
fuel pellets is converted to boron-11.
Boron concentration is increased until one third of the
activity is used and then is decreased over time.
67

68

 Lithium is removed by intermittent

operation of the CVCS Cation
Demineralizer.

69

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