NSE403 L5-8 Dimenerizer22F
NSE403 L5-8 Dimenerizer22F
NSE403 L5-8 Dimenerizer22F
Engineering
L5-8: Demineralizer
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DEMINERALIZATION and ION EXCHANGE
Demineralize is defined as the process
whereby impurities present in the incoming
fluid (water) are removed by exchanging
impure ions with H+ and OH- ions resulting
in the formation of pure water.
Ion exchange is a process used
extensively in nuclear facilities to control
the purity and pH of water by removing
undesirable ions and replacing them with
acceptable ones.
Mixed-bed demineralizer is a vessel containing resin that is a
uniform mixture of cation and anion resins in a specific volume
ratio depending on their specific gravities. Normally the ratio is 2
parts cation resin to 3 parts anion resin.
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Demineralizers or Ion exchangers
Demineralizers or ion exchangers are equipments which can hold
ion exchange resins.
Demineralization or ion exchange refers to exchange of ions
between a solid substance (called a resin) and an aqueous solution
(makeup water).
Ion exchange resins consist of very small beads, termed resin
beads, having an average diameter of 0.010 millimeters or less.
After a certain period of time, ion exchange resins are exhausted
and they have to be regenerated.
During regeneration, an acid solution (for cation exchange units)
and a caustic solution (for anion exchange units) is used, properly
diluted with water, which is typically distributed above the resins.
Regeneration is usually a multi-step process, also involving
backwashing and rinsing stages in order to remove any entrained
particles.
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ION EXCHANGE and DEMINERALIZATION
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Purpose of a demineralizer
Demineralizers (ion-exchangers) used in nuclear power plants to:
Remove ionic impurities
Filter/remove small particles
Help control pH of water
Hold ion exchange resins that remove dissolved impurities from
fluids
Dissolved impurities generate corrosion problems and foul heat
transfer surfaces
Ion exchange aids in pH control
Classified into two groups:
Single-bed ion exchangers
Mixed-bed ion exchangers
Generally, power plants use mixed-bed ion exchangers or
demineralizers for control of ionic impurities.
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Demineralizers provide filtration and ion exchange for water
going to steam generators
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Principles of demineralizer operation
Ion exchange is an exchange of ions between two electrolytes or
between an electrolyte solution and a complex solution
Ionic impurities are removed and replaced with acceptable
substitutes
Ion Exchange
Small resin beads complete ion exchange
Resin beads are porous with many exchange sites for ion
exchange
Generally will contain exchangeable ions that are harmless such
as H+ or OH-
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Layout of demineralizers or ion exchangers
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In order of decreasing strength, the relative affinities between a cation
resin and various cations are:
Similarly, the relative affinities of the anion resin for various anions are:
The higher the relative affinity the more effective the ion exchanger. This
effectiveness is expressed by the Decontamination Factor.
The reaction for removal of NaCl and CaSO4 by a mixed-bed ion exchanger
such as one containing HOH resin is as follows:
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Single bed demineralizers
A single bed demineralizer (Fig. 2) contains either cation resin
elements (a cation is an ion with a positive charge: common cations
include Ca++, Mg++, Fe++, and H+) or anion resin elements (an
anion is an ion with a negative charge: common anions include Cl-,
SO-, and OH-).
Consequently, a cation resin is one that exchanges positive ions,
whereas an anion resin is one that exchanges negative ions.
In most cases, there are two, single bed ion exchangers installed
in series; the first one being a cation bed and the second one an
anion bed.
Impurities in plant water are replaced with hydrogen ions in the
cation bed and hydroxyl ions in the anion bed. The hydrogen ions
and the hydroxyl ions then combine to form pure water.
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Figure 2: Single-Bed Demineralizer
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Resin bed becomes exhausted and not able to function at peak performance
-Indicated by increased effluent conductivity
-Resin exchange sites will run out of enough mobile ions
-Impurities in outlet indicate resin exhaustion
Restore resin bed ability to exchange ions
Regeneration strips away impurities
Chemicals used to reverse chemical process refreshing the resin bed for
further use
Single-Bed Regeneration
Three-Step Process
Backwash – Water is pumped into the bottom of the ion exchanger and up
through the resin, fluffs resin, and washes out entrained particles
Regeneration – Uses an acid solution for cation units and caustic solution for
anion units
Rinsing – Removes any excess regenerating solution
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Mixed-Bed Regeneration
More complicated than single- bed regeneration
Regenerated in place
Normal operation
-Water enters through a distribution header at the top of vessel
-Water exits through bottom of vessel
Regeneration needed when effluent water conductivity
increases
Mixed-Bed Regeneration
Normal operation
Regeneration Sequence
Backwash
Regeneration
Slow rinse
Vent and partial drain
Final rinse
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Mixed-Bed Regeneration
The mixed-bed demineralizer shown in Figure 3 is designed to
be regenerated in place, but the process is more complicated than
the regeneration of a single-bed ion exchanger. The steps in the
regeneration are shown in Figure 3.
Figure 3a shows the mixed-bed ion exchanger in the operating,
or on-line mode. Water enters through a distribution header at
the top and exits through the line at the bottom of the vessel.
Regeneration causes the effluent water to increase in electrical
conductivity.
The first regeneration step is backwash, as shown in Figure 3b.
As in a single-bed unit, backwash water enters the vessel at the
bottom and exits through the top to a drain. In addition to
washing out entrained particles, the backwash water in a mixed-
bed unit must also separate the resins into cation and anion beds.
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Figure 3
Regeneration of a
Mixed-Bed
Demineralizer
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The anion resin has a lower specific gravity than the cation resin;
therefore, as the water flows through the bed, the lighter anion resin
beads float upward to the top.
Thus, the mixed-bed becomes a split bed. The separation line between
the anion bed at the top and the cation bed at the bottom is called the
resin interface.
Some resins can be separated only when they are in the depleted
state; other resins separate in either the depleted form or the
regenerated form.
The actual regeneration step is shown in Figure 3c. Dilution water is
mixed with caustic solution and introduced at the top of the vessel, just
above the anion bed. At the same time, dilution water is mixed with acid
and introduced at the bottom of the vessel, below the cation bed. The
flow rate of the caustic solution down to the resin interface is the same
as the flow rate of the acid solution up to the resin interface. Both
solutions are removed at the interface and dumped to a drain.
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During the regeneration step, it is important to maintain the cation
and anion resins at their proper volume.
If this is not done, the resin interface will not occur at the proper
place in the vessel, and some resin will be exposed to the wrong
regenerating solution.
It is also important to realize that if the ion exchanger has been
involved with radioactive materials, both the backwash and the
regenerating solutions may be highly radioactive and must be
treated as liquid radioactive waste.
The next step is the slow rinse step, shown in Figure 3d, in which
the flow of dilution water is continued, but the caustic and acid
supplies are cut off. During this two-direction rinse, the last of the
regenerating solutions are flushed out of the two beds and into the
interface drain. Rinsing from two directions at equal flow rates keeps
the caustic solution from flowing down into the cation resin and
depleting it.
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In the vent and partial drain step, illustrated in Figure 3e, the
drain valve is opened, and some of the water is drained out of the
vessel so that there will be space for the air that is needed to re-
mix the resins.
In the air mix step, (Figure 3f) air is usually supplied by a blower,
which forces air in through the line entering the bottom of the ion
exchanger. The air mixes the resin beads and then leaves through
the vent in the top of the vessel. When the resin is mixed, it is
dropped into position by slowly draining the water out of the
interface drain while the air mix continues.
In the final rinse step, shown in Figure 3g, the air is turned off
and the vessel is refilled with water that is pumped in through the
top. The resin is rinsed by running water through the vessel from
top to bottom and out the drain, until a low conductivity reading
indicates that the ion exchanger is ready to return to service.
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Characteristics of the Mixed Bed Demineralizer used in the plant
The mixed bed demineralizers contain 30 ft3 of mixed resin.
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.
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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, Cs-137.
The cation bed is placed in service as needed to control these
isotopes.
The cation demineralizer is loaded with 20 ft3 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 Cs-137 to less than 1.0 mi/gm even with 1% failed
fuel.
Maximum flow through the cation demineralizer is 60 gpm.
Used only for one cycle
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External Regeneration
Some mixed-bed demineralizers are designed to be
regenerated externally, with the resins being removed from the
vessel, regenerated, and then replaced.
With this type of demineralizer, the first step is to sluice the
mixed bed with water (sometimes assisted by air pressure) to a
cation tank in a regeneration facility.
The resins are backwashed in this tank to remove suspended
solids and to separate the resins.
The anion resins are then sluiced to an anion tank.
The two batches of separated resins are regenerated by the
same techniques used for single-bed ion exchangers.
They are then sluiced into a holding tank where air is used to
remix them.
The mixed, regenerated, resins are then sluiced back to the
demineralizer.
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External regeneration is typically used for groups of condensate
demineralizers. Having one central regeneration facility reduces the
complexity and cost of installing several demineralizers.
External regeneration also allows keeping a spare bed of resins in a
holding tank.
Then, when a demineralizer needs to be regenerated, it is out of
service only for the time required to sluice out the depleted bed and
sluice a fresh bed in from the holding tank.
A central regeneration facility may also include an ultrasonic cleaner
that can remove the tightly adherent coating of dirt or iron oxide that
often forms on resin beads.
This ultrasonic cleaning reduces the need for chemical regeneration.
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Changes in Demineralizer Operation
Differential pressure (D/P) across the demineralizer is a valuable
tool in assessing demineralizer operation
Demineralizer filters suspend solids that cannot pass through
the resin and retention element
Differential Pressure
More materials removed results in higher resistance to flow or D/P
Low D/P could indicate demineralizer operating at a reduced capacity
High D/P could indicate clogging or the flow rate is too high
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Problem
A condensate demineralizer differential pressure (D/P) gauge
indicates 4.0 psid at 50 percent flow rate. Over the next two days,
plant power changes have caused condensate flow rate to vary
between 25 percent and 100 percent. Which one of the following
combinations of condensate flow rate and demineralizer D/P,
observed during the power changes, indicates an increase in the
accumulation of corrosion products in the demineralizer?
A: 100 percent flow, 15.0 psid (15 psi differential).
B. 75 percent flow, 9.0 psid
C. 60 percent flow, 5.0 psid
D. 25 percent flow, 2.0 psid
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SOLUTION
To solve this problem, we must apply the pump law that flow rate
is proportional to the square root of the D/P. Therefore, you have
to plug in the expected D/Ps for each flow rate and find out which
one exceeds the expected D/P.
At 100 percent flow, the D/P should be:(100/50)^2×4=16 psid
At 75 percent flow, the D/P should be:(75/50)^2×4=11.25 psid
At 60 percent flow, the D/P should be:(60/50)^2×4=5.76 psid
At 25 percent flow, the D/P should be:(25/50)^2×4=1 psid
Only the 25 percent flow rate has a higher than the expected D/P,
and therefore indicates that there is accumulation of corrosion
products. Correct answer is D.
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Decontamination Factor
Decontamination (also called demineralization) factor is used for determining
when resin bed is exhausted
Decontamination factor (DF) is inlet conductivity divided by outlet
conductivity
To determine percentage of impurities removed, divide amount of impurities
(conductivity) removed by ion exchanger by amount of impurities
(conductivity) entering the ion exchanger
Decontamination Efficiency
% 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.
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Home work
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Demonstration – Decontamination Factor
A demineralizer has been in service for 60 days. When first placed in
service, the decontamination factor was 212. Currently, the inlet and
outlet conductivities are:
35 μmho/cm entering
0.3 μmho/cm exiting
What is the decontamination factor now, what percent impurities are
removed, and would you recommend regeneration?
Solution
35μmho/0.3μmho = 117
Decontamination Factor = 117
(35-0.3) μmho removed)/(35 μmho in) =0.99 x 100 percent
impurities removed = 99 percent
The demineralizer is removing 99 percent of the inlet contaminants. Although
the decontamination factor has decreased to about 55 percent of the original
value, it is still effective at removing unwanted ions. The demineralizer should
remain in service. Normally, demineralizers are replaced or regenerated when the
DF is 25 or less.
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CHEMICAL AND VOLUME CONTROL SYSTEM (CVCS)
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Chemical and Volume Control System (CVCS)
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Chemical and Control Volume System
The reactor coolant being let down to the system is cooled by the
Regenerative Heat Exchanger and then depressurized by 3 orifices.
The reactor coolant is further cooled by Component Cooling
Water (CCW) in the Letdown Heat Exchanger before it is directed to
the demineralizers.
The water passes through two mixed bed demineralizers and a
cation demineralizer which is used in an intermittent basis when
needed to control the amount of lithium in the system.
Rb-86, Mo-99, Cs-134, Cs-137 isotopes are also removed by the
cation demineralizer.Water leaving the demineralizers is passed
through a filter and is then into the volume control tank.
The CVCS system is constructed of stainless steel.
During normal operations, two orifices are in service supplying
105-gpm letdown flow to the CVCS system.
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Reactor Make up
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Corrosion Control
Boric acid is introduced to control reactivity by absorbing neutrons. Boron and
Lithium are carefully coordinated to maintain an at temperature pH (pHt)
between 7.0 and 7.3.
By adding boric acid more fuel can be loaded which allows for longer operating
cycles.
Problem
Boron in the presence of a neutron flux leads to the formation of tritium. Boron
concentration decreases as the activity of the fuel rod decreases. Boric acid is a
weak acid only slightly ionized and exists in different forms based mostly on
system temperature as illustrated below:
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Water Purification
Two mixed bed demineralizers
Cation demineralizer contains 20ft3 of hydrogen based resin.
The mixed bed demineralizers contain 30 ft3 of mixed resin.
The cation resin used is 99.7% Lithium-7 based and the anion resin is OH- based
resin.
The anion fraction of the mixed bed in converted to the borate form when the
bed is initially placed in service.
Each mixed bed demineralizer is designed for up to 120-gpm letdown flow.
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In general, increasing flow rate through a demineralizer will
decrease the time required for an ion to diffuse across the fluid film
increasing the efficiency of the resin.
-If the contact area is increased (while maintaining optimum
velocity) a better contact is obtained which results in improved
separation. (Flowrate = area * velocity)
Higher system temperatures will result in a higher diffusion rate
thereby increasing resin performance.
-To high of a temperature (at or above 140ºF) will decompose the
resin
Higher contaminant concentrations will improve demineralizer
efficiency.
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.
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Demineralizer Operation
When placing a newly loaded mixed bed demineralizer in service
for the first time, it must be flushed to the RHUT (Recycling Hold-
up Tank) and the effluent of the bed sampled for boron, chloride,
fluoride and sulfate prior to placing it in service.
For boron the concentration at inlet and outlet must be
constant.
Chloride, fluoride and sulfate must stay below the specified
values.
If the values are not acceptable the flush must be repeated.
Using a new or previously used demineralizer will affect the
boron concentration.
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Sources of Radioactive Activity
Tritium Sources
Li-6 is minimized by using Li-7 to control the pH. (99.9 for chemical
addition or 99.7% for the resin.
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Demineralizer Activity
Ion exchange is a process used in a variety of nuclear facilities to reduce the
radioactive ion content of water by removing radioactive ions and replacing
them with nonradioactive ions. The device in which the ion exchange occurs is
commonly called a demineralizer.
The activity that accumulates within a demineralizer bed is
Equation B.11 is also to be applied individually for each isotope trapped in the
demineralizer bed. In Equation B.11, C=influent activity concentration of an
isotope entering the demineralizer (Bq/m3), F=flow rate of fluid through the
demineralizer or filter (m3/s), e= isotope specific removal efficiency of the
demineralizer bed/filter, l is the physical decay constant of the trapped material,
T is the time the demineralizer in online (valved in) and removing radioactivity
from the influent stream, and t is the time after the demineralizer is no longer in
service (valved out).
For the demineralizer application, the total removal rate is just the physical
decay constant. Equation B.11 also applies to filters. The saturation activity for
both filters and demineralizers is CFe/l .
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Problem:
A demineraizer in the primary system of a power reactor removes
100% of the Mn-54 from the coolant that flows through it a rate of
600 liters per minute. Mn-54 enters the demineralizer at a constant
concentration of 3.8x10-4 mCi/cm3. The isotope has a half-life of 313
days and emits a single gamma-ray of energy 835 keV per
disintegration.
i. If a fresh demineralizer is placed on line, what will be the total
activity of Mn-54 on it when removed after 180 days?
ii. If the demineralizer is allowed to stand in isolation for 4 weeks
after removal, estimate the radiation exposure rate from the Mn-54 at
a distance of 3 meters. Assume a point source and no shielding
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Solution: Hints
i. Activity at constant rate, K=(600 L/min)x (1000 cm3/L)x(3.8x10-4
mCi/cm3)=0.328 Ci/d
l=ln2/(313 d)=0.002/d
The rate of change of the activity on the dimeneralizer is, therefore
given by
dA/dt=K-lA
A=K/l (1-e-lt)
A=0, when t=0. For t=180 d
A=48.8 Ci
ii. With the deminerarizer removed, radioactive decay over the next
4 weeks (~28 days) reduces the activity to
A’=A e-lt
= 45.8 Ci
For a point source of C Ci, the radiation exposure at a distance r meters is
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A system called the Chemical and Volume Control System
(CVCS) or the Makeup and Purification System controls the water
level in the pressurizer. For simplicity, the term CVCS will be used
here to designate both types.
Water is injected into the primary coolant system to increase the
pressurizer water level to the set point. A let down flow system
decreases the water level.
As the name suggests, the CVCS controls more than pressurizer
level.
Two other functions of the CVCS are water purification using
filters and demineralizers and controlling soluble poison
concentration by adding or removing boric acid.
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CVCS System Letdown System - removes water from the RCS
for filtering, chemical adjustment, and radiation monitoring
Charging System - returns water to the Reactor Coolant
System (RCS) via the charging pumps from the Volume Control
tank (VCT)
Functions of CVCS
Regulate RCS chemistry for reactivity and corrosion control
Maintain pressurizer water level
Maintain seal water injection to Reactor Coolant Pump (RCP)
seals Provides a means to fill, drain, and pressure test the RCS
Provide injection to the RCS during Emergency Core Cooling
System (ECCS) initiation
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DISSOLVED GASSES, SUSPENDED SOLIDS, and pH CONTROL
Because of the presence of impurities, raw water sources
undergo treatment prior to use as makeup water in reactor facility
systems. These systems normally utilize several distinct processes
that remove solids, ionic impurities, and gases.
Pretreatment of makeup water is necessary to reduce corrosion,
minimize radiation, and limit fouling of heat transfer surfaces.
If the hydrogen and hydroxyl forms of resin are used, the result is
pure, neutral water. Other forms may be used to remove unwanted
impurities from solution and substitute another substance, such as
a base, to help control pH.
Resins also filter solids suspended in a solution, but the efficiency
for this is usually less than the efficiency for removal by ion
exchange.
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Dissolved gases are removed from reactor facility systems to limit
corrosion by any one of the following methods or combinations of
methods:
•Aeration - The spraying of the water to physically release the entrained
gasses, then venting the gas.
•Deaeration - The heating of the water to a slow boil, then vents the gas
usually to a condenser so the moisture is not lost.
•Addition of scavengers - Examples are hydrogen, hydrazine, and
morpholine, the scavenger combines with the gas and removes it
chemically
Suspended solids are removed by the use of mechanical filters. The two
basic categories of mechanical filters are gravity flow and pressure flow
filters. The pressure flow filters are more likely to be used because there
are better control capabilities.
Numerous materials are used as filter media and include sand, activated
charcoal, anthracite, diatomaceous earth, and to some extent the resin in
an ion exchanger
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Suspended solids are removed by the use of mechanical filters.
The two basic categories of mechanical filters are gravity flow
and pressure flow filters.
The pressure flow filters are more likely to be used because
there are better control capabilities.
Numerous materials are used as filter media and include:
Sand
activated charcoal
Anthracite
diatomaceous earth
and to some extent the resin in an ion exchanger
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Question and discussion
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Draw the diagram for demineralization process and write suitable
reactions involved in the process. What are the advantages and
disadvantages of the method.
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