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DEMINERALIZATION OF

WATER
FOR HIGH PRESSURE BOILERS

Dilip Kumar
NTPC Ltd.

DEMINERALIZATION
TECHNIQUES
DISTILATION

ELECTRODIALYSIS
REVERSE OSMOSIS
ION EXCHANGE

DISTILLATION
Distillation is one of the oldest
methods of water treatment and is
still in use today though not
commonly as a home treatment
method. It can effectively remove
many contaminants from drinking
water,
including
bacteria,
inorganic and many organic
compounds.

ELECTRODIALYSIS
Electro dialysis is a membrane process in which ions are
transported through ion permeable membranes from one
solution to another under the influence of an electrical
potential gradient.

REVERSE OSMOSIS
Osmosis occurs when two solutions of different
concentrations are separated from one another by a
membrane which is permeable to solvent but
impermeable to solute. Solvents flows from dilute to the
concentrated solution, until, at equilibrium, the chemical
potential of the solvent is equal on both sides of the
membrane.

REVERSE OSMOSIS
CONTI...

A pressure at which just prevent the solvent flow is


called Osmotic pressure. If the pressure greater than the
osmotic pressure is applied to the concentrated solution,
the solvent can be forced through the membrane leaving
the dissolved substances behind. This method of
purifying water is
termed reverse osmosis.

REVERSE OSMOSIS
CONTI...

REVERSE OSMOSIS
A typical reverse osmosis
plant consists of
CONTI...
the following items:

Pre-treatment including acid dosing for pH


control and dosing of scale control additives.
High pressure pumps which may be high speed
centrifugal, multi-stage centrifugal or reciprocating
type.
The reverse osmosis membranes. The
membranes or permeators are usually connected
in series/ parallel stages is used as the feed to the
latter stages. This increases the plant conversion.
A pressure regulating valve, this is used to
maintain the necessary reject flow and control the
inlet membrane pressure.
The post treatment system, this is usually
includes a degasser to remove carbon dioxide
formed when acid is used for pH control.

A TYPICAL REVERSE OSMOSIS


PLANT
RAW
WATER

LOW
PRESSURE
PUMPS

PARTICULAT
E FILTERS

HIGH
PRESSURE
PUMPS

RO
plant

Stage-1
7 modules
PRODUCT
WATER

Stage-2
4 modules

Stage-3
2 modules
STORAGE

PRODUCT
WATER
PUMPS

DEGASSING
TOWER

CONCETRATE
TO WASTE

A TYPICAL REVERSE OSMOSIS


PLANT
RAW
WATER

LOW
PRESSURE
PUMPS

PARTICULAT
E FILTERS

HIGH
PRESSURE
PUMPS

RO
plant

Stage-1
7 modules
PRODUCT
WATER

Stage-2
4 modules

Stage-3
2 modules
STORAGE

PRODUCT
WATER
PUMPS

DEGASSING
TOWER

CONCETRATE
TO WASTE

A TYPICAL REVERSE OSMOSIS


PLANT
RAW
WATER

LOW
PRESSURE
PUMPS

PARTICULAT
E FILTERS

HIGH
PRESSURE
PUMPS

RO
plant

Stage-1
7 modules
PRODUCT
WATER

Stage-2
4 modules

Stage-3
2 modules
STORAGE

PRODUCT
WATER
PUMPS

DEGASSING
TOWER

CONCETRATE
TO WASTE

REVERSE OSMOSIS
CONTI...
Water analyses from the reverse osmosis
plant at Hartlepool power station
Analyses

Pretreated
water

Product
water

Reject
water

Conductivit
y S/cm

1560

145

6050

Total
hardness

560

30

2700

100

15

600

455

15

2300

180

23

800

mg/kg
CaCO3

Sodium
mg/kg Na

Sulphate
mg/kg SO4

Chloride

DEMINERALIZATION BY
ION- EXCHANGE PROCESS

Ion exchange is the reversible interchange of


ions between a solid (ion exchange material)
and a liquid in which there is no permanent
change in the structure of the solid. Ion
exchange is used in water treatment and also
provides a method of separation for many
processes involving other liquids. It has special
utility in chemical synthesis, medical research,
food processing, mining, agriculture, and a
variety of other areas. The utility of ion
exchange rests with the ability to use and reuse
the ion exchange material.

DEMINERALISATION
SREAM

ACTIVATED CARBON
FILTER (ACF)

Sl.N
o
3.2.1

Characteristics

Unit

NTPC Specification

Total surface, Min

m2/g

850

3.2.2

Particle density, wetted in


water

g/cc

1.3 1.4

mm

0.6 0.8

mm

1.5 2.0

mg/g

1000

% by mass

95

mm

7.0

3.2.3
3.2.4

Mean particle diameter


(i)

In case of needle /
cylindrical
type

3.2.6

(ii)

In case of granular type

3.2.7

Adsorption capacity in terms


of iodine number, Min

3.2.5

3.2.8

Abrasion Number (by ASTM


method), Min.
Ash content, Max

mesh
Kg/m3

2.

2.4

4 16
400

Mean particle length


(iii)

In case of needle /
cylindrical type

(iv)

In case of granular type

Bulk Density, min

ACTIVATED
CARBON

ACTIVATED CARBON
FILTER (ACF)
Acts on principle of adsorption
which is a surface active
phenomenon .
It removes residual turbidity (<2
NTU) of water to its 1/10 level.
It removes organic molecules to
control color and odor.
It removes free residual chlorine
present in filtered water(0.5 ppm
Nil)

ACTIVATED
CARBON

PREPARATION OF RESINS

TYPES OF
RESIN

(R)

R-SO3H
Sulphonic Acid
(SAC
)

R-CH2CHCH3
|
COOH

Carboxylic Acid
(WAC
)

CH3
|
R-CH2-NH+
|
CH3

SAC: Strong Acid


Cation
WAC: Weak Acid
Cation
SBA: Strong Base
Anion
WBA: Weak Base
Anion

OH

Tertiary Ammonium

(WB
A)

CH3
|
R-CH2-N-CH3 OH
|
CH3
Quarternary Ammonium

(SBA
)

VESSEL
DESIGN

WEAK ACID CATION


(WAC)
R-CH2CHCH3
|
COOH

Weak acid cation exchange


resins derive their exchange
activity from a carboxylic group
(-COOH). When operated in the
hydrogen form, WAC resins
remove
cations
that
are
associated
with
alkalinity,
producing
carbonic
acid
as
shown:

WEAK ACID CATION (WAC)


CONT.

These reactions are also reversible and permit the return


of the exhausted WAC resin to the regenerated form. WAC
resins are not able to remove all of the cations in most
water supplies. Their primary asset is their high
regeneration efficiency in comparison with SAC resins. This
high efficiency reduces the amount of acid required to
regenerate the resin, thereby reducing the waste acid and
minimizing disposal problems.

WEAK ACID CATION (WAC)


CONT.

Weak acid cation resins are used primarily for softening


and dealkalization of high-hardness, high-alkalinity waters,
frequently in conjunction with SAC sodium cycle polishing
systems. In full demineralization systems, the use of WAC
and SAC resins in combination provides the economy of
the more efficient WAC resin along with the full exchange
capabilities of the SAC resin.

CATION EXCHANGE
MECHANISM

Ca
Mg
Na

Ca
Mg
Na

Ca
Mg
Na
Na leakage

Un-exchanged
Resin

START OF RUN

DURING THE RUN

END OF RUN

STRONG ACID CATION (SAC)


SAC resins can neutralize strong
bases and convert neutral salts
into their corresponding acids.
SAC resins derive their
functionality from sulfonic acid
groups (HSO3). When used in
demineralization, SAC resins
remove nearly all raw water
cations, replacing them with
hydrogen ions, as shown below:

Chemical structural formula of


sulfonic strong acid cation
resin (Amberlite IR-120)
(XL): cross link
(PC): polymer
chain
(ES): exchange
site
(EI):
exchangeable ion

STRONG ACID CATION (SAC)


CONTI...

Strong acid cation exchangers function


well at all pH ranges. These resins have
found a wide range of applications. For
example, they are used in the sodium
cycle (sodium as the mobile ion) for
softening and in the hydrogen cycle for
decationization.

STRONG ACID CATION (SAC)


CONTI...

A measure of the total concentration of the strong


acids in the cation effluent is the free mineral acidity
(FMA).In a typical service run, the FMA content is
stable most of the time. If cation exchange were 100%
efficient, the FMA from the exchanger would be equal
to the theoretical mineral acidity (TMA) of the water.
The FMA is usually slightly lower than the TMA because
a small amount of sodium leaks through the cation
exchanger. The amount of sodium leakage depends on
the regenerant level, the flow rate, and the proportion
of sodium to the other cations in the raw water. In
general, sodium leakage increases as the ratio of
sodium to total cations increases.
Typical effluent profile for strong
acid cation exchanger.

STRONG ACID CATION (SAC)


CONTI...

The exchange reaction is reversible. When its capacity is


exhausted, the resin can be regenerated with an excess
of mineral acid.

Thoroughfare Counter-flow
Regeneration

EXHAUSTED CATION RESIN


REGENERATION
Thoroughfare Counter-flow
Regeneration
The regeneration efficiency of WAC is very high compared to the
strong acid resin. Therefore it is possible to utilize the regenerant acid
strength from the strong acid unit to regenerate the weak acid unit.

DEGASIFIER DESIGN
In water demineralization, a degasifier, or degasser, is
often used to remove dissolved carbon dioxide after
cation exchange. The most common degassers are of
the so-called forced draft or atmospheric type.

THEORY OF
DEGASIFICATION

The solubility of CO2 in pure water is high: about


1.5 g/L or more than 30 meq/L at 25C and
atmospheric pressure. When you stir the water and
divide it into small droplets in an atmospheric
degasifier and blow air through the "rain", the gas
tends to move into the air because the partial pressure
of CO2 in air is much below the equilibrium pressure.
The residual CO2 after an atmospheric degasifier is
0.20 to 0.25 meq/L (typically 10 mg/L as CO2.
Therefore such degassers are used when the
bicarbonate concentration plus free carbon dioxide in
the feed water to separate column demineralization
systems is at least 0.6 to 0.8 meq/L.

DEGASIFIER DESIGN
After cation
exchange, the bicarbonate
and carbonate (if any) ions
are converted to carbonic
acid, or carbon dioxide. CO2
is soluble in water, but it
tends to escape into the air,
much as it does in a glass of
Cold drink when you stir it.
Using a degasser to remove
CO2 reduces the ionic load
on the strong base anion
resin, and the consumption
of caustic soda is thus

DEGASIFIER
To be effective, the degasifier must
be placed after the cation exchange
column. Before cation exchange, the
water is containing bicarbonate. After it,
the cations in water (Ca++, Mg++ and Na+
principally) are converted to H+ ions,
which
combine
with
the
HCO3
bicarbonate anions to produce carbonic
acid.

WEAK BASE ANION EXCHANGER


Weak base resin functionality originates in
primary (R-NH2), secondary (R-NHR'), or tertiary (RNR'2) amine groups. WBA resins readily re-move
sulfuric, nitric, and hydrochloric acids, as represented
by the following reaction:

STRONG BASE ANION


EXCHANGER
SBA resins derive their functionality from
quaternary ammonium functional groups. When
in the hydroxide form, SBA resins remove all
commonly encountered anions as shown below:

As with the cation resins, these reactions are


reversible, allowing for the regeneration of
the resin with a strong alkali, such as caustic
soda, to return the resin to the hydroxide
form.

STRONG BASE ANION


EXCHANGER
Demineralization using strong anion resins
removes silica as well as other dissolved solids.
Effluent silica and conductivity are important
parameters to monitor during a demineralizer
service run.

Conductivity/silica profile for strong base anion


exchanger

STRONG BASE ANION


EXCHANGER

When silica breakthrough occurs at the end of a service


run, the treated water silica level increases sharply. Often, the
conductivity of the water decreases momentarily, then rises
rapidly. This temporary drop in conductivity is easily explained.
During the normal service run, most of the effluent conductivity
is attributed to the small level of sodium hydroxide produced in
the anion exchanger. When silica breakthrough occurs, the
hydroxide is no longer available, and the sodium from the
cation exchanger is converted to sodium silicate, which is much
less conductive than sodium hydroxide. As anion resin
exhaustion progresses, the more conductive mineral ions break

EXHAUSTED ANION RESIN


REGENERATION
Strong base anion exchangers are
regenerated with a 5% sodium hydroxide
solution. As with cation regeneration, the
relatively high concentration of hydroxide drives
the regeneration reaction. To improve the
removal of silica from the resin bed, the
regenerant caustic is usually heated to 120F or
to the temperature specified by the resin
manufacturer. Silica removal is also enhanced by
a resin bed preheat step before the introduction
of warm caustic.

EXHAUSTED ANION RESIN


REGENERATION
Thoroughfare Counter-flow
Regeneration
The regeneration
efficiency of WBA is very high compared to
the strong base resin. Therefore it is possible to utilize the
regenerant alkali strength from the strong base unit to
regenerate the weak base unit.

EXHAUSTED ANION RESIN


REGENERATION
Demineralizers with weak and strong
base anion units can experience silica fouling
because of the use of waste caustic from the
strong base anion vessel to regenerate the
weak base anion resin during thoroughfare
regeneration. To avoid this, most of the
impurities from the strong base anion resin
are dumped to the drain before the
thoroughfare begins (generally, the first third
of the regenerant). To be confident that the
right amount is dumped, an elution study can
be performed.

RESIN STABILITY AND FACTORS


Oxidation
Exposing an ion exchange resin to a highly oxidative
environment can shorten resin life by attacking the
polymer crosslinks, which weakens the bead structure,
or by chemically attacking the functional groups. One
of the most common oxidants encountered in water
treatment is free chlorine (Cl2). Hydrogen peroxide
(H2O2), nitric acid (HNO3), chromic acid (H2CrO4), and
HCl can also cause resin deterioration.
Dissolved oxygen by itself does not usually cause any
significant decline in
performance, unless heavy
metals and/or elevated temperatures are also present
to accelerate degradation, particularly with anion
exchange resins.

RESIN STABILITY AND FACTORS

Oxidation
When a strong base anion resin experiences
chemical attack, the polymer chain usually
remains intact, but the quaternary ammonium
strong functional group (trimethylamine for
type 1 anion resins) splits off. Alternately, the
strong base functional groups are converted to
weak base tertiary amine groups, and the resin
becomes bifunctional, meaning it has both
strong base and weak base capacity. The
decline in strong base (salt splitting) capacity
may not be noted until more than 25% of the
capacity has been converted.

RESIN STABILITY AND


FACTORS
FAULING
Irreversible sorption or the
precipitation of a foulant within
resin
particles
can
cause
deterioration
of
resin
performance. The fouling of
anion exchange resins due to the
irreversible sorption of high
molecular
weight organic acids is
Although fouling
rarely occurs
a well-known
problem.
with cation exchange
resins,
difficulties due to the presence
of cationic polyelectrolytes in
an influent have been known to
occur.
Precipitation
of
inorganic
materials,
e.g.
CaSO4, can sometimes cause
operating
difficulties
with

RESIN STABILITY AND


FACTORS
Silica fouling:
Silica (SiO2) exists in water as a weak acid. In
the ionic form, silica can be removed by strong
base anion exchange resins operated in the
hydroxide cycle. Silica can exist as a single
unit, (reactive silica) and as a polymer
(colloidal silica). Colloidal silica exhibits
virtually no charged ionic character and cannot
be removed by the ionic process of ion
exchange. Ion exchange resins do provide
some colloidal silica reduction through the
filtration mechanism, but they are not very
efficient at this process.

MIXED BED EXCHANGERS


A mixed bed exchanger has
both cation and anion resin
mixed together in a single
vessel. As water flows
through the resin bed, the
ion exchange process is
repeated
many
times,
"polishing" the water to a
very high purity.
Due to increasing boiler
operating pressures and
the
manufacture
of
products
requiring

MIXED BED EXCHANGER


REGENERATION
During
regeneration,
the
resin
is
separated into distinct cation and anion
fractions as shown in Figures
1. SERVICE

2. BACKWASH
3. SIMULTANEOUS
REGENERATION
4. DRAIN DOWN
5. MIXING WITH AIR
6. FINAL RINSE

MIXED BED EXCHANGER


REGENERATION
The resin is separated by
backwashing, with the lighter
anion resin settling on top of the
cation resin. Regenerant acid is
introduced through the bottom
distributor,
and
caustic
is
introduced through distributors
above
the
resin
bed.
The
regenerant streams meet at the
boundary between the cation
and anion resin and discharge
through a collector located at
the resin interface. Following
regenerant
introduction
and
displacement
rinse,
air
and