The main objectives behind all controls and treatment procedure

employed in the steam power stations are to achieve

o Maximum economy
o Maximum availability and
o Maximum efficiency
The chemical controls employed to achieve these objectives all aim at
o Non-occurrence of corrosion phenomenon in the boiler, steam and
feed systems.
o Non-occurrence of deposit/ scale formation on the heating
surfaces.
o Maintaining highest purity of the steam.
1
Objectives of water chemistry
practice
 Reduce corrosion of metals
 Prevent formation of deposits
 Produce good quality steam
{ without carryover of boiler water solids }
2
 Natural water are seldom pure
Whatever is source-Water gets contaminated with
Salts ,Gases or Non-Ionic impurities by
coming in contact with air, soil or industrial
effluents.
Major impurities
Ionic-Dissolved
Non-Ionic-Suspended
Dissolved Gases.

3
 Inorganic
Silt / Mud
Salts, Na, Ca, Mg - Cl, SO4, HCO3, OH, H+
 Organics
Slime / insoluble organics.
Alcohol, Aldehydes, Acids
 Gases
O2, N2, CO2
Ammonia , H2S

4
 MAJOR IMPURITIES OF WATER

Ionic &Dissolved Nonionic and Gaseous

Undissolved
Cationic Anionic
Turbidity,silt Carbon dioxide
Calcium Bicarbonate Mud ,dirt and Hydrogen
Sulfide
Magnesium Carbonate other suspended Ammonia,
matters.
Sodium Hydroxide Colour, Methane,
Potassium Sulphate Organic matter, Oxygen
Ammonium Chloride Collodial Silica, chlorine
Iron Phosphate Micro-organism,
Manganese Silicate & Plankton,bacteria
Organic matter Oil and corrosion
products

5
 Water is seldom suitable for use without some
treatment as impurities present are harmful
depending on:
1.Nature and amount present
2.End Use
3.Tolerance for various impurities

6
 Drinking Water.
 Boiler Feed Water
 Ultrapure Water :
*High Pressure Boiler
*Semi-Conductor and Electronic
Industry
 Different Process Industries

7
 Scale Deposition.
 Corrosion
 Discolouration of Product
 Taste ,Odour ,
 Microbiological contamination imparted due to
impurities

8
 Instrument pH, TDS, Conductivity, Na / H.
 Titration Ca, Mg, SO4, Cl.
 Gravimetric.
 Volumetric.
 Colourimetric.
 Instrumentation.

9
 P.T.Plant
The clarification of water is a
process applied mostly to surface
waters for the removal of suspended solids,
finely divided particles present as turbidity
or color, and other colloidal materials
Conventionally the clarification process
involves coagulation, flocculation, and
sedimentation
10
Removal of suspended particles which will not
settle by gravity alone requires the addition of
chemical compounds commonly referred to as
coagulants
The small size of colloids coupled with their
surface charge is primarily responsible for
establishing conditions favorable for
the creation of dispersions
Further mixing of coagulant should be carried out
in such a manner that it should match the floc
strength at various stages of its formation
11
 Use of Alum; Al2(SO4)3.18H2O
(Al2O3-16%Min., Iron as Fe-0.7%Max.)
Al2(SO4)3 + 3Ca(HCO3)2 = 2Al(OH)3 + 3CaSO4 + 6CO2
Fe2(SO4)3 + 3Ca(HCO3)2 = 2Fe(OH)3 + 3CaSO4 + 6CO2

Explanation – The particles present in water are electrically

charged (negatively in most natural waters) and it is the repulsive
effects of such charges which prevent the particles forming
aggregates which will be large enough to settle out. Now, When a
coagulant (Alum) is added to water Al(OH)3 is formed which is
present as positively charged particles and ions .These will tend
to neutralise the excess negative charge of the fine particles
.Hence, there is a tendency for particles to join together forming
masses that are sufficiently heavy to settle rapidly. Alum is
probably the most widely used chemical for the coagulation of
water because of its excellent floc formation, its relative economy,
its stability, and its ease of handling.
PH range – better works between PH range 7.0-8.0

12
13
 Concept of Water Softening
Removal of Hardness (Ca2+, Mg2+)
 Hardness is an important water quality parameter in determining
the suitability of water for domestic and industrial uses
Hard waters require considerable amounts of soap to produce foam
Hard waters produce scale in hot-water pipers, heaters and boilers
Ca2+ + 2HCO3-  CaCO3 (s) + CO2 (g) + H2O
Groundwater is generally harder than surface water
Principal cations causing hardness and the major anions associated
with them (in decreasing order of abundance in natural waters)
Cations: Ca2+, Mg2+, Sr2+, Fe2+, Mn2+
Anions: HCO3-, SO42-, Cl-, NO3-, SiO32-

14
Carbonate and Noncarbonate Hardness
 Total hardness = Carbonate hardness +
Noncarbonate hardness
 Carbonate hardness = temporary hardness;
eliminated at elevated temperatures in
boilers
 Ca2+ + 2HCO3-  CaCO3 + CO2 + H2O
 Ca2+ + 2HCO3- + Ca(OH)2  2CaCO3 + 2H2O
 Noncarbonate hardness = permanent
hardness; can not be removed or
precipitated by boiling. Noncarbonate
hardness cations are associated with SO42-,
Cl- and NO3-.
15
Gravity filter

Its function is to reduce turbidity of clear water. It

operates on the principle of down flow under the
force of gravity & hence owes its name. It comprises
a bed of graded sand on the top of a bed of graded
gravel in several layers. The layers of gravels are
situated in such a manner that the coarsest gravel
rests at the bottom & the finest at the top. A
distribution system of water flow exists within
several layers of gravel to let water in &out. At times,
water flow is reduced due to accumulation of dirt on
the surface of the bed, which calls for backing of the
unit. Air scouring of the whole bed before backwash
is very effective for cleaning of the filter.

16
 ION EXCHANGE RESIN

• An organic ion exchange resin is composed of high-molecular-

weight poly-electrolytes that can exchange their mobile ions for ions
of similar charge from the surrounding medium.
• Each resin has a distinct number of mobile ion sites that set the
maximum quantity of exchanges per unit of resin.

•Ion exchange is a reversible chemical reaction wherein an ion from

solution is exchanged for a similarly charged ion attached to an
immobile solid particle. These solid ion exchange particles are either
naturally occurring inorganic zeolites or synthetically produced
organic resins.

•The synthetic organic resins are the predominant type used today
because their characteristics can be tailored to specific applications.

•The utility of ion exchange resin rests on its ability to get

regenerated so that these can be reused again and again.
•The regeneration is reversible so exchanger is not permanently
changed. Depending on the quality of inlet raw water the softener
may treat millions litres of water during an operating year of many
years.
17
 STRUCTURE OF ION EXCHANGE RESINS

Matrix: The basic polymeric structure(or the solid support) for ion exchange
resins is called matrix.

Functional Groups: The acidic/basic groups/sites attached to three

dimensional co-polymeric matrix are called Functional Groups.

Functional Polymer: The matrix along with Functional Group is called

Functional Polymer or ion exchange resin.

18
 PROCESS OF ION EXCHANGE
•Reversible: Ion exchange is a reversible process therefore, resin can be
converted from one ionic form to the other form, number of times and
reused.

•Regeneration: The process of converting resin to the desired ionic form is

called regeneration.

•Exhaustion: The resin is said to be exhausted when it cannot exchange

ions without effecting the desired quality of water.

APPLICATIONS
•Softening plant
•Demineralization plant
•Condensate polishing units
•Specific application by using chelating resins

19
 TYPES OF RESINS USED IN DEMINERALIZATION PLANT
1.Strong acid cation resins (SAC):
The strong acid cation resin derived their exchange activity from
sulphonic acid group(-SO3H) phosphonic (H2PO3-). When
operated on hydrogen cycle these remove nearly all cations
present in raw water. The strong acid cations can convert neutral
salts into corresponding acids. After exhaustion the resin can be
regenerated with HCl(4%)& NaCl(10%) for demineralization and
softening purpose, repectively.

2.Weak acid cation resins(WAC):

The weak acid cation resins have –COOH group as exchange
sites. These resins have the capability of removing all cations
associated with alkalinity to a much greater degree than SAC resin.
These do not function efficiently below pH 5.0, so these cannot split
neutral salts effectively. The main asset of WAC resins is their high
regeneration efficiency which not only reduces the amount of acid
required for regeneration, but also minimizes the waste disposal
problem. These are useful where there is high degree of hardness
and alkalinity. Frequently these are used in conjunction with a
strong acidic polishing resin. 20
4.Weak base anion resin(WBA):
•Weak anion resins derive their functionality from primary (RNH2),secondary(R-NHR’)&
tertiary amine (R3N)groups. The weak weak-base anion resins remove free minerals
acidity(FMA) such as HCl & H2SO4 but doesn’t remove weakly ionized acids such silicic
acid and bicarbonates.
• The main advantage of weak base exchangers is that they can be regenerated with
stoichiometric amount of regenerant, and are therefore, much more efficient. These have
a higher capacity for the removal of chlorides, sulphates.
• These are used in conjunction with SBA in demineralization system to reduce
regenerant cost and to attract organics thereby protecting the more susceptible strongly
basic resins, and for service in which carbon dioxide and silica are not important. Where
silica removal is not critical, WBA may be used by themselves in conjunction with air
stripper to remove CO2(degaser).

21
Role of WTP: To produce Ultra-pure water
SiO2: < 20 ppb
PH = 6.8 and k = 0.08s/cm (upto)

Role of different beds in DM plant

Unit Removes the ionic load

• Weak Acid Cation : Alkaline hardness (temporary hardness)
• Strong Acid Cation : permanent hardness +slip from
WAC+Fe+Na
• Weak Base Anion : EMA (Cl-SO-4,NO-3, F-)
• Strong Base Anion : All anions slip from WBA SiO2, slip
from degaser.*
• Mixed Bed : ionic slips from previous unit-5
(final polisher)

22
Superiority of Iso-porous Resins over
Gel and Macro-porous
 Reversibility to organic fouling
(comparable with macroporous)
 Much higher operating capacity and low silica
leakage.
 Higher regeneration efficiency.
 Longer life – because of better elasticity and ability
to withstand osmotic shock.
 Lower cost (as compared to macroporous

23
 COMPARISON BETWEEN DIFFERENT STRUCTURES OF
ION EXCHANGEER RESINS (GEL, ISOPOROUS, MACROPOROUS)
PARAMETERS GEL ISOPOROUS MACROPOROUS
Structure Non uniform, heterogeneous Uniform, homogeneous Heterogeneous structure
structure Structure With large cavities
Pore size Very small Larger than gel Very large pore size
(<40oA) (Avg. 1300oA)
Resistance to Gets easily fouled with Excellent resistance to Very good resistance
Organic fouling Organics Organic fouling To organic fouling
Operating Normally higher than Higher than gel and Lower than gel and
Capacity Macr porous but lower than Microporous types isoporous types
Isoporous type.
Operating Cost Medium Low High
Regeneration Good Excellent Less
Efficiency
Treated Water Average Excellent Good
Quality (Silica
leakage)
Osmotic Stability Good Excellent Good
Elasticity Low High Very Poor
24
DM Plants(Co-flow)

Pressure filter – It operates with the same

function and same underlying principle &
similar design as of gravity filters in respect of
filter medium, supporting bed & drain
system.
Activated carbon filter – This unit’s sole
purpose is to remove residual chlorine from
the incoming filter water which otherwise
damage the resins structures. It is not a filter
for suspended matter.

25
 Activated Carbon Filter
Service and Regeneration ( Back
wash)
SI - Service Inlet
SO - Service Outlet
BWI - Backwash In
BWO - Backwash Out
RO - Rinse Out

Air BO
vent

SI
BI

To Cation SO
Exchanger RO
Drain
26
Cation exchanger

Cation exchange reactions replacing hydrogen from resin by Ca,

Mg &Na etc.
It is of two types. Strong cation exchanger(SAC) and weak
cation exchanger(WAC).Strong cation exchangers have –SO3H
functional group and weak cation exchangers having –COOH
functional group. when strong cation resin is operated on
hydrogen cycle these remove nearly all cations present in raw
water and converts neutral salts into corresponding acids.

Exchange reactions -
NaCl + RSO3H –RSO3Na + HCl
MgSO4 + 2RSO3H - (RSO3)2Mg +H2SO4
Ca(HCO3)2 +2RSO3H - (RSO3)2Ca +2CO2 +2H2O

27
It can be seen from last equation that the alkaline salt –calcium
bicarbonate has been split into carbonic acid which being weakly
ionised can also be represented as free carbon dioxide and water.
The neutral salts have been converted into their respective mineral
acids. The treated water is therefore acidic and has a low PH.

Weak cation resins have the capacity of removing all cation

associated with alkalinity to a much greater degree than SAC resin.
These do not function efficiently below PH 5.0,so these cannot split
neutral salts effectively. These are useful where there is high degree
of hardness and alkalinity. Frequently these are used in conjunction
with a strong acidic polishing resin. The main asset of WAC resin is
their high regeneration efficiency which not only reduces the
amount of acids, but also minimises waste disposal problem.
At CTPS we use strongly acidic high capacity resin.

28
Test
If FMA (free mineral acidity) is almost constant running
exchanger is O.K. If FMA gradually decreases and anion
exchanger’s conductivity gradually increases the
exchanger is going to exhaust. FMA is measured by
alkali.

Regeneration
At CTPS New DM plant -1.Back wash -1 hr, or the
effluent coming out from exchanger is clear. 2.Charging-
2.0% H2SO4 for 20 mints 4.0-5.0% H2SO4 for 30 mints
till total acid consumed-255Kg 3.Ringing- 1 hr. If FMA is
constant bed is ready for service.
Reversible reaction (an example)-
2RSO3Na + H2SO4 - 2(RSO3)H +H2SO4

29
Degassifier

Only part of the CO2 dissolved in the ground

water remains in the combined free form. Some
of it combines with carbonates in the soil to
produce bicarbonate alkalinity. The amount of
CO2 in the water in excess of that required to
form bicarbonates is in the uncombined free
form and can be removed by aeration.

30
Anion Exchanger

anion exchange reactions replacing hydroxyl from resin by SO42- ,

Cl - , and SiO2 etc.
Two kinds of strongly basic anion exchanger exist.
Type I –with quaternary ammonium functional group – [R’ -CH2 –N
(CH3)3 ]+ OH –
Type II –with a slightly modified quaternary ammonium functional
group –
[R’-CH2-N (CH3)2CH2-CH2OH]+ OH –
Type I has somewhat less exchange capacity but more stability and
more silica removal capacity.

The weak base anion exchanger has poly amine functional groups
containing primary amine –NH2, secondary amine –NHR and
tertiary amine –NR2.
At CTPS we use strongly basic Type I high capacity resin.

31
Exchange reactions

R4NOH + HCl - R4NCl +H2O

2R4NOH + H2SO4 - (R4N)2 SO4 +2H2O
R4NOH + H2SiO3 - R4NHSiO3 +H2O

Test

If silica is almost constant and is less than 0.04 ppm

than running exchanger is O.K. If silica gradually
increases than exchanger is going to exhaust. Silica is
measured by silica reagent.

Limits

conductivity -10.0micromho/cm, silica -0.1ppm, PH -

<8.5
32
Regeneration

At CTPS New DM plant -1.Back wash -1/2 hrs or

the effluent coming out from exchanger is clear. 2.
Charging- 4.0-5.0% NaOH for 1 hr. till total alkali
consumed-260Kg 3.Ringing- 1 hr. when exchanger
achieve desired limits the bed is ready for service.
Reversible reaction(an example)-
R4NCl + NaOH -R4NOH +NaCl
The effluent of anion is almost pure water .Further
purification can be made by passing this water
through a mixed bed unit.

33
Cation Exchanger And Anion Exchanger
Regeneration line to
weak exchanger

DF - Down Flow
Weak Strong NF - Nozzle flushin

Air NF Air
Vent Vent

SI DF
BI
SI BI
Acid/Alkali injection
BO RO
SO
BO RO SO
Drain
Drain 34
Mixed bed exchanger

Limits

conductivity -0.5 micro mho/cm, silica -<0.02ppm as silica,

PH - 6.8 -7.2

Regeneration

At CTPS New DM plant -

1. Back wash -15-30 mints. 2. 4.0-5.0% NaOH for 30 mints till
total alkali consumed-35 Kg 3.Alkali rinse – ½ hrs till PH -
<8.3 3. 4.0-5.0% H2SO4 for 30 mints till total acid consumed-
40 Kg 3.Acid ringing- 1/2 hrs or till FMA is <5ppm 4.Draining
-2 mints 5. Air mixing -15 mints 6.Resin settling – 5-10 mints
7.Final rinse -1/2 hrs
When exchanger achieves desired limits the bed is ready for
service.

35
MIXED BED
Service and Regeneration

Alkali injection

SI
Air
NF Vent

Air

Drain Acid SO 36
injection
Mixed Bed
Resin Separation

Anion exchange
Resin

Cation exchange
Resin

37
 DM PLANT
From filter water
pumps For circuit rinse

ACF SBA
WAC SAC WBA MB

Air DM
water
storage
DEGASSER tank

To main plant for

boiler make up 38
 Fouling of the resin and treatments
• Irreversible adsorption of undesired inorganic/organic impurities
on resin called fouling.
• symptoms → Drop in operating capacity
→ Poor treated water quality
• Type of fouling:
I) Iron/Heavy metal fouling: Iron and Mn2+ present in regence-rauts,
catalysed oxidising action on resin in the presence of dissolved
oxygen. Cause decross linking.
Action: HCl treatment, at higher concentration .
II) Organic fouling: Due to macro molecules, humic & fulvic acids
present in waters, detergent
Action: Alkaline brine treatment with 10% Nacl +2% NaOH at 50±
2oC (8-16 hr Soaking)
III) Oil fouling: Oil present in water forms a their film on resin bead,
making unavailable the exchange sites of resin.
Action: washing with surface active agent or NaOH.
IV) CaSO4 precipitation: If H2SO4 is used for cation resin-regeneration.
Cause pressure drop and leakage of hardness.
Action: Backwash, HCl treatment.
.
39
Anion resin surface fouling
Anion resin surface

Cl + ++
+
++ +
+ +
SO4
+ + +
+ +
+ Anion resin bead
+ +
+
+ + +
+ +
Foulant + + + +
negative charge + +
+
40
FACTOR DETERMINING THE DISTRIBUTION OF IONS BETWEEN AN ION-
EXCHANGE RESIN AND A SOLUTION

a) At low aqueons concentrations and at ordinary temperatures the

extent of exchange increases with increase of valency of exchanging
ions.
Na+ < Ca2+ <Al3+ < Th4+

b) Under similar conditions and constant valency, for univalent ions the
extent of exchange increases with decrease in size of the hydrated
cation.
Li + < H + < Na+ <NH4+ < K+ < Rb+ < Cs+
While for divalent ions the ionic size is an important factor but the
incomplete dissociation of salts of bivalent metals also plays a part.
Ni++ < Co++ <Ca++ < Sr ++ < Pb++ < Ba++

41
c) With strongly basic anion-exchange resins,
univalent anions appear to behave similarly to
univalent cations.
F- < OH- < Cl- < Br- < NO3- < I-
In dilute solution polyvalent anions are
generally absorbed preferentially.

d) To exchange a higher valent ion on the

exchanger for one of lower valency in solution,
exchange will be favoured by increasing the
concentration, while if the lower valent ion is in
the exchanger and higher valent is in solution,
exchange will be favoured by high dilutions

42
Health of
a boiler

Water
Health of heat
chemistry
exchanger tubes
control

43
THANK YOU

44