Power House Water

chemistry
Dr. S. K. Pramanik
Ph.D. (Chem); MBA (TQM)
Sr. Chemist
DVC, CTPS (U# 7&8)
e-mail: sukhendu_pramanik@dvcindia.org
M: +91-9973789375


9 October 2014 2
Surface Drainage water (Rivers, Lakes and Reservoirs)
Underground Water (Shallow Well, Deep Well and Springs)
Rain Water
Sea Water
Snow Melting
WATE
R
9 October 2014 3

The purest water available naturally is the one obtained from
water vapour in the atmosphere as rain, snow or produced by
melting of ice.
This water while reaching the ground absorbs different types
of gasses from atmosphere like nitrogen, oxygen and to a
lesser extent carbon dioxide.
Other gasses like ammonia, oxide of nitrogen and oxides of
sulphur etc., also dissolves during rain depending upon the
pollution level of the atmosphere.
Apart from this, the surface water travels to various places
catch organic matters, suspended solids etc.

9 October 2014 4
SEA 95-96%
FROZEN WATER 2%
FRESH WATER 2-3%
Fresh water available to us is only 2-3% of water supply.
We, the human beings, are bent upon polluting this precious resource.
Imperative to take proper care to conserve and reuse water.
Water Supply
9 October 2014 5
WATER CHEMISTRY IS A VERY IMPORTANT DISCIPLINE IN
POWER SECTOR.

TO ACHIEVE HIGHER OPERATION EFFICIENCY, MINIMIZE
CORROSION & SCALE FORMATION PROBLEMS AND TO
REDUCE PLANT DOWNTIME, HIGH WATER QUALITY
STANDARDS ARE TO BE MAINTAINED, PARTICULARLY IN
VIEW OF UPCOMING SUPER CRITICAL BOILERS
ROLE OF CHEMISTRY IN POWER PLANT
9 October 2014 6

PRETREATMENT OF RAW WATER
FILTER WATER FOR DM PLANT
ULTRA PURE /DEMINERALISED WATER FOR
BOILER MAKE-UP/STEAM GENERATION
COOLING WATER SYSTEM.
MONITORING OF STEAM/ WATER PARAMETERS
& H.P./L.P. DOSING SYSTEMS
COAL & ASH ANALYSIS
TRANSFORMER/TURBINE OIL ANALYSIS.
POLLUTION CONTROL
PRE/POST COMMISSIONING ACTIVITIES IN PLANT
EFFLUENT MANAGEMENT
ROLE OF CHEMISTRY INVOLVES IN:
9 October 2014 7
PART - A
PRE TREATMENT
PART - B
POST TREATMENT
(DEMINERALISATION)
PART - C

COOLING WATER TREATMENT
PART D
BOILER WATER CHEMISTRY
PART -
I
9 October 2014 8
9 October 2014 9
WATER FLOW DIAGRAM
CLARIFLOCCULATOR

GRAVITY
FILTER
D.M. PLANT
HVAC COOLING
WATER
CLARIFIED
STORAGE TANK
RAW
WATER
DRINKING
WATER
BOILER
MAKEUP
C.W. MAKEUP U/G STORAGE
TANK
9 October 2014 10
1. Suspended Form (Macro size) Sand, dirt, silt are
the suspended mater in water. These contribute
turbidity to raw water.
2. Colloidal form Micro size particles(1-100 nm)
3. Dissolved form - Alkaline salts and neutral salts,
organic matter,
Alkaline salts are mainly bicarbonates rarely
carbonates and hydrates of calcium, magnesium
and sodium. Neutral salts are sulphates,
chlorides, nitrates of calcium, magnesium and
sodium.

9 October 2014 11
ORGANICS :-
Organics in water is mostly due to the decomposed
products of vegetable matters, though some man-
made organic wastes are not ruled out.
In these organics the weak acidic large molecules
called Humic acid and Fulvic acid are the most
troublesome in the W.T. plant as they attack the Anion
Resins and foul it causing problems in regenerating
the resins.
The biggest Humic Acid is of colloidal size and passes
through ion exchange beds.
There are organic impurities in the form of
microbiological species like bacteria, virus, Alagae and
fungi etc.






Contd.
9 October 2014 12
Suspended Matters :
They are generally silicious in nature along with
some oil and other unwanted things depending
upon the source of water.

If not removed in pretreatment then these things
get filtered in the ion exchange beds and cause
increase in differential pressure of the bed and
sometimes cause uneven distribution of flow.

Depending on the quantity it may give problems in
back washing also.
Contd.
9 October 2014 13
NON- REACTIVE SILICA : -

This cannot be removed by ion-exchange
process . It passes through resins and goes in
D.M. water and at high pressure and temperature
in the boiler, gets converted into
ordinary/reactive silica.

As non reactive silica cannot be analyzed by
normal methods (ANSA), It deceives normal
operation.

This non-reactive silica is called Colloidal
Silica also.


Contd.
9 October 2014 14

Chlorination
Dosing of alum/lime
Coagulation and
flocculation
Sedimentation
Filtration
De-chlorination
Pre- Treatment of water
Depending on the usage of the water it is to be treated
on different ways.
Pre-treatment takes care of organics, suspended
matter and colloidal silica to some extent.
WATER
TREATMENT
9 October 2014 15


CLARIFLOCCULATOR

GRAVITY
FILTER
D.M.
PLANT
U/G STORAGE
TANK
RAW
WATER
ALUM & Cl
2

CLARIFIED WATER
STORAGE TANK
The processes by which the aeration accomplishes the desired
results are :

Sweeping or scrubbing action caused by the turbulence of
water and air mixing together.
Oxidizing certain metals and gases


16 9 October 2014
THE TREATMENT PROCESS

Aeration. Raw water pumped from the well is
mixed with air.
The mixing releases carbon dioxide and
hydrogen sulphide gases present in the water.
Aeration also oxidizes any iron,
causing it to "precipitate" (or settle out)
removed by precipitation and filtration.



9 October 2014 17
18
Fe(HCO
3
)
2
+ 2HOH = Fe(OH)
2
+ 2H
2
CO
3
H
2
CO
3
= H
2
O + CO
2
4Fe(OH)
2
+ H
2
O+ O
2
= 4Fe(OH)
3


9 October 2014
DISINFECTION
9 October 2014 19
Disinfection is destruction of Pathogenic bacteria,
virus, germs and other organisms present in
water.
It can be achieved by
Gaseous chlorine
Chlorine compounds such as hypo-chlorites,
bleaching agent and chlorine dioxide
Ozone
Ultra-Violet radiation
Hydrogen peroxide
Heating
Combination of the above





CHLORINATION
Chlorination is the application of chlorine to water to
accomplish some definite purpose.
20
PRE-
CHLORINATION
POST-CHLORINATION
IN STILLING
CHAMBER
DOSING
IN FILTER
SUMP
9 October 2014
PURPOSE :
for the purpose of disinfection.
be used for taste and odor control.
iron and manganese removal.
and to remove some gases such as ammonia and
hydrogen sulfide.


21
Prechlorination is
the act of adding
chlorine to the raw
water after
screening and
before flash
mixing.
Postchlorination is
the application of
chlorine after water
has been treated but
before the water
reaches the
distribution system
9 October 2014
CHLORINATION
9 October 2014 22
Chlorination is the process in which chlorine gas or
chlorine compounds are added to water for the
purpose of disinfection, by killing disease producing
organism and algae.

Reaction of chlorine with water

When chlorine is dissolved in water, it is rapidly
hydrolysed to form HCl and HOCl

H
2
O + Cl
2
HCl + HOCl
HOCl H
+
+ OCl
-

( At pH more than 6.0)
Batericicidal effect of chlorine is maximum when
chlorine is in the HOCl form. Chlorine is most effective
disinfectant at pH between 5 - 6.

Reaction with organisms
9 October 2014 23
Chlorine reacts with water to produce nascent
oxygen which destroys the physical structure of the
organisms. The physical structure i.e. the cell-wall of
the organism contains amino group which is
destroyed by chlorine.

Reactions :-
NH3 + HOCl NH2Cl + H2O (monochloramine)
NH2Cl + HOCl NHCl2 + H2O (dichloramine)
NHCl2 + HOCl NCl3 + H2O (nitrogen trichloride)

In addition to disinfection, chlorine also has the
following functions:
taste and odor control as an oxidizing agent
oxidation of Fe
2+
and Mn
2+
in groundwater
ammonium removal in domestic waste treatment
slime, bio-fouling control
Disadvantages:
The formation of disinfection by-products
(trihalomethanes) presents a health risk
Not advisable at high pH and ammonical compounds

9 October 2014 24
EFFECTIVENESS OF CHLORINE AS A BIOCIDE
EFFECT OF pH ON THE DISSOCIATION OF HYPOCHLOROUS
ACID
pH
4
5
6
7
8
9
HOCl
100
99.7
96.8
75.2
20.0
Negligible
9 October 2014 25
EFFECTIVENESS OF CHLORINE AS A BIOCIDE
EFFICIENCY OF CHLORINE AT DIFFERENT pH IN CLARIFIER/ COOLING WATER
SYSTEM
4 5 6 7 8 9 10 11
80
60
40
20
0
20
40
60
80
100
OC
HOBr
P
e
r
c
e
n
t

i
o
n
i
z
e
d

f
r
o
m

(
O
C
l

-

o
r

O
B
r
-
)

P
e
r
c
e
n
t

u
n
-
i
o
n
i
z
e
d

f
o
r
m

(
H
O
C
I

-

o
r

H
O
B
r
-
)

20C
HOCI
pH
Cl
2
+ H
2
O HOCl + (H
+
+Cl

)

(Hypocblorous acid)

HOCl H
+
+ ClO


(Hypocblorite ion)
HOCl + OH

H
2
O + ClO

9 October 2014 26
9 October 2014 27
Chlorine dioxide (ClO
2
) as biocide
It is generated in-situ as per reaction:
Cl
2
+ 2NaClO
2
2ClO
2
(gas) + 2NaCl
Its advantages include:
Effective in at lower dosage than chlorine. At pH 8.5 it is at
least five times effective than chlorine.
Does not react with ammonia hence effective in ammonical
water and high organics
No disinfection by-products such as trihalomethanes
More efficient and effective in wide range of pH
High oxidation potential( E
0
= + 0.954 V at 25C)
It is more selective towards environmentally objectionable
compounds like phenol, cyanides and mercaptans.
CLARIFLOCCULATOR
9 October 2014 28

Clariflocculator is a circular concrete tank having two
zones for the removal of impurities .

The flocculator zone where the micro-flocs agglomerate
into macro-flocs with the help of slow speed agitators.
Clarification zone where the agglomarated flocs settle
leaving clear supernatent liquid
Water enters the clarifier through the central shaft and
flows on to the flocculation zone though the parts
provided at the top of the shaft.
Sludge can be cleared by gravity flow or sludge
disposal pumps. Depending on the sludge quantity ,the
bridge is to be operated continuously or intermittently.
Required chemical are dosed before water enters CCF.
CLARIFLOCCULATOR
9 October 2014 29
Raw
water
Chlorine
Alum
Lime
Flash
Mixer
Clarification
Sludge
settling
pond
Clarified
water to
filters
Flocculation
Water quality at Clarifier outlet
Turbidity - <20 NTU pH - 5.5 to 8.0
Residual Chlorine - 0.2 ppm
COAGULATION
9 October 2014 30

COAGULATION IS A PROCESS WHICH
NEUTRALIZE NEGATIVE CHARGE ON
PARTICLES WHICH ARE COLLOIDAL IN
NATURE AND HELPS TO FORM FLOCKS.

Common Coagulants
9 October 2014 31
Alum
Hydrated aluminum sulfate [Al
2
(SO
4
)
3
18H
2
O]
Alum, when added to water, will be hydrolyzed to form gelatinous
hydroxide [Al(OH)
3
] precipitate. This will carry suspended solids
as it settles by gravity. (pH 5.5-8)
Anhydrous Fe
3+
Forms Fe(OH)
3
(s) in a wide range of pH 4-11

Anhydrous Fe
2+
(copperas, FeSO
4
7H
2
O)

Must be oxidized to Fe
3+
first

at pH higher than 8.5
Natural and synthetic polyelectrolytes

Starch, cellulose derivatives, proteinaceous materials, and gums
composed of polysaccharides
Synthetic polymers
Poly electrolytes (long chain amides)
Poly Aluminum Chloride ( PAC )
Factors affecting coagulation: pH, Time, Temperature,

ROLE OF ALUM DOSING
Removes suspended particulate and colloidal substances from
water, including microorganisms.
Coagulation: colloidal destabilization
Typically, add alum (aluminum sulfate) or ferric chloride or
sulfate to the water with rapid mixing and controlled pH
conditions
Insoluble aluminum or ferric hydroxide and aluminum or iron
hydroxo complexes form
These complexes entrap and adsorb suspended particulate
and colloidal material.
9 October 2014 32
FLOCCULATION
9 October 2014 33
SMALL FLOCKS (POLYMERS) COMING TOGETHER
TO FORM BIGGER EASILY SETTLEABLE FLOCKS IS
CALLED FLOCCULATION i.e., INORGANIC
POLYMERS (ACTIVATED SILICA, ALUMINO
SILICATE), ANIONIC (ACRYLAMIDE AND ACRYLIC
ACID)

Al2(SO4)3 + 3Ca(HCO3)2 2Al(OH)3 + 3CaSO4 +
6CO2

Fe2(SO4)3 + 3Ca(HCO3)2 2Fe(OH)3 + 3CaSO4 +
6CO2

Ca(HCO3)2 + Ca(OH)2 2CaCO3 + 2H2O
SEDIMENTATION
9 October 2014 34

COAGULANT MATERIAL THAT HAS TO
SETTLE OUT OF THE WATER CONSISTS OF
PATICLES OF ENHANCE DENSITY.
CONSEQUENTLY IT CAN BE REMOVED MORE
RAPIDLY BY SEDIMENTATION.
Coagulants
Alum (aluminum
sulphate), polyaluminum
chloride and a group of
chemicals known as
polyelectrolytes .
.Large +ve Charge
attracts -ve charged clay
particles
Zeta potential

Large charge on small
ion Al+++ , Fe +++

9 October 2014 35
36
(Adsorption of neutralized colloidal particles on flocs)


3+
-
-
-
-
- -
-
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3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
-
-
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- -
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-
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3+
3+
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3+
3+
3+
3+
3+
3+
3+
-
-
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- -
-
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- -
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- -
-
-
-
-
-
-
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
-
-
-
-
- -
-
-
-
-
-
-
-
-
-
-
- -
-
-
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- -
-
-
-
-
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-
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-
- -
-
-
-
-
-
-
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
-
-
-
-
- -
-
-
-
-
-
-
-
-
-
-
- -
-
-
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-
- -
-
-
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-
-
-
-
-
-
- -
-
-
-
-
-
-
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
-
-
-
-
- -
-
-
-
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-
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-
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
-
-
-
-
- -
-
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-
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3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
-
-
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-
- -
-
-
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-
-
-
-
-
-
3+
3+
3+
3+
3+
3+
3+
3+
3+
3+
Al3+ ions
Colloidal Particles
Fast Settling
9 October 2014
9 October 2014 37


Filtration is the removal of the solid particles
from water by passing it through a filtering
medium. Filtration is usually a mechanical
process does not remove dissolved solids.
Filters used in Water Treatment are mainly of two types.
1. Pressure Filters
2. Gravity filters
Pressure filters are in closed, round steel
shells and function with the pressure of the
incoming water.
Gravity filters are in steel, wood or concrete
containers that are open at the top and
function at atmospheric pressure.
FILTRATION
9 October 2014 38
Theoretically any inert granular material can
be used for filtration.
Quarts sand, Silica sand, anthracite coal,
garnet may be used for filtration.
Silica sand and anthracite are the types of filter
media which are commonly used.
At DVC sand is used as filtering medium and
filters are Gravity sand filters (GSF).
Filter Media
9 October 2014 39
Gravity Sand Filter
IN
OUT
5
th
layer
4th layer
3rd layer
2nd layer
1st layer
Gravity Sand Filter
For back washing of
the GSF water is
passed through filter
in reverse direction
Clarified
water from
clarifier
9 October 2014 40
1st layer - 50 mm X 37 mm gravel
2
nd
layer - 37 mm X 12 mm gravel
3
rd
layer 12 mm X 6 mm gravel
4
th
layer 6 mm X 2.5 mm grit
5
th
layer 0.35 mm X 0.5 mm sand
Filter medium layers in GSF
9 October 2014 41
1. Feed water to DM plant
2. Feed water to Softening Plant
3. Drinking water Township and plant
4. Service water as cooling water for A/C
and Compressors
Uses of filtered water
PART -
II
9 October 2014 42
DM PLANT
9 October 2014
43
DM
water
storage
tank
ACF
SAC SBA MB
DEGASSER
Air
To main plant for
boiler make up
For circuit rinse
From filter
water pumps
Typically, the cation resin operates in the hydrogen cycle.
The cations in the water (i.e. calcium, magnesium and sodium) pass
through the cation exchange resin where they are chemically exchanged
for hydrogen ions.
The water then passes through the anion exchange resin where the
anions (i.e. chloride, sulphate, nitrate and bicarbonate) are chemically
exchanged for hydroxide ions.
The final water from this process consists essentially of hydrogen ions
and hydroxide ions, which is the chemical composition of pure water.
CATION EXCHANGER
ANION EXCHANGER
9 October 2014 45
Ion-exchange Reactions
Cation Exchanger
During Service
NaCl RNa + HCl
RH + CaCO
3
R
2
Ca + H
2
CO
3
MgSO
4
R
2
Mg + H
2
SO
4
Na
2
SiO
3
RNa +H
2
SiO
3
During Regenration
RNa Na
2
SO
4

R
2
Ca + H
2
SO
4
RH + CaSO
4
R
2
Mg MgSO
4

9 October 2014 46
Ion-exchange Reactions
Anion Exchanger
During Service
HCl RCl +
H
2
O

ROH + H
2
CO
3
R
2
CO
3
+
H
2
O

H
2
SO
4
R
2
SO
4
+
H
2
O

H
2
SiO
3
R
2
SiO
3
+
H
2
O

During Regenration
RCl NaCl
R
2
CO
3
+ NaOH ROH + Na
2
CO
3


R
2
SO
4

Na
2
SO
4

R
2
SiO
3
Na
2
SiO
3
The resin in the pressure vessel has about 50% free space above the resin.
This free space allows backwashing,removal of any entrained solids.

Water and acid/caustic regeneration is carried out in a down-flow direction.
CO-CURRENT FLOW REGENERATION
Coflow or Downflow Regeneration
Coflow or Downflow Regeneration
RESIN BED
Feed In
Regenerant
In
Regenerant
out
Treated Water Out
Collecting
System
The regenerant acid and caustic passes in the opposite direction to
the service flow water.
With counter-flow regeneration, the regenerant passes through
the resin near to the outlet of the unit .
COUNTER-CURRENT FLOW REGENERATION
Coflow or Downflow Regeneration
Counter flow Regeneration

ACTIVE
RESIN
BED
Feed In
Regenerant
Out
Regenerant
In
Treated Water Out
Downflow of water
During Regn
Advantage of counter current :

Lower portion of the bed ( which acts as service water effluent ) is
retained under fully regenerated conditions.

The leakage of ions is substantially reduced

Also, associated with lesser chemical consumption
Cation Exchange Mechanism
Start of run During the run End of run
Ca
Mg
Na
Ca
Mg
Na
Ca
Mg
Na
Na
Anion Exchange Mechanism
SO
4
2-

Cl
-

SiO
2

SO
4
2-
Cl
-
SiO
2

SO
4
2-
Cl
-
SiO
2

Cation exhaustion leads to Na leakage
while anion exhaustion leads to SiO
2
leakage
Polishing mixed beds come after the cation and anion standard
vessels
and, as the name implies, they are there to polish the water.
The bed is an intimate mix of anion and cation resins.
MIXED-BED DEMINERALISATION
Mixed bed:
During service step ,cation and anion resins are intimately mixed offering
innumerable close linked exchangeable sites.
Thus acid formed by contact of salt with cation bead is immediately
neutralised by neighbouring anion.
During re-generation,backwashing separates the lighter anion resin from
denser cation resin.

A collector is placed at interface between two resins facilitating
regeneration operation without removing the resins from column.

A simultaneous regeneration of cation and anion resin can be adopted.
MIXED BED
Service and Regeneration
Air
Vent
SI
SO
Drain
Alkali injection
Acid injection
NF
Air
Re generation of mixed bed exchanger :

1. Resin separation/backwash
2. acid and alkali injection
3. acid and alkali displacement using DM water
4. Drain to bed level
5. Air mix
6. Fill up
7. Final rinse
Mixed Bed
Resin Separation
Cation exchange
Resin
Anion exchange
Resin

Water quality at different stages of Demineralisation process:-

Feed water to DM plant
Turbidity - <2 NTU
ACF outlet
Residual chlorine - Nil
Turbidity - < 0.5 NTU
Cation Exchanger outlet
Na - <2 ppm
Degasser outlet
Dissolved CO
2
- <5 ppm


D.M. PLANT

Anion Exchanger out
Silica - < 200 ppb
Conductivity - < 10 s/cm
pH - 6.8 - 7.2
Mixed bed out
Silica - < 20 ppb
Conductivity - < 0.1 s/cm
pH - 6.8 - 7.2

D.M. PLANT
PART -
III
9 October 2014 60
COOLING WATER

Cooling of water is an essential process at power-
generation and industrial plants.
The most important uses of cooling water includes
condensing turbine exhaust steam, cooling
process fluids and protecting high pressure
pump bearings.
Control of cooling water chemistry is very critical in
preventing corrosion ,scaling and fouling.

COOLING WATER SYSTEMS
Type of cooling water system most suitable for
process depends upon:-

1. Process operation
2. Flow requirements
3. Availability and quality of water
4. Environment requirements regarding discharge

Types of cooling system
1. Closed Recirculating
2. Once-through
3. Open Recirculating (Evaporative cooling
towers)

Closed Recirculating System
Water circulates in a closed cycle
Alternate cooling and heating without air contact
Heat absorbed by the water in closed system is
transferred by a water to water exchange to the
recirculating water of an open recirculating
system from which the heat can be lost to
atmosphere.

Once Through System
Water makes one pass through the heat
exchanger equipment and discharged to waste.
Large quantity of water is needed.
Once-through system have advantage of not
concentrating water during its passage through
system, thus reducing scaling and corrosion
potential of water.
Water is returned to source at higher
temperature, thus cause thermal and chemical
pollution of water bodies.
Highly prone to biological fouling.

Open Recirculating( Evaporative
cooling Towers)
Water circulates through the condenser or heat
exchanger to a cooling tower and then returned to
exchanger.
Same high volume flow rate as a once through
system, but with less water discharge.
Cooling of water is by evaporation process, water
loss by evaporation and drift.
The evaporated water is very pure and the
minerals are left behind to concentrate.

Open Recirculating( Evaporative
cooling Towers)
O.R.SYSTEM have greater degree of scale formation,
corrosion & microbiological growth due to-
Higher temperature.
Make up water brings more scale forming &corrosion
forming salt.
Water is exposed to air allowing continued presence of
oxygen ,which responsible for corrosion.
Cooling tower is a scrubber ,introducing
microrganism,dirt,dust etc in circulating water which
increases fouling & corrosion.
Types of Cooling Towers
FORCED/INDUCED DRAFT COOLING TOWERS

NATURAL DRAFT COOLING TOWERS


Cooling Water Balance
Condenser
CW Make up
Evaporation and drift
Blow Down
Air + water
vapour
Water Air
Air
Natural Draft Cooling Tower
CT Basin
TERMS ASSOCIATED WITH
COOLING TOWER
Cycle of concentration ( C ) : Number of times the
circulating is concentrated in cooling tower is known as
Cycle of concentration. The maximum C depends upon the
effectiveness of corrosion and scale inhibitor programs
and on the quality of make up water.

Blow Down ( BD ) : Some water must be continually
removed from cooling water system to prevent excessive
build up of the dissolved solids. This is known as blow
down.
TERMS ASSOCIATED WITH
COOLING TOWER
Drift ( D ) : Drift is a form of blow down that
occurs due to entrainment of water droplets in
the air leaving the cooling tower. Drift typically
ranges from about 0.05% to 0.3% of the
recirculation rate depending upon the type
and efficiency of the cooling tower.
Make up ( MU ): Water added to Circulating
water sysrem to replace water lost from the
system by evaporation, drift, blown down, and
leakage.
CYCLE OF CONCENTRATION
Cycles of concentration represents the accumulation of
dissolved minerals in the recirculating cooling water

T.D.S. of Circulating Water
COC =___________________________
T.D.S. of Make up Water
As the cycles of concentration increase the water may not be
able to hold the minerals in solution. When the solubility of
these minerals have been exceeded they can precipitate
out as mineral solids and cause fouling and heat exchange
problems in the cooling tower or the heat exchangers.
Problems arises in circulating
water
CORROSION
SCALE FORMATION
BIOFOULING
Recommended CW Treatment
Acid dosing
Sulphuric acid dosing is done which reduces pH as
well as alkalinity of the system, in turn it reduces
scaling tendency of the system.(pH=7 & Conc. of
SO
4
=< 600mg/kg).

Chemical Dosing system
Descalent and corrosion inhibitors are added to
system to avoid scaling and corrosion in system.
Biocides are also added to reduce biofouling of the
system
PART -
IV
9 October 2014 75
WATER STEAM CYCLE
D.M. WATER
Storage
Tank
CONDENSER
D/A
TURBINE
STEAM
BOILER
T.S.P. DOSING
AMMONIA
DOSING
BFP
HYDRAZINE
DOSING
CEP
76 9 October 2014
WATER/STEAM CHEMISTRY

PARAMETERS MONITORED
pH
Silica
Conductivity
After Cation Conductivity
Dissolved Oxygen
Sodium
Copper
Iron


77 9 October 2014
WATER QUALITY

FEED WATER
ACC <0.02 uS/cm
pH 8.8-9.2
Total Iron+Copper <0.02 ppm
Silica <0.02 ppm
Dissolved Oxygen <7 ppb
78 9 October 2014
WATER QUALITY
CONDENSATE WATER
ACC <0.02 uS/cm

pH 8.8-9.2

Silica <0.02 ppm

Dissolved Oxygen < 40 ppb
79 9 October 2014
BOILER WATER
Conductivity <30 uS/cm

pH 9.2-9.6

Silica <0.300 ppm

Phosphate 2-4 ppm
WATER QUALITY
80 9 October 2014
STEAM
ACC <0.02 uS/cm
pH 8.8-9.2
Total Iron+Copper <0.02 ppm
Silica <0.02 ppm
Sodium <10 ppb
WATER QUALITY
81 9 October 2014
Drum Pressure Silica in Boiler Water
194 Kg/Cm
2
130 ppb
176 Kg/Cm
2
220 ppb
159 Kg/Cm
2
290 ppb
134 Kg/Cm
2
500 ppb
117 Kg/Cm
2
1000 ppb
100 Kg/Cm
2
2220 ppb
65 Kg/Cm
2
4000 ppb
Boiller Drum Pressure is to be maintained as such,
Silica value in Main Steam maintain bellow 20 ppb.
DISTRIBUTION RATIO BETWEEN
STEAM & BOILER WATER AT pH 9.5
82 9 October 2014
PARTITION COEFFICIENT AT
DIFFERENT PRESSURES
10
0


10
-1


10
-2


10
-3


10
-4


10
-5


10
-6


10
-7

226 220 200 180 160 140 120 100 50 40 30
PRESSURE ( BAR)
83 9 October 2014
By evaporation from the boiler drum
By entrainment of boiler water droplets in
saturated steam.
As impurity present in feed water used in desuper
heater spray.

SOURCES OF IMPURITIES IN
STEAM
84 9 October 2014

Silica has high partition coefficient, so it has
tendency to deposit from steam onto turbine.

Silica can deposit on turbine blades specially on
LP turbine, which can lead to significant loss of
output.
EFFECTS OF SILICA
85 9 October 2014
L.P.DOSING
AMMONIA & HYDRAZINE HYDRATE DOSING

AMMONIA IS USED TO INCREASE THE pH OF
THE SYSTEM.
N
2
H
4
+ O
2
N
2
+ H
2
O
3N
2
H
4
4NH
3
+ N
2
86 9 October 2014
COORDINATED PHOSPHATE CONTROL

Na
3
PO
4
+H
2
O Na
2
HPO
4
+ NaOH
Na
2
HPO
4
+H
2
O NaH
2
PO
4
+ NaOH
NaOH + HCl (As Impurity) NaCl + H
2
O
H.P. DOSING
87 9 October 2014
Tri sodium phosphate provides the needed alkalinity in boiler systems
as follows :
o Na
3
PO
4
+ H
2
O === NaOH + Na
2
HPO
4

Absorption

of contaminants :
o 10Ca
2+
+ 6PO
4
3--
+ 2OH
--
3Ca
3
(PO
4
).Ca(OH)
2

calcium hydroxyapetite
o 3 Mg
2+
+ 2SiO
3
2-
+ 2OH
--
+ H
2
O
3MgO.2SiO
2
.2H
2
O
serpentine
Calcium hydroxyapetite and serpentine exist as soft sludges
and much easier to remove ; typically settle in the drum
and removed by blow down
Boiler water treatment
88 9 October 2014
program favourable unfavourable
Coordinate
dphosphate
Caustic corrosion may be
eliminated; deposit form ..
easy for removal ; acids
neutralized; surface
passivation by phosphate
Possible under-deposit
corrosion by concentrated
sodium hydroxide ;
Hide-out
Congruent
Phosphate
Na:PO
4

(2.6:1)
Caustic corrosion mostly
eliminated ; deposit form ..
Easy for removal ; acids
neutralized ; surface
passivation by phosphate
Controlling molar ratio of
Na and PO
4
;
Hide-out
Sodium
hydroxide
Acid neutralization ;
No phosphate hide-out
Can cause rapid corrosion
when concentrated (specially
under deposit ) ; vaporous
carryover in steam at high
pressure ; dosing control very
essential
CHEMICAL TREATMENT PROGRAMS CHARACTERISTICS
89 9 October 2014
program favourable unfavourable
All volatile
deposition of salts can be
eliminated ; high purity
steam under ideal feed
water conditions ; no carry
over of solids
Feed water contamination may
exceed inhibiting ability of
volatile feed , leading to boiler
corrosion ; marginal acid
neutralization ; no protection
during mild hardness ingress

oxygenated
treatment
Low corrosion rates of
ferritic steels and conden-
ser tubes ; better oxide
coating , hence frequency
of chemical cleaning
increased
Can tolerate very low
concentration of impurities ; no
corrosion protection in case of
upset ; copper alloys should not
be used in the system ; requires
excellent purity feed water ;
precise chemical control required
CHEMICAL TREATMENT PROGRAMS
CHARACTERISTICS
90 9 October 2014

- Limits below 10 PPb

With low D.O. concentration, copper
corrosion is inhibited by a passive film of
Cuprous Oxide(Cu
2
O).
LOW D.O.
REGIME
91
HIGH D.O.
REGIME

- Limits 2 to 5 PPM

With high D.O. concentration, copper
corrosion is inhibited by a passive film of
Cupric Oxide(CuO).

92
Health of a
boiler
Water
chemistry
control
Health of heat
exchanger tubes

93 9 October 2014
Cycle chemistry guidelines
Most sensitive part in the plant cycle
TURBINE
Chemistry limits established for
steam





Boiler water
Feed water
Make-up
water
94 9 October 2014
Condensate plus make-up water
Virtually all impurities carried into
the boiler through the feed water

Condensate :
Corrosion in the pre-boiler section ;
subsequent transport to the economizer ,
boiler and subsequent deposition high
heat zones

Make-up water : Though less prevalent
can carry hardness salts and silica



Feed water chemistry
95 9 October 2014
Steam purity affected by carryover --- the process
by which solids are transported to steam

Carryover influenced by
silica carry over as vapour
solids become more soluble at high pressures
drum level , drum design (internals) , foaming

Contaminants can also enter via attemperator
systems ; greatly exacerbated during upset
conditions such as a condenser leak
Steam Chemistry
96 9 October 2014
Can occur anywhere in
a Boiler
Water- or steam-
cooled tubes :
Water walls
Screen / roof
tubes
SH / RH tubes

Tube failure locations in a
boiler
97 9 October 2014
Tube Sampling
^ Representative
^ Heaviest deposit
formed location
O 2 to 3 meters
above the top
most burner
Problem areas in
specific units
{ Horizontal / sloped etc }

98 9 October 2014
How tube / turbine blade failures can look like ?
99 9 October 2014

Tube failure control
starts with
Design
Manufacture
Shipping , Storage & Construction
Quality control
Cleanliness of the tube surfaces by
chemical cleaning
100 9 October 2014
New units
Internal surfaces of heat exchanger tubes to
be clean --- before put into service

^Oil , grease , sand etc removed by alkali
cleaning (acid pickling ) for removal of rust
and surfaces of the tubes to protect from
corrosion (passivation)
101 9 October 2014
Chemical cleaning of boilers
Condensate & feed water system
mechanical cleaning ; alkaline flush
Economiser & Boiler tubes
alkali boil out ; acid cleaning ; passivation
^ Super heater , steam piping & Re heater
scavenging with steam

102 9 October 2014
Magnetite , Ferric oxide ,

{ Fe
3
O
4
}

{

Fe
2
O
3
}


Colour black brownish red

Binding tightly binds flakes off easily
nature to base metal from base metal

w.r.to protects the does not protect
corrosion base metal the base metal
{significance}
Why passivation ?
103 9 October 2014
Boiler tube before cleaning
Boiler tube after
cleaning
Black magnetite layer
(protective)
104 9 October 2014
Objectives of water chemistry practice

Reduce corrosion of metals
C Prevent formation of deposits
C Produce good quality steam
{ without carryover of boiler
water solids }
105 9 October 2014
Quantity of deposit Surface cleanliness

Less than 15 mg /sq.cm. Clean surface
15 to 40 mg / sq.cm. Moderately dirty
more than 40 mg /sq.cm. Dirty

Chemical cleaning should be done whenever deposits are more than 40
mg / sq.cm .
once in 4 years as a mandatory maintenance practice
( guidelines only / not a rule or code ) BIS : 10391



Quantity of deposit and unit cleanliness
106 9 October 2014
Sources :
water borne materials
C treatment chemicals
C corrosion products
contaminants

Hardness salts { Ca & Mg salts , silica }
C Dosing chemicals { PO
4
, NH
3
, N
2
H
4
esw..}
C Pitting & pre-boiler corrosion products
Through condenser leak ; attemperation
water ; regeneration chemical slip & so on



Deposition in boiler tubes
107 9 October 2014
Reduced heat transfer
{ Ca , Mg salts & silica ..almost insulating }
Complicates subsequent post-
operational chemical cleaning
{ Cu multi-step cleaning may be
needed }
^ Chemical cleaning may be ineffective
{ Ca , Mg , Silica may not be completely
removed if present in huge quantities }
+ Under deposit corrosion







Deposition in boilers consequences
108 9 October 2014
UNDER DEPOSIT CORROSION
Water wall tube
without deposit
Water wall tube
with deposit
109 9 October 2014
UNDER DEPOSIT CORROSION

Na
3
PO
4
+ H
2
O
Na
2
HPO
4
+

NaOH
Boiler water with Na
3
PO
4
,

Na
2
HPO
4
, NaOH
enter through the pores of the
deposit.
Only water comes out as
steam, leaving the solids to
concentrate
NaOH concentrations as high as 10,000
ppm have been reported
HEAT
110 9 October 2014
WHAT IS CORROSION
CORROSION IS A NATURAL PROCESS BY VIRTUE OF
WHICH THE METALS TEND TO ACHIEVE THE
LEAST ENERGY STATE I.E. COMBINED STATE
M M
2+
+ 2e
-

ANODIC REACTION
N
2-
+ 2e N
CATHODIC REACTION
111 9 October 2014
MECHANISM OF CORROSION
Corrosion Cell
Na
+
Ca
++
Cl
-
SO
4
-
O
2
OH
Fe
++
H
+
Water
Anode Steel Cathode
Electrons
Fe
+
Fe
+
Fe
+
Fe
+
Fe(OH)
2
Fe(OH)
2
Fe
++
OH

O
2
H
+
H
2
H
+
H
+
112 9 October 2014
Corrosion of boiler steel
Factors responsible for corrosion

pH

Dissolved oxygen
113 9 October 2014
Corrosion of steel vs boiler water pH
safe range
8.5 11.0
pH

Corrosion
rate
acidic alkaline
4
8 10 12 6 14
114 9 October 2014
Forms of corrosion
Caustic corrosion
Hydrogen damage
Pitting
Pre-boiler corrosion
Stress corrosion cracking
115 9 October 2014
Caustic corrosion
Alkali-producing chemicals dosed in boiler
water to maintain the optimum pH
Na
3
PO
4
+ H
2
O Na
2
HPO
4
+ NaOH
Corrosive action of sufficiently concentrated
alkali on boiler tubes leads to corrosion
Fe
3
O
4
+ 4 NaOH 2 NaFeO
2
+ Na
2
FeO
2
+ 2H
2
O
{ black magnetite eaten away }
Fe + 2 NaOH Na
2
FeO
2
+ H
2

{ parent metal attacked }





116 9 October 2014
CAUSTIC DAMAGE

117 9 October 2014
Caustic gouging

Caustic gouging
118 9 October 2014
Hydrogen damage occurs in boilers operated
with low pH water chemistry
by aggressive anions like chlorides
concentration of acidic species under
deposits
During periods like condenser leakage ,
specially in sea-cooled power plants , lots of
acidic species are introduced

MgCl
2
+ 2 H
2
O Mg(OH)
2
+ 2 HCl
Hydrogen damage
119 9 October 2014
Atomic hydrogen can diffuse into steel
and react with iron carbide
Fe
3
C + 4 H 3 Fe + CH
4
Methane , being a bigger molecule , can not
diffuse ; but accumulate at grain boundaries
Stresses at grain boundaries produce
intergranular micro-cracks [making tube brittle ]
Thick-walled burst occurs { large , rectangular
section of the wall blown out with a big hole }
[ brick structure without mortar ]
Hydrogen damage
120 9 October 2014
HYDROGEN DAMAGE
121 9 October 2014
Hydrogen damage
thick walled burst

Hydrogen damage
rupture of the tube
122 9 October 2014
HYDROGEN DAMAGE
123 9 October 2014
General description :
^ oxygen chemical agent { plus moisture }
^ idle boiler affected more than the running boiler
protective magnetite attacked
4 Fe
3
O
4
+ O
2
6 Fe
2
O
3

^ unprotected metal attacked
2 Fe + H
2
O + O
2
Fe
2
O
3
+ H
2

^ Corrosion product carried to other parts of the
boiler ; gets deposited on the high heat zones
Pitting corrosion
124 9 October 2014
^ Entire boiler system susceptible
^ Economizer & feed water heaters
^ Re heaters , especially where moisture can
collect in bends and sags in the tubes
^ Severe oxygen contamination ,
other parts ( WW ) of the metal affected
^ Result :
deep , distinct , almost hemispherical spheres
pits may be covered with corrosion products


Pitting corrosion --- Locations
125 9 October 2014
126 9 October 2014
^ In modern high pressure boilers pre-boiler
corrosion . Largest cause of failure
^ pre-boiler condenser , feed water heaters and
deaerator
^ Corrosion products
iron oxides , copper oxides , metallic copper ,
and oxides of zinc & nickel { small amounts }
^ Corrosion products are introduced as particles
into feed water ; get deposited on high heat zones
Pre boiler corrosion
127 9 October 2014
Pre-boiler corrosion
thick layer of iron oxide
128 9 October 2014
Pre-boiler Corrosion
Elemental copper on water wall tube
along with oxides of iron
129 9 October 2014
Salient points :
Agents causing this type of corrosion
. Oxygen and ammonia
Iron and copper protected by their oxides
Fe
3
O
4
and Cu
2
O , which adhere to the metal
Oxides attacked by excess oxygen
4 Fe
3
O
4
+ O
2
6 Fe
2
O
3
2 Cu
2
O

+ O
2
4 CuO
Fe
2
O
3
& CuO get peeled off { non-protective}
and transported to economizer & boiler
Pre-boiler corrosion
130 9 October 2014
Dissolved oxygen attacks copper in the presence of
ammonia more severely as follows :
2 Cu
2
O + O
2
4 CuO
CuO + 4 NH
4
OH Cu (NH
3
)
4
(OH)
2
+ 3 H
2
O
(insoluble) ( soluble )
The corrosion product is transported more easily in
a soluble form into the boiler
The copper-ammonia complex decomposes inside
the boiler at elevated temperatures ( > 140
o
C )
The liberated free copper gets deposited on the
heat transfer surfaces


Pre boiler corrosion
131 9 October 2014
^ Result of combined interaction of
Tensile stress { internal pressure , residual
stresses induced by bends , supports , welds .. }
Corrosive environment { chlorides , sulphates ,
hydroxide..}
Susceptible material
^ Stress corrosion causes brittle failure of metals
at stresses less than those necessary to cause
failure in a non-corrosive environment

Stress Corrosion Cracking
132 9 October 2014
Stress Corrosion Cracking
Transverse crack resulting from
caustic stress corrosion in a
stainless steel super heater tube

Extensive longitudinal crack in a
stainless steel line

133 9 October 2014
Failure locations
austenitic stainless steel used SH & RH
low pressure stage turbines in contact
with saturated or wet steam
SCC produces tight , hairline cracks
sometimes difficult for visual observation
also can be thick-walled fracture
cracks may be transgranular or intergranular
microscopic examinations needed
SCC --- Critical factors
134 9 October 2014
Recommended guidelines in entire water steam cycle to
be followed always !
C Special care to be taken in controlling and monitoring
dissolved oxygen , silica , & cation conductivity
C Critical periods of water chemistry
Start ups Condenser leakage lay- up
Periodic chemical cleaning --- a routine maintenance step to
keep heat exchanger tubes clean
C Management support :
on-line and laboratory measurement facilities
updating chemical technology knowledge base


CRITICAL FACTORS IN WATER CHEMISTRY
135 9 October 2014
136 9 October 2014