ROLE OF CHEMISTRY IN

POWER PLANT

FEB
24/2004
 CONTENTS OF THE
PRESENTATION

FEB
24/2004
Feed water treatment

FEB
24/2004
Insoluble impurities are very largely
metal oxides derived from corrosion
of the plant itself, particularly the
materials of construction of the
condenser and feed systems. Such
corrosion is minimised by maintaining
the feed water at an alkaline pH and
by removing dissolved oxygen down
to very low concentrations.
Soluble impurities in feed water
most frequently arise from in
leakage of cooling water from
condensers and other coolers, but
can also results from poor quality of
make-up water.
 Parameters 200 MW 500 MW
Boiler Pressure, 150-170 185-195
Kg/cm2
pH at 25C 8.8-9.0 9.0-9.2
ACC Cond. m/cm, 0.2 0.2
Silica, ppb, (Max) 20 10
DO, ppb, (Max) 5.0 5.0

Res. N2H4, ppb 10-20 12-20

Total Fe, ppb, 10 10
(Max.)
Total Cu, ppb, 5 3
(Max.)
Ref: Code of Practice on Power Plant chemistry, by (OS) COS-ISO-00-
OGN-OPS-CHEM/015, Oct.2003
o Feed water pH- the use of volatile
alkalis (NH3)
o By making the pH of feed water slightly alkaline
(9.0-9.2) the corrosion rate of ferrous alloys
can be minimised. Where the system is also
contain copper based alloys similar benefits
can be obtained
o Oxygen Control
o Physical de-aeration
o Chemical de-aeration
There is no excessive accumulation of alkali in
the boiler water, the volatile alkali passing out
the boiler with the steam.
As condensate are formed in the lower pressure
section of the turbine, in the condensers and on
the steam side of the feed heaters, the alkali
immediately available in these parts of the
steam/water system, raising the ph of the
condensates and hence suppressing corrosion.
Ammonia (NH3) is the most widely used
volatile alkali because of its low cost, ready
available and its stability at high
temperatures
Physical de-aeration

De-
aerator
40 ppb D.O. in 5 ppb D.O
Condensate
Water Solubility Law &
Henry Law
Chemical de-aeration
The most widely used agent is Hydrazine (N 2H4).
It is steam volatile, slightly basic and reacting readily
to remove even traces of dissolve oxygen at
temperature above 1500C producing only volatile or
gaseous products, i.e.,
N2H4 + O2 N2 + H2O
At higher temperature hydrazine itself
decomposes to produce ammonia and nitrogen,
i.e.,
N 2H 4 4NH3 + N2
It is assumed that the reduction of oxygen by hydrazine probably
follows a heterogeneous reaction mechanism. It is common
experience to find that two or four weeks elapse after initiating
hydrazine treatment before a residual can be detected in the
boiler water. This is because of following reactions
6 Fe2O3 + N2H4 N2 + 2 H2O + 4 Fe3O4

4 CuO + N2H4 N2 + 2 H2O + 4 Fe3O4

likely that the actual reduction of oxygen takes place in two

steps involving the oxidation and reduction of oxides of iron.
4 Fe3O4 + O2 6 Fe2O3
6 Fe2O3 + N2H4 4 Fe3O4 + N2 + 2 H2O
To maintain boilers and turbines at a
high level of availability and efficiency,
the chemical control of water and steam
purity is aimed at the prevention of:
1.Corrosion of feed, boiler and steam
systems.
2.Scale and deposit formation on heat
transfer surfaces.
3.Deposition and corrosion of turbines.
Parameters 200 MW 500 MW

Boiler Pressure, 150-170 185-195

Kg/cm2
pH at 25C 9.2-9.5 9.1-9.4

Cond. S/cm, (Max) 30 30

Silica, ppm, (Max) 0.2 0.1

Phosphate, ppm 2-4 1-2

Chloride, ppm, 1.0 0.5

(Max.)

Ref: Code of Practice on Power Plant chemistry, by (OS) COS-ISO-00-

OGN-OPS-CHEM/015, Oct.2003
Trisodium phosphate (Na3PO4) and disodium
phosphate (Na2HPO4) can both effectively produce
alkalinity by hydrolysis in water:
Na3PO4 + H2O Na2HPO4 + NaOH
Na2HPO4 + 2 H2O NaH2PO4 + NaOH
The important difference between this source of
alkalinity and that produced by free caustic soda lies in
the reversibility of the above reactions. If acid species
appear in the boiler water they will be neutralised by
the sodium hydroxide:
HCl + NaOH NaCl + H2O
Recommended parameters of Super
heated Steam Purity Guidelines
Parameters 200 MW 500 MW
pH at 25C 8.8-9.0 9.0-9.2
ACC Cond. m/cm, 0.2 0.2
Silica, ppb, (max) 20 10
Sodium, ppb, (max) 5.0 5.0
NH3, ppm, (max) 0.5 1.0
Total Fe, ppb, (max.) 10 10
Total Cu, ppb, 5 3
(max.)
Ref: Code of Practice on Power Plant chemistry, by (OS) COS-ISO-00-
OGN-OPS-CHEM/015, Oct.2003
o Solubility of impurities in steam
decreases as steam expands in turbine
o NaCl and NaOH most corrosive chemicals
o Solubility of caustic exceeds 100 ppb at
HP turbine pressure and temp.
o In LP turbine, caustic solubility in steam
decreases and deposit concentration
goes up to 90%.
o 15 Conductivity analysers
o 5-6 pH analysers
o 1 multi-channel Silica analyser (@ 5
channels)
o 1 Hydrazine analyser
o 2-3 D.O. analysers
o 1-2 Sodium analysers
o 1 Phosphate analyser + some more...
 CEP discharge
Direct and after cation conductivity
measurements, supplemented by
sodium monitoring, to provide
warning of condenser leakage.
Dissolved oxygen measurements
are also required in order to
establish the adequacy of oxygen
removal at the condenser.
 Condensate Polishing Plant outlet
Conductivity, ACC, Reactive Silica,
Na+ in outlet water are required to
monitor the performance of the
plant and for need of resin bed
regeneration. Additionally, the
measurement of Chloride &
sulphate in the outlet water has
assumed increasing importance.
 De-aerator
D.O. measurement at Inlet & Outlet
of de-aerator.
For testing purposes it is necessary
to have the facility to sample and
monitor oxygen at both inlet and
outlet of the de-aerator to insure
satisfactory performance.
 FinalFeed Water
Conductivity, ACC, D.O, pH, Na+, Cl-,
SO--4 & Total Iron.
Comprehensive chemical monitoring
of feed water just before it enters
the boiler, to provide a final check
on quality and acceptability.
 BoilerWater
Conductivity, pH, Phosphate, Cl-,
reactive silica are required to
conform the correct boiler water
conditions are being maintained.
 Steam (SS & MS)
Measurement of pH, reactive silica,
ammonia, sodium, conductivity to
ensure that criteria based on the
need to minimize salt deposition in
the superheaters, reheaters and
turbines are being met.
A potential major source of ingress
of impurity into the boiler water
system is from leakage of cooling
water into the main condenser
steam space (because, steam space
is maintained by vacuum) which is
called condenser leakage
o Online sodium increases (normal <2ppb).
o After Cation Conductivity increases
( normal value <0.2 S/cm for 500MW
plant)
o Total hardness of condensate will be high.
o Boiler and condensate silica will go on
increasing and cannot be controlled
without CBD and/or CPU.
o Hot well makeup will be low as well as
level will be high.
o De-aerator level will go high.
1. Open CBD 100%, makeup will go
high. (Heat as well as DM water loss)
2. Increase the concentration of
phosphate and free alkalinity in
boiler.
3. Limit as for as possible the boiler
de-superheater spray water to
prevent contamination of the system.
4. Isolate one path of condenser, and
see the results and vice versa.
5. Put CPU into service if available.
If the leak is in minor in nature:
o In running units, isolate one half the
condenser at a time and minor the
chemical parameters and find out
which half is leaking.
o Isolate the leaky half portion.

o Plug or repair the leak.

o Normalise and comeback to full load.

 Firstis path detection
Flood test

Candle Test

Dye test

Foam Test

Bubbler Method
Parameters 200 MW 500 MW
pH at 25C 8.8-9.0 9.0-9.2
ACC Cond. m/cm, 0.3 0.2
Silica, ppb, (max) 20 10
DO, ppb, (max) 40 40
NH3, ppm, (max) 0.5 1.0
Total Fe, ppb, 10 10
(max.)
Total Cu, ppb, 5 3
(max.)
Sodium, ppb, max - 5

Ref: Code of Practice on Power Plant chemistry, by (OS) COS-ISO-00-

OGN-OPS-CHEM/015, Oct.2003
Condensate polishing is employed to
purify the return steam condensate
in order to meet the quality
requirements of high pressure
thermal cycles and minimize
consumption of make-up water.
 Improvement in the quality of
condensate and "cycle" clean up
Reduced blow down & make up
requirements
Improvement in boiler water quality
for drum type boilers
Quick start up and as a result, full
load conditions are reached early
giving economics
 S.NO. PARAMETER CONTROL LIMITS FREQUENCY
OF TESTING
WITHOUT WITH
ALKALIZER ALKALIZER
1. Conductivity at <1.5 <2.2 Continuous
25oC, S/cm (preferably
below 0.5)
2. Dissolved <100 <10 Continuous
oxygen, g/l
3. Total copper, <20 <20 Once in 2-
g/l months
4. Total iron, g/l <20 <20 Once in 2-
months
5. pH at 25oC 6.0-8.0 8.5-9.0 Once in 2-
months
Conductivity is the basic criteria of quality for the
stator cooling water and a low level must be
maintained to eliminate the possibility of
flashover.
Dissolved oxygen in stator water is the main
reason for corrosion.
Dissolved oxygen in stator cooling water is
generally removed by purging with nitrogen gas of
high purity (99.99%, min.). Removal of dissolved
oxygen depends on the nitrogen pressure which is
normally maintained at 0.2 kg/cm 2 with alarm for
nitrogen pressure in primary water tank set at 0.4
kg/cm2 for better efficiency.
A bypass ion exchange polishing plant is
commonly installed to control the conductivity
of the stator water and can also trap some of
the suspended matter in water.
Polishing plant is generally designed to treat
about 2-5% of total stator water flow. The
polisher contains a bed of mixed resins
consisting of strong cation resin in h-form and
strong anion resin in oh-form. Analysis of the
exhausted resin can be used to know how much
corrosion products are removed by the mixed
bed.
 IT Y N
T R IC N T
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