ROLE OF CHEMISTRY IN POWER

PLANT

Presented By: Dilip Kumar

O&M Chemistry, NTPC Ltd.

FEB 24/2004
CONTENTS OF THE PRESENTATION
FEED WATER TREATMENT

BOILER WATER TREATMENT

STEAM PURITY

STEAM WATER ANALYSIS SYSTEM

CONDENSER LEAKAGE

CONDENSATE PURIFICATION

GENERATOR CHEMISTRY

LUBE OILS/CONTROL FLUIDS OF TURBINES.

FEB 24/2004
 Feed water treatment

Feed water is the major source of soluble and

insoluble impurities entering the boiler and
therefore the principal aim of the feed water
treatment and monitoring is to minimize the
levels of such impurities.

FEB 24/2004
IMPURITIES IN FEED WATER

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.
IMPURITIES IN FEED WATER

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.
RECOMMENDED PARAMETERS OF FEED WATER
Parameters 200 MW 500 MW

Boiler Pressure, Kg/cm2 150-170 185-195

pH at 25°C 8.8-9.0 9.0-9.2

ACC Cond. µm/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, (Max.) 10 10

Total Cu, ppb, (Max.) 5 3

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

CHEM/015, Oct.2003
CONTROL OF IMPURITIES IN FEED WATER

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
ADVANTAGE OFF AMMONIAA
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
OXYGEN CONTROL WHY?
OXYGEN CONTROL
Physical de-aeration

De-aerator

40 ppb D.O. in 5 ppb D.O

Condensate Water
Solubility Law & Henry Law
OXYGEN CONTROL
Chemical de-aeration
The most widely used agent is Hydrazine (N2H4).
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.,
N2 H 4 + O 2 N 2 + H 2O
At higher temperature hydrazine itself decomposes
to produce ammonia and nitrogen, i.e.,
N2 H 4 4NH3 + N2
HYDRAZINE REACTIONS
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
BOILER WATER TREATMENT

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.
RECOMMENDED PARAMETERS OF BOILER
WATER GUIDELINES
Parameters 200 MW 500 MW

Boiler Pressure, Kg/cm2 150-170 185-195

pH at 25°C 9.2-9.5 9.1-9.4

Cond. µS/cm, (Max) 30 30

Silica, ppm, (Max) 0.2 0.1

Phosphate, ppm 2-4 1-2

Chloride, ppm, (Max.) 1.0 0.5

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

CHEM/015, Oct.2003
PH CONTROL OF BOILER WATER
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
STEAM PURITY

Recommended parameters of Super heated Steam

Purity Guidelines
Parameters 200 MW 500 MW
pH at 25°C 8.8-9.0 9.0-9.2
ACC Cond. µm/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, (max.) 5 3

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

CHEM/015, Oct.2003
STEAM IMPURITIES (SODIUM & SILICA)

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%.
STEAM WATER ANALYSIS SYSTEM
A 500 MW PLANT, SWAS WOULD HAVE
TYPICALLY,

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...
MONITORING OF STEAM/WATER CIRCUIT
CHEMISTRY
 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.
MONITORING OF STEAM/WATER CIRCUIT
CHEMISTRY
 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.
MONITORING OF STEAM/WATER CIRCUIT
CHEMISTRY
 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.
MONITORING OF STEAM/WATER CIRCUIT
CHEMISTRY
 Final Feed 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.
MONITORING OF STEAM/WATER CIRCUIT
CHEMISTRY
 Boiler Water
Conductivity, pH, Phosphate, Cl-, reactive silica
are required to conform the correct boiler water
conditions are being maintained.
MONITORING OF STEAM/WATER CIRCUIT
CHEMISTRY
 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.
CONDENSER LEAKAGE

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
DETECTION OF CONDENSER LEAKAGE

o Online sodium increases (normal <2ppb).

o After Cation Conductivity increases ( normal value
<0.2 µS/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.
PREVENTIVE/REMEDIAL ACTION

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.
LEAK LOCATION

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.

LOCATING THE SPECIFIC LEAK

 First is path detection

 Flood test

 Candle Test

 Dye test

 Foam Test

 Bubbler Method
RECOMMENDED PARAMETERS OF CONDENSATE
WATER GUIDELINES
Parameters 200 MW 500 MW
pH at 25°C 8.8-9.0 9.0-9.2
ACC Cond. µm/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, (max.) 10 10
Total Cu, ppb, (max.) 5 3
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 UNIT

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.
BENEFITS OF USING CONDENSATE POLISHING
UNITS
 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
STATOR WATER COOLING SYSTEM
 RECOMMENDED CHEMICAL CONTROL LIMITS
FOR GENERATOR STATOR PRIMARY WATER OF
500 MW SETS.
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 oxygen, <100 <10 Continuous
g/l
3. Total copper, g/l <20 <20 Once in 2-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

MONITORING AND CONTROL

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/cm2 with
alarm for nitrogen pressure in primary water tank set at 0.4
kg/cm2 for better efficiency.
STATOR POLISHING UNIT
STATOR POLISHING UNIT
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.
CORROSION OF COPPER VS. D.O.
OXYGEN VS. PH
THANKS !