WATER CHEMISTRY

GUIDELINES FOR
HIGH PRESSURE BOILERS

PUB.NO. 2003

CONTENTS
1.0 GENERAL
1.1 MAKE - UP WATER TREATMENT
1.2

INTERNAL CORROSION

1.3

EFFECT OF pH

1.4

EFFECT OF OXYGEN

1.5 BOILER WATER TREATMENT

1.6 CONDENSER LEAKAGE
FIG.1

RELATIVE CORROSION RATE OF CARBON STEEL VS pH

FIG.2

SILICA VS DRUM PRESSURE

FIG. 3

SILICA IN BOILER WATER VS DRUM PRESSURE

FIG. 4

OPERATION BETWEEN 70 - 125 kg/cm2

FIG. 5

OPERATION BETWEEN 126 - 165 kg/cm2

FIG. 6

OPERATION BETWEEN 166 - 182 kg/cm2

FIG. 7

OPERATION BETWEEN 183 - 203 kg/cm2

RECOMMENDED FEED WATER LIMITS

BOILER WATER LIMITS
GUIDELINES FOR EMERGENCY OPERATIONS
HOT WELL CONDITIONS FOR ALL VOLATILE TREATMENT

WATER TREATMENT
1.0 GENERAL
High pressure boiler (operating above 60 kg/cm2 ) design needs a close look at the limiting
conditions like heat transfer, heat exchanger metal temperature,circulation etc., The entire
exercise of Water Treatment (both internal and external treatments) is aimed at (1) corrosion
control and (2) steam quality. The cost of corrosion and deposition to electric utilities is very
high due to repairs and loss of production (shutdowns).Poor steam quality leads to deposition
on turbine blades causing efficiency loss and failures .Thus the successful operation of high
pressure boilers and turbine units require a strict vigil on the Water Treatment practices and
controls, particularly for high pressure drum type and once through boilers.
1.1 MAKE - UP WATER TREATMENT
Trouble free continuous operations of high pressure boilers call for very stringent feed water
quality. Total solids and silica, other than corrosion products,being the main constituents are
responsible for carry-over and deposition reducing the units efficiency. Make up water is
required to becontrolled and maintained at low levels. Silica in particular, is CARRIEDOVER
in the form of VAPOUR at high pressures, needs to be controlled at low levels.Feed water is
used for de-superheating spray and any contamination of feed water (either from steam
condensate or from make up water) directly enters the superheated steam . IMPURE FEED
WATER increases BLOW DOWN making the operation un-economical.Hence feed water is
required to be very pure for high pressure boilers. This inturn necessitates high purity
make up water, other than polishing the steam condensate, wherever applicable. Modern
demineralisation plants with different combinations of ion-exchangers, are capable of producing
the required quality of make up water with specific electrical conductivity less than 0.2 micro
mhos/cm and silica 0.02/0.01 ppm.
1.2 INTERNAL CORROSION
Corrosion is a common phenomenon in high pressure boilers. Corrosion in boiler circuits as
well as in pre-boiler circuits can cause tube failures followed by force shut down of boilers.

The causes of corrosion are,

i.
ii.
iii.
iv.
v.
vi.

pH ( acidity or high alkalinity )

Oxygen
Excessive ammonia (on copper base alloys )
Concentration of alkalising agents due to localised over heating
Poor quality of passivating layer or breaking of passivating layer due to thermal
shocks
Decomposition of organics into corrosive products.

1.3

EFFECT OF pH
The reaction of feed water on steel is spontaneous and rapid at high temperatures. The only
reason that boiler steel can survive normal operating conditions is that the passivated layer of
magnetite ( Fe3 O4 ) / hydrated iron oxide (FeOOH) forms a protective layer on the steel surface,
preventing corrosion. The whole exercise of maintaining alkalinity control is to maintain an
environment in which the oxide film is stable and protective. One of the objectives of Water
Treatment in boilers is to protect this film against the aggressive action of impurities introduced
into the boiler with the feed water.
The work of Bell and Van Track has been used to relate the relative corrosion of steel over a
range of pH values. It was found that the protective layer is getting dissolved at pH values
below 5.0 and above 13.0 Minimum corrosion is indicated at pH of 9.0 to 11.0 (Fig. 1)
Although corrosion is low over a wide band of pH values, unfortunately, corrosion occurs by
localised concentration of alkaline chemicals on tube metal due to starvation, localised over
heating etc. Rather than the concentrations existing in the bulk boiler water. Local concentration
changes the pH drastically and corrosion takes place. Due to limitations of chemicals used, an
optimum pH of 8.8 to 9.2 is recommended for feed water, which can be achieved by use of not
more than 0.5 pprn of ammonia. Any excess presence of ammonia (indicated by higher pH
values) will cause copper corrosion in the pre-boiler system.
Another parameter which affects corrosion rate is the temperature inside the reaction vessel.
Hence different temperature ranges or the pressure ranges call for different pH values to be
maintained in order to minimize corrosion.
Accordingly boiler water pH requirements are higher than the feed water limits and different
for different pressure ranges. Boiler water pH is elevated to the recommended levels using
Trisodium phosphate. The use of caustic soda is not recommended for this purpose as it has
the danger of concentration and destruction of protective oxide film to cause corrosion.

1.4

EFFECT OF OXYGEN
The exclusion of oxygen in feed water is essential to avoid corrosion. Small quantities of
dissolved oxygen are capable of causing severe corrosion pitting in boiler tubes. A combination
of poor oxygen control and chlorides in boiler water can result in serious hydrogen damage
type corrosion of water wall tubes. Power plants employee tight cycles to prevent oxygen
infiltration and condenser leakage are generally free from corrosion problems. Continuous
monitoring of oxygen is required in high pressure system.
Too often, oxygen enters the system undetected during periods of operation which are poorly
monitored. Poor start-up procedures are also responsible for oxygen ingress. A most common
error is the use of undeaerated water. Feed water at a temperature less than 100 deg. C contains
excessive quantities of dissolved oxygen and hence feed water should never be allowed into
the boiler at any time below this temperature.Deaerator is the main equipment to control
oxygen within 0.01 - 0.02 ppm.

The best deaeration is obtained in units which operate above atmospheric pressure at all load
conditions. A normal contamination of feed water occurs, when the deaerator pressure varies
with a turbine bleed stage from above atmospheric to vacuum at low loads. Heater drips from
low pressure system contain varied quantities of oxygen. A significant oxygen increase occurs
in the heater drips as a heater drops below atmospheric pressure at low loads. A major problem
of oxygen leakage occurs at low loads when heater drips are pumped directly to the condensate
system. It is preferable to exhaust the drains to the deaerating section of the condenser.
The most serious corrosion occurs in boilers which shut-down and start-up frequently without
incorporation of technique to minimise oxygen in the feed water. Much of the problems can
be reduced by pressurising the deaerator with steam at about 0.5 kg/cm2 (g) to exclude oxygen
from the water during any short outage. For long outages, the vapour and water contacted
surfaces of the feed water system should be pressurised with steam or nitrogen.
With the main oxygen removal by deaeration, residual oxygen in small quantities can be
reduced further by reducing agents such as sodium sulphite or hydrazine.Hydrazine being a
volatile chemical, should only be used for high pressure boilers. Hydrazine reacts with oxygen
to form nitrogen and water. This reaction is very low at temperatures below 175o C. Above
230o C, Hydrazine is decomposed rapidly to nitrogen, hydrogen and ammonia. Hence hydrazine
dozing alone cannot control oxygen without effective deaeration. Since hydrazine has also
the property of passivating the metal surfaces of the pre-boiler cycle by reducing the oxidised
form of iron and copper, it is advantageous to add hydrazine to the cycle at the outlet of the
condensate pump.
1.5 BOILER WATER TREATMENT
It is recommended to use co-ordinated phosphate - pH treatment ( Sodium to phosphate
ratio = 3) method for high treatment excludes free caustic from the boiler water. Caustic
present in boiler results in a ductile-gouging type corrosion. Even if bulk boiler water does
not contain large amount of free caustic, there is great potential for caustic to concentrate and
cause corrosion. Internal metal oxide deposits provide sites for concentration. As steam is
produced, dissolved solids concentrate in the thin film between tube wall and bulk fluid. Low
sloped tubes permit concentration. It has been well established that phosphate even concentrated
under hide-out conditions is not aggressive to the tube metal.
Congruent phosphate program (Sodium to phosphate ratio = 2.6) takes care of both caustic
and acid corrosion but control of sodium to phosphate ratio is difficult, calling for continuous
feed and blow down.
Figs. 4 to 7 provide guidelines to use either of the programmes, subject to the operators
convenience.
Volatile treatment is another method of treatment but it is primarily to control corrosion of
heater surfaces in the pre - boiler circuit. Chemicals such as ammonia, cyclohexylamine and
morpholine are volatile at high pressure boiler water temperatures. As a result there is no
significant buffering of boiler water pH due to these chemicals. Any ingress of condenser
leakage contaminants requires the immediate addition of phosphate to prevent the depression
of pH and the incidence of hydrogen damage. The main attraction of volatile treatment is that
it assures good steam purity .
5

Impurities due to vaporization of salts and mechanical carry-over are at a minimum.But it is

necessary to employ condensate polishing and have reliable instrumentation for detecting
immediately any condenser leak to safety operate with volatile treatment.
1.6 CONDENSER LEAKAGE
Condenser leakage, as mentioned earlier, is a major source for corrosion. The type of cooling
water and its interaction with boiler water determines whether b oiler water pH will become
more acidic or alkaline during a period of condenser leakage. It is very important to prevent
condenser leakage of sea water as it results in acidic boiler water. The hardness chloride salts
present abundantly in sea water generate hydrochloric acids at boiler water temperatures.
Uncontrolled large leakages of sea water can cause within hours extensive corrosion (hydrogen
damage) of water wall tubes. There should be no hesitation to shutdown and save the unit if
boiler water specifications,as recommended cannot be maintained during the condenser leakage.
Any unit should have an on-line instrument with a cation column at the outlet of condenser to
monitor conductivity continuously and detect immediately any condenser leakage.

FIG.1 RELATIVE CORROSION RATE OF CARBON STEEL VS pH

FIG.2 SILICA VS DRUM PRESSURE

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FIG. 3 SILICA IN BOILER WATER VS DRUM PRESSURE

FIG. 4 OPERATION BETWEEN 70 - 125 kg/cm2

FIG. 5 OPERATION BETWEEN 126 - 165 kg/cm2

FIG. 6 OPERATION BETWEEN 166 - 182 kg/cm2

FIG. 7 OPERATION BETWEEN 183 - 203 kg/cm2

RECOMMENDED FEED WATER LIMITS

100 and above

ONCE
THROUGH
BOILERS

DRUM OPERATING PRESSURE

Kg/cm2 (g)

61-100

TREATMENT TYPE
1. Hardness ppm (max)

P04
NIL

2. pH at 250C

8.8-9.2 8.8-9.2 8.8-9.2 8.8-9.2

3. Sp. electrical conductivity after

cation in H+ form at 250 C micro
mho s/cm (max)

0.50

0.30

0.20

0.20

4. Dissolved oxygen ppb (max)

5.0

5.0

5.0

5.0

5. Silica as SiO 2 ppb (max)

20.0

20/10* 10

10

6. Iron as Fe ppb (max)

10

10

10

7. Copper as Cu ppb (max)

10

5/3*

8. Residual Hydrazene ppb

10-20.

10-20

10-20

10-20

P04
NIL

AVT
NIL

AVT
NIL

* Should match with the corresponding values to be maintained in super heated steam
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BOILER WATER LIMITS

(FOR DRUM TYPE BOILERS NORMAL OPERATION)

DRUM OPERATING
PRESSURES Kg/cm 2 (g)

61 90

91 125

125 165

165 180

181 & above

TREATMENT TYPE

PO4

PO4

PO4

PO4

PO4

1. Total Dissolved solids

ppm (max )
2. Sp. Electrical conductivity
micro. mhos/ cm (max)
3. Silica as Sio 2 ppm (max)

100

100

50

200

200

100

10
1.0
(Note)
20
2.0

4.0

0.20

0.10

0.10

4. Chlorides
5. pH at 25o C

9.0-10.0
5 20

To be
controlled as
per fig.2&3
9.0-10.0
5 20

15
2.0
(Note)
30
4.0
(Note)
0.10
0.10

9.1-9.8
5 20

0.6
9.1-9.7
26

0.50
9.1-9.7
26

0.01
9.3-9.5
N/A

ppm (max)

6. Phosphate, residual

ppm

* NOTE : Total solids 15 & 10 ppm correspond to 10 ppb sodium steam

10

AVT

0.02
9.3-9.5
N/A

AVT

GUIDELINES FOR EMERGENCY OPERATIONS

(DRUM TYPE - PHOSPHATE TREATMENT)
SI.NoPressure Hot well solids Operational
.
range
ppm
Limitations
kg/sq c.m (g)
01

02.

03.

6 1 -1 2 5

1 2 6 -1 6 5

1 6 6 -1 8 0

0 . 5 -.2.0
(ABNORMAL)

Limited
operation
Note.1

> 2.0
(EXCESSIVE)

Emergency
operation Note.3
Limited
operation
Note. I

0 . 5 -2 . 0
(ABNORMAL)

> 2.0
(EXCESSIVE)
0 . 2 5 -1 . 0
(ABNORMAL)

> 1 .0
(EXCESSiVE)
04.

1 8 1 -2 0 3

0 . 1 -1 . 0
(ABNORMAL)

> 1.0
(EXCESSIVE)

Emergency
operation Note.3
Limited
operation
Note. 1
Emergency
operation
Note.3
Limited
Operation Note 1
Emergency
operation Note.3

Control
Limits

TDS< 200
pprn
p H 9 . 1 - 10.1
P 0 4 5 -4 0 p p m

Boiler
Water
Control
NOTE 2

NOTE 4
-D O TDS<100ppm
p H 9 . 1 - 10.1
P 0 4 5 -2 0 p p r n

NOTE2

-D O -

NOTE4

TDS<50ppm
p H 9 . 1 - 10.1
P 0 4 5 -2 0 0 ' p r n

NOTE2

-D O TDS<50ppm
pH 9 . 1 - 10.1
P 0 4 5 -2 0
PPM

NOTE4
NOTE2

NOTE4
-D O -

NOTE 1: Schedule Inspection and repair of condenser as soon as possible

NOTE 2: Immediately start chemical injection to achieve higher phosphate and pH condition
not continue operation if pH cannot be maintained above 8 total solids below specified
limits. Avoid use of desuper heating spray.
NOTE 3: Immediately reduce load to permit isolation of damaged condenser and prepare for
orderly shutdown if hot well TDS cannot be re duced quickly below specified limits.
NOTE 4: Prepare for wet lay up of the boiler
NOTE 5: Control silica in boiler water in accordance with graph provided.

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HOT WELL CONDITIONS FOR ALL VOLATILE TREATMENT

(FOR DRUM TYPE BOILERS)

PRESSURE RANGE
(Kg/sq.cm)

126-165
Above 166
Note:

HOT WELL SOLIDS (PPM)

NORMAL
OPERATION

EMERGENCY
OPERATION

< 0.05
< 0.05

< 0.1 PPM

< 0.25 PPM

Switch over to phosphate treatment when hot well solids exceed emergency operation
levels.

GENERAL INSTRUCTIONS
1 . All Feed water measurements shall be made at high pressure heater outlet or economiser inlet
.
2. Oxygen can also be additinrially measured at deaerator outlet to determine the quantity of
N2 H4 dozing .
3. The recommended pH in feed water can be obtained by dozing ammonia, morpholine or any
volatile amine. The concentration of volatile chemical in the feed water should not exceed
0.5 ppm.(expressed as Ammonia)
4. The phosphate and pH are recommended in accordance with co-ordinated phosphate curves
(Figs. 4 to 7) to prevent presence of free hydroxide in boiler water.
5. Water levels in drum should be maintained within limits during all operational modes, start-up,
load fluctuation and normal operation.
6. The allignment of drum internals should be checked and ensured to be in order atleast once
every year
7. It is needless to emphasize that correct sampling, accurate measurements with the use of
reliable instruments at adequate intervals and proper logging of readings go a long way in
ensuring trouble free operation.

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