WATER CHEMISTRY

GUIDELINES FOR
HIGH PRESSURE BOILERS

1 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

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 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 unit’s 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. pH ( acidity or high alkalinity )

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

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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.

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 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 .
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 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

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FIG. 5 OPERATION BETWEEN 126 - 165 kg/cm2

FIG. 6 OPERATION BETWEEN 166 - 182 kg/cm2

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 FIG. 7 OPERATION BETWEEN 183 - 203 kg/cm2

RECOMMENDED FEED WATER LIMITS

ONCE
DRUM OPERATING PRESSURE 61-100 100 and above THROUGH
Kg/cm2 (g) BOILERS

TREATMENT TYPE P04 P04 AVT AVT

1. Hardness ppm (max) NIL NIL NIL 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 0.50 0.30 0.20 0.20

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

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 5 10 10

7. Copper as Cu ppb (max) 10 5/3* 3 3

8. Residual Hydrazene ppb 10-20. 10-20 10-20 10-20

* 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 61 – 90 91 – 125 125 – 165 165 – 180 181 & above
PRESSURES Kg/cm 2 (g)

TREATMENT TYPE PO4 PO4 PO4 PO4 AVT PO4 AVT

1. Total Dissolved solids 100 100 50 15 2.0 10 1.0
ppm (max ) (Note) (Note)
2. Sp. Electrical conductivity 200 200 100 30 4.0 20 2.0
micro. mhos/ cm (max) (Note)
3. Silica as Sio 2 ppm (max) 4.0 To be 0.20 0.10 0.10 0.10 0.10
controlled as
per fig.2&3
4. Chlorides ppm (max) - - - 0.6 0.02 0.50 0.01
5. pH at 25o C 9.0-- 9.0-- 9.1-- 9.1-- 9.3-- 9.1-- 9.3--
10.0 10.0 9.8 9.7 9.5 9.7 9.5
6. Phosphate, residual ppm 5 – 20 5 – 20 5 – 20 2–6 N/A 2–6 N/A
* NOTE : Total solids 15 & 10 ppm correspond to 10 ppb sodium steam

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 GUIDELINES FOR EMERGENCY OPERATIONS
(DRUM TYPE - PHOSPHATE TREATMENT)

SI.NoPressure Hot well solids Operational Control Boiler

. range ppm Limitations Limits Water
kg/sq - Control
c.m (g)
01 6 1 -1 2 5 0 . 5 -.2.0 Limited TDS< 200 NOTE 2
(ABNORMAL) operation pprn
Note.1 p H 9 . 1 - 10.1
P 0 4 5 -4 0 p p m
> 2.0 Emergency
(EXCESSIVE) operation - NOTE 4
Note.3 -D O -
02. 1 2 6 -1 6 5 0 . 5 -2 . 0 Limited TDS<100ppm NOTE2
(ABNORMAL) operation p H 9 . 1 - 10.1
Note. I P 0 4 5 -2 0 p p r n

Emergency
> 2.0 operation - -D O - NOTE4
(EXCESSIVE) Note.3
03. 1 6 6 -1 8 0 0 . 2 5 -1 . 0 Limited TDS<50ppm NOTE2
(ABNORMAL) operation p H 9 . 1 - 10.1
Note. 1 P 0 4 5 -2 0 0 ' p r n

> 1 .0 Emergency
(EXCESSiVE) operation -D O - NOTE4
Note.3
04. 1 8 1 -2 0 3 0 . 1 -1 . 0 Limited TDS<50ppm NOTE2
(ABNORMAL) Operation - pH 9 . 1 - 10.1
Note 1 P 0 4 5 -2 0
PPM
> 1.0 Emergency
(EXCESSIVE) operation - NOTE4
Note.3 -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 HOT WELL SOLIDS (PPM)

(Kg/sq.cm) NORMAL EMERGENCY
OPERATION OPERATION
126-165 < 0.05 < 0.1 PPM
Above 166 < 0.05 < 0.25 PPM

Note: 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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