BOILER WATER CHEMISTRY

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KORBA SIMULATOR 340
BOILER WATER CHEMISTRY
It is important to maintain proper quality of feed water and boiler water for trouble
free operation of boilers. The quality requirements become more stringent for high-
pressure boilers, as they are designed to closer tolerances. Since the boiler, water is
primary output; it is not possible to achieve desirable steam purity for trouble free
operation of boiler and turbine, without proper control of boiler water chemistry. In
spite of good water management the internal surfaces in a boiler become dirty over a
period of operation. It is essential to periodically clean the boiler during overhauls
etc.

The principal objective of boiler water treatment is to prevent.

a. Scaling
b. Corrosion
c. Steam contamination
SCALING

Water contains many impurities like dissolved salts and/or suspended matter. The
suspended impurities such as biological growth, mud and bacterial growth can be
removed easily as compared to dissolved solids. These dissolved impurities are
insoluble at elevated temperatures. When temperature rises, solubility of these
dissolved salts decreases and some precipitation occurs locally. These precipitations
are sticky in nature and form coating on the metallic surface. This is called scaling. It
can also be described as a continuous, adherent layer of foreign material formed on
the waterside of a surface through which heat is exchanged. Scales are objectionable
because of their heat insulating effect.

The co-efficient of conductivity of several metals and some compounds of which

scales are made of, are tabulated below:

CONDUCTIVITY OF METALS

Metal
3
x 10 µ mho/cm
Copper 920
Carbon steel 110
Bessemer steel 98

Scales
Aluminium oxide fused (A12 O3) 8.0
Calcium Carbonate (Ca CO3) 2.2
Ferric oxide (Fe2 O3) 1.4
Calcium sulphate (CaSO4) 3.1
Magnetite (Fe3 O4) 6.9
Magnesium Phosphate Mg3 (PO4)2 5.1

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From the above table it is very clear that how insulating these scales are. It is
sometimes said that a thin layer of Ca CO3 (calcium carbonate) should be maintained
to protect the surface from corrosion. But it is impossible to lay down uniform
thickness of scale, because the scale thickness depends upon the amount of heat
being transferred, which is not same in all sections of boiler.

Any scale in the boiler, however, is absolutely undesirable. Scales and deposits are
formed because the compounds, of which they are composed, are insoluble under
high temperatures prevailing in the boiler. Certain anhydrous calcium salts
especially sulphate, decrease in solubility as temperature and pressure increase.
Similarly, solubility of Ca CO4 decreases rapidly with increasing temperature
producing extremely hard, adherent coating on boiler tubes, especially in locations
where heat flux is high. Accumulation in boiler drums is most often in the form of
mud or sludge. When oil is present as a contamination in boiler water, loose scales
may form particularly in water tubes. Oil serves as a nucleus and binder of scaling at
hot spots. The 'oil balls' found in steam drum and water wall headers are typical
formation in turbine flow sections.

Prevention of Scaling

The most effective method for prevention of scaling is to eliminate scale-forming

elements from the feed water, or to transform them by some means into an
innocuous form. That is the reason why dematerialised water is used in the system.
Demineralises can produce water quality with nearly zero hardness. All ionised salts
are removed in these processes, which greatly minimise the potential for boiler
deposits, corrosion and turbine fouling. On-line removal of scales forming salts is
done by phosphate treatment. These salts are inevitably present is the boiler water in
the form of residual hardness even after demineralisation.

The tri-sodium phosphate, which is used for phosphate treatment, tends to increase
the pH value while di-sodium phosphate formed as a by-product; is a neutral salt.
Tri-sodium phosphate reacts with salts of Magnesium and Calcium to form sludge
(Calcium & Magnesium Phosphate). The reaction is as follows:

2NA3 PO4 + CaSO4 = Ca3 (PO4)2 + 3Na2 SO4

Na3 PO4 + H2O = NaOH + Na2 HPO4
Na2 HPO4 + H2O = NaOH + Na3H2PO4

The advantages of phosphate treatment are:

• Adequate alkalinity can be maintained in the boiler water.

• Na2 HOP4 is additionally available to form phosphate sludge.

• Self-containing hydrolysis, hence proper control over pH (above pH =10.2

reactions reverts to left) can be observed.
• No Problem of caustic corrosion.
The only disadvantage of phosphate treatment is Phosphate hideout.

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Phosphate Hideout

Sometimes, objections are raised against co-ordinate phosphate treatment because of

the phenomenon of the phosphate hideout. At higher loads phosphate comes out of
the solution because of its low solubility at raised temperature. But when the load is
reduced it goes back into the solution adding to the total phosphate content of water.
This may lead to excessive total dissolved solids content of boiler water in drum.
However, there is no danger in phosphate hideout. It is nothing more than a
nuisance to the operators for control of boiler water chemistry regarding (PO4) - level
control. Any phosphate salts, hidden out, are available to take care of any hardness
in water. It is never advisable to resort to any boiler water treatment with free
caustic, even in small amounts. It does much more damage to the boiler tubes than
any 'phosphate hide-out'.

The recommended boiler water limits for phosphate & drum water pH are as follows:

Phosphate should be < 3 - 10 ppm

pH = 9.4 - 9.7

CORROSION

Scattered pitting in the presence of oxygen is sometimes observed in the water line in
the steam drum and in the down-corner tubes of boilers. Economiser, on account of
their high temperature, is also susceptible to corrosion by oxygen. The mechanism of
pitting in a metallic surface produced by a bubble of air is shown in the figure 10.3.
Two stages in the formation of a pit are represented by the following chemical half
reactions
Cathodic 2e- = 1/2 O2 = H2O = 2 OH

Anodic 20H = Fw = Fe (OH)2 = 2e-

It ultimately forms a cell and is continuous in nature unless surface of oxygen is

removed. Corrosion of iron and copper in condensate systems leads to formation of
porous deposits under which salts in boiler water concentrate and damage the
underlying surface of boiler steel. Then, even in absence of deposits, caustic gauging
can occur owing to the concentration of sodium hydroxide particularly in places
where the rate of heat transfer is unusually high. Other possibilities are the
corrosion of stressed metal. The severity of these effects can be controlled to some
extent by reducing the concentration of oxygen and free alkali, and by eliminating
products introduced from pre-boiler system.

Corrosion is the oxidation of metal by some oxidising agent in the environment. The
area over which the metal is oxidized is called the anode and at which the oxidising
agent is reduced is called cathode. These areas are necessarily separated but usually
are not far apart. As corrosion products, electrons flow between these areas through
the metal while ions migrate through the solution. This system constitutes an
electro-mechanical cell. In boiler the oxidation of iron is accompanied by the
reduction of hydrogen ions supplied by the hot water.

3Fe + 4H2O = Fe3O4 + 4H2) (A)

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 In case of acidic water

2 H+ + Fe = Fe ++ + H2 (B)

The reaction (A) is self-limiting on account of the barrier of Fe3 O4 that forms on the
surface of the metal. The reaction (B) on the contrary, continues until the supply of
hydrogen ions is depleted in boilers. Both reactions are posed by an irreversible
potential called the hydrogen over-voltage, which is affected, by the condition of the
surface of the metal.

PREVENTION OF CORROSION

Removal of Oxygen

Oxygen is introduced into boilers dissolved in feed water. When this water enters the
steam drum, most of the oxygen flashes into steam space, producing characteristics
pitting at the water wall lines and in the vicinity of the discharge of the feed line.

In addition in high-pressure boiler, several local corrosion, pinhole failures and

pitting in the rear furnace wall tubes are attributable to attack by the dissolved
oxygen.

The concentration of dissolved oxygen in feed water should be less than 0.03 ppm
and preferably less than 0.005 ppm in water for high-pressure boilers. Cold water
saturated with air contains about 10 ppm of oxygen. This can be reduced to 0.3 to
0.7 ppm in an open heater and about 0.01 in a spray type deaerator normally used
inn power plants. The greater part of corrosive gases, and carbon dioxide and oxygen
that are dissolved in water can be removed by de-aeration. Open heaters are suitable
for low pressure but spray type deaerating heaters are commonly used. In these
units, steam heats the feed water in primary heater and also scrubs the heated
water. Hot spray flows down through a baffle arrangement against a rising flow of
steam that sweeps the liberated gases out through a vent at the top of the vessels,
while deaerated water collects in a storage section at the bottom. The vent is
equipped with a condenser through which cold feed water flows to prevent excessive
wastage of steam. The oxygen concentration of less than 0.007 ppm can be obtained
through this method. Because of volatilisation of CO2 and thermal decomposition of
bicarbonate, the pH of deaerated water is normally maintained 8.5 - 9.5.

2 HCO3 = CO3 + CO2 + H2O

H+ + HCO3 = CO2 + H2O

So far we have discussed the mechanical method of deaeration. Let us see how
effectively the corrosive oxygen is removed with the help of chemicals. There are two
chemicals, which are primarily used to remove oxygen.

a. Sodium Sulphate
b. Hydrazine
Sodium Sulphate is commonly used in boilers operating at less than 60 Kg/cm2

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while hydrazine is the reducing agent at higher pressures. The reaction of hydrazine
is as follows:

N2H4 + O2 = N2 + 2H2O

3N2H4 = 4NH3 + N2 (at 200 0 C)

H2O

2NH3 + CO2 (NH4)2 (At 270 0 C)

Nitrogen being inert gas gets liberated and is removed as non-condensable gas.

Advantages of hydrazine treatment are

o Low equivalent weight.

o Does not increase dissolved solid content of drum water

Disadvantages of hydrazine treatment are

o Vapour toxic nature.

o Excess of hydrazine at high temp disintegrates into ammonia.
o Concentrated solution of hydrazine is flammable.

At the economiser inlet the concentration of hydrazine is to be limited to 0.050 ppm.

The presence of porous deposits on the waterside of boiler tubes lead to serious
corrosion, especially when there is free alkali in the water. Various conditioners are
added to disperse insoluble materials and prevent the accumulation of sludge on
surface, where the heat is transferred. Recently poly-crystallites and other synthetic
polymers have come into use.

Small amount of particulate matter comprising finely divided oxides of copper often
contaminate condensate. These oxides, besides causing foaming, deposit on boiler
tubes at a rate proportional to the heat flux. The rate of deposition increases rapidly
above 55 Kg/cm2. The presence of these deposits causes over heating of the tubes
and sometimes ductile gauging. Direct reaction of steel with particles of ferric oxide is
also possible.
4Fe2O3 + Fe+ = 3Fe3O4

Monitoring Feed/Condensate Water pH

The metallic surface on the waterside of a boiler tube is naturally protected by a thin
film of magnetite formed by the action of hot water on steel.

3Fe + 4H2O = Fe3O4 + 4H2

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Ideally there is no further oxidation of metal after the protective layer is formed. The
minimum rate of corrosion is realised at pH value 11 to 12. At lower pH values
hydrogen ions are discharged whereas at values greater than 12, the magnetite layer
thickens, peptises to some extent and is made porous by diffusion of ions from
underlying metal. Above pH value of 13, the magnetite layer is completely destroyed.
2
With the pressure above 40 Kg/cm , hydrogen may diffuse into metal, blistering and
weakening it severely. Hydrogen atoms react with the carbon in steel to form
methane. The pressure generated in this may cause fissures along the grain
boundaries, so ideally the pH of 8.5 to 9.5 should be maintained. The re-circulation
of a small amount of alkaline boiler water through BFP has been recommended but
this can lead to plugging of feed lines in economiser, feed water heaters by insoluble
phosphate.

At lower pH values than 8.5 in the drum, the removable sludge formed by phosphate
treatment of scale forming salts becomes very sticky itself. Also at lower pH values
the silica carry over (Distribution ratio x1/pH) increases very rapidly, not to say a
rapidly increasing rate of corrosion due to pH values lower than those recommended.

STEAM CONTAMINATION

Carry over of salts in steam occur either due to mechanical or vapour carry over.
Efficient drum internals can only reduce mechanical carry over. Silica is always
carried over in vaporous form. The vaporous carry over of remaining salts mainly
2
sodium salts is significant only at pressure above 180 Kg/cm . The carry over may
occur in four types. They are:

a. Leakage carryover.
b. Spray or mists carry over.
c. Priming.
d. Foaming.
Leakage Carryover

Leakage of water droplets through seams or gasket joints of steam purifying

equipment cause this type of carry over. It is usually highly localised and may not be
detected in steam purity test unless the sampling points are very near to the leakage
point. This will be revealed in steam purity measurement by the fact; that with
increase in load condition the purity of steam will deteriorate. The change in water
level may not alter the degree of contamination.

As this type of carry over is most frequently localised, it is responsible for localised
super heater failure. If suspected, then new gasket or seal welding may be required
to eliminate this problem.

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Spray or Mist Carry-over

In this case, atomised droplets of water will be carried with the steam. This is
common in all boilers to some extent. Spray or mist carry over can be avoided by
installing steam purification equipment. If the steam purification equipment is under
designed, this will be present even after the installation of these equipments.

Priming

It is relatively unimportant in present power plant boilers and is rarely encountered.

Carry over of this type is characterised by a sudden carry over of gross quantities of
boiler water, which would show up a drastic deterioration of steam purity. It can be
caused by the variation in pressure such as large pressure drop. In this case the
water in the boiler would swell due to expansion of steam and formation of additional
steam. This action is similar to the” bumping" experienced when water is boiled in an
open beaker. It is more violent spasmodic action, resulting in the throwing of slugs of
boiler water with the steam flow.

Foaming

The important factors that affect the carry over in steam are:

1. Drum and its internals.

2. Water level in the drum.

3. Boiler water concentration.

4. Foaming and vaporous and carry over.

To achieve the quantity or purity of steam required for power and industrial units,
mechanical contrivances are provided inside the boiler drum. These are known as
drum internals. They distribute and mix feed and chemicals added to boiler water
while removing entrained moisture from steam as it leaves the drum.
The three basic effects by the internal arrangements are:

1. Centrifugal action to produce separation force, which is many times greater than
gravity.
2. To direct the steam water mixture so that the upward velocity vector is zero.
3. Provision of drainable wetted surface in which fine spray can coalesce.

Foaming is the condition resulting from the formation of bubbles on the surface of
boiler water. The foam produced may entirely fill the steam space of the boiler or may
be relatively minor depth. In either case this foaming condition causes appreciable
entrainments of boiler water with steam. Generally presence of organic matter
and/or oil will promote foaming.

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Silica Carry Over

Certain dissolved solids in the boiler water are carried away with the steam as
vapour and the internals have no control over such vaporous carry over. One of the
detrimental constituents is silica. In order to limit silica carry over, the concentration
of silica in the drum water must be limited to a specified value for a given operation
pressure range. In order to control the silica in boiler water, the most effective
method used is blow down.

Blowdown

As steam leaves the boiler, solids introduced in feed water are concentrated in the
water left behind in the drum. If this concentration were allowed to continue, the less
soluble components in the water eventually crystallize on the internal surface and in
addition, the steam would contaminate. In ideal operation, the concentration of
solids is allowed to reach the limit after which the concentrated boiler water is bled
off at such a rate that the amount of solids entering in feed water is exactly balanced
by that method in bleed stream. This process is called continuous blow down.

Dissolved Suspended
Pressure Alkalinity Silica
Solids Matter

1000 psi 500 10 50 10

1500 psi 150 3 0 3
2000 psi 50 1 0 1

Suspended solids in the presence of iron tend to collect as sludge in the lower parts
of boiler i.e. down comers or ring header. Opening the intermittent blow down can
blow out this concentrated sludge. The turbulence caused by opening the valve
disperses the sludge. So there is no point in leaving the valve open longer than 15
sec. It is a usual boiler practice that water wall headers should never be blow down
because the circulation or water through them is usually critical when the boiler is
on load.

The outlet for CBD should be below the level where the riser tubes enter the steam
drum because this is where the dissolved solids in re-circulating water are most
concentrated.

Chemicals for internal treatment (phosphate, sulphate etc.) should be introduced

above the down comer tubes to prevent sludging on the hot risers, and also to
promote mixing and reaction with saline in the entering feed water. If the chemicals
are injected near the blow down outlet, short-circuiting will occur.

Continuous blow down is the most effective way for controlling the amount of solids
in boiler water after the rate of withdrawal has been adjusted properly. If the rate of
blow down is too high, heat and water are wasted, if too low the permissible limits
will be exceeded.

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 % Blow down Total Solid in feed
=
(In terms feed water) Total solid in water
% Blow down Total solids in feed
= x 100
(In terms of steam) Total solid-Total solid in feed

RECOMMENDED BOILER / FEED WATER LIMITS

The following are the generally recommended feed water and boiler water limits for
high pressure drum type boilers:

Total solids 50 ppb (max.)

Total iron 10 ppb (max.)
Total copper 10 pbb (max.)
Total silica 20 ppb (max.)
Total oxygen 5 ppb (max.)
Feed water pH 9.2 to 9.4
Phosphate 5-10 ppm
Boiler water pH 9.4 to 9.7

The recommended boiler and feed water limits for 210MW Korba boiler is as follows:

Recommended Feed Water Limits

2
Operating drum pressure in Kg/cm (g) 60-100 100% & above
Hardness Nil Nil

pH at 25 oC (copper alloy pre-boiler system) 8.8-9.2 8.8-9.2

pH at 25 oC (copper free pre-boiler system) 9.0-9.4 9.0-9.4

Oxygen (max.) ppm 0.007 0.007
Total iron (max.) ppm 0.01 0.01
Total copper (max.) ppm 0.01 0.005
Total CO Nil Nil
Total silica (max.) ppm 0.02 0.02
Sp. conductivity after cation exchanger (mho/cm) 0.5 0.3
Residual Hydrazine ppm (before economiser) 0.01-0.02 0.01-0.02
Oil Not allowed.

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Recommended Boiler Water Limits

2
Drum operating pressure in Kg/cm 60-125 125-165 165-180
Total dissolved solids (max.) in ppm 100 50 25

Sp. Conductivity at 25oC (mho.cm) max 200 100 50

Phosphate residual ppm 5-20 5-10 3-7

pH at 25 oC 9.1-10 9.1-9.8 9.1-9.8

To be controlled on the basis of
Silica distribution / Drum-
Silica (max.) ppm pressure curves to maintain less
than 0.02 ppm in steam leaving
the drum

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