WATER CHEMISTRY

Water, an important engineering material for thermal power plant, though abundantly
available in nature is to be treated for use in water/steam cycle of power station.

Impurities of raw water affect the performance of the efficient running of boiler plant.

The water impurities of chief concern to boiler operation are:

1. Those that form scales, sludge deposits on boiler heating surface.

2. Those that induce corrosion in the feed system and in the boiler.
3. Substance that cause foaming/priming and carryover from boiler water giving rise to
deposits in super heaters or on turbine blades.

In a power plant, many of the unit outages are related to problems due to scaling &
corrosion.

Corrosion & scaling increases power plant maintenance cost.

Water chemistry involvement in power station

 Treated water production

 Steam water production
 Cooling water
 Environmental issues

Scale formation

 The primary case of scale formation is the fact that the solubility of scale forming
salts decreases with increasing in temperature.
 Higher the temperature and pressure of boiler operation, the more insoluble the
salts become.
 Calcium and magnesium salts gives raise to scale formation. It is these salts
particularly give water its Hardness.
 Also silica and turbidity give raise to hardness.
 Hard water requires more soap to produce lather than required by soft water.
 Scaling may be seen in household kettles, immersion heaters, pressure cookers
ect. Where the supply of water is hard .Water takes long time to boil.
 If this happen in boiler tube, the transfer of heat from fuel side through the tube to
the water is very much restricted because scale is very poor conductor of heat
compared with metal.
 By restricting heat transfer, scale causes reduced steaming rate and may result in
tube failure due to over heating.
 Scale formation causes loss in boiler efficiency
 Boiler corrosion

 Corrosion is the wasting away of metal in contact with water.

 Boiler corrosion is usually caused by certain impurities in the feed water such as
chloride (from condenser leeks) and dissolved gases – oxygen and carbon –di-
oxide.
 At high temperature and pressure the rate of corrosion is much faster.
 The reaction of iron and water is accelerated by presence of oxygen.
 Oxygen present in water is called Dissolved oxygen.

PH

 It is a measure of the degree of acidity and alkalinity in water.

 It is given a scale from 0 to 14.
 7 to 14 represent increase in alkalinity.
 Neutral water has a PH of 7.
 For iron and water, minimum corrosion is indicated at PH value of 9.0 to 11.0.

Foaming, priming and carryover

Foaming is the condition resulting from the formation of bubbles on the surface of the
boiler water. This foaming condition cause appreciable entrapment of boiler water with
steam. High boiler water alkalinity causes foaming.

Priming It is a more violent action just like bumping when water is boiled in an open
vessel. Priming sis aggravated by the presence of oil in boiler water.

Carryover is the term applied to the continuous entrapment of a relatively small quantity
of boiler water solids with steam.

When boiler water solids carried over in steam, deposits will occur in non-return and stop
valve, super heaters, steam piping and turbines.

Such deposits can promote failure of the super heater tubes and loss in efficiency of the
turbine.

Carryover may result from mechanical and chemical causes.

Mechanical causes of carryover:

boiler design, high water level, method of firing, load characteristic, and boiler
circulation.

Chemical causes of carryover

High total solids of the boiler water, high suspended solids, high alkalinity, oil and
improper type of external or internal chemical treatment.

Silica carryover

Out of all the solids that are carryover, silica is the troublesome.
Silica is carried over in two forms.
1. As contained in water droplets in stem.
2. Taken up by the steam in vapor form because it is more volatile in steam and
solidifying on turbine blades forming a deposit which is very hard and difficult to
remove.

The deposits which occur in turbine due to impurities in steam lead to thermo dynamic &
mechanical inefficiencies.
Chloride salts and sodium hydroxide cause damage to turbine parts by corrosion &
deposit formation.
Silica may be present in small amount in make up water or enter the feed water because
of condenser leak.
In high pressure boiler silica must be controlled to very low level.
Prevention of carryover of water and solids Boiler drum is provided with steam driers in
its steam space of the drum and these purifier traps in its steam space of the drum and
these purifiers trap water droplets and return them to the boiler water.

Make up water treatment techniques

Impurities present n raw water is removed by employing commonly the follow

procedure:

1. Aeration – removes the undesirable gases such as CO2, H2S ect.

2. Clarification – removes turbidity or colloidal suspended matter by its addition
of chemical such as alum.
3. Coagulation – removal of finely divided or colloidal suspended matter by its
addition of chemicals such as alum.
4. Filtration - gravity or pressure filters containing graded stone gravels for the
removal of floc or sludge components.
5. Evaporation – raw water is boiled and the steam is condensed.
 Demineralization

 Ion exchange resins play a key role in providing ultra clean water for the high-
pressure boiler.

 DM water consists of filter beds, activated charcoal column, cation & anion
exchangers, degreasers, mixed bed polishers.

 Hardness & corrosion, salts, dissolved gases like CO2, free chlorine is
removed.

 To reduce the load on DM plant, plants based on reverse osmosis are

incorporated.

Reverse osmosis (RO) plant

R.O. plant is based on the difference of osmotic pressure between solvent and a
Solution

R.O. plant initially reduce loading of ion exchange resins and vice – versa for
extending the service life of the plants.

Chemical treatment of feed water (External)

 Chemical treatment in the feed water is done by dosing chemicals such as ammonia,
morpholine, cyclohexylamin.
 These chemicals are alkaline in nature which dosed rises the pH value of the feed
water in the range of 8-8 to 9.2 which minimizes corrosion in the preboiler
system.
 Though major amount of dissolved oxygen is removed in deaeration, oxygen
scavenging chemicals are employed to remove the residual oxygen.
 Most frequently used chemicals are hydrazine (N2H4) and sodium sulphite (Na2So3).

Chemical treatment of boiler water (Internal)

 Although hardness causing salts are removed in DM plant, concentration of salts occurs
because of continuous evaporation of water & addition of make up water.
 Trisodium phosphate (TSP) is added in to the boiler drum to the recommended concentration
& maintained the concentration at the required level by continuous injection.

TSP reacts with calcium and magnesium salts and keeps them as sludge, suspension
 preventing from depositing on the boiler tube interior surface as scales.

Blow down
  All dissolved and suspended solids entering with the feed water remain in the
drum and tubes as steam is generated.
 Continued addition of make up produces higher and higher solids
concentration in the boiler drum.
 Finally a point is reached beyond which operation is completely
unsatisfactory.
 The limit may be suspended solids, total solids, silica content, alkalinity ect.
 Priming and carryover occurs whom boiler is operated beyond certain limits.
 To keep the concentration of dissolved solids within prescribed limits in boiler
water, some of the concentrated boiler water is removed from the boiler.
 Boilers have blow down connection.

Condenser leakage

 Even with more make up, good deaeraton and chemical control impurities
may enter feed system from the cooling system from the cooling water if any
leakages occur in condenser tubes.
 Normally the cooling waters are very impure. They are from river, canals, sea
or ground water (bore water).
 Even small leakage of cooling water into condensate will cause serous trouble.
 The leakage will be known from the analysis of feed water which will show
marked increases in TDS, chloride and conductivity.
 To counteract the impurities entered in to the system.

More chemicals to be added to the boiler water to precipitate the dissolved

solids and chlorides.

- Blowing down the sludge formed in the boiler water.

- Finding and repairing the condenser leak.

Cooling water treatment

 Types of cooling water
 Once through (Generally sea water in used).
 Open air circulating (for condenser cooling).
 Closed circulating (for GT).

Problems associated with industrial water.

Scaling

Restricts heat transfer in condenser as in boiler tubes

Corrosion

Corrosion on condenser tubes causes leakages of cooling water and contamination

of condensate with salts like chlorides, hardness ect

Bio- fouling.

Bacterial, algae growth inside the cooling water system promotes deposition,
corrosion, loss of heat transfer, reduction in flow of fluid.

Scale and corrosion control.

 Prevention by sulphuric acid addition.

 pH of cooling water raises on circulation in cooling tower mainly due to
evaporation in cooling tower.
 pH is maintained between7.5 to 8.5 generally to minimise scaling by acid
addition.
 Make up water addition and blow down.

Control of fouling

Chlorination

Addition of chlorination to the level of about 0.5 ppm as residual chlorine controls
growth of micro- organism.
Environmental issues

Water pollution

 DM plant regeneration waste.

 Neutralization of hydrochloric acid reagent.
 Neutralization of spent alkali.
 DM plant effluent to be treated with acid/alkali to pH 6.5-8.5.
 Disposal with plenty of dilution using service water for reduction of TDS to
below 2100 ppm.
 Maintaining necessary records regarding the activities carried out for the
treatment & disposal of effluent.

Effect of Liquid Effluent On Aquatic Eco-System.

 Discharge of highly acetic /alkaline liquid effluent in to natural body changes

the water quality of receiving body, thus affecting the reparian population and
aquatic life.
 Oil population prevents the air with surface water, oil film reduces DO.
 Suspended particles in the water reduce sunlight penetration, thus affecting
photosynthesis in aquatic plants.

Ecological impact of thermal pollution

 Discharge of large quantities of heated water into natural water bodies alters
the physical, chemical and biological characteristics.
 Density, viscosity, vapours pressure and gas solubility get altered.
 DO concentration decreases while its demand increases due to increased
respiratory rate of aquatic life forms.
 When temperature exceeds the optimum level, fish may be affected due to
elimination of available food, lowering of productive potential and increased
susceptibility to disease.
 The effect varies season wise during winter, the affect may be favorable.
 As per pollution control standard the temperature of the effluent shall not be
more than 5° C higher than the intake water temperature.
Ammonia dosing rate

Ammonia will be dosed to controlled pH at 8.8 – 9.5 for minimizing corrosion in

condensation system and feed water system. The dosing rate s approx 1ppm.

Oxygen scavenger dosing rate

Oxygen scavenger will be dosed to eliminate the dissolved oxygen in water. The dosing rate
is approx.1ppm.

Tri-sodium phosphate dosing rate

Tri-sodium phosphate dosing will be dosed to accomplish two desirable objective for boiler
water; properly selected sodium phosphate result in alkaline solution that elevate the pH of
the steam generator water, and phosphate chelate or combined with calcium to minimize the
potential for the calcium to deposit on the heat transfer surface. The pH range of boiler blow
down is at 9.2-9.5. The dosing rate is approx.5ppm for high pressure drum.

Corrosion inhibitor dosing rate

Corrosion inhibitor will be dosed to avoid the corrosion in closed cooling water system.
Corrosion inhibitor dosing rate s approx.1ppm to increase pH of closed cooling system.

Calcium Hydroxide dosing rate

Calcium hydroxide will be dosed to meet the water quality of make up water for GT Eva
Cooling system according to the manufacturer requirement. The dosing rate is approx.
20ppm.
Demineralized water quality ( section 4.0)

1. pH : 6.5 - 7.5
2. Conductivity (micro sem/cm) : 0.2 ( @ 25°c)
3. Sodium (mg/l ) : < 0.01
4. Copper ( mg/l ) : <0.003
5. Iron (mg/l ) : <0.02
6. Silica (mg/l ) : <0.02

Condensate and Feed water Quality

1. Iron (T ) (mg/l) : < 0.02

2. Copper (T ) (mg/l) : < 0.003
3. Silica (mg/l) : <0.02
4. Sodium (mg/l) : < 0.01
5. TOC (mg/l) : < 0.02
6. Cation conductivity (micro sem/cm) : < 0.2
7. pH : 9 - 10
8. O2 (mg/l) : < 0.1

H P Boiler water quality

1. pH : 10
2. Cation Conductivity (micro sm/cm) : < 50
3. Phosphate (mg/l) : <6
4. Silica (mg/l) : <2
Remark
o Continuous measurement
o In the feed water the pH value shall be 9 – 10. Because of the pH in the drum water
will normally be > 8.5. The HRSG shall be shut down immediately if drum pH < 8.
H P Steam quality

1. Cation conductivity (micro sm/cm) : < 0.2

2. Iron (mg/l) : < 0.02
3. Copper (mg/l) : < 0.003
4. Sodium (mg/l) : < 0.01
5. Silica (mg/l) : < 0.02

Effluent waste water quality

 1. Max.Temp (°c) : 60
2. Floatable : None
3. pH : 6-9
4. TSS (mg/l) : 15
5. Turbidity (NTU) : 75
6. Oil & grease (mg/l) : 8

Dissolved oxygen

DO is a rough element in water chemistry, bound to cause pitting in economizer and

horizontal pipe line and also the quantum of metal transported through the feed water has got
a proportionality to the level of DO present.

As the make up water has 10 mg/l of DO present. The need persist to remove it to the bearest
possible minimum level of 0.007 to 0.005 mg/l. This is being don by three methods.

1. Thermal deaeration
2. Mechanical deaeration
3. Chemical scavenging

Thermal deaeration is nothing but raising the temperature of water thereby the dissolved
gases are expelled. LP heater and HP heater dose the duty in the feed water circuit.

Condenser is the best mechanical deaerator where dissolved CO 2 and O2 are evolved and
expelled. A well designed hermetically scaled condenser would reduce the dissolved gases to
the level of 0.01 ppm. This is the reason why the DM water is made to enter the circuit
through the condenser where the water is being through nozzles to take advantage of the
exhaust system in condenser. Air increase should be avoided in the condenser.

The deaerator tray type tube was type installed over feed tank also dose the duty of expelling
the gases in feed water.

The rest is taken care by chemical scavenging by injecting hydrazine hydrate to reduce DO to
the barest minimum level of 0.005mg/l

Hydrazine dosing system

For a number of reasons, the chemical oxygen scavenger of choice in high pressure boiler
operation is almost invariable hydrazine (N2H2). The advent of organically catalyzed
hydrazine suitable for use in boilers made the full benefits of hydrazine available to low and
medium pressure application and more extensive in high pressure system.
Hydrazine Reactions:

N2H4 + O2 ------ 2H2O + N2

It is important to note that the product of the hydrazine reaction are inert and do not add to
dissolved solids in the boiler water.
Hydrazine will also react with ferric oxide
N2H4 + 6 Fe2O3----- 4 Fe3O4 +N2 +2H2O
Of cupric acid
N2H2 + 4CuO --- 2Cuo + 2H2O +N2
Magnetite and cuprous oxide are the passivated oxide state of iron and copper. Hydrazine
therefore renders iron and copper surface less susceptible to corrosion by reducing them to a
passive state. The reduction reaction takes place on metal surface in the pre boiler, the boiler
and the after boiler, as well as on suspended ferric oxide or cupric oxide. Hydrazine is fed in
amount require to react with dissolved oxygen, ferric iron and cupric copper, plus a small
excess. The theoretical requirement for pure N2H4 is 1 ppm O2 0.048 ppm per ppm iron+3,
and 0.125 ppm per ppm cu2+

In the past, the use of hydrazine has been most expensive in high pressure boiler in which
sulfate would cause problem. Its relatively slow and sluggish reaction with oxygen prevented
it’s used in low pressure boilers. In high pressure systems, the temperature of the boiler feed
water is usually high enough to permit the effective use of hydrazine. An organic catalyst was
developed recently which increases the reaction rate of hydrazine with oxygen permitting its
effective use in boilers utilizing lower temperature feed water.

Hydrazine control:

A hydrazine residual of 0.1 to 0.3 ppm is usually maintained in the boiler water in boiler
operating at less than 600 psig, above that pressure, the residual s most commonly controlled
at 0.05 to 0.1 ppm. The extremely low hydrazine residual in the boiler as well as the inert
nature of the product of the hydrazine reaction (N2 & H2O) makes its use extremely
desirable in that system in which total dissolved solids in the boiler water constitute the
limiting factor for boiler blow down.

In such system, the substitution of hydrazine for sulphate can permit increased cycle of
concentration.
In some systems, hydrazine is controlled in the feed water rather than in the boiler water.
This is done to assure that a hydrazine driving force exists in the feed water and to assure
against over feed. When hydrazine is controlled in the boiler feed water, a residual of 0.01 to
0.01 is maintained. Because of hydrazine’s volatility, t is cycled to high concentration in the
boiler even when a relatively high feed water residual is maintained and cycle of
concentrations based on feed water are high.

Phosphate control
The scale causing substance of Ca and Mg and including silica are thrown out through CBD
by forming sludge by dosing TSP straight to the drum by means of dosing pumps.

3Ca SO4 + 2Na3 PO4---- Ca3(PO4)2 +3Na2SO4

In addition to the removal of scale forming substance phosphate is also boost the pH of the
boiler water as NaOH is formed.

Na3PO4 + H2O ------ Na2HPO4 + NaOH

Na2HPO4 + H2O ------ NaH2PO4 + NaOH

NaH2PO4 + H20 ------ H3PO4 + NaOH

The quantum of blow down to be discharged is to be decided as per the formula

% of the steam flow = 100 sf

--------
S drum sf
Sf - salt in feed water
S drum - salt in drum

Co-ordinate phosphate: pH control

It is evident from the above reactions of TSP furnished that free OH ions formed and the
alkalinity increases and presence of free hydroxide may get concentrated under narrow
cracks where rapid corrosion of steel may takes place.
If that is the case it may be required to reduce hydroxide concentration in the boiler water
and in that case Sodium di-hydrogen phosphate and sodium Meta phosphate have to be dosed
to reduce hydroxide concentration.

NaH2PO4 + 2NaOH ---- Na3PO4 + 2H2O

Na2PO4 + 2NaOH ---- Na3PO4 + H2O

Thus hydroxide concentration is reduced. This sort of combined dosing of TS, SMP, and
sodium dihydrogen is called co ordinate phosphate.

At higher temperature and pressure phosphate gets precipitated and disappears. This
phenomenon of TSP is known as HIDE OUT. The Hide out phosphate at high temperature
reappears, when load and pressure are reduced. This phenomenon of phosphate hide out can
be felt in laboratory testing and also with increased metal temperature in the boiler tubes.
Phosphate hide out also indicates indirectly that the boiler needs post operative acid cleaning.

Hydrogen peroxide (H2O2)

o Most people known Hydrogen peroxide as a compound that bleach hair. It can also
used for disinfection.
o Peroxide is a chemical compound that contain the peroxide ion (O2)2- .
o The peroxide ion consist of a single bond between two oxygen atoms (0-0) 2-. It is a
strong oxidizer.
o Hydrogen peroxide is used for different applications, because it is very selective. By
changing the reaction condition, hydrogen peroxide will attack different pollution.
o The corrosiveness of process water due to hydrogen peroxide depends on the amount
of DO that is produced. Oxygen corrodes iron containing metals. The amount of iron
and the pH are a greater influence on corrosiveness then the concentration of
hydrogen peroxide is.
o Hydrogen peroxide is mostly commonly used to remove pollutant from WW and
from air. It can test bacterial growth (bio fouling in water system) and it can enhance
bacteria growth through oxygen addition.
o It can also be used to treat pollutant that can easily oxidize (e.g. iron and sulphite) and
pollution that that is difficult to oxidize.
o Hydrogen peroxide is a strong oxidizer. It is more powerful than chlorine (cl) and
chlorine di oxide (ClO2) and permanganate.
o Most H2O2 application consists of hydrogen peroxide injection into flowing water.
o No other chemicals or equipment are required.
o This application is used to controlled biological growth, to add oxygen, to remove
chlorine residues and to oxidized sulphides, sulphite metals and other easily oxidized
materials.
o Advantage: H2O2 does not produce residues or gases; safety depends on the applied
concentration, because H2O2 is completely water soluble.
o Disadvantage: H2O2 is a powerful oxidant. It reacts with verity of substance. It is
therefore dilute during transport as a safety measure. For H2O2 disinfection higher
concentration is required.
o H2O2 slowly decomposed in water and oxygen. The concentration of H2O2 in a
solution slowly decreases. This is caused by the following reaction
2H2O2------- 2H2O+O2. This s redox reaction.