WATER TREATMENT PLANT &

COOLING WATER SYSTEMS

Raw water supplies are required for three main purposes:
To provide make up water to the water / steam cycle.
For cooling of the steam for reuse as condensate.
General domestic use.
Types of water supplies to power stations :

Deep well water

Upland surface water

Clean rivers

Industrial river water

Sea or estuary water

POTENTIAL EFFECTS OF IMPURITIES IN WATER

The main potential adverse effects of the impurities present
in raw water are to promote corrosion & scaling of plant
items.

Calcium & Magnesium salts :

Calcium & magnesium bicarbonates will deposit

carbonate scales if water is heated.

Sodium :

Sodium salts such as chloride & sulphate have to be

controlled to minimise corrosion of the boiler & turbine
sections of the plant.

Silica :

Silica has a relatively high solubility in high pressure

steam relative to other inorganic compounds. During passage
through the turbine, the pressure decreases & the solubility of
the silica decreases &
can deposit on turbine blades.

Organic Matter

The main problem arising from organic matter in the raw

water is fouling of anion exchange resins.

Suspended Solids :
These have to be removed priror to any ionexchange or
reverse osmosis process.

Phosphate

In the presence of calcium, insoluble calcium

phosphates can be deposited from raw water. The main
factors influencing deposition are concentration,
temperature & pH.

PRE-TREATMENT OF RAW AWTER

The pre-treatment should remove all of the colloidal organic

matter & a portion of the higher molecular weight species.

If non reactive silica is present some may be removed by the

pretreatment process but generally the effectiveness of
removal will be poor.

THE USUAL FORM OF PRE-TREATMENT IN THE POWER

INDUSTRY IS CLARIFICATION FOLLOWED BY
FILTRATION.

Clarification :

Clarification is the process used to encompass

coagulation, floculation& sedimentation reactions
which
are involved in the removal of suspended &
colloidal
matter from water.
When a coagulant is added to water, eg ; Aluminium
Sulphate, a chemical reaction occur:
Al2(SO4)3 + 3Ca(HCO3)2 = 2Al(OH)3 + 3CaSO4 + 6 CO2

Because of the positive charge, the repulsive forces

between particles will therefore be reduced so that there is
a tendency for particles to join together forming masses that
are sufficiently heavy to settle rapidly.

There are a number of factors which can affect the

coagulation & flocculation process,e.g; pH, Temperature,
nature of particles present in the raw water, & the chemical
composition of raw water.

Polyelectrolyte may also be used as coagulating &

flocculating agents either alone or combined with an
inorganic coagulant. These are long chained organic
molecules with chemical groups attached to chain.

Following points need to be considered in the design &

operation of clarification Plant: :

Coagulant type & quantity from laboratory test.

Concentration, Particle size distribution & surface

charge of suspended & colloidal solids.

pH conditions for the clarification process.

Coagulant mixing rate & retention time.

Contact time through sludge blanket.

The up-flow velocity limits for the maintenance of an

acceptable water quality making allowance for
seasonal effects.
Blanket floc concentration. This is a useful method of
assessing the ability of the blanket to remove floc &
remain stable.

Filtration :
Water leaving the clarification stage will contain mainly
traces of floc as suspended material. The most
frequent problem arising in the operation of clarifiers is
the carryover of floc, resulting in overloading of the
filters.
Sand or anthracite are invariably used as filter media
The normal filtration medium used is a bed of closely
size graded sand with a particle size of about 1mm.
The sand layer is about 1m deep & is supported on
gravel.
Pumps are employed to pass the water through the
filter media under pressure

Multimedia Filters :
In multimedia filters a layer of anthracite is placed on
top of a layer of sand.

Up-flow filters

The water enters at the bottom of the filter bed & flows
up through layers of sand of decreasing particle size,
thus improving the dirt holding capacity of the bed.

ION EXCHANGE PROCESS

In water treatment the three main characteristics required

from solid ion exchangers are:

Insoluble, but permeated by water.

An ability to exchange ions with those in solution.

To allow a flow of water through a bed of the material

with an acceptably low resistance, yet, when
necessary, acting as a filter medium.
Ion Exchange Reactions

RH + Nacl

R Na

+ HCl

R OH + HCl

R Cl

+ H 2O

Deterioration of Ion Exchange resins :

Physical breakdown

Chemical breakdown

Fouling

The effects of organic fouling are :

Reduced capacity.

Increase in electrical conductivity of the treated water

Prolonged rinse requirements.

Low pH of final treated water.

Treatment of waters containing organic matter :

The need to remove organics from the water

The need to remove organics from the resin to maintain
performance.

Reverse osmosis for make up water treatment :

Osmosis occurs when two solutions of different

concentration are separated from one another by a
membrane which is permeable to the solvent but
impermeable to the solute. The pressure which just
prevents such flow is called osmotic pressure.
If a pressure greater than osmotic pressure is applied
to the concentrated solution, the solvent can be forced
through the membrane leaving the dissolved
substances
behind. This method for purifying water is
termed as
reverse osmiosis.

Membranes :

A member is usually considered as being a thin sheet

of a plastic material of about 100 microm thickness & this
forms a partial physical barrier between two fluids
such
that permeation of some of the species present
in the
fluids can occur.
Deterioration of Reverse Osmosis :

Hydrolysis :

The production can increase with time, but there is a

decrease in the quality of water produced. This is due to
hydrolysis.
To minimise hydrolysis the pH should be in the range
4 6 & the temperature should be low.

Fouling :

The prime cause of fouling will be the entrapment of

material on the surface of the membrane. Two main factors
influencing the rate of fouling were particles less than 5
micron, and the dissolved organic comonents.
Reverse osmosis membranes have a relatively short
working life of 1- 5 years.
The deterioration is due to :

Physical stress

Chemical degradation

Ageing

Fouling

Cooling water :
The main use of cooling water is to cool the exhaust
steam from the turbine in a surface condenser of the
shell & tube type.
C.O. C =

Concentration of cooling water

Concentration Of river water

Scaling :
Several salts initially soluble in the river water can, as the
temperature & concentration of the cooling water increase,
be precipitated from solution onto the heat transfer surfaces
causing scaling.

Calcium Carbonate Deposits :

IR

< 6 the water is scale forming

IR

> 6 but < 7 the water is close to equilibrium

IR

> 7 the water is corrosive.

Prevention of Condenser tube Scaling

Taprogge :

It is a physical method of continuously cleaning condenser

tubes by the circulation of sponge rubber balls in the
cooling water.

Acid dosing

Acid dosing represents a chemical alternative to physical

techniques for maintaining clean condenser tubes.

Chemical additives

Chemicals are used to modify the crystal structure of

compounds precipitating from super-saturated solutions.
The additives include poly-maleic acid, poly-acrylates,
poly-methacrylates, phosphonates & quaternary ammonium
salts.

Exhaustion & regeneration of ion exchange resin :

Under coflow conditions, the water & regenerate
solutions flow in the same direction during the
exhaustion & regeneration stages.

The selective coefficients of a cation resin for

calcium, magnesium & sodium exchange when
operating in hydrogen form are:
Ca
K
H

Mg
>

K
H

Na
>

K
H

So during the exhaustion stage calcium & magnesium are

exchanged preferentially as the water passes through the
bed.

During regeneration, acid is passed through the bed

in the same direction as the water flowed during
exhaustion stage, calcium, magnesium & sodium
ions will be displaced down the column by hydrogen
ions.

But by counter flow regeneration, water leaving the

unit would be in equilibrium with the most highly
regenerated resin & extremely low levels of sodium
leakage will be obtained through out the cycle.

Corrosion : Feed & Boiler water chemistry

The corrosion of metals :

In nature, metals are usually found as relatively

stable compounds which are converted into metal by
a process of chemical reduction.

Corrosion may be defined as the reversion of the

metal to a more stable oxidised state.
The initial effects of corrosion is to produce a thin
layer of oxide or salt on the metal surface. In some
cases the oxide or salt film results in a state of
passivity preventing further corrosion. These are met
if the metal oxide is self repairing when damaged. In
moist air, aluminium & chromium readily form
protective oxide coating,
whereas the oxide formed
on low alloy steel is porous & does not prevent

An electrochemical cell :

A piece of metal, Zinc, carries no overall electric

charge. If, however, it is placed in an electrolyte
solution,
Zinc Sulfate, some of the zinc metals
dissolve
to form
zinc ions, leaving electrons on the metal.

The potential between the metal and a solution of its

ions of standard strength is called standard electrode potential
for the metal.
If the zinc & copper electrodes are joined externally, a
current will flow, zinc becoming the negative
electrode (anode) & the copper the positive electrode
(cathode). The zinc dissolves & releases electron
which
pass through the external circuit to the copper where they are
consumed in converting Cu2+ ions in
the solution in Cu
metal which deposits on the
cathode.

Galvanic Corrosion :

The corrosion of the less noble member of apair of metals

which are joined together is called galvanic corrosion.

Standard electrode potential series :

The Corrosion of Single metals :

If a piece of steel covered with a protective oxide film is

immersed in dilute hydrochloric acid, the corrosion of the
metal will initially be prevented by the oxide layer. However,
if the steel is lightly abraded, some of the will be removed
and, when placed in acidic solution, corrosion will occur
where the metal has been exposed with the retained oxide
layer acting as a cathodic area for the formation hydrogen.
Figure :

Differential aeration :

With metals forming protective oxide films the presence of

dissolved oxygen will enhance oxide formation making the
metal cathodic. Areas of the metal where the oxygen
concentrations are higher will be more cathodic than areas
where the oxygen concentrations are lower.

Corrosion due to differential areation is observed in

unprotected structures, in boiler tubes, in condenser tubes
or in other situations where deposits can impede access of
oxygen to the underlying metal surface & lead to pitting
corrosion & failure.

Boiler water treatment & steam purity :

The chemical control of water & steam purity is aimed at

the prevention of :
Corrosion in feed, boiler & steam systems
Scale & deposit formation on heat transfer surfaces
Deposition & corrosion in turbines
Formation of protective oxide film :

At the temperature that prevail in high pressure steam plant,

clean mild steel surfaces readily react with water to form,
through a series of reaction, Fe3O4 (magnetite) and / or Fe2O3
(haematite).
Fe + 2H2O
3Fe +2 + 4H2O
+2

Fe+2 + 2OH- + H2
Fe3O4 + 4 H2

In deareated water treated with alkali at high temperature,

the formation of magnetite from Fe+2 takes place very
rapidly & the magnetite is formed as a dense, almost
impervious, oxide layer firmly adhering to the metal surface.
In good boiler water the dense oxide film produced on mild
steel will only be some 20 30 micron thick after 15000 to
20000 hours of operation.
Figure :

Sources of alkalinity for boiler waters

The need to maintain alkaline conditions in boiler
water is to prevent corrosion.
However, it was found that in the high heat flux zones
of these boilers, very high localised concentrations of
alkali were formed at tube
surfaces by a process
known as hide-out.
Tri-Sodium Phosphate & di-sodium phosphate can
both effectively produce alkalinity by hydrolysis in water :
Na3PO4 + H2O

Na2HPO4 + NaOH

Na2HPO4 + 2 H2O

NaH2PO4 + NaOH

Difference between this source of alkalinity & that

produced by free caustic soda lies in the reversibility of
reaction.

Co ordinated phosphate :

Phosphate conc. and pH are controlled by using mixtures of

di-sodium & tri-sodium phosphate, such that the boiler water
had a satisfactory pH but contain very low concentration of
sodium hydroxide.
Recommended co-ordinated phosphate for operation :

Chemical treatment of boiler water drum boilers

For safe, reliable, corrosion free operation of high pressure

drum boiler, it is necessary to take care of following points :

Low, controlled levels of alkali

Very low levels of oxygen

Low levels of potential acid forming impurities

such as Chloride.

Summary of Targets for drum type boilers

Feed water treatment - drum boilers :

Feed water is the major source of soluble & insoluble

impurities entering the boiler.

Insoluble impurities :
Metal oxides derived from corrosion

Soluble impurities :
Leakage of cooling water from condenser, poor
quality of make up water.
Control of insoluble impurities

Feed Water pH the use of volatile alkalis

Advantage :
No excessive accumulation of alkali in boiler water

Ammonia is the most widely used as volatile alkali

Disadvantage :

It is very volatile in steam & it is relative weak

alkali in high temperatures.

Initial condensates formed at high temp

For example : in feed heaters, may have low pH values

resulting in only limited protection from corrosion.

Other volatile alkalis such as :

Morpholine

Cyclohexylamine

Diethyl amino ethanot

Amino methyl propanol

Methoxy propylamine

Not recommended to be used having superheater steam temp. above about 4500 C.

Monitoring & control of feed water pH :

Continuously monitor pH and / or direct conductivity of bulk

condensate at the extraction pump discharge, to ensure that
the correct chemical conditions are being maintd.
Oxygen Control

Physical de-areation

Chemical de-areation

Catalytic de-areation

Soluble ionic impurities in feed water :

Good makeup water should have conductivity

< 0.2 s / cm, low chloride, sulphate, silica & sodium.

Satisfactory quality of chemicals to be used to control

Boiler tube corrosion drum boilers :

Acid chloride corrosion :

Because of the presence of Magnesium chloride &
sodium chloride .

Caustic attack
Corrosion because of the presence of Concentrated
Sodium Hydroxide

Stress Corrosion Cracking

Tube failure because of localized concentration
conc. of dissolved salts in evaporation section .

THANKS
U