CHEMICAL TREATMENT IN

COOLING WATER SYSTEMS

BY P.K.VASUDEVAN
JUNIOR CHEMIST/MTPS
What is cooling water system?
It is the most important system in any Power
Station predominantly decides the efficiency of
stations
Heat Transfer: ( e.g. Boiler)
Hotter (source) cooler ( receiver)
Cooling water System:
Process ( source) Cool water(receiver )
Cooling water does not contact the source
directly. A Barrier that allows heat pass from
source to receiver
Water completes it job and cools the
source
This heat should be transferred to the
environment
Types of system
Once through system
Open recirculation system
Closed recirculation system
Source of water
Sea, River, Pond, etc.
Controlling Factors
1. The heat transfer characteristics
(thermal conductivity) of the barrier
2. The thickness of the heat transfer barrier
3. The surface area of the barrier
4. The temperature difference between the
source and the receiver ( cool. Water)
5. Insulating deposits on the either side of
the barrier

Types of Problems
Corrosion
Corrosion is function of water characteristics and the
metals in the system
Scale
Precipitation of compounds that become insoluble at
higher temperature
Fouling
Settling out of suspended solids, buildup corrosion
products, growth of microbial masses
Chemical treatments Corrosion Scaling Fouling Microbes
Chromates X
Zinc X
Molybates X
Silicates X
Polyphosphates X X
Polyolesters X
Phosphonates X X
All organics X X X
Natural organics X
Synthetic polymers X X
Non oxidizing
biocides
X X
Chlorine / Bromine X
Ozone X
Some of the major chemical components available for
cooling water treatment
CORROSION
Galvanic corrosion,
cell corrosion,
Dissolved gases
Stress corrosion
Corrosion fatigue cracking
Dezincification
Dissolved solids ( Chloride & Sulphate)

UNTANGLE THE TRIANGLE
The arms of the triangle encompass the
microbiological process in the centre.
Bio film contributes significantly to
microbiologically influenced corrosion and
under deposit corrosion
Bio film also possible nucleation sites for
mineral scale growth
Corrosion inhibitors
Principally
anodic
Principally
Cathodic
Both anodic &
Cathodic
Chromate
Calcium
Carbonate
Organic filming
amines
Orthophosphate Polyphosphate Phosponates
Nitrite Zinc
Silicate
Problem due to bio film
Increase microbiological influenced
corrosion
Reduction in heat transfer
Increase chemical cost
Cooling water chlorination
Dosing gaseous chlorine in cooling water
will control the organic matter growth
Cl2 + H2O HCl + HOCl
HOCL H
+
+ OCl

The above components are the primary
Toxicants that destroys microorganisms
A residual chlorine value of 0.2 to 0.4 ppm
will provide control
Continuous presence of residual chlorine
will increase contact time
In recent development HOBr , ( bromine
biocide) are available in liquid form are
used for continuous dosing .
Bromine is often a more practical
treatment than chlorine because it
remains effective at higher PH
Material % of Cl
2
Chlorine gas (Cl
2
) 100
Chlorine dioxide ( Cl O
2
) 263
Hypo chlorites ( Na or Ca)
Calcium Ca(OCl)
2
70
Sodium (NaOCl)
Industrial 12 - 15
Domestic 3 - 5
Lithium, LiOCl, laundry grade 35
Chlorinated isocyanuric acid ( CONCl)
3
85
SCALE CONTROL
Tendency to form inorganic deposits ( CaCO3,
MgCO3) on heat transfer surfaces due to cycles
of concentration
Scales are formed when inorganic constituents
are concentrated and super saturated solutions
are formed
When further concentrated in recirculation,
whereby reaching maximum concentration of
hardness (Ca,Mg) salts.

This will result precipitation of dense ,
adherent scale
These Scale act as a thermal insulator it
causes reduction in heat transfer
Scaling also increases roughness there by
increasing turbulence and pressure drop
To prevent scaling the concentration
factor is kept in the range of 1.25 to 2.0
C.F. = Concentration in cooling water
Concentration in Raw water
Calcium Carbonate solubility will decrease
while increase in temperature (inverse)
Ca( HCO
3
) CaCO
3
+ CO
2
+ H
2
O
Cooling Tower expels CO
2
from the water
To find the tendency of deposit Langlier
Index and Ryznar index are used
In recent technologies software packages
are available which are significantly more
powerful than the above methods


Control of Scaling
Scaling potential is mitigated by use of
polyphosponates or polymers
These are act as crystal modifier rather
than scale inhibitor
i.e they change the morphology of scale
not to bind each other and to precipitate
They help to keep the contaminants
suspended in bulk space

CONTROL DEPOSITS
Threshold inhibitors
Delay in precipitation / increase solubility
Dispersants
Disperse suspended solids ,adding charges, causing
mutual repulsion
Surface active agents
Penetrate and disperse biomasses. Some of them are
biocides kill slime organism
Crystal modifiers
modify the crystal structure of scale resultant will be
weak in structure will not stick on the surfaces.

Makeup
water
Condenser
Cooling
water pumps
Cooling Tower
Blow
Down
Evaporation & Drift
loss
Calcium
Magnesium
Sodium
Carbonates
Bicarbonates
Chlorides
sulphates

Pure water
Cooling water cycle
MASS BALANCE
This is the technique used to find out the
whether the system is In Balance or not
Concentration in circulation water
Concentration Ratio [ CR] = --------------------------------------------
[non precipitating ion( Cl)] Concentration of in Makeup water

From the CR the value of Calcium is calculated as follows

C.R X Calcium in make up water
Mass balance = Calculated calcium --- Actual Calcium in Cir.water
Example calculation:
Chloride in Makeup water = 22 ppm
Chloride in Circulating water = 34 ppm
Concentration Ratio = 34 / 22 == 1.545
Calcium in Makeup is = 86 ppm
Calculated calcium is = 86 X 1.545 = 133
If Actual calcium in Circulating water is:
Case (i)133 then 133 133 = 0 [ no deposition]
Case (ii) 131 then 133 131 = + 2 [Deposition ]
Case (iii) 135 then 133 135 = - 2 [ Calcium
dissolved]
Fouling
Fouling can be considered as deposition of
hardness salts and of other inorganic
particulate matter
This occurs usually in the areas where
water velocity is low
It has same effect as scale bet it promotes
severe corrosion under deposition
Sources of fouling deposits
Raw
water
Air borne Recirculation
water
Colloidal
organics
Dirt Scale: CaCO
3
,
CaSO
4
Silt, Dirt Reactive gases
H
2
S, SO
2
, NH
3
Corrosion
products: Fe
2
O
3
Microbial
contamination
Microbial
Contamination
Microbial deposits
Fouling control

Deposition fouling can be controlled
by
Filtering of makeup water
Addition of good dispersant
Controlling of scaling
Controlling of bio film formation
Latest development
Controlling the cooling water system
through latest software packages
Monitoring through on-line and real-time
Dosing chemicals and biocides according
to demand and performance based
SOME OF THE ONLINE
INSTRUMENTS
Bio film Analyser
Deposit Analyser