chembond

Fundamentals of
Cooling Water Treatment

Chembond Ashland Water Technologies Limited

Ashland

Use of Water In The Industries:

Cooling
Producing Steam DM water
Process
Drinking

Water Used for Cooling Process Fluids:

Process fluids are required to be cooled at
various stages
Water is the Cheapest Coolant Available
Process Fluids are cooled in heat exchanger,
cooler, condenser
Reactor / DG set Jacket Cooling
Heat is transferred from Hot Process Fluid to
Cold water and it becomes hot
Hot water is cooled in Cooling Tower and cold
water re-used for cooling

Types of Cooling Systems

Once through Cooling System
In this system:
cooling water passes through heat exchangers only once before
it is discharged.
Large volumes of water are required in this type of systems.

T is very negligible.

Closed Recirculating Cooling System

In this system:
Water is reused continuously
water loss is very low.
There is no evaporation loss.
Example :
Chilled water system, Engine Jacket Cooling System.

Process
Air/ C.W.
Cooled water

Closed circuit water tank

Warmed water

Secondary cooler
chiller

Cooled
water

Open Recirculating Cooling System

Water is re-circulated again and again

Heat from hot water removed with the help of cooling tower.

Permits extensive reuse of water and reduces the volume of make up

water required.

Due to evaporation, concentration of dissolved salts takes place.

H2 O

HOT WATER
MAKE UPWATER

Air, Dust, Bacteria

Process fluid out

HEAT EXCHANGER

COLD WATER

Blowdown

OPEN RECIRCULATINGCOOLING SYSTEM

TYPES OF COOLING TOWERS

Cooling Towers
Natural Draft
Design of Cooling tower is such
that cold air of the bottom of tower
push the warmer air out from top.

Mechanical Draft

Forced Draft

Induced Draft

Air is pushed in
the tower with a
fan at the side.

Air is pulled from

cooling tower by
a fan at the top
Counter Flow

Cross Flow

CROSS FLOW COOLING TOWER

COUNETR FLOW COOLING TOWER

H2O

OPEN RECIRCULATING
COOLING WATER SYSTEM
HOT WATER

Air, Dust, Bacteria

Process fluid
out

HEAT EXCHANGER

Process fluid in

MAKE UP
WATER

COLD WATER

Blowdown

Problems in
HEAT TRANSFER Equipments

CORROSION

SCALE/ DEPOSITS

MICROBIOLOGICAL
FOULING

Normal Terminology used

in Open Recirculating Cooling Water System
1. Hold up Capacity of the system : (V)
Hold up capacity of the system = water contained in basin
+
sump of cooling tower
+
water contained in piping and equipments.
2. Blowdown : (B)
Due to evaporation, concentration of Impurities / dissolved solids takes place.
Part of water is removed from system as a blowdown to control concentration of
impurities / dissolved solids in water.
3. Drift / Windage loss : (D)
Some water droplets escape alongwith air and water vapours. A usual drift loss in
conventional cooling towers is in the range of about 0.05 -0.2% of the recirculation
rate.

Contd.
4. Evaporation Losses : (E)
Water lost to the atmosphere in the cooling process is evaporation.
The rate of evaporation depends upon the temperature difference across tower.
For each 5.6 C Delta T across tower, evaporation rate is 1% of Circulation Rate.

5. System Losses : (S)

Circulating water is lost in the plant through
pumps, valves or leakages in plant etc.

Makeup Water requirements vs. cycles of

concentration

6. Concentration Cycle : (C)

Mg or Silica in cooling water
C

=
Mg or Silica in make up water

% MAKEUP WATER ( based on circulation )

12.0

10.0

8.0

6.0

50F DROP

4.0
25F DROP
2.0
10F DROP
0
0

CYCLE OF CONCENTRATION

Blowdown
& Windage losses =

E
----C-1

where E = Evaporation rate.

C = Cycle of Concentration.

10

Contd.
7. Make-up Water : (M)
This is the water which is to be added to replace the water lost by evaporation, blow down, drift and
leakage.
M=E+B+D+S

8. Holding Time Index :

Time required to reduce the concentration
of any constituent in cooling water to half.
0.693 x (Hold up capacity )
HTI

=
Blowdown

Each programme has maximum allowable HTI beyond which chemical lose its effective.

9. Approach :
Indicate efficiency of cooling tower.
Lesser is approach better is cooling tower efficiency.
Approach = Supply of C. W. temperature Wet bulb temperature

Water impurities and its effect

Impurity

Effect

Total Hardness
(Calcium + Magnesium)

Scale formation

M-Alkalinity

Corrosion - Low Alk.

Scale/Deposition. High Alk.

Chlorides

Corrosion / SCC of SS

Suspended Solids

Deposition

Sulphate
SiO2

Corrosion / Scale
formation
Scale

Organic Matters

Fouling

Iron and Manganese

Deposition

Micro-Organisms
Ammonia

Fouling / Corrosion
Nitrifying bacteria / fouling

The Corrosion Process

Occurs due to the presence of local cells with anodic and cathodic sites on the metal
mediated by electron transfer through an electrolyte.
In an aerated, neutral solution, the overall reactions are :
Anodic Reaction
Fe
Cathodic Reaction
O2 + 2H2O + 4e-

Fe++ + 2e-

(1)

4OH-

(2)

Overall Reaction
Fe++ + 2OH-

Fe(OH)2

O2
Fe (OH)3

Fe(OH)3

Water /
Electrolyte

Fe2O3 (Rust)

OH-

Fe ++

O2

H2O

Fe (OH)2
ANODE
ELECTRON FLOW

CATHOD

Pitting:

Most Common types of Corrosion in

Cooling Water Systems

Most destructive
Caused by Localized Deposition & Differential Oxygen cells.

General Type:
Uniform in nature.
Less dangerous

Contd.
Galvanised Corrosion :
It is caused due to the presence of Dissimilar metals.

Stress Corrosion Cracking :

It occurs in S.S. or Copper Alloys and is caused by high chloride and high
temperature & pressure.

Contd.
Crevice Corrosion:
Tube - Tube sheet joint
Under deposit or tubercles
Threaded joints

Erosion Corrosion:
Normally restricted to copper based
alloys.
High water velocity, High suspended solids, Turbulence accelerates.

Corrosion is Accelerated by:

Chloride in water.
Dissolved oxygen in water.
High temperature

Suspended solids (under deposit corrosion)

Contd.
Bacteria (Sulphate reducing & nitrifying )

Low pH of water.

Why Corrosion Control ?

Corrosion Leads To Leakage of Exchangers

Un-schedule Shut Down
Loss of Production
High cost of Equipment Replacement

Corrosion Control :
Selection of proper metal of construction.
Applying protective coating.
Galvanic corrosion control
Using sacrificial anodes (cathodic protection)
Galvanic corrosion control
Corrosion Control of water box in power
plant.
Chemical Treatment
Most economical and widely used.

Corrosion lnhibitor:
The commonly used corrosion inhibitors in an Open Recirculating System are :
i. Chromates
ii. Orthophosphate
iii. Molybdate
iv. Silicate
v. Zinc
vi. Polyphosphate and
glassypolyphosphates
Selection criteria
Water analysis
Metallurgy of equipments
process parameters
Environmental restrictions

: Anodic type.
: Anodic type
: Anodic type
: Anodic type
: Cathodic Type
: Cathodic Type

Scale :
Dense, adherent and hard material composed most commonly of
Calcium & Magnesium salts.
Precipitate at high temperature and get deposited on the heat transfer surfaces.

Following are some types of scale

scale::
280
240

CaCO3, Ca3 (PO4)2

Silicates - Not very common
Magnesium Silicate - very hard

ppm Soluble CaCO3

MgCO3

200

pH = 7.5
ppm TDS = 500
ppm Alk. = 100

160
120
80
40
0

60

80

100

120

140

160

180

TEMPERATURE OF

Chembond

Scale Formation leads to Low Heat Transfer.

Scale (Insulation)

Exchanger tube

Water

Scale formation is accelerated by :

High temperatures.
High hardness of water.
High pH of cooling water.
High M-Alkalinity

Ca(HCO3)2

CaCO3 + CO2 + H2O

Water Indices
Water indices make it possible to predict the tendency of
water either to precipitate or to dissolve Calcium Carbonate.

Types of Indices
Langalier Index :
L. I. = pHa - pHs
Where, pHa = Actual pH of cooling water and pHs = Saturation pH is the function
of the Total solids, Temperature, Calcium & Total alkalinity
When L.I. is positive, it denotes scale forming; and When L.I. is negative, it
denotes corrosion tendency of water.

Chembond

Stability Index [Ryznar Stability Index]

R. S. I. = 2pHs - pHa
Water Tendency :

Index

Tendency of
water

LSI

RSI

2.0

<4

Heavy scale forming,

Nonaggressive

0.5

5 to 6

Slightly scale forming

and mildly aggressive

0.0

6 to 6.5

Balanced or at CaCO3
saturation

-0.5

6.5 to 7

Nonscaling & slightly

aggressive

-2.0

>8

Undersaturated,
very aggressive

WHEN WATER IS TREATED

WITH CHEMICALS, THESE
INDICES DO NOT HAVE
ANY IMPORTANCE.

Why Scale Control ?

Scale Formation Leads To Reduction in Water Flow
Poor Heat Transfer
Reduction in Plant Load
Chemical Cleaning
Unschedule Shut Down
Shorten the Life of Equipments.

Scale Control
Removal of Ca, Mg by Ion Exchange - Cost is High.
Addition of Sulfuric Acid
Ca(HCO3)2 + H2SO4

CaSO4 +2CO2 + 2H2O

CaSO4

Higher solubility than CaCO3

Contd..
Formation of Scale can be controlled by addition of :
Polyphosphate (SHMP):
Less stable at high temperature
Revert to Orthophosphate as P-O-P bond is weak.
Reverted Orthophosphate causes deposition.
O
NaO

O
O

ONa

P
ONa

ONa
x

Zinc glassy polyphsophate:

Zinc glassy polyphosphate has high X value and no definite structure.
More stable than SHMP.
Negligible orthophosphate formation at high temperature.

Scale Control
Organophosphonates :
HEDP: ( Hydroxy Ethylidene Diphosphonate)
P-C-P bond is strong.
High stability with respect to pH and
temperature.
Keeps Calcium & Magnesium in solution.

OH

HCH

OH

OH

PBTC :
Phosphono butane-tricarboxylic acid more effective than HEDP
Synthetic Polymers:
Low molecular weight polyacrylates copolymers/Ter-polymer.
- Crystal Modification.
- Keeps precipitated Calcium salts in water.

OH

OH

Deposition / Fouling
Causes :
1. Corrosion Products.
2. Suspended solids in cooling water.
3. Dead algae in cooling tower.
4. Slime produced by microorganisms in water.
5. Low velocity.
6. Process Contaminants - Ammonia, Oil, Hydrocarbons.

Control Agents/ Methods:

1. Dispersants based on low molecular weight polymer.
2. Bio-Dispersant.
3. Providing proper velocity to water (3-5ft/sec)
4. Providing Side Sand Filter.
Capacity 3-5% of Circulation rate.
5. Backflushing / Air rumbling arrangement.

Deposition causes under deposit corrosion.

Microbiological Fouling
The major classes of microorganisms which are associated with recirculating Cooling
System are :
Bacteria - In Cooling Water.
Algae
- On cooling towers structure / distributing deck.
Fungus - On wooden structures of cooling towers.
Delignification of wood. (phto27.8)

-Temperature of cooling water is ideal for bacterial growth.

- Sun light is accelerate growth of Algae
-Abundant nutrients are available.

Different Types of Bacteria :

Sulphate Reducing Bacteria(Anarobic)- pitting type corrosion.
SRB attack

Brown deposits on top

Under brown deposit black deposit.
Under black deposit, silvery shining surface.
Nitrifying Bacteria - pH drop.
Iron Bacteria - Iron fouling.
Slime Bacteria

Why Microbiological Control ?

Microbiological Growth Leads To Fouling of Exchangers .
Less Heat Transfer.
Under Deposit Corrosion.
Reduction in plant load.
Microbiological Induced Corrosion (MIC)
-Pitting.
Un-schedule Shutdown.
Decrease in Cooling Tower Efficiency.
Damage of Wooden Parts of Cooling Tower.

Microbiological control
OXIDISING BIOCIDE

Chlorination.

Reaction Of Chlorine Activator

Microbiological action of Chlorine :

MBr + HOCl

HOBr + MCl

100

Cl2 + H2O - HOCL + HCL

HOCL is the active species and dissociates as pH

80

40
20
0

Increases
HOCl + OH- =

HOBr

HOCl

60

7
pH

OBr-

10

HOBr and
are more toxic to bacteria compared to HOCl, OClAt pH = 8.5
HOCl / OCl- = 10 / 90
HOBr / OBr- = 60 / 40

OCl- + H2O

Formation of HOCl, OCl- depends on pH of water

HOCL is mainly responsible for killing of bacteria
OCl- has very low action on bacteria
As pH increases above 8, OCl- formation takes place, chlorination
effectiveness decreases

Dosage
: 0.2
- 0.5ppm bring
for 3 -down
4hrs. the
Percooling
day water pH
Heavy
chlorination
Chlorine does not reach all the parts of the Cooling System.

Chlorine Demand:

Amount of chlorine consumed by following impurities before free

chlorine appears in Cooling Water.
Organic Matters
Ammonia
Dead Algae, Slime
Other Oxidizable Substances

Bromine
-Effective at high pH
-Effective in ammonia contaminates system compare to chlorine

Ozone
-pH is sensitive
-Produced at site by electrolysis

Chlorine Dioxide - Very effective in presence of

Ammonia
Organic

Chlorine Activator
( Chlorite based)
In-Situ Generation of Chlorine Dioxide

GENEROX
ClO2
Flow meter

BSP
connection

Electric Control Box

Emergency Shutdown Switch
Flow Indicator
2

ClO2 Generator

NaClO2 + 1/2 Cl2 - ClO2 + NaCl

(Chlorine Dioxide )

13

Loss of Cl2 Switch.

Pressure gauge

BSP
connection

Chlorine Dioxide:
Advantages :

Auto Switch

Dosing Pump

Precursor Source

Do not react with Ammonia, Organics. Hence

more effective than chlorine in contaminated

system.
Reduces chlorine consumption.
Reduces the chloride builtup due to chlorination.
Effective in high pH range also.
Negligible delignification of wood.

48"H x 42"W x 17"D

Chlorinated
water inlet

Filter

Reaction Of Chlorine Activator

MBr + HOCl

HOBr + MCl

100
80

HOBr

HOCl

60
40
20
0

10

pH
HOBr and OBr- are more toxic to bacteria compared to HOCl, OClAt pH = 8.5
HOCl / OCl- = 10 / 90
HOBr / OBr- = 60 / 40

Non-Oxidising Biocides
Methylene Bis Thiocynate ( MBT )
Very effective against SRB. It Hydrolizes above7.5 pH

Quaternary Ammonium Compounds(QAC)

Tendency to foam. Ineffective in highly oil or organic fouled systems. Effective at high pH.

Glutaraldehyde ( ALD )
Effective over wide pH range.
Isothiozoline ( THIO )
pH Insensitive
Dichlorophene
effective over wide pH range.
DBNP
EFFECTIVENESS
Bacteria
MBT
QAC
ALD
THIO
DBNP

E
E
E
E
E

Fungi
S
G
E
G
S

Algae E = Excellent
S
E
E
E
S

G = Good
S = Slight

Non--Oxidising Biocides
Non
Dosage : Once in 8 - 10 days
Bacteria develop resistance to non-oxidizing biocide.
Use of more than 1 non-oxidizing biocide is preferred to avoid immunity.

Covering the top of the distributing deck of the cooling tower will
eliminate the sunlight resulting in a reduction in the formation of algae.

Total Bacterial count / ml.

Bacterial Growth & its Control with Biocides

Biocide
Dosing
Acceptable
Range

14
Time ( in days )

21

Bio Dispersant
What is Bio-Dispersant ?
Bio-Dispersants are non-anionic type surface active agents alongwith slime
solublizing solvents.
Functions :
When Bio-Dispersant is added alongwith oxidizing or non-oxidising biocide, it :
Increase the effectiveness of biocide.
Removes slime.
Releases bacteria arrested under slime deposits so that biocides can kill free
bacteria.
Addition of Bio - Dispersant increases turbidity, increases total bacterial
count & generates foam.

Monitoring methods
Corrosion

: Corrosion Meter & Coupon Holding Rack.

Coupon holding rack

O U TL E T

22.3 x w
Corrosion rate = -----------dxaxt

18

FL OW
TEE

Mpy = mills per year

w = Loss in weight in mgs
d = Density of test coupon in gms/cm3
a = area in Inch2
t = time in days

E BO N IT E

1/2

COUP ON

W ATER IN LET
22.3 x W
C O R RO SIO N R ATE ( m p y) = ------------d xa xt
W - Loss in we ight in m g.
d - D e nsity of m etal in gm /cm 3
a - Area of coupo n in in 2
t - T im e in da ys

d for C S
= 7.85
C opper = 8.9
Brass = 8.17

Scale and deposition

: Test Heat Exchanger / Deposit Monitor

ELEC TR IC IT Y SU PPLY 230V ,

50HZ, 1Ph
TEM P. IND IC AT OR

JU N CT ION BOX

CO LD CO NDENSATE O UT
1/2 TUBE

Mains

Restart

Heater

OU TLET

Actual

RUBBER TUBE

CO OLING W ATER OUT

Set
Temp. Set

SEN SOR ( t 2 )

Ammeter
Am meter

HE ATER
T herm ostat

COO LING W ATER IN

Length about 2 - 3 feet

FLO W M ETE R

HOT CONDENSATE IN
AC R YLIC TU BE

BALL VALVE
S EN SOR ( t 1)
IN LET

FLOW C ON TR OL VA LVE

Deposit Monitor

Test Heat Exchanger

Contd..
Deposition

: Temperature & Pressure monitors of exchangers.

Bacteria analysis : T.B.C.

DP

S.R.B.

N.R.B.

Outlet

Pressure drop tube

PG
Flow Meter

Inlet

= Ball Valve
= Flow Control Valve
D.P.G.

Biofouling Monitor

= Differential Pressure Gauge

=

Strainer Valve

Online Measures for Overall improvement

in performance of Treatment Programme.
Side Sand Filter
About 5% of circulating water is to be passed through a side sand filter so as to
reduce suspended solids.
Air/Nitrogen Bumping and Back Washing :
Air bumping and back washing is very necessary for shell side water heat exchangers
and compressor jackets.
C O O L IN G W A T ER O N SH EL L S ID E

C O O L IN G W A TE R O N S H E LL S ID E
C o o lin g W a te r O u t

C o o lin g W a te r O u t

P roc e s s O u t

P ro c e s s O u t
P ro c e s s In

Air / N 2 In je ctor
p o int

P ro c es s In

C o o lin g W a te r In

T o D ra in

A lter na te A ir
In je c to r P oint

C o o lin g W a te r In

Annual Water Flushing of Heat Exchangers and cleaning sump, basin.

Biocleaning ( On-Line )
Addition of Biodispersant ( 5-10ppm)
Maximum Circulation
Addition of NonOxidizing Biocide
Blowdown after 8-12hrs. Circulations.
Turbidity of water increases.

Target Dosing:
Dosing of Biodispersant / Dispersant at inlet cooling
water of fouled Exchanger.

Precleaning / Passivation
PRECLEANING: - Removal rust etc and making
surface active for passivation.
Addition of oil dispersant ( For New System )
Reduction of pH ot 5.5 - 6.0
Addition of Dispersant
Monitoring of Iron Content
Blowdown after Fe remains constant.
Maximum circulation.

PASSIVATION : - Film formation on cleaned surface.

Bare metal

With proper passivation

Without proper passivation

Control of pH
Addition of Corrosion Inhibitor (PO4= 60-70ppm )
Circulation without blowdown for 24-48hrs.

New Exchanger (CS) - Individual precleaning/ passivation essential.

Performance Limits
Good treatment programs should ensure the following results for the parameters :

1.Corrosion rate of <2mpy of Carbon Steel and absence of under deposit corrosion.

2.No Hard Scale formation which will require acid cleaning.

3.Bacterial Count :

TVC = < 1 x 105/ml.

SRB = <100cells/100ml.

4.Non-toxic effluent. No treatment should be required for the blowdown water.