Fundamentals of

Cooling water
Treatment & CT-5
Experience

Knowledge sharing presentation, 9th Sept. ‘05 1

Prepared by : Asim Mal

 Fundamentals of CW treatment

Types Cooling water system

Why Treatment is required ?

Treatment & corrosion

Case study of Cooling tower-5

2
 Fundamentals of CW treatment

Once Through circulation

Closed Recirculation

Open Evaporative

3
 Fundamentals of CW treatment
ONCE - THROUGH SYSTEM

Cooling - Water Inlet

Heat
Load

Outlet

4
 Fundamentals of CW treatment
Once through cooling water system

 Usually located at or near oceans,

lakes or rivers
 Water supply temp. is low & rapid
cooling achieved
 Corrosion, scale, fouling & micro-
biological growth is minimum due to
low COC
 Good quality water
5
 Fundamentals of CW treatment

CLOSED RECIRCULATING SYSTEM

To
Cooling Tower

Heat
Makeup Load

Surge Tank
From
Cooling Tower
Heat Exchanger
6
 Fundamentals of CW treatment

 Close cooling system salient points

– Usually less susceptible to deposition

– primarily concerned with corrosion

– Closed defined as loss < 0.5% cir. rate.

– Operating unusually high or low water

– Temp. engine cooling jacket (72 - 82°C)

or chilled water system (4 -6°C)

– System are rarely oxygen free due to air

leak & oxygenated make up water
7
 Fundamentals of CW treatment

OPEN RECIRCULATING SYSTEM

Blowdown
Evaporation

Cooling Heat
Tower Load
Make up

Recirculating Pump 8
 Fundamentals of CW treatment
 Mass balance in Open recirculating CT
 Make up (MU)= Evaporation (E) + Blowdown (BD)

 Blowdown (non-evaporative loss) = Int. Blowdown

(Bdi)+ Windage (W)+ Drift (D) + leaks (L)

 Cycle of Conc. (C) =MU/BD

 E (m3/hr)=T (°C)x recir. Rate (m3/hr)x F/600

 BD = E/(C-1)

9
Fundamentals of CW treatment
 Mass balance in Open recirculating CT
Evaporation Loss from Cooling Towers

20%-RH 40%-RH 60%-RH 80%-RH 90%-RH

2.3

2.2

2.1
Cooling Range is 10 deg C

2
20% RH
1.9
Evap Loss, % of Circ. rate

1.8

1.7 40% RH

1.6
60% RH
1.5

1.4 80% RH

1.3
90% RH
1.2

1.1

1
13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 10
32
Wet Bulb Temp, Deg C
 Fundamentals of CW treatment
Why Treatment is required ?
Without treatment, water characteristic
Scaling side (+ve), Corrosive side (-ve)
LSI (pHa-pHs) where pHs = F ( CaH & alk)
Ryznar Index I = 2 (pHs) – pHa
If RI < 6, scaling side
If 7.0 < RI < 7.5 No scaling
Larson & scold index
(epm Cl + epm SO4)/(epm HCO3 + epm CO3)
Index < 0.8, When Index > 1.2, pitting
corrosion 11
 Fundamentals of CW treatment
The Corrosion Process
Occurs due to the presence of local cells with anodic and cathodic sites on the
metal by electron transfer through an electrolyte.
In an aerated, neutral solution, the overall reactions are :
Anodic Reaction

Fe Fe++ + 2e- (1)

Cathodic Reaction
O2 + 2H2O + 4e- 4OH- (2)
Overall Reaction

Fe++ + 2OH- Fe(OH)2 Fe(OH)3

O2 Fe2O3 (Rust)
Water / Electrolyte

Fe (OH)3 OH-
Fe ++ O2
H2O
Fe (OH)2
ANODE
ELECTRON FLOW CATHOD
12
 Fundamentals of CW treatment
MOST COMMON FORMS OF CORROSION
IN COOLING WATER SYSTEMS.
Pitting:
Most destructive
Caused by Localized Deposition & Differential Oxygen cells.

General Type:
•Uniform in nature.
•Less dangerous

13
 Fundamentals of CW treatment
MOST COMMON FORMS OF CORROSION
IN COOLING WATER SYSTEMS.

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.

14
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.

15
 Chemical treatment with Corrosion lnhibitor:

The commonly used corrosion inhibitors in an Open Recirculating System are :

i. Chromates : Anodic type.

ii. Orthophosphate : Anodic type
iii. Molybdate : Anodic type
iv. Silicate : Anodic type
v. Zinc : Cathodic Type
vi. Polyphosphate and
glassy polyphosphates : Cathodic Type

Selection criteria

•Water analysis
•Metallurgy of equipments
•process parameters
•Environmental restrictions 16
 Non Chromate Treatment Programme
(Open re-circulating cooling water system)

Stabilized Orthophosphate programme:

• Zinc - Orthophosphate - Organo phosphonate
• Polymer as a dispersant -
Alkaline

Stabilized Ortho-metaphosphate programme:

. Zinc - Ortho-metaphosphate glass

• Organophosphonates - polymer as a dispersant - Acidic to Alkaline

17
 Stabilized Phosphate Programme
(Non-Zinc)

A.
•Orthophosphate-polyphosphate-Organo-phosphonate-
polymer-azole (one drum treatment)

B.
•Orthophosphate-polyphosphate-organo-phosphonate-
azole, polymer as a dispersant
(Two pack system)

18
 Surface Reaction Product Inhibitors

Important phosphate compounds used for CW treatment are :

Name Formula Structure Ratio (Na2O / P2O5)

Ortho NaH2PO4 Tetrahedral 3

Pyrophosphate Na4P2O7 - 2 to 3
Poly Na n+2(PO3)n+1 Chain (polymetric) 1 to 2
Meta Nan (PO3)n Ring or long chain 1
{where n = 3, 4, ..…}

PO4-
Phosphates are free from
toxicity Fe++

Fe
19
 Chemistry and Structure of Phosphate

Sodium salts of the liner & condensed polymeric phosphates can be

written as :

O O

NaO P O P ONa

ONa ONa
x
where x=0 for orthophosphate
x=1 for pyrophosphate
x=2 for tri polyphosphate
x = 12 - 14 for polyphosphate

When the polymeric groups increase, the [Na2O : P2O5] ratio approaches
1. Here, the family of glassy condensed phosphate e.g. Metaphosphate
are formed. 20
 Orthophosphate Inhibition Mechanism

•Inhibition efficiency depends on pH and availability of oxygen

•Protective film gamma-Fe2O3 formed in presence of O2 /air in alk. H2O
•It is an Anodic inhibitor - interferes in oxidation of Fe2+
•Ortho-phosphate leads to the formation of FePO4 . 2H2O at anodes.

The basic reactions are:

Fe2+ + H PO - FeH PO +
2 4 2 4

FeH PO + + 2H O FePO . 2H O +2H + e -

4 2 4 2
2

FePO4 . 2H2O are deposited as plugs in FePO42H2O

the pits or defects in the oxide film
thereby inhibiting further attack.
 Fe2O3 Fe
21
 Orthophosphate Inhibition Mechanism (cont.)

•Stability of the anodic film depends on pH

•Better protection is ensured in alkaline environments

•Conc., if less than critical (when used alone) leads to pitting

•Presence of Chlorides accelerates pitting type corrosion

Cl-
FePO42H2O
CaPO4

 Fe2O3 Fe
PIT

22
 Orthophosphate - Zinc Inhibition Mechanism

• Zinc acts as a Cathodic Inhibitor

•Zinc precipitation as Zinc hydroxide at Cathode

Zn+ + 2OH- Zn(OH)2

•Reduces pitting tendency with lower Orthophosphate (Anodic Inh.)

• Combination is stabilized using Organophosphonate
FePO42H2O Zn (OH)2
CaPO4

 Fe2O3 Fe Fe
Anodic inhibition Cathodic inhibition

• Dispersant for Phosphate / Fe / Zn Stabilisation is essential

23
 Advantages + Limitations of Orthophosphate
Programme
Advantages
 Orthophosphate concentration in cooling water is known
 Dispersant levels can be monitored to avoid excessive phosphate
deposition
 Programme works well even in low hardness water

Limitations
 Protective film consists of Iron Phosphate
 Controlling excessive Iron phosphate precipitation is very critical
 This requires specific iron dispersant
 No Metaphosphate, so antiscalant requirement is high
 High Orthophosphate levels accelerates microbial growth
 Prone to pitting

24
 Synergistic Inhibition Metaphosphate -
Orthophosphate (cont.)

Ortho phosphate % PO4

100 75 50 25 0
2.0
1.8 Condition : 15mg / lt total
pH 7.5
1.6 50 C
1.4
Corrosion rate (mpy)

1.2
1.0
0.8
0.6 Ref. Corrosion Control of
Industrial Cooling Water System
0.4
By : Bennett P Baffardi
0.2 Material performance - Nov’1984
0
0 25 50 75 100
Meta phosphate
25
Success or Failure of any phosphate
based treatment program is highly
depended on the Dispersant (Polymer)
incorporated In the treatment package.

Active dispersant = f (insoluble PO4, Iron ,

TSS)

26
Cooling water treatment
 Factors affecting corrosion
• Corrosion rate approximately double for
every 20°C rise in temperature
• Increasing dissolved solids makes CW better
electrolyte & increased corrosion rate
Corrosion rate

Corrosion rate

Temperature Dissolved solids

27
Cooling water treatment
 Factors affecting corrosion
•Ammonia: Little effect on steel however it
can form Cu complex and increases corrosion
on Cu based alloy (general and stress
corrosion cracking)
•H2S: Sour water will corrode steel and copper
alloy forming soluble & insoluble sulfide
products. It reduces pH , consumes more
chlorine and reacts with Zn forming ZnS
thereby hampering cathodic protection of
treatment program.
 HC: Cause oily deposits on metal surface &
lead to differential oxygen concentration
cell resulting in under-deposit corrosion.
 Soluble Copper: Cu ions can electoplate on
steel surface and act as galvanic cell
resulting in pitting corrosion.
28
Cooling water treatment
 Corrosion product
•Corrosion product formed at anodic site may
remain in the form of tubercule

•Corrosion product of mild steel are

potential foulant as it is many time
voluminous than metal

•They may swept away and sequestered by

appropriate deposit control agent or
redeposited creating another corrosion site

•inert materials such as sand,dust,silt,

fibers form differential oxygen
concentration cell causing under-deposit
corrosion.
29
 WATER TREATMENT CONCERNS
Corrosion

Particle Entrapment
Deposition Growth Sites Biofouling

30
 TYPES OF DEPOSITION
Scaling
Mineral Scale
Fouling
Suspended Matter
Transient Corrosion Products
Process Leaks
31
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32
l=r+r+r
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f m s
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Common Scales
 Calcium Carbonate  Zinc Phosphate
CaCO3 Zn3(PO4)2
 Calcium Sulfate  Iron Phosphate
CaSO4 FePO4
 Calcium Phosphate  Calcium Magnesium
Ca3(PO4)2 Silicate
 Magnesium Silicate CaO.MgO.2(SiO2)
MgSiO3  Silica
 Aluminium Silicate SiO2
Al2O3.SiO2
33
 Monitoring of CW treatment

 Corrosion Coupons - For Average

corrosion
 Biofouling Monitor – For Slime detection
 Deposit Monitor – For Scale Monitoring
 Dip slides and Vial for MB counts
 Corrator – For online corrosion
monitoring
 Bioscan – For on the sopt MB counts
 ORP and Sniffer – For Hydrocarbon leak
Detection 34
The Problems faced in CT5

 Plugging of Exchanger Tubes

 Reduced Water Flow
 Reduced Heat Transfer
 Under deposit Corrosion
 Interferences with treatments
 Frequent cleaning of cooling tower Decks
 Bio-fouling of heat exchangers & flaring

35
MB control by Halogen
 Halogens
 Effective on planktonic organisms
 Poor penetrating power
 Inactivated by reaction with biofilm
components
 Low concentrations will not remove or
control
 High concentrations effective but
corrosive

36
38
 Algae – Main Problems

choked pipelines, nozzles etc

Produces oxygen accelerating corrosion

Some algae fix nitrogen, deteriorating nitrite

based inhibitors.

Produces slime

39
 Fungi

 Lack chlorophyll

 Depend on nutrients provided by organic matter

(heteorotrophic)

 Use CT wood as nutrient

 Reproduce by forming spores

 Difficult to kill

40
 Bacteria

Pseudomonas-Generates voluminous slime

Sulphate reducing bacteria

Iron bacteria

Nitrifying bacteria

41
 Sulphur Reducing Bacteria

o Anaerobic bacteria

o Reduces sulphur to sulphides

4Fe + SO4-2 + 4H2O FeS + 3Fe(OH)2 + 2OH-
Fe + H2S FeS + H2

o Iron sulphide is cathodic with respect to iron

o During chlorination
H2S + Cl2 2HCl + S (can attack concrete basin)

42
Characteristic SRB pit

43
In any aquatic environment, such as a cooling
water system, there are two distinct but inter-
changing microbial populations :

 Planktonic micro-organisms
free-floating

 Sessile micro-organisms
(Biofilm)
surface-attached
44
45
Properties of bacterial biofilms

 Mostly water (90 - 99 %)

 Low thermal conductivity

 Viscoelastic (deformable)

 Glycocalyx forms a matrix

 Bacteria grow in micro-colonies

 Water channels anastomose through the

biofilm.
46
 Biofouling Problems

 Reduction in plant performance

Caused by biofilm growth

 Reduction in plant integrity

Caused by microbial corrosion

 Reduction in plant safety

Caused by growth of Legionella

47
 Biofilm vs. CaCO3 as a heat insulator

Cooling Water

5 mm

Scale
Biofilm 1 mm

Heat Transfer Surface

Equivalent Reduction in Heat Transfer Rate

48
Biofilm and Scale Formation

49
Pit Beneath Biofilm

50
pH Effect vs Halogen Dissociation

100 0
% HOCl or HOBr

% OCl- or OBr-
90 10
80 20
70 30
60 40
50 50
40 Chlorine Bromine 60
30 70
20 80
10 90
0 100
4 5 6 7 8 9 10 11 12

pH
51
 pH Effect vs
Biocidal Activity

100 Bromine Kill 6

90
% HOCl or HOBr

Log Kill (cfu/ml)

5
80

70
4
60

50 3

40

30 Chlorine Kill 2

20
1
10

0 0
6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0

52
pH
WHAT IS CHLORINE DIOXIDE?

ClO2 does not react with water, unlike other oxidants,

nor does its chemical composition or biological activity
change with shifts in the water’s pH.
ClO2 in solution is actually a free radical which explains why
it has an excellent biocidal capability. This also explains
why ClO2 disperses so quickly in water yet does not
readily dissociate.
ClO2 actually uses five available electrons to disrupt cellular
metabolism of the cell to kill the organism and block
enzymes necessary for metabolism.
ClO2 has 2/3 the oxidation potential of Cl2But 21/2 times the
oxidizing capacity of Cl2.
53
A COMPARISON OF CHLORINE DIOXIDE
AND CHLORINE FOR DISINFECTION
ClO2 Cl2

Volatility Moderate High

pH maximum ca. 10 ca. 8
Reacts with NH3 / NH4+ No Yes
Tolerance to organics Moderate Poor
Corrosivity Moderate High
Hydrolyses in water No Yes
Ox. capacity (Cl2 = 1) 2·5 1·0
Forms chloro-organics No Yes
Environmental impact Low High.

55
Mode of Action of
Non-oxidizing
Biocides

56
Isothiazolone

 Target: aerobic (nitrifying bacteria)and

anaerobic bacteria, fungi, and algae
 Mode of Action - Reacts with cytoplasmic
thiol groups (enzymes and proteins)
 Speed of Kill: slow (4 to 12 hours)
 Disadvantages:
– Deactivated by reduced forms of sulfur
– Sensitizer - special handling precautions

57
Glutaraldehyde

 Target: aerobic and anaerobic bacteria, and

fungi, For SRB killing
 Mode of Action - Cross links amino groups on
cell surface (enzymes and proteins)
 Speed of Kill: medium (3 to 8 hours)
 Disadvantages:
– Reacts with ammonia (> 50 ppm)

58
Quats

 Target: aerobic (nitrifying bacteria) and anaerobic

bacteria, algae and fungi
 Mode of Action - The negatively charged cell
surface attracts the cationic biocide which affects
cell permeability.
 Speed of Kill: fast (< 2 hours)
 Disadvantages:
– Foaming
– Cationic - react with anionic components of
scale/corrosion programs

59
Carbamate

 Target: aerobic and anaerobic bacteria,

fungi, and algae
 Mode of Action:
– Strong chelating agent that ties up
essential elements in cell wall
 Speed of Kill: medium (2 to 4 hours)
 pH range 6 - 8
 Disadvantages:
– May form insoluble precipitate with iron
– Very little activity at pH 8 or higher
60
Methylene Bisthiocyanate

 Target: aerobic and anaerobic bacteria

 Mode of Action:
– Targets membrane associated enzymes
 Speed of Kill: medium to slow (6 to 12
hours)
 pH Range: 6 - 8
 Disadvantages:
– Degrades very quickly at pH of 8 or greater
61
Biodispersant

 Target: Microbiological slime

 Mode of Action - Improves biocide
penetration into slime and helps dislodge
microbial from surfaces
 Disadvantages:
– Foaming occurs if over fed
Non foaming biodispersants are today available

62
 Mechanism of Action for Biodispersants

BIODISPERSANT

METAL SURFACE
63
CW deposit analysis

 LOI 12.5 %
 Fe2O3 61.4 %
 Phosphate (P2O5) 18.6 %
 Sulphate 2.8 %
 CaO 1.6 %
 Acid insoluble 1.5 %
 Zinc oxide 0.4

64
 CT-5 chronology
Sr. No. Date Leak / upset / Remarks / steps taken
major event
1 Upto Dec. ‘03 Very few leak (2 Cooling water supply was from
exchangers) CT-2 (fresh water cooling tower)
2 Dec. ’03 (after CT-5 Coker cooling water load was
QYI) commissioning shifted from CT-2 (fresh water)
to new cooling tower based on
LTDS treated water make up
3 Feb ‘04 371-S09 B leak Opportunity shutdown taken in
(H2S & HC) June ’04. CW treatment was
modified with more addition of
Pyrophosphate, zinc & phosphate
& dispersant
4 May ‘04 371-S04 Heat exchanger was in isolated
condition, whenever taken in
line, found leak. Identified &65
isolated.
 CT-5 chronology
Sr. No. Date Leak / upset / Remarks / steps taken
major event
5 May ‘04 371-S21 First time commissioned in May
commissioned ’04
6 July ’04 – Sept ETP upset Cooling tower COC reduced
‘04 condition
7 Dec. ‘04 372-S21 & 372- S21 was isolated and 108 tubes
S10A leak was found in bad condition. S21
was retubed. S10A isolation was
not possible. Non –oxidising
biocide and other chemicals
addition was increased with
increased blowdown
8 Feb. ‘05 371-S03 leak Mechanical failure

66
 CT-5 chronology
Sr. No. Date Leak / upset / Remarks / steps taken
major event
9 Dec. ’04 – Feb ETP upset COC of the tower reduced,
.’05 managed the cooling water
quality with more addition of
sodium hypochlorite as a short
term measure and more non-
oxidising biocide addition
10 Dec. ’04-Feb. Cooling tower Coker throughput limitation. To
‘05 top deck reduce the TSS load & improve
cleaning heat transfer of critical heat
exchanger, cleaning done.
Chlorination was very high.
11 June. ‘05 371-S21 leak One tube leak. Tube plugged and
found under deposit corrosion by
analyzing the tube cut sample
67
 CT-5 chronology
Sr. No. Date Leak / upset / Remarks / steps taken
major event
12 June’05 371-S23 leak Corrosion was mainly from process
(flare gas side but heavy tube deposit &
recovery heat corrosion found from CW side also.
exchanger)
13 June ‘05 ClO2 generator ClO2 generator was commissioned as
commissioned chlorine demand was more & ingress
of H2S & HC due to frequent leak. The
commissioning was delayed. Proactive
role of vendor was not highlighted.
14 Aug. ‘05 371-S21 leak Leak of the exchanger after 45 days
from 1st leak.
15 Aug. ‘05 CW treatment Existing vendor reviewed the
review treatment by national & international
expert and suggested treatment 68
change
COKER HEAT EXCHANGER LEAKAGE TREND

69
 CT-5 Water pH Trend

8.50

Control Limit: 6.80 – 7.80

8.00
Water pH

7.50

7.00

6.50
01/01/05 16/01/05 31/01/05 15/02/05 02/03/05 17/03/05 01/04/05 16/04/05 01/05/05 16/05/05 31/05/05 15/06/05 30/06/05
70
Time
 CT-5 Water Conductivity Trend

6500
Control Limit: < 4000
6000

5500
Conductivity, uS/cm

5000

4500

4000

3500

3000

Hypochlorite Dosing
2500

2000
H2S & HC Leak

1500
01/01/05 01/02/05 01/03/05 01/04/05 01/05/05 01/06/05 71

Date
 CT-5 Water TSS Trend

140

H2S & HC Leak Control Limit: < 25

120

100
Water TSS

80

60

40

20

0
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72
Time
 CT- 5 Water Turbidity Trend

110

100
Control Limit: < 20
90

80
Water Turbidity

70

60

50

40

30

20

10

0
01/01/05 16/01/05 31/01/05 15/02/05 02/03/05 17/03/05 01/04/05 16/04/05 01/05/05 16/05/05 31/05/05 15/06/05 30/06/05
73
Time
 CT-5 Water Delta O-PO4 (Insoluble) Trend

6.50

Control Limit: < 3.0

5.50

371-S-03 Lined Up
Water Delta O-PO4, ppm

4.50

3.50

2.50

1.50

0.50
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74
Time
 Dispersants and Delta PO4 v/s Date
Delta Insoluble PO4 Active Dispersant
6.50 30

5.50 25

Active Dispersants, ppm

Delta PO4, ppm

4.50 20

3.50 15

2.50 10

1.50 5

0.50 0
01/01/05 16/01/05 31/01/05 15/02/05 02/03/05 17/03/05 01/04/05 16/04/05 01/05/05 16/05/05 31/05/05 15/06/05 30/06/05
75
Date
 CT-5 Water Iron Trend

7.00
Control Limit: < 3.0
6.00

371-S-03 Lined Up
5.00
Iron Content, ppm

4.00

3.00

2.00

1.00

0.00
01/01/05 16/01/05 31/01/05 15/02/05 02/03/05 17/03/05 01/04/05 16/04/05 01/05/05 16/05/05 31/05/05 15/06/05 30/06/05
76
Time
 CT-5 Water Chlorides Trend

1700
Control Limit: < 750
1500

1300
Chlorides, ppm

1100

900

700

Hypochlorite Dosing
500

H2S & HC Leak

300
01/01/05 16/01/05 31/01/05 15/02/05 02/03/05 17/03/05 01/04/05 16/04/05 01/05/05 16/05/05 31/05/05 15/06/05 30/06/05
77
Time
 Experience of CT-5
 Failure of tube is due to mainly under deposit corrosion &
partly MIC
 MB treatment should be stringent for Treated water CT
Chlorine along with Chlorine-di oxide
 Upset of Treated water wrt COD & TSS and treatment
change in Cooling tower end
 TVC, SRB & tower condition monitoring & accordingly
dosing of biocide
 COC ( 4.5 –8) of tower is according to the circulating
water parameters
 Monitoring of Dispersant in circulating water to avoid
deposition
 Cathodic treatment should be strong enough for sour leak
 High Chloride ion & higher conductivity is to be avoided
for pitting 78
 .

Thank You

79