THERMAX LIMITED

CHEMICAL DIVISION

CHEMICAL WATER TREATMENT

FOR

COOLING WATER SYSTEMS

CONTENTS

 1. Introduction to Cooling Water Systems

 2. Problems in Cooling Water Systems
a. Corrosion
b. Scaling
c. Fouling
d. Microbiological Growth
 CONTENTS

 3. Chemical Treatment Programs

a. Corrosion Control
b. Deposit Control
c. Microbiological Control
 4. Program Approach at Bataan2020
 5. Monitoring Methods
 6. Summary
 INTRODUCTION TO
COOLING WATER SYSTEMS
Cooling Water System

• The purpose of
cooling systems is to
transfer heat from one
substance to another
• The substance that
gives up its heat is
“cooled”
• The substance that
receives the heat is the
“coolant”
 Why Water is Used for Cooling???

• Plentiful; Readily Available; Cheap

• Easily Handled: Pumpable
• Can carry large amounts of heat
• Does not expand/contract much at
normally encountered temperatures
• Does not decompose
 Classification of cooling system

Open recirculating cooling water system

Indirect cooling
Closed recirculating cooling water system
water system
Once through cooling water system
Cooling
water system
Open recirculating cooling water system

Direct cooling
water system
Once through cooling water system
TYPICAL OPEN RECIRCULATING
HO 2
SYSTEM
HOT WATER

Process fluid
Air, Dust,
out
Bacteria

HEAT EXCHANGER

MAKE UP Process fluid in

WATER

COLD WATER

HEAT EXCHANGER/COOLING WATER

CONCERNS
Blowdown
MICROBIOLOGICAL
CORROSION SCALE/ DEPOSITS
FOULING
Water Balance for Open Circulatory
Systems
CR (5) N = E+B+W
(1) N = B+W
CM

(2) CM× M = CR× (B+W) (6) E = ΔT × R

5.8 100
CR M H
(3) N = = (7) TR≒
CM B+W B+W

(4) M = E + B + W (8) TH = 0.7×TR

N : Cycle of concentration E : Evaporation loss (m3/h)
CR : Concentration of dissolved solids in circulating water (mg/l) ΔT : Water temperature drop through cooling tower (℃)
CM : Concentration of dissolved solid in make-up water (mg/l) R : Circulating water rate (m3/h)
M : Make-up water quantity (m3/h) TR : Retention time (hr)
B : Blow down water quantity (m3/h) H : Holding water volume of cooling water system (m3)
W : Windage loss (m3/h) TH : Half life time (hr)
Benefits of Cycle-up for Cooling Tower
TB M
6
[percentage of circulating water volume]

10
1 0 TB M
Evaporation loss : 2 %
51E+14
1.8
4 2
1 #DIV/ 0! #DIV/ 0!
1.8 4
4 3 0.8 3 Windage loss : 0.2 %
Water volume

0.8 3 3 105 0.022222

4 0.466667 2.666667
2.5 2.222222
4
2.666667 6
0.3
0.2 2.4
0.466667 2.52.666667 1178 0.133333 0
2.333333
0.085714 2.285714
2.2
3 2.4 2.5 10 0.022222 2.222222 Make-up water volume
9 0.05 2.25
0.3 11 0 2.2
2.333333
0.2
2.285714 2.4
2 Evaporation
0.1 333332.25
2.333333
1
loss
0.08571 4 2.28571 4
Blow down water volume
0.05 2.25
0 Max.
0.022222 2.222222
1 2 3 4 5 6 7 8 9 10 11
0 2.2

Cycle number of circulating water (N)

CONCERNS IN COOLING
WATER SYSTEMS
 Common Cooling Water Problems
Left unchecked these
problems result in
FOULING  Loss of heat transfer
 Reduced equipment
life
 Equipment failures
 Lost production
MICROBIO  Lost profits
 Increased
maintenance costs
SCALE CORROSION  Plant shutdown
Corrosion Theory

 A natural occurring process whereby metal

reverts back to its natural state.
 In the presence of an electrolyte, metal,
oxygen & conductivity.
 Corrosion can be minimized but not
stopped.
Chemistry of Corrosion

o ANODE
o CATHODE
o ELECTROLYTE
o ELECTRON FLOW
Factors necessary for Corrosion
oANODE

oCATHODE

oELECTROLYTE

oELECTRON FLOW
Chemical Factors Affecting Corrosion

 pH
 Dissolved Salts
 Dissolved Gases
 Suspended Solids
 Microorganisms
Mineral Scale
 Cooling Water contains many
different minerals -- normally these
minerals are dissolved in water

 Under certain conditions minerals

can come out of solution and form
into hard, dense crystals called
SCALE
Factors Affecting Scale Formation

Mineral Concentration
Water Temperature
Water pH
Suspended Solids
Water Flow Velocity
 Mechanism of Scale Formation
Four Requirements for Scale Formation

• Ion Super saturation

• A Nucleation Site
• Adequate Contact Time
• Dissolution & Precipitation
Common Scales in CW Systems

(1) Calcium carbonate

(2) Magnesium silicate
(3) Calcium sulfate
(4) Calcium phosphate
(5) Zinc phosphate
Fouling
FOULING is the accumulation of
solid material, other than scale, in
a way that hampers the operation
of equipment or contributes to its
deterioration
COMMON FOULANTS
• Sand, Silt, Mud, iron
•Process contaminants like Oil
•Microbiological growth
•Corrosion Products
•Carry over -- Al
Cooling Water Micro organisms

 Bacteria
 Algae
 Fungi
Conditions Supporting Microbial Growth

 Moisture
 Correct Oxygenation
 Micronutrients
 Temperature
 Ecological Niche
 Bacterial Types

1. Slime Forming
2.Sulphate Reducing
3. Iron Oxidizing
4. Nitrifying Typical Rods Slime Formers
5. Denitrifying

Anaerobic Iron Depositing

 Bio Film Formation

Cooling
Water

① ② ③ ④
Micro organism
Micro organism and the surrounding sticky matter
Inorganism substance
Bio Films
Thermal
Foulant Conductivity
Common
More insulating than CaCO3 1.3-1.7 biofilms are
most common scales  CaSO4 1.3 4 times more
CaPO4 1.5 insulating
Reduce heat transfer than CaCO3
MgPO4 1.3
efficiency Fe Oxide 1.7 scale!
Increase dP across heat Biofilm 0.4
exchangers & reduce
flow
Health risks
(legionella)

P P
Algae

 Require sunlight to grow

 Found on tower decks & exposed areas
 Form “algae mats”
 Plug distribution holes on tower decks
 Plug screens/foul equipment
 Consume oxidants
 Provide food for other organisms
CHEMICAL TREATMENT
PROGRAMS
Corrosion Control
 Change Metallurgy
 Change Environment
– Saturation Index
– Deaeration
» MECHANICALLY
» CHEMICALLY
 Sacrificial Anode
 Chemical Inhibitors
– Anodic Inhibitors
– Cathodic Inhibitors
– Mixed Inhibitors
Commonly Applied Corrosion
Inhibitors

CATHODIC ANODIC
 Chromate
 Polyphosphate
 Molybdate
 Zinc
 Orthophosphate
 Phosphonate
 Nitrite
 Silicate

AZOLES FOR SPECIAL YELLOW METAL

CORROSION PROTECTION
Synergistic Blends for Corrosion
Control
ZINC - PHOSPHATE - PHOSPHONATE

NON HEAVY METAL:

ZINC PHOSPHONATE STABILIZED PHOSPHATE

MULTICOMPONENT ANODIC:
SYSTEMS Chromates, Nitrite,
USED Molybdates, o-PO4

CATHODIC:
Zinc, Organo/Meta
Phosphates
ALL ORGANIC STABILIZED ORTHO POLY/
PYRO PHOSPHATE
GENERAL:
Organic Oils, Azoles
Natural Inhibition: HCO3...Ca deposition,
(Tillmans Films)
Deposit Control
Deposit Control

Chemical Mechanical

Inhibition Removal

Dispersion Process Adjustments

Mechanical Methods
Mechanical

Removal Process Adjustment

Softening Increase Velocity

Clarification Increase Bleed
Filtration Design of Equip
Side Stream Reduce Temp
Cleaning pH Adjustment
Action of Chemical Inhibitors
 Crystal Modification (Organophosphonates &
Polymers)
– Prevent scale from “laying down”

 Sequestration
( Polyphosphates)
– Prevent scale from agglomerating

 Dispersion
( Polymers)
– Affect mineral charge so that scale formers repel
each other
 Organophosphonates
 Effective scale inhibitors for re circulatory systems
 Inhibit scale formation through “ Threshold effect and
Crystal distortion”
 Characteristic C-P bond. Relatively stable towards oxidation
& hydrolysis
 Commonly used Organophosphonates are

-- ATMP
-- HEDP
-- PBTC
 Resistance to Oxidation/ Hydrolysis is in the order

PBTC > HEDP > ATMP

Advance in Polymeric Dispersants
In the earlier days natural polymers from
60’s trees such as lignins and tannins were
used as cooling water dispersants.

1970’s : Synthetic polymers,

70’s Polyacrylates ( PAA),

Polymethacrylates ( PMAA) found
their way to water treatment industry
as cooling water dispersants
Advance in Polymeric Dispersants
1980’s : Technological advancements resulted
in development of synthetic co polymers,
80’s ( AA/HPA), (AA/AMPS), (AA/SAA) with
much improved dispersing capability.

2000’s : The latest development in the

cooling water technology is the
incorporation of polymers capable of
2000 operating in high stress conditions. Included
in this class of polymers is THERMAX’S
HIGH STRESS POLYMER. This includes
Terpolymers, Tetrapolymers.
Dispersion Action of Polymers

-
- -
- -
- - CO3 Ca
Ca CO3
- -
- - Ca CO3
CO3 Ca
- -
- -
- CO3 Ca
Ca CO3 -
- -
-

Large anionic polymer strands attached to crystals

leading to repulsion
 What is a Biocide??

Biocide : “a general term for a chemical agent capable of

killing or inactivating micro-organisms”

It embraces the more specific terms :

algicide; bactericide; fungicide; virucide; etc.

Have OXIDIZING and NON-OXIDIZING biocides.

 Oxidizing Biocides
Chlorine Cl2 gas; Na/Ca hypochlorite; brine
electrolysis; solid Cl2-release agent
Bromine Liquid Br2 ; solid Br2-release agents;
BrCl gas
Ozone Generated in situ from O2
Chlorine Dioxide Generated in situ from two precursor
chemicals
Peroxygens e.g. hydrogen peroxide; peracetic acid.
 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

pH
Non Oxidizing Biocides
Q UATE RNAR Y AMM O NIU M pH not an is sue
Dose 20-50 ppm Foam
Cationic na ture

Two Groups alternate to

each Other CARBAM ATE S pH not an iss ue
React with he avy m etals
S elective

M E THY LENE BIS THIO CY ANATE pH < 8.0, Fe < 3.0

Broad spec trum
E xce llent w ith c ont.

IS O THIAZO LIN ES pH lim itation

High Cost/DO SE
E xcellent w ith cont.

G LUTER ALDE HY DE Rea cts w ith NH3

V ariable Dose
E xcellent w ith cont.

Both Ex cellent in a ll respects.

S P CP highly toxic
G ood Algae cides
Bio Dispersant

 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

 Mechanism of Action for Biodispersants

BIODISPERSANT

METAL SURFACE
Biodispersant

METAL SURFACE
 COOLING WATER
TREATMENT PROGRAM AT
 System Details

Attribute Value Parameter Unit Value

pH 6.62

Conductivity Mmhos 255

1 Circulation Rate(M3/Hr) 3100
Turbidity NTU 0.5
2 Hold up Volume(M3) 360 M Alkalinity ppm CaCO3 130
3 Delta TDeg C 9 Total Hardness ppm CaCO3 110
4 EvaporationLoss(M3/Hr) 46.5 Calcium Hardness ppm Ca 80

5 Drift Loss(M3/Hr) 0.3 Magnesium ppm Mg 30

Hardness
6 Total Blowdown 46.5
Rate(M3/Hr) Chloride ppm Cl 10
7 Make up Rate(M3/Hr) 93 Sulphate ppm SO4 NA

8 Cycles of Concentration 2 Silica ppm SiO2 100

Chlorine ppm Cl2 NA
Iron ppm Fe 0.07
 Recommended Program for
Sr No Product Attribute Dosage, Frequency of dosage
ppm

1 Maxtreat 6741 Corrosion Inhibitor – Blend of Zinc & 22 Continuous on blow down
Orthophosphate
2 Maxtreat 7200 D Scale Inhibitor & Dispersant – Blend 15 Continuous on blow down
of Organophosphonates &
Polymeric Dispersant
3 Maxtreat CL - 5 Biodispersant and yellow metal 5 Continuous on blow down
corrosion inhibitor
4 Maxtreat 6910 Biocide based on Isothiazoline 50 Shock dose based on hold up
twice a month
5 Maxtreat 6940 Biocide based on Quat 50 Shock dose based on hold up
twice a month

Objective of treatment:- Clean and scale free condensor

Program Methodology

Circulating water pH 7.3 – 8.0

Orthophosphate 7.0 – 9.0 ppm

Organophosphonate 1.0 – 2.0 ppm

Total Phosphate 8.0 – 10.0 ppm

Residual chlorine 0.2 – 0.3 ppm

Non oxidizing biocides Two types with fortnightly

alternate dosing.
 Program Approach

Corrosion Control
• Combination of O-PO4 and Zinc provide corrosion protection for MS.
• O-PO4 is used as Anodic Corrosion Inhibitor. Phosphate residual
ensures optimum corrosion protection without contributing to deposit
formation. Lower O-PO4 will cause corrosion and higher O-PO4 will
cause deposition. PO4-ion accelerate gamma iron film formation

• Zn is used as Cathodic Inhibitor. With the infusion of oxygen in

water, an electrochemical reaction occurs at the cathode where hydroxyl
ions are formed causing localized high pH condition. When this occurs, a
zinc hydroxide film forms at the cathode.
• Organic Azoles form chemisorbed layer on yellow metallurgy there by
minimizing yellow metal corrosion.
 Program Approach

Deposition / Fouling Control

•Polymeric Dispersants are used in CW systems to control

deposition/fouling. To ensure corrosion protection, adequate
levels of Zn & PO4 must be present in the system. Thus, the
solubility products of calcium phosphate, zinc phosphate, zinc
hydroxide and iron phosphate are exceeded.

•Polymeric Dispersants keep the very small particles from

agglomerating into larger particles and forming troublesome
deposits. Dispersants also keep misc. small suspended solids
present in the system from agglomerating and forming deposits.
 Program Approach

Microbiological Control

• Chlorination is done as a source of Oxidising Biocide. This

program can tolerate free halogen (Cl2 or Br2) levels of 0.5 to 1.0
ppm,although 0.2-0.5 ppm will generally give satisfactory
microbiological control. The program components are tolerant of
typical free halogen levels. The polymer is also halogen resistant.
• Maxtreat – CL – 5 contains biodispersant for dispersing foulants
in the system and enhancing the penetration power of biocides.
• Maxtreat 6910 ( Isothiazoline based) & Maxtreat 6940( Quat
based) biocide also are part of the program.
MONITORING METHODS
 Water Parameters and Impact
WATER PARAMETERS AND THEIR IMPORTANCE
Sr No Parameter Significance
1 Ph Measured to confirm the corrosivity and scaling tendency of water
2 Conductivity Measure of total dissolved solids.
3 Turbidity Measured to examine the amount of suspended solids in water. The
adhesion of suspended solids lowers the thermal efficiency and causes
pitting corrosion under the deposits.
4 M - Alkalinity Has a fairly good correlation with pH of water and is measured to
predict the scaling of calcium carbonate
5 CaH Important to predict the scaling of calcium carbonate and to check
COC
6 Chloride Used as an index to calculate COC. High chlorides in water increases
corrosion potential
7 Silica Used as an index to calculate COC. Silica is one of the scale components
8 Total Iron Total iron is one of the fouling materials in water. The adhesion of iron
compounds to heat exchanger tubes causes local corrosion of carbon
steel under the deposits
10 Total PO4 Measured to confirm whether the concentration of scale and corrosion
inhibitors are maintained at desired levels.
11 TVC This is one of the indexes for predicting slime occurrence. It is
usually measured to determine the effect of biocide.
 Corrosion Control
1) General Corrosion - Corrosion Coupon Test
Copper

Cooling tower pit

Water
flow

MS or SUS
 Slime Control
1) Bacteria Count Test Comparison Chart

103 104 105 106 107

Target
 Summary
Biofouling
Pa
 Bio-Fouling, Corrosion and
rt Deposition are all inter-related
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G s tailored based on water

Corrosion Products characteristics and operating
Corrosion
Under-Deposit Corrosion
SCALING conditions is essential to maintain
the health of cooling water system
and enhance equipment life.
 Treatment monitoring is equally
important for successful
implementation of cooling water
programs
Thank You