COOLING WATER

TREATMENT
 Cooling Water System ?

• Cooling water system memegang peranan penting dalam

berbagai industri, khususnya sebagai sarana sirkulasi air
pendingin. Air pendingin dalam cooling system didistribusikan ke
beberapa media antara lain :
• Cooler
• Heat exchanger
• chiller, dan unit lainnya.
 Cooling Systems

• Once-through system
• Closed recirculating system
• Open recirculating system
Simple Cooling Water
Diagram
 Relationship of various
parameters
• Cycles Of Concentration
C = Concentration in Recirculation
Concentration In Make-up

• Evaporation Loss
E = 0.0018 x deltaT x R x TF
o
(Tower Factor)*
( T expressed in C)

* Tower factor is based on humidity/% contribution of evaporation

to delta T
 Relationship of various
parameters
• Windage Loss
W = 0.05 to 0.2 x R / 100

• Blow Down
B = E/(C–1)

• Make-up
M = E +W + B
 Cooling Water Chemistry
• pH

• Conductivity or Total Dissolved Solid

• Turbidity or Total Suspended Solid

• Total hardness

• Calcium hardness

• Alkalinity (p and m)

• Chloride

• Sulfate

• Silica
 More Parameters

• Total Iron

• Inhibitor residuals (i.e. o-phosphate, phosphonate, zinc, molybdate, etc.)

• Bacteria counts (TBC , SRB, Nitrifying )

• Chlorine i.e FRC

• ORP

• CLO2 levels
 pH

• Low pH means more hydrogen ions

• Hydrogen ions depolarizes corrosion cells
accelerating corrosion
• High pH means more hydroxyl ions
• pH range (7,2 – 8,5)
 Conductivity or TDS
• High values mean more dissolved minerals
• Higher ions movement improves electrical
conduction

• Increase the rate of electrochemical corrosion.

• Conductivity < 1500 , TDS <1500
 Turbidity and Total Suspended
Solid

• The content of suspended solid in the water - silt,

debris, air-borne materials

• Higher values indicate potential fouling due to

deposition of the solid

• Turbidity and TSS < 40

 Total Hardness
• The contents of permanent hardness - calcium,
magnesium, barium, strontium
• Generally indicates the total content of calcium and
magnesium as CaCO3
• Read as CaCO3 due to the molecular weight - 100
• High values indicate potential scales formation when
there is a presence of complexing anions
 Calcium Hardness

• The content of calcium in water read as CaCO3

• The most common component of scales in water
system
• May form calcium carbonate, calcium phosphate
and calcium sulfate scales
• High values may also indicate less corrosive
(electrochemically) water
 Alkalinity
• Acid neutralizing ability
• Free mineral acidity - CO2 at pH < 4.2
• M-alkalinity consisting of HCO3- and CO32- beginning
from methyl-orange point pH >4.2

• P-alkalinity consisting of CO32- and OH- beginning

from phenolpthalien point pH >8.2
 Chloride and Sulfate

• Corrosive ions - form metal chloride and sulfate

then mineral acids

• Cause pitting corrosion

• Chloride - environment for SCC - stainless steel
• Sulfate - required element for SRB
 Total Iron

• High values may indicate corrosion

activities

• Potential deposition of corrosion products

- fouling and under-deposit corrosion
 Inhibitor Residuals
• Depending of inhibitors used and control ranges
• Inhibitors - phosphate (ortho or total),
phosphonate, zinc, molybdate, toly-triazole

• Low level - insufficient protection

• High level - potential scales formation
(precipitative chemistry) and non economical
 Why do we treat cooling water?

• Corrosion of ferrous and non-ferrous metals -

electrochemical
• Precipitation and deposition of mineral scales
• Deposition of suspended solid
• Microbiological sludge deposit
• Biofilm or microbiological slime
• Microbiologically influenced corrosion
 Corrosion Scaling

PROBLEMS

Fouling
Fungi,
Algae,

General Fouling Microbial Fouling

 CORROSION

• Corrosion is an electrochemical process by which metals

return to their native state

• Mild Steel reverts back to Iron Oxide

• This is also true for copper alloys, Zinc, Aluminum etc.

 Localised corrosion

- Anode - 02+H2O
Fe(OH)3 OH- + Cathode +
Fe2O3
+ Cathode +
•Metal
c Fe(OH)2
e- e-
Fe++
e-
Fe e-
 Corrosion Cell

2Fe + O2 + 2H2O ---> 2Fe (OH )2

Ferrous Hydroxide

2Fe(OH)2+H2O+1/2O2 ->2Fe(OH )3
Hydrated Ferric
Oxide
 Prevention Of Corrosion

• Condition the metal

• coating (Zinc,Epoxy Resin) .
• Alloy the metal (Stainless Steel)

• Condition the environment

Remove Oxygen

• Use corrosion inhibitors

Corrosion Inhibition Mechanisms

• Oxidation
• Oxidation with film strengthening
• Cathodic polarization

• Cathodic precipitants
 Anodic Inhibitors

An anodic Inhibitor interferes with the Anodic process

• Chromate
• Molybdate
• Phosphate
• Nitrite
• Phosphonates
 Oxidation
(With
PO
complexation)
PO
4 4

Fe++ Fe3(PO4)2 FePO4

•.
2e--
 Cathodic Inhibitors

A Cathodic inhibitor interferes with the cathodic process by

precipitating an insoluble species onto the cathodic site.

• Zinc
• Calcium Carbonate
• Polyphosphate
• Phosphate
• Phosphonates
 HCO3
Cathodic Precipitants
HCO3 O2 Ca HCO3
Ca O2
HCO3 O2 Zn
Ca Zn
HCO3
O2 Zn
Ca Zn
Zn O2
HCO3
CaCO3
•. Zn CO3
OH - OH -
CO 3 Zn(OH)2
OH -
e - e-
e -
e-
e-

HCO3 + OH H2O +CO3

 Zinc

• Forms zinc hydroxide and zinc carbonate complexes at

cathode
• Good for soft water
• Above pH 8 will begin to precipitate in bulk water
• Zn is stabilised by phosphonates and polymers
• Levels from 0.25-3.0 ppm used
 Poly and Ortho-phosphate

• Form complexes with Ca at cathode

• Need to formulate stabilizing polymer with package
• Also reacts at anode to form iron phosphate complex
• Levels of 2-15ppm typically used depending on program
 Scaling
Caused by crystalline growth of salts on the system
surfaces
• CaCO3 (Calcite) : Major Scale
• Silica :Amorphous silica precipitates,when
150 ppm at pH < 8.0 .
*SiO2 >
> 180 ppm at pH
> 8.0
• MgSiO2 :Adsorption of silica on precipitated Mg(OH)2
(Brucite)
• Ca5(PO4)3OH (Hydroxyapatite)
• CaF2 (Fluorite) : Potential foulant
 Solubilities (20 / 100 deg C)
• Sodium Chloride 36% / 39%
• Sodium Sulphate 16% / 30%
• Sodium Carbonate 32% / 31%
• Sodium Bicarbonate 8% / Dec
• Sodium Phosphate 11% / Dec
• Calcium Chloride 43% / 61%
• Calcium Sulphate 0.3% / 0.06%
• Calcium Carbonate 0.005% /0.002%
• Calcium Bicarbonate 0.08% / Dec
• Calcium phosphate 0.0003%/ 0.0002%
 Solubilities ( 20 deg C )

• Silica • 0.005%
• Ferrous Hydroxide
• 0.0007%
• Ferric Hydroxide
• 0.0001%
 Formation of Hardness scale

• Calcium Carbonate has inverse solubility

• Ca(HCO3)2-------> CaCO3 + H2O + CO2

• Mg(HCO3 )2------> MgCO3 + H2O + CO2

• MgCO3+ H2O-----> Mg(OH)2 + CO2

 Scale Formation

• CaCO3 precipitates at Saturation pHs and depends

primarily upon:
• Level Of calcium hardness
• Level Of Bicarbonate alkalinity
• pH
• TDS
• Temperature
• Water velocity
 Scale Inhibition

• Remove hardness salts.

• pH control with Acid

• Dose scale inhibitor

 Acid Dosing

• Used to limit pH in hard water systems.

• Helps in inhibitor selection
• Potential for water and treatment savings by allowing an increase
in COC
• Each 1ppm M Alkalinity will require:
• 1.0 ppm sulphuric acid
• 2.0 ppm Hydrochloric acid
• 1.8 ppm Nitric acid
 Scale Inhibitors

• Added to extend Induction time beyond Retention time

• Induction time decreases with increase in Saturation level (
Driving force)
• Effectiveness of Inhibitor depends on the extent to which it
increases Induction time at lesser dosage
• Inhibitor dosage is increased with increase in Induction time
• If retention time is less than induction time there is very little
need of scale inhibitors
 Dispersion

• A process by which charged particles are prevented

from agglomerating into larger particles rendering
them less settleable.

• Most cooling water particulates have a net negative

charge. Acrylate dispersants also have a net
negative charge. Addition of dispersant increases
charge inhibiting agglomeration.
 Dispersants

• Polyacrylate
• Acrylate /Acrylamide
• Acrylate terpolymers
• Sulfonated styrene
• Maleic Acid Homopolymer
• Maleic acid co and terpolymers
 Bio Fouling

• Caused by the excessive growth of microorganisms.

• Cooling water system-ideal incubator for growth

 Problems

• Pitting corrosion-depolarising action of O2 released

during their metabolic process.

• Shield metal surfaces from the action of inhibitors

• cause legionella pneumophila disease

 Chemical Control

• Microbiocides
e.g. Bacteriacides,Fungicides,Algaecides

• Microbiostats
e.g. Bacteriastats,Fungistats,Algaestats

• Surfactants
 Microorganisms

• Viruses

• Consists of protein & DNA/RNA (Nucleic acids)

• Survive by multiplying in other

host cells - plant or Animals

 Cooling Water as a Medium
Ideal temperature (200C-600C)
pH 6 to 8
Often exposed to sunlight
Some made of wood
Nitrogen and phosphorous based inhibitors
Suspended and airborne debris
Good aeration
Presence of process fluids like ammonia, urea, other
organics and sunlight
 .

• Algae
• Photosynthesis
• Uni/Multicellular
• Diverse Forms
 Filamentous
 Colonial
 Plantlike

• Diatoms
• A Group of Algae
• Organic walls impregnated with silica
 .

• Blue Green Algae

• Photosynthetic bacteria

• Fungi
• Aerobic growth above the waterline
• Do not contain chlorophyll
 .

• Mould
• Fungus which forms visible layer on the surfaces -
Wood/Walls/Foods

• Yeast
• Unicellular Fungi
• Protozoa
• Diverse group of unicellular Microorganisms
 Bacteria

• Unicellular
• Cells may grow attached to each other in clusters , chains , rods or filaments
• Require carbon source for growth
• Different shapes
• Rods Bacillus
• Spherical Coccus
• Spiral Spirill
• Protected by slime
• Multiply by cell division
 Bacteria (Classification )

• Aerobic Requires O2 & CO2

• Anaerobic Grow in O2 free atmosphere
• Facultative Grow in both conditions
• Autotrophes Inorganic nutrients
• Heterotrophes Organic nutrients
• Psychrophiles < 22 0c
• Mesophiles 22 ~ 45 0 C
• Thermophiles > 45 0 C
• Planktonic Free floating organisms in . Water
• Sessile Surface attached growing in . Biofilm
 Methods Of Control

• Physical
• Nutrient Removal - Remove food or energy source .
e.g. Sunlight , Dead Leaves.Process Contamination.

• Temperature Control - Increase temperature

Not really practical on a Cooling System
 Methods Of Control

• Chemical
• pH Adjustment
• With the help of Acid / Caustic
(pH’s Over 10.0 Required)

• Microbiocide Control
• Kill Organisms by use of toxic material
e.g. Algaecides,Fungicides, Bacteriacides
 Chemical Control

• Microbiocides
e.g. Bacteriacides,Fungicides,Algaecides

• Microbiostats
e.g. Bacteriastats,Fungistats,Algaestats

• Surfactants
 Biocide Classification

• Oxidising Materials
• Have the ability to oxidise organic matter
• Irreversibly oxidise protein groups
• Non-Oxidising Materials
• Destroy or inhibit normal cell metabolism by any of the following ways:-
• Altering permeability of cell wall
• Destroying protein groups
• Precipitating protein
• Blocking metabolite reaction
 Sulphate Reducing Bacteria

• Anaerobic and convert dissolved sulphur compounds to H2S

10 H++ SO4-2+ 4Fe --> 4Fe+2+H2S +4H2O
H2S + Fe+2 --> FeS + H+
• H2S released corrodes Carbon steel and Copper based alloys.
• Localised pH depressions cause further attack
• Exist mainly below deposits devoid of oxygen
• Corrosion rate as high as 100 mpy occurs
 Nitrifying / Iron Bacteria

• Nitrifying Bacteria :
• Oxidation
HNO3 + H2O
of Ammonia . NH3 + 2O2 --->
• Nitrosomonas , Nitrobacter
• Iron Bacteria :
• Oxidation
.
of ferrous ions . ++
• Fe + O2 ----> Fe2O3
• Crenothrex
 Limitations Of Chlorination

• Not effective in alkaline water

Cl + H2O = HOCl + HCl

HOCl -> OCl- + H+
OCl- is 1/80 th time as effective as HOCl

Deactivated by the reducing agents H2S ,SO2,,NH3,polyacrylamide, Monoethnolamine,etc.

• Deactivates some Organo phosphonates, Does not penetrate slimes

• Extremely corrosive to many metals-maintenance of chlorinator is difficult.

• Environmental limitations - 0.1 ppm. Free Cl2 can kill fish

• When not effective use bromine compounds,chlorine dioxide,ozone

 Chlorine

A strong smelling, greenish-yellow gas

with pungent odor which is extremely
irritating to mucous membranes.
 Chlorine Gas
• Hazardous
• Heavier than air
• Strong oxidizer
• Low capital requirements
• Produces chlorinated by-products
• Efficacy - pH dependent
 Chemistry Chlorination
Chlorine gas dissolves in water and hydrolyses as:

Cl2 + H2O  HCl + HOCl (hypoclorous acid)

HOCl ↔ H+ + OCl- – (hypo chlorite ion)

The percentage distribution of hypochlorite ion and undissociated

hypochlorous acid can be calculated for various pH values.

The amount of hypochlorite ion becomes appreciable above pH 6 while

molecular chlorine is non-existent.

HOCl is about 80 times more effective than OCl- as a biocide

 Microbicidal Efficiency
• HOCl – the microbicidal efficiency is due to the relative
ease with which it can penetrate cell walls. The
penetration is quite comparable to water.

• OCl- - Poor disinfectant (about 1/80% efficiency of

HOCl). It is unable to diffuse cell wall of microorganisms
due to negative electrical charge.
 Chlorine Effectiveness
At Various pH
Percentage HOCl Percentage OCl -
100 0
90 10
80 20
70 30
60 40
50 50
40 60
30 70
20 80
10 90
0 100
4 5 6 7 8 9 10
pH Value
 Microbiological Action
• Diffusion of active agent through cell wall and attack the enzymes
group whose destruction results in death to the organism. Hence
microorganisms are not immune to chlorine

Factors affecting chlorine efficiency:

1.Concentration of Free Chlorine
2.Contact time
3.Temperature
4.Types and concentration of organisms
5.pH
6.Contaminants
 Chlorine Di-Oxide

• Draw backs of chlorine can be over come with help of

Clo2 mainly in NH3 contaminated water.
• It can be produced on site as
• 2NaClO2 + Cl2  2 ClO2 + 2NaCl
• ClO2 does not react with ammonia thus gets effective in
controlling microorganisms.
 Limitation of Chlorine
• Chlorine reacts with organics, hence exerts a
chlorine demand leading to higher chlorine
consumption and non-maintenance of
residual
• Difficult to handle and dose
• Efficacy of chlorine is pH dependent
• Chlorine is highly corrosive
 Chlorine Reactivity
1. With Ammonia
- HOCl + NH3  NH2Cl (mono chloramines) + H2O

- NH2Cl + HOCl  NHCl2 (dichloramine) + H2O

- NHCl2 + HOCl  NCl3 (trichloramine) + H2O

It means one ppm of ammonia can react with 3 ppm of chlorine,
hence will increase chlorine demand
 Chlorine Reactivity
2. With Organic Nitrogen
• Proteins hydrolyzes to amino acids.
• Chlorination chemistry of these are
extremely complex
• Because of various hydrolysis products.
• Finally the products are mono/di-
chloramines.
 Chlorine Reactivity
3. With Urea
• Urea hydrolyzes with nitrogen breaking down to ammonia in
presence of urease enzyme.
• If the hydrolysis lacks this enzyme, the formation of NH3 is greatly
inhibited.
• If significant quantity of urea-N is present and hydrolysis proceeds at
slow rate, unstable residue could result.
• Urea-N would then be reservoir for the production of ammonia.
 Chlorine Reactivity
4. Inorganic Carbon:
C + Cl2 + 2H2O  4 HCl + CO2
This takes place in dechlorination with granular
activated carbon.
5. Cyanide:
At alkaline pH 8.5 or higher,
2Cl2 + 4NaOH + 2NaCN  2NaCNO + 4NaCl + 2H2O
 Chlorine Reactivity

6. Hydrogen sulphide:
H2S + 4Cl2 + 4H2O  H2SO4 + 8HCl
Here 8.3 ppm of chlorine is required to oxidize 1 ppm of H2S.
 Chlorine Reactivity

9. Hydrocarbons:

Hydrocarbons create high chlorine

demand due to high oxidisable
organics.
 Chlorine Dioxide
Application Technology
Introduction Chlorine Dioxide
• Strong oxidizer
• Not a halogen
• Selective reactivity
• Generated on site
• pH independent
• Low capital requirements
• Rapid acting. Lower contact time for micobiological kill compared
Chlorine Dioxide (Contd.)
to chlorine

• Less corrosive compared to chlorine

• Does not hydrolyse to form acid

• Does not react to form chloramines

• Does not form trihalomethanes with organic matter like chlorine

• Does not produce any chlorinated compounds
 Chlorine Dioxide Mechanism
of Kill
 Disruption of protein synthesis or lysing of cell
 No resistivity by organisms
Chlorine Dioxide Effectiveness at
Various pHs
% Active
100
90
80
70
60
50
40
30
20
10
0
4 5 6 7 8 9 10
Lb./Equal pH
Performance 1
 Chlorine Dioxide
Safety Considerations
 Not handled as a gas
 Typical use is < 0.3% solutions
 On-site generator is required
 Selection criteria of suitable
oxidant
• Efficacy
• Safety handling
• Regulatory reporting
• Process contamination
• pH dependence
 Safety

Sodium Hypochlorite
Sodium Bromide Best

Chlorine Dioxide
Ozone
BCDMH
Worst
Chlorine Gas
 Reporting Requirements

Chlorine Dioxide Least

Hypochlorite
Bromine Compound
Ozone
Chlorine Gas
Greatest
 Performance in Contaminated
Systems
Chlorine Dioxide Best
Ozone
Bromine Compounds
Chlorine Gas
Sodium Hypochlorite
Worst
 Performance at Elevated pH

Ozone Best
Chlorine Dioxide
Bromine Compound
Sodium Hypochlorite
Chlorine Gas
Worst
 Best Alternative
• CHLORINE is still a widely used oxidant

* Inexpensive, historically established, being phased out

• HYPOCHLORITE is cheapest alternative

* Similar performance to chlorine, degradation is problem

• BROMINE CHEMISTRY, halogen alternative

* Better performance, can be costly, pH dependent

• CHLORINE DIOXIDE, non-halogen alternative Cost-effective broad
spectrum, safely fed, pH independent, non-chlorinating agent

• OZONE, New Approach

* Capital intensive, strong oxidant, no chemicals

Chlorine Dioxide
Generation
 Chlorine Dioxide
Advantages/Benefits
• Gas dissolved in water

• Strong oxidizer

• Not a halogen

• Selective reactivity
 Chlorine Dioxide
Advantages/Benefits

• Generated on-site
• Rapid acting
• pH independent
• Low capital requirements
Physical Characteristics
Color : Yellow-green
State : Gas
Odor : Similar to chlorine
Solubility: 2.9 gr/L
 ClO2 Generator
Generation Methods
Chlorine Gas Method

Three Pump Method

 ClO2 Generator
Chlorine Gas Method
ClO2
10
1 1. Electric Control Box
14
2. Flow Indicator (GPM)
11 8 3. Hand/Off/Auto Switch
2 3 4. Ball Valve
9
5. Solenoid Valve
6. Pressure Gauge
13 15
7 7. In-line Flowmeter
8. Ball Check Valve
Chlorine 9. Chlorine Eduction
6 5
4
10. Chlorine Solenoid Valve
11. Chlorine Rotameter
Water 12. Precursor Pump
12 Inlet 13. ClO2 Generator
14. Emergency Shutdown
Switch
Precursor Source 48"H x 42"W x 17"D 15. Loss Of Chlorine Switch
 ClO2 Generation
Gaseous Chlorine Method

2NaClO2 + Cl2 2ClO2 + 2NaCl

Sodium Chlorine Chlorine Sodium
Chlorite Dioxide Chloride
 ClO2 Generation
Three Pump Method

2NaClO2 + NaOCl + 2HCl 

Sodium Sodium Hydrochloric
Chlorite Hypochlorite Acid

2ClO2 + 3NaCl + H2O

Chlorine Sodium Water
Dioxide Chloride
 ClO2 Generator
Three Pump Method

ClO2 48"H x 42"W x 17"D

1
11 1. Electric Control Box
8
2. Flow Indicator (GPM)
2 3 3. Hand/Off/Auto Switch
4. Ball Valve
5. Solenoid Valve
10
7 6. Pressure Gauge
7. In-line Flowmeter
6 5
8. Ball Check Valve
4
9. Chemical Pumps
10. ClO2 Generator
11. Emergency Shutdown
Water
9 9 9 Switch
Inlet

Precursor Source Hydrochloric Acid Source

Sodium Hypochlorite Source
 ClO2 Generator
Generation Method
Three Pump Method

Advantages
• Higher Capacity
• High Back-Pressure Capacities
• Higher Turndown
• No Chlorine Gas Necessary
Disadvantages
• Slightly Higher Cost
• Additional Chemical Storage
• Incompatible Chemicals
 Typical ClO2 Dosages

Rendering Odor Control :2-10 ppm

Cooling Water Treatment : 0.1-0.5 ppm
Food Processing : 2-10 ppm
Paper Mill Slime Control :0.25-0.45 lb ClO2/ton
paper
 Sodium Chlorite Precautions

DO NOT allow
solution to dry. DO NOT use wooden
pallets or paddles.
DO NOT mix
with any other DO NOT wear leather
chemicals. or cloth external
clothing.
 Normal Shutdown Procedure

• Turn operating switch to “Off”

• Water flush occurs briefly
• Drain unit
• If chlorine used, close valve
• Drain and flush all chemical systems
 Equipment Site
Survey Location
• Well-ventilated area
• Eyewash/shower near generator
• Eyewash/shower near bulk storage
• Washdown water source available
• Approved drain
• Well lighted
 Monitoring Tools
• Corrosion coupons
• Deposit monitor - visual indication of deposit formation
• Biofouling monitor - indicate loss of pressure due to biofilm
• TBC and SRB dip slides
• Test heat exchangers
• ORP meters
• Site Management
• Daily reporting
 Corrosion Monitoring by Coupons
Method

• Corrosion Rate (MPY) = coupons wt loss in gms*365*1000/

Area of coupon in cm2*density of coupon in
(gm/cm3)*Exposure period in days*2.54

Also we know that 1 Miles = 0.001 inch =0.0254 mm

Means if corrosion rate is 3 MPY will cause the metal loss

(tube thickness reduction) by 0.0762 mm per year.