Cooling Water Treatment

COOLING WATER TREATMENT
Advanced training course

Cairo 22 to 24 May 2005
Jean Michel Fral-Saison
Technical Support Group Leader MEAGCC
Attendees
Welcome to all of you to our first Regional

Advanced Technical Training Course
Thank you for attending this training course.
We are particularly pleased to welcome our colleagues

from System Technique.
Attendance List.xls
We which you every success in this training course.
Agenda
Day 1 22 May 2005
08:30 to 08:45 Introduction

08:45 to 09:00 Pre-training Quizz
09:00 to 10:30 Water Chemistry
10:30 to 11:00 Coffee break
11:00 to 12:30 Cooling System hydraulics
12:30 to 13:30 Lunch
13:30 to 15:00 Cooling Water Treatment
15:00 to 15:30 Coffee Break
15:30 to 17:00 Scaling and Scale control
Agenda
Day 2 23 May 2005
08:30 to 10:00 Corrosion and Inhibitors

10:30 to 12:30 Corrosion control
12:30 to 13:30 Lunch
13:30 to 15:00 Microbiological control
15:30 to 17:00 Treatment and Product Guidelines
Agenda
Day 3 24 May 2005
08:30 to 10:30 Monitoring and control

11:00 to 12:00 Troubleshooting
12:00 to 12:30 Final Quizz
12:30 to 13:30 Lunch
Pre-Training Quizz (10 mn)
Read the questions carefully. Do not extrapolate.
T - F (True False): Select the right statement
A-B-C: one or more answer(s) is(are) correct

Team work
Form 4 or 5 teams (4 to 5 members in each team)
Team A:
Team B:
Team C:
Team D:
INDEX
1. Basic water chemistry
2. Cooling systems
3. Cooling system hydraulics
4. Cooling water treatment programmes
1. Scale inhibition
2. Corrosion inhibition
3. Yellow metal corrosion inhibition
4. Closed system inhibitors
5. Microbiological control
6. Treatment programme design
7. Monitoring and troubleshooting
Chap 1
BASIC WATER CHEMISTRY

Basic Water Chemistry
WATER
Pure water contains one part of oxygen and two parts

of hydrogen and is
> COLOURLESS
> ODOURLESS
> TASTELESS
PHYSICAL PROPERTIES
> Melting Point 0C (32F)
> Boiling Point 100C (212F)
> Typical Density 1 gramme / ml
> Maximum Density at 4C
Water Cycle Atmospheric
moisture
Precipitation
Evaporation and Transportation from
Surface Water Bodies, Land Surface
and Vegetation
Consumptive use
Evaporation
from
Oceans
Well
Stream flow
to Oceans
Percolation
Total Surface and Ground
Water Table Water flow to Oceans
Fresh Ground
Water Ocean
Saline Ground
Water
WATER
Water is the UNIVERSAL SOLVENT and dissolves

to some degree every known substance
Water will contain impurities in the form of
dissolved solids, suspended solids and dissolved
gasses
It is essential for industry that abundant supplies
are continuously available
SOURCES of WATER
Surface Water
> Lower quantities of Solubilised Minerals
> High amounts of Particulate Matter
> Variable Organic Matter Content
> Influences from Terrain and Geological Composition
Ground Water
> Higher Mineral content
> Less Suspended Solids
> Influences from Geological Composition
Other Water Sources
> Recycled / Reclaimed Water
> Sea Water
Purification of Water
Suspended Solids
> Clarification
> Filtration
Dissolved Salts
> Precipitating Softening
> Ion Exchange
> Reversed Osmosis
> Multiple Flash Evaporators
Dissolved Gases
> Degasification
> Deaeration
ATMOSPHERIC GASES
The atmosphere is a mixture of gases ,the main

components are Nitrogen 78 %, Oxygen 21 %,
Argon 0.9 % and Carbon Dioxide 0.033 %
> Other gases include Hydrogen, Helium and Neon
Nitrogen is Inert
Oxygen :
> The solubility is approx.10 mg/l at ambient
temperature and pressure. The solubility decreases
as temperature increases.
O2 SOLUBILITY IN WATER
TEMPERATURE, C
0 10 21 32 43 54 66 77 88 99 110 121
cm3/l 16 22.9 ppm
14 20.0
10 GAUGE PRESSURE PSI 17.2

12
8
6 14.3
10 4
2 11.4
0
VACUUM INCHES
8 MERCURY
4 8.6
8
6 12 5.7
16
4 20
2.9
24
2 28 0.0
32 50 70 90 110 130 150 170 190 210 230 250
TEMPERATURE, F
ATMOSPHERIC GASES
Carbon Dioxide :
The solubility goes up to 1,700 mg/l in water.
CO2 + H2O H+ + HCO3 =
> When Carbon Dioxide dissolves in water a

WEAKLY ACIDIC solution is produced. This is
commonly known as Carbonic Acid
> Typical pH is 6.5 to 6.8
INDUSTRIAL GASES
Industrial gases produced by burning fossil fuels

and by-products from industrial processes
include Sulphur Dioxide / Trioxide, Nitrous Oxides,
Hydrogen Sulphide and Ammonia
SO2 + H2O H2SO3 Sulphurous Acid

SO3 + H2O H2SO4 Sulphuric Acid
INDUSTRIAL GASES
Nitrous Oxides
> These include Nitrous Oxide NO
Nitrogen Dioxide NO2
Dinitrogen Tetraoxide N204
Hydrogen Sulphide
H2S in H2O H+ + HS- Bisulphide
Ammonia
NH3 + H2O OH- + NH4+ Ammonium
DISSOLVED SALTS
Water dissolves, to some extent, all known substances.

However from a water treatment point of view we are
mainly concerned with the salts of Calcium, Magnesium
and to a lesser extent Sodium and Potassium.
The salts of Calcium and Magnesium are known as
HARDNESS salts .
In most naturally occurring waters the Calcium
concentration is higher than the Magnesium
concentration.
In sea waters the reverse is true .
DISSOLVED SALTS
Typical Calcium and Magnesium salts are :
Bicarbonates Ca(HCO3)2 Mg(HCO3)2

Carbonates CaCO3 MgCO3
Chlorides CaCl2 MgCl2
Sulphates CaSO4 MgSO4
Silicates CaSiO3 MgSiO3
SILICA
Soluble ( Reactive )
> Form : Silicic Acid H2SiO3
> Removal :Adsorption on Coagulator Floc
Strong Base Anion Exchanger Resin
Colloidal ( Non-Reactive )
> Form : Complex,High molecular weight polymeric
colloid
> Removal : Adsorption on Coagulator Floc
> Converts to reactive silica in the boiler
UNITS OF CONCENTRATION
Dosage rates for continuous feed are expressed as mg/l on

either BLOWDOWN or MAKE UP water flow for cooling systems.
Shot doses are expressed as mg/l based on SYSTEM VOLUME:
> 1 ppm equals:
1 mg / l of water
1000 mg/m of water
1 g/m of water
1 kg /1000 m of water
In some instances solution strength is expressed as a
percentage:
> 1 % solution = 10,000 mg/l or 10,000 ppm
Parts per Million ppm = mg/l

Parts per Billion ppb = g/l
Normally hardness and alkalinity are expressed as mg/l CaCO3.
This allows us to calculate the concentration of the different ionic
species present in any given sample
Total hardness 150 ppm as CaCO3
Calcium hardness 100 ppm as CaCO3
Magnesium hardness 50 ppm as CaCO3
M-Alkalinity 80 ppm as CaCO3
Chloride 40 ppm as Cl-
Total hardness and Calcium hardness are obtained by

titration and therefore Magnesium hardness is
determined by difference .
> Total hardness 150 ppm as CaCO3
> Calcium hardness 100 ppm as CaCO3
> Magnesium hardness 50 ppm as CaCO3
> M-Alkalinity 80 ppm as CaCO3
> Alkaline hardness 80 mg/l as CaCO3
> Non-alkaline hardness (150 - 80 ) = 70 mg/l
EQUIVALENT WEIGHTS
Equivalent weight refers to the amount of an element combining

with a unit weight of hydrogen.
As a rule of thumb , the molecular weight divided by the valency
.
> Equivalent weight of CaCO3 = 100 g
> Molecular weight of CO3 = 60 g
> Equivalent weight of CO3 = 60/2 = 30 g
10ppm CaCO3 = 0.2 me CO3
> Atomic weight of Calcium = 40 g
> Equivalent weight of Calcium = 40/2 = 20 g
10ppm CaCO3 = 0.2 me Ca
Ionic balance should be calculated in milli-equivalents
Corrosion Rate Measurement
mils per year = 1/1000 inch per year

mm/y = millimetres per year
> 1 mpy = 0.025 mm/y (0.0254)

> 1 mm/y = 40 mpy
Other important Measurements
pH
Alkalinity
Conductivity*
Chloride
Sulphate
Soluble Iron (in Make Up Water)
Manganese
* essentially Total Dissolved Solids (TDS)
Carbon dioxide species versus pH in natural waters
100%
90%
H2CO3 HCO3- CO3--
80%
70%
Pourcentage CO2
%HCO3 -/CO3 --
60%
%HCO3 -/H2 CO2
50% %H2 CO2 /HCO3 -
%CO3 --/HCO3 -
40%
P alk.
30%
20%
M alk.
10%
0%
2 3 4 5 6 7 8 9 10 11 12 13 14
pK1=6.3 pH pK2=10.3
5 3
P Alkalinity P and M ALKALINITY
P = Alkalinity - phenolphthalein alkalinity

(pH=8.3)
> This titration includes all the HYDROXIDE and
half of the CARBONATE
+ -
H + OH H O
2
+ 2- -
H + CO HCO
3 3
M Alkalinity P and M ALKALINITY
M Alkalinity - methyl orange alkalinity (pH=4.4)

> Also known as the TOTAL ALKALINITY
> This titration includes all the HYDROXYDE and all the
CARBONATE and all the BICARBONATE.
+ -
H + OH H2O
+ 2-
2H + CO3 CO + H O
2 2
+ -
H + HCO3 CO2 + H O
2
> Other indicators used are BDH 4.5 and bromocresol
green/methyl red
Group exercise 1 (15 mn)
From the gr
1) Which are the species possibly present depending on
the pH (OH-, CO3= , HCO3-, CO2)
< 4,4
Between 4,4 and 8,3
> 8,3
2) Identify the individual above ions present and
calculate their concentration for the various scenarios:
pAlk = 0, pAlk < mAlk/2, pAlk = mAlk/2, pAlk > mAlk/2,
pAlk = mAlk
P and M ALKALINITY
P and M-Alkalinity
If we consider the series carbon dioxide,
bicarbonate, carbonate and hydroxide we find
that only adjacent pairs can co-exist
pH increase
- 2- -
CO HCO3 CO3 OH
2
Alkalinity HCO3 CO3 OH
P=0 Y
M
P=M Y
P
P = M/2 Y
M
P > M/2 Y Y
2(M - P) 2P - M
P < M/2 Y Y
M - 2P 2P
All values expressed as CaCO3

Chap 2
COOLING SYSTEMS
Cooling Systems
Once Through System
Cooling Water Inlet
Heat
Load
Heat exchanger
Outlet
Closed Recirculating System
Heat Load
Once Through
Cooling System
Make Up
Surge Tank
Water - Water
Heat Exchanger
Closed Recirculating System
Heat Load
Open Evaporative
Cooling System
Make Up
Surge Tank
Water - Water
Heat Exchanger
Open Evaporative System
Heat Load
Evaporation
Cooling
Tower
Make Up
Blowdown Recirculating Pump

Induced Draft Cross Flow Cooling Tower
Induced Draft Counter Flow Cooling
Tower
6 Cell
Forced Draft Cooling Tower
Splash Packing
Wood
Plastic
Splash Fill
Plastic Film Packing
Chap 3
COOLING SYSTEM HYDRAULICS

Cooling System Hydraulics
Evaporation
Evaporation
Drift
D E
W Windage
Make Up
MU RR
L Leaks
P Purge
Blowdown or Non Evaporative Losses =

Purge + Windage + Drift + Leaks
LATENT HEAT OF VAPORISATION
Latent Heat of Water is 556 kcal/kg

Evaporation of 1 kg water dissipates 556 kcal
Evaporation of 1 kg water from 100 kg of the
(recirculating) water or 1% of the (recirculating)
water reduces temperature by 5.56 C
EVAPORATION RATE (E)
E (t/h) = RR (m/h) x T C x Ef @ 30 C
580
TC = TRC - TSC Ef
where :
R = Return Water
S = Supply Water 1.0 %
0.9 %
RR T 0.8 %
E = 0 ,8 0.7 %
580
0.6 %
I.e. 1,4% of RR at 10C T or 1% RR at 6 to 7C de T

Ef Vs. wet-bulb temperature
Cycles
Definitions of Concentration
Cycles of Concentration (Cy)
Cy = Concentration of X in Recirculating Water
Concentration of X in Make Up Water
Blowdown Rate (BD)
BD(m/h) =E(m/h)
(Cy - 1)
Make Up Rate (MU)
MU(m/h) = E(m/h) + BD(m/h)
MU (m/h) = BD(m/h) x Cy
or
BD (m/h) = MU (m/h)
Cy
Make Up and Blowdown Rates
m3/h
Water consumption Rates relative
10x to Evaporation Rate
n
io
Up
at
n
e
or
w
5x ak
do
ap
w
Ev
o
Bl
1E
0
1 3 5 7 9
Cycles
Group Exercice #2 (15 mn)
Depletion:
1) How can you establish the equation for the
depletion of a species in an open system as a
function of the initial concentration C0, the
volume of the system V (m3) and the flow rate
of the blow down b (m3/h)
2) Calculate the system half life time (CT = C0/2)
DEPLETION
Depletion rate is proportional to time and to the initial
level of the concerned species in the system
dC = - a.C dt
dC = - a.dt
C
C = K.e -at
@ t = 0 => C = Co= K
C = Co e at
a = b (blowdown) = 1 ;
V (volume) (residence time)
Ct = Co e -bt
V
DEPLETION
-bt
Ct = C e V
[ ( )]
t = - V In Ct
b C
[ ( )]
b = - V In Ct
t C
DEPLETION a
100
90
% of Initial Concentration
80
70
60
50
40
30
20
10
0
0 5 10 15 20
Days
-bt
Ct = C e V
SYSTEM HALF-LIFE
t = - V In Ct = - V k Iog101 = V k Iog10 2
b C b 2 b
t1/2 = V(m) x 0.6931

b(m/h)
Note :
This can be approximated to
t1/2 = V x 0.7
b
Chap 4
OPEN EVAPORATIVE COOLING

SYSTEM
TREATMENT PROGRAMMES
Treatment Objectives
The general objectives of the cooling water treatment
program are:
Control corrosion rate to prevent equipment failure.
Prevent scale formation and deposition on heat transfer

surfaces to maximise system performance
Control microbiological activity and maintain system

cleanliness.
Allow the cooling system to operate at the optimum cycles of

concentration
Scaling/corrosion as pH function
% %
100 100
CORROSION
75
SCALING
75
50 50
25 25
0 0
pH
Water Treatment Concerns
Corrosion
Pr o
Scaling
on
du
osi
Ha
cts
cts
orr
bit
of
du
c
Me
sit
t, (
Pro
Sc
tab
Nu
ale
ep
i on
tri
o li
rd
De
en
sm
rro
de
po
t)
Un
Co
sit
s
Particle Entrapment
Deposition Biofouling
Habitat
pH
6.8 7.8
AGGRESSIVE WATER
STRONG CORROSION INHIBITORS

GE Betz Technologies
pH
6.8 7.8
DIANODIC
pH
7.8 9.0
SCALING WATER
STRONG SCALING (DCA) INHIBITORS

GE Betz Technologies
pH
7.8 9.0
CONTINUUM
Chap 4.1
SCALE INHIBITION
Scaling in Cooling Systems
CaCO3 Al2O3 , SiO2
CaSO4 Zn3(PO4)2
Ca3(PO4)2 Zn(OH)2
MgSiO3 FePO4
CaF2
CaO.MgO.(SiO2)2 Calcium phosphonate
SiO2
Insoluble material formed by oxidation of

incoming soluble salts within the cooling system
Fe2O3 MnO2
SCALE
Mineral Scale can form when

SOLUBILITY IS EXCEEDED
FACTORS AFFECTING CALCIUM
CARBONATE SCALE FORMATION
Calcium (bicarbonate) concentration

M alkalinity (bicarbonate concentration)
Temperature (hottest skin temperature)
pH (of the bulk water)
Dissolved solids concentration (activity)
LANGELIER SATURATION INDEX
1936 Professor Langelier
Conditions at which a given water is in equilibrium with calcium carbonate.
pHs = (pK2 - pKs) + pCa + pAlk

pK2 = 2 dissociation constant of CaCO3
pKs = solubility product of CaCO3
pCa = -log calcium concentration
pAlk = -log alkalinity
LSI = pHa - pHs

LSI -ve : water tends to dissolve calcium carbonate and hence the water has
corrosive tendency
LSI +ve : water has a calcium carbonate scaling tendency

LANGELIER SATURATION INDEX
pHs = pCa + pAlk + C

Group exercise #3 (15 mn)
Calculate LSI for the following water qualities and conclude:

1) Calcium Hardness 200 mg/l CaCO3
M Alkalinity 160 mg/l CaCO3
Total Dissolved Solids 400 mg/l
Temperature 60 C
pH of Cooling Water (pHa) 7.80
2) Calcium Hardness 40 mg/l CaCO3

M Alkalinity 35 mg/l CaCO3
Temperature 60 C
pH of Cooling Water (pHa) 7.10
C Scale
10C 16C 21C 27C 32C 38C 43C 49C 54C 60C 66C 71C 77C 82C 88C 93C pCa
Example pAlk
Calcium Hardness 200 mg/l CaCO3 pCa 2.70
M Alkalinity 160 mg/l CaCO3 pAlk 2.50
Temperature 60 C C at 60 C 1.56
pH of Cooling Water (pHa) 7.80 Total (pHs) 6.76
LSI = pHa - pHs= +1.04
C Scale
10C 16C 21C 27C 32C 38C 43C 49C 54C 60C 66C 71C 77C 82C 88C 93C pCa
Example
pAlk
pH of Cooling Water (pHa) 7.10 Total (pHs) 8.05
LSI = pHa - pHs = -0.95
RYZNAR STABILITY INDEX
Ryznar studied the actual operating results obtained
with waters of various Saturation Indices
RSI = 2pHs - pHa
Ryznar Stability Index
> 7.5 or 8 probability of corrosion increases

>7 scaling may not occur
<6 scaling tendency increases,
probability of corrosion decreases
RSI = 2pHs - pHa
Ryznar Stability Index
> 7.5 or 8 probability of corrosion increases
>7 scaling may not occur
<6 scaling tendency increases
probability of corrosion decreases
Examples:
Total (pHs) 6.76
pH of Cooling Water (pHa) 7.80 LSI = pHa - pHs = +1.04
SCALING
RSI = 2pHs - pHa = 5.72

SCALING
Calcium Hardness 40 mg/l CaCO3 pCa3.40
Total (pHs) 8.05
pH of Cooling Water (pHa) 7.10 LSI = pHa - pHs = -0.95
CORROSIVE
RSI = 2pHs - pHa = 9.00
CORROSIVE
Cycle up software: LSI Calculation
and water quality simulation
Cyclup.xls
Group exercise # 4 (15 mn)
1) Using Cyclup, prepare water simulation for a cooling system

with the following characteristics:
Volume: 1800 m3, RR: 4000 m3/H,
MU Water - pH:7.3, mAlk: 250 ppm, Ca: 230 ppm, Mg:100 ppm,
SiO2: 20mg/l, Cond: 1000 S/cm, Cl: 155mg/l, SO4: 20 mg/l
Group A: Ef: 1,3, T: 6C, Max Skin T: 98C, Max Bulk T: 90C
Group B: Ef: 1,5, T: 7C, Max Skin T: 70C, Max Bulk T: 55C
Group C: Ef: 1,4, T: 8C, Max Skin T: 85C, Max Bulk T: 70C
Group D: Ef: 1,5, T: 6C, Max Skin T: 90C, Max Bulk T: 85C
2) Comment
3 SCALE INHIBITION
Ca COMECHANISM
SCALE INHIBITION
INHIBITION
CHELATING (COMPLEXING)
ADSORPTION
CRYSTALL GROWTH INHIBITION
DECREASE OF CRYSTALL GROWTH CYNETICS
DISTORSION OF THE CRYSTALL
DISPERSION OF PARTICLES
DISPERSION
CaCO3 SCALE INHIBITION CHEMISTRIES
INHIBITION EDTA
CHELATING (COMPLEXING) PHOSPHONATES

AEC
ADSORPTION
CRYSTALL GROWTH INHIBITION
DECREASE OF CRYSTALL GROWTH CYNETICS
DISTORSION OF THE CRYSTALL
DISPERSION OF PARTICLES TETRAPHOSPHONATES
DISPERSION
POLYACRYLATES
POLYCARBOXYLATES
POLYMALEATES
Ca CO3 SCALE FORMATION MECHANISM
Ca2+ + CO32- CaCO3
Ca2+ ions adsorb on CaCO3
Ca2+ + CaCO3 CaCO3
Fast
INITIALISATION (adsorption and ionic interactions )
CO32- + CaCO3 CaCO3

Slow
CRYSTALL GROWTH
CaCO3 + Ca2+ CaCO3
CO32- + CaCO3 CaCO3

SCALE INHIBITION MECHANISMS
ADSORPTION OF Ca2+ IONS ON CaCO3
Ca2+ + CaCO3 CaCO3
Fast
MODE OF ACTION OF THE DISPERSANT (Adsorption and ionic interaction)
CaCO3 CaCO3
Fast
Very slow
CaCO3 + CO3- CaCO3
Ionic effect
Very slow
Ca2+ + CaCO3 CaCO3
Active sites blocked
by the dispersant
POLYPHOSPHATES
- Tripolyphosphate
O O O
NaO - P - O - P - O - P - ONa
ONa ONa ONa
- Hexametaphosphate
O O O
NaO - P - O - P - O - P - ONa
ONa ONa ONa
n
- Pyrophosphate
O O
KO - P - O - P - OK
OK OK
POLYPHOSPHATES
Sensitive to hydrolysis (into oPO4 ) depending on :
temperature (50 - 60C)
residence time
pH in the system
PHOSPHONATES
Chelating effect
Blocks the generation of CaCO3 crystalls
Reduce speed of growth
Depending on the type of phosphonate
Sensitivity to chlorination (oxidation)
Little to no risk of Ca phosphonate precipitation
CONCENTRATION (mg/l)
Phosphonate C mg/l 40 C 80 C
after 1/2 h after 24 h after 1/2 h after 24 h
PBTC 10 10 9 9 8
HEDP 10 9 5 5 1
AMP 10 3 0 1 0
Resistance to hydrolysis pH 7 : 20 mg / l de Cl2

POLYACRYLATES
POLYACRYLATES
- CH2 - CH - CH2 - CH -
n
COOH COOH
POLYMETHACRYLATES
CH3
- CH2 - C - CH2 - CH -
n
COOH COOH
POLYMER SPECIFICATIONS
Ionic charge pattern (copolymers)
Size of the molecules (number of monomers)
Molecular weight : 500 - 30 000
Resistance to Hydrolysis
Specifically adsorbed
The lower the molecular weight, the better

the scale inhibiting effect,
Optimum mw 500 1500

AEC : Alkyl Epoxy Carboxylate
GE Water & Process Technologies patented technology
No Phosphorus
Only contains C, H, O
Environmental fiendly
Produced in Europe
CaCO3 inhibitor limited dispersion capability
Formulated with HPS I
Continuum AEC
AEC : Alkyl Epoxy Carboxylate
Major technology breakthrough since phosphates have been
developed 25 years ago
CaCO3 inhibition
No PHOSPHORUS
Totally resistant to Cl2 et Br2
AEC fully compatible with soluble iron unlike HEDP
No Ca/AEC precipitate formation , no need for dispersant
(HPSII), unlike Ca/HEDP
Effective to avoid scaling with Zn (OH)2, Ca F2 and Ba SO4.
How can AEC be used ?
In conjunction with a polymer

- as a Deposit Control Agent
In conjunction with Zn, oPO4 and polymer
- as a low Zn, low P corrosion inhibitor
programme
In conjunction with Zn and polymer
- as a low Zn, non P corrosion inhibitor
programme
In conjunction with oPO4
- as a low P corrosion inhibitor programme
CONTINUUM AEC
CONTINUUM AEC IS THE FIRST CHOICE ALKALINE

PROGRAMME FOR MOVING TO AN ALKALINE
PROGRAMME IN ORDER TO REDUCE OR
ELIMINATE ACID
CONTINUUM AEC
LATEST ADVANCED TECHNOLOGY IN CaCO3

INHIBITION
LOW P / ZERO P PROGRAMMES
APPLICABLE TO A WIDE RANGE OF HARDNESS

CONTINUUM AEC
CONTINUUM AEC CAN OPERATE AT L.S.I. > +2.5
CONTINUUM AEC IN CERTAIN CIRCUMSTANCES

CAN OPERATE WITH NO ACID FEED FOR pH
CONTROL
THE LOWER P CONTENT OF CONTINUUM AEC

MAY ASSIST IN DISCHARGE COMPLIANCE
CONTINUUM AEC
CONTINUUM AEC IS MORE Ca TOLERANT THAN

TYPICAL PHOSPHONATE BASED PROGRAMMES
CONTINUUM AEC IS MORE TOLERANT TO

HALOGENS, PARTICULARLY HIGH LEVELS OF
CHLORINE, THAN TYPICAL PHOSPHONATE BASED
PROGRAMMES
Calcium tolerant
does not form an insoluble calcium compound in high

calcium / high alkalinity waters
can operate at higher pH, given LSI is within upper limits
- lower or no acid use
- less corrosive conditions at higher
pH
- lower pitting tendency
lower polymer demand
Results under stressed conditions
High LSI
- can operate at LSI > + 2.5 limit most
phosphonate technology is limited
- LSI up to + 2.8 and + 3.0 have been
successfully treated
High pH
- pH up to 9.3 and 9.5 have been
successfully treated
Results under stressed conditions
High calcium
- calcium up to 2,000 mg/l as CaCO3
have been successfully treated
High temperature
- Exchangers with skin temperatures
of 80C and 95C have been successfully
treated
Benefits of Continuum AEC
CaCO3 inhibitor concentration not reduced due

to reversion by halogens
- do not have to overfeed scale

inhibitor to counter reversion
Limitations of Continuum AEC
LSI
- Calcium
- pH
- Dissolved Solids
- Temperature
- Alkalinity
Max + 2.8 Industrial Systems

Low velocity
As with all treatments, deposit control
(and corrosion inhibition) is difficult at
low velocities
< 0.7 m/s becomes more difficult

< 0.5 m/s difficult
< 0.3 m/s question any claims
AEC is not effective CaCO3 inhibitor at concentrations

< 6 mg/l
- low concentrations of AEC through
dosing or control difficulties would be
accompanied by low polymer (and other component)
concentrations
* like all other treatment products does not effectively

treat systems if left in the drum or under dosed.
As with any programme

- if the system is not under control or
is difficult to control, the programme
is difficult to control
* system half-life
* system pH control
* system BD control
* system water (MU water) variance
* operational variance
As with any programme
- you cannot get satisfactory results by
operating all or majority limiting
constraints at the constraining limits
- Upper limit of Ca, pH, LSI (Cl, SO4
conductivity), temperature
- Lower limit velocity, corrosion inhibitior,

scale inhibitor, dispersant, (biocide)
Agenda
Day 2 23 May 2005
08:30 to 10:00 Corrosion and Inhibitors

10:30 to 13:00 Corrosion control
13:00 to 14:30 Lunch
14:00 to 15:00 Microbiological control
15:30 to 17:00 Treatment and Product Guidelines
Pretraining Quizz CWT Corrected.pdf

Chap 4.2
CORROSION INHIBITION
Key Technology Milestones
78-81 Betz 2020 copolymer patented

Dianodic II launched
Heavy Metal Elimination (CrO4)
81-84 Modify 2020 -improve
stability/performance
High Cycles & High pH Extension
1988 Introduction HPS-I
Becomes Industry Standard
89-91 HPS I & HPS-II for Full pH Spectrum
Key Technology Milestones
91-94 Develop AEC, only non-PO4 scale inhibitor

94-98 Develop HRA (halogen resistant azole)
Launch Dianodic PLUS family of
treatments Halogen Stable
99-01 HPS I, TEMPS, CAPS polymer package
Launch Continuum AEC Halogen Stable
01-02 Development of 4th generation polymer
03 Launch of APES
Corrosion
Corrosion is the result of two semi-reactions

> Anode reaction
Electrons are lost by metals (reducing agent), which
are therefore oxidized
Metals corrode and solubilize: Fe 2+, Cu +, Al 3+
> Cathode reaction
Electrons are gained by the oxidant, which is
reduced, transfer requires electrolyte (conductivity)
O2, H+ are usual oxidants in aqueous environment
OH- and H2 are the reduced forms.
Units of Corrosion Rate
mils per year = 1/1000 inch per year
mm/y = millimetres per year
1 mpy = 0.025 mm/y

1 mm/y = 40 mpy
< 4 mpy 0.1 mm/y Generally regarded as acceptable

< 3 mpy 0.075 mm/y Good
< 2 mpy 0.05 mm/y Very good
< 1 mpy 0.025 mm/y Excellent
Pitting
Pitting at a break
in the protective film
Pitting and Tuberculation
Tubercule
Sand Grain
Tuberculation
Fouling by Corrosion Products
CORROSION
Domain of stability for iron and iron oxides at 25C
Fe, Fe(OH) 2, Fe(OH) 3

E (V)
1.2
1.0 Fe 3+
0.8
0.6
E = 1.23 - 0.059 * pH
0.4 Fe (OH) 3
0.2
Fe ++
0
- 0.2
- 0.4
Fe(OH) 2
- 0.6 FeOOH -
- 0.8 E = - 0.059 * pH
Fe
- 1.0
- 1.2
- 1.4
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 pH
CORROSION
Domain of stability for iron and iron oxides at 25C
Fe, Fe3O4 , Fe2O 3

E (V)
1.2
3+
1.0 Fe
0.8
0.6
E = 1.23 - 0.059 * pH
0.4 Fe2O3
0.2
Fe ++
0
- 0.2
- 0.4
- 0.6 Fe3O4
- 0.8 E = - 0.059 * pH
Fe
- 1.0
- 1.2
- 1.4
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 pH
Classic Iron Corrosion Cell
Anode reaction Cathode reaction

Fe0 Fe++ + e- O2 + 2H2O + 4e- 4OH-
Fe++ + 2OH- Fe(OH)2
4Fe(OH)2 + O2 + 2H2O 4Fe(OH)3
TYPES DE CORROSION
Uniform Corrosion chemical, electrochemical
Galvanic Corrosion bi-metallic
Crevice Corrosion /pitting electrochemical

differential aeration
chemical
Intergranular Corrosion attack at the grain joints
Selective De-metallisation loss of one metal in an alloy
Erosion Corrosion mechanical
Stress corrosion cracking stress + agressivity du milieu
(Hydrogen)
(Bacterial)
GALVANIC CORROSION
When there is an electrochemical potential difference beween two metals

immersed in an electrolyte
When these metals are in contact (or if there is an electrical connection), a
corrosion cell is created
The more noble metal is the cathode
The less noble metal is the anode
The more noble metal is protected, more than in the absence of contact
(cathodic protection)
The less noble metal is corroded (anode)
GALVANIC CORROSION Electropositivity
Scale
The corrosion rate will be lower, as the location is more
The less Na
remote end the conductivity is lower noble
The corrosion rate will be very high id the ratio between Mg
the surface area of the cathode to the anode is high. Al/Zn
(Current density)
Fe
The most frequent galvanic corrosions:
> Steel/Copper Sn
> Steel/SS Cu
> Al/Steel SS
> Al/SS
Mn
> Al/Copper
Ag
Galvanic corrosion requires
Au
> A contact between 2 different metals
> An electrolyte (ambient humidity can be enough) The more Pt
noble
GALVANIC CORROSION
There is a risk for having galvanic corrosion when

copper corrosion products deposit on mild teel
Cu 2+ + 2e Cu
Fe Fe 2+ + 2e
CuO
MS
GALVANIC CORROSION
DIFFERENTIAL AERATION CORROSION
The electrochemical potential of a metal is in water is driven by the
oxygen concentration:
O2 + 2e- + H2O 2OH-
E = EO -+ 0.06/2 * log [ p(O2) / (OH-)2 ]

2 / OH
The area under the deposit contains less oxygen than the one at the
surface in the vicinity (p(O2) under deposit < p(O2) outside
deposit), Therefore the electrochemical potential under the
deposit is lower.
A corrosion cell is created where the anodic part is under the deposit
d (lower potential)
Any deposit (organic or inorganic) can generate this process
and create under deposit corrosion.
PITTING CORROSION
Very localised corrosion
The most dangerous Type of corrosion

> Difficult to detect: the metal loss is very limited
> Damageable: lead to heat exchanger leakages
A pit is a very active anodic zone

The corrosion process is identical to the one for crevice corrosion.
The pit protects cathodicly the bulk of the metal surface.
The reaction can start due to:

> Defect in the metal
> Erosion
EROSION CORROSION
Mechanical attack due to:
> Solids
> Too high fluid velocity
> Water dropplets (fan in cooling towers)
> Cavitation
Can be easily identified because there is a visible pattern (like

waves) and the metal surface is clean.
All metals can be subject to erosion corrosion. The most sensitive
parts are elbows, T pieces, valves, pumps, eductors and
spraying equipments
EROSION CORROSION
Case history:
Metallurgical Investigations
Sample 2 Sample 3
Sample 1
Filtered water collection line

Backwash inlet line 8
Backwash inlet line 8 (after cleaning)
Under deposit
corrosion
Biological (SRB)
corrosion pit
Visual Investigations
Flow restriction Under Deposit Corrosion
Erosion Corrosion
Welding ANAEROBIC ZONE ARAETED ZONE
Biological Corrosion
O2 migration

Visual Investigations
Flow restriction
SRB corrosion pit
Water flow
Growing colonies
Welding ANAEROBIC ZONE ARAETED ZONE
Deposition
Pipe wall Water flow
Erosion
corrosion
Causes for corrosion
Deposition underdeposit (supply lines)
Erosion on elbows weldings for turbulent flow
Microbiological stagnant anaerobic conditions
(little access for biocides)
Favoured by geometry
Uneven throughout the filter lines
Galvanic corrosion?
Deposition on the top caused by grease released
under stagnant conditions?
Causes for corrosion
Geometry (contd)
Extended volume of stagnant water in the back
wash/air scour line
Aerobic/anaerobic conditions possible in the
same piping section (underdeposit corrosion)
Long intervals between back wash operations
Valve/elbow/welding configuration
CORROSION INHIBITORS
General mechanism of corrosion inhibitors
PASSIVATING FILM
> ANODIC INHIBITION
> LOW FOULING TENDENCY
> RESISTANCE TO pH FLUCTUATIONS (REMANENCE)
> VERY THIN ( ~ 100 A)
PRECIPITATING FILM
> CATHODIC INHIBITION
> REDUCE PITTING
> REQUIRES ACCURATE pH CONTROL
ADSORBED FILM(ORGANIC)
> PROTECTION FOR SPECIFIC METALLURGIES
ANODIC INHIBITION MECHANISM
PASSIVATING FILM ANODIC INHIBITION
METAL
22--
CrO
CrO44
2-
MoO4 hc
-
NO2
3-
PO4 hc
Na3SiO4
Poly PO4 hc
INHIBITORS
CHROMATES
CrO42-
ANODIC INHIBITOR
NO OXYGEN NEEDED (STRONG OXIDANT)
BANNED DUE TO TOXICITY
HIGH CONCENTRATION IF USED ON ITS OWN
SENSITIVE TO REDUCING AGENTS
INHIBITORS
NITRITES
NO2-
ANODIC INHIBITOR
OXYGEN NOT NEEDED, EVEN NOT SUITABLE
HIGH DOSE RATE REQUIRED
POSSIBLE BIODEGRADATION
FOR CLOSED SYSTEMS ONLY
INHIBITORS
SILICATES
ANODIC INHIBITORS
ENVIRONMENTAL FRIENDLY
LONG TIME TO ESTABLISH PROTECTION
OXYGEN NOT NECESSARY BUT HIGHER DOSAGE IF NO O2
INHIBITORS
HIGH CONCENTRATION ORTHOPHOSPHATES

oPO43- > 10 ppm
ANODIC INHIBITOR
OXYGENE NEEDED
OXIDES FILM PASSIVATION
Ca PHOSPHATES DISPERSANT NECESSARY
NEUTRAL pH CONTROL
INHIBITORS
HIGH CONCENTRATION MOLYBDATES

MoO4 > 200 ppm
ANODIC INHIBITOR
OXYGENE OR OXYDANT NEEDED
ENVIRONMENTAL FRIENDLY
SENSITIVE TO CHLORIDES
HIGH DOSE RATE (>200 ppm)
pH FLEXIBILITY
FOR CLOSED SYSTEMS ONLY
INHIBITORS
ORGANIC
PHOSPHONATES (HEDP, AMP) OH OH OH
HO P C P OH
O CH3 O
ANODIC INHIBITOR HEDP
OXYGENE NEEDED OH
DOSE RATE CRITICAL (>4,5 ppm)

CH2 P OH
O
OH
RISK OF PRECIPITATION N CH2 P OH
HIGH pH CH2
OH
P OH
AMP
INHIBITION CATHODIC MECHANISM
POROUS
PRECIPITATING FILM - CATHODIC INHIBITION
METAL
CaCO3
Ca3 (PO4)2
POLY PO4
ZINC
INHIBITORS
ZINC
Zn2+ > 1,5 ppm
CATHODIC INHIBITOR
EFFECTIVE AT LOW CONCENTRATION (>1,5 ppm)
USED IN COMBINATION WITH OTHER INHIBITORS
LIMITED LEVEL FOR DISCHARGE
DEPOSITION
INHIBITORS
LOW CONCENTRATION ORTHOPHOSPHATES

0 < oPO43- < 10 ppm
CATHODIC INHIBITOR
CALCIUM PHOSPHATE FILM
RISK OF FOULING
ALKALINE pH CONTROL
INHIBITORS
POLYPHOSPHATES
> 2ppm O O
KO - P - O - P - OK
OK OK
CATHODIC INHIBITOR pyrophosphate
FILM FORMATION
NEUTRAL OR ALKALINE pH CONTROL
POSSIBLE REVERSION TO ORTHOPHOSPHATES
(temperature, residence time)
INHIBITORS
LOW CONCENTRATION MOLYBDATES
5 < MoO4 < 20 ppm
NOT ACTING AS ANODIC INHIBITOR

SYNERGY WITH CATHODIC INHIBITORS
FILM STABILIZATION:
> Fe3+/MoO4,, Zn3(OH)2(MoO4)2, Zn2(OH)2MoO4,
Zn2OHPO4/MoO4
ANTIPITTING:
> Transformation MoO42- Mo70244-/Mo8O284- PO4
> Phosphomolybdic acid (H3PO4, 12 MoO3)
precipitation (polarization of the anode)
PHOSPHATE INHIBITORS
HC Orthophosphate
High Concentration
Primarily anodic inhibitor
Passive iron oxide film
Requires calcium phosphate inhibitor
Neutral pH control range
Neutral pH phosphate treatment
Introduced 1979
10-20 mg/l orthophosphate
2 - 5 mg/l polyphosphate
Calcium Phosphate Inhibitor (Copolymer)
Calcium Carbonate Inhibitor (HEDP)
pH 7 - 8
Passivation
80 % ANODE Fe0 + oPO4 Fe3O4
O2
Precipitation
Ca + CO3 CaCO3
20 % CATHODE
Ca + oPO4 Ca3(PO4)2
Ca + pPO4 Ca(pPO4)
DIANODIC
CHROMATE LIKE PERFORMANCE
HAS BECOME AN INDUSTRIAL STANDARD IN MANY

PARTS OF THE WORLD
APPLICABLE TO MANY VARIED SYSTEMS AND WATER

CHEMISTRIES
MORE THAN TWO DECADES OF EXPERIENCE

DIANODIC
FLEXIBLE, VERSATILE, FORGIVING TREATMENT
APPLICABLE TO A WIDE RANGE OF HARDNESS
EASY AND SIMPLE TO MONITOR AND CONTROL

DIANODIC
OPERATES AT pH 6.8 to 7.8
MOST APPLICATIONS REQUIRE pH CONTROL
FOR SYSTEMS CONTAINING YELLOW METALS

REQUIRES INCLUSION OF AN AZOLE
DIANODIC
Components
ORTHOPHOSPHATE
(high concentration)
CORROSION INHIBITOR
Predominantly Anodic inhibitor
DIANODIC
Components
POLYPHOSPHATE
CORROSION INHIBITOR
Cathodic inhibitor
Useful as an inhibitor against pitting
DIANODIC
Components
CALCIUM PHOSPHATE INHIBITOR
> POLYMER HPS I
Superior calcium phosphate inhibitor and
dispersant for iron and suspended solids
CALCIUM CARBONATE INHIBITOR
HEDP/CAPS
DISPERSANT
HPS I vs. Polymer dispersant
Calcium Phosphate
% Inhibition
100
BetzDearborn HPS I copolymer
80
60
Polymer Dispersant
40
AMP
20
Pol. an. HEDP

0
0 5 10 20 40
Active concentration (ppm)
Calcium Phosphate
0.8
Turbidity (NTU's)
High Temp
0.6
0.4
0.2
0
HPS-I Polymer dispersant
12
10 Iron
Turbidity (NTU's)
0
HPS-I Polymer dispersant
DIANODIC
Components
TTA/HRA
YELLOW METAL CORROSION INHIBITOR
> HRA is a GE Betz patented

Halogen Resistant Azole
DIANODIC
Programme Mechanism
Anode Fe0 + oPO4 Passive Iron Oxide layer (mainly magnetite)

80%
Cathode Ca + oPO4 Ca3(PO4)3
20% Ca + pPO4 Ca polyphosphate

CONTINUUM
CONTINUUM
CONTINUUM AT
AT CONTINUUM
CONTINUUM AEC
AEC
L.S.I.< +2.5 L.S.I.< +2.8 (+3.0)

CONTINUUM AT
AN EXTENSION OF DIANODIC TECHNOLOGY TO

ALKALINE pH
FOR LOW CALCIUM WATERS AND pH UP TO 8.2,

DIANODIC PHOSPHATE LEVELS ARE USED AND
POLYPHOSPHATE INCLUDED
FOR HIGHER CALCIUM WATERS THE PREDOMINANT

CORROSION INHIBITOR IS BASED ON PHOSPHONATE
AND CaCO3
CONTINUUM AT
FOR HIGHER CALCIUM WATERS ORTHOPHOSPHATE IS

PROGRESSIVELY REDUCED AS CALCIUM and / or pH
INCREASES
PROGRAMMES WITH NO ORTHOPHOSPHATE, ONLY

ORGANIC PHOSPHATE, ARE AVAILABLE
PROGRAMMES CONTAINING MOLYBDATE ARE AVAILABLE

CONTINUUM AT
OPERATES AT pH 7.8 to 9
SOME APPLICATIONS MAY STILL REQUIRE pH

CONTROL
FOR SYSTEMS CONTAINING YELLOW METALS

REQUIRES INCLUSION OF AN AZOLE
LC Orthophosphate
Low Concentration
Primarily cathodic inhibitor
Requires calcium hardness
Calcium phosphate formation at the cathode
Alkaline pH control range
Alkaline pH phosphate treatment
2 - 10 mg/l total inorganic PO4
Calcium Carbonate Inhibitor (4 - 10 mg/l HEDP)
pH = 8.0 - 9.0
Passivation
Precipitation
Ca + CO3 CaCO3
80 % CATHODE
Ca + oPO4 Ca3(PO4)2
Ca + pPO4 Ca(pPO4)
Ca + HEDP CaHEDP
CONTINUUM AT
Components
ORTHOPHOSPHATE
CORROSION INHIBITOR
Anodic and Cathodic inhibitor
Predominantly Anodic at Low Hardness and Low
Range pH
Cathodic at High Hardness and High range pH
CONTINUUM AT
Components
POLYPHOSPHATE
CORROSION INHIBITOR
Cathodic inhibitor
Only included in programmes for low hardness and pH

up to 8.2
Useful as an inhibitor against pitting
Organic Phosphates
Phosphonates considered both anodic and

cathodic
Alkaline pH control range
Organic phosphate treatment
1980s
5 - 10 mg/l organic phosphate
Calcium Carbonate Inhibitor (Phosphonate)
Calcium Phosphonate Inhibitor (Copolymer)
pH 8.0 - 9.0
Passivation
30 % ANODE Fe0 Passive Film
Organic PO4
Precipitation
Ca + CO3 CaCO3
70 % CATHODE
Ca + Phosphonate Ca (Phosphonate)
CONTINUUM AT
Components
HEDP
CORROSION INHIBITOR
at concentrations above 4.5 mg/l PO4
CONTINUUM AT
Components

> POLYMER HPS I
Superior calcium phosphate inhibitor and dispersant for
iron and suspended solids
DISPERSANT
CALCIUM PHOSPHONATE INHIBITOR
CONTINUUM AT
Components
TTA

CONTINUUM AT
Programme Mechanism
Anode Fe0 + HEDP Passive Film

(60%) Other anodic inhibitors if included oPO4 MoO4

(40%)
Ca + CO3 CaCO3
Ca + HEDP Ca phosphonate
Alkaline AEC phosphate treatment
4 - 10 mg/l total inorganic PO4
Calcium Carbonate Inhibitor (AEC)
Calcium Phosphate Inhibitor (Copolymer)
pH = 8.0 - 9.5
Passivation
Precipitation
Ca + CO3 CaCO3
80 % CATHODE
Ca + oPO4 Ca3(PO4)2
CONTINUUM AEC
Components
ORTHOPHOSPHATE
CORROSION INHIBITOR
Anodic and Cathodic inhibitor
Predominantly Anodic at Low Hardness and Low
Range pH
Cathodic at High Hardness and High range pH
CONTINUUM AEC
Components
DTPMP
CORROSION INHIBITOR
Primarily as a source of oPO4 in halogenated
systems (included for formulation reasons)
It can be a corrosion inhibitor in its own right
CONTINUUM AEC
Components
AEC
Non Phosphorous, non Phosphonate
Calcium Carbonate Inhibitor
Tolerant to high Chlorine concentrations
High Calcium tolerance
CONTINUUM AEC
Components
POLYMER HPS I
Superior calcium phosphate inhibitor and
dispersant for iron and suspended solids
DISPERSANT
CONTINUUM AEC
Components
HRA
HRA is a GE Water & Process Technologies

patented
Halogen Resistant Azole
CONTINUUM AEC
Components
MOLYBDATE
TRACER
Concentrations typically too low to be an
effective corrosion inhibitor
CONTINUUM AEC
Programme Mechanism
Anode Programme is mainly cathodic inhibition

Other anodic inhibitors if included MoO4
Cathode
Ca + oPO4 Ca3(PO4)3
Ca + CO3 CaCO3
PHOSPHONATE INHIBITORS
Organic phosphate based programmes are often

supplemented with other carbon steel corrosion
inhibitors
Orthophosphate
Zinc
Molybdate
CONTINUUM AEC
How much PO4 is required ?

- depends on Ca and pH
How much AEC is required ?
- 6 to 8 mg/l active for CaCO3
inhibition
How much polymer is required ?
- depends on Ca and pH and PO4
CONTINUUM AEC
Various ratios of polymer to AEC required to

cover a range of conditions:
100 to 1,200 mg/l Ca

pH (7.0) 7.8 to 9.5
(0) 2 to 8 (20) mg/l oPO4
(top off: 0.5 to 2.5 mg/l Zn)
Benefits of CONTINUUM AEC
Benefits of Continuum AEC

> Wide range of waters and systems can be
treated
> Wide range of programmes or approaches
available
> Wide range of products to cater for the wide
range of applications, waters and approaches
High Fe
High suspended solids
> Create additional polymer demand
which may be accomodated with higher
polymer concentrations up to a given limit
which depends on system design and
operation
Comparative Phosphates Programme
Guidelines
DIANODIC II CONTINUUM AT CONTINUUM AEC
pH (6.8) 7.0 - 7.8 (> 7.8) 8.2 - 9.0 (> 7.8) 8.2 - 9.0 (9.5) LSI MgSiO2 CaMgSiO2
Calcium (35) 100 - 1200 (75) 100 - 1200 (100) 250 - 1200 mg/l CaCO3
+ 2.8 Industrial Systems

max LSI N/A + 2.5
+ 3.0 Low Heat, High Flow
Depends on exchanger
max t C 65 C 60 C 70 C
and velocity
Theoretical cycled
Iron < 3 mg/l Fe < 5 mg/l Fe < 10 mg/l Fe
MU mg/l Fe
max SiO2 defined by

Reactive Silica < 200 mg/l SiO2 < 200 mg/l SiO2 < 200 mg/l SiO2
MgSiO2 CaMgSiO2
Conductivity < 6000 S cm-1 Chloride < 1500 mg/l Cl Sulphate < 2500 mg/l SO4
PHOSPHATE PROGRAMMES
Comparative Phosphates Programme
Guidelines
DIANODIC II CONTINUUM AT CONTINUUM AEC
Filtered oPO4 10 - 17 (30) 0 - 12 (15) 4 - 7 (10) 0.2 micron filter
pPO4 (0) 2 - 6 (8) 0-2 Typically pyro PO4
(0) 1.5 - 2.5 (1.5) 4.5 - 6.5 (7.5) Diphosphonate

Phosphonate
as PO4
0-6 Pentaphosphonate
AEC 6 - 8 (15) 6 mg/l AEC MINIMUM
HPS I (17) 20 - 90 (>90) (30) 40 - 90 (>90) 30 - 70 Ca, PO4 pH Demand
Azole 0-3 0-3 0-3 Typically TTA
Zinc 0 (up to 2.5 top off) 0 0 ( 0.5 - 2.5 Zn AEC) Zn AEC may need PO4
MoO4 typically used as
Molybdate 0 (- 8) 0-8 0-3 a tracer if < 5 mg/l MoO4
ALKALINE ZINC
AND
ZINC PHOSPHATE INHIBITORS
Zinc Programmes
Cathodic inhibitor
Used on its own or in conjunction with
phosphate
Neutral to alkaline control range
Some potential discharge concerns
ZINC BASED PROGRAMMES
ZINC BASED
> Neutral to alkaline pH programme
> Predominantly cathodic inhibition

ZINC BASED PROGRAMMES
PRECIPITATING PROGRAMME
> ZINC PHOSPHATE DOES NOT DEPEND UPON
CALCIUM FOR FILM FORMATION
> FILM FORMATION A FUNCTION OF ZINC
SOLUBILITY WITH pH
> POLYMERS CONTROL POTENTIAL FOR BULK
WATER PRECIPITATION OF ZINC AND CALCIUM
PHOSPHATE
ZINC PHOSPHATE TREATMENT
2 - 5 mg/L Zn
3 - 10 mg/L total inorganic PO4
[Zinc Phosphate Inhibitor (Copolymer)]
pH 7.0 - 8.5
Passivation
10 % ANODE Fe0 Fe3O4
O2 / PO4
Precipitation
Zn + oPO4 Zn3(PO4)2
90 % CATHODE
Ca + oPO4 Ca3(PO4)2
Components
ZINC
CORROSION INHIBITOR
> Cathodic Inhibitor
Components
ORTHOPHOSPHATE
CORROSION INHIBITOR
> Cathodic inhibitor
Programme Mechanism
Anode Programme is mainly cathodic inhibition

Anodic inhibiton by PO4 depending upom calcium hardness and
pH range or by HEDP or AMP if included

Zn + OH Zn(OH)2
Ca + CO3 CaCO3
Zn + PO4 Zn2(PO4)3
Ca + HEDP/AMP Ca phosphonate
ZINC ORGANIC TREATMENT
1 - 4 mg/L Zn
5 - 10 mg/L Organic Phosphate
[Zinc Phosphate Inhibitor (Copolymer)]
pH 8 - 9
Passivation
30 % ANODE Fe0 Passive Film
Organic PO4
Precipitation
Ca + CO3 CaCO3
70 % CATHODE
Zn + OH4 Zn(OH)2
Components
HEDP and AMP

CORROSION INHIBITOR
> at concentrations above 4.5 mg/l PO4
Components
POLYMER (HPS II/HPS I)
> INHIBITOR FOR

> CALCIUM PHOSPHATE
> ZINC HYDROXIDE & PHOSPHATE
> CALCIUM PHOSPHONATE
> CALCIUM CARBONATE
> DISPERSANT FOR

> Iron and suspended solids
Programme Mechanism (Alkaline Zinc)
Anode
Fe0 + HEDP Passive Film
Cathode Zn + OH Zn(OH)2
Ca + CO3 CaCO3
Ca + HEDP Ca phosphonate
Low Hardness Waters
Calcium < 100 mg/l CaCO3 difficult to treat effectively

particularly if Cl and/or SO4 is high
> lack of cathodic inhibition
pitting
> approaches
high PO4
Zn3(PO4)2 or Zn (top off)
high MoO4
Silicate
Nitrite
Microbiological control problems
Molybdate Programmes
Primarily an anodic inhibitor

Used at high levels in closed systems
Used at low levels in open systems
Neutral to alkaline control range
Does not require hardness
Requires oxygen
Low toxicity
MOLYBDATE TREATMENT
5 - 10 mg/L MoO4
5 - 10 mg/L phosphonate
Calcium Carbonate Inhibitor (Phosphonate and PMA)
pH 8 - 9
Passivation
O2
30 % ANODE Fe0 + MoO4 Fe3O4 - MoO4
Organic PO4
Precipitation
Ca + CO3 CaCO3
70 % CATHODE
Adsorbed Layer Films
Chemi-sorbed films that provide single or

multiple layer protection against corrosion
Both anodic and cathodic sites are covered.
Silicate
Adsorbed film
Slow development for protection
Does not require hardness
Environmentally acceptable.
SILICATE TREATMENT
20 - 100 mg/L SiO2

pH 7.5 - 8.5
Passivation
100 % ANODE Fe0 + SiO3 Fe3O4 - SiO3
Fe
CATHODE
Chap 4.3
YELLOW METAL CORROSION

INHIBITION
Yellow Metal Corrosion
Inhibition
COPPER CORROSION
Domain of stability of Copper and Copper Oxides at 25C
E (V)
Cu, Cu2O, CuO
1.2
1.0
0.8
Cu++
0.6
E = 1.23 - 0.059 * pH
0.4 CuO
0.2
HCuO2-
0 Cu2O
- 0.2
Cu
- 0.4
- 0.6
- 0.8 E = - 0.059 * pH
- 1.0
- 1.2
- 1.4
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 pH
COPPER CORROSION
Aggravating factors are :

> pH
In any case it should be >7
The best range is between pH 8 and pH 8.5
> Oxidants : Copper is very sentitive to strong
oxidants (hypochlorite, H2O2, bromine)
> High level of chlorides (less sentive than SS
however)
> H2S, CN, NH3
> Stagnancy (or low water velocity)
Inhibition of Yellow Metals by Azoles
Cupric Oxide
Cuprous Oxide
Copper Metal
Uninhibited
CuI / Azole Inhibitor Film

Cuprous Oxide
Copper Metal
Inhibited
CU Corrosion inhibition
Copper oxide film formation (duplex film)
O2
2 CUPRIC OXIDE ( NOT PROTECTIVE )

CUPROUS OXIDE ( ADHERENT AND PROTECTIVE )
1 COPPER METALLURGY
The corrosion rate is controlled by the equilibrium between 1 and 2

Cu Corrosion inhibition
Cupper protection mechanism
Corrosive agent
Cu (I) / INHIBITOR Complex
CUPROUS OXIDE ( ADHERENT AND PROTECTIVE )
CUPPER METALLURGY
Cu (I) / INHIBITOR complex controls oxidation

of Cu (I) into Cu (II) ( the real protective agent is the complex and not
the filming inhibitor ).
Azoles (TTA, BZT, MBT)
z Adsorbed films
z Used primarily for copper / copper alloy

protection S SH
z Fed on a continuous basis N
N
N Mercaptobenzothiazole (MBT)
N CH3
H N CH3 N
N N
Benzotriazole (BZT) N N
H H
4-methylbenzotriazole (TTA) 5-methylbenzotriazole (TTA)
Azoles (bBZT)
z Fed on an intermittent basis
C4H9 N
N
N
H
Butylbenzotriazole (bBZT)
Yellow Metal Corrosion Inhibition
R
N
N
N
Azole H Deprotonation
R H+
N
N
Azole Anion
N
-
Yellow Metal Corrosion Inhibition
Bridging by Copper Ions
N N N N N N
N N N
Cu Cu Cu Cu
Chemical Structure of Azoles
N
N
N
H
Y
Halogen Resistant Azole (HRA)
Persistency of Azole Films
0.008
BZT
Copper Corrosion Rate (m m /y)
0.006
TTA
0.004
HRA
0.002
bBZT
0.000
0 5 10 15 20 25 30 35 40
Days
Chap 4.4
CLOSED SYSTEM CORROSION

INHIBITION
Dangerous Inhibitors
Anodic inhibition only
A 2e
C Pitting 2 mpy
A 2e
C Pitting 2 mpy
Overall corrosion 4 mpy

C Pitting 0 mpy
C Pitting 0 mpy

C Pitting 0 mpy
2e
A 2e
C Pitting 4 mpy

Closed System Inhibitors
Nitrite based
CorrShield NT Series
Nitrite
Promotes anodic films

No oxygen required - generally used in closed
systems
Used at high levels
Susceptible to biodegradation
Affected by Halogens
NITRITE TREATMENT
600 - 1200 mg/L NO2

pH 7 - 9.5
Passivation
100 % ANODE Fe0 + NO2 Fe3O4
CATHODE
CorrShield NT Series
mg/l NO2
NT4201 3000 - 6000 600 - 1200 TTA
NT4290 20000 - 40000 600 - 1200
NT4292 2250 - 4500 600 - 1200
NT4293 8000 - 16000 600 - 1200 MBTZ PAA NO3 SiO2 Borate
Compatibility
All NT products are compatible with Alcohol and Glycol
NT4293 is not compatible with NaCl or CaCl2 Brines
Others are compatible with NaCl and CaCl2 Brines
If Al present keep pH < 8
Molybdate based
CorrShield MD Series
MOLYBDATE TREATMENT
200 - 300 mg/L MoO4
Calcium Carbonate Inhibitor (PAA)
pH 7.5 - 9.5
Passivation
100 % ANODE Fe0 + MoO4 Fe3O4 - MoO4
O2
CATHODE
Molybdate
Promotes anodic films

Requires some oxygen
Used at high levels Requires some oxygen
Used at high levels
CorrShield MD Series
mg/l MoO4 NO2

MD4100 2400 - 3600 200 - 300 160 - 240 PAA TTA
MD4101 2300 - 4600 100 - 200 PAA TTA Morpholine
MD4103 1000 - 3000 200 - 600 PAA TTA
MD4151 2000 - 6000 200 - 600 PAA TTA
MD4152 300 - 1200 25 - 100 PAA TTA SiO2 PBTC
MD4153 600 - 2400 100 - 400
MD4154 2400 - 3600 70 - 100 200 - 300 PAA TTA
Compatibility
All MD products are compatible with Alcohol and Glycol
Not compatible with NaCl or CaCl2 Brines
Organic based
CorrShield OR Series
CorrShield OR Series
mg/l HPA as PO4
OR4400 2000 - 4000 17 - 34 HPS I TTA Triazine pH 8 - 10
OR4411 2000 - 4000 17 - 34 HPS I TTA Triazine Control on
Organic PO4
DE9886 2000 - 4000 17 - 34 HPS I Triazine
Compatibility
Above products are compatible with Alcohol and Glycol
Not compatible with NaCl or CaCl2 Brines
Specifically Designed for CaCl2 Brine HPA as PO4
OR4401 12000 - 18000 240 - 360 HPS I
Low conductivity programme DEHA

OR4410 50 - 100 5 - 10 BZT Cyclo

Chap 5
MICROBIOLOGICAL CONTROL
Microbiological Control
Microbial Fouling
Microbiological Corrosion
Certain forms of MB can attack metal directly and/or indirectly
Sulphate reducing bacteria
Sulphur bacteria
Iron and manganese bacteria
Biofilm formers / bacteria, fungi, algae
Microbiological Control
Oxidising Biocides
> Indiscriminate oxidation
Non-Oxidising Biocides
> Specific Reactions
OXIDISING Vs NON-OXIDISING
BIOCIDES
OXIDISING NON-OXIDISING
non-specific specific mode of action
react also with suspended organisms may acclimatise
solids and organic matter to the biocide
halogenated by-products more expensive
may be formed
Oxidising Biocides
Chlorine gas
Sodium hypochlorite
Calcium hypochlorite
Chlorine dioxide
Solid halogen donors
Activated Bromide
Hydrogen Peroxide
Peracetic Acid
Ozone
total residual Cl2 (ppm)
Oxidation of organic compounds
Co
m
bin
ed Formation of chloramines
Ch
BREAK POINT
lor
ine
Destruction of chloramines
Fr
e e
re
sid
Break point
ua
lC
hlo
rin
e
Combined residual chlorine
Cl2 added (ppm)

OXIDO-REDUCTION POTENTIAL
pH<4,5 chlorine can form
HClO + H+ + e- Cl2 + H2O
E = E30 0,06 pH
4,5<pH<7,5 pre-eminence of HClO

HClO + H+ + 2e- Cl- + H2O
E = E20 0,03 pH
potential (E)
pH>7,5 pre-eminence of ClO-
HClO ClO- + 2H+ + 2e- Cl- + H2O
- E = E10 0,06 pH
Cl2 ClO
-
Cl
1 2 3 4 5 6 7 8 9 10 11 12 13 14 pH
PRE-EMINENCE OF THE IONISED AND NON IONISED
SPECIES
% HOX
100%
90%
80%
HOBr / BrO-
70%
HOCl / ClO-
60%
50%
40%
30%
20%
10%
0%
4 5 6 7 8 9 10 11
7.5 8.6
pH
ACTIVE FORM VS. PH
pH % HOCl % HOBr HOBr / HOCl
6 97 100
7 76 98
7,5 50 94 1,9 / 1
8 24 83 3,5 / 1
8,5 9 60 6,7 / 1
9 3 33 11 / 1
50 % HOCl - 50 % ClO- pH 7,5
50 % HOBr - 50 % BrO - pH 8,6

REACTION WITH NITROGEN COMPOUND
HOX + NH3 ----- NH2X + H2O
HOX + NH2X ----- NHX2 + H2O
HOX + NHX2 ----- NX3 + H2O
WITH Cl WITH Br
NH2Cl NH2Br
NHCl2 NHBr2
NCl3 NBr3
REACTION WITH NITROGEN COMPOUND
Ex : pH 8
Br Cl
HOBr 90 % HOCl 19 %
BrO- 10 % ClO- 81 %
PRODUCTS FORMED
WITH Cl WITH Br
NH2Cl 100 % NH2Br < 10 %

HOCl 0 % HOBr 82 %
ClO- 0 % BrO- 8 %
Bromamines are almost as toxic HOBr

BENEFIT FROM BROMINE
REDUCTION OF CORROSION
BROMINE IS A WEAKER OXIDANT

Br2 / 2Br- : 1,065V Cl2 / 2Cl- : 1,36V
HOBr / BrO:- 1,33V HOCl / ClO- : 1,49V
BrO- / Br- : 0,7V ClO- / Cl- : 0,9V
REDUCTION OF ELECTROCHIMICAL CORROSION
Iron
Copper
TOLERANT VIS A VIS METALS
IRON
2 Fe (HCO3)2 + X2---> 2 Fe (OH)3 + CaCl2 + 6 CO2
MANGANESE
MnSO4 + 4 NaOH + X2---> MnO2 + 2 NaCl + Na2SO4 + H2O

BROMINATED PRODUCTS
Formation of bromine (HOBr)
Solide compound Oxidation of bromine salt

(BCDMH) by sodium hypochlorite
Bromine donnor: ClO- + Br- BrO- + Cl-

. pellets Bromine salt (40 %)
. granules
SOLIDE BROMINE
1-Bromo-3-Chloro-5,5-Dimthylhydantone
Br
CH3 N
C
CH3
C O
C
O N
Cl
N - Cl can be Hydrolysed
N - Br can be Hydrolysed
C5H6BrCIN202 + H2O C5H7ClN202 + HOBr
C5H7ClN202 + H2O C5H8N202 + HOCl
HOCl + Br- HOBr + Cl-

Dans le systme
BROMINATOR INSTALLATION
MAKE-UP
BROMINATOR
Recommended installation
Alternative installation
Modes of Action
Metabolic Inhibitors
Interrupt metabolic cycles
Enzyme poisons
Alter protein structures
Irreversibly bind to active sites
Surface Active Agents
> Alter permeability of cell membrane
> Undesirable compounds enter cell
> Nutrients and intracellular materials escape
Metabolic Inhibitors
> Bromonitrostyrene (BNS)
> Methylene bisthiocyanate (MBT)
> Dodecylguanidine hydrochloride (DGH)
> Isothiazolin (ISZ)
> Bromo-nitropropane-diol (BNPD)
> Triazines (TBZ) (photosynthesis blockers)
> Dibromo-nitrilo propionamide (DBNPA)
Surface Active Agents (membrane disrupters)

> Quaternary ammonium salts (Quats)
> Dodecylguanidine Hydrochloride (DGH)
> Cocodiamine
Multiple Active Formulations
Mixed Populations in Cooling Systems
Competition controls growth
When populations are balanced, growth is
limited
Removal of one group upsets balance
Multiple Actives
Proprietary biocides
Expand the kill spectrum
Synergism
Reduce growth of resistant strains
Better microbe control at lower dosages
Biocide Enhancement
Physical Methods
Non-Oxidising Biocide Feed Point
Highly mixed areas at front end of tower basin
Physically separate feedpoint of biocides and polymeric
dispersant (oxidisers and non halogen stable chemicals
- phosphonates - azoles)
Satellite feed biocide(s) to critical equipment prone to
MB fouling
Feed to hot return to control slime on fouled decks and
fill
Biocide Enhancement
Physical Methods
Time of Day
Algaestats
- Peak daylight hours
Biocides (halogens) which are not UV-stable
- Feed at night to minimise photo degradation
Feed Duration
Shot Feed over a short time period
- Develop maximum treatment level
High levels of free halogen will accelerate corrosion
Biocide Enhancement
Chemical Methods
Biocide - Free Halogen Compatibility
Incompatible with free halogen
> BNS
Little or no effect
> MBT, DGH, Quats, DBNPA
Synergistic with free halogen
> BNPD, isothiazolin
Biocide Enhancement
Chemical Methods
Bio-Surfactants
> Improve penetration of biocide into biofilm
> Increase transport of biocide into cell
> Interfere with cell attachment mechanisms
> Assist in sloughing off biomass accumulations
> Reduce oil and grease accumulations
Biocide Enhancement
Chemical Methods
Feeding Bio-Surfactants
> Effective with oxidising and non-oxidising biocides
> Compatible with free halogen residuals
> Once-through or recirculation systems
> Intermittent
> - High levels
> Continuous
> - Low levels
Biocide Enhancement
Chemical Methods
Bio-Surfactants
Biocide Enhancer
> Wets biofilm aiding penetration of biocide
> Low amount of removal of biofilm without biocide
Biodispersant
> Aids penetration of biocide
> Removes biofilm without biocide
GE Betz
Spectrus BD1550
Environmentally friendly
biodegradable biodispersant
for biofilm removal and
control in industrial cooling
systems
Spectrus BD1550
A true BIODISPERSANT
> Not just a biocide enhancer or surfactant for
wetting biofilm to aid penetration of biocides
Spectrus BD1550 REMOVES a significant
proportion of biofilm ON ITS OWN
Spectrus BD1550
Spectrus BD1550 has no biocidal activity

on its own
> a non-biocidal biofilm control additive
Spectrus BD1550 improves the effectiveness
of biocides in control of bulk water
microorganisms
Spectrus BD1550 with biocides
Effectiveness on bulk water populations
100
90 Non-oxidiser
80
plus BD1550
% Decrease from Control
70
Non-oxidising NaOCl
60
Biocide plus
50 BD1550
40
NaOCl
30
20
10
0
Spectrus BD1550
Removes biofilm from cooling system surfaces
> Can be used on its own to remove biofilm
> Has no biocidal activity on its own
> Enhances effectiveness of oxidising and non-
oxidising biocides for biofilm removal
Readily and ultimately biodegradable
Compatible with GE Betz cooling water treatment
programmes
Mixture of non-ionic and anionic components
Patented
Spectrus BD1550
Ideal (on its own or in conjunction with biocides) for
cleaning system experiencing biofilms or biofouling
> After system upsets such as process leaks
> After loss of biocide dosing or biocide effectiveness
> During cleaning and sterilisation procedures for
minimising risk of Legionella
Improves effectiveness of biocides
> May lead to lower biocide usage and discharge
Lower concentrations of biocide may be
applicable
May replace some biocide additions during the
year
Spectrus BD1550
Biodegradable
> Readily and ultimately biodegradable
Zahn-Wellens Test
71% degradation in 7 days
96%degradation in 14 days
Does not Bioaccumulate
> Log Kow ranges from < 0 to 2.4
Range is due to multiple components and
surfactant properties
Log Kow is < 3 and the degradation indicates no
potential for bioaccumulation
Spectrus BD1550
Typically shot dosed (based on system volume) on its
own or in conjunction with intermittent or continuous
biocide dosing for biofilm removal
> 20 to 50 mg/l BD1550 shot dosed
if system is significantly fouled higher doses up to
100 mg/l may be required
> Frequency of addition depends on several factors
degree of biofouling
nutrient concentration / ingress
system half-life
supplemental biocide programme
Legionella
LPTALK.PPS
Legionella.pdf
Legionella Best Practices.pdf
Legionella Sampling and testing.pdf
Legionella Routine Desinfection.pdf
Chap 6
TREATMENT PROGRAMME
DESIGN
Guidelines
Cooling system guide.pdf

CWT application guidelines.pdf
CWT Product Guide 2004 .pdf
Using the Cycle up simulation from Group exercise 4

and the application guidelines, design a treatment
programme for scale and corrosion control.
1) Define the optimum operating conditions
2) Propose two treatment options if appropriate, one
at free pH and the other one with pH control
3) The cost of water is $ 0.7 /m3 and 62 Baum
sulfuric acid costs $ 0.2/kg.The price for all the
treatment products is $ 7/kg.
Which is the best economical option?
Agenda
Day 3 24 May 2005
09:00 to 10:30 Monitoring and control

11:30 to 12:30 Troubleshooting
12:30 to 13:00 Final Quizz
13:00 Lunch
Chap 7
MONITORING AND
TROUBLESHOOTING
An effective treatment programme
should :
Inhibit corrosion
Minimise deposition and fouling
Be effective under broad operating conditions
Be economical
Have low impact on the environment
Appropriate Treatment Levels are
maintained through :
Cooling System Monitoring and Control

Poor Chemical Control
Overfeed
Underfeed
Highly variable results
Overfeed
High chemical costs

Poor treatment programme performance
Risk of environmental violations and fines
Underfeed
High corrosion rates

Increased equipment maintenance and
replacement (i.e. replacing or cleaning of fouled
or corroded heat exchanger tubes or bundles)
Reduced equipment performance (i.e. reduction
in heat transfer)
Highly variable results
Unable to evaluate effectiveness of treatment

programme
Unable to identify changes which affect
performance
Poor Chemical Control
can lead to :
Inconsistent product quality
Reduced throughput
Higher energy costs due to waterside fouling
High labour costs due to increased maintenance
or monitoring
Risk of equipment damage or failure
Typical Feed Control Methods
Manual
Semi-Automatic
Automatic
Manual
Periodic addition to tower sump

Manual addition to day tank
Chemical pump(s) manually operated (on / off)
Manual control of blowdown
Semi-Automatic
Chemical shot-fed by on/off timer control of

pump(s)
Automatic
Microprocessor based Chemical
Monitoring and Control System
Key features
Continuous monitoring of important parameters
Continuous pH monitoring and control
Continuous control of blowdown
Precise chemical feed
Local indication and remote alarm capabilities
for out of limit parameters
Control Regulation of cooling water circuit
Version with controller
AccuTrak Multifunction
Model 100/300/900
blowdown
conductivity circuit
Make-up
flow
AccuTrak Controllers
Cooling & Boiler water

controllers
Unique Biocide & Oxygen
scavenger control strategies
Control up to 3 analogue
inputs
11 different controllers in
ONE
AccuTrak Controllers
Model 100 Model 300
Blow down pH control
Inhibitor Blow down
Biocides (2) Biocides (2)
Model 200 Model 900

pH control (2) Blow down
Biocide
Model 600 Free Chlorine
(Boiler)
Blow down
O2 Scavenger
Inhibitor
Control Regulation of cooling water circuit.
Version with PLC/PC PaceSetter Platinum
E S modem
N O
T R 24h/24
R T
E I
E E
S S
conductivity 1
pH
blowdown
conductivity 2
Make-up
flow
HMI
Panel mounted instruments
Benefit of Improved Control
Reduced risks associated with chemical

underfeed or overfeed
Compliance with environmental regulations
Improved quality of plant operation
Increased water and energy savings
Improved plant productivity
Monitoring Tools
Tower
Inspection
Inspection during operation is critical

-Screens -Distributors
- Mist eliminators - Buildup on surfaces
- Deck - Air flow louvers
- Fill - Basin
Field Testing
Water Analysis
Required to monitor and control treatment

programme
Supply important information
Enable identification of low level contaminants
Water Analysis
Recirculating tower water

Make Up Water(s)
Analysis
Performed
ON SITE
Parameters monitored (operating
data)
Testing can include :
pH
Conductivity
Suspended solids
Alkalinity
Hardness
Phosphate
Other treatment components depending on programme
Microbiological populations
Deposit Analysis
Samples taken from :
Critical heat exchangers

Cooling tower
Areas of low water velocity and/or high heat flux
Frequency
Test Frequency will vary depending on :
Cooling System
Plant process
Plant personnel available
Reporting
Never leave the site before you have prepared your
analytical report including:
> Analyses performed on site
> Results from specific investigations
> Conclusions about the treatment performance
> Changes possibly needed
Present and discuss you report, and agree on actions
with the responsible manager and the the operators
Set the date for the next service visit
Compilation/Data Analysis
Manual
Weekly log sheets

Results can be graphed for data trending
Weekly Log Sheets
Day 1 2 3 4 5 6 7
O-PO4 (ppm) 6 8 10 12 14 16 12
Day 8 9 10 11 12 13 14
O-PO4 (ppm) 10 10 8 10 12 18 14
Day 15 16 17 18 19 20 21
O-PO4 (ppm) 12 13 15 19 13 10 9
Day 22 23 24 25 26 27 28
O-PO4 (ppm) 11 10 13 16 15 13 10
Data Analysis
Reading
6-7 8-9 10-11 12-13 14-15 16-17 18-19
(ppm)
Frequency
1 3 8 8 4 2 2
(number)
Graphing Results
9
Days
8
6-7 8-9 10-11 12-13 14-15 16-17 18-19

Orthophosphate, ppm
Compilation/Data Analysis
Data Acquisition/Management
Replaces daily log sheet with a database

Permits easy retrieval of historical data
Improves operator control - out of limit results are
highlighted
Incorporates statistical process control
Provides graphing capabilities
Generates reports
Data management
InfoCalc Data Manipulation
InfoCalc Multiple Display
InSight
Overview
Monitoring, diagnostics & control system
Developed based on customer needs
Delivers
Improved data management
Reduced overall spend in water, energy and labor
Improved reliability of customer systems
Insures regulatory compliance
Reduced maintenance
InSight
Digital service for utility and process systems
Remote monitoring and diagnostic programme to
protect assets and reduce operating costs
Web based Monitoring Service
Automation Packages
Chemical Treatment Programmes
On site Service Programme
Data collection, storage and analysis dashboard
InSight delivers Reduced Spending on Water, Energy
and Labor.
CD Marcom/Insight
Corrosion Monitoring
Coupons
Corrosion rate meter
Corrosion Coupon Test Specimen : Open-
Loop Bypass Installation
CORROSION LOOP
RACK DE MONITORING
Integrated systems comprised of all or part of:

> Flowmetering (rotameters)
> Biobox
> Biomonitoring
> Corrosion coupons
> Corrosion meter probe
> Steam test exchanger
MONITORING RACK CORROSION COUPONS
CORROSOMETER
DATA COLLECTION
BIOMONITOR
1000 l/h
500 l/h
BIOBOX
100 l/h
1400 l/h
10 l/h
COOLING WATER
C
0 5
C 0 120 bar
C
0 120
0 120
TEST EXCHANGER
0 10
bar
STEAM
MONITORING RACK
Deposition Monitoring
Coupons
Monitall
Test heat exchanger
Model Condenser
MONITALL
Fouling electric control
Heating probe equiped with thermocouple (skin probe temperature
bulk water temperature) adjustable heat flux
Water circulates around the probe.
Monitor T (skin temperature bulk temperature)
Visual aspect of the probe (inox) deposit analysis
Temperature Skin Temp.
Bulk Temp.
Time
Plot temperature/ T graphs
Water flowrate: 50 to 150 l/h
Power 220V single phase 3A
Non ATEX MonitAll.pdf
Microbiological Monitoring
Micro-Organism counts
> ATP
> Dipslides
> PetriFilm
> Plate Counts
Biobox
Biofilm fouling monitor
Delta-P monitor
Stainless Steel coupons
> Ni-Cr mesh coupon
Total Free
ATP ATP
ATP
Adenosinetriphosphate NH2
N
N
O O O
N N
O- P O P O P O C H2
O
- - -
O O O
OH OH
Energy source for biochemical reactions

Produced in ALL living cells
Decreases if cell dies
ATP DETECTION
micro-
organism ATP is
released into
lysing
+ agent
buffered
solution
Light
+ Luciferin
ATP Luciferase
Overall System Monitoring
U-Coefficients
Computer analysis
- Trends
- Predictive programmes
Field Analytical Equipment
Global and Advanced WAL test kits
> GE Betz DR/2400 GE Betz DR/890
> pH, Conductivity meter
> Digital titrator (Titrimetric analysis)
Portable Field Microscope
Microbiological Monitoring
> Cultivation methods : dipslides, petrifilm
> ATP method : Bioscan II
Laboratory - Analytical Services
1. Standard Analysis - Monitoring

Fluids (water & oil)
Deposits
Coupons
Microbiological Cultural Examinations
Resins
Metallurgy
2. Problem Solving
Laboratory - Analytical Services
Inorganic & Organic Analysis
Microbiological Analysis
Metallurgy
> Characterization & Quantification

> ppb, ppm to % levels
> Bulk & localized surface analyses
> No certification of customer end product or
conformance towards local regulations
Analytical Instrumentation
Inorganic Analysis
> Inductive Coupled Plasma Emission Spectroscopy
(Radial and Axial)
> Flame - Atomic Absorption Spectroscopy
> Ion Chromatography
> Segmented Flow-UV Analysis
> Automated Titrimetric Analysis
> Wavelength Dispersive X-ray Fluorescence Analysis
> ECS 3000 Coulometric Analysis
Organic Analysis
> Thermo Gravimetric Analyzer
> FT Infra-Red Spectroscopy
> CHNS-Analyzer
> Mass Spectrometry
> Gas & Liquid Chromatography
> Total Organic Carbon Analyzer
> Total Kjeldahl Nitrogen Analyzer
Microbiology Testing
> Cultivation methods counts.

> Product evaluations.
> Toxicity testing (Microtox, Respiration studies)
> Microscopic examinations.
> Evaluation of rapid microbiological monitoring tools for use on
site.
> Activated Sludge characterization.
> Macro-fouling characterization.
Metallurgy
1. Surface Analysis
Scanning Electron Microscope
2. Failure Analysis
Investigations & Recommendations
3. Corrosion Coupons
Corrosion Rate, Pit depth
Metallurgical Analysis
Failure Analysis & Problem Solving
Expertise
- Cooling
- Boiler
- Metals Process
- Hydrocarbon Process
Boiler -Tube
Water Separation Equipment LT Overheating
long term Overheating
Damage
Membrane Autopsy Good
- Spiral Wound
- Hollow Fiber
Laboratory - Application
1. Cooling
Tower Rig : ELT (NCC), BTU
Steriliser Treatment, Scale Inhibition, Cleaning
2. Sentinel (central heating)
Domestic Heating Rig
BSI-Rig (Metallic/Non-Metallic)
3. Water/Waste water
Clarification, Emulsion breaking, Flotation
Metals Removal, Sludge dewatering, Antifoam
Laboratory - Application
4. Hydrocarbon
Anti-fouling, Oxidation Stability
Desalting, High Temperature corrosion
Oil Characterization
5. General Process
Paint Spray Booth simulation
Dust Control, Deposit Inhibition
Foam Control, Cleaning
New Services 2004
Metal Processing Simulation Line

Corrosion Performance
Neutral Salt Spray
Passivation Drying
Rinse Spray Mechanical Performance

Impact
Liquid Paint Pencil hardness
Pretreatment Drying Drying Bending
Coating
The Future: Lab On A Disk
Quickly, accurately, simply tests eight key
analytes in water:
1. Calcium
2. Molybdate
3. pH
4. t-Alkalinity
5. o-Phosphate
6. Sulfite
7. Magnesium
8. Chlorine
What systems can I test?
Targeted at..
Steam Boilers
Cooling Towers
Also works on.

Closed-loop cooling
Mid-pressure Boilers
How does it work?
1. Inject 5 ml filtered water in sample device
2. Allow 2-minute reaction time
3. Close sampling device to dry disk and allow 6
minutes development time
4. 2-minute read and report cycle all automatic
10 Minutes Total
Disks
DVD Reader
Results!
(Developing USB driver for PocketPC)
Trouble shooting Exercise.pdf

Training Quizz (30 mn)
Read the questions carefully. Do not extrapolate.
T - F (True False): Select the right statement
A-B-C: one or more answer(s) is(are) correct
Results of calculation as appropriate

Cooling Water Treatment

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COOLING WATER TREATMENT

Advanced training course

Welcome to all of you to our first Regional

We are particularly pleased to welcome our colleagues

08:30 to 08:45 Introduction

08:30 to 10:00 Corrosion and Inhibitors

08:30 to 10:30 Monitoring and control

Read the questions carefully. Do not extrapolate.

T - F (True False): Select the right statement

A-B-C: one or more answer(s) is(are) correct

Form 4 or 5 teams (4 to 5 members in each team)

BASIC WATER CHEMISTRY

Pure water contains one part of oxygen and two parts

Water is the UNIVERSAL SOLVENT and dissolves

The atmosphere is a mixture of gases ,the main

10 GAUGE PRESSURE PSI 17.2

> When Carbon Dioxide dissolves in water a

Industrial gases produced by burning fossil fuels

SO2 + H2O H2SO3 Sulphurous Acid

Water dissolves, to some extent, all known substances.

Typical Calcium and Magnesium salts are :

Bicarbonates Ca(HCO3)2 Mg(HCO3)2

Dosage rates for continuous feed are expressed as mg/l on

Parts per Million ppm = mg/l

Total hardness and Calcium hardness are obtained by

Equivalent weight refers to the amount of an element combining

mils per year = 1/1000 inch per year

> 1 mpy = 0.025 mm/y (0.0254)

P = Alkalinity - phenolphthalein alkalinity

M Alkalinity - methyl orange alkalinity (pH=4.4)

All values expressed as CaCO3

Cooling Water Inlet

Blowdown Recirculating Pump

COOLING SYSTEM HYDRAULICS

Blowdown or Non Evaporative Losses =

Latent Heat of Water is 556 kcal/kg

I.e. 1,4% of RR at 10C T or 1% RR at 6 to 7C de T

t1/2 = V(m) x 0.6931

OPEN EVAPORATIVE COOLING

Control corrosion rate to prevent equipment failure.

Prevent scale formation and deposition on heat transfer

Control microbiological activity and maintain system

Allow the cooling system to operate at the optimum cycles of

STRONG CORROSION INHIBITORS

STRONG SCALING (DCA) INHIBITORS

Insoluble material formed by oxidation of

Mineral Scale can form when

Calcium (bicarbonate) concentration

Conditions at which a given water is in equilibrium with calcium carbonate.

pHs = (pK2 - pKs) + pCa + pAlk

LSI = pHa - pHs

LSI +ve : water has a calcium carbonate scaling tendency

pHs = pCa + pAlk + C

Calculate LSI for the following water qualities and conclude:

2) Calcium Hardness 40 mg/l CaCO3

RSI = 2pHs - pHa

Ryznar Stability Index

> 7.5 or 8 probability of corrosion increases

RSI = 2pHs - pHa = 5.72

1) Using Cyclup, prepare water simulation for a cooling system

CHELATING (COMPLEXING) PHOSPHONATES

INITIALISATION (adsorption and ionic interactions )

CO32- + CaCO3 CaCO3

CaCO3 + Ca2+ CaCO3