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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


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

08:30 to 10:30 Monitoring and control


10:30 to 11:00 Coffee break
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
UNITS OF CONCENTRATION

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-
UNITS OF CONCENTRATION

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
TREATMENT PROGRAMMES
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
Total Dissolved Solids 120 mg/l
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
Total Dissolved Solids 400 mg/l
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
Calcium Hardness 40 mg/l CaCO3 pCa 3.40
M Alkalinity 35 mg/l CaCO3 pAlk 3.15
Total Dissolved Solids 120 mg/l
Temperature 60 C C at 60 C 1.50
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
RYZNAR STABILITY INDEX
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:
Calcium Hardness 200 mg/l CaCO3 pCa 2.70
M Alkalinity 160 mg/l CaCO3 pAlk 2.50
Total Dissolved Solids 400 mg/l
Temperature 60 C C at 60 C 1.56
Total (pHs) 6.76
pH of Cooling Water (pHa) 7.80 LSI = pHa - pHs = +1.04
SCALING

RSI = 2pHs - pHa = 5.72


SCALING
RYZNAR STABILITY INDEX
Calcium Hardness 40 mg/l CaCO3 pCa3.40
M Alkalinity 35 mg/l CaCO3 pAlk 3.15
Total Dissolved Solids 120 mg/l
Temperature 60 C C at 60 C 1.50
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


Limitations of Continuum AEC

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
Limitations of Continuum AEC

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.
Limitations of Continuum AEC

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
Limitations of Continuum AEC
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


10:00 to 10:30 Coffee break
10:30 to 13:00 Corrosion control
13:00 to 14:30 Lunch
14:00 to 15:00 Microbiological control
15:00 to 15:30 Coffee Break
15:30 to 17:00 Treatment and Product Guidelines

Pretraining Quizz CWT Corrected.pdf


Chap 4.2

CORROSION INHIBITION
TREATMENT PROGRAMMES
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
Filtered water collection line
Flow restriction Under Deposit Corrosion

Erosion Corrosion

Welding ANAEROBIC ZONE ARAETED ZONE

Biological Corrosion
O2 migration

Filtered water collection line


Visual Investigations
Filtered water collection line
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)
HPS I vs. Polymer dispersant

Calcium Phosphate

0.8
Turbidity (NTU's)

High Temp
0.6

0.4

0.2

0
HPS-I Polymer dispersant
HPS I vs. 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
20 % ANODE Fe0 + oPO4 Fe3O4

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
CALCIUM CARBONATE INHIBITOR
CONTINUUM AT

Components

CALCIUM PHOSPHATE INHIBITOR


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

Components

TTA

YELLOW METAL CORROSION INHIBITOR


CONTINUUM AT

Programme Mechanism

Anode Fe0 + HEDP Passive Film


(60%) Other anodic inhibitors if included oPO4 MoO4

Cathode Ca + oPO4 Ca3(PO4)3


(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
20 % ANODE Fe0 + oPO4 Fe3O4

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
CALCIUM CARBONATE INHIBITOR
Non Phosphorous, non Phosphonate
Calcium Carbonate Inhibitor
Tolerant to high Chlorine concentrations
High Calcium tolerance
CONTINUUM AEC

Components
CALCIUM PHOSPHATE INHIBITOR
POLYMER HPS I
Superior calcium phosphate inhibitor and
dispersant for iron and suspended solids
DISPERSANT
CONTINUUM AEC

Components

HRA
YELLOW METAL CORROSION INHIBITOR

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
Limitations of Continuum AEC

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
ZINC PHOSPHATE TREATMENT

Components

ZINC
CORROSION INHIBITOR
> Cathodic Inhibitor
ZINC PHOSPHATE TREATMENT

Components

ORTHOPHOSPHATE
CORROSION INHIBITOR
> Cathodic inhibitor
ZINC PHOSPHATE TREATMENT

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

Cathode Ca + oPO4 Ca3(PO4)3


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
Ca + Phosphonate Ca (Phosphonate)
Zn + OH4 Zn(OH)2
ZINC ORGANIC TREATMENT

Components

HEDP and AMP


CALCIUM CARBONATE INHIBITOR

CORROSION INHIBITOR
> at concentrations above 4.5 mg/l PO4
ZINC ORGANIC TREATMENT

Components

POLYMER (HPS II/HPS I)

> INHIBITOR FOR


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

> DISPERSANT FOR


> Iron and suspended solids
ZINC ORGANIC TREATMENT

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
Ca + Phosphonate Ca (Phosphonate)
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
TREATMENT PROGRAMMES
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
TREATMENT PROGRAMMES
Dangerous Inhibitors

Anodic inhibition only

A 2e
C Pitting 2 mpy

A 2e
C Pitting 2 mpy

Overall corrosion 4 mpy


Dangerous Inhibitors

Anodic inhibition only

C Pitting 0 mpy

C Pitting 0 mpy

Overall corrosion 0 mpy


Dangerous Inhibitors

Anodic inhibition only

C Pitting 0 mpy

2e

A 2e
C Pitting 4 mpy

Overall corrosion 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
Closed System Inhibitors

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
If Al present keep pH < 8
Closed System Inhibitors

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

If Al present keep pH < 8


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
Non-Oxidising Biocides
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
Non-Oxidising Biocides
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
Group exercise #5 (30 mn)

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


10:30 to 11:00 Coffee break
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)
Group exercise #6 (30 mn)

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