CHIMEC S.p.A.

Water Technology Unit - Cooling Systems Handbook -

COOLING SYSTEMS
OPERATORS HANDBOOK







CHIMEC S.p.A.
WATER TECHNOLOGY UNIT






CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators Handbook -
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Table of Contents

1. Water Fundamentals ................................................................................ 6
1.1. Water Sources ........................................................................................ 6
1.2. Physical, Chemical and Organic properties of Water ..................................... 7
1.3. Gross Inorganic chemical properties of water .............................................. 9
1.4. Organic chemical properties of water ....................................................... 15
1.5. Naturally Occurring and Synthetic Organic contaminants ............................ 16
1.6. Determination of Organic content of water ............................................... 17
1.7. Measuring Water Parameters .................................................................. 17
2. Introduction to Cooling Water ................................................................. 21
2.1. Heat Transfer in Cooling Water ............................................................... 21
3. Cooling Systems Layouts ........................................................................ 23
3.1. Once Through Cooling System ................................................................ 23
3.2. Closed Circulating Cooling System ........................................................... 24
3.3. Open Evaporative Cooling System ........................................................... 24
3.4. Types of towers for Open Evaporative Systems. ........................................ 25
4. Design of Recirculating Cooling System .................................................... 28
4.1. Mass and Energy Balance for Open Evaporative Towers ............................. 29
4.2. A practical Example (1) .......................................................................... 31
4.3. A practical Example (2) .......................................................................... 31
5. Common issues in Cooling System .......................................................... 33
5.1. Scaling in Cooling Water ........................................................................ 33
5.2. Corrosion in Cooling Water ..................................................................... 36
5.3. Fouling in Cooling Water ........................................................................ 38
5.4. Microbiological Growth, Contamination and Induced Corrosion .................... 38
6. Common chemical treatments programmes in cooling systems ................... 42
6.1. Scaling and Fouling Control Programmes .................................................. 42
6.2. Corrosion Control Programmes ................................................................ 43
6.3. Microbiological Growth Control Programmes ............................................. 44
7.1. Cooling System: CHIMEC Analyses .......................................................... 46
7. Troubleshooting of Cooling Systems ........................................................ 48



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List of Tables

Table 1-1: Classification of Water Impurities (solid matter). .................................... 8
Table 1-2: major ions in waters and other parameters. ........................................... 9
Table 1-3: pH level and water characteristics. ..................................................... 10
Table 1-4: some typical alkalinity values. ............................................................ 12
Table 1-5: ionic species responsible for hardness. ................................................ 13
Table 1-6: relative hardness of waters. ............................................................... 13
Table 1-7: Water Example for Hardness Calculation ............................................. 13
Table 1-8: hardness calculation summary in mg/L. .............................................. 14
Table 1-9: hardness calculation summary in meq/L. ............................................. 14
Table 1-10: typical conductivity ranges for different waters. .................................. 15
Table 1-11: Common impurities found in fresh water. .......................................... 19
Table 1-12: Summary of water properties. .......................................................... 20
Table 3-1: Once Through cooling System Advantages and Disadvantages. ........... 23
Table 3-2: Closed Recirculating cooling System Advantages and Disadvantages. ... 24
Table 3-3: Open Evaporative cooling System Advantages and Disadvantages. ...... 25
Table 4-1: fundamental parameters in open evaporative cooling systems. ............. 29
Table 4-2: initial set of parameters (1). .............................................................. 31
Table 4-3: complete set of parameters (1). ......................................................... 31
Table 4-4: initial set of parameters (2). .............................................................. 31
Table 4-5: complete set of parameters (2). ......................................................... 32
Table 4-6: results comparison between Case 1 and Case 2. .................................. 32
Table 5-1: comparison table for microbiological control. ........................................ 41
Table 7-3: CHIMEC Routine Analyses. ................................................................. 46
Table 8-1: Cooling Water Troubleshooting ........................................................... 48

List of Figures

Fig: 1-1: The Water Cycle. .................................................................................. 6
Fig: 1-2: particle size classification and instrumental methods for determination. ...... 8
Fig: 1-3: average concentration range of inorganic substances in surface water. ....... 9
Fig: 1-4: pH-scale of water with common substances. .......................................... 11
Fig: 1-5: corrosion rate vs. pH. .......................................................................... 11
Fig: 1-6: relative amounts of alkalinity species at various pH levels........................ 12
Fig: 1-7: Laboratory bench pH meter. ................................................................ 17

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Fig: 1-8: Portable conductivity-meter. ................................................................ 17
Fig: 2-1: working principle of a heat exchanger. .................................................. 21
Fig: 2-2: heat transfer and resistance in tubes. ................................................... 22
Fig: 3-1: Once Through cooling System layout. ................................................... 23
Fig: 3-2: Closed Circulating cooling System layout. .............................................. 24
Fig: 3-3: Open Evaporative cooling System layout. .............................................. 25
Fig: 3-4: Open Evaporative cooling system (detailed view) ................................... 25
Fig: 3-5: induced multicell cooling tower. ............................................................ 25
Fig: 3-6: multicell cooling towers. ...................................................................... 26
Fig: 3-7: internal view of a mechanical draft cooling tower. ................................... 26
Fig: 3-8: details of plastic fillings. ...................................................................... 26
Fig: 3-9: hyperbolic natural draft cooling towers. ................................................. 26
Fig: 3-10: side view of a hyperbolic cooling tower with construction details (1)........ 27
Fig: 3-11: side view of a hyperbolic cooling tower with construction details (2)........ 27
Fig: 3-12: wood filling of a hyperbolic tower. ....................................................... 27
Fig: 4-1: complete open evaporative cooling system layout. ............................... 28
Fig: 4-2: parameters for simplified mass and energy balance. ............................... 29
Fig: 5-1: tube walls affected by scale. ................................................................ 34
Fig: 5-2: scale coupons of different shapes and sizes. .......................................... 35
Fig: 5-3: pilot heat exchanger. .......................................................................... 35
Fig: 5-4: electrochemical corrosion process. ........................................................ 36
Fig: 5-5: a corrosion coupon severely affected by electrochemical corrosion. ........... 36
Fig: 5-6: corrosion rate vs. conductivity. ............................................................. 36
Fig: 5-7: corrosion rate vs. pH. .......................................................................... 37
Fig: 5-8: corrosion as a function of oxygen content and temperature. .................... 37
Fig: 5-9: corrosion (and scale) coupon rack. ....................................................... 37
Fig: 5-10: rod shaped bacteria. ......................................................................... 38
Fig: 5-11: Unicellular (left) and Filamentous Fungi (right). .................................... 38
Fig: 5-12: microbiological induced corrosion MIC. .............................................. 40
Fig: 5-13: corrosion coupon affected by MIC prior to pickling. ............................... 40
Fig: 5-14: corrosion coupon affected by MIC after pickling: under deposit corrosion
occurred. ........................................................................................................ 40
Fig: 5-15: VIALS for Aerobic Bacteria. Original colour is Red, in presence of aerobic
bacteria vials turn into yellow. ........................................................................... 40

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Fig: 5-16: VIALS for Anaerobic Bacteria. Original colour is Yellow, in presence of
anaerobic bacteria vials become turbid and black if S.R.B. exist. ............................ 40
Fig: 5-17: Easicult TTC Slide and its comparison chart. ......................................... 41
Fig: 5-18: Luminometer for quick analyses. ........................................................ 41
Fig: 6-1: undistorted lattice (left) and microscope picture (right) of precipitating
crystals........................................................................................................... 42
Fig: 6-2: distorted lattice by addition of DCA (left) and microscope picture (right) of
non precipitating crystals. ................................................................................. 42
Fig: 6-3: adsorption (left) and stabilisation/dispersion (right) process of DCA. ......... 42
Fig: 6-4: anodic film on tube wall....................................................................... 43
Fig: 6-5: cathodic film on tube wall .................................................................... 43
Fig: 6-6: chlorination break point. ...................................................................... 45
Fig: 6-7: chlorine and bromine dissociation curve vs. pH. ..................................... 45






























CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators Handbook -
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1. Water Fundamentals
Pure Water is colourless, tasteless
and odourless; its chemical formula is
H
2
O; this means that one molecule of
water, is formed by two atoms of
Hydrogen and one of Oxygen.

Water is fundamental for Life (see
Fig: 1-1) and it covers four fifth of the
Earths surface;

Fig: 1-1: The Water Cycle.
Water has different properties (later
described in details) such as that of
being able to dissolve partially, almost
any substance found on earth or
atmosphere; for this reason, water is
called the universal solvent.
Although there is abundance of
water, it is not readily available in the
conditions we desire for industrial
needs.
Water used in industry, in fact,
contains impurities, responsible for
problems such as deposition, corrosion
and microbiological fouling in pipes,
conduits, heat exchangers etc, etc.

1.1. Water Sources
All water Sources originate by
evaporation from terrestrial and oceanic
masses, followed by rain and snowfall.

While raining, water droplets enter
in contact with dissolved gases in the
atmosphere, but also with suspended
particles, dust, smog and other
industrially-originated pollutants.

The two most important sources of
Fresh Water are surface water and
ground water.

Water flowing in rivers, varies in
composition according to the grounds
characteristics.

Ground water is characterised by a
relatively constant temperature and a
lower level of suspended solids; these
are properties highly desirable for
water-use in the industry.
On the other hand, ground water
has a higher level of dissolved solids
(minerals) respect to surface water.

Recycled water and Sea Water also
represent another source; the first
must be used for economical and
environmental reasons, the latter for

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cooling systems only (if more
economical alternatives do not exist).

1.2. Physical, Chemical and
Organic properties of Water
Water is never pure, except possibly
in its vapour state. Water always
contains impurities, which are
constituents of natural (and manmade)
origin.
For instance, the presence of the
chemical impurities of calcium and
magnesium ions (Ca
++
and Mg
++
) in
ground water are usually of natural
origin, being due to the dissolution of
these minerals from the soil and
underground rocks.
Impurities in water vary in quantity
and nature too.
The acceptability of a water for its
defined use depends on its physical,
chemical and biological properties.
The composition of water is the end
result of physical and/or chemical
and/or biochemical processes.

Physical properties of water that
show wide variation in magnitude
include:
Colour caused by dissolved
minerals, dyes or humic acids from
plants. The decomposition of lignin
produces colour compounds of tannins
and humic acids. The latter causes a
brown-yellow to brown-black colour.
Dyes or pulp and paper plants also
cause colour, as does the presence of
iron, magnesium and plankton.
Turbidity is a measure of the
cloudiness. It is caused by the presence
of suspended matter which scatters and
absorbs light. In lakes, turbidity is due
to colloidal or fine suspensions.
Turbidity is measured by a visual
comparison test with standard turbidity
suspensions.
Odour clean (distilled) water is
odourless. Many organic and inorganic
chemicals are odorous, including algae
and other organisms. Hydrogen
sulphide (H
2
S), sometimes present in
ground water and in waste water is
malodorous.
Taste taste, like odour, may be
due to the decaying of micro-organisms
or algae. It may also be due to high
concentration of salts such as Ca
2+
and
Mg
2+
and Cl
-
. Taste is usually only an
issue in drinking water, and rarely in
waters not used for drinking.
Temperature is perhaps the most
significant parameter for shallow waters
(lakes, ponds, etc). If large
temperature gradients are reported,
stratification may occur between the
upper (warmer) body and the lower
(colder) body. In river environment
higher temperature reduces the amount
of oxygen in water, making the river

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less desirable for fish. In waste water
treatments plants, temperature may
also be significant in that, above 36C,
the aerobic micro-organisms population
tends to be less effective as purifiers.
Solids the solids content of water
is one of the most significant
parameters.
The amount, size and type of solids
depend on the specific water. Several
classifications occurs for solids, usually
they are annotated as shown in Table
1-2.

Table 1-1: Classification of Water
Impurities (solid matter).
Suspended
Solids
- SS-
Refers to Undissolved
Matter in water
Dissolved Solids
- DS-
Refers to the Total
amount of dissolved
matter in water
Total Solids
- TS -
Refers to the sum of
DS and SS
Dissolved Gases
- DG-
Refers to the gases
Dissolved in water

A useful classification of solids is
also based on particle size, as seen in
Fig: 1-2 here below.

Fig: 1-2: particle size classification and
instrumental methods for determination.
All waters contain variable
concentrations of dissolved salts that
are likely to dissociate in charged
particles called ions.
Cations are positive, anions are
negative; the chemical equation below
shows dissociation of NaCl (sodium
chloride) in water:
NaCl Na
+
+ Cl
-
The assessment of a water quality
may be either Specific or General.
Specific assessment refers to the
analyses of major ions (Ca
2+
, Mg
2+
) or
heavy metals (Pb, Cu, Zn, Sn)
General refers for tests such as
alkalinity, hardness, electrical
conductivity, pH, etc.

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The major ions species in some
natural waters are listed in .
Table 1-2: major ions in waters and other
parameters.
Cations: Ca
2+
, Mg
2+
, Na
+
, K
+

Anions: HCO
3
-
, SO
4
=
,Cl
-
,NO
3
-

General
Characteristics:
pH, Total Hardness,
Alkalinity, TDS

Minor ions may be present at trace
levels, and are mainly cations such as
Iron (Fe
2+
, Fe
3+
) and Manganese (Mn
2+
)
and anions like Phosphate (PO
4
3-
).
The presence of Silica (a non-ionic
mineral) along with calcium,
magnesium, iron and aluminium can
cause scaling (mainly in boilers). Its
content should be kept as low as
possible.
Nutrients the two nutrients of
importance in water are Nitrogen and
Phosphorous. They are both essential
nutrients for plant and organisms
growth but they are highly undesirable
in cooling systems.
In water environment, nitrogen may
exist in the form of ammonia (NH
3
)
and its ion ammonium (NH
4
+
), nitrites
(NO
2
-
) and nitrates (NO
3
-
).

Ammonia is toxic to organism while
nitrates are harmful.

Phosphorus is the limiting nutrient
for eutrophication
1
; natural sources are
phosphorous-bearing rocks, soil erosion
and organisms cellular activity.

Additional intake is due to fertilizers,
detergents, animal feed supplements,
etc.

Common phosphorous compound in
water are sodium-phosphates (Na
3
PO
4
,
Na
2
HPO
4
and NaH
2
PO
4
) and
diammonium hydrogen phosphate
(NH
4
)
2
HPO
4
.

Fig: 1-3 below, shows the average
concentrations of inorganic substances
in surface waters (excluding
groundwaters and wastewaters).

Fig: 1-3: average concentration range of
inorganic substances in surface water.

1
An increase of the concentration of nutrients in an
aquatic ecosystem causing the increased productivity of
autotrophic green plants, leading to the blocking out of
sunlight, elevated temperatures within the water body,
depletion of waters oxygen resources and increased algal
growth.

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1.3. Gross Inorganic chemical
properties of water
The gross inorganic chemical
properties of water are:
pH
Alkalinity and acidity
Hardness
Conductivity
pH is defined as the negative
logarithm (base 10) of the hydrogen
concentration i.e.:
pH = -log[H
+
]
Water dissociates slightly into
hydrogen ions [H
+
] and hydroxide ions
[OH
-
] as shown in the equation below:
H
2
O = H
+
+ OH
-

Taking into account the Ion Product
(or dissociation constant for water as
Kw = 10
-14
mol/L @ 25C), in absence
of any foreign substance, the
concentration of hydrogen and hydroxyl
ions is the same (at 25C).
Very useful information on water
characteristics can be obtained by
knowing the value of the pH.
pH ranges from 0 to 14 with
neutrality at 7.
Acidity occurs at pH lower than 7,
Basicity at pH higher than 7.

The pH of most mineral waters is 6
to 9.

The pH remains reasonably constant
unless the water quality changes due to
natural or manmade influences, adding
acidity or basicity (see Table 1-3).

Table 1-3: pH level and water
characteristics.
pH value Water Characteristics
pH < 7 Acidity
pH = 7 Neutrality
pH > 7 Basicity

The pH of water is a key parameter
and is also dependant on:
The type of rock/soil from which
acid/alkaline compounds can be
eroded.
The Carbonate System and the
concentration of carbonates and
carbon dioxide; waters with low
carbonate concentrations are
usually acidic.
The exposure to atmospheric
pollutants or wastewater.



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Examples of the pH-scale variation,
due to common substances are
reported in Fig: 1-4 below.




Fig: 1-4: pH-scale of water with common substances.

As seen in Fig: 1-4, it is possible to
modify the pH of a given water, by
adding acid or alkaline substances.
For example, the addition of H
2
SO
4

(sulphuric acid) will contribute with H
+

ions in water, lowering the pH.
The addition of NaOH (caustic soda),
will, instead, contribute with OH
-
ions
to raise the pH.



Low or high pH may cause
corrosion
2
in cooling systems;

Fig: 1-5 shows the safe pH range to
keep in the water to avoid corrosion.


2
Corrosion will be described in details in Paragraph 5.2.


Fig: 1-5: corrosion rate vs. pH.

The carbonate system can be
explained by introducing the concepts
of Alkalinity and Acidity.

Alkalinity (the capacity of water
to accept H
+
ions), is a measure of its
acid neutralising capacity (ANC) and is
often described as the buffering
capacity.


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Acidity similarly to alkalinity, it is
a measure of the base neutralising
capacity (BNC).
Alkalinity and acidity are capacity
factors of the water.

Carbonate System it is closely
related to alkalinity and acidity;
the following species contribute to
alkalinity in relative amounts (see Fig:
1-6):
Hydroxide, OH
-

Carbonate ion, CO
3
2-

Bicarbonate ion, HCO
3
-

Carbon Dioxide, CO
2



Fig: 1-6: relative amounts of alkalinity
species at various pH levels.
It can be noted that for pH values
lower than 6, the predominant specie
contributing to alkalinity is carbon
dioxide;
on the other hand, for pH between 8
and 9, bicarbonates are in majority.

At very high pH, carbonates first and
then hydroxides do exist mainly.

Beside the carbonate system
species, other salts of weak acids such
as borates, silicates and phosphates
also contribute to alkalinity.
Typical values of alkalinity are
reported in Table 1-4:
Table 1-4: some typical alkalinity values.
Application
Alkalinity
(mg
CaCO
3
/L)
Upland (limestone) river 50 200
Lowland Lake 10 - 30
Drinking Water 50 200
Domestic Wastewater 200 400
Anaerobic
3
Sludge
Supernatant
2000 8000
Acidic Stream 10 20
Non-Acidic Stream 700 800
Acidic Soil water 10 -20

Hardness is expressed principally
by the sum of bivalent metallic cations,
Ca
2+
and Mg
2+
.
These cations react with soap to
form precipitate and with other ions
present in water to form scale.
The ions causing hardness have
their origin in soil and geological
formations.

3
Refers to microbial life or processes that occur in
absence of oxygen. Also refers to processes which do
not use oxygen directly from the atmosphere or water
(such as bacterial growth). Can also refer to
environmental conditions in the ocean or lakes where
all the dissolved oxygen has been removed.

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Table 1-5 lists the dominant ionic
species, all responsible for hardness.
Table 1-5: ionic species responsible for
hardness.
Cations Anions
Ca
2+
HCO
3
-

Mg
2+
SO
4
2-

Si
2+
Cl
-

Fe
2+
NO
3
-

Mn
2+
SiO
3
2-


Hardness is a water parameter used
mainly in potable water (not usually for
waste water).
It is calculated in mg/L as CaCO
3

(similar to alkalinity) or as meq/L(
4
).
A qualitative listing of waters rated
on hardness is given in Table 1-6.
Table 1-6: relative hardness of waters.
Degree of
Hardness
meq/L
mg/l
as CaCO
3

Soft < 1 0 75
Moderately Soft 1-3 75 150
Hard 3 6 150 300
Very Hard > 6 > 300

Hardness is made up of:
Carbonate Hardness (or
Temporary Hardness TH) since
this form is removed on
prolonged boiling:
Carbonate Hardness =
(bicarbonate + carbonate) Alkalinity.

4
Meq/L: milli-equivalents per Litre = mg/L/equivalent
weight.
This is so when alkalinity is lower
than total hardness.
Non Carbonate Hardness
(NCH).

Furthermore, since Ca
2+
and Mg
2+

are the dominant hardness-producing
ions, it may be relevant to quantify
their contributions, should softening
5
be
considered a treatment process.
Hardness is computed in mg/L as
follows:
Hardness in mg/L as CaCO
3
=
M
2+
(in mg/L) X (50/eq weight
of M
2+
)
Where M
2+
is any divalent metallic
ion (e.g. Ca
2+
, Mg
2+
).
Hardness in mg/L as CaCO
3
=
M
2+
(in meq/L) X 50
Here follows an example to help
familiarise with hardness-related
calculations:
Example Determine the various
hardness of the following water sample
(see Table 1-7):
Table 1-7: Water Example for Hardness
Calculation
Constituent
Concentration
mg/L Meq/L
Ca
2+
60 3
Mg
2+
29.3 2.4
HCO
3
-
366 6


5
Softening: the removal of calcium and magnesium
from water by means of ion-exchange resins or addition
of Ca(OH)
2
.

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Recall:
Concentration (meq/L) =
concentration (mg/L) /
equivalent weight (mg/meq)
Equivalent Weight (mg/meq) =
Atomic Weight / Valence
Hardness (mg/L) as CaCO
3
=
Concentration (mg/L) X 50/eq
weight
Hardness (mg/L) as CaCO
3
=
Concentration (meq/L) X 50
The solution (using mg/L) is
summarised in Table 1-8 here below:
Table 1-8: hardness calculation summary in mg/L.
Ion
Concentration
[mg/L]
Atomic
Weight
Valence
Equivalent
Weight
Hardness
[mg/L as CaCO
3
]
Ca
2+
60 40 2 40 / 2 = 20 60 X 50/20 = 150
Mg
2+
29.3 24.31 2
24.31 / 2=
12.16
29.3 X 50/12 = 120
HCO
3
-
366 61 1 61 / 1 = 61 366 X 50/61 = 300

Total Hardness (TH) = Ca
2+
+
Mg
2+
= 270 mg/L as CaCO
3
.

Carbonate Hardness (CH) = HCO
3
-

= 300 mg/L as CaCO
3
.

However, the CH cannot exceed
the TH and the CH is therefore
represented as 270 mg/L as CaCO
3
.
The solution (using meq/L) is
summarised in Table 1-9.
Table 1-9: hardness calculation
summary in meq/L.
Ion
Concentration
[meq/L]
Hardness
[mg/L as
CaCO
3
]
Ca
2+
3 3 X 50= 150
Mg
2+
2.4 2.4 X 50 = 120
HCO
3
-
6 6 X 50 = 300

Conductivity also known as the
electrical conductivity, is a measure of
the ability of an aqueous solution to
carry an electric current.

The electric current is conducted in
the solution by the movement of ions
and so the higher the number of ions
(e.g. the greater the concentration of
dissolved salts) the higher the ionic
mobility and so the higher the
magnitude of conductivity.

Chemically pure water does not
conduct electricity since the only ions
present are H
+
and OH
-
and so the
conductivity of very pure water is about
0.05 S/cm (microsiemens/cm).

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On the other hand, a seawater with
high salts, has a conductivity of about
40,000 S/cm.
Typical values are reported in Table
1-10.
Table 1-10: typical conductivity ranges
for different waters.
Water
Conductivity
[S/cm]
Chemically Pure 0.05
Distilled 0.1 4
Rainwater 20 - 100
Soft Water 40 - 150
Hard Water 200 500
Range of Rivers 100 1000
Ground Water 200 1500
Estuarine Water 200 2000
Seawater 40,000

In most waters, conductivity is
due to the dissociation of inorganic
compounds, as organic compounds
dissociate little.
Therefore, a positive measure of
conductivity is indicative of the
concentration of dissolved inorganic
salts.

1.4. Organic chemical properties
of water
The main element of organic
compounds is carbon C. Organic
substances may be natural or man-
made.
In fact, most are natural, and they
are produced by plants and animals.
The presence of organic compounds
in water is as a contaminant, whether it
be naturally occurring or man-made.
The objective in cooling water
treatment is to minimise these
compound by biological, physical or
chemical treatment processes.
Organic compounds in water are
typically divided into four groups,
depending on their chemical structure:
1. Hydrocarbons these are organic
compounds containing only carbon
C and hydrogen H; (e.g. ethane
C
2
H
6
, ethylene CH
2
=CH
2
, benzene
C
6
H
6
, toluene C
6
H
5
-CH
3
).
2. Halogenated Compounds these are
organic compounds in which a
halogen is the principal atom (atoms
include fluorine, chlorine, bromine
and iodine); e.g. chloroform CHCl
3
,
dichloromethane CH
2
Cl
2
, carbon
tetrachloride CCl
4
.
3. Carboxylic acids and esters these
are organic compounds built around
the carboxylic group (a carbon
linked to oxygen with a double
bond) and other with two functional
groups attached to an oxygen atom,
e.g. acetone CH
3
COCH
3
,
formaldehyde CH
2
O, ethyl ether
CH
3
CH
2
COH
2
CH
3
.
4. Other organic compounds


CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators Handbook -
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1.5. Naturally Occurring and
Synthetic Organic
contaminants
The naturally occurring organic
substances in water, wastewater and
bottom sediments are:
1. Proteins made up of carbon,
hydrogen, oxygen, sulphur and
nitrogen, with the basic building
blocks of amino acids; e.g. bacteria
are mainly protein (C
5
H
7
NO
2
).
2. Lipids comprise fats, waxes, oils
and hydrocarbons, which are
insoluble in water but soluble in
some organic chemical solvents, and
are slowly biodegradable.
3. Carbohydrates contain carbon,
hydrogen and oxygen. They include
cellulose, starch and lignin which are
readily biodegradable (except
lignin). An example is glucose
(C
6
H
12
O
6
).
4. Plant Pigment these are made of
chlorophyll, haemins and carotenes
and include alcohols, ketones and
carotenoids.

The synthetic organic chemicals
which are the products of the chemical,
petroleum and agricultural industries
include:
1. Agrichemicals and Pesticides most
show a low solubility in water and
are thus prone to vaporisation. The
95% degradation period for several
pesticides is 1 to 25 years.
2. Surface Active Agents used for
washing, emulsifying, wetting,
foaming, etc as they lower the
surface tension of water when
placed in it. The molecule of a
surfactant (detergent) has two
parts, a hydrophobic part which is
insoluble in water and soluble in non
polar liquids such as oils, and a
hydrophilic part which is soluble in
water and insoluble in non-polar
liquids. It is this dual property that
makes them suitable for the earlier
listed uses. Surfactants may cause
foaming and reduce the diffusion of
atmospheric oxygen to the water.
3. Halogenated Hydrocarbons these
are end products of the reaction of
halogen with hydrocarbons, with
chlorinated hydrocarbons being of
key interest. The most significant
halogenated hydrocarbons are
trihalomethanes (THMs) or
haloforms. Further details on THMS
will be provided in the
microbiology control chapter.


CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators Handbook -
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1.6. Determination of Organic
content of water
The determination of organic
content of water can be by:
Specific tests to measure the
concentration of specific compounds
(Standard Methods apply)
Non-Specific tests to measure the
overall concentration of the organic
content.
Tests for the overall concentrations
include:
1. BOD a biochemical test that
uses micro-organisms
2. COD a chemical test
3. TOC an instrumental test
4. TOD an infrequently used
instrumental test.
Before introducing more details on
the above tests, the concept of
Dissolved Oxygen will briefly be
mentioned.
Oxygen from the atmosphere is
transferred across the air/water
interface by the principle of mass
transfer. The amount of transfer
depends on how much oxygen can be
solubilized in water.
Oxygen is regarded as weakly
soluble in water with levels usually less
than about 10 mg/L (or 10 ppm), with
the concentration decreasing with
increasing water temperature.
BOD biochemical oxygen demand
is the amount of dissolved oxygen used
up from the water sample by micro-
organisms as they break down organic
material at 20C over a 5 day period.
1.7. Measuring Water
Parameters
pH is easily measured by a pH-
meter: a laboratory device is shown in
Fig: 1-7 here below.

Fig: 1-7: Laboratory bench pH meter.

Conductivity is easily measured by a
Conductivity-Meter, and is expressed in
S/cm.
Fig: 1-8 below, shows a portable
conductivity-meter.

Fig: 1-8: Portable conductivity-meter.


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As already introduced in the
previous paragraphs, the amount in mg
of a substance, in 1 kg (1 Litre) of
water represents the concentration of
a particular substance;
A more common, and useful unit to
express concentration of impurities in
water, is ppm (parts per million).

ppm expresses the amount, in mg of
a substance in 1 kg (1 Liter) of water,
in a clearer way for little values of
concentration.

Its sub multiple, ppb (parts per
billion) expresses the amount in g,
and is used to determine traces of
substances.
Table 1-11 and Table 1-12 show
many common substances found in
water, the issues they are responsible
for, as well as the usual treatments.

The Tables also help familiarize with
common water-related terms.

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators Handbook -
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Table 1-11: Common impurities found in fresh water.





CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators Handbook -
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Table 1-12: Summary of water properties.



Common and routine analyses are
based on titration methods; for more
precise results, photometer-based or
other techniques, are preferred.



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2. Introduction to Cooling
Water
In any industry and almost in every
production cycle, heat is necessary.

Heating is used to allow physical or
chemical reactions to take place and
often, this heat has to be taken away
after serving the main units.

The refrigerant medium used in
cooling circuits is water, because its
transfer coefficient is much greater
than that of air, is fully recoverable,
does not pollute the process and is
widely available
6
.

2.1. Heat Transfer in Cooling
Water
Heat transfer takes place in devices
called Heat Exchangers.
Two fluids at different temperatures
exchange heat by means of a
contacting surface.
The fluid at higher temperature
releases energy (cools down) to the
fluid at lower temperature (warms up).

6
Water-reuse programmes are now more common
than the past.

Fig: 2-1: working principle of a heat
exchanger.
Temperature is not the only factor
contributing to heat exchange, but
other may have even a more relevant
role:
The characteristics of the two
exchanging fluids
The velocity of the flowing fluids
The extent of contacting surface
The metallurgy involved
Apart from the above mentioned
characteristics, that are already fixed at
the design stage, particular attention
should be paid to the cleanliness of the
surface among the contacting fluids.
The heat transfer equation is the
following:
Eq. 1
m
T A U Q A =
The Eq. 1 states that the amount of
heat Q [W] is proportional to:
Exchanging Area A [m
2
]
Logarithm Mean Temperature
Difference between Fluids T
m

[C]
Heat Transfer Coefficient U
[W/m
2
C]

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The heat transfer coefficient U
represents the thermal conductance of
a heat exchanger; the higher its value,
the more easily heat is transferred from
one fluid to another.
U can be represented as the
reciprocal of heat transfer resistance
7
:
Eq. 2
T
R
U
1
=
The total resistance R
T
to heat flow
is given by the sum of several,
individual contribution:
Eq. 3
5 4 3 2 1
r r r r r R
T
+ + + + =
Where the 5 contributions are the
following:
r1: heat flow resistance of the
process-side film
r2: heat flow resistance of the
process-side fouling (if any)
r3: heat flow resistance of the
exchanger tube wall
r4: heat flow resistance of the
water-side fouling (if any)
r5: heat flow resistance of the
water- side film

The 5 resistances are shown in Fig:
2-2.

7
A similarity is represented by the concepts of electrical
resistance and conductivity.

Fig: 2-2: heat transfer and resistance in
tubes.

As discussed, heat exchanger design
stage involves the knowledge of fluid
properties such as viscosity, specific
heat, thermal conductivity and the
equipment layout (number of passes,
velocity in tube side and shell side).
All these design parameters can be
optimised for better performance and
results.

Heat flow resistance due to fouling
both on process-side and water-side
severely increases.
Very limited variations in fouling
extent can reduce heat transfer to
unacceptable levels.
Heat exchange is fundamental for an
effective control of process
temperatures so, when this feature is
negatively affected, it may result in the
failure of an entire Plant.

The aim of treating the water of a
cooling system is to reduce to a
minimum degree the fouling in the
water side.

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3. Cooling Systems Layouts
The water cooling systems can be
classified as follows:
Once Through
Closed Recirculation
Open Evaporative Tower

The choice of the best circuits
layout depends on plants location,
water availability, economics and health
& safety.

Their working principle, as well as
advantages and operational limits, are
described here briefly.
3.1. Once Through Cooling
System
The first cooling system here
described is the Once Through.
Fig: 3-1 shows a Once Through
layout with possible injection points of
chemicals.

Fig: 3-1: Once Through cooling System
layout.

This layout is often found in cooling
systems placed near the sea side.

In these systems, the temperature
drop is very limited, therefore, a large
amount of water is necessary
8
.

The limitation to the temperature is
due to the high salts concentration in
sea water
9
.

A once through system can be
characterised by the following
advantages and disadvantages:
Table 3-1: Once Through cooling System
Advantages and Disadvantages.
Advantages Disadvantages
Low Capital Costs
Large Water
Consumption and
Thermal Discharge in
the receiving body
Low Operating
Costs
Biological fouling from
water intake, slit and
sand in intake may fall
at low-velocity points
Low Temperature
Sink
Expensive heat
exchange metallurgy
for sea water or
brackish
Obtaining water intake
and discharge permits
may be difficult



8
The amount of heat extracted is given by Q= McpAT.
Because AT is small, M has to be large.
9
If the temperature drop was relevant, severe
precipitation would occur.

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3.2. Closed Circulating Cooling
System
Another common cooling system
presented here is the Closed
Circulating System.
It consists of two circuits
connected by a heat exchanger.
Fig: 3-2 shows how a closed circuit
works.

Fig: 3-2: Closed Circulating cooling System
layout.

The cooling water is kept circulating
in the proper cooling circuit;
very limited make-ups are
necessary to replace the water losses,
or when the quality/characteristics of
the water, are no longer satisfactory.

The Closed System can be seen as
the highest water-saving option.

Its advantaged and disadvantages,
compared to those of once through
systems are shown in Table 3-2:

Table 3-2: Closed Recirculating cooling
System Advantages and Disadvantages.
Advantages Disadvantages
Minimum Make
Up Water Rate
Additional Expense of
Second Cooling System
Hi Quality Make
Up
Heat Load Limitations
Limited Biological
Fouling
Additional Pumps &
Piping

3.3. Open Evaporative Cooling
System
The most common, modern solution
for cooling purposes, is the Open
Recirculating layout.
It consists of a cooling tower (with
natural or mechanical draft), a
Blowdown and a Make-Up stream to
control.

This systems allow a considerable
water saving, compared to that of once
through, with a good and practical
control of the key parameters such as
the Blowdown.

Limited windage and drifts exist due
to the tower shape and its exposure to
the open space.

An open evaporative cooling system
is shown in Fig: 3-3 (possible injection
points of chemicals are shown, and
Fig: 3-4)

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Fig: 3-3: Open Evaporative cooling System
layout.


Fig: 3-4: Open Evaporative cooling system
(detailed view)


The Make up, evaporation/drift
losses and Blowdown are visible.

The advantages and disadvantages
of this layout, to be read in comparison
with those of once through and closed
circulating systems, are summarised in
Table 3-3.
Table 3-3: Open Evaporative cooling
System Advantages and Disadvantages.
Advantages Disadvantages
Low Make Up
Water Rate
High Capital Costs
Low discharge
Water Rate
Power for Fans
(mechanical draft) and
Pumps
Good control of
key parameters
such as Blow
Down
Fogging, Icing and
corrosion of
surroundings
High Temperature Sink


3.4. Types of towers for Open
Evaporative Systems.
Cooling towers are classified as
Natural draft or Mechanical draft.

The most prevalent mechanical draft
tower type, is the induced multicell unit
(see Fig: 3-5 below for construction
details and Fig: 3-6 for a real view)

These towers are suitable for fresh,
salt or brackish water.

Fig: 3-5: induced multicell cooling tower.


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Fig: 3-6: multicell cooling towers.

The internal view of a cooling tower
helps understand the way it works.

The inlet water is distributed from
the top, passes through a series of
fillings to maximise the air/water
contact surface and then enters the
basin for re-circulation (see Fig: 3-7
and Fig: 3-8).

Fig: 3-7: internal view of a mechanical draft
cooling tower.


Fig: 3-8: details of plastic fillings.
Natural draft cooling towers
10
(Fig:
3-9) are the alternative to mechanical
draft ones.

They take advantage of temperature
difference between ambient air and hot
air inside the tower.

Their design creates a chimney
effect in which, cold air from the
bottom of the tower, pushes warmer air
out of the top.

Fig: 3-9: hyperbolic natural draft cooling
towers.


10
Also called Hyperbolic Tower.

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Hyperbolic towers, as well as
mechanical draft towers use a filling
medium to maximise the contact
between air and water (Fig: 3-10, Fig:
3-11, Fig: 3-12).


Fig: 3-10: side view of a hyperbolic cooling
tower with construction details (1).

Fig: 3-11: side view of a hyperbolic cooling
tower with construction details (2).


Fig: 3-12: wood filling of a hyperbolic
tower.









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4. Design of Recirculating
Cooling System
An Open evaporative system is
characterised by a cooling tower, a
basin for cooled water and a
recirculating piping-system serving the
plants
11
.

In this section, fundamentals of
design will be provided.

In Fig: 4-1 a complete scheme of
open evaporative cooling system is
shown:

Fig: 4-1: complete open evaporative
cooling system layout.
The system is characterised by
several streams and parameters;
all of them contribute to the
increase or loss of efficiency;


11
It can be said that these systems represent an
intermediate configuration between open and closed
circuits.

here follows a brief explanation of
each stream and parameter .

Evaporated [EL] is the amount of
water that leaves the tower as
vapour
12
(expressed in m
3
/h);
inlet water is cooled due to
subtraction of latent heat; its
quantity depends on the heat load.
Windage Losses [WL] is a relatively
small amount of (loss) water that
leaves the tower as entrained
droplets.
This amount is usually between
0.5% and 3% of the recirculated
water.
It depends mainly on the hydraulic
characteristics of the tower
(expressed in m
3
/hr).
Blowdown [BD] of the system is
necessary to control concentration
of salts (and other impurities) likely
to precipitate, leading to deposition,
corrosion, as well as to
microbiological growth related
problems
13
.
Blowdown can be continuous
(expressed in m
3
/hr) or intermitted
(m
3
/day).

12
Water turns into steam due to contact between air
and tiny particles of warm water. This surface contact is
maximised by the tower filling.
13
Deposition and corrosion are common problems in
cooling systems; these phenomena are encouraged by
the existing warmer temperatures, relatively high salts
concentration and long residence time conditions.

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Make-up [MU] is the amount of
water required to restore the water
losses, due to evaporation, Windage
and Blowdown (expressed in m
3
/hr).
Number of Cycles
14
[Nc] is the ratio
between the concentration of a
given salt in the recirculating water
and the concentration of the same
salt in the make-up water.
The Nc number is fundamental for
the correct management of the
cooling system, both in terms of
economics and energy savings.
[Refer to A practical Example (1)
and A practical Example (2)].
Recirculation Rate [RR] is the
feedrate of water circulating in the
system (expressed in m
3
/hr).
Delta T [T] is the temperature
difference existing between the top
of the tower (inlet water) and the
bottom (outlet water).
Volume [V] is the total amount of
water (expressed in m
3
).
Residence Time is the average time
a non settling salt molecule stays in
the system (expressed in hours).
Table 4-1 below, summarizes the
above mentioned parameters:
Table 4-1: fundamental parameters in
open evaporative cooling systems.
Parameter Comments Units

14
Also known as Number of Concentration.
EL Evaporation losses m
3
/hr
WL Windage Losses m
3
/hr
BD Blow Down m
3
/hr
MU Make-Up m
3
/hr
Nc Number of Cycles
RR Recirculation Rate m
3
/hr
V
Total water in the
system
m
3

All these parameters influence the
operativeness of the tower(s).

A complete picture of their effects
can be obtained only by performing a
mass and energy balance, as developed
in the next chapter.

4.1. Mass and Energy Balance
for Open Evaporative
Towers
Fig: 4-2 shows an open evaporative
cooling systems with the parameters
described in Table 4-1;

Fig: 4-2: parameters for simplified mass
and energy balance.


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A simplified scheme allows to write
the following equation for global mass
balance and partial mass balance:
Eq. 4: global mass balance

BD EL MU + =

Eq. 5: partial mass balance
15


EL BD MU
X EL X BD X MU + =
Eq. 6: expression of Number of Cycles

| |
| |
MU
BD RR
C
X
X
BD
MU
N
=
= =
A heat balance between the RR (its
specific heat cp and temperature
difference T) and steam latent heat
(), allows to write the following
equation:
Eq. 7: heat balance

T cp RR EL A =
from which EL can be determined as
follows:
Eq. 8: evaluation of EL

T cp RR
EL
A
=
( has an average value of
kg
kcal
550 and
cp =
C kg
kcal

1 .

15
The concentration of salt X in steam EL has been
considered zero.



By combining Eq. 4, Eq. 6, Eq. 8, it
is possible to express the BD as a
function of EL and Nc as follows:
Eq. 9: BD as a function of EL and Nc

1
=
Nc
EL
BD
This equation is fundamental,
because Blowdown can be determined
by knowing Evaporation Losses and
Number of cycles.;

Blowdown is the key parameter for
economical and energy reasons.

Economics of the whole system is
driven by Blowdown because, apart
from evaporation losses, it is actually a
waste stream used to control maximum
allowable concentration of salts so:
the lower the Blowdown, the lower
the waste stream
the lower the Blowdown, the closer
the actual working conditions related
to the maximum acceptable
concentration of substances likely to
precipitate.

From an energy & economical point
of view, a lower blowdown means lower
makeup, so less expenses for water
supply and chemical treatment.


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4.2. A practical Example (1)
In this paragraph a practical
calculation will be shown to familiarise
with key parameters and their meaning.

An open evaporative cooling
system has the operating
characteristics as summarised in Table
4-2.
Table 4-2: initial set of parameters (1).
Parameter Units
Tot. Volume 3,000 m
3
/hr
Recirculation
Rate
9,000 m
3
/hr
Temperature
Difference
in 29C out
22C
C
Number of
Concentration
2.5

These parameters can now be used
to determine the Evaporation Losses
(EL):
115
550
7 1 9000
=

=
A
=

T cp RR
EL [m
3
/h]
and the Blow down rate:
4 . 76
5 . 1
115
1 5 . 2
115
1
= =

=
Nc
EL
BD [m
3
/h].
The Make Up is the sum of all the
streams leaving the system:
4 . 191 4 . 76 115 = + = + = BD EL MU
[m
3
/h].

At this point, the complete set of
parameters is available in
Table 4-3.

Table 4-3: complete set of parameters
(1).
Parameter Units
Tot. Volume 3,000 m
3
/hr
Recirculation
Rate
9,000 m
3
/hr
Temperature
Difference
in 29 out 22 = 7 C
Evaporation
Losses
115 m
3
/hr
Blow Down 76.4 m
3
/hr
Make Up 191.4 m
3
/hr

4.3. A practical Example (2)
As blowdown was stated to be the
key operating parameter, in this
paragraph another NC will be
considered.

The difference in the set of
parameters will be clearly visible in
terms of energy and economics.

The same open evaporative cooling
system has now the operating
characteristics as summarised in Table
4-4.
Table 4-4: initial set of parameters (2).
Parameter Units
Tot. Volume 3,000 m
3
/hr
Recirculation
Rate
9,000 m
3
/hr
Temperature
Difference
in 29C out
22C
C

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Number of
Concentration
1.5
These parameters can now be used
to determine the Evaporation Losses
(EL):
115
550
7 1 9000
=

=
A
=

T cp RR
EL [m
3
/h]
same as Case 1, and the Blow down
rate:
230
5 . 0
115
1 5 . 1
115
1
= =

=
Nc
EL
BD [m
3
/h]
considerably higher than that for Case
1.

Again, The Make Up is the sum of
all the streams leaving the system:
345 230 115 = + = + = BD EL MU [m
3
/h].

At this point, the complete set of
parameters is available in Table 4-5.
Table 4-5: complete set of parameters
(2).
Parameter Units
Tot. Volume 3,000 m
3
/hr
Recirculation
Rate
9,000 m
3
/hr
Temperature
Difference
in 29 out 22 = 7 C
Evaporation
Losses
115 m
3
/hr
Blow Down 230 m
3
/hr
Make Up 345 m
3
/hr

The different results form the two
cases are summarised in
Table 4-6.

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Table 4-6: results comparison between
Case 1 and Case 2.
Parameter Case 1 Case 2 Units
Blow Down 76.4 230 m
3
/hr
Make Up 191.4 345 m
3
/hr
Number of
Concentration
2.5 1.5

By comparing the results from Case
1 and Case 2, the BD passed from 115
to 230 [m
3
/h] and MU from 191.4 to
345 [m
3
/h].

As seen and demonstrated
previously, the blowdown rate is
directly related to the NC.

Because the design of a Cooling
Water treatment is based on the BD, it
can be understood that a limited BD
means lower consumption of chemicals,
as well as a saving in water discharge
and consequent make up.

5. Common issues in Cooling
System
The design and operational
conditions of a cooling system have a
relevant impact on water chemistry.
This means that scaling/fouling,
corrosion and microbiological behaviour
of a cooling water, can greatly influence
both design and operating settings.

All the preliminary characteristics
of water given in the Water
Fundamentals chapter will now be
associate to chemical and biological
behaviour.

5.1. Scaling in Cooling Water
Water formed deposits result from
naturally occurring minerals
precipitating from water to form scale.
The most common scales are
calcium carbonate, calcium sulphate
and silica or silicates.

Many factors affect the formation
of scale, such as the mineral
concentration in the cooling water:
water temperature, pH, availability of
nucleation sites (the point of initial
crystal formation) and the time allowed
for scale formation to begin after
nucleation occurs.
Calcium carbonate and magnesium
hydroxide, for example, are inversely
temperature soluble so, the higher the
temperature, the lower their solubility.

Scale build-up on surfaces can be
extremely hard and difficult to remove
(Fig: 5-1 shows a series of tubes
affected by scale).

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators Handbook -
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Fig: 5-1: tube walls affected by scale.

Scaling will drastically reduce heat
transfer capacity and system energy
efficiency.

A useful index for the evaluation of
the scale forming or corrosive
behaviour of a given water is the
Langelier Saturation Index LSI.
The LSI expresses the degree of
saturation of water as related to
calcium carbonate solubility.
LSI is then a calculated number
used to predict the calcium carbonate
(CaCO
3
) stability of a water;
In other words it means that a water
will precipitate, dissolve, or be in
equilibrium with calcium carbonate.
The Langelier saturation level
approaches the concept of saturation
using pH as a main variable, and the
LSI can be interpreted as the pH
change required to bring water to
equilibrium.

Three conclusions may be given
depending on the value of the LSI as
follows:
1. If LSI is negative: No potential to
scale, the water will dissolve
CaCO
3
.
2. If LSI is positive: Scale can form
and CaCO
3
precipitation may
occur.
3. If LSI is close to zero: Borderline
scale potential. Water quality or
changes in temperature, or
evaporation could change the
index.

In order to calculate the LSI, it is
necessary to know:
the alkalinity (mg/l as CaCO
3
)
the calcium hardness (mg/l Ca
2+

as CaCO
3
)
the total dissolved solids (mg/l
TDS)
the actual pH
and the temperature of the water
(C).

A useful and practical expression for
the LSI, calculated at the maximum
skin temperature (60C) is the
following:
Eq. 10: LSI practical formula.
LSI
(60C)
= pH 11.32 + log
10
(CaH
*

Alk)
where CaH stands for Calcium
Hardness.

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As an example, if the analyses of a
water were the following,:
pH = 8.7
CaH = 405 ppm (CaCO
3
)
Alkalinity = 4405 ppm (CaCO
3
)
substitute them into the LSI @ 60C
equation, the result would be:
LSI
(60C)
= 8.7 11.3 + 5.2 = 2.6

The LSI is positive: Scale can form
and CaCO
3
precipitation may occur.

At LSI > 2.5, the water is
definitively scale-forming and no
antiscale/antifouling chemicals will be
able to work properly.

If this happened there would be two
alternatives (scenarios) to apply:
1. Reduction of NC
or,
2. Addition of Acid (controlled pH)
to lower pH and reduce alkalinity
according to the following
chemical equation:
Eq. 11: Acid Addition for controlled pH.
H
2
SO
4
+Ca(HCO
3
)
2
=CaSO
4
+2H
2
O +
2CO
2


The calcium bicarbonate is
converted to volatile carbon dioxide and
calcium
sulphate (Calcium sulphate is more
soluble than calcium carbonate).

If the makeup water is high in
sulphates, hydrochloric acid may be
used to reduce the alkalinity but,
chloride ions may cause problems
because they can penetrate oxide films,
setting up local anodic cells and causing
corrosion (for details refer to paragraph
5.2).

Monitoring of scale can be
performed by:
scale coupons

Fig: 5-2: scale coupons of different
shapes and sizes.
Fouling Factor Calculation
Pilot Heat Exchangers

Fig: 5-3: pilot heat exchanger.



CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators Handbook -
36
5.2. Corrosion in Cooling Water
Cooling Systems are exposed to
many types of corrosion, from general
electrochemical corrosion, to pitting
caused by deposits, electrolysis, or
microorganisms.

Electrochemical corrosion takes
place when a metal is placed in an
aqueous environment (H
2
0).
Several chemical (and physical)
reactions will occur.
At the Anode (the negative side of
the electrochemical cell, an oxidation
occurs), the metal dissolves (Fe = Fe
2+

+ 2e
-
) and, at the Cathode, a reduction
reaction takes place (O
2
+ H
2
O + 4e
-
=
4OH
-
).

The overall corrosion process in
cooling water systems is then:
2Fe(OH)
2
+ 1/2O
2
Fe
2
O
3
H
2
O + H
2
O,
with formation of rust (Fe
2
O
3
H
2
O)
whose mechanical and thermal
properties are definitively not
comparable with those of steel.

Fig: 5-4 shows corrosion processes
in details and Fig: 5-5 shows a
corrosion-coupon severely affected by
corrosion.



Fig: 5-4: electrochemical corrosion
process.


Fig: 5-5: a corrosion coupon severely
affected by electrochemical corrosion.


Factors contributing to corrosion
are:
Conductivity (also referred to
chlorides content).

Fig: 5-6: corrosion rate vs.
conductivity.
pH: extreme values of pH
should be avoided.

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators Handbook -
37

Fig: 5-7: corrosion rate vs. pH.

Oxygen: as it is an oxidising
agent it will contribute to Redox
reactions.

Fig: 5-8: corrosion as a function of
oxygen content and temperature.

Free Chlorine residual.
Corrosion can reduce the life-span
of equipment by years, requiring
expensive replacement.
Corrosion can lead to costly
equipment repairs and production
downtime.
Its related deposits lead to reduced
capacity and wasted energy because of
heat transfer efficiency losses.

Corrosion monitoring is performed
by the insertion of selected corrosion
coupons.
These coupons are weighted before
insertion and left in the circuit, by
means of a proper coupon-rack, for a
given period.


Fig: 5-9: corrosion (and scale) coupon
rack.

Once removed, they are cleaned by
acid pickling and weighted again.

The comparison between initial, final
weight, exposure time and Area Factor
of the coupon, give the corrosion rate
expressed by Milli-Inch per Year MPY,
or millimetres per Year mmY.

Sometimes, on-line corrosion-
meters are applied to circuits and give
instant corrosion rate.


CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators Handbook -
38
5.3. Fouling in Cooling Water
Fouling occurs when solid materials
form or contribute to the formation of
deposit on equipment surfaces.
They are introduced to the system
as suspended solids and may enter by
the makeup water, from corrosion by
products, or as airborne materials.
Examples include mud, sand, silt,
clay oils, debris, organics, microbes,
etc.
These materials adhere to heat
transfer surfaces and reduce heat
transfer and water flow.

5.4. Microbiological Growth,
Contamination and Induced
Corrosion
Microbial problems associated with
industrial cooling water systems are
caused by algae, fungi, and bacteria.

Bacteria are single-celled
organisms that have a simple structure.

All life processes are carried out
within a single cell, which is generally
only 1-5 mm in length (Fig: 5-10 shows
rod-shaped bacteria).

Fig: 5-10: rod shaped bacteria.

The Fungi are filamentous
organisms, much larger than bacteria.
They can produce a network of
interlacing filaments (filamentous fungi)
or exist at a unicellular state (see Fig:
5-11).
Fig: 5-11: Unicellular (left) and
Filamentous Fungi (right).


Algae are photosynthetic organisms
like green plants; they require sunlight
to provide the energy for growth, using
specialized pigments called chlorophylls
to trap the light energy.

Many different species may exist in
cooling water systems:
Aerobic bacteria need oxygen to
grow and reproduce, using it as an
electron acceptor for the oxidation of
organic and inorganic compounds.
This biological process is known as
respiration.

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators Handbook -
39
Some species of microorganisms
can grow in the absence of oxygen,
using fermentation of organic
compounds as a source of energy.
These organisms are described as
Facultatively Anaerobic.

The small number of
microorganisms that are able to break
down organic compounds or carbon
dioxide only in the absence of oxygen
are described as Anaerobic.

Oxygen is actually toxic to many of
these organisms. Anaerobic metabolism
is commonly found in many bacterial
and fungal species.

Respiration generates more energy
for the organism than anaerobic
fermentation and results in greater
microbial growth.

Some of the problems this living
matter causes, include severe bacterial
slimes and fouling, hydrogen sulphide
(H
2
S), underdeposit corrosion and
health hazards.

Underdeposit corrosion is one of
the most serious concern for cooling
systems;
corrosion takes place below the
microbiological layer that the organisms
develop to protect and feed
themselves.

As the corrosion phenomena is
hidden by biological fouling, it would
not be noticed easily.

Strictly anaerobic bacteria, growing
well only in the absence of oxygen;
such as species of sulphate reducing
bacteria (S.R.B.) are responsible for
severe Microbiological Induced
Corrosion processes:

MIC refers to corrosion that is
influenced by the presence and
activities of micro-organisms and/or
their metabolites (the products
produced in their metabolism).

Bacteria, fungi and other micro-
organisms can play a major part in
corrosion; the mechanisms potentially
involved in MIC are summarized as:
Cathodic depolarization, whereby
the cathodic rate limiting step is
accelerated by micro-biological
action.
Formation of occluded surface cells,
whereby micro organisms form
"patchy" surface. Sticky polymers
attract and aggregate biological and
non-biological species to produce
crevices and concentration cells, the
basis for accelerated attack.

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators Handbook -
40
Fixing of anodic reaction sites,
whereby microbiological surface
colonies lead to the formation of
corrosion pits, driven by microbial
activity and associated with the
location of these colonies (see Fig:
5-12, Fig: 5-13 and Fig: 5-14 for
corrosion coupons).

Fig: 5-12: microbiological induced
corrosion MIC.

Fig: 5-13: corrosion coupon affected by
MIC prior to pickling.

Fig: 5-14: corrosion coupon affected by
MIC after pickling: under deposit
corrosion occurred.

Underdeposit acid attack, whereby
corrosive attack is accelerated by
acidic final products of the MIC
"community metabolism", principally
short-chain fatty acids.

Monitoring of microbiological
activity can be performed in several
ways, according to the species being
investigated:
Vials: for Aerobic and
Anaerobic/SRB
16
bacteria

Fig: 5-15: VIALS for Aerobic Bacteria.
Original colour is Red, in presence of
aerobic bacteria vials turn into yellow.


Fig: 5-16: VIALS for Anaerobic
Bacteria. Original colour is Yellow, in
presence of anaerobic bacteria vials
become turbid and black if S.R.B. exist.


16
Sulphate Reducing Bacteria.

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators Handbook -
41
Easicult TTC Slides for Aerobic
bacteria.

Fig: 5-17: Easicult TTC Slide and its
comparison chart.

The two methods, either by Vials or
TTC Slides, express the result in terms
of Colony Forming Unit/ml C.F.U./ml.

For example, Fig: 5-15 shows the
colour changed at the third vial; this
means that the C.F.U./ml is 10
3
.

The fastest method for
microbiological analyses is by means of
luminoscan; in this portable
instrument, selected reagents are used
to evaluate the microbiological activity
in few seconds.

The Luminometer is shown in Fig:
5-18

Fig: 5-18: Luminometer for quick
analyses.

Microbiological control performance
can be evaluated by comparing the
results with Table 5-1:
Table 5-1: comparison table for
microbiological control.
C.F.U/ml Comments
0 10 No pollution
10 - 10
2
Under Control
10
2
- 10
4
Attention Threshold
> 10
4
Immediate Action


CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators Handbook -
42
6. Common chemical
treatments programmes in
cooling systems
In this chapter a brief description of
the chemicals and technologies used for
the control of water in cooling system is
given.

The fundamental issues to deal
with, as described in the previous
paragraphs, will be highlighted.

6.1. Scaling and Fouling Control
Programmes
Scale & Fouling
Inhibitors/Dispersant (also called
Deposit Control Agent - DCA) are
complex chemical compounds, dosed at
sub-stoichiometric amounts, that have
very marked effects on the growth rate
of crystals deposited in a scaling
environment.

These threshold inhibitors act by
adsorbing onto the growing crystals and
distorting the lattice, which disrupts the
crystal growth process.

This crystal distortion prevents
deposition, and the highly irregular
stressed crystals tend to slough off as
crystal growth occurs (see Fig: 6-1 and
Fig: 6-2).



Fig: 6-1: undistorted lattice (left) and
microscope picture (right) of
precipitating crystals.



Fig: 6-2: distorted lattice by addition of
DCA (left) and microscope picture
(right) of non precipitating crystals.

The most commonly used threshold
scale inhibitors are inorganic
polyphosphates, organophosphorous
compounds, synthetic organic
dispersants and natural organic
dispersants.

In Fig: 6-3, the working
mechanism of dispersing agents is
shown: first, adsorption of the
dispersing agent molecule occurs.

Fig: 6-3: adsorption (left) and
stabilisation/dispersion (right) process
of DCA.


CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators Handbook -
43
This is followed by both crystal
structure modification and by a charge
repulsion mechanism of negative
charges, which leads to
destabilization/dispersion of the
crystals.


6.2. Corrosion Control
Programmes
Corrosion inhibitors are added to
water systems to reduce the corrosion
rate of metals to a negligible level.
Corrosion Inhibitors are chemicals
that react with a metallic surface, or
the environment this surface is exposed
to, by giving the surface a certain level
of protection.

Inhibitors often work by adsorbing
themselves on the metallic surface,
protecting it by forming a film; they are
normally distributed from a solution or
dispersion.

The two most common ways for
inhibiting corrosion are related to the
reactions taking place at the Anode
(oxidation) and at the Cathode
(reduction).

However, the other common way
to protect metal surface from corrosion,
consists of the development of films
on metals surface.
Anodic inhibitors aim at developing a
stable, tightly adherent layer of -
iron oxide film on the surface by
causing a large anodic shift of the
corrosion potential, forcing the
metallic surface into the passivation
range (see Fig: 6-4).

Fig: 6-4: anodic film on tube wall.
Organic or inorganic compounds
molecules, such as ortho-phosphates
(@ high levels), phosphonates, nitrites
and molybdates are anodic inhibitors.

Cathodic inhibitors work by either
slowing the cathodic reaction itself,
or selectively precipitating on
cathodic areas to increase the
surface impedance and limit the
diffusion of reducible species
(hydrogen gas evolution is
prevented), to these areas.

Fig: 6-5: cathodic film on tube wall
The precipitate is less tenacious
and more porous than that of the anode

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators Handbook -
44
film; organic or inorganic compounds
molecules, such as ortho-phosphates
(@ low levels), polyphosphates and
metals like zinc, are cathodic inhibitors.

6.3. Microbiological Growth
Control Programmes
The issues associated with
biofouling have involved the use of
chemicals known as Biocides and
certain surfactant chemicals known as
Biodispersants.
Biocides are chemicals that kill living
organisms or inhibit their ability to
grow and reproduce.

A chemical can be a growing
inhibitor to certain organisms at a low
concentration and act as a killing
biocide to the same organisms at a
higher concentration, over a definite
time period (e.g., 6-12 hours).
This way of using biocides is known
as Shock Dosage, while growing
inhibitors are generally added
continuously to the system at lower
levels.

Biocides are classified as:
non-oxidizing biocides because they
do not oxidize other chemicals or
oxidize them only very slightly.

Biocides are classified as:
oxidizing biocides (e.g., chlorine)
since they very strongly oxidize
many organic and inorganic
molecules, becoming reduced
themselves.

Another class of chemicals that can
be used to remove microbial slimes are
surfactants commonly known as
Biodispersants.
They allow other chemicals to
contact surfaces and deposits to some
extent.

Biodispersants increase the
effectiveness of biocides by allowing the
biocides to penetrate the microbial
slime, killing the microbial cells and
eventually causing sloughing of the
slime.

Quaternary ammonium salts and
amine salts (being cationic), attach to
the negatively charged molecules in the
slime layer and reduce the surface
tension, thus allowing water to contact
the slime layers to a greater extent.

The addition of an oxidizing biocide
helps break them up further by
oxidizing the exposed charged atoms
on the slime layers.

The oxidizing inorganic biocides,

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators Handbook -
45
such as Chlorine, may be fed on a
continuous basis to maintain a free or
total residual level (Fig: 6-6).

Fig: 6-6: chlorination break point.

Free residual chlorine, present as
hypochlorous acid, is a much more
effective and faster-acting biocide than
combined chlorine, present as
chloramines, (e.g., NH
2
CI).

Because microorganisms find it
difficult to adapt to chlorine, it is
possible to feed chlorine on a
continuous basis.

Bromine (as hypobromic acid,
HBrO) shows higher oxidising
properties, respect to chlorine, at a
given pH.
Sodium Hypochlorite and
Hypobromine reactions are the
following:
NaClO OCl
-
+ Na
+

and
NaBrO OBr
-
+ Na
+
.



Fig: 6-7 shows chlorine and
bromine dissociation curve vs. pH.

Fig: 6-7: chlorine and bromine
dissociation curve vs. pH.
Because the amount of bromine
un-dissociated molecule (the effective
biocide), at a given pH is higher than
that of hypochloric acid (see Fig: 6-7),
bromine should then be preferred as
oxidising biocide.

The main drawback with the
oxidizing biocides is their high reactivity
to reduce compounds such as iron, H
2
S
and organic matter so, there may be
little residual left to control
microorganisms in case of process
(hydrocarbons) leaks.
They do not effectively penetrate
and disperse microbial slimes.
These facts imply that chlorine is
supplemented by the addition of non-
oxidizing biocides and dispersants in
many systems.

Examples of useful oxidizing
biocides are:
halogens such as chlorine (Cl
2
)

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators Handbook -
46
chlorine dioxide (ClO
2
)
hydrogen peroxide (H
2
O
2
)
ozone (O
3
)
Peracetic Acid
and chlorine, bromine donors such
as chlorinated isocyanurates and
hydantoins.

Non-oxidizing biocides are organic
molecules that react with various parts
of the microbial cell, generally at a
specific site.

The most common groups of
nonoxidizing biocides are:
aldehydes
organo-sulphur biocides
organo-nitrogen biocides
and
amine salts.
7.1. Cooling System: CHIMEC
Analyses
The aim of performing routine
water analyses, is to check whether the
proposed dosages of product is correct.

By doing so, not only it will be
possible to take corrective actions, but
also to monitor the performance of the
treatment.

The analyses include:
characterisation of make up and
recirculating water
specific analyses for CHIMEC
products
microbiological counts

Common set of analyses and their
use are shown in Table 6-1.

Table 6-1: CHIMEC Routine Analyses.
Parameters
Water
Characterisation
pH, Alkalinity and
Hardness for the
calculation of Langelier
Saturation Index LSI.
Chlorides, Sulphates
and Iron.
Concentration Number
Nc based on Chlorides
and Calcium.
Microbiology
VIALS or TTC count for
microbiological activity
monitoring
System
Parameters
Calculated Evaporation,
NC, BD, MU and
Temperatures.
















CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators Handbook -
47

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators Handbook -
48
7. Troubleshooting of Cooling
Systems
The information here in presented,
are intended only as a support for
cooling systems operators.
As an integrated CHIMECs policy,
this document will introduce the
operators to a list of:
Problems found
Possible Causes
Suggested Solutions to
problems

that may be common in cooling
systems operating conditions.

The Table below (Table 6-1),
provides common Troubleshooting Tips
for the following steps:
Cooling Water

Once again, the information here in
reported, should always be supported
by the experience of the operators.

Table 7-1: Cooling Water Troubleshooting
Problem Found Possible Causes Suggested Problems Solution
Too High pH Water
17

Number of Concentration
Approaching Chemical & Physical
Limits
Acid Addition Inadequate
Increase Blowdown Rate
Check/Increase Acid Injection
Rate
Lower pH Water
No Concentration Occurs
Acid Injection Exceeds Limits
Reduce Blowdown Rate
Check/Reduce Acid Injection
Rate
Coupons affected by
Scale
High pH
Number of Concentration
Approaching Chemical & Physical
Limits
Low Antiscale Dosage
Increase Blowdown Rate
Check/Increase Antiscale
Injection Rate
Coupons affected by
corrosion
Low pH
Low Corrosion Inhibitor Dosage
Microbiological Induced
Corrosion M.I.C.
Check/Lower Acid Injection
Check/Increase Corrosion
Inhibitor Injection Rate
Refer to Microbiological Growth
Microbiological
Growth
Presence of Nutrients, Process
(Hydrocarbons) Leaks
Long Retention Time
Low Biocide(s) Dosage
Check/verify/reduce availability
of Nutrients and/or Process
Leaks
Check/Verify Systems Streams
Check/Increase Biocide(s)
Injection Rate and/or Shock
Frequency/Dosage.


17
Values are referred to design conditions.