COOLING SYSTEMS’

OPERATORS’ HANDBOOK

CHIMEC S.p.A.
WATER TECHNOLOGY UNIT

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

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

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1. Water Fundamentals and microbiological fouling in pipes,

Pure Water is colourless, tasteless conduits, heat exchangers etc, etc.

and odourless; its chemical formula is

H2O; this means that one molecule of 1.1. Water Sources
water, is formed by two atoms of All water Sources originate by
Hydrogen and one of Oxygen. evaporation from terrestrial and oceanic
masses, followed by rain and snowfall.
Water is fundamental for Life (see
Fig: 1-1) and it covers four fifth of the While raining, water droplets enter
Earth’s surface; 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 ground’s
Fig: 1-1: The Water Cycle.
characteristics.
Water has different properties (later
described in details) such as that of
Ground water is characterised by a
being able to dissolve partially, almost
relatively constant temperature and a
any substance found on earth or
lower level of suspended solids; these
atmosphere; for this reason, water is
are properties highly desirable for
called the universal solvent.
water-use in the industry.
Although there is abundance of
On the other hand, ground water
water, it is not readily available in the
has a higher level of dissolved solids
conditions we desire for industrial
(minerals) respect to surface water.
needs.
Water used in industry, in fact,
Recycled water and Sea Water also
contains impurities, responsible for
represent another source; the first
problems such as deposition, corrosion
must be used for economical and
environmental reasons, the latter for
CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators’ Handbook - 6
cooling systems only (if more brown-yellow to brown-black colour.
economical alternatives do not exist). Dyes or pulp and paper plants also
cause colour, as does the presence of
1.2. Physical, Chemical and iron, magnesium and plankton.

Organic properties of Water Turbidity – is a measure of the

cloudiness. It is caused by the presence
Water is never pure, except possibly
of suspended matter which scatters and
in its vapour state. Water always
absorbs light. In lakes, turbidity is due
contains impurities, which are
to colloidal or fine suspensions.
constituents of natural (and manmade)
Turbidity is measured by a visual
origin.
comparison test with standard turbidity
For instance, the presence of the
suspensions.
chemical impurities of calcium and
Odour – clean (distilled) water is
magnesium ions (Ca++ and Mg++) in
odourless. Many organic and inorganic
ground water are usually of natural
chemicals are odorous, including algae
origin, being due to the dissolution of
and other organisms. Hydrogen
these minerals from the soil and
sulphide (H2S), sometimes present in
underground rocks.
ground water and in waste water is
Impurities in water vary in quantity
malodorous.
and nature too.
Taste – taste, like odour, may be
The acceptability of a water for its
due to the decaying of micro-organisms
defined use depends on its physical,
or algae. It may also be due to high
chemical and biological properties.
concentration of salts such as Ca2+ and
The composition of water is the end
Mg2+ and Cl-. Taste is usually only an
result of physical and/or chemical
issue in drinking water, and rarely in
and/or biochemical processes.
waters not used for drinking.
Temperature – is perhaps the most
Physical properties of water that
significant parameter for shallow waters
show wide variation in magnitude
(lakes, ponds, etc). If large
include:
temperature gradients are reported,
Colour – caused by dissolved
stratification may occur between the
minerals, dyes or humic acids from
upper (warmer) body and the lower
plants. The decomposition of lignin
(colder) body. In river environment
produces colour compounds of tannins
higher temperature reduces the amount
and humic acids. The latter causes a
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 36°C,
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 Fig: 1-2: particle size classification and
instrumental methods for determination.
1-2.
All waters contain variable
concentrations of dissolved salts that
Table 1-1: Classification of Water are likely to dissociate in charged
Impurities (solid matter).
particles called ions.
Suspended Refers to Undissolved
Solids Matter in water Cations are positive, anions are
- SS-
Refers to the Total negative; the chemical equation below
Dissolved Solids
amount of dissolved
- DS- shows dissociation of NaCl (sodium
matter in water
Total Solids Refers to the sum of chloride) in water:
- TS - DS and SS
NaCl  Na+ + Cl-
Dissolved Gases Refers to the gases
- DG- Dissolved in water
The assessment of a water quality
may be either Specific or General.

A useful classification of solids is Specific assessment refers to the

also based on particle size, as seen in analyses of major ions (Ca2+, Mg2+) or

Fig: 1-2 here below. 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 Phosphorus is the limiting nutrient
natural waters are listed in . for eutrophication1; natural sources are

Table 1-2: major ions in waters and other phosphorous-bearing rocks, soil erosion
parameters.
and organisms’ cellular activity.
Cations: Ca2+, Mg2+, Na+, K+
Additional intake is due to fertilizers,
Anions: HCO3-, SO4=,Cl-,NO3-
detergents, animal feed supplements,
General pH, Total Hardness,
Characteristics: Alkalinity, TDS
etc.

Minor ions may be present at trace Common phosphorous compound in

levels, and are mainly cations such as water are sodium-phosphates (Na3PO4,

Iron (Fe2+, Fe3+) and Manganese (Mn2+) Na2HPO4 and NaH2PO4) and

and anions like Phosphate (PO43-). diammonium hydrogen phosphate

The presence of Silica (a non-ionic (NH4)2HPO4.

mineral) along with calcium,

magnesium, iron and aluminium can Fig: 1-3 below, shows the average

cause scaling (mainly in boilers). Its concentrations of inorganic substances

content should be kept as low as in surface waters (excluding

possible. groundwaters and wastewaters).

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 Fig: 1-3: average concentration range of
inorganic substances in surface water.
exist in the form of ammonia (NH3)
and its ion ammonium (NH4+), nitrites
(NO2-) and nitrates (NO3-).

Ammonia is toxic to organism while

nitrates are harmful.
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 water’s oxygen resources and increased algal
growth.

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1.3. Gross Inorganic chemical The pH remains reasonably constant

properties of water unless the water quality changes due to

natural or manmade influences, adding
The gross inorganic chemical
acidity or basicity (see Table 1-3).
properties of water are:
 pH
 Alkalinity and acidity Table 1-3: pH level and water
characteristics.
 Hardness
pH value Water Characteristics
 Conductivity
pH < 7 Acidity
pH is defined as the negative
pH = 7 Neutrality
logarithm (base 10) of the hydrogen
pH > 7 Basicity
concentration i.e.:
pH = -log[H+]
The pH of water is a key parameter
Water dissociates slightly into
and is also dependant on:
hydrogen ions [H+] and hydroxide ions
 The type of rock/soil from which
[OH-] as shown in the equation below:
acid/alkaline compounds can be
H2O = H+ + OH-
eroded.
Taking into account the Ion Product
 The Carbonate System and the
(or dissociation constant for water as
concentration of carbonates and
Kw = 10-14 mol/L @ 25°C), in absence
carbon dioxide; waters with low
of any foreign substance, the
carbonate concentrations are
concentration of hydrogen and hydroxyl
usually acidic.
ions is the same (at 25°C).
 The exposure to atmospheric
Very useful information on water
pollutants or wastewater.
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.

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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 H2SO4
(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. Fig: 1-5: corrosion rate vs. pH.

The carbonate system can be

explained by introducing the concepts

Low or high pH may cause of Alkalinity and Acidity.

corrosion2 in cooling systems;

Alkalinity – (the capacity of water

Fig: 1-5 shows the safe pH range to to accept H+ ions), is a measure of its

keep in the water to avoid corrosion. acid neutralising capacity (ANC) and is
often described as the buffering
capacity.

2
Corrosion will be described in details in Paragraph 5.2.

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 Acidity – similarly to alkalinity, it is At very high pH, carbonates first and
a measure of the base neutralising then hydroxides do exist mainly.
capacity (BNC).
Alkalinity and acidity are capacity Beside the carbonate system
factors of the water. species, other salts of weak acids such
as borates, silicates and phosphates
Carbonate System – it is closely also contribute to alkalinity.
related to alkalinity and acidity; Typical values of alkalinity are
the following species contribute to reported in Table 1-4:
alkalinity in relative amounts (see Fig: Table 1-4: some typical alkalinity values.
1-6): Alkalinity
 Hydroxide, OH - Application (mg
CaCO3/L)
 Carbonate ion, CO32- Upland (limestone) river 50 – 200
-
 Bicarbonate ion, HCO3 Lowland Lake 10 - 30
 Carbon Dioxide, CO2 Drinking Water 50 – 200

Domestic Wastewater 200 – 400

3
Anaerobic Sludge
2000 – 8000
Supernatant
“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,
Ca2+ and Mg2+.
These cations react with soap to
Fig: 1-6: relative amounts of alkalinity
species at various pH levels. form precipitate and with other ions
It can be noted that for pH values present in water to form scale.
lower than 6, the predominant specie The ions causing hardness have
contributing to alkalinity is carbon their origin in soil and geological
dioxide; formations.
on the other hand, for pH between 8
and 9, bicarbonates are in majority. 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 This is so when alkalinity is lower
species, all responsible for hardness. than total hardness.

Table 1-5: ionic species responsible for  Non Carbonate Hardness

hardness.
(NCH).
Cations Anions

Ca2+ HCO3- Furthermore, since Ca2+ and Mg2+

Mg2+ SO42- are the dominant hardness-producing
2+ -
Si Cl ions, it may be relevant to quantify
2+
Fe NO3- their contributions, should softening5 be
Mn2+ SiO32- considered a treatment process.
Hardness is computed in mg/L as
Hardness is a water parameter used follows:
mainly in potable water (not usually for  Hardness in mg/L as CaCO3 =
waste water). M2+ (in mg/L) X (50/eq weight
It is calculated in mg/L as CaCO3 of M2+)
(similar to alkalinity) or as meq/L(4). Where M2+ is any divalent metallic
A qualitative listing of waters rated ion (e.g. Ca2+, Mg2+).
on hardness is given in Table 1-6.  Hardness in mg/L as CaCO3 =
Table 1-6: relative hardness of waters. M2+ (in meq/L) X 50
Degree of mg/l Here follows an example to help
meq/L
Hardness as CaCO3
familiarise with hardness-related
Soft <1 0 – 75
calculations:
Moderately Soft 1-3 75 – 150
Example – Determine the various
Hard 3–6 150 – 300
hardness of the following water sample
Very Hard >6 > 300
(see Table 1-7):

Hardness is made up of: Table 1-7: Water Example for Hardness

Calculation
 Carbonate Hardness (or
Temporary Hardness TH) since Concentration
Constituent
mg/L Meq/L
this form is removed on
Ca2+ 60 3
prolonged boiling: 2+
Mg 29.3 2.4
Carbonate Hardness = 
HCO3- 366 6
(bicarbonate + carbonate) Alkalinity.

5
Softening: the removal of calcium and magnesium
4
Meq/L: milli-equivalents per Litre = mg/L/equivalent from water by means of ion-exchange resins or addition
weight. of Ca(OH)2.

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 Recall:  Hardness (mg/L) as CaCO3 =
 Concentration (meq/L) = Concentration (meq/L) X 50
concentration (mg/L) / The solution (using mg/L) is
equivalent weight (mg/meq) summarised in Table 1-8 here below:
 Equivalent Weight (mg/meq) =
Atomic Weight / Valence
 Hardness (mg/L) as CaCO3 =
Concentration (mg/L) X 50/eq
weight
Table 1-8: hardness calculation summary in mg/L.

Concentration Atomic Equivalent Hardness

Ion Valence
[mg/L] Weight Weight [mg/L as CaCO3]

Ca2+ 60 40 2 40 / 2 = 20 60 X 50/20 = 150

24.31 / 2=
Mg2+ 29.3 24.31 2 29.3 X 50/12 = 120
12.16
HCO3- 366 61 1 61 / 1 = 61 366 X 50/61 = 300

Total Hardness (TH) = Ca2+ + Conductivity – also known as the

2+
Mg = 270 mg/L as CaCO3. electrical conductivity, is a measure of
the ability of an aqueous solution to
-
Carbonate Hardness (CH) = HCO3 carry an electric current.
= 300 mg/L as CaCO3.
The electric current is conducted in
However, the CH cannot exceed the solution by the movement of ions
the TH and the CH is therefore and so the higher the number of ions
represented as 270 mg/L as CaCO3. (e.g. the greater the concentration of
The solution (using meq/L) is dissolved salts) the higher the ionic
summarised in Table 1-9. mobility and so the higher the

Table 1-9: hardness calculation

magnitude of conductivity.

summary in meq/L.
Chemically pure water does not
Hardness
Concentration conduct electricity since the only ions
Ion [mg/L as
[meq/L]
CaCO3]
present are H+ and OH- and so the
Ca2+ 3 3 X 50= 150
conductivity of very pure water is about
Mg2+ 2.4 2.4 X 50 = 120
0.05 S/cm (microsiemens/cm).
HCO3- 6 6 X 50 = 300

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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.
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.

Table 1-10: typical conductivity ranges

The objective in cooling water

for different waters. treatment is to minimise these

compound by biological, physical or
Conductivity
Water
[S/cm]
chemical treatment processes.
Organic compounds in water are
Chemically Pure 0.05
typically divided into four groups,
Distilled 0.1 – 4
depending on their chemical structure:
Rainwater 20 - 100
1. Hydrocarbons – these are organic
Soft Water 40 - 150
compounds containing only carbon
Hard Water 200 – 500
“C” and hydrogen “H”; (e.g. ethane
Range of Rivers 100 – 1000
C2H6, ethylene CH2=CH2, benzene
Ground Water 200 – 1500
C6H6, toluene C6H5-CH3).
Estuarine Water 200 – 2000
2. Halogenated Compounds – these are
Seawater 40,000
organic compounds in which a

In most waters, conductivity is halogen is the principal atom (atoms

due to the dissociation of inorganic include fluorine, chlorine, bromine

compounds, as organic compounds and iodine); e.g. chloroform CHCl3,

dissociate little. dichloromethane CH2Cl2, carbon

Therefore, a positive measure of tetrachloride CCl4.

conductivity is indicative of the 3. Carboxylic acids and esters – these

concentration of dissolved inorganic are organic compounds built around

salts. the carboxylic group (a carbon

linked to oxygen with a double

1.4. Organic chemical properties bond) and other with two functional
groups attached to an oxygen atom,
of water
e.g. acetone CH3COCH3,
The main element of organic
formaldehyde CH2O, ethyl ether
compounds is carbon “C”. Organic
CH3CH2COH2CH3.
substances may be natural or man-
4. Other organic compounds
made.

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1.5. Naturally Occurring and 95% degradation period for several

Synthetic Organic pesticides is 1 to 25 years.

contaminants 2. Surface Active Agents – used for

washing, emulsifying, wetting,
The naturally occurring organic
foaming, etc as they lower the
substances in water, wastewater and
surface tension of water when
bottom sediments are:
placed in it. The molecule of a
1. Proteins – made up of carbon,
surfactant (detergent) has two
hydrogen, oxygen, sulphur and
parts, a hydrophobic part which is
nitrogen, with the basic building
insoluble in water and soluble in non
blocks of amino acids; e.g. bacteria
polar liquids such as oils, and a
are mainly protein (C5H7NO2).
hydrophilic part which is soluble in
2. Lipids – comprise fats, waxes, oils
water and insoluble in non-polar
and hydrocarbons, which are
liquids. It is this dual property that
insoluble in water but soluble in
makes them suitable for the earlier
some organic chemical solvents, and
listed uses. Surfactants may cause
are slowly biodegradable.
foaming and reduce the diffusion of
3. Carbohydrates – contain carbon,
atmospheric oxygen to the water.
hydrogen and oxygen. They include
3. Halogenated Hydrocarbons – these
cellulose, starch and lignin which are
are end products of the reaction of
readily biodegradable (except
halogen with hydrocarbons, with
lignin). An example is glucose
chlorinated hydrocarbons being of
(C6H12O6).
key interest. The most significant
4. Plant Pigment – these are made of
halogenated hydrocarbons are
chlorophyll, haemins and carotenes
trihalomethanes (THMs) or
and include alcohols, ketones and
haloforms. Further details on THMS
carotenoids.
will be provided in the
“microbiology” control chapter.
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

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1.6. Determination of Organic BOD – biochemical oxygen demand

content of water is the amount of dissolved oxygen used

up from the water sample by micro-
The determination of organic
organisms as they break down organic
content of water can be by:
material at 20°C over a 5 day period.
 Specific tests to measure the
concentration of specific compounds
1.7. Measuring Water

(Standard Methods apply) Parameters

 Non-Specific tests to measure the pH is easily measured by a pH-
overall concentration of the organic meter: a laboratory device is shown in
content. Fig: 1-7 here below.
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. Fig: 1-7: Laboratory bench pH meter.

Before introducing more details on

the above tests, the concept of Conductivity is easily measured by a
Dissolved Oxygen will briefly be Conductivity-Meter, and is expressed in
mentioned. S/cm.
Oxygen from the atmosphere is Fig: 1-8 below, shows a portable
transferred across the air/water conductivity-meter.
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
Fig: 1-8: Portable conductivity-meter.
increasing water temperature.

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators’ Handbook - 17

 As already introduced in
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.
CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators’ Handbook -
the 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.
18
Table 1-11: Common impurities found in fresh water.

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators’ Handbook - 19

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.

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators’ Handbook - 20

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
Fig: 2-1: working principle of a heat
often, this heat has to be taken away exchanger.
after serving the main units. Temperature is not the only factor
contributing to heat exchange, but
The refrigerant medium used in other may have even a more relevant
cooling circuits is water, because its role:
transfer coefficient is much greater  The characteristics of the two
than that of air, is fully recoverable, exchanging fluids
does not pollute the process and is  The velocity of the flowing fluids
6
widely available .  The extent of contacting surface
 The metallurgy involved
2.1. Heat Transfer in Cooling Apart from the above mentioned
Water characteristics, that are already fixed at

Heat transfer takes place in devices the design stage, particular attention

called Heat Exchangers. should be paid to the cleanliness of the

Two fluids at different temperatures surface among the contacting fluids.

exchange heat by means of a The heat transfer equation is the

contacting surface. following:

The fluid at higher temperature Eq. 1

releases energy (cools down) to the Q  U  A  Tm
fluid at lower temperature (warms up). The Eq. 1 states that the amount of
heat Q [W] is proportional to:
 Exchanging Area “A” [m2]
 Logarithm Mean Temperature
Difference between Fluids “Tm”
[°C]
 Heat Transfer Coefficient “U”
6
Water-reuse programmes are now more common 2
[W/m °C]
than the past.

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators’ Handbook - 21

 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
7
reciprocal of heat transfer resistance : Fig: 2-2: heat transfer and resistance in
tubes.
Eq. 2
1 As discussed, heat exchanger design
U
RT
stage involves the knowledge of fluid
The total resistance RT to heat flow properties such as viscosity, specific
is given by the sum of several, heat, thermal conductivity and the
individual contribution: equipment layout (number of passes,

Eq. 3 velocity in tube side and shell side).

RT  r1  r2  r3  r4  r5 All these design parameters can be

optimised for better performance and
Where the 5 contributions are the
results.
following:
 r1: heat flow resistance of the
Heat flow resistance due to fouling
process-side film
both on process-side and water-side
 r2: heat flow resistance of the
severely increases.
process-side fouling (if any)
Very limited variations in fouling
 r3: heat flow resistance of the
extent can reduce heat transfer to
exchanger tube wall
unacceptable levels.
 r4: heat flow resistance of the
Heat exchange is fundamental for an
water-side fouling (if any)
effective control of process
 r5: heat flow resistance of the
temperatures so, when this feature is
water- side film
negatively affected, it may result in the
failure of an entire Plant.
The 5 resistances are shown in Fig:
2-2.
The aim of treating the water of a
cooling system is to reduce to a
minimum degree the fouling in the
7
A similarity is represented by the concepts of electrical
water side.
resistance and conductivity.

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators’ Handbook - 22

3. Cooling Systems Layouts In these systems, the temperature

The water cooling systems can be drop is very limited, therefore, a large

classified as follows: amount of water is necessary8.

 Once Through
 Closed Recirculation The limitation to the temperature is

 Open Evaporative Tower due to the high salts concentration in

sea water9.

The choice of the best circuit’s

layout depends on plants location, A once through system can be

water availability, economics and health characterised by the following

& safety. advantages and disadvantages:

Table 3-1: Once Through cooling System –

Their working principle, as well as Advantages and Disadvantages.

advantages and operational limits, are

Advantages Disadvantages
described here briefly.
Large Water
3.1. Once Through Cooling Low Capital Costs
Consumption and
Thermal Discharge in
System the receiving body

The first cooling system here Biological fouling from

Low Operating water intake, slit and
described is the “Once Through”. Costs sand in intake may fall
at low-velocity points
Fig: 3-1 shows a Once Through
Expensive heat
layout with possible injection points of exchange metallurgy
for sea water or
chemicals. Low Temperature
brackish
Sink
Obtaining water intake
and discharge permits
may be difficult

Fig: 3-1: Once Through cooling System

layout.

This layout is often found in cooling

systems placed near the sea side.
8
The amount of heat extracted is given by Q= McpT.
Because T 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 Table 3-2: Closed Recirculating cooling
System – Advantages and Disadvantages.
System
Another common cooling system Advantages Disadvantages

presented here is the “Closed

Minimum Make Additional Expense of
Circulating System”. Up Water Rate Second Cooling System

It consists of “two circuits” Hi Quality Make

Heat Load Limitations
connected by a heat exchanger. Up

Fig: 3-2 shows how a closed circuit Limited Biological Additional Pumps &
Fouling Piping
works.

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
Fig: 3-2: Closed Circulating cooling System Blowdown and a Make-Up stream to
layout.
control.

The cooling water is kept circulating

in the proper cooling circuit;
very limited make-ups
necessary to replace the water losses,
or when the quality/characteristics of
the water, are no longer satisfactory.
This systems allow a considerable
water saving, compared to that of once
are
through, with a good and practical
control of the key parameters such as
the Blowdown.

Limited windage and drifts exist due

The Closed System can be seen as
to the tower shape and its exposure to
the highest water-saving option.
the open space.

Its advantaged and disadvantages,

An open evaporative cooling system
compared to those of once through
is shown in Fig: 3-3 (possible injection
systems are shown in Table 3-2:
points of chemicals are shown, and
Fig: 3-4)

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators’ Handbook - 24

 Table 3-3: Open Evaporative cooling
System – Advantages and Disadvantages.

Advantages Disadvantages

Low Make Up
High Capital Costs
Water Rate

Power for Fans

Low discharge
(mechanical draft) and
Water Rate
Pumps
Good control of Fogging, Icing and
key parameters corrosion of
such as Blow surroundings
Fig: 3-3: Open Evaporative cooling System Down High Temperature Sink
layout.

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)
Fig: 3-4: Open Evaporative cooling system
(detailed view) These towers are suitable for fresh,
salt or brackish water.

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.
Fig: 3-5: induced multicell cooling tower.

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators’ Handbook - 25

Fig: 3-6: multicell cooling towers.
Fig: 3-8: details of plastic fillings.

The internal view of a cooling tower Natural draft cooling towers10 (Fig:

helps understand the way it works. 3-9) are the alternative to mechanical
draft ones.

The inlet water is distributed from

the top, passes through a series of They take advantage of temperature

fillings to maximise the air/water difference between ambient air and hot

contact surface and then enters the air inside the tower.

basin for re-circulation (see Fig: 3-7

and Fig: 3-8). Their design creates a chimney
effect in which, cold air from the
bottom of the tower, pushes warmer air
out of the top.

Fig: 3-7: internal view of a mechanical draft

cooling tower.

Fig: 3-9: hyperbolic natural draft cooling

towers.

10
Also called “Hyperbolic Tower”.

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators’ Handbook - 26

 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: 3-11: side view of a hyperbolic cooling

tower with construction details (2).

Fig: 3-10: side view of a hyperbolic cooling

tower with construction details (1).

Fig: 3-12: wood filling of a hyperbolic

tower.

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators’ Handbook - 27

 here follows a brief explanation of
4. Design of Recirculating each stream and parameter .

Cooling System
 Evaporated [EL] is the amount of
An Open evaporative system is
water that leaves the tower as
characterised by a cooling tower, a
12 3
vapour (expressed in m /h);
basin for cooled water and a
inlet water is cooled due to
recirculating piping-system serving the
subtraction of latent heat; its
plants11.
quantity depends on the heat load.

In this section, fundamentals of  Windage Losses [WL] is a relatively

design will be provided. small amount of (loss) water that
leaves the tower as entrained
In Fig: 4-1 a complete scheme of droplets.
open evaporative cooling system is This amount is usually between
shown: 0.5% and 3% of the recirculated
water.
It depends mainly on the hydraulic
characteristics of the tower
(expressed in m3/hr).

 Blowdown [BD] of the system is

necessary to control concentration
of salts (and other impurities) likely
to precipitate, leading to deposition,
Fig: 4-1: complete “open evaporative corrosion, as well as to
cooling system” layout. microbiological growth related
The system is characterised by problems13.
several streams and parameters; Blowdown can be continuous
all of them contribute to the (expressed in m3/hr) or intermitted
increase or loss of efficiency; (m3/day).

12
Water turns into steam due to contact between air
and tiny particles of warm water. This surface contact is
11
maximised by the tower filling.
13
It can be said that these systems represent an Deposition and corrosion are common problems in
intermediate configuration between open and closed cooling systems; these phenomena are encouraged by
circuits. the existing warmer temperatures, relatively high salts
concentration and long residence time conditions.

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators’ Handbook - 28

 Make-up [MU] is the amount of
EL Evaporation losses m3/hr
water required to restore the water
WL Windage Losses m3/hr
losses, due to evaporation, Windage
3
BD Blow Down m3/hr
and Blowdown (expressed in m /hr).
MU Make-Up m3/hr
14
 Number of Cycles [Nc] is the ratio
Nc Number of Cycles
between the concentration of a
RR Recirculation Rate m3/hr
given salt in the recirculating water
Total water in the
and the concentration of the same V m3
system
salt in the make-up water. All these parameters influence the

The Nc number is fundamental for operativeness of the tower(s).

the correct management of the

cooling system, both in terms of A complete picture of their effects

economics and energy savings. can be obtained only by performing a

[Refer to A practical Example (1) mass and energy balance, as developed

and A practical Example (2)]. in the next chapter.

 Recirculation Rate [RR] is the

feedrate of water circulating in the 4.1. Mass and Energy Balance
system (expressed in m3/hr). for Open Evaporative

 Delta T [T] is the temperature Towers

difference existing between the top Fig: 4-2 shows an open evaporative
of the tower (inlet water) and the cooling systems with the parameters
bottom (outlet water). described in Table 4-1;

 Volume [V] is the total amount of

water (expressed in m3).

 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.
Fig: 4-2: parameters for simplified mass
Parameter Comments Units and energy balance.

14
Also known as Number of Concentration.

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators’ Handbook - 29

 A simplified scheme allows to write
the following equation for global mass By combining Eq. 4, Eq. 6, Eq. 8, it
balance and partial mass balance: is possible to express the BD as a

Eq. 4: global mass balance

function of EL and Nc as follows:

Eq. 9: BD as a function of EL and Nc

MU  EL  BD
EL
BD 
Nc  1
Eq. 5: partial mass balance15
This equation is fundamental,
because Blowdown can be determined
MU  X MU  BD  X BD  EL  X EL
by knowing Evaporation Losses and
Eq. 6: expression of Number of Cycles Number of cycles.;

MU X RR  BD
NC   Blowdown is the key parameter for
BD X MU 
economical and energy reasons.
A heat balance between the RR (its
specific heat cp and temperature
Economics of the whole system is
difference T) and steam latent heat
driven by Blowdown because, apart
(), allows to write the following
from evaporation losses, it is actually a
equation:
waste stream used to control maximum
Eq. 7: heat balance allowable concentration of salts so:
 the lower the Blowdown, the lower
EL  RR  cp  T
the waste stream
from which EL can be determined as
 the lower the Blowdown, the closer
follows:
the actual working conditions related
Eq. 8: evaluation of EL to the maximum acceptable
concentration of substances likely to
RR  cp  T
EL  precipitate.

kcal
( has an average value of 550 and From an energy & economical point
kg
of view, a lower blowdown means lower
kcal
cp = 1 . makeup, so less expenses for water
kgC
supply and chemical treatment.
15
The concentration of salt X in steam “EL” has been
considered zero.

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators’ Handbook - 30

4.2. A practical Example (1)
Table 4-3: complete set of parameters
In this paragraph a practical (1).
calculation will be shown to familiarise
Parameter Units
with key parameters and their meaning.
Tot. Volume 3,000 m3/hr

Recirculation
An open evaporative cooling 9,000 m3/hr
Rate
system has the operating
Temperature
in 29 – out 22 = 7 °C
characteristics as summarised in Table Difference

4-2. Evaporation
115 m3/hr
Losses
Table 4-2: initial set of parameters (1). Blow Down 76.4 m3/hr

Parameter Units Make Up 191.4 m3/hr

Tot. Volume 3,000 m3/hr

Recirculation
9,000 m3/hr 4.3. A practical Example (2)
Rate
Temperature in 29°C – out As blowdown was stated to be the
°C
Difference 22°C key operating parameter, in this
Number of paragraph another NC will be
2.5
Concentration
considered.

These parameters can now be used

The difference in the set of
to determine the Evaporation Losses
parameters will be clearly visible in
(EL):
terms of energy and economics.
RR  cp  T 9000  1  7
EL    115 [m3/h]
 550
The same open evaporative cooling
and the Blow down rate:
system has now the operating
EL 115 115
BD     76.4 [m3/h]. characteristics as summarised in Table
Nc  1 2.5  1 1.5
The Make Up is the sum of all the 4-4.

streams leaving the system: Table 4-4: initial set of parameters (2).
MU  EL  BD  115  76.4  191.4
Parameter Units
[m3/h].
Tot. Volume 3,000 m3/hr

Recirculation
At this point, the complete set of 9,000 m3/hr
Rate
parameters is available in
Temperature in 29°C – out
°C
Table 4-3. Difference 22°C

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators’ Handbook - 31

 Number of Table 4-6.
1.5
Concentration
These parameters can now be used
to determine the Evaporation Losses
(EL):
RR  cp  T 9000  1  7
EL    115 [m3/h]
 550
same as Case 1, and the Blow down
rate:
EL 115 115
BD     230 [m3/h]
Nc  1 1.5  1 0.5
considerably higher than that for Case
1.

Again, The Make Up is the sum of

all the streams leaving the system:
MU  EL  BD  115  230  345 [m3/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 m3/hr

Recirculation
9,000 m3/hr
Rate
Temperature
in 29 – out 22 = 7 °C
Difference
Evaporation
115 m3/hr
Losses
Blow Down 230 m3/hr

Make Up 345 m3/hr

The different results form the two

cases are summarised in

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators’ Handbook - 32

Table 4-6: results’ comparison between
All the preliminary characteristics
Case 1 and Case 2. of water given in the Water

Parameter Case 1 Case 2 Units Fundamentals chapter will now be

associate to chemical and biological
Blow Down 76.4 230 m3/hr
behaviour.
Make Up 191.4 345 m3/hr

Number of
2.5 1.5
Concentration 5.1. Scaling in Cooling Water
Water formed deposits result from
By comparing the results from Case
naturally occurring minerals
1 and Case 2, the BD passed from 115 precipitating from water to form scale.
to 230 [m3/h] and MU from 191.4 to
The most common scales are
345 [m3/h]. calcium carbonate, calcium sulphate
and silica or silicates.
As seen and demonstrated
previously, the blowdown rate is Many factors affect the formation
directly related to the NC.
of scale, such as the mineral
concentration in the cooling water:
Because the design of a Cooling water temperature, pH, availability of
Water treatment is based on the BD, it nucleation sites (the point of initial
can be understood that a limited BD crystal formation) and the time allowed
means lower consumption of chemicals, for scale formation to begin after
as well as a saving in water discharge nucleation occurs.
and consequent make up. Calcium carbonate and magnesium
hydroxide, for example, are inversely
5. Common issues in Cooling temperature soluble so, the higher the
System temperature, the lower their solubility.
The design and operational
conditions of a cooling system have a Scale build-up on surfaces can be
relevant impact on water chemistry. extremely hard and difficult to remove
This means that scaling/fouling, (Fig: 5-1 shows a series of tubes
corrosion and microbiological behaviour affected by scale).
of a cooling water, can greatly influence
both design and operating settings.

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators’ Handbook - 33

 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
CaCO3.
2. If LSI is positive: Scale can form
Fig: 5-1: tube walls affected by scale.
and CaCO3 precipitation may
occur.
Scaling will drastically reduce heat
3. If LSI is close to zero: Borderline
transfer capacity and system energy
scale potential. Water quality or
efficiency.
changes in temperature, or
evaporation could change the
A useful index for the evaluation of
index.
the scale forming or corrosive
behaviour of a given water is the
In order to calculate the LSI, it is
Langelier Saturation Index “LSI”.
necessary to know:
The LSI expresses the degree of
 the alkalinity (mg/l as CaCO3)
saturation of water as related to
 the calcium hardness (mg/l Ca2+
calcium carbonate solubility.
as CaCO3)
LSI is then a calculated number
 the total dissolved solids (mg/l
used to predict the calcium carbonate
TDS)
(CaCO3) stability of a water;
 the actual pH
In other words it means that a water
 and the temperature of the water
will precipitate, dissolve, or be in
(°C).
equilibrium with calcium carbonate.
The Langelier saturation level
A useful and practical expression for
approaches the concept of saturation
the LSI, calculated at the maximum
using pH as a main variable, and the
skin temperature (60°C) is the
LSI can be interpreted as the pH
following:
change required to bring water to
equilibrium. Eq. 10: LSI practical formula.
LSI(60°C) = pH – 11.32 + log10(CaH *

Alk)
where CaH stands for Calcium
Hardness.

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators’ Handbook - 34

 As an example, if the analyses of a If the makeup water is high in
water were the following,: sulphates, hydrochloric acid may be
 pH = 8.7 used to reduce the alkalinity but,
 CaH = 405 ppm (CaCO3) chloride ions may cause problems
 Alkalinity = 4405 ppm (CaCO3) because they can penetrate oxide films,
substitute them into the LSI @ 60°C setting up local anodic cells and causing
equation, the result would be: corrosion (for details refer to paragraph
LSI(60°C) = 8.7 – 11.3 + 5.2 = 2.6 5.2).

The LSI is positive: Scale can form Monitoring of scale can be

and CaCO3 precipitation may occur. performed by:
 scale coupons
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: Fig: 5-2: scale coupons of different
1. Reduction of NC shapes and sizes.
or,
 Fouling Factor Calculation
2. Addition of Acid (controlled pH)
 Pilot Heat Exchangers
to lower pH and reduce alkalinity
according to the following
chemical equation:

Eq. 11: Acid Addition for controlled pH.

H2SO4+Ca(HCO3)2=CaSO4+2H2O +
2CO2

The calcium bicarbonate is Fig: 5-3: pilot heat exchanger.

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

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators’ Handbook - 35

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.

Fig: 5-4: electrochemical corrosion

Electrochemical corrosion takes
process.
place when a metal is placed in an
aqueous environment (H20).
Several chemical (and physical)
reactions will occur.
At the Anode (the negative side of
Fig: 5-5: a corrosion coupon severely
the electrochemical cell, an oxidation
affected by electrochemical corrosion.
occurs), the metal dissolves (Fe = Fe2+
+ 2e-) and, at the Cathode, a reduction
reaction takes place (O2 + H2O + 4e- =
Factors contributing to corrosion
4OH-).
are:
 Conductivity (also referred to
The overall corrosion process in
chlorides content).
cooling water systems is then:
2Fe(OH)2 + 1/2O2  Fe2O3·H2O + H2O,
with formation of rust (Fe2O3·H2O)
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
Fig: 5-6: corrosion rate vs.
corrosion-coupon severely affected by
conductivity.
corrosion.
 pH: extreme values of pH
should be avoided.

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators’ Handbook - 36

 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: 5-7: corrosion rate vs. pH.

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

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

rack.

Once removed, they are cleaned by

Fig: 5-8: corrosion as a function of acid pickling and weighted again.
oxygen content and temperature.

The comparison between initial, final

 Free Chlorine residual.
weight, exposure time and Area Factor
Corrosion can reduce the life-span
of the coupon, give the corrosion rate
of equipment by years, requiring
expressed by Milli-Inch per Year “MPY”,
expensive replacement.
or millimetres per Year “mmY”.
Corrosion can lead to costly
equipment repairs and production
Sometimes, on-line corrosion-
downtime.
meters are applied to circuits and give
Its related deposits lead to reduced
instant corrosion rate.
capacity and wasted energy because of
heat transfer efficiency losses.

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

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
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).
CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators’ Handbook -
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:
heat 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.
38
 Some species of microorganisms develop to protect and feed
can grow in the absence of oxygen, themselves.
using fermentation of organic
compounds as a source of energy. As the corrosion phenomena is
These organisms are described as hidden by biological fouling, it would
Facultatively Anaerobic. not be noticed easily.

The small number of Strictly anaerobic bacteria, growing

microorganisms that are able to break well only in the absence of oxygen;
down organic compounds or carbon such as species of sulphate reducing
dioxide only in the absence of oxygen bacteria (S.R.B.) are responsible for
are described as Anaerobic. severe Microbiological Induced
Corrosion processes:
Oxygen is actually toxic to many of
these organisms. Anaerobic metabolism “MIC” refers to corrosion that is
is commonly found in many bacterial influenced by the presence and
and fungal species. activities of micro-organisms and/or
their metabolites (the products
Respiration generates more energy produced in their metabolism).
for the organism than anaerobic
fermentation and results in greater Bacteria, fungi and other micro-
microbial growth. organisms can play a major part in
corrosion; the mechanisms potentially
Some of the problems this living involved in MIC are summarized as:
matter causes, include severe bacterial  Cathodic depolarization, whereby
slimes and fouling, hydrogen sulphide the cathodic rate limiting step is
(H2S), underdeposit corrosion and accelerated by micro-biological
health hazards. action.
 Formation of occluded surface cells,
Underdeposit corrosion is one of whereby micro organisms form
the most serious concern for cooling "patchy" surface. Sticky polymers
systems; attract and aggregate biological and
corrosion takes place below the non-biological species to produce
microbiological layer that the organisms crevices and concentration cells, the
basis for accelerated attack.

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators’ Handbook - 39

 Fixing of anodic reaction sites,
whereby microbiological surface Monitoring of microbiological
colonies lead to the formation of activity can be performed in several
corrosion pits, driven by microbial ways, according to the species being
activity and associated with the investigated:
location of these colonies (see Fig:  Vials: for Aerobic and
16
5-12, Fig: 5-13 and Fig: 5-14 for Anaerobic/SRB bacteria
corrosion coupons).

Fig: 5-15: VIALS for Aerobic Bacteria.

Original colour is Red, in presence of
aerobic bacteria vials turn into yellow.

Fig: 5-12: microbiological induced

corrosion “MIC”.

Fig: 5-13: corrosion coupon affected by Fig: 5-16: VIALS for Anaerobic
Bacteria. Original colour is Yellow, in
MIC prior to pickling. presence of anaerobic bacteria vials
become turbid and black if S.R.B. exist.

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.
16
Sulphate Reducing Bacteria.

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators’ Handbook - 40

 Easicult TTC Slides for Aerobic The Luminometer is shown in Fig:
bacteria. 5-18

Fig: 5-17: Easicult TTC Slide and its

comparison chart. Fig: 5-18: Luminometer for quick
analyses.

The two methods, either by Vials or

Microbiological control performance
TTC Slides, express the result in terms
can be evaluated by comparing the
of Colony Forming Unit/ml “C.F.U./ml”.
results with Table 5-1:

Table 5-1: comparison table for

For example, Fig: 5-15 shows the microbiological control.
colour changed at the third vial; this
C.F.U/ml Comments
means that the C.F.U./ml is 103.
0 – 10 No pollution

The fastest method for 10 - 102 Under Control

microbiological analyses is by means of 102 - 104 Attention Threshold

“luminoscan”; in this portable > 104 Immediate Action

instrument, selected reagents are used
to evaluate the microbiological activity
in few seconds.

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators’ Handbook - 41

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

The fundamental issues to deal

with, as described in the previous
paragraphs, will be highlighted.

6.1. Scaling and Fouling Control Fig: 6-2: distorted lattice by addition of
DCA (left) and microscope picture
Programmes (right) of non precipitating crystals.
Scale & Fouling
Inhibitors/Dispersant (also called The most commonly used threshold
Deposit Control Agent - DCA) are scale inhibitors are inorganic
complex chemical compounds, dosed at polyphosphates, organophosphorous
sub-stoichiometric amounts, that have compounds, synthetic organic
very marked effects on the growth rate dispersants and natural organic
of crystals deposited in a scaling dispersants.
environment.
In Fig: 6-3, the working
These threshold inhibitors act by mechanism of dispersing agents is
adsorbing onto the growing crystals and shown: first, adsorption of the
distorting the lattice, which disrupts the dispersing agent molecule occurs.
crystal growth process.

This crystal distortion prevents

deposition, and the highly irregular
stressed crystals tend to slough off as
Fig: 6-3: adsorption (left) and
crystal growth occurs (see Fig: 6-1 and stabilisation/dispersion (right) process
Fig: 6-2). of DCA.

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators’ Handbook - 42

 This is followed by both crystal  Anodic inhibitors aim at developing a
structure modification and by a charge stable, tightly adherent layer of -
repulsion mechanism of negative iron oxide film on the surface by
charges, which leads to causing a large anodic shift of the
destabilization/dispersion of the corrosion potential, forcing the
crystals. metallic surface into the passivation
range (see Fig: 6-4).

6.2. Corrosion Control

Programmes
Corrosion inhibitors are added to
water systems to reduce the corrosion
rate of metals to a negligible level.
Fig: 6-4: anodic film on tube wall.
Corrosion Inhibitors are chemicals
Organic or inorganic compounds
that react with a metallic surface, or
molecules, such as ortho-phosphates
the environment this surface is exposed
(@ high levels), phosphonates, nitrites
to, by giving the surface a certain level
and molybdates are anodic inhibitors.
of protection.

 Cathodic inhibitors work by either

Inhibitors often work by adsorbing
slowing the cathodic reaction itself,
themselves on the metallic surface,
or selectively precipitating on
protecting it by forming a film; they are
cathodic areas to increase the
normally distributed from a solution or
surface impedance and limit the
dispersion.
diffusion of reducible species
(hydrogen gas evolution is
The two most common ways for
prevented), to these areas.
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, Fig: 6-5: cathodic film on tube wall

consists of the development of “films” The precipitate is less tenacious

on metal’s surface. and more porous than that of the anode

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators’ Handbook - 43

film; organic or inorganic compounds Biocides are classified as:
molecules, such as ortho-phosphates  oxidizing biocides (e.g., chlorine)
(@ low levels), polyphosphates and since they very strongly oxidize
metals like zinc, are cathodic inhibitors. many organic and inorganic
molecules, becoming reduced
6.3. Microbiological Growth
themselves.
Control Programmes
The issues associated with Another class of chemicals that can
biofouling have involved the use of be used to remove microbial slimes are
chemicals known as Biocides and surfactants commonly known as
certain surfactant chemicals known as Biodispersants.
Biodispersants. They allow other chemicals to
 Biocides are chemicals that kill living contact surfaces and deposits to some
organisms or inhibit their ability to extent.
grow and reproduce.
Biodispersants increase the
A chemical can be a growing effectiveness of biocides by allowing the
inhibitor to certain organisms at a low biocides to penetrate the microbial
concentration and act as a killing slime, killing the microbial cells and
biocide to the same organisms at a eventually causing sloughing of the
higher concentration, over a definite slime.
time period (e.g., 6-12 hours).
This way of using biocides is known Quaternary ammonium salts and
as Shock Dosage, while growing amine salts (being cationic), attach to
inhibitors are generally added the negatively charged molecules in the
continuously to the system at lower slime layer and reduce the surface
levels. tension, thus allowing water to contact
the slime layers to a greater extent.
Biocides are classified as:
 non-oxidizing biocides because they The addition of an oxidizing biocide
do not oxidize other chemicals or helps break them up further by
oxidize them only very slightly. oxidizing the exposed charged atoms
on the slime layers.

The oxidizing inorganic biocides,

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators’ Handbook - 44

such as Chlorine, may be fed on a Fig: 6-7 shows chlorine and
continuous basis to maintain a free or bromine dissociation curve vs. pH.
total residual level (Fig: 6-6).

Fig: 6-7: chlorine and bromine

dissociation curve vs. pH.

Fig: 6-6: chlorination break point. Because the amount of bromine

Free residual chlorine, present as
hypochlorous acid, is a much more
effective and faster-acting biocide than
combined chlorine, present
chloramines, (e.g., NH2CI).
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
as oxidising biocide.

The main drawback with the

Because microorganisms find it oxidizing biocides is their high reactivity
difficult to adapt to chlorine, it is to reduce compounds such as iron, H2S
possible to feed chlorine on a and organic matter so, there may be
continuous basis. little residual left to control
microorganisms in case of process
Bromine (as hypobromic acid, (hydrocarbons) leaks.
HBrO) shows higher oxidising They do not effectively penetrate
properties, respect to chlorine, at a and disperse microbial slimes.
given pH. These facts imply that chlorine is
Sodium Hypochlorite and supplemented by the addition of non-
Hypobromine reactions are the oxidizing biocides and dispersants in
following: many systems.
- +
NaClO ↔ OCl + Na
and Examples of useful oxidizing
- +
NaBrO ↔ OBr + Na . biocides are:
 halogens such as chlorine (Cl2)

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators’ Handbook - 45

 chlorine dioxide (ClO2)  specific analyses for CHIMEC
 hydrogen peroxide (H2O2) products
 ozone (O3)  “microbiological counts”
 Peracetic Acid
 and chlorine, bromine donors such Common set of analyses and their
as chlorinated isocyanurates and use are shown in Table 6-1.
hydantoins.

Table 6-1: CHIMEC Routine Analyses.

Non-oxidizing biocides are organic
molecules that react with various parts Parameters

of the microbial cell, generally at a pH, Alkalinity and

Hardness for the
specific site. calculation of Langelier
Saturation Index LSI.
Water
Chlorides, Sulphates
Characterisation
The most common groups of and Iron.
Concentration Number
nonoxidizing biocides are: Nc based on Chlorides
and Calcium.
 aldehydes
VIALS or TTC count for
 organo-sulphur biocides Microbiology microbiological activity
 organo-nitrogen biocides monitoring

and Calculated Evaporation,

System
NC, BD, MU and
Parameters
 amine salts. Temperatures.

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

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators’ Handbook - 46

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators’ Handbook - 47
7. Troubleshooting of Cooling that may be common in cooling

Systems systems’ operating conditions.

The information here in presented,

The Table below (Table 6-1),
are intended only as a support for
provides common Troubleshooting Tips
cooling systems’ operators.
for the following steps:
As an integrated CHIMEC’s policy,
 Cooling Water
this document will introduce the
operators to a list of:
Once again, the information here in
 Problems found
reported, should always be supported
 Possible Causes
by the experience of the operators.
 Suggested Solutions to
problems

Table 7-1: Cooling Water Troubleshooting

Problem Found Possible Causes Suggested Problems’ Solution

 Number of Concentration
 Increase Blowdown Rate
Approaching Chemical & Physical
Too High pH Water17 Limits  Check/Increase Acid Injection
Rate
 Acid Addition Inadequate
 Reduce Blowdown Rate
 No Concentration Occurs
Lower pH Water  Check/Reduce Acid Injection
 Acid Injection Exceeds Limits
Rate
 High pH
 Number of Concentration  Increase Blowdown Rate
Coupons affected by
Approaching Chemical & Physical  Check/Increase Antiscale
Scale
Limits Injection Rate
 Low Antiscale Dosage
 Low pH  Check/Lower Acid Injection
Coupons affected by  Low Corrosion Inhibitor Dosage  Check/Increase Corrosion
corrosion  Microbiological Induced Inhibitor Injection Rate
Corrosion M.I.C.  Refer to Microbiological Growth
 Check/verify/reduce availability
of Nutrients and/or Process
 Presence of Nutrients, Process
Leaks
(Hydrocarbons) Leaks
Microbiological
 Check/Verify System’s Streams
Growth  Long Retention Time
 Check/Increase Biocide(s)
 Low Biocide(s) Dosage
Injection Rate and/or Shock
Frequency/Dosage.

17
Values are referred to design conditions.

CHIMEC S.p.A. Water Technology Unit - Cooling Systems Operators’ Handbook - 48