Cooling Water Systems – Theory And Operations…

1. Cooling Water Systems-Problems

Open recirculatory cooling water systems are commonly used for industrial cooling purposes
to efficiently dissipate unwanted process heat. In this kind of system, water is recycled a
number of times before being discharged as blowdown, thereby reducing water consumption.

The main problems associated with such systems are corrosion, scaling, fouling and
microbiological growth. If left untreated, these problems can lead to reduced operating
efficiency, increased maintenance cost, loss in heat transfer efficiency and energy and
ultimately shutdowns.

Corrosion

Corrosion is an electrochemical phenomenon by which a metal returns to its natural state, i.e.,
metal oxide.

Being an electrochemical process, for corrosion to occur, a corrosion cell consisting of an

anode, a cathode and an electrolyte must exist. At the anode, metal ions dissolve into the
electrolyte (water). As the metal ions go into solution, electrons are left behind which migrate
through the metal to the other points (cathode), where the electron is consumed.

Fe à Fe++ + 2e-

(At the anode)

O2 + 2H2O + 4e- à 4OH-

(Principal mode of electron consumption at the cathode)

The hydroxyl ions formed at the cathode combine with the ferrous cations forming ferrous
hydroxide.

Fe+2 + 2OH- àFe (OH)2

Ferrous hydroxide is rapidly oxidized to ferric hydroxide at the metal water interface. Ferric
hydroxide, under cooling water conditions, loses water and produces the so called corrosion
product, ferric oxide, also known as rust. The net result of all this activity is the loss of metal
(Fe) accompanied with the formation of a deposit (Fe2O3).

Factors that affect Corrosion

pH: The rate of corrosion is dependent on the pH. Generally corrosion is more severe in
acidic pH as most protective metal oxide films are soluble in acidic pH.

Oxygen and other dissolved gases: Oxygen increases the rate of cathodic reaction and thus
increases corrosion.

CO2 – forms carbonic acid and reduces pH.

NH3 – selectively corrodes Cu, particularly in the presence of oxidizing agents.

H2S – Lowers pH and forms iron Sulphids which being cathodic to iron promotes galvanic
corrosion.

Cl2 – Forms HOCl + HCl and thus reduces pH. It retards the formation of certain protective
films. It can also oxidize corrosion inhibitor films already formed.

Dissolved and Suspended solids: Conductivity of water increases with increasing dissolved
solids. Corrosion being an electrochemical phenomenon, one would accept higher corrosion
with increasing dissolved solids. However higher dissolved solids also imply higher hardness
salts and alkalinity. Hardness salts and alkalinity retard corrosion by forming a corrosion
inhibiting film on the metal surface. This factor far outweighs the corrosion induced by
higher conductivity. Thus DM water is more corrosive than soft water, which in turn is more
corrosive than hard water. Distilled water is most corrosive as not only is it devoid of all
minerals but is also slightly acidic due to dissolved carbonic acid.

Chloride and sulphate ions present in the water are capable of penetrating passive films
leading to pitting type corrosion.

Suspended solids influence corrosion by erosive or abrasive action. They can also settle on
metal surfaces producing localized corrosion cells.

Microbial Growth: Microorganisms promote the formation of corrosion cells. Also, the by-
products of some organisms are corrosive. Nitrifying, iron oxidizing and sulfate reducing
bacteria are particularly harmful.

Velocity: In high velocity and turbulent waters, oxygen is rapidly distributed and reaches the
metal surface. High velocity also removes passivation layer of corrosion inhibitors. The net
result is increased corrosion.

High velocity can also lead to erosion of metal surfaces, protective films and oxides. At the
same time, low velocity can lead to deposition giving rise to localized corrosion cells.

Temperature: As temperature increases, diffusion of oxygen to the metal surface also

increases, promoting corrosion. Above 70oC the loss of dissolved oxygen exceeds the amount
made available by diffusion, and a decrease in the corrosion rate occurs.

Scaling

Scaling is the precipitation of hard and adherent salts of water soluble constituents, like
calcium and magnesium, on the metal surface. These salts have very poor thermal
conductivity and their control is therefore absolutely essential for proper heat transfer
efficiency.

The most commonly encountered scale is calcium carbonate and it forms an extremely hard
and adherent deposit.

Ca (HCO3)2 àCaCO3 + CO2 + H2O

Calcium bicarbonate is present in all cooling waters. At higher temperatures and pH the
bicarbonate decompose to calcium carbonate and carbon dioxide. Calcium carbonate is
highly insoluble in water and precipitates at the hot spots of the heat exchanger forming a
dense adherent scale.

Calcium sulphate does not pose much of a problem because of its higher solubility. This
solubility is the basis of scale control by acid feed. Adding sulfuric acid, replaces the
alkalinity with sulfate ions enabling operation at higher cycles of concentration without
exceeding the carbonate solubility limits.

Silicate scales are extremely difficult to remove once formed. The best option is to prevent
their deposition and this can be achieved by limiting the silica to 180 ppm as SiO2, and Mg *
SiO2 product below 100,000 ppm with proper treatment.

Orthophosphate is formed by the reversion of polyphosphate and/or is used as such for

corrosion inhibition. This orthophosphate readily combines with the calcium ions present,
forming the highly insoluble and troublesome orthophosphate sludge. It is important to
control this sludge formation as it has poor thermal conductivity and can induce under deposit
corrosion.

Magnesium has lower scaling potential because magnesium salts are more soluble than
calcium salts and their concentration is generally much lower than that of calcium salts.

Iron oxide can form by the oxidation of soluble iron in the water. It can also be produced as a
result of corrosion. Iron oxide poses deposition problem and also acts as a nutrient for iron
bacteria.

Factors that affect scaling

Temperature: The common scalants found in cooling water exhibit inverse solubility, i.e.,
their solubility decreases with increasing temperature. Therefore scaling increases with
temperature.

pH or alkalinity: The solubility of CaCO3 decreases with increasing pH. Scaling potential
increases with increasing pH.

Solubility: For water borne deposits to form, the potential scaling material should be carried
as a soluble constituent of the cooling water to some degree. Under the conditions, each
potential scalants exhibits a definite solubility limit. Once this limit is exceeded, the solution
gets supersaturated and a precipitate forms leading to scaling. Also, higher the level of scale
forming dissolved solids, greater the chances of scale formation.

Fouling

Fouling is the deposition of suspended matter, insoluble in water. They can be water borne or
air borne. Some of the common foulants are:

 Dirt and silt

 Sand
 Corrosion products
  Natural organics
 Microbial matter

The particulate matters generally accumulate in the low velocity areas or in areas where there
is an abrupt change in the direction of flow or flow velocity.

Factors that affect fouling

Water Characteristics: Water containing suspended material will cause fouling e.g. distilled
water will not foul. Similarly surface waters have greater fouling tendency, as the amount of
suspended matter picked up by them is greater.

Temperature: Fouling tendency increases with increasing temperature. Heat transfer

surfaces which are hotter than the cooling water accelerate fouling.

Velocity: Fouling is greater in areas of low velocity while it is less severe in areas of high
velocity. Normal velocity is 3 to 5 feet/second.

Microbial Growth: Microorganisms can deposit on any surface. Certain bacteria like iron
bacteria utilize corrosion products leading to voluminous deposits. Also, slime secreted by
bacteria, acts as a binder and entraps material, which normally would not have deposited.

Corrosion Products: Insoluble corrosion products mix with other foulants like debris,
microorganisms, etc., and aggravate fouling. It also serves as a nutrient for iron bacteria.

Oil: Oil adheres to the metal surface and has the ability to bind deposits. Oil has very poor
thermal conductivity and can seriously affect heat transfer. Oil serves as a nutrient for
microorganisms. It also forms a barrier to the protective film forming inhibitors preventing
them from reaching and passivation the metal surfaces.

Microbial Growth

Cooling towers provide optimum conditions for microbial growth. Temperature and pH are
ideal for their growth and there is an abundance of nutrients and sunlight. Under these
conditions, microorganisms may multiply six million times, while during the same time,
inorganic salts may concentrate only six times.

Microorganisms enter the cooling water through the make up water and air. The major
problem microbes are;

 Algae
 Fungi
 Bacteria

Algae:Air, water and sunlight are the three basic requirements for algal growth. The
distribution decks and side walls of a cooling tower fulfill all these requirements and
therefore represent an excellent growth environment for algae.

Excessive growth of algae can lead to choked pipelines, nozzles etc., and hampering effective
distribution of water in the cooling tower.
All algae produce oxygen, which can depolarize the corrosion reaction and accelerate system
corrosion. Blue green algae can fix nitrogen and are responsible for the accelerated
deterioration of nitrite based corrosion inhibitors. Algae also produce slime which can act as
nutrient for other microorganisms.

Fungi: Fungi lack chlorophyll and are therefore non-photosynthetic, resulting in a

dependence on nutrients provided by organic matter (heterotrophic). Fungi use wood as
nutrient and can destroy cooling tower wood.

Fungi reproduce by forming spores. Spores can remain dormant for a long time and
proliferate when conditions become favorable. In their dormant state they are harmless.
Spores are generally resistant to most microbicides and can present very difficult situations.

Bacteria

The commonly found bacteria in CW systems that are detrimental to the system are:

Pseudomonas: These are slime forming bacteria. The slime acts as a binding agent for dust
and precipitates thereby causing voluminous deposits. Material which normally would not
have deposited gets deposited by the binding action of the slime.

Sulphur Reducing Bacteria: These are anaerobic bacteria and generate the energy required
for their growth by reducing sulphate to Sulphids and in the process corrode iron.

4Fe+SO42- + 4H2O àFeS+3Fe (OH)2+2OH-

It also indirectly corrodes iron by the formation of H2S (acid).

Fe + H2S àFeS + H2

During chlorination in the presence of SRB, the pH drops due to the formation of HCl.

H2S + Cl2 à2HCl + S

This is significant in the attack on concrete basins.

Iron Bacteria: These bacteria utilize iron for their growth and create iron deposits as a by-
product of their metabolism.

4FeCO3 + O2 + 6H2O à 4Fe(OH)3 + 4CO2 +81000 cal.

To generate the energy requisite for their growth they must produce large quantities of ferric
hydroxide. This gets entrained in the organism producing voluminous deposits which can
cause plugging, pitting corrosion and reduced heat transfer.

Nitrifying Bacteria: These bacteria convert nitrogenous compounds like ammonia to nitric
acid. This leads to lowering of pH due to the acid formed and directly leads to corrosion.
They can be easily detected by the continual drop in pH of the circulating water. The pH
seldom falls below 5, as these organisms are killed at a pH lower than this.
2. Cooling Water Systems – Solutions

Corrosion Inhibition

Corrosion inhibitors prevent the metal from reverting to its natural oxide state. Depending on
the corrosion reaction it controls, a corrosion inhibitor can be anodic, cathodic or general.

Anodic inhibitors are initiated at the anode and eventually may cover the entire metal surface.
Anodic inhibitors in low concentrations are dangerous because the entire corrosion potential
will occur at the unprotected anodic sites leading to severe pitting.

Cathodic inhibitors are initiated at the cathode and a thin protective film is formed. It forms a
barrier between the metal surface and oxygen. Low concentration of cathodic inhibitors lead
to general attack as the corrosion rate is increased in direct proportion to the increase in the
unprotected area.

Corrosion inhibitors that protect the metal surface by filming all metal surfaces, whether
anodic or cathodic are called general or filming type corrosion inhibitors.

The inhibitive action of two corrosion inhibitors used together is far greater than the sum of
the individual actions. This is because of the so called synergistic effect. The best protection
is obtained when one of the two inhibitors is cathodic and the other anodic.

Orthophosphate is an excellent anodic inhibitor but one has to carefully control

orthophosphate sludging when using it as a corrosion inhibitor. The same caution has to be
exercised when using polyphosphates because of their reversion to orthophosphates under
cooling water conditions.

Organophosphonates and polymers, though not corrosion inhibitors by themselves at use

levels, exhibit excellent synergism with other corrosion inhibitors. They also have excellent
thermal and hydrolytic stability.

Nitrites are good corrosion inhibitors for aluminum, tin and ferrous materials at pH 9 to 10.
They are the inhibitors of choice for closed systems. Silicates are effective in preventing
dezincification. Besides closed systems, silicates are often used in potable water systems.

Zinc is very popular due to its ability to form a film rapidly. This ability of zinc is used by
most formulations but is never used alone since the film formed by zinc is not very durable.

Molybdates are new generation corrosion inhibitors and their performance as corrosion
inhibitors is enhanced in the presence of oxygen and alkalinity. They are very effective in
DM or soft water conditions.

Azoles are excellent corrosion inhibitors for copper and copper based metallurgy. They also
afford some corrosion protection to steel when used with other inhibitors.

Whichever inhibitor one chooses, pretreatment is absolutely necessary for good corrosion
protection. Corrosion inhibitor at 2 to 4 times their normal dose is applied for the first few
days over a clean metal surface. This ensures the formation of a durable passivation film on
the metal surfaces rapidly. Pretreatment should also be instituted after any system upsets, pH
excursions, corrosive contaminants and prolonged low inhibitor levels.

Scaling and Fouling Control

Scaling and fouling can be controlled in a number of ways

 Limiting the cycles of concentration

 Softening the make up water
 Acid feed to maintain pH
 Mechanical means like increasing water velocity or designing exchangers with large
surface areas
 Treat with chemical inhibitors

Treatment with chemical inhibitors is the most practical and cost effective method to control
deposition.

Scale formation is controlled by the mechanism of threshold inhibition and crystal distortion.
Threshold phenomenon is a mechanism by which substoichiometric amounts of the chemical
prevents or retards the growth of scale forming crystals. The chemical is adsorbed on the
crystal surface interfering with the nucleation of the scalants crystals and preventing orderly
lattice type growth. Crystal’s growth is retarded and if and when they are formed, they are
highly distorted leading to a soft friable scale which can be easily dispersed by the movement
of water. The CW systems can therefore bt operated at higher cycles of concentration and
alkaline pH.

The antiscalant commonly used are;

 Organophosphonates
 Polyphosphates
 Low molecular weight anionic polymers.

Organophosphonates are the antiscalant of choice. They are far more effective antiscalant
than polyphosphates and exhibit much superior thermal and hydrolytic stability.

Specific low molecular weight polymers are particularly designed for the control of
orthophosphate sludging. These are a very important class of compounds that keep
orthophosphate in solution and use their anodic corrosion control capability synergistically.

Control of iron and heavy metals is obtained by the sequestering property of

organophosphonates and polymers. The net result is that the CW systems can be operated at
higher cycles and pH whereby corrosion potential is substantially reduced. An additional
benefit is that they can also clean the system of existing scales.

Low molecular weight anionic polymers function as excellent dispersants. They are adsorbed
on the dirt and suspended particles and enhance the partial negative charge that these particles
carry. The particles repel each other and agglomeration is prevented.

Microbial Control
Biocides are chemicals that kill microorganisms. The efficacy of a biocide depends upon the
nature and amount of pollutants such as hydrocarbons, pH, temperature and nutrients such as
orthophosphate present.

Biocides are mainly classified as:

 Oxidizing
 Non-Oxidizing

Oxidizing Biocides: Oxidizing biocides are the primary mode of control. They literally burn
up the microbes and microorganisms can never develop immunity to these oxidizers. It is
widely used and is very cost effective. They are usually added continuously. However,
organic matter, oil, masses of algae or slime and presence of reducing agents impairs their
effectiveness. While using this class of microbicides the oxidant demand has to be met,
before free oxidant is available for biocidal action.

The commonly used oxidants for CW systems are:

 Chlorine or chlorine releasing compounds

 Bromine or bromine releasing compounds
 Ozone
 Chlorine Dioxide
 Sodium Hypochlorite

Chlorine enhancers are compounds that in certain combinations yield one of the above
species in circulating water. Bromine and chlorine dioxide are particularly effective in
alkaline medium where chlorine loses its activity.

Non-Oxidizing Biocides: Each of these biocides has their specific mode of action and kills
the microbes by interfering with their life process. Most are enzyme poisons. They are added
periodically and are shock dosed. A combination of two or more non-oxidizing biocides is
usually used to prevent microbes developing immunity to the biocide.

Some of the commonly used eco friendly non-oxidizing biocides are:

 Methylene Bisthiocyanate
 Quaternary ammonium compounds
 Dodecyl guanidine hydrochloride
 Dichlorophene
 Isothiazolines
 Dibromonitrilopropionamide
 Thiocarbamates
 Glutaraldehyde/formaldehyde

Each of these products has their own strengths and limitations and a combination is usually
selected to suit the needs of a particular system and installation.

Biodispersants: Biodispersants are a class of compounds that enhance the effectiveness of

the biocides used. These are surface active compounds. They loosen microbial deposits which
can then be flushed away. This exposes the new layers of microbial slime or algae to the
attack of biocides. They increase the penetrating power of active ingredients of biocides by
exposing the underlying microbial deposits which would have otherwise been covered and
sheltered.

Chemical Treatment Programme

A chemical treatment programme is therefore designed to control

 Corrosion
 Scaling
 Fouling
 Microbial Growth

Today, every treatment programme is non chromate because of the acute toxicity of
chromate. Most programmes are operated at alkaline pH (7.0 to 8.3). The systems are also
operated at high cycles of concentration as, today, chemicals are available that can permit
operation at hardness levels upto 1500 ppm as CaCO3. Under these conditions, corrosion
potential is lowered and inhibitors like orthophosphate and zinc and their various
combinations easily provide corrosion inhibition well within the required limits.

Based on the chemicals used and the system needs, the various treatment programmes
available, are:

 Zinc Phosphate Programme

 Non Metallic Programme
 All Organic Programme
 Soft Water Molybdate Programme
 Stabilized Phosphate Programme

The above effectively controls corrosion, scaling and fouling. Microbial control is achieved
with chlorine or a halogen source as the primary mode of control. This is supplemented with
the regular use of a biodispersant. Depending on the system and the extent of microbiological
contamination, a combination of non-oxidizing biocides is selected for periodic addition
alternately.

The water parameter limits are set for individual installations and the system is operated
within these limits for optimum performance.

3.0 Cooling Water Systems-Operation

The effectiveness of any cooling water treatment programme depends on its proper

implementation. It begins with the start-up of cooling water systems.

A newly installed cooling water system should be properly cleaned before it is put to actual
use. The cooling tower basin, pump sump, tower deck and heat exchangers should be cleaned
of mud, construction debris, loose lumber, mill scale, oil, grease etc., to prevent choking of
heat exchanger tubes or pipelines. The following sequence should be followed for optimum
performance of the system.
Physical Cleaning: The cooling tower basin, sump, distribution deck, large pipelines and
inlet and outlet of exchangers should be manually cleaned to remove the debris before filling
the basin with water.

Flushing with water: After physical cleaning flush the system with water. At this stage, it is
necessary that the water velocity is as high as possible. Many times, all the circulating pumps
are not ready at this stage. In such an eventuality, it is advisable to take the system in line in
loops and change the loops every hour or two. It should be ensured that before closing any
loop it is sealed with water.

This operation removes most of the mud and loose matter from the pipelines and brings it
into the basin. Constant turbidity is the indication of completion of the flushing operation.
Blowdown at maximum rate with simultaneous make up to remove the deposits from the
system. Continue till the circulating water is clear.

Stop the pumps and drain the basin. Clean the basin and sump manually. During this period
the jump over’s can be removed and the heat exchangers can be taken on line.

Surfactant Cleaning; Start circulation after filling the basin with water. Ensure that the
exchangers are in line and the ID fans are running. Drain individual heat exchangers till drain
water is clear. Close the drains and add the recommended surfactant at the suggested dose
level. Circulate for 24 hrs without blowdown. Heavy foaming may be observed. During this
stage oil, grease and other loose suspended matter is removed from the system. This is then
flushed by giving heavy blowdown with make up till circulating water is clear and foaming
completely subsides.

Acid Cleaning: Acid cleaning removes corrosion products from the system. It is usually
carried out at pH of 3.5 to 4.5. It is absolutely necessary to use an acid inhibitor at this stage.
The acid inhibitor forms a temporary protective layer on the bare metal surfaces as soon as
the corrosion product on the metal surface dissolves in the acid at low pH. Continue low pH
cleaning till iron content in the circulating water is constant.

Once constant iron readings are obtained increase pH gradually. Quick pH increase will
redeposit the dissolved iron. Keeping turbidity below 15 NTU, increase pH slowly with
blowdown and simultaneous make up. Incase pH increases rapidly, use acid to arrest the
rapid increase of pH. Also, take the side stream filters on line at this stage. Continue
blowdown and make up till iron in the circulating water is below 1 ppm.

Cleaning with Microbicides: The system is chemically clean after low pH cleaning. It is
now necessary to clean it microbiologically. A shock dose of the recommended biocide at the
suggested use level should be added. Close blowdown and circulate for the required period (8
to 24 hours). Then blowdown heavily to flush the microbial mass out of the system.

Passivation: Passivation is required for the formation of a protective film on the metal
surface rapidly. This is achieved by maintaining a high concentration of the corrosion and
deposit control chemicals for a certain period. In case of no or low heat load, the passivation
period is extended as passivation is good and rapid if heat load is available.

Chlorination should be started immediately after system cleaning.

Once passivation is complete, maintain regular levels of treatment chemicals and follow the
microbial control regime as advised by the treatment vendor. Maintain water parameters
within the recommended limits and analyse water parameters and chemical treatment levels
regularly as required.

4.0 Cooling Water System-Monitoring & Evaluation

The success of any treatment programme depends on maintaining the various parameters
within the recommended limits at all times. Therefore careful monitoring is an integral part of
a good treatment programme.

The parameters that should be monitored continuously are:

 pH
 Water level in sump
 Blowdown rate
 Make up rate

Free oxidant level should be monitored every shift. Free oxidant level should be analyzed
every shift. The complete analysis of circulating water and make up water should be done
daily and should include;

 pH
 Alkalinity
 Conductivity
 Turbidity
 Hardness
 Chlorides
 Silica
 Iron
 Ammonia, nitrates, if required
 Any frequent pollutant
 Treatment Chemicals

The sampling point should be located in the return header.

Acid, if required and treatment chemicals should be added continuously.

Evaluation of the Treatment Programme: The treatment programme should be regularly

evaluated for;

 Corrosion control
 Deposit control
 Microbial control

Corrosion control: Effectiveness of a treatment programme for corrosion control can be

evaluated by measuring corrosion rate. This is normally measured by corrosion meter and
corrosion coupons.
Corrosion meter measures the instantaneous corrosion rate due to electrochemical corrosion.
It does not reflect microbial induced corrosion. It is effective in reflecting the corrosion trend
on day to day basis.

Corrosion coupons are exposed for a period of 30 days in a specially designed rack and are
placed in the return header. The exposed coupons provide an average corrosion rate for the
period and it also reflects microbial corrosion during the period.

Deposit control: It is difficult to measure the exact extent of scaling and fouling since it
varies depending on the local thermal and hydrodynamic conditions. An indication of deposit
control can be obtained by observing the performance of test heat exchangers.

Selected critical exchangers can be monitored with the help of heat transfer data. Periodic
inspection of an exchanger that can be isolated without disturbing plant operation also
provides significant information regarding the treatment effectiveness for deposit control.

Devices like deposit monitors can also be installed and besides visual inspection, it affords
quantitative data on deposition rate.

Microbial control: Regular microbial analysis of the circulating water should be carried out.
This should include the total viable count and also the sulfate reducing bacteria count. Any
other bacteria, specific to the system, can also be identified and analysed.

Regular inspection of the cooling tower especially louvers and deck for algae and fungus
growth will also help in evaluating the microbial treatment programme effectiveness.

Biofouling monitors are also quite effective in monitoring the microbial treatment
performance. Here the pressure drop across a stainless steel pipe indicates the degree of
microbial fouling in the system.

Heat Exchanger Inspection: All the above methods are indicative and serve as comparative
methods for evaluation of the treatment programme. The actual conditions in the system vary
depending on the thermal and hydrodynamic parameters as well as metallurgy of the system.
Often there are leaks altering the environment conditions. It is not possible to simulate all
these conditions in the evaluation methods mentioned earlier.

The inspection of heat exchangers during annual turnaround therefore gives the best
indication about the effectiveness of the overall treatment programme. Couple this with the
deposit analysis of the deposits collected from different parts of the exchangers provides an
excellent overview of the effectiveness of the treatment programme.

Integrated programme approach is just not mere selection of good chemicals but also
supplementing it with good monitoring practices and proper devices for tracking the
performance. The combination of these factors will certainly make the treatment programme
a total success even with less tolerant and non-forgiving non-chromate programmes.