Cooling Water Treatment For Industrial Use

Note: The source of the technical material in this volume is the Professional
Engineering Development Program (PEDP) of Engineering Services.

Warning: The material contained in this document was developed for Saudi
Aramco and is intended for the exclusive use of Saudi Aramcos
employees. Any material contained in this document which is not
already in the public domain may not be copied, reproduced, sold, given,
or disclosed to third parties, or otherwise used in whole, or in part,
without the written permission of the Vice President, Engineering
Services, Saudi Aramco.
Chapter : Process For additional information on this subject, contact
File Reference: LAB20705 R. A. Al-Husseini on 874-2792
Engineering Encyclopedia
Saudi Aramco DeskTop Standards
Cooling Water Treatment
Engineering Encyclopedia Process
CONTENTS PAGES
TYPES OF COOLING WATER SYSTEMS AND PARTS OF COOLING
TOWERS AND HEAT EXCHANGERS................................................................. 1
Open Evaporative Recirculating Cooling Systems....................................... 1
Typical Cooling Tower Design .................................................................... 1
Cooling Tower Water Balance: Evaporation, Make-Up, Blowdown,
and Drift ....................................................................................................... 2
Principal Parts of Cooling Towers................................................................ 5
Heat Exchangers........................................................................................... 6
Components of a Shell and Tube Heat Exchanger ....................................... 6
Components of a Plate Heat Exchanger ....................................................... 7
Common Materials of Construction ............................................................. 7
Once-Through Cooling Systems .................................................................. 8
Closed Recirculating Cooling Systems ........................................................ 9
CONTROL OF CORROSION IN COOLING WATER........................................ 11
Factors Affecting Corrosion in Cooling Water........................................... 13
Corrosion Inhibitors.................................................................................... 14
Chromate .................................................................................................... 15
Zinc............................................................................................................. 16
Orthophosphates and Polyphosphates ........................................................ 16
Nitrite.......................................................................................................... 18
Silicates ...................................................................................................... 19
Molybdate................................................................................................... 19
Phosphonates.............................................................................................. 20
Copper Alloy Inhibitors.............................................................................. 22
Nonchromate Cooling Tower Treatment Packages .................................... 24
Monitoring Corrosion................................................................................. 26
Avoiding Galvanic Corrosion..................................................................... 28
Precleaning and Pretreatment ..................................................................... 29
PREVENTION OF SCALE FORMATION IN COOLING WATER.................... 31
Effect of Scale on Heat Transfer ................................................................ 31
Scales Formed in Cooling Water and Their Prevention ............................. 33
Calcium Carbonate Scale ........................................................................... 33
Calcium Sulfate Scale................................................................................. 36
Calcium Phosphate Scale ........................................................................... 36
Magnesium Silicate Scale........................................................................... 37
Effect of Water Chemistry, Temperature, and pH...................................... 37
PREVENTION OF THE HARMFUL EFFECTS OF MICROBIOLOGICAL
GROWTH IN COOLING WATER....................................................................... 40
Microorganisms Responsible for Biofouling.............................................. 40
Chemicals for Control of Biofouling.......................................................... 42
Oxidizing Biocides ..................................................................................... 43
Nonoxidizing Biocides ............................................................................... 43
Surfactants.................................................................................................. 45
Mechanical Means for Control of Biofouling ............................................ 45
Biofouling Monitors ................................................................................... 45
Prevention of Macrofouling by Jellyfish, Mussels, Etc.............................. 46
CONTROL OF GENERAL FOULING IN COOLING WATER.......................... 47
Oil and Dust in Cooling Water ................................................................... 47
Means of Control........................................................................................ 48
Sidestream Filtration .................................................................................. 48
Dispersants and Surfactants........................................................................ 48
Cleaning General Deposits ......................................................................... 48
MONITORING AND CONTROL REQUIRED TO OPERATE COOLING
WATER SYSTEMS .............................................................................................. 49
Chemical Feed Equipment ......................................................................... 49
pH and Blowdown Controllers ................................................................... 49
Frequency of Chemical Analysis................................................................ 50
GLOSSARY .......................................................................................................... 51
Saudi Aramco DeskTop Standards 1
TYPES OF COOLING WATER SYSTEMS AND PARTS OF COOLING TOWERS
AND HEAT EXCHANGERS
Three types of cooling water systems are used in the petroleum and chemical industries:
open evaporative recirculating, once-through, and closed recirculating. The system used
will depend on the process or equipment to be cooled, the availability and quality of
water, and the ease with which the water can be disposed. The types of systems found
vary from small engine jackets to large once-through systems and open recirculating
cooling towers. It is not uncommon to have several different systems in a refinery or plant.
Open Evaporative Recirculating Cooling Systems
Open recirculating cooling systems allow reuse of cooling water and provide efficient
dissipation of heat. For these reasons, they are commonly used where water conservation
is important.
Typical Cooling Tower Design
Figure 1 depicts a schematic of an open evaporative recirculating cooling system. Heat is
dissipated by the evaporation of some of the recirculating water. The evaporation takes
place most commonly in a cooling tower, although spray ponds and evaporative
condensers are also used.
FIGURE 1. OPEN EVAPORATIVE RECIRCULATING COOLING SYSTEMS
Cooling Tower Water Balance: Evaporation, Make-Up, Blowdown, and Drift
The amount of heat dissipated by a cooling tower is governed by the rate at which water is
evaporated. The evaporation rate is a function of the recirculation rate, cooling range, and
the atmospheric temperature and humidity. The following equation approximates this
relation:
e = 0.8 L (Cp) (dT) / Hv
where
e = evaporation rate, grams per minute (gpm)
L = circulation rate, gpm
Cp = heat capacity of cooling water, 1.0 Btu / lb F
Hv = latent heat of water, 1050 Btu/lb
dT = cooling range, difference between the hot and cold water temperatures, F
The factor, 0.8, arises from the fact that under typical atmospheric conditions 20 % of the
temperature drop is due to sensible heat transfer rather than latent heat transfer.
For example, a cooling tower circulating water at 25,000 gpm with a 11 C (20 F)
temperature drop will evaporate 380 gpm. This corresponds to about 4 million Btu/minute
of heat transferred.
As the water vapor leaves the tower through evaporation the remaining dissolved salts
naturally present in the water increase in concentration. These increased concentrations
make the water more corrosive and increase the tendency of scales to form. Dissolved
salts are generally allowed to concentrate by a factor of 3 to 8. This factor is called the
cycles of concentration or cycles. The degree to which salts are allowed to concentrate is
controlled by the blowdown or bleed off rate.
The volume of fresh make-up water required by a cooling tower system is governed by the
loss of water through evaporation, blowdown, and drift. Drift or windage is
nonevaporative loss, which is typically 0.05 to 0.1 % of the circulation rate. It is
considered negligible in many calculations. For our example tower, the drift typically
would be less than 0.1 % of the circulation rate or 25 gpm.
Blowdown and drift are related to the cycles of concentration and the evaporation rate as
follows:
b + d = e/( r - 1 )
where
b = blowdown rate, gpm
d = drift, gpm
r = cycles of concentration
The water mass balance for the example cooling tower water is:
m = e + b + d
where
m = make-up rate, gpm
The make-up rate for our example tower is 380 + 102 + 25 = 507 gpm.
If our example tower is run at four cycles, b=102 gpm. Often the cycles of concentration
are measured by the ratio of the chloride concentration of the circulating water to that of
the make-up water. Chloride is used because it is usually present at a concentration which
can be measured easily and accurately, and it does not form insoluble salts. However,
chloride concentration will not be an accurate measure of the cycles if chlorination is
used, since chloride is a by-product of this treatment. If there are ions in a tower water
which are being cycled less than chloride, they are being deposited or otherwise lost from
the recirculating water.
These basic cooling tower calculations are useful for establishing chemical feed rates. The
dosage of most treatment chemicals is based on their concentration in the circulating
water. When a system is filled with untreated water, the initial dosage is proportional to
the volume and the initial demand of the system. Since most treatment chemicals do not
evaporate they are removed from the system in the blowdown and drift; during operation,
the feed rate is proportional to the rate of blowdown and drift. By decreasing the rate of
blowdown, and therefore increasing the cycles of concentration, the chemical feed rate
can be decreased proportionately. Since the corrosivity and scale-forming tendency of
water increases as the number of cycles increase, an increase in cycles must be balanced
by the ability of the treatment chemicals to perform effectively. As shown in Figure 2,
with each incremental increase in cycles there are decreasing incremental savings in water
and chemicals. It is generally not necessary to operate towers at more than eight cycles
where incremental savings are small.
3 4 5 6 7 8
200
B
L
O
W
D
O
W
N

(
g
p
m
)
CYCLES OF CONCENTRATION
25,000 gpm RECIRCULATION
11 C (20 F)
0
150
100
50
FIGURE 2. BLOWDOWN EFFECT OF CYCLES OF CONCENTRATION
A wide range of corrosion inhibitors, antifoulants, antiscalants, and biocides are used in
open recirculating cooling systems. The predominant corrosion inhibitors in the refining
and chemical industries are blends of chromates, phosphates, zinc, and copper alloy
inhibitors. Organic phosphates, polymers, and copolymers are used as antifoulants and
antiscalants. Chlorine is the most common biocide. Other oxidizing and nonoxidizing
biocides are also available.
Principal Parts of Cooling Towers
The principal parts of a cooling tower are the fan(s), fill material, water distribution deck
or header, drift eliminator, structural frame, and cold water basin. Cooling towers use
recirculating ambient air to cool warm water primarily through evaporation as the water
cascades down through fill material and air passes up or across the fill. The fill serves to
maintain an even distribution of water across the horizontal plane of the tower and
maximizes the surface area of the water to enhance evaporation and sensible heat transfer.
The principle parts of an induced, draft, counterflow cooling tower are shown in Figure 3.
The parts of an induced draft crossflow cooling tower are shown in Figure 4.
FIGURE 3. INDUCED DRAFT COUNTERFLOW COOLING TOWER
FIGURE 4. INDUCED DRAFT CROSSFLOW COOLING TOWER
Heat Exchangers
Heat exchangers are critical parts of a cooling system designed to efficiently pass the heat
from the process being cooled to the water. Since the heat transfer surface is the hottest
area exposed to cooling water it is the most prone to corrosion and fouling. The primary
objective of a cooling water treatment program is to protect the heat transfer surfaces from
corrosion and fouling.
Components of a Shell and Tube Heat Exchanger
Shell and tube heat exchangers come in many different shapes and sizes depending upon
the service for which they are to be used. The size and, to some extent, the type of heat
exchanger are controlled by the use, temperatures in and out, flow rates, and other factors.
Cleanability, alloys for one or both sides, design temperatures, pressures, and corrosion
must be considered in the selection of a heat exchanger. The principle parts of one of the
most common types of shell and tube heat exchangers are shown in Figure 5. Cooling
water is most often on the tube side. When cooling water is on the shell side, corrosion
and fouling are more likely due to pocketing and deposits at baffle dead corners.
FIGURE 5. SHELL AND TUBE HEAT EXCHANGER
Components of a Plate Heat Exchanger
Plate heat exchangers are sometimes used in once-through seawater cooling systems
especially where space and weight are at a premium, such as on offshore structures.
Figure 6 shows the typical components of a plate heat exchanger.
FIGURE 6. TYPICAL PLATE HEAT EXCHANGER
Common Materials of Construction
Many factors must be considered in choosing the materials of construction for a heat
exchanger including the temperature, composition of the process stream, and the cooling
water. Carbon steel may provide sufficient corrosion resistance in treated cooling water.
Titanium, inherently more corrosion resistant and expensive, may be required in seawater
applications. Carbon steel is the primary material of construction in cooling tower system
heat exchangers. Copper and copper alloys such as brasses, Cu-Ni, and stainless steels, are
also important due to their greater corrosion resistance than steel.
Cast iron, steel, copper, copper alloys, aluminum, and solders are found in closed systems.
Various copper-base alloys, such as 90-10 Cu-Ni, 70-30 Cu-Ni, and aluminum brasses and
bronzes have been successfully used in seawater. However, these materials are susceptible
to premature failure when flow velocities are high, when seawater contains significant
concentrations of sand, and when pollutants such as sulfide and ammonia are present.
Alternatives include titanium, certain high-alloy austenitic stainless steels, high-alloy
ferritic stainless steels, and duplex stainless steels.
Once-Through Cooling Systems
As the name implies, systems which use water once and then discharge it are called once-
through systems. Figure 7 is a typical schematic of a once-through cooling system. These
systems are used only where a large volume supply of water is available at a low cost,
because even small systems require large volumes of water. Saudi Aramco uses large
once-through seawater cooling systems.
Corrosion, scale, and biological growths are inherent problems in these types of systems.
Generally, the only treatments applied are coarse screening and chlorination. Screening is
used to remove foreign matter such as seaweed which may damage pumps or foul heat
exchange equipment. Chlorination is necessary to prevent biological fouling. Since large
volumes of water pass through these systems it is not economical to use any scale or
corrosion inhibitors. Corrosion resistant materials and limits on flow and temperature are
necessary to prevent corrosion.
FIGURE 7. ONCE THROUGH COOLING SYSTEM
Closed Recirculating Cooling Systems
A closed recirculating cooling system is one in which the water is recirculated in a closed
loop with negligible evaporation or exposure to the atmosphere. Figure 8 depicts a
schematic of this type of system. A closed system has essentially a constant volume with
little or no added (make-up) water. These systems are frequently employed for critical
cooling applications where deposit formation on heat transfer surfaces would be
disastrous. In a typical closed system, heat is transferred to the system from the loop by
heat exchange equipment and is removed from the closed loop by a second exchanger.
The secondary system could use open evaporative cooling, once-through water cooling, or
air cooling.
FIGURE 8. CLOSED RECIRCULATING COOLING SYSTEM
Closed systems are well suited to cool gas engines and compressors. Diesel engines in
stationary or locomotive service normally use closed radiator systems similar to
automobile systems. Closed systems are also used in the chilled water systems of air
conditioners or for industrial processes in need of reliable temperature control.
Water velocities in closed systems are generally 0.9 to 1.5 m/sec (3 to 5 ft/sec) and the
temperature rise is typically 6 to 8 C (10 to 15 F). Generally, little make-up water is
needed except for that necessary to replenish pump seal leaks, expansion tank overflows,
and losses through vents. Service water can generally be used because there is no
evaporation and concentration of salts. However, the use of condensate, desalinated,
demineralized, or softened water is preferred, if available.
The possibility for dissolved oxygen attack is relatively low, since oxygen generally enters
only in the make-up water. However, untreated systems and systems with excessive
exposure to the atmosphere may suffer from oxygen pitting, galvanic action, and crevice
attack.
High concentrations of nitrite-, chromate-, and silicate-based corrosion inhibitors are
commonly used in closed systems.
CONTROL OF CORROSION IN COOLING WATER
In cooling water, corrosion results from an electrochemical reaction between a metal and
an impurity in the water. The corrosion of steel is discussed in this Module, but the same
principles apply to other metals used in cooling water systems. In cooling water, dissolved
oxygen, copper and ferric ions, acids, and chlorine are the primary impurities, called
oxidants or corrodants, which react with steel.
A simple corrosion cell is shown in Figure 9. Oxidation, i.e., dissolution of a metal or
formation of a metal oxide, occurs at the anode. For steel, the anodic reaction involves the
production of ferrous ions (Fe
2+
) and electrons (e
-
) from iron metal (Fe).
Fe > Fe
2+
+ 2 e
-
FIGURE 9. CORROSION CELL
The oxidation reaction must be balanced by a reduction reaction in which the corrodant
accepts the electrons at the cathode. The primary cathodic reaction in cooling water is:
1/2 O2 + H2O + 2 e
-
> 2 OH
-
where oxygen (O2), water (H2O), and electrons combine to form hydroxide ions (OH
-
).
These two reactions can be combined and written as follows:
Fe + 1/2 O2 + H2O > Fe
+2
+ 2 OH
-
Further reactions often occur in water. Ferrous and hydroxide ions combine to form
ferrous hydroxide.
Fe
+2
+ 2 OH
-
> Fe(OH)2
Ferrous hydroxide can be further oxidized by oxygen to ferric hydroxide, which is
common iron rust.
2Fe(OH)2 + 1/2 O2 + H2O > 2Fe(OH)3
The function of a corrosion inhibitor is to slow the rate of one or more of these reactions.
Anodic inhibitors (e.g., chromate, nitrite, molybdate, orthosilicate, and phosphate) slow an
anodic reaction, i.e., the rate at which the metal is dissolved. They often form stable
gamma-Fe2O3 films on steel. A disadvantage of these inhibitors is that when they are
underfed, corrosion is severely localized in the form of pitting.
Cathodic inhibitors function by precipitating films of salts at locally high pH generated at
the cathodic site. These films are less protective than those generated by anodic inhibitors.
Examples of cathodic inhibitors are polyphosphates, polysilicates, and zinc. Inhibitors
which affect both cathodic and anodic reactions are termed mixed inhibitors.
Phosphonates are mixed inhibitors.
Factors Affecting Corrosion in Cooling Water
In cooling water, the rate of the corrosion is dependent on several variables which
includes the following:
pH: Low pH accelerates corrosion, generally the pH is maintained above 6.0 in
cooling water.
Temperature: High temperatures accelerate corrosion, the upper limit depends
on the composition of the water and inhibitor used.
Velocity of the water: Figure 10 gives the recommended velocities for water in
the tubes of shell and tube exchangers.
Concentration of the corrodant: e.g., dissolved oxygen.
Concentration of dissolved solids: Figure 11 shows corrosion increases with
increased dissolved solids.
Pretreatment and pre-filming of the metal surface can significantly decrease
corrosion rates.
Presence of scale, sludge, biological growths increase corrosion.
Dissimilar metals should be avoided.
m/sec ft/sec
Carbon Steel 1.8 to 3.0 6.0 to 10.0
Admiralty 1.2 to 2.4 4.0 to 8.0
Cupro nickel 1.2 to 3.6 4.0 to 12.0
FIGURE 10. RECOMMENDED COOLING WATER VELOCITIES
FIGURE 11. EFFECT OF DISSOLVED SOLIDS ON CORROSION RATE
Several forms of corrosion can occur in cooling water including uniform and local attack.
Local forms of attack include galvanic, pitting, crevice, and leaching corrosion.
Intergranular corrosion, transgranular corrosion, and stress corrosion cracking are also
possible. Microbiological corrosion, corrosion fatigue, and erosion-corrosion can also
occur.
The control of corrosion in cooling water is a complicated task involving mechanical and
chemical factors.
Corrosion Inhibitors
There are several general requirements for an effective corrosion control program.
Although the principle function of such a program is to protect the heat exchanger, it must
also protect the other surfaces exposed to the cooling water and should rapidly establish
corrosion control at low concentration. The treatment program should be effective under a
wide range of pH, temperature, heat flux, and water quality conditions. It should also be
forgiving of overfeed, the loss of feed, or other system upsets. Methods for easily
monitoring the concentration of the major components should be available. The corrosion
inhibitor must be compatible with other treatment components, e.g., the biocide and
antifoulant.
A variety of metallic, nonmetallic, organic, and inorganic chemicals are useful corrosion
inhibitors in cooling water systems. Often a cooling treatment program will consist of two
or more corrosion inhibitors along with other component(s) for control of scale, fouling,
or biological growth. Some additives serve more than one purpose.
The primary corrosion inhibitors used in cooling water are discussed in the following
sections.
Chromate
Chromates are the most effective corrosion inhibitors which protect both ferrous and
nonferrous alloys. They are anodic inhibitors which form a tenacious oxide film which
protects the underlying metal. Chromates are effective with the water temperatures up to
71 C (160 F), and over a wide pH range of 6 to 11. Cooling systems are rarely operated
above pH 10.
When used alone there is a critical chromate concentration necessary to maintain
protection which is dependent on the sulfate and chloride ion concentrations of the cooling
water. If underfed, attack is localized and manifested in the form of pitting. When used
alone (e.g., in a closed system), control can be maintained with 200 to 500 mg/l chromate
in the circulating water after an initial pretreatment of up to 1,000 mg/l. Naturally, the use
of such high doses is very costly. These high levels are only used in closed systems which
are seldom emptied.
Because of their toxicity and the expense of disposing of water treated with high doses,
chromates are used at about 5 to 25 mg/l CrO4, together with one or more other inhibitors,
such as zinc, phosphates, phosphonates, polymers, and others.
Addition of zinc is an excellent means of lowering the chromate usage. Zinc chromate has
become one of the most effective cooling water inhibitors. Zinc chromate is not a single
salt as the name implies, but a mixture of a zinc salt (usually chloride or sulfate) and
sodium dichromate. These ions exist as individual ions in solution without forming a
specific compound or intermediate. As little as 5 % of either ion in the presence of the
other shows great improvement over the performance of the major ion alone. Generally, a
blend of 20 % zinc and 80 % chromate is used. A typical dosage is 2 to 10 mg/l zinc and
up to 25 mg/l CrO4. The recommended pH range is 6.2 to 7. Above a pH 7.5, zinc
precipitates as the hydroxide, Zn(OH)2. Below 6.2, the protection of copper alloys
decreases. The pH range can be extended upwards with additives which prevent the
precipitation of zinc hydroxide.
Protection is established very quickly with zinc chromate when there is free access to the
surface. Old corrosion products and deposits impede the development of protection. Zinc
chromate protects copper alloys and aluminum. It inhibits the galvanic attack of Al
coupled to Cu and lowers the corrosivity of dissolved Cu ions.
The dosage of most chromate containing inhibitors is controlled by monitoring the
chromate level. High concentrations (10 to 100 mg/l as CrO4) can be detected by titration
with thiosulfate. Low concentrations (less than 30 mg/l) can be detected colorimetrically
by the reaction of chromate with diphenylcarbazide.
To lower the dosage of chromate required in order to maintain the protection of cooling
systems and to introduce deposition control, polyphosphates and zinc have been used
together with chromate. A typical dosage would be 10 to 25 mg/l CrO4, 2 to 5 mg/l
polyphosphate, and 2 to 5 mg/l zinc. Phosphonates also enhance the performance of zinc
chromate by providing threshold inhibition of calcium carbonate, calcium sulfate
precipitation, and adding detergency to decrease deposits and debris. Phosphonates also
allow excursions above pH 7.5 since they stabilize zinc hydroxide. In addition, they do
not have the drawback of polyphosphates, i.e., possible zinc and calcium phosphate
precipitation.
Zinc
The zinc cation (Zn
+2
) is a powerful cathodic inhibitor used in cooling water. It is seldom
used alone and is commonly used in combination with chromates, phosphates,
phosphonates, molybdate, and other anodic inhibitors. The addition of zinc often allows
the decreased use of the anodic inhibitor with increased corrosion protection. Control of
pH and/or the use of zinc stabilizers are required with zinc to prevent the precipitation of
zinc salts at high pH.
Orthophosphates and Polyphosphates
Phosphate has been used as a corrosion inhibitor in cooling water for many years. Before
the late 1970s phosphate was used in combination with chromate and/or zinc. Various
phosphates in combination with nonmetals have become widely used in cooling water
because of increasing restrictions on heavy metal usage. Modern phosphate programs
provide excellent corrosion control under certain conditions in cooling water. However,
these programs are more expensive than chromates, require greater control of operating
parameters, and require the continuous feed of dispersants to prevent the deposition of the
calcium phosphate scale in the heat exchangers.
Several forms of phosphates are used for corrosion control in cooling water, including
orthophosphate, polyphosphates, phosphonates, and other organic phosphates.
Orthophosphate (PO
4
-3) is an inorganic anion which is primarily an anodic inhibitor.
Orthophosphate exists in aqueous solution in interchangeable forms depending on the pH.
Phosphoric acid (H3PO4) predominates below pH 2, and the tribasic ions (PO4-3)
predominates above pH 12. At these extremes steel is not protected. In the pH range of
interest in cooling water, pH 6 to 8.5, both the monobasic (H2PO4-) and the dibasic
(HPO4-2) forms are present and are effective corrosion inhibitors.
Orthophosphates are anodic inhibitors which require a divalent cation, commonly calcium
or zinc, to be effective. The calcium concentration must be at least 50 mg/l as CaCO3;
therefore the orthophosphates are not useful in softened water, demineralized water, or
steam condensate. When zinc is used in conjunction with phosphate, typically 0.5 to 1.0
mg/l soluble zinc is sufficient to maintain corrosion control with approximately 6 to 10
mg/l orthophosphate at pH 7.3 to 7.8.
The mechanism of corrosion inhibition of steel with phosphate is not clear. However, it is
known that oxygen, calcium, or zinc and phosphate are required. It is thought that
dissolved oxygen reacts slowly with steel to form a thin film of gamma-Fe2O3. During the
production of this film, precipitation of iron or calcium phosphate occurs at voids in the
film. These precipitates are not completely protective, and allow the gradual formation of
a protective iron oxide film. Zinc ions are thought to inhibit corrosion by precipitating zinc
hydroxide or phosphate at the cathodic sites due to locally elevated pH. These precipitates
also form protective films.
Protection by orthophosphate is sensitive to the water quality, pH, oxygen, and the
chloride concentrations. A minimum orthophosphate concentration is required depending
on these variables. Below this minimum level pitting attack occurs.
Polyphosphate is a generic term for a variety of materials formed by dehydrating and
polymerizing orthophosphates. Polyphosphates are cathodic inhibitors on steel. Some
sodium polyphosphates frequently used in water treatment are shown in Figure 12.
FIGURE 12. SODIUM POLYPHOSPHATE
Polyphosphates slowly decompose or revert to orthophosphates in cooling water. This
reversion can be accelerated by low pH and high temperatures. It is catalyzed by certain
metal ions and enzymes. In cooling water the half-life of polyphosphates typically ranges
from several hours to two days. Polyphosphates revert instantaneously at boiler
temperatures and are sometimes used as a source of orthophosphate.
Polyphosphate can be considered both an anodic and cathodic inhibitor, although it is
generally considered the latter. It requires both calcium or zinc and oxygen like
orthophosphate. In cooling water 10 to 15 mg/l polyphosphate as PO4 is normally
maintained after an initial pretreatment of at least twice this dosage for a few days. When
copper alloys and steel are present, the pH should be maintained higher than about 7.0.
Unfortunately, orthophosphate is an excellent nutrient for the growth of bacteria; chlorine
and/or other biocides are often required.
Polyphosphates will minimize normal galvanic corrosion. They are ineffective when
cathodic metals (e.g., copper) are deposited on more anodic metals (e.g., carbon steel).
Operation below pH 7.0 aggravates this problem. The use of a copper-specific inhibitor is
required to alleviate this problem.
Polyphosphates are useful for the prevention of CaCO3 and CaSO4 scales formation. They
also stabilize dissolved iron and manganese in well water and are approved for use in
potable water up to 10 mg/l.
In cooling towers polyphosphate is often used with chromate, zinc, and phosphonates. It is
low cost, nonhazardous, and nontoxic. It is an effective alternative to chromate, although
it has more restraints and requires more control.
Nitrite
Nitrite, commonly used as the sodium salt (NaNO2), is an anodic inhibitor which generates
protective gamma-Fe2O3 on carbon steel. Nitrite is effective when oxygen is not present. It
is frequently used in closed systems not exposed to air. Often, borate is added to buffer the
pH at about 9. Copper alloy inhibitors and dispersants may be added to complete the
program. Unlike chromates, nitrites are compatible with glycols which are added as an
anti-freeze or raise the boiling point of the water in hot systems. Typically, 300 to 500
mg/l NO2 is required. The precise level is dictated by the chloride and sulfate
concentrations. Often, excess nitrite is used since closed systems are not monitored
frequently.
Nitrite is seldom used in cooling towers since it is decomposed by bacterial action and air
oxidation to nitrate (NO3-
).
Nitrite is easily monitored by titrating it against a standard oxidizing agent, potassium
permanganate. Biological activity should also be monitored with nitrite.
Silicates
Silicates are useful corrosion inhibitors in mildly corrosive systems. They form a weak
chemi-sorbed film on carbon steel. The development of protection is slow, and it does not
require hardness to be present in the water in order to be effective.
Like phosphates, various silicates are available ranging from simple ionic forms, such as
salts of silicic acid (H2SiO2), to complex colloidal ions with variable compositions of the
form nNa2O-mSiO2. An m/n ratio of 2.5 to 3 is most effective.
Silicates are most effective when used at a level of 25 to 40 mg/l SiO2 at pH 8 to 9.5 in
water with low salt concentrations (less than about 500 mg/l TDS); that is, under mildly
corrosive conditions. Silicates are not generally recommended for cooling tower systems,
but are suitable for some closed systems. Water with a high magnesium content must be
avoided because magnesium silicate scale forms when the magnesium concentration
exceeds approximately 150 mg/l as CaCO3.
Silicates can be used for the control of dissolved iron and manganese in potable water
systems at a level of 10 mg/l SiO2. It is an economical, nontoxic, nonhazardous option for
mild corrosion problems.
Molybdate
Sodium molybdate (Na2MoO4) forms passive anodic iron oxide films on steel. It is a
weaker oxidant than chromate and requires an oxidant, either oxygen in open systems or
nitrite in closed systems, to form a protective film. It is an environmentally acceptable
alternative to chromate, although less effective and slower acting.
In cooling tower systems high molybdate concentrations (e.g., 1,000 mg/l) are required if
it is to be used alone. Cost of such high doses are prohibitive. Typically, a molybdate
formulation for a cooling tower system might provide 8 to 15 mg/l Mo, 2 mg/l Zn
+2
, 1 to 5
mg/l phosphonate and similar levels of a dispersant and/or copper inhibitor. Unlike other
nonchromate inhibitors molybdate does not require hardness in the water; it is useful in
systems where the water is naturally soft or where condensate is used for make-up.
Molybdate formulations have also been used to protect reactor jackets which are exposed
to both cooling water and water heated with steam intermittently. Higher concentrations
are necessary in these systems.
In closed systems, molybdate-nitrite formulations have been used at lower nitrite
concentrations than classical nitrite-borate treatment levels of 300 to 500 mg/l NO2.
Molybdate can be monitored by a colorimetric method using mercaptoacetic acid.
Phosphonates
Phosphonates are a class of organic phosphorous compounds containing a carbon atom
directly bonded to a -PO3 group, which gives them greater hydrolytic stability than
polyphosphates. Three phosphonates commonly used in water treatment are shown in
Figure 13. The complete chemical name and common abbreviation follow: nitrilotri-
(methylene-phosphonic acid) or AMP, hydroxy-ethylidene-1, 1-di(phosphonic acid) or
HEDP, and 2-phosphono-butane-1,2,4-tricarboxylic acid or PBTC. They are only
marginally effective corrosion inhibitors when used alone under mild conditions.
However, they are very useful in conjunction with chromate, zinc, and polyphosphates in
open and closed systems.
O
II
P
I
OH CH
I
C
OH
3
OH
I
P
II
O
HO OH
HEDP
HO-P-OH HO-P-OH HO-P-OH
CH
2
N
O O O
AMP
CH C OH
2
C
CH
2
2
O
C
O
OH
O
O
P
OH
HO
PBTC OR PBSAM
CH
2
CH
2
I
CH C OH
FIGURE 13. PHOSPHONATES USED IN WATER TREATMENT
AMP, HEDP, and PBTC have the added advantage in that they control calcium carbonate
and sulfate deposition. They also stabilize iron and manganese which otherwise would
cause fouling. Many proprietary iron dispersants will contain HEDP and a polymeric
component. Phosphonates also extend the pH range over which zinc is soluble, which
makes zinc containing formulations more useful. One disadvantage of phosphonates is
that, due to their strong interaction with copper ions, they accelerate the corrosion of
copper alloys when used at high concentrations. Often they require the use of a copper-
specific inhibitor in mixed systems.
AMP is degraded by high doses of chlorine. HEDP is sufficiently stable under most
chlorinating conditions. PBTC is the most stable.
The phosphonate is oxidized to orthophosphate for monitoring, which is detected using
the conventional ortho procedure. If present, poly and orthophosphates interfere and must
be determined separately and subtracted from the total orthophosphate determined in the
phosphonate test.
Copper Alloy Inhibitors
Three organic compounds are used as copper-alloy inhibitors in cooling water. They are
TTA, BZT, and 2-MBT, as shown in Figure 14. These materials form strong complexes
with copper ions in solution and films on the surfaces of copper alloys. They offer little
protection to ferrous metals and are affected adversely by chlorination. 2-MBT is the most
readily oxidized and the inhibition is rapidly lost. The protection by TTA and BZT lapses
temporarily after chlorination and then returns after the chlorine dissipates. It is thought
that a reversible chlorine adduct is formed with the triazoles, which reverts to the triazole
when the chlorine dissipates. Copper inhibitors are generally used at about 2 mg/l. They
are all sparingly soluble in water, except at high pH where the soluble sodium form exists;
therefore, they are supplied as liquids at high pH.
N
N
N
N
N
N
-
Na
+
H C
3
TOLYLTRIAZOLE, TTA
BENZOTRIAZOLE, BZT
MERCAPTOBENZOTHIAZOLE, 2-MBT
N
S
SH
N
FIGURE 14. COPPER ALLOY INHIBITORS
Nonchromate Cooling Tower Treatment Packages
There are three generic, nonchromate chemical cooling water treatments used as typical
alternatives to chromate programs. These treatments include combinations of the
inhibitors and dispersants for control of corrosion, scale formation, and fouling in cooling
towers. Copper corrosion inhibitors and a biocide are frequently part of the total treatment
program.
In well-designed, well-operated systems with close control of water chemistry and
inhibitor injection these treatments effectively control corrosion, scaling, and fouling. In
all these treatments pH/alkalinity control is critical. At pH values below the recommended
operating range corrosion will occur. Above the range, scaling will be a problem. Oil
ingress is the most common operating upset which can foul the system and interfere with
biological and corrosion control in refineries.
Corrosion is mitigated by pH control in combination with continuous injection of
corrosion inhibitor. Scaling is controlled by pH adjustment and continuous injection of
chemicals to either inhibit scale formation or disperse scale deposits after formation.
Fouling is controlled by intermittent or continuous use of polymeric dispersants. The
microbiological control program is often based on chlorination. These programs require
close control of the inhibitor injection rate and the cooling water chemistry limits. Typical
guidelines for each type of treatment are given in Figure 15. General guidelines which
apply to water quality in most cooling tower systems are given in Figure 16.
FIGURE 15. TYPICAL NON-CHROMATE COOLING WATER PROGRAMS
FIGURE 16. GENERAL COOLING CHEMISTRY GUIDELINES FOR NON-
CHROMATE INHIBITORS
Monitoring Corrosion
Corrosion should be monitored in major cooling water systems with either coupons or
probes. A coupon rack placed on the hot water return is shown in Figure 17. Guidelines
for assessing corrosion rates in cooling water are given in Figure 18. The corrosion rates
given are for uniform corrosion. Low rates of pitting are acceptable on carbon steel, but
are not acceptable on copper-alloys or stainless steels.
FIGURE 17. COOLING WATER CORROSION TEST LOOP (OPEN-
ENDED DISCHARGE INSTALLATION)
Metal
Corrosion Rate
mils/yr Comment
Carbon Steel 0 - 2 Excellent corrosion resistance
2 - 3 Generally acceptable for all systems
3 - 5 Fair corrosion resistance; acceptable
with iron fouling-control program
> 5 Unacceptable corrosion resistance:
Migratory corrosion products may
cause severe iron fouling
Admiralty Brass 0 - 0.2 Generally safe for heat- exchanger
tubing and mild-steel equipment
0.2 - 0.5 High corrosion rate may enhance
corrosion of mild steel
> 0.5 Unacceptable high rate for long term;
significantly affects mild-steel
corrosion
Stainless Steel 0 - 1 Acceptable
> 1 Unacceptable corrosion resistance
FIGURE 18. GUIDELINES FOR ASSESSING UNIFORM CORROSION IN
COOLING WATER
Avoiding Galvanic Corrosion
Because seawater and most cooling waters are good electrolytes, severe corrosion can
occur when different metals are coupled together. The degree of attack depends on the
relative position of the two metals in the galvanic series and on the relative size of the
components. The alloys at the top of the series are more prone to corrosion than those
below them. Large differences in potential drive the corrosion. The worst case occurs
when the anode component (metal which corrodes) is small, and the cathode component
(protected metal) is large. An abbreviated list of the galvanic series in seawater is shown
below:
Active Metals (Anodic):AluminumCarbon steelNaval rolled
brassCopperAdmiralty brassCopper-Nickel alloysTitaniumHastelloy CMonel
400Type 300 series Stainless Steels (passive)
Noble Metals (Cathodic)
One way to avoid galvanic attack is to electrically insulate the metals from each other.
The following list gives examples of metal couples that should be avoided in seawater:
Magnesium: Low alloy steel causes attack of magnesium and danger of hydrogen
damage on the steel.
Aluminum: Copper causes pitting of Al and copper ions also attack the Al.
Bronze: Stainless steel causes pitting of bronze.
The following couples are borderline and have occasionally presented problems:
Copper - Solder
Graphite - Titanium or Hastelloy C
Monel 400 - Type 316 SS
The following couples are generally compatible:
Titanium - Inconel 625
Lead - Cupronickel
Precleaning and Pretreatment
Corrosion control in cooling water is based on forming a film on the metal surface which
protects the underlying metal. The rate at which the film or barrier forms will largely
determine the effectiveness of the treatment. Materials that do not form films rapidly will
permit corrosion to take place. The result will be incomplete film formation and continued
corrosion. The rate at which the film forms is related to the inhibitor concentration, the
temperature, and cleanliness of the metal.
The function of pretreatment is to permit rapid formation of a uniform, impervious film.
After a film is formed, the lower, normal treatment levels will keep the film intact and
avoid the accumulation of corrosion products.
For new systems or heavily fouled systems, precleaning is usually necessary prior to
pretreatment. Precleaning may require high concentrations of inhibited acids, chlorine,
and/or detergents specifically designed to remove the deposits present. Laboratory testing
is recommended to choose the proper precleaning procedure for a particular system.
After cleaning, a system is flushed and filled with water containing a pretreatment
product. This may simply be the inhibitor to be used at a high dosage to be maintained up
to one week. More effective pretreatment is possible with high doses of surfactant and a
polyphosphate. The treatment is time, concentration, and temperature dependent. Figure
19 shows three typical pretreatment procedures for carbon steel.
FIGURE 19. DOSAGE Mg/L PO4 /TIME/TEMPERATURE
Laboratory corrosion rate measurements at 49 C (120 F) with untreated specimens in
raw water (A) and with untreated (B) and pretreated (C) specimens in treated water are
shown in Figure 20. These experiments clearly demonstrate the benefits of pretreatment.
FIGURE 20. EFFECTIVENESS OF PRETREATMENT IN DECREASING
INITIAL CORROSION RATES
PREVENTION OF SCALE FORMATION IN COOLING WATER
Several forms of deposits can occur in cooling systems including scale formation,
biological fouling, and general fouling. Deposition of such materials may result in
plugging, loss of cooling, and underdeposit corrosion.
Scale formation is characterized by the formation of insoluble inorganic compounds. This
occurs by the precipitation of slightly soluble ions such as calcium, magnesium, or zinc
together with carbonate, sulfate, phosphate, hydroxide, or silicate.
Scale formation is different from fouling. Fouling can be either general or microbiological
in nature. General fouling is caused by the settling of any suspended matter such as iron
oxides, silt, mud, oil, and other debris. Microbiological fouling results from the growth of
algae, bacteria, or fungi.
Effect of Scale on Heat Transfer
In a heat exchanger, thermal energy is usually transferred by conduction from a process
fluid across a metal barrier to the cooling water. In conduction, heat is transferred through
or between stationary media such as metals, water, or air. It results from short range
interactions of molecules and/or electrons. In the metals, electrons contribute to this
process. In gases and liquids, energy is also conducted by molecular collisions. The heat
transferred (Q) across a flat plate by conduction is described by the following equation:
Where
Q = heat transferred, Btu/hr
K = thermal conductivity, Btu/hr F
A = cross sectional area, ft
2
t2-t1 = temperature difference across the plate, F
L = thickness of the plate, ft.
From this equation, it follows that thin plates made from materials with high thermal
conductivities, e.g., metals, are the best conductors of heat. Scales and fouling deposits
have lower thermal conductivities than metals and effectively increase the thickness and
lower the thermal conductivity of the barrier.
The basic equation for a steadily operated exchanger follows, in which U is the overall
heat transfer coefficient and the dT and dt values are the terminal temperature differences
for the process and watersides. In this simple case we are assuming constant U, constant
mass flowrates, no changes in phase, constant specific heats, and negligible heat loss.
Q = U A dTm
where
Q = Heat transfer rate, Btu/hr
U = Heat transfer coefficient Btu/hr ft
2
F
A = Heat transfer surface area, ft
2
dTm = Log mean temperature difference, F
where
dT = T2 - t1, dt = T1 - t2
t1 = Inlet water temperature, F
t2 = Outlet water temperature, F
T1 = Inlet process temperature, F
T2 = Outlet process temperature, F
The rate of heat transfer from the process to the cooling water is proportional to the mass
flow rate of the material, its heat capacity, and the temperature change the material
undergoes. Since we are neglecting heat losses:
Q = Mw Cpw (t2-t1) = Mp Cpp (T1-T2)
where:
Mw, Mp = mass flow rates for water and process, lb/hr
Cpw, Cpp = heat capacity of the water and process, Btu/hr F
Heat capacity is an intrinsic property of a material. Tables of heat capacity data can be
found in chemical handbooks. The heat capacity of pure water is 1.00 Btu/lb F, by
definition.
When an exchanger is designed, a design heat transfer coefficient, UD, can be calculated.
After being put in service, an actual heat transfer coefficient (UA) can be calculated using
these equations. The fouling factor (Rf) is the difference between the reciprocals of the
actual and designed coefficients.
The fouling factor is the resistance to heat flow caused by fouling. Plotting the fouling
factor over time is a useful way to monitor the amount of fouling occurring in an
exchanger. If the factor increases, the system is becoming fouled. A general rule of thumb
for fouling factors is that when they are on the order of 0.001 to 0.002 hr ft
2
F/Btu, the
system is clean. If the factor is greater than 0.005, the system is fouled.
Scales Formed in Cooling Water and Their Prevention
As water evaporates in an open-evaporative system, the inorganic salts naturally present in
the water and those added for corrosion control increase in concentration. Consequently,
the tendency for many of these ions to precipitate from solution increases, resulting in
scale formation.
The rate of scale formation depends on temperature, alkalinity or acidity of the water, the
velocity of the water, and other factors as well as the concentration of the scale-forming
ions. Calcium carbonate, calcium sulfate, calcium phosphate, and magnesium silicate are
the scales most likely to form in open-evaporative systems.
Calcium Carbonate Scale
Calcium carbonate is the most common scale found in cooling water systems. It forms
when the calcium hardness and bicarbonate alkalinity, naturally present in water, are
concentrated and/or are subjected to increased pH and temperature.
Ca
+2
+ CO3-2
> CaCO3 (solid)
In 1936, Langelier published a formula for calculating the tendency of water to either
deposit or to dissolve the calcite form of calcium carbonate. The formula expresses the
effect of pH, calcium, total alkalinity, dissolved solids, and temperature on the solubility
of calcium carbonate for water from pH 6.5 to 9.5. The equation is:
pHs = (pK2 - pKs) + pCa + pAlk
where pHs is the pH value at which water with a given calcium content and alkalinity is in
equilibrium with calcite. The terms pK2 and pKs are the negative logarithms of the second
dissociation constant for carbonic acid and the calcite solubility product constant. The last
two terms are the negative logarithms of the molar and equivalent concentrations of
calcium and titratable alkalinity. The Langelier Saturation Index (LSI) is a qualitative
index of the tendency of calcium carbonate to deposit or dissolve, expressed as the
following equation:
LSI = pH - pHs
A simple formula for calculating LSI is given in Figure 21. A positive LSI indicates a
tendency to deposit calcite. A negative LSI indicates an undersaturation condition exists;
therefore, solid calcite will dissolve. If LSI = 0, the water is in equilibrium with respect to
calcium carbonate saturation.
FIGURE 21. LANGELIER-RYZNAR INDEX CALCULATIONS
The LSI is a measure of the directional tendency or driving force of a water towards
calcite formation. It is not a reliable indicator of the corrosivity of a water. It is possible
that two waters, one with low hardness which is corrosive, and the other with high
hardness which is not corrosive, can have the same LSI. In an attempt to develop a
quantitative indicator of the corrosive nature of water, Ryznar proposed the empirical
Ryznar Stability Index (RSI) defined as follows:
RSI = 2 (pHs) - pH
RSI < 6 Scaling tendency increases as the index
RSI > 7 Calcite formation may not lead to a protective corrosion inhibitor film
RSI > 8 Mild steel corrosion becomes an increasing problem
Calcium Sulfate Scale
Calcium sulfate is more soluble than calcium carbonate. Like calcium carbonate, calcium
sulfate is less soluble in low pH waters. In cooling water, calcium carbonate will often
deposit before calcium sulfate.
The following rule of thumb can be used to estimate the safe upper limit of calcium and
sulfate concentrations in many cooling waters in the absence of treatment chemicals.
(Ca
+2
) (SO4-2
) < 500,000
The product of the ionic concentrations (mg/l) must not exceed 500,000 or precipitation
will occur. When high levels of dissolved solids are present or treatments are used, this
limit can be exceeded.
Calcium Phosphate Scale
Deposition of calcium phosphate is a potential problem in cooling water treated with
phosphate-based corrosion inhibitors. It forms a dense, difficult-to-remove scale. In the
absence of a specific polymer to control precipitation, if the calcium hardness is 500 mg/l,
as little as 5 mg/l orthophosphate will cause deposition if the pH exceeds about 7.5. For
this reason, phosphate-based inhibitors were limited to pH 6.5 to 7.2 until effective
calcium phosphate deposit control polymers were developed.
The most common of these agents in use today are poly (acrylic-acid-co-hydroxypropyl
acrylate) (AA/HPA), poly (maleicanhydride-co-sulfonated styrene) (MA/SS), and poly
(acrylic acid-co-AMPS) (AA/SA). These copolymers allow the use of phosphate-based
inhibitors at pH values up to 9.0.
Magnesium Silicate Scale
Magnesium silicate is another dense, difficult-to-remove material. There are no additives
which readily inhibit its deposition. To prevent it from forming, the silica content of the
circulating water should be limited to less than 150 mg/l as SiO2 at neutral pH values. At
pH 8.5, 200 mg/l SiO2 is soluble. The solubility is proportional to temperature; therefore,
this scale forms in the colder regions of the system.
Effect of Water Chemistry, Temperature, and pH
There are several methods for preventing calcium carbonate scale. Removing or
decreasing the concentration of the calcium or magnesium by softening, ion exchange, or
other means is seldom economical except for closed systems. Decreasing the pH by acid
addition is commonly used to prevent calcium carbonate and phosphate scale formation.
The use of polyphosphate, phosphonates, polyacrylates, and other copolymers will
decrease calcium carbonate, sulfate, and phosphate formation. A list of treatments that are
commonly used for the control of scaling and fouling is given in Figure 22. Often, two of
these materials are used in a blend that is more effective than the individual materials. For
example, it is common to use a phosphonate (e.g., HEDP) together with a polymer or
copolymer as a general scale control agent.
Treatment
Calcium
Carbonate
Calcium
Sulfate
Calcium
Phosphate
Iron
Oxide
Zinc
Hydroxide
Suspended

Matter
Oil
pH Control H E H - H - -
Phosphonates H E E H - -
Polyacrylates E H E E H -
Polyphosphates H E H - - -
Polyamaleic acid H - E -
Polyamaleic acid
Copolymers
H H H -
Phosphinocarboxylic
acids
H H E H E -
Poly(Maleic
Anhydride-co-Sulfonated
Styrene)
E E H H H -
Poly(Acrylic
acid-co-Hydroxypropyl-
acrylate)
E E E H H -
Poly(Acrylic
acid-co-AMPS)
E H H H H -
Phosphonobutane-
tricarboxylic acid
H H - E H - -
Surfactants - - - - - - H
Notes:

H = Highly Effective
E = Effective
- = Low Effectiveness or Ineffective

AMPS is 2-acrylamido-2-methylpropylsulfonic acid
E
E
E
E
E
E
E
E
FIGURE 22. WATER TREATMENT CHEMICALS FOR SCALE AND FOULING
CONTROL
Figure 23 summarizes the effects of water composition, temperature, pH, and the
effectiveness of dispersants in the control of scale formation in cooling water.
Increase in
Concentration of
Scaling Ions Causes
Temperature
Increases Causes
pH Increases
Causes
Dispersants
Effective?
Calcium Carbonate + + + Yes
Calcium Sulfate + + N Yes
Calcium Phosphonate + + + Yes
Magnesium Silicate + - - No

+ : Increase in scale formation
- : decrease in scale formation
N : no effect
FIGURE 23. EFFECTS OF PROCESS VARIABLES ON SCALE FORMATION
Prevention of the Harmful Effects of Microbiological Growth in Cooling Water
Cooling water systems, particularly open-recirculating systems, offer a favorable
environment for growth of microbiological organisms leading to deposition, fouling, and
corrosion. Microbiological masses, generally referred to as slime deposits, result from the
accumulation of algae, fungi, or bacteria and their excretions. These masses can trap
debris and sediment, cause plugging of lines, reduce heat transfer, and cause corrosion by
creating differential oxygen concentration cells or generating corrosive by-products or
environments. Biofouling refers specifically to fouling caused by plants or animals when
such organisms attach themselves to materials submerged in the water.
Microbiologically influenced corrosion (MIC) has been reported on iron, carbon, steels,
stainless steels, copper alloys, aluminum, and aluminum alloys. Although it is probably
widespread in the petroleum and chemical industries, less technology is available for
combating MIC compared to traditional forms of corrosion. Control of biofouling can be
maintained by mechanical and chemical means.
Microorganisms Responsible for Biofouling
Algae, fungi, and bacteria may exist in a cooling system and result in fouling when
uncontrolled.
Algae are photosynthetic organisms, relatively large, sometimes motile (able to move
about) and usually colored. As a group, they can tolerate from very little to high intensity
light, a pH range of 5.5 to 9.0, temperatures from -18 to 40 C (0 to 104 F), and a wide
range of salinities. They require only light, water, air, and a few inorganic nutrients for
growth. Algae are widely recognized for the severe fouling problems created by their
stringy green slime masses which can reduce heat transfer and even plug tubes. They also
provide the food necessary for the growth of higher organisms such as bacteria and fungi.
Fungi include yeasts and molds. Yeasts are not important in the corrosion of metals, but
are important in the deterioration of wood. Molds are a diverse group which require
oxygen and organic materials for growth. They can contribute to white rot or brown rot of
cooling tower wood.
Bacteria found in a system can be varied and include spore-forming, nitrifying, nitrogen-
fixing, denitrifying, sulfate-reducing, iron, sulfur bacteria, and others. They are universally
found in nature and usually do not require light for growth. Bacteria are motile, allowing
them to seek favorable environments. They generally thrive from about 21 to 46 C (70 to
115 F), although some have been found from -10 to 100 C (14 to 210 F). Thermophilic
bacteria grow in higher temperature waters and are found on heat exchanger surfaces. The
preferential pH range is 5.5 to 8.5, but certain types have been reported from about pH 0
to 10.5.
General guidelines for allowable levels of total bacteria count, corrosive or iron depositing
bacteria, fungi, and algae in a cooling system are given in Figure 24. Obviously, a
complete microbiological analysis of a system is required to determine the counts of these
different organisms present. Such an analysis is recommended if a severe biofouling
problem is suspected. Figure 25 gives general guidelines for interpreting a general cooling
water biocount. These analyses indicate the concentration of organisms in the water, i.e.,
the planktonic organisms. This is generally useful, but not always. Of greater interest are
the organisms which are attached (sessile) to heat transfer surfaces. A biofouling monitor,
or simply the presence of slime on coupons, are more direct methods of identifying
problems.
Constituent Unit Limit
Total bacteria count Colonies/ml 500,000
Bacteria (corrosive) or
iron depositing
Colonies 0
Fungi 100
Algae Few
FIGURE 24. MICROBIOLOGICAL GUIDELINES FOR NON-CHROMATE
INHIBITORS
Count Range (colonies/ml) Significance
0 - 10,000 Essentially sterile
10,000 - 500,000 System under control
500,000 - 1,000,000
System may be under control
but should be monitored.
1,000,000 - 10,000,000
System out of control -
requires biocide.
Over 10,000,000
Serious fouling may be occuring -
immediate biocide addition required.
FIGURE 25. SIGNIFICANCE OF A BIOLOGICAL COUNT IN COOLING
WATER
Chemicals for Control of Biofouling
Many variables influence the biological development and growth process. Treatment of
each system should be considered individually, and different programs may be required
for different seasons of the year. Selection of a biocide and dosage should ideally be based
on a comprehensive biological survey. Often, this is not feasible, and a multicomponent
approach is used. In the past, chromates were effective in controlling biological deposits
and some, sulfate reducers in particular, could not exist where even a trace of chromate
was used. However, with the change to nonchromate (particularly phosphate-based
treatments), the need for biological control is crucial for success of the overall program.
Toxicants for biological control are normally classified as either oxidizing or
nonoxidizing.
Oxidizing Biocides
These are compounds which, in addition to their disinfection action, chemically oxidize
constituents of the water. Chlorine gas is the most commonly used oxidizing biocide.
Chlorine is widely used because of its effectiveness under many conditions and its low
cost. A free residual of 0.2 to 1.0 mg/l usually destroys most organisms in only minutes.
Using less than 1 mg/l chlorine on an intermittent basis should not damage cooling tower
wood. However, higher doses or continuous doses at more than 1 ppm may be
detrimental. Oil, reducing agents (e.g., H2S), and organic debris are oxidized by chlorine,
creating high chlorine demand and decreasing the attack on microorganisms.
The effectiveness of chlorine is pH dependent. In water, chlorine gas forms hypochlorous
acid and hydrochloric acid. The latter is not an effective biocide. The former is effective,
but dissociates to the less effective hypochlorite ion as the pH increases above about pH
7.5.
Bromine and bromine-donating compounds are more effective in the high pH range than
chlorine. Bromine can be generated in-situ by the reaction of chlorine and bromide.
Bromochlorohydantoins are another source of bromine. The latter are solids and eliminate
the potential hazard of chlorine gas.
Chlorine dioxide and hypochlorite compounds are other oxidizing biocides. Ozone is
another, which is not frequently used in cooling water.
Nonoxidizing Biocides
A wide variety of generic and proprietary nonoxidizing biocides are available. Some of
the more commonly used compounds are listed in Figure 26. They differ in effectiveness,
dosage, and contact time required, compatibility with other treatment chemicals, and other
factors. The proper biocide should be selected after obtaining a sample of the mass to be
treated, homogenizing it, and testing the candidate biocides. Dosing should be systematic
and results monitored by organism counts, biofouling monitors, or heat transfer
coefficients.
Active Compound Type/Effectiveness Compatibilities
Glutaraldehyde Broad spectrum non-oxidizing.
Good against SRBs
Control test available
Resistant to chlorine.
Very good at high pH.
Ammonia and primary amines
incompatible.
Isothiazolins Broad spectrum
Non-oxidizing
Good against SRBs
Low dosage required
Probably most likely to be
effective.
Incompatible with more than 1
mg/l chlorine.
Methylene bis(thiocyanate) Broad spectrum
Non-oxidizing
Good against SRBs
Incompatible with chlorine and
pH > 8.0.
Quaternary amines (Quats) Broad spectrum
Non-oxidizing
Oil, debris, amonia
dispersants and high
hardness are incompatible.
Not effective in heavily fouled
systems.
Foaming.
Tri-n-butyl tin oxide
(TBTO)-Quaternary amines
Effective against algae,
molds, wood rot.
Non-oxidizing.
Same as Quats.
Ecologically questionable due
to heavy metal.
Foaming.
Calcium hypochlorite (HTH) Broad spectrum
Oxidizing
Oil and reducing agents create
demand, less effective at pH >
7.8.
Bromochlorohydantoins Broad spectrum
Oxidizing
Control with chlorine tests.
Alternative to chlorine at high
pH, in small systems.
Ineffective in heavily fouled
systems.
Carbamates Broad spectrum
Non-oxidizing
Slow acting, high dosages,
best at high pH.
Incompatible with chlorine and
chromate.
Dibromonitrilo-propianamide
(DBNPA)
Oxidizing.
Not effective against algae.
High dosages often
necessary.
Not recommended in fouled
systems and at pH > 7.5.
Thermal instability.
Copper Salts Algicide for cooling ponds. Corrosion of steel possible,
environmentally restricted.
FIGURE 26. PROPERTIES OF COMMON BIOCIDES
Surfactants
It is often useful to precede the shot dose of biocide with an effective biodispersant, which
enhances the ability of the biocide to penetrate and kill the organisms. Surfactants or
surface active agents are effective biodispersants.
Mechanical Means for Control of Biofouling
Maintaining proper flow velocity, backflushing, screening, filtration, and air-bumping are
mechanical means of removing macroorganisms and microorganisms. In certain instances,
thermal backwash has been used to kill macroorganisms in their juvenile stage. Just as
surfactants aid the ability of the biocide to penetrate the biomass, mechanical means of
disrupting the slimes also increase the effectiveness of the toxic chemicals.
Biofouling Monitors
The vast majority of bacteria in a cooling water system are sessile, i.e., attached to
surfaces. It is believed that in a typical system there may be 1,000 to 10,000 sessile
organisms for every planktonic (free floating) organism. This observation has led to the
development of biofouling monitors. The basic design of the most popular monitor is
shown in Figure 27. The principle of operation is quite simple. As a biofilm develops in a
piece of tubing, an increased pressure drop develops across the tubing if the flow rate is
held constant. The pressure drop is monitored and any increase is an indication of fouling.
Treatment which removes the biofilm will restore the pressure drop to the initial, clean
level.
FIGURE 27. BIOFOULING MONITOR
In addition to the biofouling monitor, fouling monitors developed by organizations such as
NACE and the water-treatment vendors are available. They involve the measurement of
heat flux through a heat-transfer surface, under water-velocity, and temperature conditions
matched to the systems heat exchangers. The decay of the overall heat transfer coefficient
(U) can be monitored with time and generally corrosion rates can also be recorded.
Since it is difficult to match conditions in the exchanger accurately, results from fouling
monitors may be ambiguous. They will indicate extremely clean or fouled conditions, but
require analysis by an experienced observer in many intermediate cases.
Prevention of Macrofouling by Jellyfish, Mussels, Etc.
Plant and animal life may contribute to both fouling and corrosion in seawater cooling
systems. The two basic types of animals are the soft plant-like slimes: bacteria, algae
and hydroids, and the hard (shell-like) organisms: barnacles, mussels, oysters, tube
worms, and sea squirts.
The tendency of such organisms to adhere to materials submerged in seawater depends on
the nature of the material itself as to the resultant manifestations of corrosion, scaling,
plugging, etc.
Metals and alloys that produce toxic salts (e.g., copper, lead, and zinc) resist hard-fouling
by barnacles and the like, although they may accumulate soft-fouling organisms under the
same conditions. Chlorination further aids in the control of biofouling.
Even with cupronickel exchangers, and certainly with other materials more susceptible to
fouling, chlorination is recommended for the control of biofouling. This is due to the
ingress of microbiological organisms, embryos, and spawn of the shellfish and crustacea.
In a once-through system there is little danger of developing chlorine-resistant organisms;
continuous chlorination is not only permissible but preferred. A chlorine residual of about
0.5 mg/l free available chlorine is usually adequate. The dosage is system-dependent and
continuous residuals as high as 1.0 mg/l may be required.
Chlorine may be added as a gas or generated in situ by electrochemical oxidation of the
chloride present in seawater with in-line electrolysis cells. Hypochlorite salts (e.g., sodium
or calcium hypochlorite) are effective, but are not normally economically competitive
with chlorine gas.
Control of General Fouling in Cooling Water
General fouling is the accumulation of suspended solids, corrosion products, process and
make-up contaminants, oil, dust, mud, silt, debris, and other foreign materials on heat
transfer surfaces.
Oil and Dust in Cooling Water
All surface waters contain suspended solids which are potential foulants. Dissolved iron
and manganese in deep well water form fouling oxides when the water is exposed to air.
Process leaks, carryover from clarifiers, and air-borne dirt are also potential foulants.
Oil in cooling water interferes with heat transfer, binds suspended matter, reduces zinc and
chromate to ineffective forms, promotes biological growth, increases chlorine demand,
and can turn a marginally operated system into a troublesome one.
When oil is visible or exceeds 10 mg/l, several steps should be taken immediately. The
leaking exchanger should be located, shut off or isolated, or its outlet water diverted to a
sewer. The cooling tower and distribution deck should be cleaned. Oil should be skimmed
where possible. The corrosion inhibiter dosage (no chromate-zinc) should be monitored,
and doses of surfactant should be administered. Chlorination should be continuous and
cooling water flow increased if possible. The system then should be blowndown heavily
until less than 10 mg/l oil is obtained. The cycles of concentration should then be
increased to normal, and surfactant doses continued for four days. Oil, biofouling, and the
corrosion inhibitor should be monitored closely. Before returning to normal operation an
increased dosage of inhibitor should be applied for four days in order to repassivate the
system.
Means of Control
One of the most important factors in achieving effective corrosion control is the
maintenance of clean surfaces.
Low water velocities and the use of cooling tower water on the shell side of the shell and
tube heat exchangers can lead to fouling. Recommended water velocities are presented in
Figure 28.
m/sec ft/sec
Carbon Steel 1.8 to 3.0 6.0 to 10.0
Admiralty 1.2 to 2.4 4.0 to 8.0
Cupro nickel 1.2 to 3.6 4.0 to 12.0
FIGURE 28. RECOMMENDED COOLING WATER VELOCITIES
Sidestream Filtration
Continuous sidestream filtration of one to five percent of the recirculation rate has been
used to reduce fouling. Proper selection of a filter to remove the particles in a cooling
tower is required. When used in conjunction with good chemical treatment, sidestream
filters have been effective. However, they are not a replacement for the proper control of
corrosion, scale, and biofouling.
Dispersants and Surfactants
Dispersants and surfactants are useful for minimizing general fouling. The chemicals
suspend the foulants, preventing their deposition and allow removal through blowdown.
Cleaning General Deposits
On-line or off-line cleaning are required in all cooling tower systems. Acids, chlorine,
abrasive salts and materials, sponge balls and other substances have been used to clean
systems on-line. On-line cleaning should only be attempted with experienced personnel
with consideration for the impact of the cleaning on potential plugging, corrosion and
safety. Hydroblasting is generally sufficient to clean systems off-line. If hydroblasting is
insufficient, several options for mechanical and chemical cleaning are available. Testing is
the best means for selecting the optimum cleaning procedure.
Monitoring and Control Required to Operate Cooling Water Systems
Chemical Feed Equipment
Chemicals are available in wet and dry forms. The choice is usually based on economics
and location. The majority of chemicals fed to cooling water systems are in liquid form.
The feed system should be furnished as a prefabricated, skid-mounted package with
pump, tank, tank stand, shut-off valves, suction piping, agitator, and accessories in place.
Where dilution is required, two day tanks are recommended.
Instrumentation commonly includes level indicators on tanks, pump discharge pressure
indicator, flow sensors, and a draw down tube to measure feedrate. The control cabinet
should contain pump stroke control, on-off pushbuttons and indicators, tank level
indicators, and alarms.
Tanks must be sized based on delivery schedules and shelf-life of products. Duplicate
positive displacement pumps are commonly provided. Piping and tanks should be
designed for easy cleanout. In large cooling towers, the feed pump is often automatically
controlled based on the flow of make-up water.
pH and Blowdown Controllers
Automatic pH and blowdown controllers are recommended for all large cooling towers,
especially when nonchromates are required. Accurate control of pH is required for the
reliable control of scale and corrosion. The pH controller activates the feed of acid
(usually sulfuric), or base (usually soda ash), depending on the alkalinity in the make-up
water. pH probes should be equipped with alarms to indicate any low pH excursion.
The automatic control of blowdown can usually be justified based on the resulting savings
in water and chemicals. Blowdown controllers operate based on the conductivity of the
recirculating water. The blowdown valve is opened when the conductivity exceeds a
preset limit and closes when the conductivity is low.
ORP (oxidation reduction potential) probes are relatively new devices which can be used
to sense residual chlorine in water and can be used to control the feed of chlorine.
Frequency of Chemical Analysis
The recirculating water in a process cooling tower should be monitored routinely for
corrosion inhibitor, chlorine, concentration of salts (usually conductivity), and process
leaks, and monitored often for the ion which limits the cycles of concentration (e.g.,
calcium or silicate). Complete water analyses should be conducted twice per year to detect
any long-term problems or trends. Large process towers which are not equipped with on-
line monitors may require testing as frequently as every four hours. In well automated
towers it may be sufficient to test once per day. Corrosion coupons should be evaluated
quarterly, and microbiological counts should be run quarterly or more frequently. In all
cases, more frequent monitoring is recommended if problems are detected.
Generally, closed cooling systems can be monitored quarterly. Once-through systems
should be monitored for chlorine at least daily.
GLOSSARY
acid A chemical that lowers the pH by reacting with the
alkalinity
algae Simple aquatic plant life requiring sunlight for growth.
alkalinity The total of carbonate, bicarbonate, and hydroxide ion
impurities expressed in mg/l as CaCO3.
anodic inhibitor A chemical added to cooling water which reduces
corrosion by forming a protective film at the anodic
surface of a metal.
bacteria One cell microbiological life which grow everywhere in
cooling systems; excessive growth forms slime deposits.
biocide A chemical which is toxic to biological life.
biological fouling In cooling water, accumulations of algae and bacteria on
components.
blowdown Water removed from a cooling system used to control
the concentration of impurities in the recirculated water.
cathodic inhibitor A chemical added to water which reduces corrosion by
forming a protective film at the cathodic surface of the
metal.
chlorination The addition of a chemical containing free chlorine
which is used to prevent biological fouling.
chromate Chemical containing hexavalent chromium. It was used
as an anodic inhibitor until it was found to cause cancer.
cycles of concentration The number calculated by dividing the concentration of
salts in the recirculated cooling water by the
concentration of salts in the make-up water.
deposit External material adhering to the original components in
a cooling system.
drift Loss of recirculated cooling water (with its impurities) to
the heated cooling air leaving the cooling water.
fungi Microbiological plant life.
hardness The concentration of calcium and magnesium ions in
water expressed as mg/l as CaCO3.
in situ In natural or original position.
induced draft Pulling of atmospheric air through a cooling tower by
fans.
precipitation The formation of insoluble salts from soluble salts due to
a chemical change.
Ryznar Stability Index A number based on the Langelier Index which indicates
either corrosion or scaling.
silica The chemical silica dioxide. An inorganic impurity in
water expressed as SiO2.
slime Insoluble organic matter of a viscous gelatinous
composition normally resulting from microbiological
growth which traps other suspended impurities in the
cooling water.
solubility The amount of salt dissolved in water.
windage Water lost from a cooling tower due to the wind.

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Note: The source of the technical material in this volume is the Professional

Engineering Development Program (PEDP) of Engineering Services.

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