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Cooling Tower Water Treatment

The Second Law of Thermodynamics clearly states it is impossible to use heat solely to generate
work in a cyclic process. Even in the most efficient cycles, some heat must be exhausted for the
cycle to operate. In power plants, that means the primary heat sink is the water-cooled or air-cooled
steam condenser. Similar heat exchange is often required at large, non-utility plants as well.
Waterside scaling or fouling seriously impedes heat transfer in condensers, and can literally increase
large plant fuel costs by hundreds to thousands of dollars per day.

Basic Cooling Tower Flow Path

Cooling Tower Heat Transfer Basics

The figure below illustrates the fundamental flow path of a cooling tower, and indicates one set, of an
obviously vast number, of conditions that are possible with regard to temperature and moisture
content of the process streams.
As water evaporates in a cooling tower, dissolved solids (and suspended solids) remain behind.
These solids concentrate and increase the scaling, corrosion, and fouling potential of the water.
Even with the best chemical treatment program, impurities in the cooling tower can only be allowed
to accumulate to a certain level before the scaling potential overwhelms the chemical treatment.
The amount to which the impurities are allowed to concentrate over those in the cooling system
makeup water is known as the cycles of concentration (COC).
The COC is controlled by periodic blowdown of a fraction of the cooling water, whose volume is
replenished with makeup water.
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Blowdown Rate vs. COC - 2

The "law of diminishing returns" applies as the COC increases. A common COC range is 4 to 8. But
if the tower is located in an arid environment or blowdown quantity is restricted, a higher COC may
be mandated. However, this comes at a cost, as the higher COC means a greater concentration of
dissolved solids in the cooling water, which increases the scaling and corrosion potential.

Modern Chemistry Control

In towers supplied by fresh water, and in the absence of any treatment, almost always the first scale
to form would be calcium carbonate (CaCO3).
Calcium ions (Ca2+) love to combine with bicarbonate ions (HCO3-), especially as temperatures rise
in condensers and other heat exchangers.
Ca2+ + 2HCO3- + heat → CaCO3↓ + CO2↑ + H2O
So, in the middle of the last century a very common treatment program was utilized, which
addressed both scaling and corrosion via a two-chemical process.
The first step was feed of sulfuric acid to maintain a cooling water pH within a range of about 6.5 to
7.0. Acid converts bicarbonate to carbon dioxide, which of course escapes as a gas. This was
coupled with feed of sodium dichromate to the water. Chromium forms a surface layer on carbon
steel and gives it stainless steel-like qualities. In common vernacular, this program was almost a "no-
brainer," although upsets in acid feed could and did cause serious corrosion.
Blowdown is the common method to prevent excess dissolved solids buildups. But by itself
blowdown typically cannot prevent scale formation, as several compounds will exceed saturation
level and precipitate on condenser tubes and other system internals.
Table 1 shows how insulating the typical hardness compounds as compared to the metals they may
coat. Conversely, other foulants such as silica compounds and slime from microbiological deposits
can be even worse than the hardness deposits regarding heat transfer.
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Formation of calcium carbonate (CaCO3 ):

In the absence of any treatment programs, the primary scale-forming reaction produces calcium
carbonate deposits.
Ca+2 + 2HCO3- + heat → CaCO3+ CO2 + H2O
Unlike many salts, calcium carbonate is inversely soluble with temperature. Thus as temperatures
rise in a condenser or heat exchanger, the potential for CaCO3 scaling increases.

Treatment with Sulfuric Acid (H2AO4):

A straightforward and often used method to reduce the potential for calcium carbonate scaling is to
treat the makeup with sulfuric acid (H2SO4), where the hydrogen ions (H+) from the acid convert the
bicarbonate to carbon dioxide (CO2). The gas exits from the cooling tower.
H+ + HCO3- → CO2 + H2O
However, acid feed alone may not eliminate scaling. Upsets of acid feed can lead to corrosion or
scaling, and sulfuric acid introduces sulfate ions (SO4-2) to the water. Over time, this may lead to
calcium sulfate deposition. Accordingly, supplemental chemicals are normally used in cooling tower
programs to further minimize scale formation.

Treatment with the feed of Phosphates:

An early treatment method was feed of phosphates, either ortho-phosphate (PO4-2) or phosphate
complexes that would revert to ortho-phosphate, to precipitate calcium as [Ca3(PO4)2]. These
programs also provided corrosion protection because phosphate will react with ferrous ions (Fe+2)
produced at anodic sites to form a protective barrier, while [Ca3(PO4)2] precipitates in the local
alkaline environment at cathodic sites. Zinc was a common corrosion protection supplement, as zinc
ions will also precipitate (as zinc hydroxide [Zn(OH)2] at cathodic sites) thus enhancing the barrier
film.
Phosphonates primarily function as crystal modifiers and attach to crystals as they form, and thus
alter their structure and reduce the crystals’ adhesiveness to condenser tubes and other surfaces.
Excess phosphonate feed can result in calcium-phosphonate scale formation and fouling of heat
transfer surfaces.
Also, many of the early phosphonates are susceptible to rapid degradation by oxidizing biocides
such as chlorine, bromine, chlorine dioxide and so on. A newer phosphonate, phosphino succinc
oligomer (PSO), offers excellent calcium carbonate scale inhibition combined with good resistance to
degradation. Often in phosphonate programs, a few parts-per-million (ppm) of ortho-phosphate [PO4]
are used for both cathodic and anodic corrosion inhibition, as outlined earlier. However, at the higher
pH of these treatments, a strong possibility exists for calcium phosphate [Ca3(PO4)2] scale formation.
Thus, a small dosage of organic polymer is frequently used in the formulations to keep calcium
phosphate in suspension, such that it leaves the cooling system in the blowdown. Modern
treatments may use or rely on co- or ter-polymersin which active groups include carboxyl and
sulfonic acid ions (COO- and SO3-, respectively) and amide OC-NH2. These products are designed
to control a variety of sales. A thorough evaluation of the cooling water is necessary when
considering and implementing any of these programs.

Control of Microbiological Fouling:

While scaling and corrosion are very important concerns in cooling systems, microbiological fouling
often by far causes the most problems.
Cooling systems provide an ideal environment, warm and wet, for microbes to grow and establish
colonies. Bacteria will grow in condensers and cooling tower fill, fungi on and in cooling tower wood,
and algae on wetted cooling tower components exposed to sunlight. Biocide treatment is absolutely
essential to maintain cooling system performance and integrity.
Bacteria are separated into the following three categories,
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 Aerobic: Utilize oxygen in the metabolic process.

 Anaerobic: Live in oxygen-free environments and use other sources, i.e.,
sulfates, nitrates, or other donors for their energy supply.
 Facultative: Can live in aerobic or anaerobic environments.
Dissociation of HOCl as a Function of pH - 7

Fungi will attack cooling tower wood in an irreversible manner, which can eventually lead to
structural failure. Algae will foul cooling tower spray decks, potentially leading to reduced
performance and unsafe working locations.

Treatment with Chlorine:

The core of most microbiological treatment programs is feed of an oxidizing biocide to kill organisms
before they can settle on condenser tube walls, cooling tower fill, and other locations. Chlorine was
the workhorse for many years, where when gaseous chlorine is added to water the following reaction
occurs.
Cl2 + H2O ⇔ HOCl + HCl
HOCl, hypochlorous acid, is the killing agent. The functionality and killing power of this compound
are greatly affected by pH due to the equilibrium nature of HOCl in water.
HOCl ⇔ H+ + OCl-
OCl- is a much weaker biocide than HOCl, probably due to the fact that the charge on the OCl- ion
does not allow it to penetrate cell walls. The killing efficiency of chlorine dramatically declines as the
pH goes above 7.5. Thus, for the common alkaline scale/corrosion treatment programs, chlorine
chemistry may not be efficient.
.
A common alternative is bromine chemistry, where a chlorine oxidizer and a bromide salt, typically
sodium bromide (NaBr), are blended in a makeup water stream and injected into the cooling water.
The chemistry produces hypobromous acid (HOBr), which has similar killing powers to HOCl, but
functions more effectively at alkaline pH.
Chlorine dioxide (ClO2) is becoming more popular for several reasons. Its killing power is not
affected by pH, the chemical does not react with ammonia, and it does not form halogenated organic
compounds. Also, chlorine dioxide is more effective in attacking established bio-deposits.
ClO2 is unstable and must be generated on-site. In the past, a common method was reaction of
sodium chlorite (NaClO2) and chlorine in a slipstream fed to the cooling water.
2NaClO2 + Cl2 ® 2ClO2 + 2NaCl
However, this technique required storage of large quantities of hazardous chemicals, and was
several times more expensive than bleach or even bromine treatment. Much improved technology is
now available, with one design based on the following chemistry.
NaClO3 + 1/2 H2O2 + 1/2 H2SO4 → ClO2 + 1/2 O2 + 1/2 Na2SO4 + H2O
Sodium chlorate (NaClO3) is the core chemical rather than sodium chlorite.