Choose the Right Cooling Tower

Chemicals
07/01/1998

Choose the Right Cooling Tower Chemicals

Environmental, safety and performance-based issues all affect the choice of appropriate chemical treatment for
cooling tower water.

By Brad Buecker, Contributing Editor

Control of the three major microbiological classes, bacteria, algae and fungi, and macroorganisms including
zebra mussels, is essential for healthy cooling tower operation. For many years, chlorine was the treatment
chemical of choice. However, chlorine use is declining due to environmental, safety and performance-related
issues. This article examines the positive and negative aspects of chlorine and of replacement oxidizing biocides.

Microbiocides generally belong to one of two groups: oxidizers and non-oxidizers. The former attack cells by
oxidizing (an electron transfer reaction) microorganism cell components. Non-oxidizers react with cell
components via different chemical processes. Oxidizing biocides are still the most common biological control
agents, and even though chlorine use is declining, it continues to be an important player in the cooling water
treatment industry.

Chlorine

When chlorine is injected into a cooling water stream, it disproportionates into hypochlorous and hydrochloric
acid as follows:

Cl2 + H2O Æ HOCl + HCl

HOCl is the oxidant that attacks cell structures. An increase in pH increases the dissociation of HOCl into the
hypochlorite ion (OCl-):

HOCl H+ + OCl-
Although both HOCl and OCl- are oxidants, OCl- is a much weaker disinfectant, possibly because the charged
OCl- ion has a more difficult time penetrating the cell wall. Chlorine`s biocidal efficiency greatly decreases as the
pH rises above neutral. (See sidebar.)

For years, the most popular cooling water treatment program at many facilities was low-level sulfuric acid feed to
control calcium carbonate formation, with supplemental feed of chromate and zinc for corrosion inhibition. This
suited chlorine as a microbiocide because the mildly acidic pH maintained the chlorine residual predominantly as
HOCl. However, chromate discharges to the environment have been banned due to the potential release of toxic
hexavalent chromium. Modern cooling tower treatment programs operate in the less corrosive alkaline range of
pH 8.0 to 9.0, in which advanced calcium carbonate scale inhibitors have replaced sulfuric acid. Such programs
do not favor chlorine as a microbiocide. This problem has been exacerbated by the development of more
efficient cooling tower fill (Figure 1), whose close spacing makes the material susceptible to pluggage.

Safety issues are another factor in chlorine`s reduced popularity. Chlorine gas is quite hazardous, and
regulations governing its storage and leak detection are becoming increasingly stringent. Rather than deal with
the safety requirements for gaseous chlorine, many plant managers are opting for alternatives.

The potential for formation of chlorinated organics has also become an important issue. Many halogenated
organics are known or suspected carcinogens, and tighter restrictions are being placed on the amount of
allowable halogenated organics. In 1979 the Environmental Protection Agency (EPA) set an interim maximum
contaminant level (MCL) of 0.100 ppm for total trihalomethanes (TTHM`s). The agency has proposed to reduce
the MCL to 0.080 ppm, and may lower the standards even further in the future.

In 1982, the power industry was required to meet optimized technology-based standards for chlorine use. The
requirements limited the maximum chlorine discharge from cooling towers to 0.5 ppm, with an average discharge
of 0.2 ppm for no more than two hours per day. In 1985 the EPA announced more stringent ambient water quality
criteria, which applied to all industries. These guidelines limited fresh-water chlorine concentrations at the
boundary of a calculated effluent mixing zone to 0.011 ppm over a four-day average, or 0.019 ppm average for
one hour. Restrictions for salt water are even more stringent at 0.0075 ppm and 0.013 ppm, respectively.

The regulations have made it particularly difficult to use chlorine to control cooling water biological fouling. The
situation has been further complicated by the spread of macrofouling species, the most notable of which are
zebra mussels and Asiatic clams. Continuous or semi-continuous chlorination is necessary to control the growth
of macrofoulers, especially adults, but continuous chlorination is expensive, particularly when bleach is the
biocide. Continuous chlorination can also harm non-target organisms in once-through cooling systems. Many
facilities must dechlorinate their cooling water prior to discharge in order to comply with water quality standards.
This process typically requires the feed of a reducing agent, such as sodium bisulfite, into the effluent.

Bromine

A popular substitute for chlorine is bromine (Br2). Like chlorine, bromine reacts with water to produce a
hypohalous acid, in this case HOBr. Bromine has nearly the same oxidizing power as chlorine, but it offers
several advantages over chlorine in certain conditions. First, the dissociation of HOBr occurs at a higher pH than
HOCl (Figure 2), which makes it more effective in alkaline environments. Second, bromine does not react
irreversibly with ammonia as does chlorine. Chloramines are much less effective disinfectants than free chlorine,
which makes chlorination of ammoniated waters problematic. Third, bromine is less corrosive than chlorine to
copper alloys.

Bromine may be introduced into a cooling water system by several different methods. Most common is to react
liquid sodium bromide (NaBr) with chlorine or sodium hypochlorite in a sidestream loop of the cooling water
makeup. Chlorine activates the bromide salt to hypobromous acid as follows:

NaBr + HOCl Æ HOBr + NaCl

Sodium bromide, being the bromine analog of common table salt (NaCl), is stable and may be stored in a simple
bulk tank. NaBr is usually supplied as an aqueous solution of approximately 40 percent concentration. The
sodium bromide and chlorine or sodium hypochlorite should be fed separately into the slipstream to obtain at
least a 100:1 dilution. This prevents the formation of undesirable bromate byproducts.

Like chlorine, bromine is toxic to non-target organisms and it can form halogenated organics. For these reasons
plant cooling water discharges containing bromine are regulated similarly to chlorine, although some states or
EPA regions have established more restrictive standards for bromine residuals.

Even though the cost of sodium bromide adds to the total delivered cost of the oxidants, users often find it
possible to reduce the overall quantity of oxidant required to achieve the equivalent performance. Frequently, the
reduction in chlorine consumption more than offsets the cost of the sodium bromide, especially where liquid
sodium hypochorite is the chlorine source.

Solid Choices

For smaller cooling water systems, solid bromine donors may be a cost-effective alternative to the arrangement
mentioned above. One of the most common solid biocides is bromo- chloro-dimethyl-hydantoin, or BCDMH,
which releases bromine as it dissolves in water. Several of the major water treatment vendors supply solid
bromine or chlorine donors in granules, pellets, or tablets along with a feed system. As water passes through the
dissolving vessel, the BCDMH dissolves at a controlled rate to release HOBr and HOCl:

C5H6O2N2BrCl + 2H2O Æ C5H8O2N2 + HOBr + HOCl

Solid donor systems are also available for strictly chlorine-releasing products. Some of the most common
chlorine-based solid donors include dichloro-dimethyl-hydantoin, calcium hypochlorite [Ca(OCl2)] and chlorinated
isocyanurates. The latter two compounds are widely used as swimming pool chemicals, but will also work well in
some cooling water applications. Specific feed systems are available for each halogen donor. All of these
products are strong oxidizers and must be handled and stored properly; it can be hazardous to use one
compound in a feeder designed for another.

Prominent advantages of the solid halogen donors are:

Handling--no potential for liquid spills;

Stability--stable compared to bleach;

Effectiveness--strong oxidizers that work well at alkaline pH and in the presence of ammonia;
Water Chemistry--less corrosive to system materials; do not significantly alter cooling water pH; and

Environmental and Safety Factors--no chance of toxic gas or liquid release.

The solid halogen donors are best for systems with a low or moderate chlorine demand, and where simple
operation is desirable. Solid donors are generally more expensive than chlorine and even bleach, and can be
slow to dissolve at water temperatures below 60 F.

Sodium Hypochlorite

Sodium hypochlorite (NaOCl) may be a suitable non-gaseous alternative. It comes in bulk solution, at a
concentration ranging from 10 percent to 12.5 percent as NaOCl. The hypochlorite can be metered directly into
the cooling system. An important point to remember about NaOCl is its effect on cooling water pH. Gaseous
chlorine lowers the pH due to the production of both HOCl and HCl. Sodium hypochlorite tends to raise the pH.

Sodium hypochlorite will degrade over time to form sodium chloride, oxygen, and sodium chlorate (NaClO3).
Temperature and impurities greatly affect decomposition. (See sidebar for specifications and storage guidelines
for sodium hypochlorite.)

The improved safety and convenience of sodium hypochlorite versus gaseous chlorine has a tradeoff in cost.
Chlorine gas in ton cylinders costs $0.15 to $0.20 per pound delivered. By contrast, 12.5 percent sodium
hypochlorite costs around $0.60 per gallon ($0.059 per pound) delivered in bulk. This corresponds to $0.50 per
pound on an equivalent Cl2 basis, or approximately three times the cost of gaseous chlorine.

Chlorine Dioxide

Chlorine dioxide (ClO2) is a powerful oxidizer with excellent biocidal properties. It offers several potential
advantages compared to chlorine. Chlorine dioxide:

does not form halogenated organics,

is less corrosive to copper alloys than chlorine,

does not react with ammonia and primary amines,

efficiently destroys phenols and sulfides,

is not affected by pH like chlorine and works well in alkaline waters, and

is more effective against mollusks.

These advantages come at a price, however. Chlorine dioxide is a very reactive compound that is hazardous to
transport at practical concentrations. It must be generated on-site from other reactive chemicals that also present
some handling risks. Chlorine dioxide does not react with water or ionize in solution, thus it remains as a
dissolved gas that is easily stripped across a cooling tower. The principal reaction product, chlorite, affects some
forms of aquatic life at low levels. Chlorite can be difficult to neutralize with reducing agents.
Chemical costs for sodium chlorite are typically in the $0.50 to $1.00 per pound range for a 25 percent aqueous
solution. This corresponds to $2.00 to $4.00 per pound of active ClO2. The costs of bleach or acid for reaction,
along with the 80 percent to 95 percent efficiency of the ClO2 generation reactions, can push the price above
$3.50 per pound, or over seven times the cost of chlorine. Still, there are some situations where the effectiveness
of chlorine dioxide may offset the added cost.

Ozone

Ozone (O3) is a powerful, short-lived oxidant that is generated by passing air through an electric discharge. The
air stream is then bubbled into the cooling water through a diffuser.

Ozone is too reactive to transport or store on-site, so it must be generated at the point of use. This requirement
has so far limited ozone`s application to relatively small cooling systems. Ozone is the most powerful oxidant of
all, but its oxidizing strength can be a mixed blessing. Ozone rapidly destroys biofilms and produces sparkling
clear water, but it also breaks down most scale and corrosion inhibitors, and it slowly degrades plastic, rubber
and gasket materials. Similar to chlorine dioxide, ozone does not ionize in water but remains a dissolved gas,
which can be stripped during passage through the cooling tower. Ozone offers environmental advantages in that
its residuals are short-lived, it does not produce halogenated reaction products, and it breaks down into oxygen,
which can be beneficial. However, ozone can produce secondary oxidants if bromide is present, and it can also
produce aldehydes and ketones via reaction with organics.

One of the major advantages of ozone is that no hazardous chemicals are transported, stored or handled on-site.
For small cooling systems in sensitive locations, ozone can be an attractive alternative to chlorine. Researchers
continue to investigate methods of ozone treatment for larger systems. p

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Figure 1. Cooling tower film fill.

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BCDMH

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Dichloro-Dimethyl-Hydantoin

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Trichloro Isocyanurate

pH Effect

At a pH of 6.5 tests have shown that a 1.0 ppm chlorine solution will kill 99 percent of all microorganisms within
30 seconds. At this pH, a large percentage of the dissolved chlorine exists as HOCl. The percentage rapidly
decreases as pH rises.

Thus, in an alkaline cooling water treatment program with a pH between 8 and 9, the available hypochlorous acid
is well below 50 percent (Figure 2).

Sodium Hypochlorite

Sodium hypochlorite will decompose into oxygen, sodium chloride, and sodium chlorate. The decomposition rate
is affected by temperature and by the catalytic action of some metals, most notably iron and copper. A
specification for bulk quantities of sodium hypochlorite should contain the following:

Iron concentration less than 0.5 ppm;

Copper concentration less than 1.0 ppm; and

pH range from 11.0 to 11.2.

Temperature can have a dramatic impact on hypochlorite solutions. For example, the half-life of a hypochlorite
solution is reported to be 800 days at a temperature of 59 F. At 77 F the half-life drops to 220 days, and at 140 F,
the half-life is only 3 days. Bulk storage tanks of sodium hypochlorite should be kept as cool as possible by sun-
shading, painting them white, or both.
 Fiberglass-reinforced-plastic is the recommended construction material for bulk storage tanks. Poly ethylene was
once the material of choice, but cracking problemshave been reportedafter exposure to hypochlorite.

Acknowledgement:

The author wishes to express his appreciation for the technical support given by Ray Post of BetzDearborn.

Author--

Brad Buecker is a Power Engineering contributing editor and author of Power Plant Water Chemistry: a Practical
Guide, published by PennWell Publishing Co. He resides in Lawrence, Kansas.

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