Cooling Towers: A Critical but Often Neglected Plant Component – Part 2
Cooling-tower or heat-exchanger failure from waterside fouling and/or corrosion can potentially shut down a unit process or perhaps even the entire chemical or manufacturing facility.
Other potentially problematic microbes include algae and fungi. Algae (Figure 3) are photosynthetic organisms and grow in areas exposed to the sun, most notably the decks of crossflow cooling towers. Many crossflow towers have covered decks to block sunlight, but algae can appear in other sunlit areas.
Fungi are non-photosynthetic organisms. Yeast is one form of fungi, and some species are critical for food and beverage production. Fungi are also important organisms for many waste-treatment processes because they help decompose organic material. However, in industrial cooling water systems some fungi will attack cooling-tower wood. This concern has decreased over the years, as many newer towers are constructed of fiberglass-reinforced plastic (FRP) materials, which are resistant to fungal attacks. Also, fungi prefer mildly acidic environments and are less active in modern cooling water systems per typical operation within a moderately basic pH range.
Microorganism Control: Oxidizing Biocides
For most recirculating and once-through cooling waters, oxidizing biocides are the foundation of a microbial control program. In the United States, chlorine gas was the standard for drinking water and then cooling-water treatment for many years. One-ton cylinders became the common method of storage, but safety issues prompted many industrial plant personnel to switch to liquid sodium hypochlorite (NaOCl), typically industrial-grade bleach with a common active chlorine concentration of 12.5%.
An alternative method is on-site hypochlorite generation. On-site hypochlorite generation systems produce a mixed oxidant from three common consumables: water, salt and electricity. Saltwater electrolysis generates chlorine and some peroxide.
When chlorine is added to water, the following reaction occurs:
Cl2 + H2O ⇌ HOCl + HCl
Hypochlorous acid, HOCl, is the killing agent, and it functions by penetrating cell walls and then oxidizing internal cell components. The efficacy and killing power of the compound are greatly influenced by pH due to the equilibrium nature of HOCl in water.
HOCl ⇌ H+ + OCl–
OCl– is a much weaker biocide than HOCl, probably because the negative charge on the OCl– ion does not allow it to effectively penetrate cell walls.
The dissociation of HOCl dramatically increases in relation to rising pH. Because most modern cooling tower scale/corrosion treatment programs operate at an alkaline pH, often near or slightly above 8.0, straight chlorine chemistry may not be the best choice.
Additionally, chlorine reacts with some water impurities, which reduces the halogen’s effectiveness. Chlorine combines irreversibly with ammonia and many organic compounds. These losses are referred to as chlorine demand. From an environmental perspective, some halogenated organic compounds are considered harmful and whose concentrations may be regulated in the plant discharge permit.
For these reasons, alternative oxidizers have gained support. These include bromine, chlorine dioxide, monochloramine and non-halogens.
A Closer Look at Alternative Oxidizers
Bromine
A popular alternative has been bromine chemistry, where a chlorine oxidizer (bleach is the common choice) and sodium bromide (NaBr) are blended in a slipstream and injected into the cooling water.
HOCl + NaBr ⇌ HOBr + NaCl
The reaction produces hypobromous acid (HOBr), which has similar killing powers to HOCl but functions more effectively at alkaline pH. Bromine also has a halogen demand, but unlike chlorine the bromine-ammonia reaction is reversible. Bromine can also form halogenated organics, and these compounds may be of concern.
Halogen Stabilizers
Several chemical compounds are available that stabilize chlorine and bromine and then release the oxidizers gradually to provide more uniform distribution. The most common stabilizers are sulfamate, dimethylhydantoin and isocyanurates.
Chlorine Dioxide
Chlorine dioxide (ClO2) must be prepared on site via the reaction of either sodium chlorite (NaClO2) or sodium chlorate (NaClO3) with an additional oxidizing agent under acidic conditions. Chlorine dioxide is more expensive than the halogens, but modern production techniques have lowered the cost.
Chlorine dioxide exhibits a high degree of reaction selectivity, and it can penetrate biofilms to attack microbes. ClO2 selectivity makes it advantageous for other water treatment applications, including wastewater odor control.
Because chlorine dioxide exists as a gas in solution, it is easily stripped by passage through cooling towers. ClO2 should be introduced below the surface of the tower basin water, preferably near the inlet of the circulation pumps. Handling of the core compounds for chlorine dioxide production, which may include sulfuric acid, requires attention to safety, although modern ClO2 generators are typically designed with safety in mind.
Chloramines
Chloramines have served for microbial control in potable water systems for many years.
Monochloramine is the compound of interest for modern cooling water biofouling control, and technologies are now available to produce a pristine stream of NH2Cl for this purpose. When compared with sodium hypochlorite, monochloramine is less reactive but almost equally toxic. The reduced reactivity allows it to penetrate biofilms and attack underlying organisms. However, monochloramine generally needs a longer contact time than hypochlorite to achieve the desired results.
Peroxide Oxidants: Hydrogen Peroxide, Peracetic Acid, Percarbonic Acid
Several peroxide-based biocides/disinfectants are on the market, and all can produce the peroxide radical (OH·) as the reactive compound. The most common products are hydrogen peroxide, peracetic acid and percarbonic acid. Unlike chlorine dioxide, peroxides react indiscriminately with a wide array of compounds, including microbes. Oxygen is the byproduct of reactions or auto-decomposition of the biocide.
Peroxides react rapidly and do not have long residence times. Thus, their usefulness as a standard treatment may be limited. However, for periodic offline cleaning, peroxide is extremely effective at removing biofilms and other organic-based deposits, especially when used in combination with caustic, a surfactant, and at warm temperatures. A very informative paper on this subject was given at the 33rd Annual Electric Utility Chemistry Workshop in 2013.