PRACTICAL GUIDE

w a t e r t r e a t m e n t

Water Treatment for HVAC&R Systems

By Bennett P. Boffardi, Ph.D.

ater treatment for HVAC&R systems encompass both open recirrculating cooling water systems and closed systems. Open recirculating cooling systems reject heat through cooling towers. Closed systems can be either cooling or hot water systems. These systems convey chilled or hot water to areas that require cooling or heating.

Cooling towers come in a variety of sizes, shapes, construction materials, and fill or packing. Two major problems currently exist with towers. Galvanized towers are prone to a unique corrosion phenomenon known as white rust. High efficiency fill fouls with biological deposits and incrustation. Both of these problems can be controlled by proper water treatment. Cooling tower operation is simple. The circulating cooling water picks up heat from the process heat exchangers and passes through the cooling tower. Evaporation cools the recycled water as it passes through the tower. As a result of evaporation, the dissolved solids in the water become concentrated. The water lost to evaporation and drift is replaced by fresh makeup water. The rate of water discharge (blowdown) stabilizes the dissolved content of the water. The evaporative process absorbs gases from the air, particulate matter, and nutrients for biological growth. It also reduces the solubility of the solids that remain in the recirculating water. These combined effects increase the corrosivity of the cooling water, cause tenacious deposits that impede heat transfer, and create sites where microbes grow. Adding chemical treatment inhibitors to open recirculating cooling water systems provides an array of protection to the cooling water circuit: It reduces the corrosive attack on the systems metallurgy. It prevents dissolved solids in the water from precipitating and adhering to heat transfer surfaces where they would reduce heat transfer efficiency. It provides dispersive action to keep insoluble particulates from depositing on heat transfer surfaces.
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It provides biocidal action that limits growth of bacteria, fungus, and algae. Chemical treatments must be effective at low concentration and must have minimal toxic effects when discharged into the environment. Closed chilled water systems are usually cooled by compression-type or steam-absorption type refrigeration equipment (chillers). Makeup or initial fill water quality can vary from zeolite-softened water that removes only hardness to potable water that is supplied by the local municipality. Hot water systems obtain heat from a boiler. This heated water then circulates through the building. Water loss in closed systems should be minimal: less than 5% makeup per year. Competent water treatment is required for all three systems. Open recirculating cooling water systems require the most attention. Closed system requirements are less demanding. With open recirculating cooling water systems, corrosion, scale, deposit, and biological control are necessary. With closed systems, corrosion control is the main concern due to the better water quality and low makeup rates.

Open Recirculating Systems Open recirculating cooling water systems normally operate in a pH range of 6.5 to 9. Typically, the pH is in the alkaline range of 7.8 to 8.8. As the pH of the circulating water increases, the corrosivity of the water decreases. This reduction in corrosivity comes at a price. The scaling tendencies of limited solubility salts such as calcium carbonate and calcium phosphate increase. Precipitation of these scales on heat transfer surfaces reduces thermal efficiency and accelerates under-deposit corrosion. Initial fill and makeup water quality has strong impact on system performance. Hard waters, defined as water with hardness values greater than 500 mg/L as CaCO3,
Bennett P Boffardi, Ph.D., is an internationally recog. nized expert in aqueous corrosion and its control with more than 30 years experience in the water treatment industry. He has published numerous articles and has been granted many U.S. and foreign patents. Boffardi is a Fellow of NACE International (formerly the National Association of Corrosion Engineers). He owns a water treatment consulting firm in Bethel Park, Pa.
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are less corrosive than soft water, defined as water with hardness values less than 100 mg/L as CaCO3. As hardness increases, corrosivity decreases. As with increasing pH, high hardness waters tend to precipitate sparingly soluble salts. Temperature is the other major parameter of concern. Corrosion rates double every 10C (20F). Also, some sparingly soluble salts such as CaCO3 and CaSO4 have inverse solubility with temperature. They are less soluble as the temperature increases. Keeping the distribution system and heat transfer surfaces clean and free of deposits will improve corrosion protection and overall efficiency. Cleanliness is next to godliness. Corrosion control in open recirculating cooling water systems encompasses 5 or 6 inhibitors used alone or in synergistic combination to provide multimetal (carbon steel, copper alloys, etc.) protection to the cooling water system.

Orthophosphate Currently, phosphate chemistry is used in a majority of HVAC&R sites. A variety of corrosion-inhibiting phosphates is available. Orthophosphate is the simplest species in this family of inhibitors. It effectively inhibits corrosion of carbon steel at treatment concentrations of 10 to 20 mg/L if the pH of the cooling water is above 7.5. Below this pH, orthophosphate is not as effective. This chemistry is sensitive to water quality, especially chloride content. High concentrations of chloride (above 300 mg/L) reduce the efficiency of this inhibitor by promoting localized pitting attack. When orthophosphate can be used, protective film formation is rapid and tenacious. Orthophosphate is synergistic with other inhibitors to provide excellent corrosion protection. Some of the combined inhibitor treatments consist of zinc/orthophosphate, polyphosphate/ orthophosphate, and phosphonate/orthophosphate. A major concern with orthophosphate-based treatments is the potential for calcium orthophosphate precipitation in high pH and hard waters. Adequate calcium orthophosphate inhibitor is absolutely necessary under these conditions. (See section on calcium orthophosphate.) Polyphosphates Another member of the phosphate family is polyphosphates. They provide corrosion protection for carbon steel at concentrations of 10 mg/L to 20 mg/L in an effective pH range of 6.5 to 7.5. Water hardness is essential for polyphosphates to inhibit corrosion. Therefore, makeup water should not be softened when polyphosphates are used. Polyphosphates are not sensitive to water quality (chlorides). They are usually combined with zinc to improve the corrosion inhibition. A concern with polyphosphate is that they revert to orthophosphate and increase the potential for calcium phosphate precipitation.
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Figure 1: Usable pH range for various water treatment programs.

Phosphonates Organic phosphate compounds are called phosphonates. They rarely are used alone for corrosion control but are combined with other phosphonates or inorganic phosphates (polyphosphate or orthophosphate). Some of the more common phosphonates are: 1-hydroxethylidene 1diphosphonoic acid, (HEDP), aminotri (methylenephosphonic acid), (AMP) 2-phosphonobutane-1,2,4tricarboxylic acid, (PBTC) and hydroxyphosphono acetic acid, (HPA). These phosphonates used in combination with each other or with zinc can provide good corrosion protection. Treatment concentration is 10 to 20 mg/L, within a pH range of 7 to 9. HPA requires calcium in the water for effective protection of carbon steel. Usually phosphonates are not sensitive to water quality. Because of their organic nature, phosphonates do not revert to orthophosphate so reduce the concern over calcium orthophosphate deposition. Molybdate Molybdate provides corrosion protection to both carbon steel and aluminum but requires high concentrations of 75 mg/L to 150 mg/L when used alone. To avoid the need for high concentration, molybdate is usually combined with a phosphorus inhibitor. The pH range for molybdate is 5.5 to 8.5. Calcium molybdate can precipitate in moderate to hard calcium waters. Also, inhibition by molybdate is sensitive to both chloride and sulfate concentrations in the water. One of the strengths of molybdate is its ability to inhibit pitting and underdeposit corrosion attack. Molybdate is used sometimes at concentrations of 2 mg/L to 4 mg/L as a tracer for chemical treatment programs. Tracers are used to monitor the concentration of the chemical treatment program. Some components of the chemical treatment program are difficult to analyze
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in the field. By including an easily monitored tracer like molybdate, the correct concentrations of all components in the chemical treatment program are assumed to be present when the tracer concentration is at the desired level.
*Effectiv eness Against: Microbiocide B acteria Fungi Algae C omments Reacts wi th -NH2 groups; effecti ve at neutral pH; may be less effecti ve at hi gh pH. Use concentrati on: 0.1mg/L to 0.2 mg/L conti nuous free resi dual; 0.5 mg/L to 1.0 mg/L i ntermi ttent free resi dual.

C hlori ne (C l2)

Silicate pH i nsensi ti ve; can be used i n presence of C hlori ne This inorganic material is normally NH2 groups. Use concentrati on: 0.1 mg/L to E G G di oxi de (C IO2) used in soft waters to provide cor1.0 mg/L i ntermi ttent free resi dual. rosion protection to both carbon Substi tute for C I2; effecti ve over broad pH steel and copper-base alloys. Treatrange. Use concentrati on: 0.05 mg/L to 0.1 ment concentrations are usually 10 Bromi ne E S S mg/L conti nuous free resi dual; 0.2 mg/L to 0.4 to 20 mg/L above the background mg/L i ntermi ttent free resi dual. silica concentration in the water. They are effective above 7 pH. The Effecti ve over broad pH range, 7 to 9. protective film develops slowly over Ozone E G G C onti nuous or i ntermi ttent feed of 0.2 ppm to 0.5 ppm time, usually in a matter of weeks. For comparison, phosphate-base *E = Excellent G = Good S = Sli ght NA = Not Appli cable chemical treatments develop a protective film within a few days. Sili- Table 1: Oxidizing biocides. cate is not a common chemical treatScale and Deposit Control ment for open recirculating cooling waters. The potential for scale formation on heat exchanger Zinc surfaces increases as the cooling tower evaporates more The addition of zinc is usually synergistic to corrosion water. Scale formation depends on: inhibitor formulations. Some benefits of adding zinc to water temperature at the heat transfer surfaces, any formulation are: alkalinity of the cooling water, and improves protection, the amount of scale-forming material in the water. a more tenacious film, Scales that occur most frequently in cooling water sys reduced rate of film formation, and tems are calcium carbonate and calcium phosphate. a reduction in the concentration of the complementing inhibitor compared to its use alone. Calcium Carbonate Zinc concentration is usually 0.5 mg/L to 2 mg/L Historically, calcium carbonate was controlled by addwhen combined with other inhibitors. The effective ing sulfuric acid to convert the scale to the more soluble pH for zinc-containing systems is below 7.5 unless a calcium sulfate by the following chemical reaction: zinc stabilizer is incorporated into the overall treatment. Zinc is never used alone as a corrosion inhibiCa(HCO3)2 + H2SO4 CaSO4 + CO2(gas) + 2H2O tor in open recirculating cooling water systems. Some calcium + sulfuric calcium + carbon + water common treatments containing zinc include zinc/orbicarbonate acid sulfate dioxide thophosphate; zinc/polyphosphate; zinc/phosphonate; and zinc/molybdate. Non-zinc or non-heavy metal corBecause of safety concerns related to acid in the facilrosion inhibitor treatments consist of orthophosphate/ ity or fluctuations in the acid feed rate that accelerate polyphosphate, orthophosphate/molybdate, and com- corrosion, this approach to calcium carbonate scale conbined phosphonates. There are many combinations, trol is losing favor. both with and without zinc, that provide good corroA more recent approach is chemical addition to consion protection to carbon steel. trol scale. The commonly used chemicals include polyphosphate, phosphonates, and some polymers Copper Corrosion Inhibitors particularly polyacrylates. Concentrations of scale inhibiTwo common copper corrosion inhibitors used in open tors are usually less than 2 mg/L to 3 mg/L. recirculating cooling water systems are benzotriazole and tolyltriazole. Both materials provide excellent protection The Langelier Index to copper-base alloys at concentrations of 1 mg/L to 2 The chemistries described previously are limited to a mg/L when the pH range is 6 to 9. It is important to add Langelier Index of about 2typical of most cooling waters one of these materials if the system has copper alloy heat systems. This index is a predictive tool that determines exchangers or copper piping. calcium carbonate precipitation. It is the difference be54
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*Effectiv eness Against: Microbiocide Organo-bromi de (D BNPA) Methylenebi s-thi ocyanate (MBT) Isothi azoli ne B acteria E E Fungi S S Algae S S C omments pH range 6 to 8.5. Use concentrati on: 0.5 mg/L to 24 mg/L, i ntermi ttent feed. Hydrolyzes above pH 8. Use concentrati on: 1.5 mg/L to 8 mg/L, i ntermi ttent feed. pH i nsensi ti ve; deacti vated by HS and -NH2 groups. Use concentrati on: 0.9 mg/L to 13 mg/L, i ntermi ttent feed. Tendency to foam; surface acti ve; i neffecti ve i n hi ghly oi l or organi c-fouled systems. Use concentrati on: 8 mg/L to 35 mg/L, i ntermi ttent feed. Tendency to foam; functi ons best i n alkali ne pH. Use concentrati on: 7 mg/L to 50 mg/L, i ntermi ttent feed. D eacti vated by -NH2 groups; effecti ve over broad pH range. Use concentrati on: 10 mg/L to 75 mg/L, i ntermi ttent feed. Broad spectrum acti vi ty; pH range 5 to 9. Good i n hi gh suspended soli ds systems; not compati ble wi th chromate treatment programs. Use concentrati on:15 mg/L to 100 mg/L. Broad spectrum acti vi ty; pH range 6 to 9. Use concentrati on 25 mg/L to 100 mg/L. Speci fi c for algal control; must be used wi th other bi oci des. pH range 6 to 9. Use concentrati on: 2 mg/L to 7 mg/L. NA = Not Appli cable

Quaternary ammoni um salts Organo-ti n/quaternary ammoni um salts

Glutaraldehyde

C arbamate

D odecylguani di ne (D GH) Tri azi ne

NA *E = Excellent

NA G = Good

E S = Sli ght

Table 2: Non-oxidizing biocides.

tween the actual pH of the water and the saturation pH (pHs). The saturation pH is a function of calcium hardness, alkalinity, temperature, and dissolved solids. Langelier Index values less than zero imply the water is undersaturated with respect to calcium carbonate; that is, the calcium salt will remain dissolved in solution. A zero value means stable water in which calcium carbonate will neither dissolve nor precipitate. A value greater than zero indicates oversaturation and the potential for calcium carbonate precipitation. The Langelier Index was developed in 1936 by W F. . Langelier as a measure of the tendency of calcium carbonate to dissolve or deposit in potable water mains. The theory was that a thin coating of calcium carbonate on the distribution pipe walls would protect the steel from corrosive attack by the water. The Langelier Index has been extended to areas that are inappropriate for its use, e.g., heat exchangers. In a heat exchanger, the temperature varies from inlet to outlet. Therefore, calcium carbonate formation may occur at the hottest area. Deposition rate and thickness are unknown factors. There are many shortcomings to using this index to predict the behavior of calcium carbonate in cooling water systems.
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There is no relationship between water corrosivity and the Langelier Index. At present, no viable index exists to monitor water corrosivity.

Calcium Orthophosphate Increasing pH, calcium concentration, and phosphate addition from chemical treatment raises the potential for calcium phosphate scale to form on heat transfer surfaces. The solubility of calcium phosphate decreases with increasing pH. The solubility is also slightly affected by temperatures in the range of 75F to 160F (24C to 71C). Years ago, calcium phosphate scale was extremely difficult to inhibit; however, polymers now are capable of controlling deposition of calcium phosphate. These polymers modify the morphology and size of the scale particles markedly, while acting as a dispersant to prevent its adherence to heat transfer surfaces. Normal concentrations of these polymers are 10 mg/L to 15 mg/L. Foulants and Biological Control These materials are waterborne deposits that settle on heat transfer surfaces, interfere with cooling water flow, and stimulate corrosion. Foulants encompass such di55

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verse substances as particulate matter scrubbed from the air, transported corrosion by-products, silt, clays, organic contaminants (oils), and biological matter. Synthetic polymers are the most commonly used treatment to prevent foulant deposits. Polyacrylates, polymaleates, partially hydrolyzed polyacrylamides, and acrylate-base co- and terpolymers constitute the majority of dispersant chemicals. Treatment concentrations are normally 2 mg/L to 3 mg/L. Biological fouling caused by algae, fungi, and bacteria interfere with cooling water flow through heat exchangers and other conduits. Fouling reduces heat transfer rates and contributes to corrosion and the general deterioration of the cooling water system. These species can be controlled through judicious application of microbiocides. Oxidizing and non-oxidizing biocides are available for use in cooling water systems. The common oxidizing biocides are chlorine and bromine. Both provide broad-based control of microbiological problems. Biocide efficacy is a function of pH. Chlorine is suitable at pH levels up to 8. Above this pH, chlorine effectiveness dramatically decreases. Bromine chemistry is most cost effective at an alkaline pH above 8. Treatment levels are 0.1 mg/L to 0.5 mg/L free residual chlorine or bromine. There are a variety of non-oxidizing biocides, which are used primarily in closed cooling water systems. In open recirculating cooling water systems, non-oxidizing biocides should be limited to those situations in which oxidizing biocides are not effective. A concern is that constant use of a specific non-oxidizing biocide can lose effectiveness due to a build up of resistance by the bacteria. Alternating non-oxidizing biocides reduces this problem. Tables1 and 2 list some of the biocides presently in use. More effective and less restrictive biocides are being developed. systems. The passivating properties of nitrite ions have been related to the fact that an Fe2O3 oxide film forms on the steel surface, thereby impeding the corrosion process. Usually treatments containing nitrite are formulated with a high pH buffer (borax) to control the cooling water pH at approximately 9 to 9.5. Treatment concentrations can range from 250 mg/L to 1,000 mg/L. Nitrite concentrations can be reduced when combined with molybdate. Approximately 300 mg/L of each constituent is required plus a buffer. The major concern with nitrite is the high potential for degradation by bacteria. Decomposition products can be either nitrate or ammonia, depending upon the bacteria species. Additional components required for any closed cooling water system are copper corrosion inhibitor and polymer dispersant. Non-oxidizing biocides are required to control nitrifying or denitrifying bacteria.

Hot Water Closed Systems Makeup water is normally zeolite-softened. Chemical treatment is required only for corrosion control, since makeup water usage is low and of good quality. pH Control pH adjustment of the feed water to 9.0 to 10.5 is required to reduce its corrosive tendencies. This can be accomplished by the addition of alkaline chemicals: caustic soda or soda ash. Constant testing is required to maintain the hot water pH. Nitrite Blended products similar to nitrite-borax or nitritemolybdate with copper inhibitor and a dispersant will provide good carbon steel and copper corrosion control. The use of this treatment eliminates the need for caustic soda or soda ash for pH control. The borax buffer will provide pH control in the range of 9 to 10.5. Nitrite concentrations should be maintained at 500 mg/L. Magnetic Water Treatment Devices These devices are touted as a means of preventing hardness scales from developing on heat transfer surfaces without chemical treatment. Their effectiveness has been the subject of long-standing controversy. There are a variety of configurations for these devices, but the basic principle is that a magnetic field oriented perpendicular to the direction of water flow induces an interference that restricts the movement of ionic or colloidal particles, thus preventing scale formation. The majority of the research and development information from universities and large corporations shows that these devices do not work. Manufacturers of the devices contend that the studies were flawed or not properly performed. However, the manufacturers claims have not been substantiated with performance data. v
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Closed Cooling Systems A closed cooling water system should have no more than 5% makeup in volume per year. Normally, good quality makeup water is used, zeolite-softened or potable water. Corrosion control is a major concern. Scale and deposits are rarely a problem unless there is continuous makeup with hard water. Biological control is extremely important to avoid slime or biofilm on tube surfaces. Slime or biofilm reduces heat transfer and accelerates underdeposit corrosion. Before using a chemical treatment program, the closed system should be clean and free of deposits (oils, debris, mill scale, etc.). A clean surface is essential because protection only can be achieved by having the corrosion inhibitor reach the metal surface to form a protective film. Clean surfaces will passivate rapidly. Nitrite Its use is confined primarily to closed cooling water
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