1991 Summer

Municipal Wastewater Reuse for Cooling:

Implications and Proper Treatment
By Paul Puckorius
Introduction Decreasing fresh water supplies and emphasis on water conservation have caused many municipalities and industry officials to examine the use of secondary treated municipal wastewater for makeup to open recirculating cooling systems. In most industries, cooling creates the single largest demand for water within a plant. Consider that a small, 40,000 bbls per day, petroleum refinery or a small to mediumsized, 250 MW, utility power plant will need in the range of 1-2 mgd for makeup to open recirculating cooling systems. Reuse of municipal wastewater for cooling is realistic and workable, however, a successful experience will take into consideration the industrial plant's physical system, the anticipated municipal wastewater quality, and the proper treatment of makeup and recirculating cooling waters. General Corrosion Recycled municipal wastewater's due to increased silica, alkalinity, hardness, and phosphate content are often less corrosive than "fresh" waters. In a cooling system, general corrosion will extract a slow toll on equipment life. In addition, products of corrosion, primarily iron and copper, are troublesome. Because of the concentrating mechanism of the cooling tower, even low to moderate corrosion rates can cause iron and copper to concentrate in the recirculating cooling water. Iron is oxidized to an insoluble form which can settle out within the system creating deposits. Copper can plate out on steel establishing a galvanic corrosion cell. Corrosion rates of less than I mil per year (mpy) on steel and less than .05 mpy on copper and copper alloys are considered excellent. Rates less than 3 mpy on steel and 1 mpy on copper and copper alloys are considered good and are acceptable in most open recirculating cooling systems. The impact of municipal wastewaters, recycled for cooling, is not directly significant on general corrosion rates. Its impact, however, is very dramatic on what corrosion inhibitors can be applied to the cooling water. The water treatment industry employs a variety of chemical inhibitors such as zinc, chromate, inorganic phosphate, silicate, molybdate, some organic materials, and combinations for corrosion control in cooling systems. Chromate or a zinc/ chromate combination is the most effective inhibitor that has been used but due to environmental considerations the use of chromate is being discouraged. All other corrosion inhibitors have greater limitations than chromate, and their weaknesses are often amplified when a wastewater makeup source is used.

1991 Summer Inorganic phosphate, present in many treated wastewaters, can enhance corrosion protection. Much of this phosphate, however, is often complexed with iron and organics and may not be present in a form available to provide corrosion protection. Galvanic Corrosion Assuming that dissimilar metals have not been coupled as a result of system design, galvanic corrosion can be very subtle in a cooling system. Consider the effects of a wastewater containing 0.2 mg/l of copper or nickel entering a cooling system which operates at ten cycles of concentration. Levels of copper or nickel in the cooling system would reach 2.0 mg/l. Much of this metal would plate out on steel with copper or nickel becoming a cathodic site to the steel anode. Localized attack due to the galvanic action of dissimilar metals could rapidly penetrate a steel heat exchanger tube with a tube wall thickness of 1/16" or less. Under-deposit Corrosion Deposits in cooling systems result from the settling of suspended solids, accumulation of corrosion products, precipitation of salts such as calcium carbonate, sulfate, or phosphate, and magnesium silicate, and from bacterial growth on heat exchange surfaces. Such deposits cause a localized area of metal to be shielded from the bulk cooling water flow creating two different chemical environments or a differential concentration cell. The effect of localized corrosion or pitting attack can be severe on thin walled heat exchanger tubes. Microbiologically Induced Corrosion The most common corrosion causing organisms in cooling systems are sulfide producing bacteria (Desulfoviborio, Clostridium, and Thiobacillus). These are anaerobic bacteria which utilize a sulfur source for metabolism and produce hydrogen sulfide. Being anaerobic, sulfide producers occur beneath deposits causing pitting corrosion, most severe on mild and stainless steels. In cooling waters containing high ammonia content, nitrifying bacteria can proliferate. These bacteria including Nitrobacter and Nitrosomonas can convert ammonia and ammonia compounds to nitric acid. Such occurrences have caused pH depressions, increasing corrosion on most metals. The need for good microbiological control programs when using a wastewater makeup source cannot be too strongly emphasized. Salt Precipitation In all open recirculating cooling systems the solubility of many salts can quickly be exceeded and must be controlled by blowdown and with chemical scale inhibitors. The most common cooling water precipitates are calcium carbonate, calcium sulfate, calcium orthophosphate, silica, and magnesium silicate. Scale formation is strongly influenced by pH and temperature. With the exception of silica these scales generally show inverse

1991 Summer solubility to increasing pH and temperature. One result is that scale first appears in hottest spots of a cooling efficiency. Chemical scale inhibitors include polyphosphates, organic phosphonates, and carboxylated polymers. These materials function by holding the precipitating species in solution or by modifying crystal growth so that the precipitate is in a non-adherent form. All cooling systems must still blowdown so that dissolved solids do not concentrate beyond the capabilities of chemical scale inhibitors. Most cooling systems also feed acid for pH control in the range of 6.5-8.5. When a wastewater makeup is being considered, salt solubilities must be predicted. Because of high phosphate content in most secondary wastewaters, calcium orthophosphate is commonly the most troublesome salt. Phosphate is also troublesome due to its tendency to precipitate as iron phosphate or as an iron/calcium/phosphate complex. In the presence of aluminum, aluminum phosphate precipitation will occur. Suspended Solids Suspended material tends to drop out in low flow areas of a cooling system or onto biologically active sites. The amount of suspended solids which chemical treatment can keep dispersed depends upon characteristics of the cooling system. When there are low cooling water velocities and certainly when "shell side" cooling is present, suspended solids levels below approximately 50 mg/l the cooling water must be maintained. In systems with consistently high flow velocities chemical treatments can effectively disperse suspended solids of several hundred mg/l. Microbiological Fouling The high nutrient value of wastewater plus warm and well aerated conditions are ideally suited for bacteria and algae growth. The area most sensitive to microbiological growth is heat exchange surfaces where even a slight growth will dramatically reduce equipment efficiency and provide sites for suspended material to adhere. On cooling tower distribution decks exposure to sunlight promotes algae growth; and if not controlled, distribution nozzles can become clogged. In many cooling systems using a makeup water with high nutrient content, cooling tower decks are covered. Cooling tower fill, the tower's heat transfer media, can also be susceptible to microbiological fouling. Splash fill due to turbulent flow which it promotes is much less susceptible to microbiological fouling. Due to quiescent flow conditions in film filled towers, algal, bacterial, and fungal material can more easily attach to the fill surface. With a large surface area and tight spacing in film fill, flow can be interrupted, and a uniform layer of microbiological growth will add considerable weight to the fill section of the cooling tower.

1991 Summer Water and Treatment Chemical Use It is clearly -desirable to operate at high cycles of concentration. As cycles increase less makeup water is required. And as cycles increase, treatment chemical (corrosion and scale inhibitors, dispersants, and microbiocides) use decreases (these chemicals are lost from the system only by blowdown). However, as cycles of concentration increase, dissolved and suspended solids in the cooling water increase proportionately. Most cooling systems are operated in the range of 5-10 cycles of concentration. Above this range, the small amount of water saved is rarely justified by the increased risk of scaling and suspended solids deposition. When a wastewater source is being compared to a "fresh water" source for cooling tower makeup, engineers must determine how many cycles of concentration can be achieved using either water. A simple comparison can be made based on calcium, silica, or suspended solids although makeup water must be thoroughly analyzed. Cost of chemical treatment also increases when using wastewater makeup compared to a "fresh" water source. The largest increase will be realized for microbiological control chemicals, dispersants, and antifoams. Increases of 50-100 percent in these costs can be expected. Operator Attention Cooling systems are rarely tended full time by an operator. In very large systems an operator will typically spend one half hour to one hour per shift checking system chemistry and making the necessary adjustments to treatment chemical feed-rates. Operating personnel accustomed to this ease of operation when using a "fresh" water source for makeup will resist a change to treated wastewater for makeup. Conversion to wastewater makeup will often result in new systems, such as a phosphate removal plant, that will need to be monitored. Acid systems for pH control, common trouble spots, must operate efficiently; pH control becomes more critical. Chlorination equipment which is also a common trouble spot must be reliable. Proper residuals of chemical inhibitors carried in the cooling water become more important. Additional lab testing, particularly bacterial monitoring will be required. Operator and "Neighborhood" Health Risk Probably the greatest concern to operator safety when using a wastewater makeup source is the health risk posed by drift from a cooling tower. If the cooling tower is located near a residential community or other populated area the concern becomes greater. A high organic content in wastewater makeup will contribute to foaming within a cooling tower. Many organic microbiocides and surfactants also contribute to foaming. If not controlled, foaming can become unsightly and increase drift from the tower. Because of the need for extensive microbiological control programs in cooling systems using a wastewater

1991 Summer makeup, concern has also been expressed regarding the effects of these biocidal agents carried by drift to work areas and surrounding neighborhoods. Solutions to these concerns must involve effective disinfection and bacteria removal before wastewater enters the cooling system, effective microbiological control with the cooling system, effective foaming control, improved mechanical drift eliminator sections of the tower, and placement of the cooling tower where cooling tower drift will not contact workers or surrounding neighborhoods. Discharge Limitations Due to the concentrating mechanism of the cooling system, dissolved and suspended solids present in makeup water can conceivably concentrate to levels unacceptable for discharge. Heavy metals, for example, present in low concentrations within the makeup may increase in concentration by 5-10 times causing cooling tower blowdown to be unacceptable for discharge even when diluted by other plant waste streams. Consistent Makeup Water Quality A cooling system is dynamic due to constant evaporation, makeup, and blowdown. The cooling tower operator attempts to find a steady state where water and treatment chemical use rates are optimized. A set of narrow chemical control ranges are usually developed as guidelines. Control parameters will include pH, calcium, T.D.S., silica and desired residuals for corrosion and scale inhibitors. Upsets in makeup water chemistry can quickly change chemistry within the cooling system particularly if the system is being monitored only one time per shift or less. Even after upsets have been discovered there will be some lag time before the problem is corrected. The result is frequently increased rates of corrosion, fouling, or scaling. Thus, the cooling tower operator will be very interested in the reliability of wastewater treatment steps and holding capacity or flow equalization which precedes the cooling system. Treatment It is important to consider the composition of wastewater makeup relative to cooling system characteristics and its operation. Most secondary municipal wastewaters will contain high nutrient content and high and fluctuating levels of phosphate. Biofouling and calcium phosphate scaling are the most common problems associated with a wastewater makeup source. High temperature cooling systems are more prone to scaling. Low flow conditions, shell side and jacket cooling are more prone to deposition of suspended material. On the other hand, heat exchangers with tube side cooling and high flow velocities are self cleaning; suspended solids deposition is not a major problem. Carbon steel is much more susceptible to corrosion and fouling than copper and copper alloys. Although stainless steel is very resistant to general corrosion, sulfide producing bacteria or concentration of chlorides beneath deposits can cause severe pitting attack. Ammonia will also accelerate corrosion

1991 Summer of copper and copper alloys. Wastewater makeup can be successful if proper physical and chemical treatment of makeup and recirculating cooling water is selected and implemented. Table 1: Criteria In Examining A Wastewater Makeup Source Makeup Water Cooling System Nutrient Value Phosphate Suspended Solids TDS Metals Content Ammonia/sulfide pH Scaling Potential Bacteriological Content Consistency of Composition Within the recirculating cooling water system, treatment must include acceptable levels of the following: 1. Steel corrosion inhibition 2. Copper corrosion inhibition 3. pH control 4. Calcium phosphate scale inhibitors or dispersants 5. Bio-mass control with oxidizing and non-oxidizing microbiocides 6. Suspended solids dispersants 7. Calcium carbonate scale inhibitors, surfactants to enhance microbiological control, side stream filtration, and antifoams are also often required Table 2: Steel Corrosion Inhibition Control Range for Film Inhibitor Chromate Inorganic Phosphate Zinc Polysilicate Molybdate Maintenance 5-20 ppm 10-30 ppm 3-5 ppm 10-20 ppm 5-20 ppm Metallurgy Flow Velocities Maximum Temperatures Cooling Tower Construction Varying Operation Process In-leakage Side Stream Filtration Operator Attention/Sophistication

1991 Summer Several of these inhibitors when used together have a synergistic effect. For example, 1-2 ppm of zinc fed with chromate, phosphate, or molybdate allow lower levels of chromate, phosphate, or molybdate. When chromate is not permitted, steel corrosion inhibition should take advantage of the inorganic phosphate present in makeup water. Remember, however, that much of this phosphate will be complexed with iron and organics; it may not all be available for corrosion inhibition. Even when there is a phosphate removal step on the makeup water, some phosphate (usually 1-2 ppm) will enter the cooling system and concentrate to 5-15 ppm or higher. Because of this calcium phosphate content, successful treatment must include reliable pH control and calcium phosphate dispersants. The pH should be controlled between 6.8-7.5. Dispersants may permit operation at high pH; however, there will be much greater risk of calcium phosphate deposition particularly if phosphate levels fluctuate in makeup water. Steel corrosion inhibition with a wastewater makeup should be accomplished with the addition of 2-4 ppm zinc, 5-15 ppm. molybdenum, or polysilicate at 10-30 ppm, or a zinc/ molybdenum combination. These materials will act synergistically with the phosphate which is already present. Zinc is also strongly influenced by pH; zinc salts can begin to precipitate when pH is greater than 7.5. Molybdenum is insensitive to pH but loses efficiency in high TDS (greater than 5000 ppm) waters. There are some "all organic" steel corrosion control programs currently available. These programs generally require relatively high pH operation (above 7.5 up to 9.0). With wastewater makeup, containing some phosphate, the pH ranges required for many organic programs would likely cause calcium phosphate scale. To summarize, successful steel corrosion control programs with a wastewater makeup will require strict pH control below approximately pH 7.5 to prevent calcium phosphate precipitation. Phosphate present in makeup water should be supplemented with zinc, molybdenum, or polysilicate to achieve synergistic corrosion control. Copper Corrosion Control Even with high ammonia content in makeup waters, corrosion protection of copper and copper alloys can be achieved with proper addition of copper inhibitors such as tolyltriazol or benzotriazole. These materials are normally maintained at 1.5-3.0 ppm. High ammonia may require levels of 3-5 ppm. Calcium Phosphate Inhibition Strict pH control is the best method of calcium phosphate inhibition. There are also many new polymeric materials which increase the solubility of calcium phosphate or distort the crystal growth of calcium phosphate so that a non-adherent precipitate is formed.

1991 Summer Sulfonated polymers such as sulfonated styrene maleic anhydride (SSMA) are proving to be the most effective calcium phosphate inhibitors. Other acrylate-based copolymers and polymaleics are also effective. To date, however, only incremental improvements have been made in this technology. When using a wastewater makeup, a suitable polymeric inhibitor should be applied to maintain approximately 15-40 ppm. These materials should not be the sole source of calcium phosphate inhibition. Consistent pH control is the first requisite. Because of the constant risk of calcium phosphate precipitation, a wastewater makeup source cannot tolerate sloppy pH control. It is desirable to increase pH (to reduce the aggressiveness of the cooling water); however, too high a pH will still cause calcium phosphate precipitation. Non-chromate programs should operate in the range of 7.0-7.5. If phosphate residuals are consistently below 15-20 ppm and good calcium phosphate dispersants are applied, pH control may be raised to pH 7.0-8.0. Microbiological Control Because of their cost effectiveness, oxidizing biocides, chlorine or bromine, should be the basis for microbiological control in the recirculation cooling water. In wastewaters with some ammonia content, chloramines and bromamines will be formed; bromamines are the most effective microbiocidal agents. These materials are typically fed to maintain 0.10.3 ppm free available halogen on a continuous basis or slug fed on time per day (or more often) to achieve a free available halogen residual of 1.0 ppm for 2-4 hours. With wastewater makeup, total bacterial counts should be maintained below 10' colonies per milliliter in the recirculating cooling water. Non-oxidizing microbiocides will generally be required in addition to chlorine or bromine because of the high nutrient content of wastewaters. Remember that most polymeric scale inhibitors and dispersants added to the cooling water are anionic; thus, suitable non-oxidizing biocides should also be anionic or non-ionic and be effective in the pH range anticipated within the cooling water. Suspended Solids Dispersion Low molecular weight (approximately 1000) acrylate based polymers provide the best available suspended solids dispersion. Levels will vary from 5-40 ppm depending upon the needs of the cooling system and makeup water characteristics. Low foaming, nonionic surfactants enhance microbiological control programs by allowing penetration of biological slimes. This type of treatment may be necessary with a wastewater makeup. Foaming in the cooling systems with a wastewater makeup is common and can be attributed to wetting agents present in makeup or added to enhance microbiological control. Organic components of makeup waters or organic microbiocides will also cause foaming. Silicone or hydrocarbon based antifoams may be added periodically.

1991 Summer Summary Treated municipal wastewater can and is successfully used to replace fresh water as a cooling tower makeup in utility and industrial cooling water systems. Success first depends upon a thorough knowledge of potential problems possibly related to the contaminants in the wastewater and how they can and should be controlled. It also requires matching the entire cooling water system characteristics and operation with the water treatment chemicals to enable continuous efficient operation. Using wastewater in place of fresh water not only enables water conservation but can lead to overall cost reduction for cooling tower operation. Chemical treatment costs for corrosion, scaling, and microbiological control will, however, likely increase. Greater attention and testing means higher labor costs with wastewater versus fresh water. Plus, the potential for scaling, fouling, and corrosion is always higher with wastewater makeup. Still the use of municipal wastewater as cooling tower makeup is a viable approach in fresh water short regions and should be considered. However, only with sufficient knowledge and experience in matching it with the cooling system will it stay protected.