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BOILER-WATER TREATMENT WHY, WHAT AND HOW

Michael G. Sendelbach Mogul Div., The Dexter Corp. Whatever its source, water used to generate steam contains various impurities, the most typical being compounds of calcium, magnesium and iron. In an untreated system where impurities are allowed to reach excessive concentrations, steam quality can be impaired. In addition, hardness salts can precipitate from the boiler water to form sludge and eventually scale, which deposits on the internal surfaces of the boiler. The result: a serious loss of boiler efficiency, and possibly boiler failure. In addition, constant exposure of metal surfaces to feedwater, boiler water, or condensate containing oxygen will result in rapid corrosion and deterioration of steam-system components. Without treatment to inhibit corrosion, the boiler and associated equipment will require excessive maintenance and premature replacement. This article provides an understanding of the causes and consequences of scaling, corrosion, and solids carryover in steam systems. It identifies conditions that can prevent or minimize the occurrence of these phenomena, and outlines measures to optimize boiler-water condition and steam quality, thereby improving steam-production efficiency and extending equipment life. The article covers the treatment of both the feedwater and the water within the boiler (i.e., ``internal'' treatment). It details how to forestall corrosion due to dissolved oxygen and/or low condensate pH, and provides guidelines on selecting a chemical-treatment program. Previous CE articles covering boiler operation include: ``Operating boilers intermittently,'' July 8, 1985, pp. 115-118; ``Airflow measurement for boilers,'' Jan. 20, 1986, pp. 87-88; and ``Chelant/phosphate treatment for boiler water,'' June 11, 1984, pp. 105-108. Problems with impurities Scale is a buildup of solid material formed on internal boiler surfaces when the concentration of impurities in the boiler water exceeds their solubility limit and precipitation occurs. Hardness compounds predominantly calcium and magnesium salts collect on heat-transfer surfaces in the form of a sludge that typically also contains iron, organics and other impurities. These compounds' crystal-building characteristics and their tendency to adhere to metal surfaces, combined with heat from the fireside of boiler tubes, results in a baked-on film that continues to grow as long as the conditions that caused it exist. Scale formation adversely affects heat transfer and energy efficiency in the boiler, resulting in excessive fuel consumption. The U.S. Bureau of Mines has found, for example, that about 7% of fuel is wasted when scale reaches a thickness of 1/32 inch, and that a scale thickness of 1/9 inch causes a fuel loss of approximately 16%. Loss of steam-production efficiency and wasted fuel are not the only adverse effects of scale formation. Because the scale acts as an insulator inhibiting heat transfer higher-than-normal temperatures must be maintained on the fireside of boiler tubes. This results in overheating of the tubes, with eventual tube failure and other equipment damage. Fouling is the deposition of materials normally in suspension, onto heat-transfer or other surfaces in the boiler system. In contrast to materials that are in solution, these suspended materials can be removed from boiler makeup water by filtering. Loose sludge or deposits inside the boiler can usually be removed by washing waterside surfaces with high-pressure water. Corrosion is the destruction of a metal by electromechanical reaction with its environment. In boiler systems, that environment includes hot water with a low pH or slightly acid condition and some degree of oxygen entrainment. Those conditions are ideal for corrosive action. Loss of metal from boiler tubes and other boiler or steam-system surfaces is the most serious problem caused by corrosion. Expensive equipment that is damaged by corrosion must be repaired at considerable

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cost. And, while materials and labor for repairs can run into big dollars, a boiler shutdown slowing or even halting production can be much more serious. Corrosion-prevention measures include the use of deaeration equipment and chemicals to remove oxygen and other gases from boiler feedwater. This treatment can be extended to include continuous feeding of oxygen scavenger material to the boiler waterside and in steam and condensate lines. Removal of carbon dioxide and oxygen from boiler feedwater is essential to preventing boiler-system corrosion. Condensation of CO2in the condensate system results in the formation of highly corrosive carbonic acid (H2CO3). Much more importantly, the presence of oxygen in the feedwater leads to oxygen pitting, which, while it does not involve excessive metal losses, can result in premature equipment failure due to the formation of small pits that can penetrate boiler metal very quickly. Rapid and economical degasification or deaeration of feedwater, then, must be given high priority. Chemistry is important Control of boiler-water chemistry (i.e., its makeup), before and after the water enters the steam generating system, is vital to efficient operation, acceptable maintenance costs, and satisfactory equipment service-life. This is accomplished by: softening as part of raw-water pretreatment, as well as treatment in the boiler that consists of alkalinity control, sludge conditioning, and control of cycles of concentration. (Cycles of concentration is a measure of the degree to which dissolved solids are concentrated in the boiler water. It is defined as the ratio of the concentration of a specific nonvolatile substance in the recirculating water to its concentration in the feed or makeup water. The term ``cycles'' refers to how many times the water has been recycled before the concentration of dissolved solids reaches the saturation level.) Softening removes hardness, or scale-forming materials, that cannot be removed by filtration. This involves precipitating such constituents, or exchanging them for non-hardness constituents via ion exchange. Hydrogen-cycle softening substitutes hydrogen ions for calcium and magnesium, and the exchange resin is regenerated with an acid solution (normally sulfuric acid). In sodium-cycle softening, calcium and magnesium ions are replaced by sodium, and the resin is regenerated with a sodium chloride solution. For boilers operating at pressures over 900 psig, complete deionization is usually necessary, removing not just the calcium and magnesium, but all the ions (e.g., sulfates, fluorides and carbonates). This is done in a two-stage ion exchange where the substituting ions are hydrogen and hydroxide, which combine to form water. Control of alkalinity (which reflects the water's capacity to react with hydrogen ions) is important as a means of regulating the solubility of calcium and magnesium compounds. Alkalinity generally represents the concentration of bicarbonate, carbonate and hydroxide ions. Some water contains so much sodium bicarbonate that its alkalinity is higher than its total hardness. If used without adequate treatment, such water will produce excessive alkalinity within the boiler, often leading to foaming and the production of impure steam, as well as corrosion. Sludge conditioning involves control of boiler water pH and precipitation of calcium and magnesium compounds as a flocculent sludge that can be washed away in boiler blowdown and not deposited on heattransfer surfaces. Cycles of concentration must be monitored and controlled to prevent precipitation of deposit-forming compounds. Some internal boiler-water treatments can hold hardness compounds in solution at high concentrations, allowing operation at higher cycles of concentration. When cycles of concentration approaches the value at which precipitation will occur, a portion of the boiler water is discharged as blowdown and replaced with fresh makeup water. This blowdown/makeup cycle is necessary because the boiler is releasing pure water vapor in the steam-generation process, while retaining dissolved solids in the boiler water.

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Deaerating the feedwater Feedwater oxygen and carbon dioxide are normally removed by one of the various types of mechanical deaeration equipment, which eliminates the gases before the feedwater enters the boiler. Vacuum deaerators employing mechanical pumps or steam-jet ejectors can remove 02and CO2, reducing 02content to 70 ppb or less. Steam-scrubbing deaerators, or deaerating heaters, are much more effective they can normally remove all CO2and reduce O2levels down to 7 ppb. In such pressure-type deaerating heaters, steam breaks up water into a spray or film, and then sweeps across or through the exposed film or spray to carry away dissolved gases. The typical unit includes a heating/deaerating section, and storage capacity for hot, deaerated water. One of two general designs, spray or tray, or a combination of the two, may be used. Entering steam contacts the hottest water first and thoroughly scrubs out dissolved gas, which is carried along with the steam as it passes through the deaerator. The steam, which may move in a crossflow, downflow or countercurrent relationship to the water, continues to pick up additional noncondensable gas as it passes through the unit, condensing as it heats the feedwater. In addition to mechanical deaeration, it is advisable to employ a chemical scavenger to eliminate any remaining traces of oxygen. Since oxygen removal has to be very quick (within seconds) to minimize corrosion, cobalt or other water-soluble salts are employed as a catalyst to speed the reaction. The most frequently used oxygen scavengers are sulfites and hydrazine. Sulfites were used first, in systems operating at pressures up to 600 psig. These compounds react with oxygen and are changed to sulfates, which are not normally detrimental to the boiler system. At higher pressures, sulfites break down, producing corrosive SO2and H2S, and must be used with caution by experienced operators, accompanied by thorough testing, and with tight control of the sulfite feedrate. Sulfites should not be used at all at pressures above 1,000 psig. Hydrazine has been an alternative to sulfites, especially in high-pressure systems, because the products of its reaction with oxygen are inert and do not add to the dissolved-solids content of the boiler water. Also, hydrazine has a passivating effect on iron and copper surfaces, reducing their vulnerability to corrosion. A major drawback to the use of hydrazine is its possible carcinogenic effect. This has led to the development of other organic oxygen scavengers, such as hydroquinone, carbohydrazide, erythorbic acid, diethylhydroxylamine (DEHA) and methylethylketoxamine. The latter is a reducing agent, with reactions and products much like those of hydrazine and DEHA. Although not presently known to be cancer-causing agents, these compounds have a major disadvantage of being very expensive. Proper treatment of the feedwater will normally prevent corrosion by dissolved oxygen. To be assured of complete oxygen removal, an excess of the chemical deaerant must be maintained in the boiler water. Daily (or more-frequent) tests will show the level of excess. A record of how much chemical deaerant has been added will serve as a continuing check on the efficiency of mechanical deaeration; it will also indicate any infiltration of dissolved oxygen, and help detect other malfunctions in the steam-generating system. Sulfite residuals in the boiler water should be in the range of 20-60 ppm, depending on the type and pressure of the boiler. The normal range for hydrazine is 0.1-0.5 ppm, with the control based on a feedwater excess of 0.05-0.1 ppm or more. Differences in sulfite residuals are more easily detected than differences in hydrazine residuals. Controlling pH Corrosion in the steam and condensate systems as a result of low condensate pH is due to the formation of carbonic acid, which is produced by the reaction of condensate with CO2. The CO2is formed when bicarbonate and carbonate alkalinities in the boiler water break down due to the high temperatures. The CO2is produced in the boiler, leaves with the steam and mixes with condensate as it is formed. Acid buildup reduces condensate pH, contributing to metal loss and grooving of condensate piping. This process is accelerated in the presence of oxygen. Volatile, alkaline neutralizing-chemicals have traditionally been added to offset excess acidity. Chemicals of this type that have been in general use include morpholine, cyclohexylamine, diethylaminoethanol (DEAE), 2-amino-2-methyl-1-propanol, and ammonia. Added to the feedwater, these neutralizers volatilize and carry over with the steam, dissolving in

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the condensate and neutralizing the carbonic acid. The efficiency of an amine in neutralizing carbonic acid is related to its volatility, which determines where in the after-boiler section it will be most effective. The amine's distribution ratio (i.e., the ratio of the amount of amine in the steam to the amount in the condensate, which indicates how far the amine will be carried throughout the system before condensing out) is also an important factor in determining where the amine will achieve the desired results. Amines with higher distribution ratios tend to remain in the steam and control corrosion in equipment or piping far from the boiler, or where pressures are lowest (less than 50 psig). Lower-ratio amines condense earlier in the cycle and control corrosion in locations closer to the boiler, or where steam is condensing at higher pressures. The distribution ratio can be used to determine which amine or combination of amines will be most effective in a given application. Condensate-line protection programs may include two or three amines used in combination. Control of amine concentration, a critical consideration, is most often accomplished by maintaining pH in the range of 7.5-8.5. But control can also include the monitoring of iron levels in condensate and ongoing examination of corrosion coupons. Care must be taken not to confuse acceptable pH levels with acceptable concentrations of amine in regards to U.S. Food and Drug Administration (FDA) limits. There is no direct correlation between amine concentration and pH level. The only way to ensure that FDA limits are being met is to conduct a steam-sampling program in which the amines are analyzed directly. The disadvantages of neutralizing-amines in steam and condensate treatment include: the chemicals' high cost in treating high levels of CO2; excessive dispersion of iron deposits in the event of overfeeding; and poor control of oxygen corrosion. Also, DEAE has been identified as the cause of toxic reactions (including eye and skin irritations) when used in systems supplying steam for humidification of occupied spaces. As a result, DEAE is not generally recommended for steam that is used for air humidification. At present, there is no evidence of potential hazard in steam-line treatments containing other commonly used amines. Because neutralizing-amines can control only CO2-caused corrosion, film-forming amines have come into more general use for protecting against both O2and CO2corrosion with a single treatment. These filmingamines feature large molecular structures with both water-compatible and water-resistant components. Bonding of the water-compatible components with moist metal surfaces forms an adherent, non-wettable layer, or film. The film prevents corrosive condensate from contacting the metal surface, inhibiting corrosion caused by oxygen or low pH. Octadecylamine (ODA), the most widely-used of the filming-amines, has been effective in many applications. Such a treatment must be applied under certain exacting conditions; however, total coating of the pipingsystem surface is necessary for success with any filming-amine. The presence of deposits on the metal surface prevents formation of a complete film, leaving areas under the deposit vulnerable to corrosive attack. Another drawback to the use of filming-amines is that they do not offer good protection where pitting has already occurred. Also, formation of the film on metal surfaces physically blocks the discharge of hydrogen gas and metal ions. ODA, in particular, has a strong affinity for unoxidized metal surfaces and tends to undercut iron oxide deposits. That causes rapid removal of the oxide immediately following ODA application. Loose oxide tends to block steam traps and valves in the condensate system, and can form deposits when carried into the boiler. ODA also tends to degrade, especially in the presence of ferric iron, forming products that can combine with other degradation products in the condensate and accelerate corrosion. The filming action of ODA occurs in the relatively narrow pH range of 6.5-8.0, resulting in control difficulties. For these reasons, filming-amines are not widely used. Filming-amines are fed into the main steam header at one or more points, which will ensure good distribution. Care should be taken to avoid areas where a free flow of steam cannot be counted on. Many filming-amines must be mixed with condensate or demineralized water before they are introduced. Any dissolved solids would contaminate steam, and could cause formation of unstable amine emulsions. Removing solids Pretreatment of boiler makeup water is necessary to remove impurities that can cause deposits to form inside the boiler, or result in wasted water and energy through excessive blowdown. Dissolved solids in the boiler water increase in concentration as pure water is lost from the system in the steam-generation cycle. All natural waters contain varying amounts of suspended and dissolved material, depending on their source

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and geographical location. Suspended solids, including mud, salt, clay, and some metallic oxides, can be removed by filtration. Dissolved solids, on the other hand, while they precipitate and form deposits on boiler internals at elevated temperatures, can be removed from makeup water only by chemical means. Since complete removal of dissolved solids from boiler makeup-water is possible only through costly evaporation or distillation, effective treatment of the water inside the boiler is needed to prevent scaling and its consequences. Boiler-water internal treatment Direct, or internal, treatment of boiler water is used to provide alkalinity control and thus prevent corrosion, and to prevent scale formation caused by hardness constituents. In all cases, care must be taken not to exceed manufacturers' recommendations regarding boiler-water pH, conductivity, cycles of concentration, and chemical residuals. Those conditions can be achieved through effective operator training, installation of automated feed and control equipment, and the use of effective treatment chemicals. Deposits and corrosion can be controlled by a properly structured chemical-treatment program. Further, it is often possible to remove significant scale deposits and restore heat-transfer efficiency, while avoiding costly downtime and offline cleanup. An effective chemical program may allow only limited formation of precipitation products that do not form deposits and can be removed in boiler blowdown. Or it may completely prevent the precipitation of hardness salts. In either case, the program will normally include oxygen scavengers and neutralizing amines. Maximum recycling of boiler water is economically desirable. Appropriate chemical treatment increases the cycles of concentration that can be tolerated before precipitation occurs. Ideally, chemical treatment keeps solids in solution or suspension at high cycles of concentration, minimizing blowdown, and thus reducing thermal losses and feedwater requirements. The need to control operating costs makes it desirable to use cost-effective water treatment products that can be applied with a minimum of operator involvement. Currently available instruments and controls permit automation of the blowdown function and offer additional savings in labor, thermal energy, and water usage. Precipitation programs The trend in development of water treatment chemicals has been to capitalize on the benefits of traditional programs, while minimizing or eliminating their shortcomings. In particular, carbonate precipitation programs have been used for years to treat boiler systems operating at pressures less than 150 psig, and under conditions of high feedwater hardness (50 ppm or above). As a preventive for calcium sulfate scaling, sodium carbonate was introduced to precipitate calcium carbonate, which could be removed in boiler blowdown. Carbonate programs are less effective at higher pressures and high steam-production rates. At higher boilerwater temperatures, sodium carbonate decomposes to form sodium hydroxide and carbon dioxide. When the carbon dioxide leaves the boiler with the steam, it increases corrosivity of the steam condensate, as discussed before. Another flaw in the carbonate treatment is the greater tendency of precipitated carbonates (compared to precipitation products of other programs) to adhere to boiler internals at higher pressures and steam-generation rates. Phosphate precipitation programs, the most common boiler-water treatments, are normally used at pressures up to 600 psig, in systems with feedwater quality up to 10-ppm hardness. The phosphate ion, introduced in the form of a sodium phosphate product, is less vulnerable to decomposition than is the carbonate ion at higher boilerwater temperatures. Phosphate programs eliminate calcium-carbonate scaling problems. These programs require a hydroxyl alkalinity level of at least 200 ppm. The sludge is more easily disposed of than the precipitation products of carbonate cycle treatment, however, and can be reasonably well-controlled with appropriate blowdown practices.

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Nonprecipitation programs Boiler-water treatments that employ chelating agents (chelants) provide cleaner boiler surfaces than either the carbonate or phosphate precipitation treatments. They inhibit scale formation and permit increased heat flow, with less danger of tube failure. Chelants are organic chemicals that form complex molecules (chelates) with calcium, magnesium, and other metal ions; those molecules are very stable and remain in solution, unavailable for reactions that would lead to the formation of deposits on boiler surfaces. Chelants are effective at pressures up to 1,300 psig, and are usually used in feedwater with a hardness of 1.5 ppm or less. Chelant/metal complexes are generally stable even at higher pressures, if they are formed at lower temperatures. Because they tend to degrade at boiler-water temperatures, chelants are normally added to the feedwater. Thermal degradation also makes it impractical to monitor free chelant residuals in boiler water. Undetected overfeeding causes corrosion of boiler internals, whereas underfeeding results in scale formation. As a deterrent to scale formation, chelant treatments are supplemented with scale-control polymers (e.g., polyacrylates). Monitoring and control of chelant treatments is extremely difficult. In addition, large amounts of chelants are needed for systems using high-hardness feedwater, making this type of treatment economically unattractive in many applications. Sequestrant, or threshold, treatments also use chemicals with chelating characteristics. Phosphonates are the most common. Such solubilizing agents, like chelants, keep calcium and iron in solution, but are less corrosive and can be fed into either the boiler water or feedwater. Such treatments can be used successfully in cases of varying feedwater hardness and in boilers operating at pressures up to 600 psig. These formulations typically contain phosphonates, polyacrylates, polymethacrylates, or other dispersants; they do not contain phosphates, chelants, or carbonates. Operating at threshold levels (as opposed to the stoichiometric reaction of chelant programs), the polymers and phosphonates function primarily by altering or distorting the crystalline structure of hardness precipitates. Treatment levels necessary for virtual elimination of scale-building tendencies are relatively low, ensuring the cost-effective maintenance of clean waterside surfaces. It was learned in the early 1980s that a group of synthetic copolymers is effective in eliminating iron deposits. Polymers, phosphonates and copolymers are all compatible with carbonate- and phosphate-cycle treatments, as well as with neutralizing-amines programs, and can be used over a wide range of pressures and temperatures. In one three-component treatment, the phosphonate reduces precipitation and modifies the crystal structure of hardness salts, the polymer disperses solids and inhibits sludge formation, and the copolymer controls iron deposition while helping to disperse solids, deter crystal structure, and control precipitation. This combination of synthetic sludge conditioners delivers performance superior to that of previously used boiler-water treatments. The new technology eliminates corrosion problems associated with chelants, and the excessive precipitation common with phosphate treatments. Any limited precipitation that occurs consists of fine-particle, nondeposit-forming compounds that are easily washed away in boiler blowdown. By minimizing sludge deposits and holding feedwater iron in suspension, this technology greatly reduces blowdown requirements resulting in reduced thermal losses and reduced water usage. Sludge conditioners Traditionally, natural organic materials, such as potato-skin starch, tannins from coffee grounds, lignins from wood processing, and various seaweed derivatives, have been used to condition boiler sludge and scale. These materials, usually derived from waste matter, are added to the boiler water and are absorbed on calcium or magnesium crystals, altering the crystals' shape and acting as dispersants. Modification of these natural products by reaction with sulfonates, sulfites or other compounds leads to increased solubility and improved performance. These materials are low in cost and in some cases can be controlled easily because of their effect on boiler-water color. These natural organic materials are best suited for use in systems operating at no more than 125 psig, in the conditioning of calcium carbonate scale. They are less effective in the treatment of calcium and magnesium phosphates. As phosphates were more generally used in treating feedwater hardness, the need for improved sludge and deposit conditioners became apparent.

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Development of synthetic organic sludge-conditioners over the last three decades has increased the effectiveness of carbonate and phosphate water-treatment programs. Water-soluble carboxylated polymers, such as polyacrylates and polymethacrylates, have rendered the carbonate and phosphate precipitation approaches more effective in the prevention of boiler scale. The threshold-reaction characteristics of these carboxylated polymers account for the materials' effective dispersant action at relatively low concentrations. Their high thermal stability makes them suitable at pressures of 800 psig or higher. The limited effectiveness of polyacrylates in controlling the deposition of iron oxide, which enters the boiler with returned condensate, has led to the development of synthetic polymers and copolymers with improved capabilities. These newer synthetics combine effectiveness in metal-oxide control and control of carbonate or phosphate deposits with enhanced thermal stability and satisfactory performance, at dosage levels as low as 2 to 3 ppm. Difficulties in monitoring and controlling concentrations of these newer polymers have led to their being blended with earlier synthetics in current deposit-control technology. Polyacrylates and polymethacrylates, with their excellent cost-performance characteristics, often play leading roles in today's most-advanced treatment programs. Biography Michael G. Sendelbach is boiler products manager at the Mogul Div. of Dexter Corp. (P.O. Box 200, Chagrin Falls, OH 44022; tel. 216-247-5000), where he is responsible for marketing of the firm's boiler-watertreatment programs. During his ten years with Mogul, he has also been involved in research and development and technical service. He holds a B.S. in biology from Kent State University and an M.B.A. from Cleveland State University. He belongs to the Cogeneration Institute and the American Soc. of Energy Engineers.

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