associates, inc.

a subsidiary of UAI Group, Inc.

CLIENT UPDATE
6 Commerce Drive, Reading, PA 19607 Phone: (610) 777-5346 Fax: (610) 777-4136 www.uaiassociates.com

BOILER WATER TREATMENT PRINCIPLES - Part 1

The purpose of these white papers are to discuss technical topics of interest in the areas outside of the production of high purity water. Within various industries, discussion of general water treatment applies to boiler water treatment, condensate treatment, wastewater treatment, and others. This and other series of white papers should serve to inform about general water treatment technologies.
The first series of white papers will deal with the subject of Boiler Water Treatment. The production of hot water or steam for heating or process use is accomplished within a vessel called a boiler. The product of that vessel is used for a variety of purposes. But when industrial plants generate their own hot water or steam, the availability of the boiler becomes a very important consideration. The loss of that boiler can drastically affect one or more plant operations. Therefore the need for water treatment in these systems must be recognized. Boiler water treatment programs have increased both in complexity and in technical sophistication. The ultimate goal of these programs has not changed - maximize the efficiency of the boiler system and prolong its useful life. The size of the boiler system and the use of its product will dictate the degree of complexity of the treatment program. But the specific objective is to control corrosion and deposition. Operating efficiency requires control over deposits that will otherwise interfere with proper heat transfer. Corrosion control is needed to prolong the life of the equipment. As a preface to the discussion of the various treatment approaches, corrosion and deposition in boiler systems should be discussed.

Corrosion

Corrosion is often defined as the deterioration of a material, usually a metal or alloy, because of a reaction with its environment. Basically, corrosion is a process of oxidation, in which the metal attempts to return from its refined state of combination with other elements, as to its original ore. Nearly all metals used in industry are unstable in their normal environment against this kind of change. Mild steel and other metals used in boilers are no exception. They are able to retain their structural integrity during prolonged contact with hot water or steam only because the initial corrosion products deposit as a protective surface film (magnetite Fe3O4), which effectively inhibits further attack. Corrosion becomes a problem only when conditions are such that the protective film breaks down. This can happen if the boiling process produces very high local concentrations of contaminating
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acids or salts in the boiler water. Additionally, it can happen if weak spots in the film offer a focus for corrosion enhanced by mechanical stresses or by the presence of dissolved gases, such as oxygen. Corrosion can manifest itself in several forms. Two of the more predominant forms in boiler systems are a general loss of metal on a large area, or a pinpoint (a highly localized area). With in a boiler system, a generalized kind of corrosion is usually associated with low pH. Localized pitting is most often caused by the presence of oxygen. Corrosion control in boiler systems is based on two principles: removing oxygen from the water or preventing oxygen from reaching metal surfaces; and maintaining an alkaline environment (high pH), which minimizes the potential for iron to corrode.

Deposition

The term "scale" is as old as water treatment. It probably contributed to the birth of the water treatment industry more than any other factor. Frequently what is referred to as scale could well be a baked-on sludge, sludge in oil, or corrosion products. True scale is formed as a result of the precipitation, caused by a change in equilibrium conditions, of soluble solids from a solution. This reaction occurs where the deposit is found. As steam or hot water is generated, the water remaining in the boiler becomes more and more concentrated with the impurities introduced by the feedwater. When the concentration of a material exceeds its solubility, the water can no longer hold it in the dissolved state, and a precipitate is formed. This precipitation of scale usually occurs in a crystalline form, which tightly bonds to the metal surface. When these crystals grow, they form a very dense and hard mass. The more common materials encountered in true scales are calcium carbonate, calcium sulfate, calcium silicate, and metallic oxides. The type of deposition that results depends upon the quality of the makeup water, the treating chemicals used, the amount of concentration allowed, the degree of overheating amount of corrosion products in solution, and possible condensate contamination. The deposits on the water side of the boiler tubes act as a barrier, causing an insulation and a loss in heat transfer. The thicker the deposit, the greater the heat driving force required and the higher the metal temperature developed. If the metal gets too hot, it can soften and rupture. Metallic oxides and metal ions reduced at active corrosion sites also form insoluble deposits with equally severe heat transfer interference properties. Deposition control is based on effective pretreatment of makeup water and internal chemical treatment to prevent both scale and sludge deposits. The basic types of internal treatment programs are based on phosphates, chelants, and/or polymers. This initial series of white papers will discuss each of these basic types of treatment programs.

Phosphate Treatment Programs Conventional phosphate treatment

Conventional phosphate control involves maintaining phosphate residual and a hydroxide residual in the boiler water. Phosphate residuals are normally maintained
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in the range of 20 to 40 ppm PO4. Hydroxide alkalinities, if controllable without excessive blowdown, are maintained in the range of 100 to 350 ppm NaOH. This treatment provides the ideal conditions for precipitation of calcium as calcium hydroxyapatite and magnesium as serpentine. Calcium hydroxyapatite and serpentine are desired because they are relatively non-adherent to boiler metal and are easily removed by manual blowdown. The conventional phosphate treatment also provides a residual of alkalinity to neutralize any acidic contamination. It may, however, promote foaming, especially if organic contaminants enter the boiler. The use of this treatment in boilers operating at pressures above 1,000 psig results in increasing probability of concentrated sodium hydroxide attack. At pressures below 1,000 psig, boiler failures due to concentrated caustic attack are rare.

Coordinated phosphate treatment

Coordinated phosphate control was developed to eliminate the problem of concentrated sodium hydroxide attack. The ability to condition hardness contamination is compromised slightly and the ability to neutralize acidic contaminants is reduced, as compared to conventional phosphate control. Coordinated phosphate treatment requires an alkalinity-free makeup source. This is commonly achieved using evaporator, reverse osmosis, ion exchange, or a combination system. Coordinated phosphate treatment involves maintenance of a trisodium residual with no free sodium hydroxide. Phosphate residuals are typically maintained in the range of 5 to 25 ppm PO4. Small concentrations of hydroxide will exist due to hydrolysis of the trisodium phosphate. Sodium hydroxide should not concentrate since no free hydroxide should exist in the water, with the exception of the hydroxide formed as result of trisodium hydroxide hydrolysis. The hydrolysis reaction should reverse as the boiler solids concentrate on the tube surface. Small amounts of acidic or alkaline contaminants may enter the boiler. It is then necessary to add sodium hydroxide, disodium phosphate, or monosodium phosphate to the boiler water to restore the proper phosphate/pH relationship (3.0 Na/PO4). Coordinated phosphate treatment is generally very effective for boilers operating in the 1,000-1,500-psig pressure range. However, application of coordinated phosphate control to boiler pressures greater than 1,500 psig often results in concentrated sodium hydroxide attack. The cause of the sodium hydroxide attack in coordinated phosphate treatment results, indirectly, from the phenomenon of hideout. Boiler water solids concentrate or dry out on the boiler heat transfer surfaces. Tnsodium phosphate, however, does not precipitate or dry out as trisodium phosphate. As hideout occurs in a boiler containing trisodium phosphate, sodium hydroxide forms in the boiler water. The sodium hydroxide formed is then available to concentrate on the tube surfaces. This is most likely to occur under heavy accumulations of corrosion products or in sloped tubes where pockets of steam may accumulate and prevent rinsing of concentrated solids from the tube wall.

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Congruent phosphate treatment

Congruent boiler water control was developed to assure that hydroxide formation does not occur under hideout conditions. This treatment is based on the premise that the Na/PO4 ratio in the boiler water should be no greater than the congruent ratio. If this is achieved, there should be no free sodium hydroxide formed anywhere in the boiler and attack by sodium hydroxide will be eliminated. The composition of the sodium phosphate compound formed in hideout may vary slightly, depending on the boiler pressure. In order to be sure that the boiler water Na/PO4 ratio is maintained below the ratio for the hideout compound, and to allow a slight margin of safety, the boiler water control ratio is normally set at 2.6. In order to control the treatment, the pH and the total phosphate concentration are determined and adjustments are made as required to keep the pH below the 2.6 curve. Phosphate residuals for congruent phosphate control are normally maintained in the range of 2 to 20 ppm PO4. Congruent control requires makeup using evaporator, reverse osmosis, ion exchange, or a combination system. The further reduction in alkalinity for congruent control (relative to coordinated control) results in additional sacrifice of the ability to condition contaminants that enter the boiler. The chelant, polymer, and all-volatile (AVT) treatment programs will be discussed in the UAI Associates White Paper series to follow.

UAIs Water Technologies group can assist clients with the technical and/or economic evaluation of boiler water, cooling water or wastewater treatment programs. For more information on this subject and/or other UAI Associates, Inc. technical/engineering services UAI Associates, Inc., please contact the following:
Dave Fetterman Water Technology Scientist (610) 777-5346 x248 E-mail: dfetterman@uaigroup.com Carl Hager Water Technology Engineer (610) 777-5346 x254 E-mail: chager@uaigroup.com Ken Burris Director of Water Technologies (610) 777-5346 x285 E-mail: kburris@uaigroup.com Or visit the following web sites: www.uaiassociates.com, www.uaienvironmental.com, and www.uaiconstructors.com
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