CLIENT UPDATE

associates, inc.
a subsidiary of UAI Group, Inc. 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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 Boiler Water
Treatment Principles
Part 1

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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Treatment Principles
Part 1

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.

UAI’s 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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