Phosphate Treatment

Phosphate treatment almost appears to be a combination of EPT and con-

gruent or coordinated treatment. Phosphate residuals are maintained between
2.5 to near 10 ppm, with a sodium-to-phosphate ratio of 2.8 to 1 or greater. As
with EPT, caustic alkalinity is held to 1 ppm maximum. Hideout in PT-condi-
tioned systems has been reported. Although such deposits are more alkaline in
nature than those in a congruent program, hideout can still create difficulties for
the chemist. Possibly for this reason, EPT appears to be the more preferred
replacement for congruent or coordinated programs.

Chelants and Polymer Treatments

Chelants are compounds that chemically bind (chelate) certain elements.
Two of the most commonly used chelants for boiler water treatment are ethyl-
enediamine-tetraacetic acid, or EDTA (Fig. 3-13), and nitrilotriacetic acid.
These chelate cations such as calcium, magnesium, iron, and copper through
interac- tion of the positively charged ions with the partially negative oxygen
and nitro- gen atoms of the chelant. The cation in a chelated structure appears
as if it is in a cage. Chelants do not form precipitates like the phosphates, but
rather keep hardness and other ions in solution so that they can be removed in
the boiler blowdown. EDTA has been effective in boilers operating at pressures
up to 1500 psig, but the compound will begin to break down at a temperature of
400˚F to produce byproducts that also chelate, but less effectively. NTA is
typically limit- ed to boilers of less than 900 psig pressure.
The chelants react on a 1 to 1 basis with cations, thus a significant residual
may be needed to tie up contaminants. An EDTA molecule has a molecular
weight of 288, while the respective molecular weights of calcium and
magnesium

Figure 3-13
HOOC-CH2
CH2-COOH
N-CH2-CH2-
HOOC-CH2
N CH2-COOH
Structure of the ETDA Molecule.
68 Power Plant Water Chemistry: A Practical Guide

are 40 and 24.3. This indicates that 7.2 and 11.9 ppm of EDTA would theoreti-
cally react with 1 ppm of calcium and magnesium, respectively.
The use of chelants must be carefully considered because they can cause
prob- lems in boiler systems. For example, chelants are attacked by dissolved
oxygen and should not be added to the feedwater until after the deaerator. More
importantly, improper control and overfeed of chelants can cause dissolution of
the protective magnetite layer on the boiler tubes. Serious corrosion has been
known to occur.
Polymers of the acrylate (Fig. 3-14), sulfonated styrene (Fig. 3-15), and
other families are also used for boiler water scale control. Most often the poly-
mers are employed as part of a combined program with phosphates or chelants.
The polymers modify the crystalline structure of precipitates, making them less
sticky and more easily removable by blowdown. These chemicals do not act on
a stoichiometric basis with the compounds being treated, and typical dosages
may range from 1 to 10 ppm.
One area where sequesterants such as polymethacrylate (Fig. 3-16) or sul-
fonated styrene appear to be particularly effective is iron control, especially
after unit startup. The sequesterants will bind free iron and allow it to be
removed by the boiler blowdown rather than precipitate on the tube walls.
Chelants and polymers have been
Figure 3-14 effectively used for boiler water chemistry

~ CH CH control. However, proper selection of the

correct chemical or combination of
chem- icals may not be easy. Monitoring
CH2 CH2 ~
of the
COOH COOH
Structure of Polyacrylic Acid. chemical residuals is more difficult than
in phosphate programs. Many people in
Figure 3-15
the electric utility industry appear to
favor the
H H H more “simple” phosphate or volatile
~ C C C ~ treat- ment programs. For low-pressure
indus- trial treatment, however, a
H chelant/poly- mer program may perform
very well. Certainly polymers should be
SO3H SO3 considered for iron control during unit
H startups.
Structure of Sulfonated Polystyrene.

Figure 3-16 Caustic Treatment

Caustic treatment, wherein sodium
CH3
COOH
CH2 CH
~ C
CH3 h xide is the principal boiler water
~ y conditioning chemical, is used at a num-
C
d ber of overseas utilities. In a caustic
COOH r treat- ment program, boiler water pH is
o main- tained within a range of 9.4 to
9.6 by
Structure of Polymethylmethacrylate. addition of caustic to maintain a NaOH
 Boiler Water Chemistry 69

level of 1.0 to 1.5 ppm. Feedwater chemistry in a caustic treatment program must be well
controlled to prevent excessive deposit formation in the boiler, which might lead to
underdeposit caustic corrosion. Caustic treatment of high- pressure boilers has not caught
on in the United States, although caustic control of low-pressure boiler water chemistry was
once a common technique. Sodium nitrate is frequently added with the caustic to prevent
stress corrosion cracking of boiler tubes.

All-Volatile Treatment
All-volatile treatment (AVT) was principally developed for once-through boilers, since
these units cannot tolerate dissolved solids. Because once-through boilers have no drum,
boiler water chemistry is a function of feedwater chem- istry. AVT chemistry guidelines for
a once-through unit call for a pH range of 9.3 to 9.6 with less than 2 ppm dissolved solids.
Ammonia levels may range from 1 to 2 ppm. Condensate polishers are an absolute
requirement for once-through units because a condenser leak or demineralizer upset would
introduce uncon- trollable contamination to the boiler.
AVT is also used in some very high-pressure, drum-type units where the pressure
approaches critical. As boiler pressures increase to this value, the den- sity of steam and
water approach each other. Thus, it becomes much more diffi- cult to separate water from
steam in the boiler drum internals, so boiler water must be quite pure to prevent carryover.
AVT minimizes mechanical carryover, but it does not protect drum boilers from
contaminant introduction due to a condenser leak or other problems. Condensate polishers
are the most effective buffer against chemistry upsets. For units without polishers, the
chemical feed system should contain an emergency phosphate unit so that phosphate can be
immediately injected into the drum in the event of an upset. This must be considered as
only a temporary measure, because the sudden increase in dissolved solids due to
contaminant inleakage and phosphate injection will greatly increase the potential for
carryover and deposition.
Several problems with AVT have become