POWER

AN OVERVIEW OF CURRENT FEEDWATER AND BOILER WATER

TREATMENT PROGRAMS
up. Since these waters contained calci- 10Ca-2 + 6PO4-3 + 2OH- →

A
successful cy-
cle chemistry
program re-
quires both the selection of the appro-
priate program and the proper and con-
sistent application of that treatment ap-
proach. The cycle chemistry program
has to minimize or prevent the following
concerns:
● The transport of corrosion products
from the condensate/feedwater cy-
cle to the boiler.
● Corrosion of boiler tube metal.
● Transport of detrimental anions (e.g.,
chloride & sulfate) or metals (e.g.,
copper) to the turbine.
Where We’ve Been
In the history of feedwater and boiler
water treatment, the two traditional bug-
aboos have been oxygen and caustic.
Oxygen has been a concern because of
oxygen pitting attack, while caustic is
associated with caustic gouging.
Drum boilers. Phosphate treatment
has long been the staple for treating
drum boilers. Before the advent of ion-
exchange (IX) makeup water treatment,
phosphate provided both pH control
and protection against the ingress of
scale forming ions.
Before the development of IX technol-
ogy, there were no “high-pressure” boil-
ers (by today’s standards) and untreat-
ed or “raw” waters were used for make-
um and magnesium, the formation of
mineral scales was a serious problem.
Internal “softening” treatments were
used to prevent the formation of the
least desirable scales such as calcium
sulfate and silica scales. Caustic soda
and soda ash (sodium carbonate) were
commonly used. The so-called “car-
bonate cycle” caused calcium carbon-
ate to precipitate preferentially over
calcium sulfate (a more adherent scale).
The high boiler water pH also protected
boiler surfaces from corrosion. Equa-
tions 1 and 2 represent the carbonate
cycle reactions.
Ca+2 + SO4-2 + Na2CO3 →
CaCO3 + Na2SO4 Eq. 1
CaCO3 + H2O + Heat →
Ca(OH)2 + H2CO3 Eq. 2
Later, it was found that phosphate
chemistry could completely prevent the
formation of calcium sulfate scale and
would form a sludge (calcium hydroxy-
apetite) that was more “free flowing”
than calcium carbonate. The calcium
hydroxyapetite sludge could be re-
moved by blowdown. Equation 3 repre-
sents the calcium hydroxyapetite reac-
tion.
3Ca3(PO4)2·Ca(OH)2 Eq. 3
As boiler pressures increased, the
hydroxide levels led to problems such
as caustic gouging. This is caused by
the dissolution of iron oxide by high
levels of caustic, particularly underneath
deposits. In conjunction with an im-
provement in makeup treatment tech-
niques, the phosphate control regimen
changed to protect against caustic at-
tack. This regimen was coordinated
phosphate treatment. This program was
designed to eliminate the free hydrox-
ide formed by the reaction of phosphate
and water. It is illustrated in Equation 4.
PO4-3 + H2O → HPO4-2 + OH- Eq. 4
Mixtures of trisodium phosphate and
disodium phosphate or monosodium
phosphate were fed to maintain phos-
phate in the range of approximately 5 to
15 parts per million (ppm) as phosphate
(PO4) and a pH range equivalent to a
sodium to phosphate ratio of 2.85:1 to
3.0:1. This was no longer a precipitating
program. This program required a high
purity and consistent feedwater. The
primary purpose was to control pH but
some protection against the ingress of

By K. Anthony Selby
Water Technology Consultants Inc.

ISSN:0747-8291. COPYRIGHT (C) Tall Oaks Pub-

lishing, Inc. Reproduction in whole, or in part,
including by electronic means, without permission
of publisher is prohibited. Those registered with the
Copyright Clearance Center (CCC) may photocopy Figure 1. Typical CPT control chart.
this article for a flat fee per copy.

ULTRAPURE WATER® OCTOBER 2004--UP210749 49


Figure 2. Schematic of PT, CPT, and EPT.
hardness salts was maintained.
So-called “caustic attack” (some of
this could have been acid phosphate
corrosion) was still experienced, espe-
cially as boiler pressures increased
above 1,500 pounds per square inch
gauge (psig). As a result, congruent
phosphate treatment (CPT) was devel-
oped to further reduce boiler water pH
and ensure against caustic attack. C PT
operated with a phosphate concentra-
tion of approximately 2 to 5 ppm of PO4.
It could go up to 10 ppm. The sodium-
to-phosphate ratio was often in the range
of 2.3:1 to 2.6:1, although this varies
from a low of 2.1:1, and a high of 2.8:1.
In many, but not all cases, CPT was
linked to severe “phosphate hideout”
and boiler tube failures due to acid
phosphate corrosion.
A chart showing a typical CPT control
range is shown in Figure 1. This chart
shows the CPT control “box” with a
phosphate concentration of 2.0 to 4.5
ppm of PO4 and a Na:PO4 ratio of 2.3 to
2.6:1.
The equilibrium phosphate treatment
(EPT), using low levels of phosphate,
and allowing a small amount of free
caustic, was designed to minimize phos-
phate hideout and prevent acid phos-
phate corrosion. EPT was typically op-
erated using trisodium phosphate. The
phosphate control range was less than
2 ppm of PO4 with up to 1 ppm of free
hydroxide (OH). EPT does minimize
phosphate hideout but provides little
protection from corrosion resulting from
anionic species such as chloride and
sulfate. According to the Electric Power
Research Institute (EPRI), EPT has been
associated with incidences of hydro-
50
gen damage.
EPRI also had a phosphate treatment
(PT) regimen with phosphate in the 2.5
to 10 ppm (as PO4) range and a pH
generated by TSP +1 ppm of OH.
Figure 2 is a chart that summarizes the
control ranges that were used for PT,
CPT and EPT. It should be noted that
CPT and EPT are no longer part of
EPRI’s recommended programs.
Once-through/supercritical boilers.
Once-through boilers came into play in
the 1960s. Many, but not all, once-
through boilers operate in the supercrit-
ical pressure range. Since there is no
steam drum in a once-through boiler, all
feedwater is converted to steam and
enters the turbine. Therefore, there are
no separate “feedwater” and “boiler
water” treatment programs. The feed-
water must protect the feedwater cycle
and the boiler and be compatible with
the turbine.
The original all-volatile treatment (AVT)
programs used only volatile chemicals
to control pH and dissolved oxygen.
The development of IX condensate pol-
ishers made the concept possible by
producing feedwater of sufficient purity
to protect the turbine. In many cases,
however, control of anionic impurities
was not sufficient to prevent turbine
corrosion. There were numerous in-
stances of turbine corrosion in the 1980s.
As a result, control of AVT programs has
been tightened considerably.
The AVT regimen consisted of adding
ammonia to control pH and hydrazine
as an oxygen scavenger/reducing
agent. The targeted pH range was
typically greater than 9.4 for all-ferrous
ULTRAPURE WATER® OCTOBER 2004--UP210749
systems and 8.8 to 9.2 for mixed metal-
lurgy systems. Hydrazine was often in
the range of 20 to 50 parts per billion
(ppb) at the economizer inlet, but con-
trol of the upper part of the range was
not considered to be important. The use
of hydrazine and other reducing agents
was found to be a significant factor in
flow accelerated corrosion (FAC) in feed-
water systems.
FAC concerns. FAC has been a prob-
lem in feedwater systems and heat re-
covery steam generator (HRSG) evapo-
rators. Single-phase FAC typically oc-
curs within a specific temperature range
(approximately 300oF) and is accelerat-
ed by a pH below 9. A strongly reducing
environment destabilizes the magnetite
film protecting the feedwater piping and
allows a gradual thinning of the pipe
wall. FAC failures are serious and have
resulted in loss of life in several cases.
Figure 3 shows a feedwater line with an
FAC failure. Figure 4 shows the scal-
loped surface in the area of the failure,
which is characteristic of single-phase
FAC.
Where We Are Today
The choice of a treatment program for a
particular plant is a function of several
factors, including system metallurgy and
feedwater purity. There are several pro-
grams to choose from, depending on
cycle design and water chemistry con-
siderations. Available programs con-
sist of oxygenated treatment (OT), AVT
(reducing and oxidizing), phosphate
programs, and treatment with caustic.
Oxygenated treatment. Over the years,
there have been a number of “sacred
cows” associated with boiler water treat-
ment. Chief among these was the role of
dissolved oxygen. OT was developed
in Germany in the early 1970s and used
successfully there until it was finally
used in the United States in 1991. At the
present time, more than 100 supercriti-
cal once-through units in the United
States use OT. OT is also applicable to
drum units, but is not yet widely used in
this country.
Feedwater purity requirements are
stringent with OT. Cation conductivity
must be less than 0.15 microsiemens
per centimeter (µS/cm). Oxygen is con-
trolled 30 to 150 ppb at the economizer
inlet. The result is significantly reduced
iron transport from the feedwater train to
the boiler.
 Figure 3. Feedwater line FAC failure.
Current AVT concepts. Because of
concerns for FAC, EPRI has taken a
close look at AVT concepts. They are
currently recommending two separate
AVT regimens, depending on system
metallurgy (1). Oxidizing all volatile
treatment [AVT(O)] applies to plants with
all-ferrous metallurgy, which is defined
as having no copper in the cycle except
for possibly the condenser. Reducing
all volatile treatment [AVT(R)] applies to
plants with copper alloys in the conden-
sate/feedwater cycle. With AVT(O), no
reducing agent is added and the oxida-
tion-reduction potential (ORP) is approx-
imately 0 millivolts (mV). AVT(R) pro-
vides the reducing atmosphere needed
to limit copper corrosion but minimizes
the risk of FAC. A reducing agent is
used, but ORP is maintained in the range
of –300 to –350 mV. Both regimens use
ammonia for pH control.
Current EPRI recommendations for
operation of an AVT program (either
AVT(O) or AVT(R) regimens) are to main-
tain a feedwater and steam cation con-
ductivity limit of less than 0.2 µS/cm.
The sodium, chloride and sulfate limit in
steam is 2 ppb.
Phosphate treatment concepts. Once
acid phosphate corrosion was identi-
fied, the use of CPT was greatly re-
duced. EPT replaced CPT in many
cases. However, EPT has been associ-
ated with the occurrence of hydrogen
damage. EPRI has now developed the
concept of a “phosphate continuum”
where the phosphate concentration is a
function of feedwater and steam purity.
EPT as such no longer exists in the EPRI
phosphate continuum. An important
aspect of the EPRI recommendations is
that only trisodium phosphate is used
ULTRAPURE WATER® OCTOBER 2004--UP210749
Figure 4. Scalloped appearance characteristics of FAC.
rather than mixtures containing disodi-
um or monosodium phosphate and that
polymers not be used (2). .
The phosphate continuum establish-
es a minimum phosphate concentration
of 0.2 ppm of PO4. The treatment range
is bounded by the sodium (Na) to PO4
molar ratio line of 3.0 and the TSP+1
ppm NaOH line. The phosphate contin-
uum provides for a range of phosphate
levels depending on feedwater purity.
At low phosphate levels, feedwater pu-
rity requirements are the same as the
AVT programs. High phosphate levels
are used in response to poorer feedwa-
ter quality (e.g., 0.3 µS/cm cation con-
ductivity).
This phosphate continuum is shown in
Figure 5 (2). .
Caustic Treatment
In the United States, the fear of caustic
gouging led to the abandonment of the
use of caustic and the development of
“caustic-free” programs such as CPT.
The whole basis of CPT was to keep the
sodium to phosphate ratio in a range
where there could be no free caustic. In
other parts of the world, particularly in
the United Kingdom, caustic treatment
for high-pressure boilers is the stan-
dard. Caustic treatment (CT) uses less
than 2 ppm of sodium hydroxide (NaOH)
in the boiler water. EPRI guidelines
currently include caustic treatment.
Continuum of treatments. EPRI has
tied these treatment choices into a “con-
tinuum of treatments” that is applied,
depending on condenser “tightness”
and/or presence of a condensate pol-
isher with additional consideration giv-
en to air in-leakage control (1). This
concept is shown in Figure 6.
OT is the regimen of choice in all
ferrous systems with very high feedwa-
ter purity, as represented by a tight
condenser or a well-operated conden-
sate polisher, in conjunction with good
air in-leakage control. In the United
States, OT is used in once-through units
but, in reality, is applicable to drum-type
units with appropriate feedwater quali-
ty. Very few HRSG plants in the United
States operate with the level of feedwa-
ter purity needed for successful appli-
cation of OT.
AVT(O) is applicable to those all fer-
rous systems where feedwater quality is
not quite good enough for OT. AVT(R) is
applicable to systems containing cop-
per alloys in the feedwater heater train.
AVT programs are applicable to
HRSGs, as well as conventional boilers
if feedwater purity is adequate. AVT
chemistry is required in HRSG low-pres-
sure units that provide feedwater to boil-
er sections operating at a higher pres-
sure.
The phosphate continuum, or caustic
treatment regimens are also applicable
to both HRSGs and conventional fossil
units. Lower levels of phosphate treat-
ment are applicable to plants with better
feedwater quality. Higher levels are
needed in cases where feedwater qual-
ity is not quite so good.
Summary
The cycle chemistry program in an elec-
tric utility plant must simultaneously pro-
tect the boiler and the turbine. Over the
years, it had been necessary to develop
new treatment programs as increasing
boiler pressures generated new chal-
lenges. There is a range of choices
available today that take advantage of
51
 the ability to produce high-quality make-
up water and feedwater. The treatment
regimens are applicable to both con-
ventional boilers and HRSGs, depend-
ing on feedwater quality.■

References
1. Dooley, B.; Shields, K. “Cycle Chemistry
for Conventional Fossil Plants and Com-
bined Cycle/HRSGs”, Seventh Interna-
tional Conference on Cycle Chemistry in
Fossil Plants, Houston, Texas (June 2003).
2. Dooley, B.R.; Paterson, S.R.; Pearson,
J.M. “HRSG Dependability”, Power Plant
Chemistry 5(12) (December 2003). .

Author K. Anthony Selby is president of

Water Technology Consultants Inc.,
based in Evergreen, Colorado. Mr. Sel-
Figure 5. Phosphate continuum for HRSGs.
by has more than 35 years of experience
in the field of water and wastewater
technology. He has a background in
boiler water technology, cooling water
operations, makeup water pretreatment,
ion exchange, membrane systems, wa-
ter reuse, and overall plant water man-
agement.

Key words: ALL-VOLATILE TREAT-

MENT, BOILERS, CONDENSATE, COR-
ROSION, ION EXCHANGE, OXYGEN,
OXYGENATED TREATMENT, PHOS-
PHATE, POWER

This paper was originally given at the 24th annual

Electric Utility Chemistry Workshop, which was con-
ducted in Champaign, Ill., May 11-13, 2004.

Figure 6. EPRI continuum of treatments.

52 ULTRAPURE WATER® OCTOBER 2004--UP210749