Case History

I
n looking back at the history of boiler
water treatment, chemical treatment
has been designed to control either
deposit accumulation (e.g., scale)
or corrosion. The original phosphate
treatment programs for scale prevention
in boilers used high levels of phosphate.
Caustic
Treatment of
As boiler pressures increased, tube dam-
age attributed to caustic attack was expe-
rienced and phosphate levels were de-
creased.

Phosphate Treatment
Phosphate treatment has long been
the staple for treating drum boilers. Be-
fore the advent of ion exchange makeup
Electric Utility
Drum Boilers
water treatment, phosphate provided
both pH control and protection against
the ingress of scale-forming ions.
At that time, there were no “high-
pressure” boilers (by today’s standards)
K. Anthony Selby, Water Technology Consultants, Inc., Evergreen, Colorado
and “raw” untreated or partially softened
waters were used for makeup. Since these
waters contained calcium and magne-
sium, the formation of mineral scales was
a serious problem. Internal “softening” Until recently, caustic water treatment was not
treatments were used to prevent the for-
mation of the least desirable scales such
as calcium sulfate (CaSO 4) and silica
used in high-pressure electric utility drum boilers in
scales. Caustic soda and soda ash (sodium
carbonate [Na2CO3]) were commonly
the United States because of concern over caustic
gouging. Meanwhile, it was being used successfully
used. The so-called “carbonate cycle”
caused calcium carbonate (CaCO3) to
precipitate preferentially over CaSO4
(a more adherent scale). The high pH of in other countries. Many U.S. electric utilities have
boiler water also protected boiler surfaces
from corrosion. The carbonate cycle re- now converted their drum boilers to caustic
actions are represented by Equations (1)
and (2).
treatment. Tis article describes the basics of caustic
Ca+2 + SO4–2 + Na2CO3 →
CaCO3 + Na2SO4 (1) treatment and presents two case histories of
successful use in the United States.
CaCO3 + H2O + Heat →
Ca(OH)2 + H2CO3 (2)

Later, it was found that phosphate

chemistry could completely prevent the
formation of CaSO4 scale and would
October 2009 MATERIALS PERFORMANCE 39
C H E M I C A L T R E AT M E N T Caustic Treatment of Electric Utility Drum Boilers

FIGURE 1

Mixtures of trisodium phosphate

(Na 3 PO 4 ) and disodium phosphate
(Na2HPO4) or monosodium phosphate
were fed to maintain phosphate in the
range of ~5 to 15 ppm as PO4 and a pH
range equivalent to a sodium-to-phos-
phate ratio of 2.85:1 to 3.0:1. This was
no longer a precipitating program. This
program required a high-purity and con-
sistent feedwater. The primary purpose
was to control pH but some protection
against the ingress of hardness salts was
maintained.
So-called “caustic attack” (some of this
Typical CPT control chart. could have been acid phosphate corro-
sion) was still experienced, especially as
boiler pressures increased to >1,500 psig.
FIGURE 2 As a result, congruent phosphate treat-
ment (CPT) was developed to further re-
duce boiler water pH and ensure against
caustic attack. CPT operated with a phos-
phate concentration of ~2 to 5 ppm PO4
but possibly up to 10 ppm. The sodium-
to-phosphate ratio was often in the range
of 2.3:1 to 2.6:1 but this varies from a low
of 2.1:1 and a high of 2.8:1. In many cases,
but not all, CPT was linked to severe
“phosphate hideout” and boiler tube
failures due to acid phosphate corrosion.
Figure 11 is a chart showing a typical
CPT control range. This chart shows the
CPT control “box” with a phosphate
Schematic of PT, CPT, and EPT. concentration of 2.0 to 4.5 ppm PO4
and a sodium-to-phosphate ratio of 2.3
to 2.6:1.
form a sludge (calcium hydroxyapatite) dissolution of iron oxide by high levels of Equilibrium phosphate treatment
that was more “free flowing” than caustic, particularly underneath deposits. (EPT), utilizing low levels of phosphate
CaCO 3. The calcium hydroxyapatite In conjunction with an improvement in and allowing a small amount of free caus-
sludge could be removed by blowdown. makeup treatment techniques, the phos- tic, was designed to minimize phosphate
The calcium hydroxyapatite reaction is phate control regimen changed to protect hideout and prevent acid phosphate cor-
represented by Equation (3): against caustic attack. This regimen was rosion. EPT was typically operated using
coordinated phosphate treatment. The Na3PO4. The phosphate control range
10Ca+2 + 6PO4–3 + 2OH– → coordinated phosphate treatment pro- was <2 ppm PO4 with up to 1 ppm free
3Ca3(PO4)2{Ca(OH)2 (3) gram was designed to eliminate the free hydroxide. EPT does minimize phos-
hydroxide formed by the reaction of phate hideout but provides little protec-
As boiler pressures increased, the hy- tion from corrosion resulting from an-
phosphate and water in Equation (4):
droxide levels led to problems such as ionic species such as chloride and sulfate.
caustic gouging. This is caused by the PO4–3 + H2O → HPO4–2 + OH– (4) According to the Electric Power Research

40 MATERIALS PERFORMANCE October 2009

 C H E M I C A L T R E AT M E N T

FIGURE 3

Institute (EPRI), EPT has been associated

with incidences of hydrogen damage.
EPRI also had a phosphate treatment
(PT) regimen with phosphate in the 2.5
to 10 ppm as PO4 range and a pH gener-
ated by Na3PO4 +1 ppm OH.
Figure 2 is a chart that summarizes the
control ranges that were used for PT,
CPT, and EPT.2 It should be noted that
CPT and EPT are no longer part of
EPRI’s recommended programs.

Current Phosphate Solution pH vs. pH due to NaOH for various concentrations of NH3.
Treatment Concepts
Once acid phosphate corrosion was
identified, the use of CPT in high-
water chemistry. This is because the a negative ORP. This program is labeled
pressure boilers was greatly reduced. EPT
common enemy of all boiler water treat- AVT(R) by EPRI. Note that both of
replaced CPT in many cases. However,
ment programs is the production of cor- these programs rely on low air inleakage
EPT has been associated with the occur-
rosion products in the condensate/ (<10 ppb dissolved oxygen) and a cation
rence of hydrogen damage. EPRI has now
developed the concept of a “phosphate feedwater cycle and subsequent transport conductivity (acid conductivity) of <0.2
continuum” where the phosphate concen- to the boiler. Deposit accumulation in µS/cm.
tration is a function of feedwater and the boiler creates an environment where
concentration cells accumulate harmful
steam purity. EPT as such no longer exists Caustic Treatment
in the EPRI phosphate continuum. An ions such as chloride, sulfate, phosphate, Basics
important aspect of the EPRI recommen- caustic, etc.
dations is that only Na3PO4 was used Modern electric utility boilers operate Overseas Experience
rather than mixtures containing Na2HPO4 the condensate/feedwater systems on For many years, power plants in the
or monosodium phosphate and that poly- some type of AVT. Current approaches United Kingdom, Ireland, Hong Kong,
mers not be used.3 to AVT attempt to balance iron trans- and South Africa reported operating
The phosphate continuum establishes port, copper transport (if present in the high-pressure electric utility drum boilers
a minimum phosphate concentration of system), and flow-accelerated corrosion with 1 to 2 ppm NaOH in the boiler
0.2 ppm PO4. The treatment range is (FAC). In all-ferrous condensate/feed- water. This elevated boiler water pH and
bounded by the Na to PO4 molar ratio water systems, EPRI currently recom- protected against corrosion caused by
line of 3.0 and the Na3PO4+1 ppm so- mends a program where ammonia (NH3) acidic salts such as chloride. They used
dium hydroxide (NaOH) line. The phos- is added to increase pH into the 9.2 to an empirical relationship of NaOH being
phate continuum provides for a range of 9.6 range but no reducing agent (oxygen equal to 2.5 times the chloride level. This
phosphate levels depending on feedwater scavenger) is used. This results in a posi- would result in a boiler water pH of 9.2
tive oxidizing reduction potential (ORP).
purity. At low phosphate levels, feedwater at ~20 ppb chloride and a pH of 9.5 at
purity requirements are the same as the EPRI labels this program AVT(O) for ~500 ppb chloride.
all volatile treatment (AVT) programs. oxidizing. The purpose of the AVT(O) Caustic treatment of high-pressure
High phosphate levels are used in re- feedwater program is to minimize FAC electric utility boilers is therefore rela-
and minimize iron transport to the
sponse to poorer feedwater quality (e.g., tively simple. Low levels of NaOH are
0.3 µS/cm cation conductivity). boiler. added to maintain pH within the target
If the condensate/feedwater train range. NH3 does have some impact on
Importance of utilizes feedwater heaters with copper the pH, especially below 9.2. As pH in-
Feedwater Control alloy tubes, the typical feedwater pro- creases above 9.2, NaOH becomes the
Good control of feedwater chemistry gram operates at a lower pH (9.0 to 9.3) major driving force. This is shown in
is a prerequisite to controlling boiler and utilizes a reducing agent to maintain Figure 3.4
October 2009 MATERIALS PERFORMANCE 41
C H E M I C A L T R E AT M E N T Caustic Treatment of Electric Utility Drum Boilers

FIGURE 4

serve to better track boiler water impuri-

ties and facilitate impurity control via
blowdown.

Case History #2
Verib discusses the FirstEnergy Corp.
conversion to caustic treatment in drum
boilers.6 FirstEnergy Corp. operates 23
coal-fired boilers. Of these, 16 are drum
boilers and seven are once-through boil-
ers. Boiler pressures range from 2,000 to
2,400 psig (13.8 to 16.6 mPag). All boilers
utilize once-through condenser cooling.
All of the drum boilers were on a low-
Specific and cation conductivity trends, 2,200 psig drum boiler. level phosphate treatment. One boiler
experienced a chronic inability to main-
tain an adequate phosphate level, and
was converted to caustic treatment as a
This shows that at pH 9.0, the impact ity instrumentation, and began monitor- trial. The caustic treatment was found to
of NH3 can be significant. A measured ing corrosion product transport. Hydra- be easy to control. As a result, all of the
pH of 9.0 with 0.2 ppm NH3 means that zine treatment was eliminated in boilers at this station were converted to
the actual pH due to NaOH is only 8.65. all-ferrous drum boiler systems. These caustic treatment. Finally, all drum boil-
Above a pH of 9.2, the NH3 impact is steps significantly reduced corrosion ers were converted.
much less. At a pH of 9.6, the impact of product transport. The utility is operating with a pH
0.2 ppm NH3 is ~0.1 pH unit. Another factor was higher than nor- range of 9.1 to 9.6, a specific conductivity
mal steam cation conductivity in one range of 5 to 20 µS/cm, and a cation
Case Histories— boiler. Since there was no appreciable conductivity range of <10 µS/cm. Figure
Caustic Treatment in sodium in the steam sample, it was likely 4 shows boiler water specific and cation
United States that the elevated cation conductivity was conductivity for the first boiler switched
due to carbon dioxide (CO2). In order to to caustic treatment.
Case History #1 keep the CO2 in the water phase, some The utility has found the caustic treat-
Barnes reported on the conversion of caustic was added along with the Na3PO4 ment program much easier to control
Northern Indiana Public Service Co. to elevate pH. The addition of caustic was than the phosphate programs that pre-
(NIPSCO) drum boilers from phosphate then implemented in the other boilers as ceded it.
treatment to caustic treatment.5 NIPSCO well. It was felt that operation at the
operates four drum-type boilers in the higher pH was providing additional pro- Conclusions
2,400 to 2,600 psig range (16.6 to 17.9 tection against acid phosphate corrosion. In the past, operation of high-pressure
mPag). These boilers utilized NH3 and Finally, all boilers transitioned to an boilers with free caustic was strictly
hydrazine (H2NNH2) for feedwater treat- all-caustic program. Phosphate swings avoided. Due in part to experience in the
ment and CPT (5 to 30 ppm) depending were still occurring and the utility felt United Kingdom, operation of electric
on drum pressure. The CPT was used that feeding only one solid alkali would utility boilers with low levels of caustic in
because of fear of caustic gouging. It was simplify the program. Reductions in total the boiler water is becoming common.
difficult to control the CPT, and boiler tube and turbine deposits have been Electric utility boilers lend themselves to
tube failures were generally attributed to observed. caustic treatment for several reasons:
this problem. Control of the caustic treatment pro- • The cycle is simple—steam is gener-
Throughout the 1990s, NIPSCO in- gram is relatively simple. The utility is ated in the boiler, powers the tur-
stituted compliance with EPRI action also planning to add boiler water cation bine, is condensed, and returns to
levels, significantly improved water qual- conductivity instrumentation. This will the boiler.
42 MATERIALS PERFORMANCE October 2009
 C H E M I C A L T R E AT M E N T

• Pathways for impurities to enter the and feedwater purity needed to allow 5 S. Barnes, “Evolution to Caustic
feedwater/boiler cycle are limited. caustic treatment to function. Treatment in NIPSCO Drum Boilers,”
27th Annual Electric Utility Chemistry
The main pathways are the makeup
Workshop (Champaign, IL: University
treatment system and the main References
of Illinois, 2007).
condenser. If good makeup treat- 1 S.T. Costa, L.O. Brestel, “Managing a
Captive Alkalinity Boiler Treatment 6 Verib, op.cit.
ment control is exercised and con-
Program,” Calgon Corp. Technical
denser leakage is controlled, an Bulletin 10-345. This article is based on CORROSION
electric utility boiler will operate
2 B.R. Dooley, W.P. McNaughton, 2009 paper no. 62, presented in Atlanta,
with minimal impurity ingress. “Appropriate Controls for Phosphate Georgia.
• Because of high-quality feedwater, Boiler Water Treatments to Avoid Acid
deposit accumulation within the Phosphate Corrosion and Hydrogen K. ANTHONY SELBY is president of Water
boiler is minimized. This limits un- Damage,” PowerPlant Chemistry 3, 3 Technology Consultants, Inc., PO Box 249,
(2001). Evergreen, CO 80437-0249, e-mail: tselby@
der-deposit corrosion and the con-
centration of boiler water impurities 3 B.R. Dooley, S.R. Paterson, J.M. comcast.net. He has a B.S. degree in chemistry
Pearson, “HRSG Dependability,” from Wichita State University and has more than 40
(and caustic) underneath deposits.
PowerPlant Chemistry 5, 12 (2003). years of experience in the field of water and
There are other types of industrial wastewater technology. He has been a member of
4 G.J. Verib, “Caustic Treatment in
boilers where caustic treatment would not Boilers at FirstEnergy Corp.,” ASME NACE International for 24 years.
be appropriate. Many industrial boilers Research Committee on Power Plant &
do not operate with the level of makeup Environmental Chemistry, April 2008.

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October 2009 MATERIALS PERFORMANCE 43