Corrosion Control

in HRSGs
By Brad Buecker, Contributing Editor

D
ue to the uncertainty over fiiture car-
bon dioxide emissions regulations, many
power companies are turning to com-
bined-cycle power technology for fiiture
generation. Of course, the combustion
turbine is the key component of a com-
bined-cycle plant, but so are the heat re-
covery steam generator (HRSG) and steam turbine. Minimizing
corrosion in HRSGs can sometimes be a daunting task, particu-
larly if the plant cycles fi'equendy. This article examines a number
of the most important issues regarding corrosion mechanisms
and prevention.
HRSG Design issues
One factor that influences some of the corrosion issues in
HRSGs is the steam generator design. Most HRSGs are of the
horizontal gas passage configuration with two or three drum-
type pressure circuits. A common three-pressure HRSG out-

Figure 1 THREE-PRESSURE HRSG

RHIn-

LP Feedwater
IP Feedwater
HP Feedwater
HP Steam
RHOut

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Figure 2 MAGNETITE DISSOLUTION BEHAVIOR
100
90
80
s- 7°
S 60
^ \
I soi
S 40
•^ 30 i
20
10
0 212
Magnetite dissolution as a function of ammonia concentration (actually pH)
Source: Date from 1986 EPRI Interim Consensus Guidelines, now out of print.
line is shown in Figure 1.
The water/steam flow path is from
the low-pressure circuit to the interme-
diate- and high-pressure circuits, with
attendant economizer, superheater and
reheater loops. The important concept
for this discussion is that the HRSG con-
tains many multiple-tube networks with
short-radius elbows at header inlets and
outlets. Another important factor with
regard to now-accelerated corrosion, is
that most HRSGs generally do not have
any feedwater heaters between the con-
denser and the low-pressure (LP) drum,
with the common exception of a deaera-
tor.. Temperature is a critical influence to-
wards flow-accelerated-corrosion (FAC),
identified by the Electric Power Research
Institute (EPRI) as the most prevalent
corrosion mechanism in HRSGs'.
Flow Accelerated Corrosion
I wrote on FAC in Power En^ineer-
inß magazine^ several years ago, after an
FAC-induced failure caused two fatali-
ties in a coal-fired unit that was a sister
at the plant where I was working at the
time. In short, the condensate/feedwater
treatment program that was once popu-
lar fbr steam generators of all kinds, all-
volatile reducing AVT(R), is now known
to cause dissolution of the protective
magnetite (Fe,O^) layer at a temperature
range and chemical conditions common
to the fbedwater network of conventional
boilers and the LP circuits of HRSGs.
Areas particularly susceptible are flow
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in HRSG waterwall tubes that have many
tight-radius elbows. The low-pressure
circuits of HRSGs often operate near the
temperature of highest corrosion poten-
—•— 0,1 ppm
tial shown in Figure 2, which exacerbates
— • - 0,2 ppm
0,3 ppm
FAC mechanism.
-^»— 0,45 ppm
—»— 1 ppm FAC Prevention
—•— 2 ppm The preferred method, from a chem-
istry standpoint, to address single-phase
^ \
FAC issues in HRSGs is to implement
a program developed by EPRI known
as all-volatile treatment (oxidizing), or
its acronym AVT(O). The concept is
that AVT(O) establishes a différent pro-
tective oxide layer (ferric oxide hydrate,
FeOOH) on evaporator tubes and other
•
302 392 482 components. FeOOH is not only tougher
than magnetite, but the oxidizing envi-
Temperature (F)
ronment does not cause iron dissolution.
AVT(O) is what might be called a
"natural" program. Where condenser air
in-leakage is minor and condensate dis-
solved oxygen levels stay at or below 10
disturbances such as elbows or other fit- ppb, the FeOOH protective layer forms
tings. The graph in Figure 2 shows the naturally. Ammonia feed to the conden-
potential magnetite dissolution rates in sate is used to maintain LP economizer
solutions that have been treated with an inlet pH within a range of 9.2 to 9.6. For
oxygen scavenger to remove all oxygen the program to work properly and not
and which establishes a reducing envi- influence corrosion, the feedwater cation
ronment. conductivity should remain at or below
Note that pH in high-purity water is 0.2 mS/cm, Excursions in dissolved oxy-
a direct function of the ammonia con- gen concentration and cation conductiv-
centration. It is the lower pH, at low ity, particularly the former, indicate ex-
ammonia concentrations in a reducing cess air in-leakage within the condenser.
environment, which is responsible for Increased air in-leakage also introduces
magnetite dissolu-
tion. This explains
why corrosion can
be much higher at
an N H , concen-
tration of 0.1 ppm
than in any other
case. The ammonia
does not attack the
magnetite directly.
The effects of
this phenomenon,
known as single-
phase FAC, are
shown in Figure 3,
FAC continually
erodes tube or pipe
wall structure and
eventually reduces
pipe strength to
the point of sudden
failure.
Single-phase
FAC has been a
particular problem
excess carbon dioxide, which influences
corrosion. Thus, for a unit on AVT(O)
any air in-leakage difficulties that raise
condensate dissolved oxygen concentra-
tions significantly above 10 ppb should
be investigated and corrected as quickly
as possible. One point needs to be noted,
however. Recent research suggests some
areas in the condensate/teedwater sys-
tem, such as boiler feed pump discharge
nossles, may sufter from single-phase
FAC even when AVT(O) is maintained
within the current guidelines.' Further
data hopefully will be forthcoming with
regard to this issue.
One issue that has become much bet-
ter known regarding flow-accelerated
corrosion is that of two-phase FAC. At
a number of points in the steam generat-
ing system, zones of physical separation
between water and steam will develop;
deaerators in particular come to mind.
With a program such as AVT(O), the
oxygen will separate with the steam and
leave a less protective fluid that contacts
water-touched components. Particularly
susceptible location are LP economizer
and evaporator elbows, and, generally to
a much lesser extent, IP elbows. Thus,
FAC can occur when chemistry param-
eters are seemingly in acceptable ranges.
Two-phase FAC is difficult to control
chemically, but the issue can be ad-
dressed mechanically in the design phase
by using 1.25-chrome steel in affected
areas, particularly LP elbows.
The Rest Of the HRSG
What about corrosion prevention in
the intermediate- and high-pressure
circuits.' For the multi-pressure drum
HRSG examined here, boiler water treat-
ment for the IP and HP evaporators has
largely evolved from the chemistry de-
veloped for conventional steam genera-
tors. The critical issue in these circuits is
operation at a suitably alkaline pH with
chemistry that can prevent hydrogen
damage by even trace levels of chloride
(Cl) or sulfate (SO^ ^).
For decades, some form of phosphate
treatment has been most popular for
steam generation chemistry control. The
backbone of any program was feed of tri-
sodium phosphate (NajPO^) to generate
an alkaline pH.
« Na.HPO^ + NaOH
For many years, chemists would blend
di-sodium phosphate (Na^HPO^) and
POWERENGINEERING -' JULY 2011 / www.power-eng.com
sometimes even mono-sodium phos-
phate (NaHjPO^) to produce what were
known as coordinated or congruent
phosphate programs. Evidence has since
shown that the propensity for phosphates
to precipitate at high temperatures would
set up direct corrosion of tube metal by
these phosphate blends.
Phosphate treatment has evolved in
almost all cases to EPRI's phosphate
continuum (PC), where tri-sodium
phosphate is the only chemical used, ex-
cept for perhaps a small amount of caus-
tic (NaOH) at startup. The program is
defined as either PC(L) for phosphate
continuum (low) and PC(H) for phos-
phate continuum (high), where the ap-
proximate demarcation point between
the two is a 3.0 ppm phosphate con-
centration. The lower control limit for
PC(L) or (H) is a sodium-to-phosphate
ratio of 3.0 to 1, with an upper control
limit of 1 ppm free sodium hydroxide.
Many utility personnel have opted
for the PC(L) program to minimize
phosphate hideout. Careful control of
the 1 ppm free hydroxide limit is im-
portant to prevent caustic gouging.
However, the low phosphate/alkalin-
ity concentrations provide only minor
protection against contaminant ingress.
Also, at these low concentrations, am-
monia introduced to the feedwater for
pH control in the LP evaporator circuit
can influence pH readings, such that
protection may not be adequate to pre-
vent chloride-induced hydrogen dam-
age. Conversely, excess hydroxide can
cause direct caustic damage of evapora-
tor tubes.
Alternatives to phosphate programs
include caustic treatment or reliance
simply on the AVT(O) utilized in the
LP economizer inlet and evaporator
circuit. Caustic treatment is a consider-
ation for units where condenser leaks or
other impurity ingress is problematic, as
sulfates and particualrly chlorides can
lead to corrosion and hydrogen dam-
age of waterwall tubes. Caustic is also
an alternative for units that suffer from
phosphate carryover to superheater and
reheater tubes.
Additional HRSG Corrosion Factors
Although combined-cycle units can
now achieve 60 precent efficiency, they
are still often used for cycling operations.
Naturally, this imposes thermal stress on
the HRSG. Simple fatigue will reduce
component life. Furthermore, even with
reasonable chemistry, corrosion fatigue
often develops in various locations. In this
mechanism, areas that are stressed become
more vulnerable to attack by impurities in
the water. These may include chloride, sul-
fate or even the hydroxide ions generated
by chemical treatment programs.
Steam chemistry should not be over-
looked. Research over the last tew de-
cades has shown that even minor car-
ryover (>2 parts per billion) of chloride,
sulfate and caustic can induce pitting,
corrosion fatigue and stress corrosion
cracking in turbine components. Of
course, chemistry control in the evapora-
tors can influence impurity transport to
the turbine. However, other factors in-
cluding equipment design and operation
can cause ditBculties. Excessive ramp
rates can cause fluctuations in boiler
drum levels that mechanically push im-
purities into the steam.
The upshot is that good water/steam
sampling and monitoring is critical to-
wards maintaining HRSG reliability and
longevity. A second part of this article, to
be published in a future issue, will cover
sampling and monitoring guidelines.
References
1. Cycle Chemistry Guidelines for
Combined Cycle/Heat Recovery
Steam Generators (HRSGs). The
Electric Power Research Institute,
Palo Alto, California, 2006.
2. B. Buecker, "Flow Accelerated Cor-
rosion: A Critical Issue Revisited";
Power Engineering, July 2007
3. Information presented at the ASME
Research Committee on Power Pnant
& Environmental Chemistry Commit-
tee sprinß meeting, April 2008, Austin,
Texas.
Author: Brad Buecker is a contributing
editorfor Vowcr Engineering. He serves as
a Process Specialist for Kiewit Power En-
¿fineers of Lenexa, Kan. Buecker has over
30 years of experience in or affiliated with
the power industry, much of it in chemis-
try, water treatment, air quality control,
and results en£Íneerin¿ipositions with City
Water, Li^ht &• Power (Sprinßfield, III.)
and Kansas City Power &Li^ht Co.'s La
Cy£[ne, Kansas station. He has an A.A. in
pre-en¿fineerin£[ from Sprinßfield College
in Illinois and a B.S. in chemistry from
Iowa State University. He has written
many articles and three booksfor PennWell
Publishing on steam generation topics.
Buecker is a member of the ACS, AIChE,
ASME and NACE.
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