The Evolution of Power

Plant Water/Steam
Chemistry
10/01/2012
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By Brad Buecker, Contributing Editor

Water and steam are the lifeblood of any steam-driven power facility, and proper
chemistry control is critically important to plant operation, reliability, the bottom line,
and especially personnel safety.
In the last three decades, our understanding of high-pressure water/ steam chemistry
has greatly advanced through direct experience and from excellent research and
funding by organizations such as the Electric Power Research Institute (EPRI).
In spite of this research and numerous publications regarding steam generation
chemistry, many in the power industry have not yet been properly informed of new
developments. This problem is exacerbated by the retirement of many power plant
Baby Boomers, which is creating a void in operational knowledge.
Also, it is becoming quite evident that natural gas combined-cycle power production will
be replacing coal-fired generation at a rapidly increasing pace. Many of the lessons
learned from the coal-fired power industry are directly applicable to high-pressure heat

recovery steam generators (HRSGs), but sometimes the message is not transferred
adequately. So, let's dig into the most important issues.

Condensate/Feedwater Treatment
When I began my utility career in 1981, widely-accepted condensate/feedwater
chemical treatment consisted of ammonia or amine feed to establish an alkaline
environment. This treatment was combined with feed of an oxygen scavenger/metal
passivator to eliminate any oxygen not removed by a deaerator and/or a deaerating
condenser. The combination of ammonia and oxygen scavenger feed came to be called
all-volatile treatment reducing, [AVT(R)]. The thinking was that all oxygen must be
eliminated from the feedwater system.
"This changed in 1986. On December 9 of that year, and elbow in the condensate
system ruptured at the Surry Nuclear Power Station [near Rushmere, Virginia, USA]. The
failure caused four fatalities and tens of millions of dollars in repair costs and lost
revenues." [1]. Researchers learned from this accident and others that the reducing
environment produced by oxygen scavenger feed results in single-phase flowaccelerated corrosion (FAC).
The corrosion is most prevalent at directional changes and flow disturbances, e.g.,
feedwater and economizer elbows, valve perturbations, feedwater heater drains, and
other locations. The pipe wall gradually thins, and catastrophic failures occur when the
corroded area can no longer withstand the internal pressure. The chart in Figure 1 shows
that the phenomenon is primarily influenced by pH and temperature.
The corrosion mechanism typically reaches a maximum at a temperature of 300o F,
which in the case of HRSGs can initiate severe FAC in the LP evaporator circuit with its
many short-radius elbows. IP and HP evaporator elbows can also suffer from FAC at
times even though the temperature is greater than in the LP. In addition to the accident
noted above at the Surry Nuclear Plant, during the last decade a FAC-induced
attemperator line failure occurred at a sister plant to one at which I worked, in which the
failure killed two plant personnel. I cannot overemphasize the importance of this issue.
The feedwater treatment program now employed for most drum units is all-volatile
treatment oxidizing [AVT(O)]. In this program, the (typically) small amount of air that
leaks in through the condenser is allowed to remain, with ammonia injection to raise the
pH to a range of 9.2 to 9.6. If the cation conductivity of the feedwater is maintained
below 0.2 S/cm, the magnetite (Fe3O4) layer that naturally develops on carbon steel
becomes interspersed and covered with a coating of ferric oxide hydrate (FeOOH),
which is not susceptible to FAC. AVT(O) is an offshoot of oxygenated treatment (OT),
which was developed in Europe almost 40 years ago as a condensate/treatment method
for once-through steam generators. With OT, pure oxygen is deliberately injected into
the condensate and feedwater to induce formation of the FeOOH protective coating. The
condensate must be very pure (cation conductivity 0.15 S/cm) for this treatment to
work properly.

An important point to note is that if the feedwater system contains any pre-heaters with
copper-alloy tubes, AVT(O) or OT cannot be employed, as the oxygen would quickly
corrode the copper. AVT(R) is the only choice when copper alloys are present, but
chemistry must be carefully monitored and controlled to achieve a balance between
minimized copper corrosion and FAC. [2]
With regard to HRSGs, single-phase FAC can be addressed in the design phase by
fabricating evaporator elbows from 2.5 percent chromium steel as opposed to straight
carbon steel. Even a small amount of chromium imparts great resistance to FAC.
Admittedly, however, this method will increase material costs for the LP steam
generator.
Another phenomenon that may affect high-pressure steam generators is two-phase FAC.
This corrosion occurs in locations where water and steam exist simultaneously, such
that any protection offered by AVT(O) or OT is lost when the oxygen flashes away with
the steam. A primary location is the deaerator in both conventional units and HRSGs.
Two-phase FAC is not easy to control, so regular inspections of locations susceptible to
the corrosion are important. I have personally inspected or observed situations of twophase FAC corrosion of deaerators and feedwater heater drains in coal-fired units. The
latter actually caused a failure, fortunately when no personnel were in the area at the
time of the occurrence.
Other location(s) for two-phase FAC are the distribution headers and cooling circuits of
air-cooled condensers. Two-phase condensate from the LP turbine exhaust can be quite
damaging in these locations.
A different issue regarding oxygen corrosion must be noted. For low-pressure boilers
such as industrial units or power plant auxiliary boilers, an oxygen scavenger/metal
passivator is often quite beneficial, as the makeup may contain high levels of dissolved
oxygen. For units at pressures below 600 psig, sodium sulfite (Na2SO 3) is a practical
choice. The compound removes oxygen thusly,
2Na2SO3 + O2 2Na2SO4
For higher pressures, one of the substitutes for hydrazine (N2H4) is a better choice, as
sodium sulfite will break down to produce sulfur dioxide (SO 2) and perhaps some
hydrogen sulfide (H2S). Both of these decomposition products can cause considerable
damage in boilers.

Boiler Water Treatment

Boiler water chemistry for drum units has evolved for two primary reasons. First, much
more is known about waterwall corrosion mechanisms, particularly with regard to
traditional treatment programs. Secondly, issues related to carryover of products from
boiler drums to steam turbines are also much better understood.

Phosphate treatment of drum boilers is still a common method to protect against

corrosion, but gone are the days of coordinated and congruent phosphate treatment,
where the chemical feed consisted primarily of tri-sodium phosphate (Na3PO4) but with
some di-sodium phosphate (Na2HPO4) and even sometimes mono-sodium phosphate
(NaH2PO4) blended in. It is now well known that phosphate will precipitate on boiler
internals at high temperatures (in a phenomenon known as hideout), and where the old
programs can produce low sodium-to-phosphate ratio deposits that directly corrode
steel. At present, the most common phosphate program, in the U.S. at least, is the
Electric Power Research Institute's (EPRI) phosphate continuum (PC). Only tri-sodium
phosphate (Na3PO4) is utilized, with perhaps a bit of caustic (less than 1 part-per-million
[ppm]). While the recommended phosphate range is 0.2 ppm (absolute minimum) to 10
ppm, most chemists tend to control chemistry at the lower end of the range. This
relates back to the phosphate hideout issue mentioned above and to the potential for
solids carryover into steam, which we will soon examine. The typical pH range for this
program is 9.0 to 10.0, with no more than 1 ppm of free caustic. A very critical aspect of
these programs is that even minor in-leakage of contaminants from a condenser tube
leak may introduce chlorides and sulfates to the boiler water. These contaminants, and
chlorides in particular, can concentrate underneath deposits and initiate hydrogen
damage of boiler tubes.
An alternative to phosphate is straight caustic treatment of evaporator circuits. Two
features of caustic treatment stand out. One, the elimination of phosphate also
eliminates phosphate carryover to the turbine, which has been a problem at numerous
plants. Secondly, caustic is best at neutralizing chloride or sulfate salts that may enter
the system. However, NaOH chemistry must be carefully monitored as caustic can
directly attack boiler tubes, particularly under deposits.
Once-through steam generators must operate on some form of AVT, with OT being the
preferred choice. OT is also possible for drum units, in which case the only other
chemical feed besides oxygen is ammonia. A point to be noted about AVT, whether it be
AVT(R), AVT(O), or OT, is that the chemistry offers no protection towards an influx of
impurities, say from a condenser tube leak, makeup treatment system upset, or other
source. Continuous, on-line chemistry monitoring is vital to detect problems and make
quick corrections. I hope to also address this issue in more detail in a future Power
Engineering article.

Steam Purity
The steam turbine is, of course, a highly-tuned piece of equipment that has to operate
under high stress conditions. Even in the absence of ingress of catastrophic impurities,
or concentrations thereof, the recirculating nature of drum boilers will cause an increase
in dissolved solids within the boiler water. If these are not controlled properly, the solids
will carry over with steam to foul downstream components. Carryover occurs by two
mechanisms, either mechanical, where impurities enter the steam path via water
droplets entrained in steam, or vaporous, where contaminants volatilize. Mechanical
carryover typically results from poor boiler operation, improper chemistry control, or
poor design/maintenance of the drum and its water/steam separating devices. Even in

the best systems, a minor fraction of water will carry over with steam. Boiler pressure
plays an important part in mechanical carryover, as the density of water and steam
approach unity as the pressure approaches the critical point of 3208 psia. With vaporous
carryover, the impurities volatilize, and are not entrained in moisture droplets as they
enter the steam. Boiler pressure also is very important with regard to vaporous
carryover issues, as higher pressure typically equates to greater carryover of these
products.

The list below outlines many of the major carryover products, and the difficulties they
cause in the steam system. The list also includes common limits for reheat steam purity.
These limits have been lowered over the decades, and may be lowered even more, as
knowledge improves regarding the influence of impurities on turbine components.
Sodium phosphates. Phosphates carry over mechanically and settle out in the
superheater and reheater, particularly the latter. Many plants have had to deal
with overheating in reheater U-bends due to sodium phosphate deposition.
Sodium limit, 2 parts-per-billion (ppb).
Chlorides. The majority of chlorides will carry over mechanically although some
vaporous carryover may occur as ammonium chloride (NH4Cl) or even some
hydrogen chloride (HCl). Chloride's most notorious reputation in steam circuits
is as a pitting and stress corrosion cracking agent in low-pressure turbines.
Limit, 2 ppb.
Sulfates. Sulfate is another anion that will carry over as sodium sulfate or in AVT
units as ammonium sulfate [(NH4)2SO4]. Volatile carryover is lower than from
chlorides. Sulfate causes similar problems as chloride, but is not quite as nasty.
Limit, 2 ppb.

 Silica. Vaporous carryover is silica's primary transport mechanism. Silica will

precipitate in the high-pressure end of the turbine as steam pressure decreases
during its path through the turbine blades. Silica forms a tenacious and hard
deposit that is difficult to remove. Limit, 10 ppb.
Copper. Copper carries over vaporously, particularly in steam generators
operating at 2400 psi and above. Like silica, copper precipitates on highpressure turbine blades, where only a few pounds of deposition will alter the
aerodynamics to the point that megawatts will be lost. Steam purity limits for
copper are not standard, but a common limit for feedwater is 2 ppb.
The allowable concentration of impurities varies from unit to unit and is dependent upon
operating pressure, system configuration, and other factors. While general charts and
graphs are available to calculate maximum impurity control limits, proper monitoring of
each unit is necessary to determine the limits for that particular steam generator.
This article only briefly touched upon many important issues related to high-pressure
water steam chemistry. The reader should refer to the literature and consider attending
events such as the Electric Utility Chemistry Workshop for additional information.

References
1. Guidelines for Controlling Flow-Accelerated Corrosion in Fossil and Combined-Cycle
Plants, EPRI Report 1008082, Final Report, March 2005, the Electric Power Research
Institute, Palo Alto, California.
2. Buecker, B., and S. Shulder, "The Basics of Power Plant Cycle Chemistry"; preconference seminar for the 27th Annual Electric Utility Chemistry Workshop, May 15-17,
2007, Champaign, Illinois, USA.
Many of the lessons learned from the coal-fired power industry are directly applicable to
high-pressure heat recovery steam generators.

Author
Brad Buecker is a contributing editor for Power Engineering and also serves as a
process specialist with Kiewit Power Engineers, in Lenexa, Kan.