The Integral Benefits of Iron Monitoring for Steam

Generation Chemistry Control

01/21/2019
By Brad Buecker, Ken Kuruc and Luke Johnson

In the early 1980s, researchers had concluded that dissolved oxygen

(DO) ingress into condensate/feedwater was a prime factor for carbon
steel corrosion (and unarguably corrosion of copper alloys) during
normal operation of utility steam generators.

So, both mechanical deaeration and chemical methods (i.e., oxygen

scavenger feed) were typically utilized to reduce DO concentrations to
near zero as measured at the economizer inlet of conventional fossil-
fired utility boilers. Oxygen scavenger (the more correct term is
reducing agent) treatment combined with ammonia or a neutralizing
amine for pH control came to be known as all-volatile treatment
reducing [AVT(R)]. The chemistry induces formation of the familiar
gray-black magnetite (Fe3O4) layer on carbon steel surfaces.

In 1986, the foundations of this chemistry received a severe jolt.

 “On December 9 of that year, an elbow in the condensate system

ruptured at the Surry Nuclear Power Station (Virginia),” according to a
2005 report from the Electric Power Research Institute (EPRI). “The
failure caused four fatalities and tens of millions of dollars in repair
costs and lost revenues.”

Researchers learned from that accident and others since then that
the reducing environment produced by oxygen scavengers is the
prime ingredient for single-phase flow-accelerated corrosion (FAC) of
carbon steel. The attack occurs at flow disturbances such as elbows in
feedwater piping and economizers, feedwater heater drains, locations
downstream of valves and reducing fittings, attemperator piping; and,
most notably for combined-cycle heat recovery steam generators
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(HRSGs), in low-pressure evaporators, where the waterwall tubes, aka
harps, have many short-radius elbows. In fact, FAC is typically the
leading on-line corrosion mechanism in HRSGs.

Gradual metal loss occurs at these locations, as is illustrated in the

figure below:

Figure 1: Photo of tube-wall thinning caused by single-phase FAC.

Wall thinning progresses until the remaining material at the affected

location can no longer withstand the process pressure, with sudden
failure as the end result.

Figure 2: Catastrophic failures induced by FAC. Photos courtesy of Steve

Shulder, Electric Power Research Institute (EPRI), per the 35th Annual
Electric Utility Chemistry Workshop

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Two other factors, temperature and pH, also strongly influence FAC.

Figure 3: Influence of temperature and pH on iron dissolution from carbon

steel. (Photo courtesy of Shulder, per the 35 thAnnual Electric Utility
Chemistry Workshop)

The temperature aspect is why FAC is typically most pronounced in

the feedwater system and LP evaporator of HRSGs. Based on the
method of oxygenated treatment (OT) that arose in Europe in the
early 1970s, EPRI developed a program to replace AVT(R) for drum
units, known as AVT(O), which stands for all-volatile treatment
oxidizing. If the condensate/feedwater system contains no copper
alloys, which is true for virtually all HRSGs, then AVT(R) is not
recommended, rather AVT(O).

In brief, with AVT(O) chemistry the oxygen scavenger feed is

eliminated, and a small residual concentration [5 to 10 parts-per-
billion (ppb)] of dissolved oxygen is maintained at the economizer
inlet. Ammonia or an ammonia/neutralizing amine blend is still
utilized for pH control. High-purity condensate (cation conductivity
≤0.2 μS/cm) is a requirement for AVT(O), but when proper conditions

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are established, magnetite becomes overlaid and interspersed with a
tighter-bonding oxide, known variously as hematite, or ferric oxide
hydrate. It is noticeable for its distinct red color.

Figure 4: Properly passivated surfaces in a unit with AVT(O). (Photo

courtesy of Dan Dixon, Lincoln Electric System)

Also gaining momentum is use of film-forming products (FFP) to

protect all metal surfaces from both on-line and off-line corrosion. A
discussion of FFP chemistry is beyond the scope of this article, but the
subject will be reviewed in more detail at the 39th Annual Electric
Utility Chemistry Workshop, June 4-6 in Champaign, Illinois. For more
information, go to www.conferences.illinois.edu/eucw.

The key point of this article, is that whether a unit is on AVT(O), or

AVT(R) for those older, conventional units with copper-alloy feedwater
heater tubes, or film-forming chemistry, monitoring of
condensate/feedwater iron concentrations is key towards proper
chemistry control and minimization of FAC, including another
mechanism known as two-phase FAC that occurs in certain locations
of both HRSGs and conventional units where a water/steam
environment co-exists.

A Key to Success is Iron Monitoring

For years, EPRI-established guidelines suggest that with proper

chemistry, the total iron concentration in boiler feedwater can be
maintained below 2 parts per billion, even for those units on AVT(R).
But if FAC is underway, the iron concentration is typically well above
that value. Thus, regular iron analyses are critical for establishing and
maintaining the correct chemistry to control FAC. A complicating
factor, however, is that typically 90 percent or greater of the steel
corrosion products exist as particulate iron, with only a small fraction
of dissolved iron. So, any analyses obviously need to account for the
particulate iron. Two common techniques are on-line particle
counting, and corrosion product sampling. The latter incorporates
both filtration and ion exchange to capture particulate and dissolved
metals, which are then analyzed to determine the metal

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concentrations. Common is to collect a sample for a week or so, and
then have the filters and ion exchange resin analyzed for results.
While these techniques have been successful, other methods have
emerged that offer good results at reasonable cost.

Simple colorimetric lab methods have traditionally been used to

monitor dissolved iron contamination. The common colorimetric
method for dissolved iron is based on the extremely sensitive
ferrozine-ferrous iron complex described by Stookey in his 1970 piece
for Analytical Chemistry. Ferrozine complexes with dissolved ferrous
iron to form an intensely colored purple complex. The dissolved
ferrous iron concentration may be determined by measuring the
absorbance of this complex. Modifications of this traditional method
now allow for the determination of both dissolved iron and particulate
iron oxides at very low concentrations. (Kuruc, K., Johnson, L. “Further
Advances in Monitoring Low-Level Iron in the Steam Cycle.”
PowerPlant Chemistry, 2015)

The reductive dissolution of iron oxides via thiol-containing

compounds has been thoroughly investigated by Waite et al.
Thioglycolic acid (TGA) has been used to successfully dissolve and
reduce various iron oxides. While magnetite is dissolved relatively
easily with TGA, hematite has been shown to be much more resistant
to this method, according to work by Waite, Torikov and Smith and by
Baumgartner, Maroto and Blesa.

However, TGA is compatible with the sensitive ferrozine reagent and

is commercially available as a combined reagent. This combination
digestion-reduction-detection reagent is particularly useful for
simplifying analysis and minimizing contamination.

Figure 5: Combination reagent, digestion vials and heater block (left); 1”

sample cell (center) and spectrophotometer (right)

Complete dissolution of particulate magnetite and hematite can be

achieved with a 135°C, 30 min closed vessel digestion using 240 μL of
combination reagent and 12 mL of sample. The digestion is carried
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out in a 20 mL glass vial heated in an aluminum block. After the
sample has cooled the absorbance is read with a spectrophotometer
and a 1” cell. The calibrated range using this procedure is 1-100 μg/L
with a method detection limit (MDL) of 0.3 μg/L.

A combination of a simple colorimetric total iron laboratory analysis

with a sensitive laser nephelometric analyzer can also provide a
method for cost effective, quantitative, real-time corrosion
monitoring. When properly calibrated, the nephelometric units
provided by a nephelometer can be correlated to total iron
concentration values. The iron concentration of the process water is a
direct indicator of steel corrosion.
As the process waters used in power generation are extremely pure, it
can be assumed that almost all insoluble matter present in a ferrous
metallurgy process stream is due to steel corrosion in the form of
particulate or colloidal iron oxides. Corrosion of steel components in
power generation is generally found as iron oxides and hydroxides,
primarily, iron (II, III) oxide (magnetite), α-iron (III) oxide (hematite),
or dissolved iron. Each of these species produces a different
nephelometric response to visible light. Black magnetite absorbs
more and reflects less light than red hematite. Dissolved iron does not
produce any nephelometric response.

Figure 6: Suspended particles of magnetite (black) and hematite (red) in

water

Corrosion products range in size from sub-micron to 10 μm in

diameter, with an average diameter of 1 μm (Kuruc and Johnson,
2015). This range of diameters poses another challenge for particle
monitoring because nephelometers respond differently to different
particle sizes.

The variables associated with iron corrosion products (species, color,

particle size) make it impossible to create a universal nephelometric
calibration for quantification of corrosion products. A nephelometric
calibration which is appropriate for a particular sample location with
particular corrosion characteristics will not be accurate for a different
location with different corrosion characteristics.

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Therefore, quantification of total iron via nephelometry must be
accomplished through site-specific calibration. Variability in water
chemistry, phase, and local piping configurations contribute to
variable corrosion characteristics. Site-specific calibration ensures
that nephelometric response is correlated to the specific corrosion
characteristics present at each installation.

Figure 7. Laser nephelometer mounted on a water panel/view of the

sample cell
About the authors: Brad Buecker is Senior
Technical Publicist with ChemTreat. He has 35 years of
experience in or affiliated with the power industry,
much of it in steam generation chemistry, water
treatment, air quality control, and results engineering
positions with City Water, Light & Power (Springfield,
Illinois) and Kansas City Power & Light Company’s La
Cygne, Kansas station. He also spent two years as
acting water/wastewater supervisor at a chemical plant.
Most recently he was a technical specialist with Kiewit
Engineering Group Inc. Buecker has a B.S. in chemistry
from Iowa State University with additional course work
in fluid mechanics, energy and materials balances, and
advanced inorganic chemistry. He may be reached at
bradley.buecker@chemtreat.com.

Ken Kuruc is Industry Account Manager for Fossil

Power with Hach. He has 24 years of experience in
working with the power industry, primarily surrounding
the steam cycle. His focus in early years has been with
dissolved gases for corrosion monitoring as part of
Orbisphere, which has since been integrated into Hach.
Kuruc has a B.S. in Chemistry from John Carroll
University (University Heights, OH) and has presented
on this subject along with others at power conferences
across the U.S. He may be reached
at kkuruc@hach.com

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 Luke Johnson is Product Applications Manager with
Hach. He has over 17 years of experience in a variety
of technical fields. Johnson has a B.A. in Chemistry from
Colorado State University and an M.S. in Chemical
Engineering from North Carolina State University. He
can be reached at lujohnso@hach.com.

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