Flow-Accelerated

Corrosion: A Critical Issue

Revisited
07/01/2007
Email
Print
0
Facebook
0
Twitter
1
LinkedIn

1
Share

By Brad Buecker, Contributing Editor

Sudden failures of high-pressure, high-temperature feedwater piping by flowaccelerated-corrosion (FAC) continue to claim lives in the utility industry, which is, of
course, the ultimate catastrophe. The conventional condensate/feedwater treatment of
oxygen-scavenging/pH-conditioning, used for many years by utilities throughout the
country, has proven to be the culprit. The reducing environment generated by this
chemistry will induce FAC, where gradual thinning of pipe or tube walls in a very
localized area leads to sudden and catastrophic failure. The following discussion of FAC,
and methods to prevent it, is taken from a seminar given at the 2007 Electric Utility
Chemistry Workshop.1

Fundamental Feedwater Chemistry

Mild steel is the universal material for condensate/feedwater piping as it offers excellent
strength at economic value. However, iron is just one of several metals that exhibit
amphoteric behavior, in that the corrosion rate is minimized within a narrow pH range
and increases as conditions move either to acidic or strongly alkaline territory. Figure 1

outlines the general corrosion pattern for iron and shows that in acid or alkaline
conditions, corrosion rates can be quite significant.

Click here to enlarge image

The safe range for condensate/feedwater systems is much more restricted than that
shown on the graph and is typically held between the pH values of 9.0 and 9.6.
When a steam generator is placed on line, and where subsequent oxygen
concentrations in the condensate and feedwater remain at levels within a low part-perbillion (ppb) concentration, steel develops a protective coating of iron oxide known as
magnetite (Fe3O4). This mechanism also occurs on boiler waterwall tubes.
Similarly, copper alloys develop a protective layer of cuprous oxide (Cu 2O). Formation of
protective oxide layers is a very important concept.
Optimizing chemistry in the condensate/feedwater system is critical for two reasons.
First, to prevent corrosion of the piping and heater tubes themselves, and second to
minimize the formation and transport of corrosion products that travel to the boiler and
beyond. The two primary corrosion control issues in condensate/feedwater systems
involve pH and oxygen. It is these control issues that influence FAC.
As outlined above, excursions of pH outside a relatively narrow range induce corrosion,
most notably in iron-based materials. Feedwater piping and heat exchanger tubes
exhibit minimal corrosion at a mildly alkaline pH. For a feedwater system of all steel
metallurgy the optimum pH range is 9.2 to 9.6. (These conditions are different in
oxygenated treatment systems, as will be described in a later section.) Corrosion control
in mixed-metallurgy systems is more complicated. Admiralty brass exhibits minimum
corrosion within a pH range of 8.5 to 9. Copper-nickel alloys, particularly the 90-10

material, are most stable around a pH of 9.3. So the question becomes, What is the
best pH for a system containing carbon-steel piping and copper-alloy heat exchanger
tubes? In years past, a commonly recommended pH range for mixed-metallurgy
systems was 8.8 to 9.1, but this recommendation was recently raised to 9.0 to 9.3.
Ammonia or organic amines are the pH-conditioning chemicals of choice. Amines
decompose to produce ammonia in feedwater. However, in high-pressure utility boilers
where the steam is quite pure, decomposition of amines can potentially introduce
unwanted organic acids and CO2 to the turbine. For this reason, some experts
recommend ammonia as the best pH-conditioning chemical.

Dissolved Oxygen Corrosion and Treatment Issues

Uncontrolled oxygen ingress into a steam generator can cause problems, as Figure 2
illustrates.

Figure 2 Oxygen pitting of an economizer tube

Photo courtesy of Mel Esmacher, GE Water Systems.

Click here to enlarge image

So, virtually all conventional utility steam generators have been designed with
condenser air removal compartments, deaerators in the condensate/feedwater system
and chemical feed systems to inject not only the pH-conditioner but also an oxygen
scavenger/metal passivator into the feedwater. The latter constitutes the primary
difficulty.
Into the 1980s (in the United States at least), conventional wisdom called for complete
removal of oxygen from feedwater. It was thought-incorrectly as we shall see-that the
total absence of oxygen was best for corrosion control in the feedwater network. Thus,

mechanical oxygen removal was supplemented with chemical treatment. The workhorse
for many years was hydrazine (N2H4), which reacts with oxygen as follows:
Hydrazine proved advantageous because it does not add any dissolved solids to the
feedwater, it reacts with oxygen in a one-to-one weight ratio and it is supplied in liquid
form at 35 percent concentration.
A primary benefit of hydrazine is that it will passivate oxidized areas of piping and tube
materials as follows:
Hydrazine residuals were typically maintained at relatively low levels of perhaps 20 to
100 ppb.
Hydrazine or its safer alternatives are now no longer recommended unless the
feedwater system includes copper-alloy heater tubes.

Flow Accelerated Corrosion

The use of a pH-conditioner and oxygen scavenger-particularly the latter-constitutes
what is known as an all-volatile treatment (reducing) AVT(R) program. In the 1980s
and 1990s, researchers began to discover that AVT(R) was the cause of previously
unspecified problems. Most notable is the dissolution of magnetite at a temperature
range and chemical conditions common to the feedwater network.
A special note should be made that pH in high-purity water, like condensate and
feedwater, is a direct function of the ammonia concentration. It is the lower pH, at low
ammonia concentrations in a reducing environment, which is responsible for magnetite
dissolution. This explains why corrosion can be much higher at an NH 3 concentration of
0.1 ppm than in any other case. (Figure 3.) The ammonia does not attack the magnetite
directly.

Click here to enlarge image

While it is well documented that dissolved oxygen can induce serious boiler and
feedwater corrosion, especially during unit shutdown, the complete removal of oxygen
during normal operation can be very troublesome. FAC develops at flow disturbances
and direction changes; for example, feedwater and economizer elbows, reducers, and
tees, steam attemperating lines: essentially all flow-disturbed areas touched
continuously by feedwater, in strongly reducing environments.
To understand the problem, first consider the nature of the protective magnetite (Fe 3O4)
layer. The compound is actually a joint mixture of FeO and Fe 2O3 that often exhibits a
rippled pattern. Iron exists in a +2 (ferrous) oxidation state in FeO and +3 (ferric) in
Fe2O3. The ferrous ions are those that are susceptible to FAC and in affected zones the
ions migrate out of the magnetite matrix. The reducing environment continually
regenerates ferrous iron, whose constant migration weakens the wall structure and

eventually reduces pipe strength to the point of sudden failure. From a straight-on view,
the corrosion has the texture of an orange peel. Figure 4 illustrates a side-view of FAC.

Figure 4 Feedwater pipe thinned by FAC.

Photo courtesy of Mel Esmacher, GE Water Systems

Click here to enlarge image

As is clearly evident, the pipe wall gradually thins. Catastrophic failures occur when the
affected area can no longer withstand the inside pressure. Sudden ruptures of hightemperature feedwater lines have killed approximately 10 utility workers at several
stations in the last decade or so. It is imperative that potentially affected areas be
checked ultrasonically for wall thinning, particularly at plants that once used or continue
to use AVT(R).
FAC has also been a problem in heat recovery steam generator (HRSG) waterwall tubes
that have many tight-radius elbows. The low-pressure circuits of HRSGs often operate
near the temperature of highest corrosion potential (Figure 3), which exacerbates FAC
potential. A particular difficulty with HRSGs is that the two or three semi-independent
waterwall circuits make chemistry control rather difficult. One extra-cost solution for
controlling FAC in HRSGs in the design phase is to specify tube material, at least in
elbows, of 1.25 percent chrome steel. This material is resistant to attack.

FAC Prevention
Often, chemical methods are effective for controlling FAC. Sometimes only mechanical
means are suitable.
Oxygenated treatment (OT) is a feedwater treatment that also serves to protect the
boiler. In an OT program, oxygen is deliberately introduced to the condensate and
feedwater system. Two variations of oxygenated treatment are most popular. In the first,
oxygen is injected alone without any pH-conditioning chemicals. This program is known
as neutral water treatment (NWT). More often, ammonia is injected for pH control. This
is known as combined water treatment (CWT).
OT was developed in Germany some 30 years ago for replacement of AVT(R) in oncethrough steam generating units. The program was adopted by other European utilities
and has gained large acceptance at once-through utilities in the U.S. The treatment
requires the controlled injection of oxygen into the condensate/feedwater system.
Common injection points are just after the condensate polisher and again at the
deaerator outlet. In CWT programs, which are most common in the U.S., oxygen is
dosed to maintain a 30 to 150 ppb residual. Ammonia is added to raise the pH within a
range of 8.0 to 8.5. Typically, 20 to 70 ppb of ammonia will produce this pH.
The chemistry of oxygenated treatment is interesting and explains why the program has
become popular. In conventional AVT(R) programs, it may be difficult to keep
dissolved/suspended iron concentrations in the feedwater below 2 ppb and excursions
above 10 ppb are not uncommon. Iron particulates are the primary product that carries
over to the boiler. With oxygen injection however, the base layer of magnetite becomes
covered and interspersed with an even tighter film of ferric oxide hydrate (FeOOH). This
compact layer is more stable than magnetite and releases very little dissolved iron or
suspended iron-oxide particles to the fluid. A properly orchestrated OT program should
lower feedwater iron concentrations to less than 1 ppb.
The keys to an OT program are controlled oxygen feed and high-purity condensate,
where cation conductivity can be maintained 0.15 S/cm. Such parameters are typical
in once-through units anyway, as makeup and feedwater must be highly pure because
contaminants would enter the steam directly. Pure feedwater in once-through units is
usually a given, as these steam generating systems are always equipped with
condensate polishers. OT has also been applied to a number of drum units throughout
the world, as it is a condensate/feedwater treatment and thus can function regardless of
boiler design. OT cannot be used in systems that contain copper-alloy feedwater heater
tubes, as copper corrosion would be much too severe.
An issue that has come to light regarding OT programs is that of two-phase FAC. At
points in the steam generating system, particularly deaerators and feedwater heater
drains, zones of physical separation between water and steam will develop. Chemicals
in the feed solution that prevent FAC may settle in one phase leaving the other without
protection. Thus, FAC can occur when all chemistry parameters are seemingly in
acceptable ranges. Two-phase FAC is virtually impossible to control chemically. The issue

can be addressed mechanically by utilizing 1.25-chrome steel in affected areas, as was

mentioned earlier for HRSG elbows.
An offshoot of OT is a program developed by EPRI known as all-volatile treatment
(oxidizing), or AVT(O). The idea continues to be establishing a FeOOH layer on the
feedwater piping, but by a less intensive mechanism. What the researchers found is that
in condensate/feedwater networks where condenser air in-leakage is minor and where
condensate dissolved oxygen levels stay at or below 10 ppb, discontinued feed of the
oxygen scavenger allows the FeOOH protective layer to form naturally. As with OT, this
program is only for systems with all-ferrous metallurgy. One difference from OT,
however, is that the pH should be maintained within a range of 9.2 to 9.6. An operating
guideline is cation conductivity 0.2 S/cm. Excursions in dissolved oxygen
concentration and cation conductivity-particularly the former-indicate excess air inleakage within the condenser. Increased air in-leakage also introduces excess carbon
dioxide, which influences corrosion. Thus, for a unit on AVT(O) any air in-leakage
difficulties that raise condensate dissolved oxygen levels much above a mid-teen ppb
concentration should be investigated and corrected as quickly as possible.
For mixed-metallurgy systems, OT and AVT(O) are not acceptable, as they would initiate
excessive copper corrosion. However, operation with complete absence of oxygen leads
to FAC. So, the correct program is to feed an oxygen scavenger, but at reduced
concentrations to minimize FAC. This can be quite difficult when relying upon standard
dissolved oxygen and oxygen scavenger analyses. The technique of oxidation-reduction
potential (ORP) monitoring is becoming popular for mixed-metallurgy
condensate/feedwater chemistry. In short, on-line ORP monitors measure the
electrochemical potential of the solution versus a standard electrode, most commonly
silver/silver chloride.
A general rule-of-thumb is that the oxygen scavenger should be fed to maintain an ORP
within a range of -350 to -300 millivolts (mV). This corresponds to a range of -150 to
-100 mV for a standard hydrogen electrode (SHE). However, chemists have found that
this guideline should not be considered an absolute. 2 A better plan is to set up
comprehensive tests that include dissolved iron and copper analyses, and coordinate
the optimum ORP range with minimized copper and iron concentrations.
The important point is that plant personnel establish chemistry to prevent severe
copper corrosion but also to prevent FAC. Feedwater heater tubes can be replaced.
Human life cannot.
References: 1. Buecker, B., and S. Shulder, The Basics of Power Plant Cycle Chemistry;
from the 27th Annual Electric Utility Chemistry Workshop, May 15-17, 2007,
Champaign, Ill.
2. S. Shulder, Practical Application of Oxidation Reduction Potential (ORP) to Control
Oxygen Scavenger Injection to Fossil Power [Systems]; in the proceedings for the 21st
Annual Electric Utility Chemistry Workshop, May 8-10, 2001, Champaign, Ill.

Author: Brad Buecker is an air quality control specialist at a large Midwestern power
plant. He has previous experience as a chemical cleaning services engineer, as a water
and wastewater system supervisor and as a consulting chemist for an engineering firm.
He also serves as a results engineer, flue gas desulfurization (FGD) engineer and
analytical chemist for City Water Light & Power, Springfield, Ill. Buecker has written
more than 70 articles on steam generation, water treatment and FGD chemistry, and he
is the author of three books on steam generation topics published by PennWell
Publishing, Tulsa, Okla. Buecker has an A.A. in pre-engineering from Springfield College
in Illinois and a BS in Chemistry from Iowa State University. He is a member of the ACS,
AIChE, ASME and NACE.