Steam Generation Chemistry: Correcting

Outdated Beliefs and Misconceptions

12/02/2015
By Brad Bueckerv

Proposals for new power plants include sections that cover water
treatment and steam-generation chemical treatments. Despite the
extensive research and reporting that have been conducted by such
organizations as the Electric Power Research Institute (EPRI), the
International Association of the Properties of Water and Steam
(IAPWS), and others over the last several decades, many outdated
and incorrect chemistry concepts continue to appear in project
specifications. In some cases, the ideas can lead to situations that are
downright dangerous for plant personnel. Most notable is the
continued call for the use of a reducing agent (oxygen scavenger) in
steam generators that contain no copper alloys, but others abound as
well. At the least, outdated chemistry can establish conditions that
lead to steam generator damage and forced outages.

Ditch the Oxygen Scavenger

In years past, conventional wisdom suggested that any dissolved
oxygen which entered the condensate/feedwater system of utility
boilers was harmful. At that time, over 50 percent of the power
produced in the U.S. came from coal. Coal-fired units typically have
extensive condensate/feedwater networks with numerous feedwater
heaters. The prevalent thinking was that any trace of dissolved
oxygen (DO) would cause corrosion, and indeed dissolved oxygen can
be very problematic if excessive or if copper alloys are present.
Admiralty metal and copper-nickel were common feedwater heater
tube materials a few decades ago, and therefore virtually all
feedwater systems for high-pressure steam generators were equipped
with a deaerator for dissolved gas removal. A properly operating
deaerator can lower DO concentrations to 7 parts-per-billion (ppb).

However, even this residual DO concentration was still considered

harmful, so chemical deaeration was also at most plants. The
workhorse chemical for many years was hydrazine (N2H4), a reducing
agent which reacts with oxygen as follows:

N2H4 + O2 → 2H2O + N2↑

Hydrazine proved advantageous because it does not add any

dissolved solids to the feedwater. Additionally, it reacts with oxygen
in a one-to-one weight ratio, and it is supplied in liquid form at 35
percent concentration. More importantly, hydrazine will passivate
oxidized areas of piping and tube materials as follows:

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N2H4 + 6Fe2O3 → 4Fe3O4 + N2↑ + 2H2O

N2H4 + 4CuO → 2Cu2O + N2↑ + 2H2O

Single-phase FAC showing an orange peel texture Photo courtesy:

ChemTreat.

Hydrazine residuals were typically maintained at relatively low levels

of perhaps 20 to 100 ppb. Oxygen scavenger treatment was coupled
with feed of ammonia or an amine to maintain feedwater pH within a
mildly alkaline range (8.8 to 9.1 for mixed-metallurgy feedwater
systems and a bit higher for all-ferrous systems).

NH3 + H2O ⇔ NH4+ + OH-

This program became known as all-volatile treatment reducing

[AVT(R)]. The alkaline pH minimizes general corrosion.

Due to the suspected carcinogenic nature of hydrazine, alternative

chemicals such as carbohydrazide, methyl ethyl ketoxime, and others
gained popularity. Regardless, all had the same purpose, to establish
a reducing environment in the feedwater circuit, thus inhibiting
oxidation of metal. The technique became a standard in the industry.

This changed in 1986 when an elbow in the condensate system of the

Surry Nuclear Power Station near Rushmere, Virginia ruptured. The
failure caused four fatalities and tens of millions of dollars in repair
costs and lost revenues. Researchers learned from this accident that
the reducing environment produced by oxygen scavenger feed results
in single-phase, flow-accelerated corrosion (FAC).

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 Tube-wall thinning caused by single-phase FAC. Photo courtesy:
ChemTreat.

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 the combined-cycle industry, in low-pressure
evaporators. To a lesser extent, it also occurs in intermediate-
pressure circuits.

During single-phase FAC , wall thinning occurs gradually until the

remaining material at the affected location can no longer withstand
the process pressure, whereupon catastrophic failure occurs. So, what
are possible solutions?

Approximately 40 years ago, researchers and chemists in Europe

began developing a program known as oxygenated treatment (OT) to
minimize carbon steel corrosion and iron dissolution in supercritical
steam generators. The key component of the program was deliberate
injection of pure oxygen into the condensate/feedwater network to
establish oxygen residuals of up to 300 ppb. Chemists discovered that
in very pure feedwater (cation conductivity ≤ 0.15 μS), the oxygen
will intersperse and overlay magnetite to generate a tenacious and
tight layer of ferric oxide hydrate (FeOOH). OT typically lowered
feedwater iron concentrations to 1 ppb or less, and, as researchers
have subsequently confirmed, greatly minimized single-phase FAC.
Now, OT is the preferred feedwater treatment for most once-through
utility steam generators around the world. Common in the United
States is an oxygen residual range of 30 to 200 ppb, with a
recommended pH range of 8.0 to 8.5.

Although OT has been successfully applied to drum boilers, efforts by

EPRI have established an offshoot of OT that has become very popular
for condensate/feedwater conditioning in drum units. It is known as
all-volatile oxidizing treatment [AVT(O)]. With AVT(O), oxygen is
allowed to remain in the condensate from the (normally) small
amount that enters via condenser air in-leakage. Researchers have
also discovered that pH has a strong effect on FAC, with higher pH
establishing more protective conditions. Current AVT(O) guidelines
call for the following conditions at the economizer inlet and low-

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pressure evaporator circuit in heat recovery steam generators
(HRSG).

 Recommended pH range of 9.2 to 9.8 (in units in which

phosphate or caustic provide boiler water treatment)
 Feedwater DO concentration of 5 to 10 ppb

Hydrogen damage showing thick-lipped failure, indicative of weakened

metal without much metal loss. Photo courtesy: ChemTreat.

As with OT, the condensate must be quite pure to allow oxygen to

generate the FeOOH protective layer rather than cause pitting.
However, the normal cation conductivity limit with AVT(O) is a bit
more relaxed (as compared to OT) at ≤ 0.2 μS/cm. The higher pH
range also helps to combat a phenomenon known as two-phase FAC.

Condensate/Feedwater Chemistry vs. Boiler Water

Chemistry
On a number of occasions, specifications have arrived that say "HRSG
boiler water treatment will be AVT." What many people do not seem
to realize with drum boilers is that AVT(O) and AVT(R) is primarily a
condensate/feedwater treatment. Yes, the ammonia or amine injected
into the condensate will establish mildly alkaline conditions and
protect carbon steel from general corrosion, but that is all. Given that
most units still rely on water-cooled condensers, it's important to
understand one of the most common and severe corrosion
mechanisms that can occur in a boiler if a condenser tube develops a
leak, and raw water enters the condensate.
Raw water contains many impurities, especially if the water has been
cycled-up in a cooling tower or if it is brackish to begin with. While
many of the impurities can cause damage, particularly in high-
pressure circuits, the most troublesome impurity is chloride. If
chloride is not neutralized by the chemical treatment program, it will
concentrate under deposits where the following reaction may occur.

MgCl2 + 2H2O + heat → Mg(OH)2 ↓ + 2HCl

A product of this reaction is hydrochloric acid (HCl). Although HCl may

cause general corrosion in and of itself, the compound will
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concentrate under deposits, where the reaction of the acid with iron
generates hydrogen, which in turn can lead to hydrogen damage of
the tubes. In this mechanism, the very small hydrogen molecules
penetrate into the metal wall where they then react with carbon
atoms in the steel to generate methane (CH4):

2H2 + Fe3C → 3Fe + CH4↑

Formation of the gaseous methane and hydrogen molecules causes

cracking in the steel, greatly weakening its strength.

Hydrogen damage is very troublesome because it cannot be easily

detected. After hydrogen damage has occurred, the plant staff may
replace tubes only to find that other tubes continue to rupture. In
some instances, entire power boilers must be re-tubed because of
hydrogen damage.

For a unit solely on an AVT program, the ammonia or amine simply

will not neutralize these reactions. Thus, the necessity for extra
protection of the boiler has driven development and use of separate
boiler water treatment programs for decades. Phosphate treatment
continues to be the most popular choice, although caustic (NaOH)
treatment is gaining ground. A primary factor in the choice of either is
that they provide additional alkalinity to the boiler water to help
neutralize acidic conditions. The reaction of tri-sodium phosphate
(Na3PO4) with water is shown below.

Na3PO4 + H2O ⇔ Na2HPO4 + NaOH

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Paradoxically, the free caustic concentration for either program
should be limited to around 1 part-per-million (ppm), as otherwise
under-deposit caustic attack of waterwall tubes is a possibility. For
units with air-cooled condensers or that have condensate polishers
downstream of water-cooled condensers, the potential for
contaminant ingress to the boiler is greatly reduced. These steam
generators can potentially get by on an AVT-only program. However,
unless the condensate/feedwater circuit contains copper alloys, only
AVT(O) should be used.

Another outdated concept persists regarding congruent phosphate

treatment in high-pressure, high-temperature boilers. Phosphate
treatment was introduced in the 1930s, but as steam generators
became more sophisticated and pressures increased, chemists began
to notice that at normal unit load, the bulk phosphate concentration
would decrease to very low levels. The phenomenon is commonly
termed "hideout," and is quite understandable per the following
solubility chart.

At the typical operating temperatures of modern high-pressure steam

generators, which are above 600oF, sodium phosphate has very low
solubility. Researchers mistakenly concluded that the compound
precipitated at a sodium-to-phosphate ratio within a range of 2.2-
2.6:1. (Tri-sodium phosphate has a sodium-to-phosphate ratio of 3:1.)
From this mistaken belief evolved coordinated and then congruent
phosphate treatment programs, which called for some di-sodium
phosphate (Na2HPO4), and sometimes even a bit of mono-sodium
phosphate (NaH2PO4), to be blended with each tri-sodium phosphate
charge. It has been known for quite some time that these blended
phosphates can precipitate at much lower sodium-to-phosphate ratios
than even 2.3:1, which can then cause direct acid phosphate
corrosion of the internal metal and wide swings in boiler water pH as
boiler load changes. Thus, congruent phosphate treatment for high-
pressure boilers has been discredited, and only tri-sodium phosphate
should be utilized. (EPRI and IAPWS offer the proper control
guidelines.) However, some chemical suppliers still reference
congruent treatment when discussing boiler water chemistry. This is
not correct.

Do Not Neglect Shutdown, Layup, and Startup

Chemistry
With all of the focus given to operational chemistry, quite often plant
personnel do not recognize the importance of shutdown, layup, and
startup chemistry. Yet, much more severe corrosion may occur during
these times than occurs during normal operation. The primary
difficulty is due to air in-leakage as a boiler cools upon shutdown.
Oxygen that infiltrates will severely attack steam generator metals in
cold, moist environments. Also, in many cases boilers are drained for
a maintenance outage, but water is allowed to remain in the
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condenser hotwell. The condenser steam-side, when opened to the
atmosphere, then develops a humid environment that envelopes the
low-pressure turbine. During normal operation the trace quantities of
salts, including chlorides, that carry over with steam precipitate in the
very lowest stages of the turbine. The environment moistens these
salts, which then may cause pitting of turbine blades and rotors.
Pitting subsequently can lead to stress corrosion cracking and
corrosion fatigue.

It is important that plant personnel have concrete plans in place for

unit protection, whether an outage is short (perhaps a half-day to two
days), intermediate (up to a week), or long-term. Techniques to
protect the boiler include:

For short-term wet layup:

 Maintaining condenser vacuum

 Nitrogen blanketing (A confined-space entry is always a critical
safety concern with this program.)
 Steam pegging from an auxiliary boiler or sister unit

For intermediate or longer-term wet layup:

 Nitrogen blanketing
 Chemistry adjustments

- pH elevation
- Oxygen scavenger use (not recommended if the oxygen scavengers
are not used during normal operation)
- Boiler water circulation to keep chemicals properly distributed

Fouled condenser tubes and tubesheet. Photo courtesy: ChemTreat

For long-term dry layup:

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  Draining the boiler while it is still hot to allow for flash
evaporation
 Nitrogen blanketing
 Warm, dehumidified air circulation through the condenser,
backfeeding through the steam system to the boiler,
economizer, and condensate systems. Also, dry air circulation
through the furnace.

Boiler fill process:

 De-oxygenation of the makeup. Modern membrane systems are

available that can reduce DO concentrations to well under 100
ppb.

No Such Thing as "Standard" Water

Often specifications will be issued in which the raw water quality data
is minimal or non-existent. Sometimes project or estimating engineers
stipulate "design to standard water," but the only thing standard
about water is that it is wet. Proper design of makeup water
treatment systems relies on accurate and historical water quality
data. Systems have been known to fail at startup because they were
not designed to handle particular impurities in the water. For
example, the hardness ions calcium and magnesium can react with
alkalinity, sulfate, and silica anions to form scale. Other metals such
as barium and strontium may, even in trace concentrations, cause
scale formation. Suspended solids will foul many water treatment
systems, most notably reverse osmosis (RO) membranes. Large
organic compounds can foul RO membranes and ion exchange resins.
Ammonia, phosphate, and other compounds in municipal wastewater
plant effluent provide additional nutrients for microbes that collect in
and form colonies within cooling water systems.

Some ions (chloride in particular) can cause severe corrosion of

stainless steels that depend upon a surface oxide layer for protection.
Thus, materials selection for cooling system components is very
dependent upon accurate raw water analyses. Cooling towers cause
impurities to "cycle up" in concentration, so impurity concentrations
that may seem relatively harmless in raw water can be at much
higher levels in the circulating water.

It is extremely importance to accurately evaluate raw water chemistry

prior to project design. It is also important to coordinate with
environmental regulators regarding the plant discharge permit,
typically as governed by National Pollutant Discharge Elimination
System (NPDES) regulations. A number or permits indicate that owner
or owner's engineers have added impurities well beyond what typical
guidelines call for, or where the units were improperly listed. In many
cases, permit language shows impurity limits with a ppb-

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concentration when only ppm-concentrations are needed. Without
corrections, the costs for wastewater treatment would have been
enormous, if treatment was possible at all.

Author
Brad Buecker serves as a process specialist in the Process
Engineering and Permitting group of Kiewit Engineering and Design
Company.

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