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Issue Revisited
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 NH3 concentration of 0.1 ppm than in
any other case. (Figure 3.) The ammonia does not attack the magnetite directly.
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 Fe2O3 that often exhibits a rippled
pattern. Iron exists in a +2 (ferrous) oxidation state in FeO and +3 (ferric) in Fe 2O3. 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.