Copper-Alloy Corrosion and Preventive Measures

Corrosion of copper alloys and the effects on steam generating systems

have been receiving a great deal of attention. Foremost is that cuprous and
cupric oxides carry over with boiler steam and deposit in the afterboiler, and in
partic-
20 Power Plant Water Chemistry: A Practical Guide

ular on the high-pressure turbine blades. Reports abound of electric utility units
whose output decreased over an operating period because of copper deposition
on the turbine blades. Copper corrosion and deposition also cause other diffi-
culties. For example, copper deposition in boiler tubes can greatly increase the
difficulty of a boiler chemical clean. The tube deposits may become layered
with copper and magnetite, which can require a multistaged chemical cleaning
process for complete removal. Copper inclusion in deposits can also increase
the potential for under-deposit corrosion.
As Equation 2.4 illustrated, copper corrosion is initiated when copper metal
or the protective cuprous oxide film is oxidized to cupric oxide. For this to hap-
pen, the oxidation potential (as measured in millivolts or volts) of the solution
must be greater than zero. Continual feed of the oxygen scavenger will maintain
a reducing environment and keep the ORP well below zero. However, a
reducing environment is the primary triggering mechanism for flow-accelerated
corrosion.
Copper corrosion is exacerbated in cycling units. Several mechanisms may
be at work here. Mechanical stresses imposed during frequent load changes or
startups and shutdowns will fracture the cuprous and cupric oxide films on
heater tubes and cause corrosion and spalling. Oxygen corrosion of unprotected
feedwater heaters during an outage has caused severe corrosion and exfoliation
of heater tubes. In fact, this problem can be so serious that the heater steam-side
should be blanketed with steam or nitrogen during extended outages. More
details about off-line corrosion protection are presented in chapter 3.
The upshot of these difficulties with copper corrosion is that many experts
now recommend that feedwater heater tubes be fabricated from stainless steel,
or that existing copper-alloy heaters be replaced. Sometimes the latter
recommen- dation may not be economical, at least in the short term. Good water
treatment practices are a fallback for such situations.

Additional Corrosion Control Requirements

While oxygen and carbon dioxide are primary corrodents in utility and
industrial steam generating systems, the pH of the feedwater also is an
important factor. Feedwater piping and heat exchanger tubes exhibit minimal
corrosion at a mildly alkaline pH. For a system containing all steel metallurgy
the optimum pH range is 9.0 to 9.6, while for a system with a mixed metallurgy
of iron and copper, the recommended pH range is 8.8 to 9.1. Ammonia or
volatile amines provide this needed basicity. Table 2–2 lists some of the most
common neutral- izing agents. The choice of which compound to use
depends upon the nature and pressure of the steam generating system, and the
characteristics of the pH- conditioning chemical. Of the compounds listed in the
table, cyclohexylamine is most basic, while morpholine is significantly less
basic. The basicity of diethy-
Condensate/Feedwater Chemistry 21

laminoethanol and ammonia lies in between. Thus, the chemist has a number of choices for
finding a product that maintains condensate/feedwater pH within rec- ommended guidelines.
Amines will decompose to produce ammonia in feedwater. Whether the ammonia is
generated by direct ammonia feed or amine decomposition, a gener- al rule of thumb
suggests that ammonia concentrations be limited to 0.5 ppm in systems with copper-alloy
tubed heaters. Even this level may be too high where frequent inleakage of air is a problem.
In high-pressure utility boilers, where the steam is quite pure, decomposi- tion of
amines can potentially introduce unwanted organic acids and CO 2 to the turbine. For this
reason, ammonia is widely recommended as the best pH-con- ditioning chemical. The
situation may be vastly different in an industrial boiler where bicarbonate decomposition
causes heavy carryover of CO2 to condensate lines. Amines can be a good product for
neutralization of the carbon dioxide. A particular aspect of importance is the amine
distribution ratio. This is the per- centage of amine that carries over with the steam versus
that which remains in the boiler water. The distribution ratio varies with the product and
with the pres- sure of the boiler (Fig. 2–11). Selection of the neutralizing chemical based on
dis- tribution ratio can be very important. If protection of afterboiler condensate lines is
required, an amine with a high steam-to-liquid distribution ratio is best. Where
corrosion prevention in the boiler is more critical, a more appropriate neutralizing amine is
one whose distribution ratio allows most of it to remain in the boiler water. Often, a blend of
two amines is used to provide universal pro- tection.