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DAVID N . FRENCH, INC.

, METALLURGISTS
ONE LANCASTER ROAD

WINTER 1989 NORTHBOROUGH. MASSACHUSETTS 01532


VOL. V, No. 4
(617) 3 9 3 - 3 6 3 5

A VIEW FROM THE PENTHOUSE: USEFUL INFORMATION FOR THE WORLD OF BOILERS

In an e f f o r t t o imprwe a i r quality and stainless-steel burner components.


reduce acidic emissions, powelcplant operators Burner parts of austenitic stainless s t e e l ,
have been forced t o change t h e i r combustion coal nozzles, gas burner rings, ignition
technology. Reductions i n emissions of sulfur tubes, coal spreaders, oil-burner t i p s and
oxides (S%) have been achieved mainly by a i r nozzles all operate a t high metal
using lower-sulfur fuels. Reductions i n temperatures, temperatures i n the
nitrogen oxide ( q l l e v e l s have been achieved neighborhood of perhaps 1500°0r 1600°F. The
principally by reducing combustion-flame use of austenitic stainless s t e e l for these
temperatures. Of course some new power plants parts prwides adequate oxidation and
have installed scrubbers t o remove these corrosion resistance a t these elevated
harmful oxides. temperatures. However under reducing
While some nitrogen oxides are present conditions, the corrosion of stainless s t e e l
within the fuel i n the form of nitrates, most may proceed a t unexpectedly and unacceptably
NCf, comes from the reaction of atmospheric high rates due t o the carburization of these
nitrogen and oxygen a t combustion-flame alloys.
temperatures. Under normal firing conditions, Under f u l l y oxidizing conditions of
as the flame temperature increases, so does combustion, the fuel would be burned
the formation of nitrogen oxide. Thus the completely t o water vapor and carbon dioxide.
simplest way t o reduce conbustion-formed N4, A l l fuels contain both hydrogen and carbon.
is t o reduce the flame temperature. The To i l l u s t r a t e the principle consider methane,
schemes for achieving t h i s are t o use off- (3%. Complete combustion is as shown i n
stoichimetric or staged combustion firing. Equation 1.
Corbustion a i r is divided. Primary a i r is CHq + 202 = 2H20 + C02 En 1
mixed with the fuel and is l e s s than required
for complete combustion. Secondary a i r is Usually a small amount of arcess oxygen,
added through w e l c f i r e a i r ports. Other perhaps 2% or so, is added t o assure complete
schemes may use concentric ducts with the combustion t o carbon dioxide (C02) and water
primary a i r port along the center and (H20). Flame temperatures under these firing
secondary a i r i n a concentric ring displaced conditions would be i n the neighborhood of
f r m the center by some distance. The intent 3000°F or higher, and the combustion would be
is t o burn the fuel i n stages. The f i r s t said t o be llstoichiometric".
stage combustion would burn the hydrogen t o Staged combustion would reduce the amount
water vapor, and carbon t o carbon monoxide. of oxygen available i n the primary flame so
Later i n the combustion sequence, the carbon that the combustion would be accomplished i n
monoxide would be burned completely t o carbon several steps, as shown i n Equations 1, 2, 3,
dioxide. However, the formation of carbon & 4.
monoxide leads t o reducing atmospheres in the CH4 + O2 = 2H20 +C EQ 2
vicinity of the burners.
The advantage t o t h i s combustion technique
is t o reduce flame temperatures and thus
prevent or a t l e a s t reduce the formation of
any nitrogen oxides. The drawback is t o form
reducing conditions i n the vicinity of the Note that the f i n a l product is s t i l l water
burners, and this topic w a s discussed i n VOL. vapor and carbon dioxide but the carbon
IV, No. 1 of A View from the Penthouse. What dioxide is formed i n three steps. The
may not be f u l l y appreciated is the damage advantage from a Ng, formation viewpoint is
that these reducing conditions can do t o that flame temperatures are considerably
lower and the formation of nitrogen oxides is temperature, these microstructures can also
considerably reduced. Note also, however, form structures that a r e similar t o pearlite
that in two stages of this combustion i n a plain-carbon s t e e l , as shown i n Figure
sequence, carbon (C) and carbon monoxide 3. These microstructures a r e all taken from
(CO) , both reducing elements, are formed. a coal nozzle made of 304 stainless s t e e l .
Austenitic stainless s t e e l s , similar t o 304, Other aramples have been seen i n gas-burner
readily form carbides a t temperatures as low rings and stainless-steel castings for oil-
as 1400°F, but more typically, 1500°F. The burner service.
addition of carbon t o a s t e e l is called In order t o prevent this form of rapid
"carburization." The reaction of soot, or degradation t o burner components under
unburned carbon, directly with the surface of staged-combustion conditions, alloys more
the stainless s t e e l , w i l l form a chromium resistant t o carburization need t o be used.
carbide by the reaction shown in EQuation 5.

The chromium carbide is quite complar and has


the chemical composition of Cr23C6. Carbon
monoxide can also react on the surface of
stainless s t e e l t o form carbon dioxide and
elemental carbon, as shown i n Equation 6.

Either unburned carbon or carbon monoxide thus Fig. 1. Normal austenitic, stainless-steel
are available t o carburize the surface of microstructure is equiaxed grains. 500x.
these burner components. etched.
The formation of these chromium carbides
depletes the surface of the stainless of
chromium and thus reduces the corrosion
resistance. Stainless s t e e l s get t h e i r
excellent resistance t o high-temperature
oxidation by the addition of more than 12%
chromium. When the chromium content is
reduced t o below 12%,the oxidation resistance
is more ordinary. Thus the formation of
chromium carbides by the reaction of stainless
s t e e l s with carbon monoxide or elemental
carbon leads t o a depletion of chromium alom
the surface of the &eel. With the chromium- Fig. 2. Carburization of 304 stainless leads
content reduced t o below 12%,the oxidation t o the formation of tiny carbide particles.
resistance f a l l s and the result is a rapid 500x, etched.
loss of material. Burner components ca& f a i l
i n only a few months rather than several
years.
The microstructures t h a t result can be quite
striking. Figure 1 shows the normal.
austenitic, stainless-steel microstructure, as
would be expected in a 304 stainless-steel
burner component a f t e r several thousand hours
of operation. Here the grain s i z e has grown
and there is essentially an all-austenite
microstructure. Figure 2 shows the
microstructure a t the surface t o be composed Fig. 3. Depending on the temperature of
of austenite with a myriad of fine carbide carburization, the microstructure can
particles. Depending on the time and resemble a p e a r l i t i c s t e e l . 500x, etched.

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