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All fossil fuels contain both hydro en and carbon in
various amounts and compounds. ~aturaf as is neady pure
methane. CHI 75% carbon, and 25% hy%rogen by welght.
Fuel oils usually have less carbon and more hydrogen. Coals
are widely different in their com ositions but all contain car-
bon and other hydrocarbons. AR ive off heat enerp when
burned, and behave in a similar fapfiion when burne with alr
In a boller.
The hydrogen, Hz, component burns first and com-
pletely In air or oxygen, 02, to water vapor, H20:
2H2 + 02 = 2H20 EQ 1
this gives off considerable heat energ The carbon C, be-
haves in a different fashion. There are L o comm,on,&idp~ of
carbon carbon monoxlde, CO, and carbon dloxlde, CO2.
De ending,on the relative amount of air, (oxygen) one or both
of Wese oxides of carbon will form. thus:
2C + 02= 2CO EQ 2
C + 02=C02 EQ 3
Combinations of hydrogen and carbon in fuel, e.g. CH4,
will burn to water vapor and carbon monoxlde or carbon dlox-
ide:
CH4 + 202 = C02 + 2H20 EQ 4
2CH4 + 302 = 2C0 + 4H20 EQ 5
What is important in EQ's 4 and 5 is the ratio of oxygen
to methane, 211 In EQ 4 and 3R in EQ 5. When lack ox en
occurs, the carbon won't burn at all and comes out oyyhe
flame as soot or carbon black:
CH4+02=C +Hz0 EQ 6
The oxy en methane ration here is 111. EQ 6 is the
basis for man%ciuring of carbon black used as a pigment in
paints and automobile tires. Unbumed carbon ives a candle
%
k light. Carbon particles are heated to a glow combu,stion
of the hydrogen in the wax. Prove it to yoursel?bby holdlng a
clean plece or glass or steel well above the burnlng candle
for a few minutes.
Boiler steels develop oxidation and corrosion resistance
by the formation of an lron oxrde scale In air or oxygen:
4Fe + 302 = 2Fe20~ EQ 7
Once this oxide forms, the steel underneath is pro-
tected from further oxldatlon.
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The DNFM Quarterly Newsleffer
DAVID N. FRENCH METALLURGISTS
There are three oxides of iron3e0, Fe203 and FeaOd.
The temperature and oxygen concentration will determine
which oxrde will form when steel is oxidized in a boiler. Con-
versely, the manufacturin of steel from iron ore, mainly
Fez03 plus impur~t~es, s t a k with the reduction of iron oxide
by carbon or carbon monoxlde:
3C + Fez03 = 2Fe + 3C0 EQ 8
3C + 2Fe203 = 4Fe + 3C02 EQ 9 or:
When methane is burned with inadequate oxy en in
EQ 4 for complete combust~onto carbon dloxlde an%water
vapor,. conditions are said to be "off stoichiomekic" or
"reducln The ratlon of COlCOzcan be large enough to
destroy protective oxide scale on the external surface of
furnace tubes. "Reduc~ngcondition corros~on"is the name
glven to this attack on the boller.
This is a simple, single fuel system with ure methane
as fuel. Most real situahons involve impure f u e l that contain
measurable amounts of sulfur. Sulfur bums In alr to form
sulfur dioxide and sulfur trioxide:
S + 0 2 = SO2 EQ 11
2s + 302 = 2S03 EQ 12
These ases alone do enou h dama e, but under
reducin con&ions, the sulfur is in We form 09 hydro en sul-
fide. HZ.! When reducing c?nditiovs exist, alqn a !urnace
wall, some of h e protective lron oxlde scale will %e replaced
by sulfides.
CO+2H2S = Fez03 = 2FeS + 2H20 + C02 EQ 13
Sulfide scales are not as dense, hard or protective as
oxide scales. They are porous, fragile, and easily abraded,
and come,off with ash and slag removal. Corrosion deposits
that contaln sulfides are clear evldence of "reducing condl-
tion corrosion" has occurred. Sulfides are also the easlest
compound to detect, slnce they leave a sulfur print.
The ap earance of this form of corrosion will show a
rather smootl! surface and may have severe wastage, see
Figure 1. The wall thickness on the fireside is 0.191" and on
the cold side is 0.286" two years after low NOx burners were
installed. If the corrosion deposits are still intact they will con-
tain sulfides. Stress is not a factor in this morphology. There
may or may not be a liquid phase present.
Another form of "reducing condition corrosion" results in
deep, fin er like circumferential penetrations into the tube
wall, see$igure 2 There is also the metal loss as the wall
thickness has been reduced compared to the cold side of the
water wall tube. The wall thickness, excludin the grooves is
0.149" while on the cold side it is 0.269". #us most of {he
corrosion wastage is confined to the deep grooves. Corrosion
deposits also contain sulfides. There is aso a llquld phase
resent. and an axial stress necessarv. Thus. this is a form of
borrosion fatigue.
"Reducing Condition Corrosion" has three condition
requirements: reducin conditions variable axial stress, and
liquid phase in the as\ de osit keducing conditions attack
the iron oxide, and form sulldes: as has been discussed. The
axial stress comes from sharp tem erature spikes that follow
soot blower action, The liquid witRin the ash weakens the
ash, promoting slag falls, and also causes tern erature
spikes. Chordal thermocouple measurement recorls show
temperature increases up to 200°F. As the ash reforms, the
tem erature returns to normal until the next soot blower cycle
or sLg fall occurs.
The temperature increase may crack or craze the oxide
film especially when it is already weakened by the reducing
coditions. These cracks from an axial stress are found goin
across or circumferential to the tube surface. With repeate
cycles, the cracks grow into the tube wall as shown in Figure
!
2. lnvarlabl , the ash deposlts contam free carbon from un-
burned coayand are reducing.
Correction qr revention of "reducing condition
corrosion'' is easier sald tRan done Adequate a r to produce
complete combustion of the CO2 with little (a trace) or no CO
and carbon free ash de osits, is required, excess oxygen in
the flue is not enough. 8 n average eve thing may look like
an oxidizing atmosphere, but local conxtions can be quite
different. Burners may be out of alignment, fuel and air may
not be pro erly mixed, staged combustion to reduce NOx
productiqn lo meet environmental requirements may lead to
a fuel rlch condltlon along some zones of the furnace , etc.
All of these factors and more lead to localized reducing con-
ditions, resultant tube wastage, and finally tube failures.
I