Corrosion and Cracking in Recovery Boilers: W. B. A. Sharp
Corrosion and Cracking in Recovery Boilers: W. B. A. Sharp
Corrosion and Cracking in Recovery Boilers: W. B. A. Sharp
5.4-1
carbon steel usually provides adequate corrosion spikes develop tensile stresses in the stainless
resistance for floor tubes. Composite floor tubes surface layer that remain when the boiler cools to
have been installed in some boilers, but are room temperature in a shutdown. It also shows that
unnecessary and problematic except in smelt runs. tubes clad with Alloy 825 and Alloy 625 develop
much lower tensile stresses than conventional tubes
FIRESIDE CRACKING OF COMPOSITE clad with Type 304L stainless steel. Therefore,
FLOOR TUBES tubes clad with these alloys should be used as
replacements in boilers with floor tube cracking
About 65 of the approximately 340 recovery boilers problems.
in North America have composite floor tubes.
Although fireside cracking of composite floor tubes Temperature spikes in floor tubes that develop
had been found in about two-thirds of the European tensile stresses in the surface of composite tubes
recovery boilers with composite floor tubes by propagate cracks by thermal fatigue. This can be
1992, it was not noticed in North American boilers minimized by installing a layer of packed refractory
until 1993. Cracking is not usually found in or interlocking tile over the floor tubes. Since floor
composite floor tubes unless it has been previously tubes are not designed to supply much of the heat to
found in composite spout opening tubes and the boiler water, the loss of steaming capacity of the
composite floor panel membranes in the same boiler will be small.
boiler. In sloped floor units, cracking is more likely
to occur near the spout openings and where floor LOCALIZED CORROSION OF AIR PORT
tubes bend down towards the supply header. TUBES
Fortunately, when deep cracks reach the stainless
steel-carbon steel interface, they either end in a Both carbon steel and composite tubes suffer
corrosion pit in the carbon steel or turn and run localized corrosion in the corners of port openings
parallel to the interface. in high pressure boilers (7). Localized wastage on
the furnace side of air port tubes is caused by high
There is increasing evidence that floor tube temperatures produced by the exothermic
cracking is initiated during shut downs and water combustion of unburnt liquor on these tubes in the
washes rather than during operation (5, 6). jet of air entering the boiler from the port.
Laboratory testing has shown that the concentrated
solutions of sodium sulfide and sodium hydroxide The windbox side of air port tubes can also suffer
formed by dissolving a large amount of smelt in a localized corrosion. This has been attributed to the
small amount of water cause stress-corrosion presence of molten sodium hydroxide in stagnant
cracking in the Type 304L stainless steel cladding areas where it has not reacted to form sodium
in the temperature range160-200ºC (320-392ºF). carbonate. Corrosion products that would
To avoid the conditions that can produce cracking otherwise protect carbon steel tubes (sodium ferrite)
in composite floor tubes, do not begin to water and composite tubes (chromic oxide) are fluxed
wash until floor tube temperatures fall below 160ºC (dissolved) away by molten sodium hydroxide,
(320°F), and be sure that all the smelt is removed allowing rapid corrosion. On composite tubes, this
from the floor tubes before the boiler is fired up fluxing can rapidly thin the stainless steel outer
again. layer. Fortunately the thinning slows when the
stainless steel outer layer is consumed and the
Stress-corrosion cracking only occurs when tensile underlying carbon steel is exposed. Typical
stresses are present. Finite element analysis has corrosion rates might be 0.01 - 0.05" per year on
shown that the surface of composite tubes is in the stainless steel layer but only 0.03 - 0.08" per
compression when a boiler is at its operating year on the exposed carbon steel. Because the
temperature. However, temperature monitoring has corrosion rate slows down when the underlying
shown that floor tubes can experience brief carbon steel is exposed, it produces expanding (but
temperature spikes of several hundred degrees. not deepening) bald spots that expose the
Stress modeling shows that these temperature underlying carbon steel, beginning at the top inner
5.4-2
corners of air port tubes. This balding can be weld- same as the smelt temperature, simulating the case
repaired with Alloy 625 before serious damage is where tubes have boiled dry. Smelt flow across the
done. tube surface accelerates the corrosion rate because
THERMAL FATIGUE CRACKING OF WALL the replenished smelt delivers more heat and wears
TUBES BESIDE SMELT SPOUTS AND AIR away the insulating frozen smelt layer. To avoid
PORTS this, smelt spouts are designed with internal water-
cooling systems to keep their surface temperature
Thermal fatigue cracking has been reported in both low. Lowering the temperature of smelt spout
carbon steel tubes and composite tubes at (primary) cooling water 40oF can increase spout life four
air ports and spout openings since about 1983. times. However, the temperature of spout cooling
Around air ports the cracking is generally limited to water must be kept above 140oF to avoid dew point
the tubes that form the port opening itself, while condensation that could risk smelt-water
around spout openings the cracking can spread to explosions.
several tubes on either side. These tubes experience
temperature excursions when the insulating frozen Smelt that freezes across air ports or smelt spouts
smelt layer is removed by rodding and when molten interferes with the operation of the boiler, and must
smelt washes up against the tubes. Cracking in be removed by rodding. The removal of this frozen
tubes that form air ports is aggravated by residual smelt suddenly exposes the tubes to hot molten
tensile stresses from the forming of tube bends and smelt, and cycles of sudden heating can produce
from attachment welds. Although the fireside thermal fatigue cracking on the metal surface.
cracks in composite floor tubes discussed below Washing of the smelt bed up and down against wall
turn at the base of the clad layer and propagate tubes causes similar heating cycles. Because the
parallel to the tube surface, cracks in air port tubes outer stainless layer of composite tubing is
and smelt spout tubes can continue to propagate restrained by the inner carbon steel layer, composite
into the carbon steel layer. This propagation tubes are more vulnerable than carbon steel tubes to
appears to be driven by residual stresses introduced thermal fatigue cracking, particularly at fireside
during the formation of the air port tube bends. attachment welds.
Because the cracks can penetrate the carbon steel
portion of these tubes this type of cracking must be CORROSION OF UPPER FURNACE AND
inspected and repaired with particular care. SCREEN TUBES
Recent work by Tran and others (8) shows that Corrosion rates on upper furnace wall tubes, roof
improved firing practices can eliminate tube tubes and furnace screen tubes are two to three
cracking by reducing the occurrence of thermal times slower than on lower furnace tubes because
spikes. If improved operational control does not the addition of secondary and tertiary combustion
eliminate the cracking, the cracked wall tubes air raises the oxygen partial pressure enough to
should be replaced with Alloy 825-clad or Alloy stabilize protective iron oxides on carbon steel
625-clad composite tubes. tubes. Additionally, radiative heat fluxes are lower
and gas temperatures are lower, so tube surface
MOLTEN SMELT ENVIRONMENTS temperatures are slightly lower. For this reason,
Molten smelt can dissolve carbon steel and composite tubes are not required in the upper
composite tubes at rates equivalent to many inches furnace water walls.
per year. Fortunately the flow of water through Upper furnace wall tubes that are not seal welded to
boiler tubes keeps them cool, so the smelt freezes one another can suffer cold-side corrosion on the
rapidly on them and insulates the tube surface from side of the tubes that faces away from the furnace.
the corrosive effects of molten smelt. Flowing Deep and isolated pits and irregular channels of
smelt produces higher corrosion rates than stagnant corrosion running down the length of the tubes can
molten smelt. Student research at IPST has shown be produced by cold-side deposits acidified by
that rates up to the equivalent of 50" per year have furnace gases where they are wetted by water
been measured when the metal temperature is the washing. This cold side corrosion propagates when
5.4-3
moist furnace dusts remain on the tube surface for tube in the plane of vibration (11). Fatigue cracking
long periods (e.g. when a unit is water washed but is aggravated by locally severe restraints, such as
not fired to dry the tubes during an extended sharp corners on vibration bars produced by flame
outage). Laboratory measurements show that moist cutting, and by thinning caused by external wear
tube deposits will corrode carbon steel at about from loose components like worn vibration bars.
0.001" per day at ambient temperatures.
Empirical studies have concluded that generating
Recovery boilers operated with relatively cool bank vibration bars are more trouble than they are
smelt beds and consequently high concentrations of worth unless the drum-to-drum distance exceeds
SO2 and SO3 in the flue gases tend to form sodium 31’ (12). Where vibration bars are required,
bisulfate deposits in the upper furnace (9). These making them from an oxidation resistant alloy such
have low melting point temperatures. If the melting as Type 304L stainless steel extends their life.
point temperature of a deposit is lower than the
surface temperature of an upper furnace tube, the Similar cracking can occur at attachment welds on
molten deposit will flux off the oxides that would pendant tubes in the upper part of the boiler. If
otherwise protect the tube. The corrosion initiates these welds are subject to excessive stresses, e.g. as
as pits that can appear in parallel lines like cat's a result of the “freeze up” of sliding tube
claw scratches. It is likely that this pitting initiates connectors, or as a result of unexpectedly high
where stresses in the tube have cracked the mill amplitude vibration of the tubes, fatigue cracks will
scale. nucleate adjacent to the attachment weld on the
outside of the tube. Through-wall cracks can cause
Pitting in upper furnace tubes can also be caused by severe damage by directing jets of water onto
the reduced sulfur gases that exist under adjacent tubes that thin large areas and produce
partially-burned liquor particles. This type of fish-mouth ruptures.
corrosion only occurs when the liquor droplets are
incompletely burned in the lower furnace (i.e. in SUPERHEATER CORROSION
heavily loaded boilers with inadequate mixing of
combustion air) where partially-burned liquor In the absence of molten deposits and unburned
droplets carry over and are deposited on upper liquor carryover, rates of superheater corrosion
furnace tubes. depend only on the tube temperature and oxygen
partial pressure. The corrosion rate is limited by
FATIGUE CRACKING OF GENERATING the transport of reagents through the thickening
BANK TUBES AND PENDANT TUBES AT surface oxide. Therefore, superheater materials can
RESTRAINTS be made more corrosion-resistant by adding
alloying elements that form oxides with lower solid
Fireside fatigue cracking in generating bank tubes state diffusion coefficients.
(10) and in pendant tubes at restraints is a
significant cause of critical leaks. Cracks initiate at When a superheater temperature is high enough to
the node where a vibrating tube is held stationary, produce unacceptably high corrosion rates on
e.g. unalloyed carbon steel, tube materials with alloying
• where a generating bank tube passes into a additions of chromium are required. Although
drum chromium oxidizes more readily than iron,
• where an economizer tube is welded into a chromium oxides have much lower diffusion
header coefficients than iron oxides. Commonly used
• where pendant tubes are held by vibration bar superheater tube materials, in order of increasing
clamps corrosion resistance, are as follows:
These fatigue cracks proceed inwards from the
fireside of the tubes and are largely unaffected by Carbon steel
corrosion processes. They often appear as pairs of T11 steel (1% Cr)
cracks close to the restraint and on either side of the T22 steel (2.25% Cr, 1% Mo)
5.4-4
Type 347 stainless steel (19% Cr) by low melting point acidic sulfate deposits as on
Alloy 310 (25 % Cr) superheater and furnace screen tubes, and by
erosion-corrosion caused by water droplets
Because the most corrosion-resistant of these alloys entrained in the sootblower steam.
(the austenitic stainless steels like 347 and 310)
would be vulnerable to waterside stress-corrosion Generating bank tubes often suffer "near drum
cracking if the boiler water became contaminated thinning" (13). This is localized fireside thinning
by chlorides, some mills prefer to install composite within about 0.5" of the outer surface of the mud
superheater tubes with a Type 310 stainless steel drum. It produces an elliptical depression on the
(25% Cr) outer layer and a 2.25% Cr inner layer. tube (shaped as if the tube was clay and you had
These are more expensive than solid Type 347 pressed your thumb into it) where the tube faces the
superheater tubes, but combine the high oxidation lowest sootblower. The thinning appears where dust
resistance of the stainless steel outside layer with particles are blown off the surface of the mud drum
the high temperature strength and immunity to and against the tubes by sootblower jets. During
stress-corrosion cracking of the carbon steel inner each sootblower cycle, the dust particles scour a
layer. little oxide off the tube surface that was formed
since the previous sootblowing cycle. Special
Unburnt liquor particles carried over because of ultrasonic equipment has been developed to detect
incomplete combustion (high loading and and quantify this type of thinning from inside the
inadequate reaction with combustion air in the tubes (14).
lower furnace) can destabilize protective oxides on
the windward side of superheater tubes in the same CAUSTIC STRESS-CORROSION CRACKING
way as was described earlier for screen tubes. IN BOILER DRUMS
If the surface temperature of a superheater tube Slow leakage of boiler water out of boiler drums
exceeds the melting point of the deposits on its where generating bank tubes are not completely
surface, the surface oxides will dissolve rapidly into sealed into the drum can produce caustic stress-
the molten deposits. For example, a 5oF increase in corrosion cracking. The leaking water flashes to
tube temperature (beyond the deposit melting point) steam when it reaches the outer surface of the drum,
can increase corrosion rates four- or five-fold. To concentrating the water treatment chemicals.
avoid this rapid superheater corrosion, a mill should Caustic stress-corrosion cracking, also known as
minimize the formation of molten bisulfates by caustic embrittlement, occurs in carbon steel under
reducing the excess volume of combustion air that tensile stress in caustic concentrations above about
produces SO3, minimizing the S/Na2 ratio in the 5% at temperatures above about 300ºF. The tensile
flue gases and optimizing sootblower operation to stresses may arise from operating pressures or from
keep the tubes clean. residual stresses produced by welding. The inside
of the holes in a boiler drum contain residual tensile
The most aggressive conditions in superheaters are stresses from the rolling (inside-out expansion) of
found at the front corner of the bottom bends in the the tubes to seal them into the drum. The
hottest platens. These bends experience not only combination of hot concentrated caustic and tensile
the highest heat flux but also erosion from particles stress can drive caustic stress-corrosion cracks from
entrained in the flue gases. hole to hole in a boiler drum and produce water
leaks (15), particularly if the drum is made from
CORROSION AND EROSION IN high strength steel. Re-rolling generating bank
GENERATING BANK TUBES tubes to improve the seal between tube and drum
will eliminate the cracking only if every seal is
Since generating bank tubes are relatively cool and perfect. Otherwise the additional rolling merely
serve in a relatively oxidizing environment, raises the tensile stresses that are driving the cracks.
corrosion allowances are generally small and Seal welding leaking tubes to the drum is
sometimes zero. However, thinning can be caused problematic also, because it introduces additional
5.4-5
stresses that tend to loosen the seals of adjacent increases the fireside temperature. A related form
tubes. A final solution to generating bank tube of under-deposit corrosion can occur where sodium
leaks often requires either very careful seal welding hydroxide becomes concentrated from the boiler
of all the tube seals or replacement of the water chemicals by a departure from nucleate
generating bank tubes. boiling, by boiling under porous deposits or by
waterline evaporation. Corrosion in concentrated
caustic solutions under deposits is sometimes called
CORROSION IN ECONOMIZERS, caustic gouging. It produces localized corrosion
PRECIPITATORS AND STACKS with a smooth or wavy contour.
Economizer tubes rarely suffer corrosion damage, Waterside deposits are most likely to form where
although sootblower erosion can occur and external heat transfer is highest, i.e. on tubes at the smelt
fatigue cracking has occasionally caused tube line (smelt-gas interface), around fuel burners, and
ruptures. Rates of thermal oxidation are low, and under pin studs or other weld attachments that
temperatures of water-filled economizer tubes are funnel heat into the tube. Tube samples are cut out
far below deposit melting temperatures. However, of these regions to measure the deposit thickness
corrosion can be caused by dew point condensates. and determine whether the boiler needs chemical
If surface metal temperatures in an economizer, cleaning,
precipitator or stack fall below the dew point
temperature (typically 155-170oF), moisture will Upset conditions that produce thick, insulating
condense out of the flue gases onto these surfaces. waterside deposits that restrict water flow can
This moisture will readily dissolve acid furnace produce rapid fireside corrosion even on composite
gases (e.g. CO2, NOx, SOx) and its pH can fall as tubes.
low as 3.0 or 2.5. This acidic condensate will
dissolve carbon steel. Dew point condensation The waterside of boiler tubes is also vulnerable to a
generally occurs during low-load operation, where form of corrosion fatigue cracking known as stress-
the flue gases are coolest, and in the winter. In assisted corrosion (16). During the first year when
precipitators it tends to occur first where shell inspections for waterside cracking in recovery
heating or insulation are inadequate. Most boiler boilers became common (1992), nearly half the
operators find it is more cost-effective to insulate or units inspected showed indications of cracking. In
heat the precipitator shell than to raise the flue gas units over 12 years old, this percentage was over
temperature. Where carbon steel precipitator or 80%. Cracks found in these inspections forced
stack temperatures cannot be maintained above the many companies to replace carbon steel lower
dew point, Type 316L stainless steel or polymeric furnace tubes. The cracking occurs on the
coatings provide useful protection. waterside of tubes at locations where attachment
welds are present on the outside of the tube.
WATERSIDE CORROSION Despite cautionary bulleting from boiler
manufacturers (17), pulp and paper companies had
Corrosion damage on the waterside of boiler tubes rarely, if ever, inspected for this type of cracking
is usually caused either by inadequate feedwater until a smelt-water explosion in the Stone Container
purity or by improper chemical cleaning. A well- Missoula, MT mill in May 1991 was traced to this
monitored water treatment program and efficient cause. Recent research (18) has shown that stress-
deaerator operation are essential to avoid the assisted corrosion is caused by local dissolution
corrosion damage and heating losses caused by during water quality upsets at sites where the
insulating waterside deposits. Excessive waterside waterside oxide is fractured by tensile thermal
deposits cause two types of corrosion. They cause stresses. Tensile residual stresses are generated
localized “oxygen pitting” under deposits where the within about 1” of attachment welds by temperature
environment is starved of oxygen, and they cycles to the boiler operating temperature and back
accelerate fireside corrosion by insulating the tube (19). The locations most vulnerable to stress
from the cooling effect of the water inside it which assisted cracking are floor-to-sidewall seals and
5.4-6
attachment welds at air ports and smelt spouts. recovery boilers – a state of the art review”,
Specialized radiographic techniques have been pages 1001-1023 in Proceedings of TAPPI
developed to detect these cracks and estimate their Engineers and Papermakers Conference,
severity (20). published TAPPI, 1997.
4. O. Moberg, “Recovery Boiler Corrosion,” 11. J. C. Reid, “Inspection for cracking in black
pages 125-136 in Pulp and Paper Industry liquor recovery boiler tubes,” pages 1049-1071
Corrosion Problems, Volume 1, published in Proceedings of TAPPI Engineers and
NACE, 1974. Papermakers Conference, published TAPPI,
1997.
5. D. Singbeil, R. Prescott, J. Deiser and R.
Swindeman, “Composite tube cracking in Kraft 12. D. C. Bennett (Corrosion Probe, Incorporated),
5.4-7
Private Communication, October 1998. 20. W. B. A. Sharp, “The Strength of Recovery
Boiler Tubes Containing Stress-Assisted
13. R. Thompson, D. Singbeil, C. Guzi, and D. Corrosion”, 11th International Symposium on
Streit, "Corrosion of generating bank tubes at Corrosion in the Pulp and Paper Industry,
the mud drum interface in kraft recovery Charleston, SC, June 8-11, 2004, published
boilers," p.309-318 in Corrosion Problems in TAPPI Press, Atlanta, GA, 2004.
the Pulp and Paper Industry, Volume 7,
published TAPPI Press, 1992.
5.4-8