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Fireside corrosion in kraft recovery boilers

Article · July 1988

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 ENVIRONMENT TREATMENT & CONTROL

Fireside Corrosion in Kraft Recovery

Boilers-An Overview
H.N. Tran and D. Barham
The Pulp nnd Pnper Center, Uniuersity of Toronto, Toronto, Canada

Mikko Hupa
Aho Akndemi, Turku, Finland

t-T'l
I his paper reviews causes and corrective mea- 7970s examined the corrosion mechanism and the
I rnr"t io, ,"rr"ral common types of fireside performances of waterlrrall tube materials in the
corrosion in kraft recovery boilers. Corrosion differs io*"r furnace.r-s These studies revealed three im-
significantly with location in the boiler due to the portant findings: 1) elemental sulfur vaPors and hy-
gr-eat differences in metal surface temperature and drogen sulfide (HrS) gas are the main corrosive
deposit and flue gas chemistry. Sulfidation corro- agents; 2) stainless steels are much more corrosion
sion associated with sulfur-bearing gases under re- resistant than carbon steels, particularly when their
ducing conditions is dominant in the lower furnace, chromium content is higher than 78Vo;and 3) corro-
while sulfidation/oxidation resulting from gas- sion is much less severe if the metal is covered with
deposit-metal reactions is important in the uPper a thick layer of frozen smelt. As a result of these
boiler. findings, chromized tubes, metal-sprayed tubes,
and composite tubes have commo_nly been used to
combat lower furnace corrosion.6-7 Carbon steel
lntroduction
tubes with studs that can hold a thick smelt layer
Fireside corrosion in kraft recovery boilers is a were also used in some boilers to prevent the tubes
persistent problem for many PulP mills. It occu_rs from direct exposure to corrosive gases.s
ilmost everywhere in the boiler from waterwall In recent years, a trend has emerged toward
tubes in the lower furnace to boiler bank tubes to buildilg larger boilers with higher steam Pres-
precipitators. As shown iin Figure 1, the most com- sures,' operating boilers at high bed tempera-
monly observed types oft corrosion include sulfida- tures,ro and tightly controlling chemical losses from
tion corrosion of waterwall tubes in the lower fur- mills, which leads to the accumulation of chloride
nace, molten hydroxide corrosion around air ports, and potassium in the liquors.rl'l2 These trends have
cracking of smelt spout opening tubes and sulfida- inevitably increased the corrosion risk, making it
tion/oxidation corrosion of superheater tubes. Less more difficult to predict. Examples include the lo-
common corrosron occurrences include acidic sul- calized corrosion of composite tubes around air
fate corrosion in the boiler bank, oxidation corro- ports,l3-l5 the cracking o-f composite smelt spout
sion of casing steels in the boiler bank and econo- bpening tubes in mariy high-pressure boiler-s,r7-1e
mizer regions, and coldside corrosion of waterwall 20-23
ut'rd th"" frequent failuie of" superheater tubes.
tubes due to moist conditions during boiler out-
ages. Corrosion has also been observed on screen
Flue Gas Ghemistry
tubes and upper boiler wall tubes near the furnace
roof. Because metals corrode by reacting with depos-
Of these corrosion types, waterwall tube wast- its and/or flue gases to form nonprotective scale,
age in the lower furnace has attracted the most at- the chemistry of deposits and flue gases greatly im-
tention because a tube failure in this area can lead pacts corrosion. The combustion of black liquor pro-
to catastrophic smelt-water explosions. Extensive duces a flue gas consisting of N2, HtO and CO2,
laboratorv and field studies in the mid 1960s and 02, CO, and H2, with small concentrations of SO2

40 MP/July1988
 ENVIRONMENT TREATMENT & CONTROL

I llaterrall (Fireside) Sulphidation

2 Air Ports lbltnn alkali hydrorides

t0 3 Sclt Sport @ening SCC,Thenal Fatigue

1 Superheater Sulphi dati on/&i dati on
5 Eoiler Bank . Acidic sulphates
6 Screen Tubes lcidic sulphates ?
7 Tubes on llud llrr.o . Erusion corrosion
8 Baffles, Casing Oridation
9 lfaterrall (Cold sidel. lloist conditlons
t0 E P. . . Acid der point
I
0 0 0 0 000[ 0 0
rrfftffttaaa,jal':i-l

FIGURE1
Types of corrosionidentifiedin Kraft recoveryboilers.

SOr, HrS, COS, HCl, and vapors of sodium and on the metal surface, providing a barrier that may
potassium compounds. The flue gas composition protect the metal from further attack. For instance,
varies widely with location depending on the atmo- as carbon steel is oxidized in air, a scale is formed
sphere (reducing or oxidizi.g), temperature, and on the steel surface. It consists of an outer layer of
the degree of turbulence and mixing of the gases. hematite (Fe2O3)and an inner layer of magnetite
Of these gases, sulfur- and chlorine- bearing (FerOn). Fe3Oa is comparatively dense, permitting
gases are the most important from the corrosion little O, diffusion and thus can be an effectively
standpoint. A general concern exists for recovery protect against continued oxidation corrosion. At
boiler corrosion in mills that use high sulfidity li- temperatures above 570 C, however, porous FeO
quors (high sulfur content) in the pulping_process (Wustite) forms at the metal-scale interface, permit-
and mills that have a high chloride input.''" ting a much higher rate of 02 diffusion. Carbon
steels are thus not suitable for applications in oxi-
Deposit Ghemistry dizing conditions at temperatures higher than
Recovery boiler fireside deposits consist mainly 570 C.
of NarCOr, NarSO E, drrd Na2S, with a small The corrosion resistance of carbon steels is even
amount of NaCl and potassium salts.23Deposit poorer in the presence of HrS and sulfur vapor,
composition is strongly influenced by the mecha- which always accompany a reducing atmosphere.
nisms by which deposits are formed. Deposits Sulfidation of iron can readily occur, forming iron
formed from smelt or by the impaction of carryover sulfides, FeS and FeS2.Iron sulfide forms a scale
contain a high amount of Na2CO3, while deposits that is much less coherent to the metal than iron
formed by the condensation of vapors of sodium oxide scale and thus provides little protection.
compounds contain mostly Na2SOn with little Improved corrosion resistance, can be obtained
NatCO3. As shown in Figure 2, deposits in the by alloying steels with elements such as Cr and Al
lower furnace generally contain more Na2CO3 and which form dense scale layers. Chromium, for in-
NarS and less Na2SOa, NaCl, and potassium salts stance, rapidly reacts with sulfur or oxygen, form-
than deposits in the upper furnace. ing respectively a compact layer of CrS or Cr2O3 or
spinel films (with Al), which have low internal dif-
MetallurgicalGonsiderations fusion rates. The superiority in high-temperature
For corrosion reactions to occur, metals must be oxidation and sulfidation corrosion resistance of
in contact with corrosive gases and/or deposits. As stainless steels (high Cr content) over carbo_n- steels
the corrosion reaction proceeds, a scale layer grows has been demonstiated in recovery boilers.s'21'23

M P / J u l y1 9 8 8 41
 ENVIRONMENT TREATMENT & CONTROL

r00
Na2S0

80

A
l.r
F
c9
t-
lrl
-

l{a2C03

SI'IELT LO}'ER SI'PEB- BOILER ECO]IO- PRECIPI-

FURI{ACE HEATER BAIIK IIIZER TATOR

FIGURE2
Compositionof firesidedepositsat differentlocationsin Kraft recoveryboilers.

posits, which means that the effect of chloride and

Nickel is excellent for oxidation corrosion resis-
tance. Under high-temperature-reducing conditions, potassium on the lower furnace corrosion through
nickel reacts ."u"dily wiih sulfur in gases-and depos- th" d"ptession of deposit melting point is insignifi-
its to form nickel sulfides (NiS") which form a low- cant.
temperature eutectics of, about 630 c with metallic Deposits in the lower furnac-e 9oni9i1 a large-
nickel. amouni of Na2CO3, which could shield the metal
from HCI and SO2 attack by converting these gases
Gorrosion in the Lower Furnace to NaCl and Na2SOn. The most likely cause of
lower furnace corrosion is the direct attack of metal
WaterwallCorrosion by sulfur-bearing gases, which are H2S- and/or ele-
The metal temperature of waterwall tubes is mental sulfur-produced from gas-deposit reactions.
generally low, 300-to 370 C depending on the satu- The solution to such sulfidation attack seems to
iated steam temperature inside the tubes and the be the creation of a "gas-tight" barrier on the tube
thickness of deposits outside. This temperature surface. Plasma-sprayed coating of carbon steel wa-
range is about iSO to 200 C lower than the lowest terwall tubes with Cr-Ni alloys has successfully re-
first-melting temperature of smelt. Corrosion in- duced lower furnace corrosion. The use of comPos-
volving tt oTt"n smelt is unlikely-unless smelt also ite tubes (commonly carbon steel SA 210 tubes with
contaiis a significant quantity of polysulfide, which a I.65 mm layer of SS 304L on the outside) for wa-
melts at about 250 to 280 C. terwall tubes in the lower furnace ha-s-alsosignifi-
Corrosion is rarely observed on the furnace cantlv reduced sulfidation corrosion.''t' In modern
floor tubes which suggests that there is little or no r".orr.ry boilers, the use of composite bars with
polysulfide is presentin smelt at the metal surface' smaller-widths has minimized corrosion of the
the attack by iorrosive gases is also in-significant membrane bars.
due to the thick layer of smelt on the floor.
Air Port Corrosion
Maximum waterwall tube corrosion is usually
observed just above the smelt pool. The tube-sur- One serious drawback of composite fubes, how-
face temperature at these locations can be as high ever, has been the experience of localized corrosion
as 400 C^becauseof radiant heat transfer and thin- on the coldside of tubes around air ports. This cor-
ner deposits. Such a temperature, however, is still rosion occurs mostly in high-pressure boilers and
too lo* to make deposits melt, thus ruling out the selectively attacks the staiiless steel cladding.l3-1e
possibility that corrosion is caused by molten de- Strong evidence suggests that molten alkali hydrox-

M P / J u l y1 9 8 8
42
 ENVIRONMENT TREATMENT & CONTROL

T-22 PROBE 840 ]lours I]ICOLOYSOOHPROBE 840 llours

6 2
E5 E
E E
Windward
u
(ni 4 Ui Windward
(n
o
J3 91 \
J
flz
UJ
Leeward F
UJ
=l o/ = Leeward
I
0l- 0l-
400 450 500 550 600 650 700 400 450 s00 550 600 650 700
T EMP ER AT U R O
E ,C OC
TE MP E R A TU R E ,

FIGURE3
Corrosionof T-22 and Incoloy800 probes in superheaterregion.21

ides are the cause.73'16 Molten atkali hvdroxides re- Accelerated corrosion caused by molten depos-
act with chromium ofde, the protective layer on its can only be avoided if the metal surface temper-
the stainlesssteel, to form sodium chromate, which ature is lower than the deposit's first melting tem-
then dissolves in molten alkali hydroxides, resulting perature, which limits the superheated steam tem-
in caustic fluxing of the stainlesssteel. perature of a recovery boiler to tube metal. This
limit, however, may be lower for boilers that have
Smelt Spout Corrosion an uneven flue gas temperature distribution, since
Smelt spouts are exposed to severeoperating this distribution results in 'hot spots" in the super-
conditions; smelt is flowing through the spout at heater region where accelerated corrosion may oc-
approdmately 800 C. Nonetheless, the servicelife cur. The effect of chloride and potassium on super-
of carbon steel smelt spouts can be up to 2 y due to heater corrosion has been studied extensivelv. A
the low temperature at the spout metal surface re- laboratory study showed that within the range of
sulting from water cooling. chloride levels encountered in recovery boiler depos-
its, the effect of chloride on superheater corrosion
Smelt becomesextremely aggressiveif the metal was insignificant. Field studies using air-cooled
surface temperature is higher than the first melting probes inserted in the superheater region in various
point of the smelt. This for instance, can occur as a recovery boilers, showed a higher corrosion rate for
result of improper water conditioning, which causes boilers witfr higher chloride input.2O Potassium
salts
water side scaling and high metal temperatures. in high-chloride synthetic superheater deposits
The crackirg of smelt spout openings, particu- were found to accelerate the corrosion of carbon
larly in high-pressure boilers, constitutes another steel T-22 and SS Incoloy 800H in air.20
problem.lT'1e'Althoughthe exactmechanismof
smelt spout opening cracking is unknown, it is be- The most important cause of superheater corro-
lieved to be causedby thermal fatigue and stress sion is probably the local reducing conditions at the
cracking of welds and studs attached to the stain- metal-d-eposit interface .27'23Reducing conditions are
less steel cladding of compositetubes. In many in- likely caused by the presence of reduced sulfur
stances,the cracks penetrated into the inner carbon compounds and unburned black liquor particles in
steel layer of the compositetubes.17Smelt spout deposits. Field studies using air-cooled probes
corrosion seemsto be more severein boilers where showed that on the windward side of the probe
a high chloride input exists. reducing conditions prevail, thus facilitating sulfida-
tion corrosion similar to that observed in the lower
furnace. On the leeward side, corrosion was mini-
Gorrosion in the Upper Furnace
mal due to the oxidizing condition on that side
Superheater Corrosion (Figure 3).

The metal surfacetemperature of superheater Because reducing conditions are far less likely
tubes varies typically from 350 to 550 C depending to occur in deposits at locations further downstream
on the temperature of the superheatedsteam inside from the superheater where the carryover and the
and the flue gas temperature on the outside. The flue gas temperature are lower, superheater corro-
first melting temperature of superheaterdeposits is sion may be minimized by having the steam flow
typically about 560 C, ranging from 520 to 600 C cocurrent with the flue gas flow. Cocurrent flow,
depending on chloride and potassiumcontent.2o however, ffi?y not provide sufficient heat transfer

MP/July1988 43
 ENVIRONMENT TREATMENT & CONTROL

to produce high-temperature superh-eatedsteam. pressure water jet from a pinhole leak i. ul adja-
Nevertheless,locurrent is probably better than ient tube. Carbon steel casing and baffles that are
countercurrent from the corrosion standpoint, be- not cooled may suffer ordinary oxidation corrosion
causeit would lower the metal temperature at the if the flue gas temperature in the economizer ex-
location where maximum heat flux prevails. More ceeds450 C.
importantly, perhaps, it would gtve rise to the for-
mahon of t'noncorrbsive" deposits (i.e. oxidized Screen Tube and Furnace Roof Corrosion
deposits) at the location where the metal tempera- Screentubes and furnace roof fubes are water-
ture is highest. cooled, and their surface temperatures are similar to
As in the lower furnace, stainless steels have the waterwall tube temperatures. Deposits on these
been used at the lowest superheaterbends with tubes usually consist of two distinctly different lay-
some successfor boilers that are oPeratedat a su- ers. The inner laver in contact with metal is formed
perheated steam temperature close to the uPPer by condensedmitetial similar to deposits observed
limit 480 C, though care must be taken in the oPer- in the boiler bank and economizer, while the outer
ating and maintenance procedures to minimize layer is formed by carryover similar to deposits in
steamside stress corrosion cracking of stainless the lower superheater.
steels. Ensuring a uniform distribution of flue gas Pitting corrosion has occasionallybeen observed
temperature acioss the boiler also helps minimize in the upper section of screentubes, on screen
localized superheatercorrosion. tubes close to the boiler bank inlets and on the fur-
nace roof tubes. The corrosion pattern, the chemis-
Boiler Bank Gorrosion try of the inner layer deposits, and the tube surface
Although the metal surface temperature of temperature suggest corrosion of these tubes is
boiler bank-tubes is about the same as that of wa- probably causedby acidic sulfates like the boiler
terwall tubes, corrosion in this region is rarely a bank corrosion describedabove.
concern becauseboth deposits and flue Sasesare
much less corrosive. Deposits contain small Summary
amounts of Na2COg,which neutralize acidic gases Corrosion in kraft recovery boilers varies in dif-
such as HCI and SO* before these Sasescan attack ferent locations in the boiler becauseof great differ-
the metal. The flue gas in this region typically con- encesin metal temperature and flue gas and de-
tains about 2Voexcess02, minimizing reducing con- posit chemistry. Corrosion by H2S and free sulfur
ditions that aggravate corrosion. seemsto be dominant in the lower furnace. Corro-
The low percentageof NatCO3 in deposits may, sion in the superheateris more severebecauseof
however, allow corroiion (due to the presenceof the possible molten deposits involved.
acidic sulfates) to occur in the boiler bank region if
References
there is sufficient SO* concentration in the flue gas
to convert Na2SOato sodium bisulfate. 1. A. L. Plumley, E. C. Lewis, R. G. Tallent, "Ex-
ternal Corrosion of Waterwall Tubes in Kraft Re-
Sodium bisulfate melts in a temperature range covery Furnaces,"Tappi, Yol. 49, No. 1.,724,
of 300 to 350 C, and thus acceleratescorrosion via a 1965.
molten phase. This ffPe of corrosion is uncommon 2. O. Stelling, Vegeby, "Corrosion on Tubes in
and caneasily be avoided by operating the boiler at Black Liquor RecoveryBoilers," Pulp & Paper
high bed temperatures to minirnize the concentra- Magazineof Canada,Vol. 70, No. 8, T236, 7969.
tion of SO* in the upper boiler by lowering the sul- 3. R. G. Tallent, A. L. Plumley, "Recent Research
fur input and by improving sootblo-i.g efficienry on External Corrosion of Waterwall Tubes in
in the boiler bank. Kraft RecoveryFurnaces,"Tappi, Vol. 52, No. l'0,
Metal loss mav also be causedby erosion due L955,L969.
to the abrasiveaction of the sootblowing steam jet 4. T. Hayashi, T. Yoshi, T. Oda, T. Kaibara, "On
and salt cake particles on the boiler bank tubes Smelt Corrosion Resisting Overlay-Weld for Wa-
close to the mud drum. This problem can be me- ter Wall Tubes of RecoveryBoilers," Proceedings
chanically correctedby changing sootblower nozzle of the Symposium on Recoveryof Pulping
design and sootblowing steam Pressure. Chemicals,Helsinki, 1968.
5. "Investigation of Alloyed SteelsFor Use in Black
Economizer Corrosion Liquor RecoveryBoilers," Report Nos. 1-4 , joint
Corrosion in the economizer region is rarely a Report from the Swedish Corrosion Institute and
problem becauseof the low tube surface tempera- the Finnish RecoveryBoiler Committee, 1972.
lurer about 150 C at the feed water inlet and 280 C 6. A. L. Plumley, W. R. Roczniak,"RecoveryUnit
at the outlet. Tube failure is primarily caused by Waternrall Protection, A Status Report," Tappi,
thermal fatigue.le In some instances,tube thinning Vol. 58, No. 9, t78, 1975.
occurs as a result of the impingement of a high- 7. T. Odelstam, "BLRB CompositeTubes - 15 Years

44 MP/July1988
 ENVIRONMENT TREATMENT & CONTROL

of Experience," Kraft RecoveryOperations Semi- Port Corrosion of Composite Tubes in Kraft Re-
nars, Tappi Press,p. 277, 7987. covery Boilers," Proceedingsof Tappi Engineer-
8. l. A. Dickinson, M. E. Murphy, W. C. Wolfe, ing Conference/September7987.
"Kraft Recovery Boiler Furnace Corrosion Protec- 17. S. Ingevald, F. Bruno, "Composite Tubes in Re-
tion," Tappi Engineering ConferenceProceed- covery Boiler Furnace - A Summary of Ten Year
ings, Tappi Press,1981. Experiencein Sweden," Black Liquor Recovery
9. I. D. Blue, R. F. Dudex, S. Suda, "Some Consid- Boiler Symposium, Helsinki, 1982.
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High Temperature and PressureApirlicationi' Damage in Recovery Boilers," Kraft Recovery
Tappi, Yol. 64, No. 9, 101,1981. Operations Seminar, Tappi Press,p. 259, 1987.
10. B. Blackwell,T. King, "Chemical Reactionsin 19. M. D. Moskal, "Corrosion of High Pressure
Kraft RecoveryBoilers," Sandwell and Co. Ltd., Kraft RecoveryBoilers," Kraft RecoveryOpera-
1985. tions Seminar, Tappi Press, 1988.
11. D. W. Reeve, "The Effluent-FreeBleachedKraft 20. D. W. Reev€,H. N. Tran, D. Barham, "Super-
Pulp Mill. Part VII: Sodium Chloride in Alkaline heater Fireside Deposits and Corrosion in Kraft
Pulping and Chemical Recovery," Pulp & Paper RecoveryBoilers," Tappi, Yol. 64, No. 5, 109,
Canada,Yol. 77, No. 8, T126, 1976. 1981.
12. A. F. Gilbert, W. H. Rapson, "The Effluent-Free 2I. H. N. Tran, D. C. Pryke, D. Barham, D. W.
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Paper Canada,Vol. 81, No. 2, T43, 1980. I-Jnits," Tappi, Vol. 58, No. 6, L02, L985.
13. F. Bruno, "Primary Air Port Corrosion," the 4th 22. A. Plumley, B. Lefebre, "Recovery Unit Super-
International Symposium on Corrosion in the heater Wastageand Control-ProgressReport ll,"
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Sweden, Muy 1983. Symposiurn, p. D3-'1.,Helsinki, 1982.
14.I.L. Barna,I. B. Rogan,Proceedingsof 7986 23. R. Backman, M. Hupa, "Fouling and Corrosion
Tappi Engineering Conference,Tappi Press,p. Mechanismsin the RecoveryBoilers Super-
377, 1986. heater Area," Tappi lournal, Yol. 70, Nb. 6,
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16. T. Odelstam, H. N. Tran, D. Barham, D. W. This paperu)asfirst presented
at CORROSION/89,Paper
Reeve,M. Hupa, R. Backman, "Primary Air No. 437, St. Louis,MO.

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