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The Role of Fireside Corrosion on Boiler Tube Failures, Part I

The Role of Fireside Corrosion on Boiler Tube Failures, Part I

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Published by Adam Othman

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Published by: Adam Othman on Jun 04, 2012
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06/04/2012

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One of the primary challenges of reliably burning coal is managing the corrosion experienced by the furnace heat transfersurfaces. Fireside corrosion remains a leading cause of failure in superheater and reheater tubes. Also, tubes affected by thefireside corrosion mechanism may lose 15 mils per year (mpy) and more in extreme cases. Five case studies (threepresented here in Part 1) examine the different failure modes experienced by tubes located throughout the furnace. Fireside corrosion in the superheaters and reheaters of coal-fired units is known as coal ash corrosion, in oil-fired units as oilash corrosion, and in refuse-fired boilers as ash corrosion. Sometimes, fireside corrosion is also referred to as hot corrosion.The mechanism in each case is similar, but the low-melting species in each is different. In coal ash corrosion, the low-meltingspecies would be sodium or potassium iron trisulphates (Na
3
Fe(SO
4
)
3
or K
3
Fe(SO
4
)
3
); in oil ash corrosion they would beV
2
O
5
-Na
2
O or V
2
O
5
-Na
2
SO
4
; and in refuse-fired boilers they would be chlorides of iron and zinc along with other possibilities[see references 1 and 2 in the sidebar]. High temperatures (above 1,000F) of the superheater/reheater favor the formation ofthese low-melting compounds. The corrosion rate in coal ash corrosion, between 1,100F and 1,250F, is very high. In this temperature range, Na
2
SO
4
 /K
2
SO
4
reacts with surface oxides in the presence of SO
3
to form complex liquid sulfates (Na
3
Fe(SO
4
)
3
or K
3
Fe(SO
4
)
3
) that result inrapid corrosion [3, 4]. Above 1,250F the corrosion rate is decreased significantly due to decomposition of these complexliquid trisulfates. Once the liquid phase has been removed, the corrosion is due to oxidation in contact with flue gas. The corrosion constituents in oil ash corrosion are vanadium, sodium, potassium, and sulfur. The combustion of fuel oil mayproduce low-melting species V
2
O
5
-Na
2
O, V
2
O
5
-K
2
O, V
2
O
5
-Na
2
SO
4
, and V
2
O
5
-K
2
SO
4
. The melting points of thesecompounds range between 1,000F and 1,550F, depending on composition [4, 5, 6]. The oil ash corrosion mechanism issimilar to coal ash corrosion: a low-melting-point liquid forms and it dissolves the protective iron oxides. In refuse-fired boilers, chloride and sulfate species lead to the formation of low-melting- point liquids on the tube surface thatmay contain iron, zinc, lead, and sodium. These species dissolve the protective iron oxide and expose the bare steel to thecorrosive environment, resulting in significant wall loss [7]. Reducing conditions inside the furnace may lead to the formationof iron sulfide instead of iron oxide. The presence of carbon and iron sulfide within the ash deposits indicates the presence ofreducing conditions. Hydrogen chloride can more easily attack iron sulfides, rather than oxides, to form iron chloride as acorrosion product. This iron chloride has a relatively low boiling point, and therefore iron chloride vapors form in thesuperheater/reheater temperature range, and the corrosion mechanism is by loss of iron as a vapor. The porous sulfideformed in reducing conditions allows easier formation and removal of iron chloride vapor. Furnace wall tubes are also subject to fireside corrosion, but the low-melting species differ from superheater/reheaters.Sodium and potassium pyrosulfate (Na
2
S
2
O
7
or K
2
S
2
O
7
) have been responsible for furnace wall corrosion [1]. Both of thesespecies melt below 800F, where the furnace wall tubes operate. The melting points of Na
2
S
2
O
7
and K
2
S
2
O
7
are 750F and570F, respectively [4, 8, 9]. Mixtures of these two compounds could melt at even lower temperature. Melting points as low as635F to 770F have been measured. One finishing superheater tube sample, from a coal-fired unit, was received for metallurgical analysis. The tube was specifiedas 1.875-inch outer diameter (OD) x 0.330-inch medium wall tubing (MWT), SA-213 T22 Cr-Mo steel. It had been in servicefor 23 years. Figure 1 illustrates the as-received tube sample and the inner diameter (ID) view. Significant wall thinning wasobserved on the flanks of the tube, characteristic of coal ash corrosion. Very hard scale was observed on the tube OD. On
The Role of Fireside Corrosion on Boiler Tube Failures, Part Ihttp://www.coalpowermag.com/print/ops_and_maintenance/The-Role-of...1 of 171/6/2012 9:40 PM
 
the steam side, there was a thick oxide. 
1.
As-received tube and view of ID. Courtesy: David N. French MetallurgistsThe tube sample was cross-sectioned, mounted, polished, and etched for metallographic examination. A 3% nital etchant(100 ml ethanol and 3 ml HNO
3
) was used to reveal the existing microstructure. Metallographic examinations wereconducted via optical microscopy. Figure 2 shows thick scales at the tube OD and ID. A thick ID scale can raise the tube walloperating temperature significantly. Figure 3 is a view of coal ash corrosion that had occurred on the OD. 
The Role of Fireside Corrosion on Boiler Tube Failures, Part Ihttp://www.coalpowermag.com/print/ops_and_maintenance/The-Role-of...2 of 171/6/2012 9:40 PM
 
2.
Cross-section of the tube wall facing the gas flow at 4.5x magnification. (Note that numbers on the images do notnecessarily correspond to the numbering in this article.) Courtesy: David N. French Metallurgists
3.
View of coal ash corrosion at 100x magnification. Courtesy: David N. French MetallurgistsAs shown in Figure 4, the microstructure of the T22 tube had transformed to ferrite with spheroidized carbides.Metallographic examination was also performed at the 8:00 orientation of the tube to look for creep damage, if any. Themicrostructure was the same, irrespective of the specimen location, and there was no evidence of creep. 
4.
Ferrite with spheroidized carbides, mid-wall at 400x magnification. Courtesy: David N. French MetallurgistsTube wastage will often be evident and manifested as flat spots on either sides of the upstream of flue gas flow, as can beseen in Figure 5a. A ring sample, Figure 5b, was sectioned from the tube for dimensional and hardness measurements(Table 1). The tube had thinned significantly at the 4:00 and 8:00 positions due to coal ash corrosion. The thinnest section ofthe ring (0.291 inch at the 8:00 position) was at 88% of MWT. The hardness, averaging 73 Rockwell B (RB), showed that thetube had softened after 23 years of service.
The Role of Fireside Corrosion on Boiler Tube Failures, Part Ihttp://www.coalpowermag.com/print/ops_and_maintenance/The-Role-of...3 of 171/6/2012 9:40 PM

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