SULFUR AND VANADIUM INDUCED HOT CORROSION OF BOILER TUBES1

Ismail Andijani and Anees U. Malik

Saline Water Conversion Corporation Research & Development Center P. O. Box 8328, Al-Jubail 31951, Saudi Arabia E-mail : rdc@swcc.gov.sa

ABSTRACT Failure of boiler tubes by S- and V- induced hot corrosion has been quite a common phenomenon in boilers burning heavy oil like Bunker C. The phenomenon is usually noted on fire side of boiler tubes. Due to presence of sulfur in the combustion gases at high temperature, Ni, Cr, Fe or Al present in the boiler tube material undergo sulfidation which resulted in the formation of sulfide/sulfate. Vanadium compounds present in the combustion gases undergo fluxing reaction with oxide and/or sulfate scales on metal causing accelerated corrosion. The accelerated corrosion can cause pitting, cracking, fissure or rupture of the tubes. In this paper, the failure of some boiler tubes brought about mainly by S- and Vinduced hot corrosion will be described. An account of the possible mechanism(s) and the ways to combat such a type of corrosion is presented. INTRODUCTION Hot corrosion is an accelerated form of corrosion in which molten salt(s) form a film on a metal surface that fluxes, destroys or disrupts the normal protective oxide layer [14]. Sulfur compounds and/or other contaminants such as sodium or vanadium usually form molten salt. In fuel oil, the important impurities are Na (up to 300 ppm), V (up to 150 ppm) and S (0.6 to 3.6%). temperature of the specific species. Hot corrosion is generally initiated by sulfur. In combustion products of fuel oil, sulfur is typically present as Na2SO4. At high temperature it dissociates according to the following reaction:
Presented at Chemistry & Industry Conference, King Saud University, Riyadh, on 11 to 15 Dec., 2004.
1

During combustion, these impurities melted or

vaporized and get deposited on metal at temperatures below the condensation

c:\documents and settings\u100960\desktop\volume 14\sulfur and vanadium.doc

Na2SO4

Na2 O + SO3

In a typical hot corrosion reaction, molten Na2SO4 attacks protective layer on metal and undergoes fluxing reaction causing rapid metal consumption. In boilers, high temperature attack could be due to fire side corrosion, sulfidation or hot corrosion. Fire side corrosion is observed at about 550oC or above with industrial and marine boilers using high sulfur fuel. It falls into 2 categories: (1) (2) Under deposit corrosion of furnace wall evaporator tubes, Under deposit corrosion of superheater and reheater tubes and the upper end of the furnace chamber and in the convection pass. Fire side corrosion of above categories is frequently observed in the fuel oil containing impurities like S, V, Na, Cl, etc. in appreciable concentrations [5,6]. Na2SO4 induced corrosion attack involves salt fluxing and sulfidation [3]. Vanadium as an impurity in fuel oil causes serious corrosion problems because of the formation of V2 O5 which has a m.p. of 670 oC [7]. The problem is often compounded if sodium (Na) is present because some V-Na mixed oxides have still lower m.p. For example, sodium vanadyl vanadate 5Na2 O. V2O5 . 11 V2 O5 melts at 545 oC. Liquid deposits formed in this way flux the protective oxide layers on structural alloys, making them vulnerable to rapid corrosion. Figure 1 shows melting points of the deposits formed on superheater tubes [8]. Figure 2 shows the regions where oil ash corrosion can be expected to occur as a function of tube metal and gas temperature [9]. SOME CASE STUDIES 1. Boiler Tube Failure in Medina/Yanbu Plant-I Introduction The water wall boiler tubes had big pits with a hole in the center on fire side near the bend. Longitudinal section of the failed tubes cleaned with 3% HCl did not show any sign of chemical attack or development of cracks or fissure on either steam or fire sides of the tube. The boiler tubes were initially coated with aluminum.

Figures 3 and 4 show SEM pictures of fire side surfaces of boiler tubes showing holes in the failed areas. The material of the tube is carbon steel type 201 A-I [C:0.27, Mn:0.93, Si:0.1]. EDX Studies EDX of the scales scrapped from outer surface (fire side) shows the presence of Al and V as indicated by the following EDX data : Elements: Weight %: Fe 5.4 Al 10.6 V 14.3 Cr 0.01 Ni 0.10

Figures 5 to 7 show scanning electron images, EDX profiles and X-ray maps of the scales formed on the fire side surface of the failed area of boiler tubes. Dot mapping and line profile of EDX (Figs. 8 and 9) show the distribution of different elements in multilayers scales as follows: V, Al, S V, S,Al,P Fe upper layer middle layer lower layer

The source of Al appears to be alumina (Al2O3) formed initially on the outer surface of the boiler tubes. Mechanism Al2O3 and Al2S3 would have formed initially on fire side of the boiler tube. Some locations of the fire side might have overheated and V2O5 would have reacted with Al2O3 to undergo fluxing reaction. This V-induced attack resulted in the consumption of the material and formation of deep pits or holes. The effect of corrosion appears to be maximum on the surface region which were locally overheated. temperature appears to increase with time as steam side scale grows. Conclusion Failure of boiler tubes was due to localized overheating and subsequent dissolution of protective Al2O3 in the molten vanadium compounds followed by fluxing reaction resulting in the accelerated corrosion attack on the tube material. The metal

2.

Boiler Tube Failure in Medina/Yanbu Plant-II

Introduction Fire tubes failure was reported in an oil fired boiler which was in service for 15 years. The fire tubes were located in the central portion of the boiler floor area situated about 1.5 meters from water drum. Fire side temperature was 1640oC (max.) and steam side temperature around 455 oC (max). Results and Discussion The failed portion in one of the tubes contained a large pit, which had perforated the tube from top surface (Fig. 10). The perforation made a hole of diameter approx. 10 mm which was surrounded by number of deep pits. In other tubes there were a number of deep pits but no perforation. Figures 11 and 12 show the perforated and pitted areas of the boiler tubes, respectively. The region near the pit which is thinned due to corrosion had shown the layers of deposits over the surface. The deposits when analyzed by EDX showed the presence of V, S, Al, Si and O (Fig. 13). Electron probe microanalysis (EPMA) showed that the deposits were rich in V compounds near the pit (Fig. 14). Although, floor area tube temperature is normally between 300-450oC, the deposit would increase the temperature due to poor heat transfer effect, which is sufficient to cause melting of the salt compounds in the deposit. Once these salts are in molten state they would undergo fluxing reaction destroying the protective layer and consequently, metal undergo hot corrosion. The presence of V and S as noticed on pits is originated from fuel oil suggesting that V and S compounds attacked the tubes during service and subsequently led to their failure. Conclusions Failure of the tubes is most likely due to fuel ash corrosion. Presence of V and S in the tube surface deposits had accelerated the corrosion leading to perforation of the tubes. Use of Cr - containing steel SA 213-T22 (K21590) was recommended to minimize corrosion.

3.

Failure Analysis of Boiler Tubes of Al-Khobar Phase-II

Leakages were reported in 4 sections of boiler tubes (three secondary superheater tube ( A to C and one division wall tube D). Three tubes had a working temperature of 485oC at steam side and 85 bar pressure. The 3 sections of the tube had circumferential cracks while the fourth one had blown up at one location. All the failures were on the fire side. Figures 15-18 show photographs of boiler tubes in as received condition. Following were the main observations: Tube A : Cracked circumferentially at the HAZ of the weld. Fire side was covered with a brown color adherent oxide scale while steam side covered with black oxide scale. Tube B : 30 mm long 20mm wide burst was found. Thickness of the lip of the burst was same as that of tube wall indicating that this area of the tube had blown up without bulging of the tube. In addition large number of circumferential cracks, originating at fire side surface of the tube and going deep into the metal matrix were also observed. Tube C : Brown scale at the fireside and black scale on the steam side. At one location of the fire side surface, a depression and a hairline crack was observed. Tube D : It is a longitudinal section of tube, two deep dents were found on fireside. A wide circumferential crack, originating from the center of the dent, was found. Materials Tube A and C had similar composition: 1.25 Cr, 0.5 Mo steel (ASTM Grade A 213 T12). Tube B has the composition : 2% Cr, 1.0 Mo (A213 T 22) Tube D has the composition : Carbon steel ASTM A210; C: 0.3, Mo: 0.85, S: 0.05.

Metallography Microstructures of the cross-sections of the boiler samples show the following features: Tube A : Tube B : Corrosion is intergranular (Fig. 19). Many grooves starting from the surface going deep into the matrix from fire side. Grooves showing corrosion products within the canals. Scales very fragile (Fig. 20). Tube C : Tube D : The cross section of the cracked area show a broad crack originating from the fire side surface. Formation of multilayered fragile scales (Fig. 21). Wide cracks with few branches. White inclusions of Cu within the crack can be seen. Cracks are intergranular. Depletion of carbide near the scale/metal interface was found (Fig. 22). EPMA Results Tube C, A, D : Fire side scales S is identified in the inner most layer of the scales (Fig. 23). Tube B : Tube D : Discussion Deposition of S on the fire side surface of the tubes and increase in the tube metal temperature were found to cause the above failure. Above 500oC (tube metal temperature), S containing salts become molten. The molten deposits dissolve protective oxide scales causing accelerated corrosion of the tube. Corroded areas of the boiler tubes have revealed selective corrosion at the grain boundaries. Sulfur is one of the major causes of failure of fire side surfaces. In tube A residual stresses and in Tube C steam impingement might have enhanced the corrosion process and caused cracking of the tube. In tube D the corrosion was only due to the presence of low melting point deposits whereas in tube D it occurred due to liquid metal embrittlement. Corrosion products found in the grooves of fire side scales. S present in the grooving tips (Fig. 24). S was identified in the cracks and its branches (Fig. 25).

Conclusions Presence of S in the fuel oil ash deposits on the fire side surfaces of the tubes appears to be the main cause of failure. Cracking of tube A at the weldment is due to combined effect of S-induced corrosion and welding stresses. 4. Failure of generation bank tube of boiler in Medina-Yanbu Plant

Leakages were reported in the generation bank tube of boiler # 4 of Medina-Yanbu plant. The plant had been in operation for approximately 13 years. Rupture was noticed in one tube (#9) and pinholes were found at 6 0 clock position. Physical Examination Figures 26 and 27 show ruptured bank tube in as received condition showing side A (front view) and side B (back view), respectively. The picture of the portion of The ruptured generation tube shows localized attack and metal losses (Fig. 28).

photograph of the splitted ruptured tube after removal of internal (steam side) scales show pitting ((Fig. 29). The photograph of the ruptured tube after removal of fire side scales show pitting and thinning of the tube (Fig. 30). The tube material was ASTM SA-210A-I (carbon steel). EDX Studies The external scale (fire side) deposits determined by EDX showed the presence of Fe, V, Al, O, S and Cu in significant concentrations (Fig. 31). Inner scales showed the presence of Fe, O and Si in significant concentrations and K, Mg, S and V in low concentration (Fig. 32). Hydrojetting was carried out during shut down by alkali to remove external deposits on the tube. The S-containing deposits were acidic in nature forming aqueous solution of acid (mainly H2SO4) and salts by reacting with alkali. While most of the acidic liquid is drained off, some of the liquid remaining adsorbed on the refractories attacked the adjacent boiler tubes. With the gradual thinning down of metal and due to high pressure (70 bar) inside the tube, rupturing of the tube would facilitate.

During the start of the shut down period, the combustion gases contaminated with S could also condense as H2SO4 at the dew point temperature and initiate dew point corrosion. Vanadium compounds present in the combustion gases react with the scales in presence of oxygen, forming low melting vanadates which undergo fluxing reaction resulting in accelerated corrosion. The thinning of tube wall by residual adsorbed acid along with combination of dew point and hot corrosion resulted in rupture of the tube. Conclusions Rupture appeared to be mainly as a result of corrosion attack at the external surface of the tube. During hydrojetting, the region of the tube located near the refractories suffered acid attack resulting in thinning of the tube and consequently, due to high pressure (70 bar) inside the tube, rupture of the tube is facilitated. During initial stage of shut down, S in the combustion gases condensed and formed H2SO4 at dew point resulting in dew point corrosion of the tube. S and V initiated hot corrosion at the fire side of the tube by forming low melting point vanadates. The vanadates undergo reaction with the scales at the surface of the tube resulting in severe corrosion. 5. Failure of Economizer Tubes in Medina-Yanbu Plant

Leakages were reported in the economizer tube in boiler #7. The tube was welded and most of the corrosion activity was confined to weld or surrounding areas. The front side (A) and back side (B) have different morphologies. Side A : Corrosion products are concentrated at the weldment and metal is eaten away at the weld. Side B : Micropits, pinholes and macroholes were found at or in the vicinity of weldment. The surface is wrinkled and there is marked reduction in thickness of tube wall in the vicinity of weld. Photographs (Figs. 33 and 34) show frontal and back side views of the economizer tube, respectively. Figure 35 shows thinning of the tube wall of the economizer tube (back side).

EDX Studies The external corrosion products collected from depressed area of the weld (side A) contain high concentration of S and moderate concentration of V (Fig. 36). Near the pits (side B), presence of V, S, Cu, Fe and Ni was detected (Fig. 37). Discussion Considering side A of the economizer tube, the weld surface was preferentially attacked by a liquid like H2SO4 which is presumably formed by the condensation of SO2 and water vapors at the temperature below the dew point of the acid. The reaction between H2SO4 and the metal resulted in the corrosion of weld and formation of FeSO4 and other corrosion products. The other side (back side B) appears to be more corroded and has pits and holes and thinning of the wall. Here again, the flue gas temperature drops down and approached to dew point resulting in condensation of H2SO4 which attacked the metal. The corrosion at this location is more severe due to fluxing reaction between molten vanadium oxide and FeSO4. This results in pitting, hole formation and thinning of wall at reaction site. Conclusions The leakages in economizer tube where final preheating of the feed water occurs before it passes into steam drum appear to be caused by dew point corrosion. The dew point was localized mostly to weld regions. The intensity of corrosion attack is further aggravated by the fluxing reaction between irons sulfate and vanadium compounds (present in the flue gas) with the protective scales on steel. CONCLUDING REMARKS Hot corrosion is an accelerated form of corrosion in which fused salts in the form of fuel ash or otherwise attack the protective oxide film resulting in the severe chemical damage to the material. This phenomenon is quite familiar in boilers, turbines and other power generating systems using fuel oil containing S, Na, V-containing impurities in

substantial concentrations. A fairly large number of cases concerning the failures in industrial and marine boilers have been reported in which hot corrosion had played a predominant role. Furnace wall evaporator tubes, superheater and reheater tubes and to some extent economizer are severely affected by hot corrosion. The hot corrosion can directly affect the boiler by initiating the attack at fire side or it may synergetic to a corrosion attack which has already been underway by some other process such as overheating, acid condensation or weld attack. In this paper, some cases of boiler tube failures have been reported in which aggressive attack by hot corrosion appears to play a key role in corroding the boilers. REFERENCES 1. 2. 3. 4. 5. 6. 7. 8. 9. Stringer, J, (1977), Hot Corrosion, Annual Reviews Material Science, 7, 477. Rapp, R.A, (1986), Chemistry and Electrochemistry of Hot Corrosion of Metals, Corrosion, 42, 568. Brnstein, N.S, DesGrescenti, M.A., (1971), Met. Trans., 2, 2875. Malik, A.U., et.al, (1989), Materials Trans., JIM, 30, 70716. Wright, I.G., (1987), Hot Corrosion in Coal- and Oil-Fired Boilers, Metal Hand Book, Vol. 13, 995, ASM. Reid, W.T., (1971), External Corrosion and Deposits Boilers and Gas Turbines, Elsvier, NY. Swisher, J.H. and Shankarnarayan, S., (1994), Inhibiting Vanadium Induced Corrosion, Materials Performance, 33 (9), 49. Kawamura, T. and Harada, Y., (1980), Control of Gas Side Corrosion in Oil Fired Boilrs, Mitsubish Tech. Bulletin, 139, May. Fujikawa, H. and Makiura, H. (1982), J. Mater. Energy, System, 4, 3.

Figure 1.

Melting points of deposits formed on superheater tubes (Ref. 8)

Figure 2. Regions where oil ash corrosion can be expected to occur as a function of tube metal and gas temp. (Ref 9)

Figure 3. SEM picture of fire-side surface of the boiler tube showing hole in the failed area

Figure 4. SEM picture of fire-side surface of the boiler tube showing hole in the failed area

Figure 5. SEM and EDX analysis of the scales formed on the fire-side surface of the failed area (very near to the hole) of the boiler tube

Figure 6. SEM and EDX analysis of the oxide scales formed on the fire-side surface of the failed area (slightly away from the hole) of the boiler tube

Figure 5. SEM and EDX analysis of the scale formed on the fire-side surface of the failed area (very near to the hole) of the boiler tube

Figure 7.

SEM and EDX analysis of the oxide scales formed on the fire-side surface of the boiler tube without any failure

Figure 8. SEM and EDX analysis of the transverse section failed area of the boiler tube showing chemistry of oxide scales formed on fire side surface

Figure 9.

SEM and EDX analysis of the transverse section failed area of the boiler tube showing chemistry of oxide scales marked in the figure

Figure 10. Photograph of failed boiler tubes. Note a large size hole caused by pitting corrosion in one of the tube.

Figure 11. Close up view of pitted areas of the tubes showing perforated area of the pit in the first tube

Figure 12.

Close up view of pitted areas of the tubes area showing clusters of pits without perforation in the second tube

Figure 13.

SEM-EDX analysis of the pitted area of the boiler tube

Figure 14. Electron probe microanalysis of the pitted surface of the boiler tube. Note the enrichment of vanadium in the line scan of the surface deposit.

Figure 15.

As received failed tube samples of boiler of AlKhobar power and desalination plant

Figure 16. Boiler tube-A showing crack at the weldment

Figure 17.

As received boiler tube-B with circumferential cracks and failure opening

Figure 18. As received condition of boiler tube-C

Figure 19. Magnified view showing intergranular corrosion by molten ash X800

Figure 20. Optical micrograph of cross section of grooving of tube B X100

Figure 21. Optical micrograph of cross-section of crack on fire side of tube-C X100

Cu

Figure 22. EDX micrograph of cross-section of boiler tubeD showing embedded particles of copper within crack X 100

Figure 23. EPMA micrograph and composition profile of oxide scale formed on fireside surface of the boiler tube A

Figure 24. EPMA micrograph and composition profile of cross-section of grooving on the fire side surface of the boiler tube B

Figure 25. EPMA micrograph and composition profile of oxide scale formed on fireside surface of the boiler tube D

Figure 26. Front view of ruptured generation bank tube # 9 in as received condition

Figure 27. Back view of ruptured generation bank tube # 9 in as received condition

Figure 28. Picture of the portion of ruptured generation tube showing localized attack and metal loss

Figure 29. Photograph of the ruptured tube after removal of the scales (internal side) showing pitting

Figure 30. Photograph of the ruptured tube after removal of the scales (external side) showing pitting and thinning of the tube

cps

Fe 20

15

V 10 O Al

5 Cu Si

S Fe Ca K V Mn Ni Cu 10 15 20 Energy (keV) Cu

0 0 5

Figure 31. EDX profile of the outside scale deposits formed on bank generation tube # 9
cps 60 Fe 50

40

30

20

10 Fe

Si Fe Al Mg K S K V Mn

0 0 5 10 15 20 Energy (keV)

Figure 32. EDX profile of the scales formed at the steam side (inner) of generation bank tube # 9

Figure 33.

Photograph showing economizer tube # 52, boiler # 7 Madina-Yanbu Plant frontal view (Side A)

Figure 34.

Photograph showing economizer tube # 52, boiler # 7 Madina-Yanbu Plant backside view (Side B)

Figure 35. Photograph showing thinning of the tube wall of the economizer tube (side B)

Figure 35. Photograph showing thinning of the tube wall of the economizer tube (side B)

cps

15

S Fe

10

Fe

0 0 5 10 15 20 Energy (keV)

Figure 36.

EDX profile of the corrosion products collected from the weld (side A) outside surface

cps

Fe 15

10 Cu O Cu

5 V P S

Fe Ni Cu

0 0 5 10 15 20 Energy (keV)

Figure 37.

EDX profile of the corrosion products deposited on the pitting area (side B) of economizer tube # 52