O V ER H EA TI N G A N D FU EL A SH C O R R O SI O N FA I LU R E O F BO I LER TU BES I N SW C C PO W ER PLA N TS - Some Case Studies1

N aus ha A s rar,A nees U .M al i k and Shahreer A hm ed Research and Development Center Saline water Conversion Corporation P.O.Box 8328, Al-Jubail, Kingdom of Saudi Arabia. D hi b Al Subai i Al-Khobar Power and Desalination Plant, Al-Khobar And I zdei n M .Sai d Al-Khafji Power and Desalination Plant, SWCC A BSTR A C T Res ul t s of i nves t i gat i ons of t he f ai l ur e of boi l er t ubes of SW CC power pl ant s at Al Khaf j iand Al Khobar ar e pr es ent ed. Caus e and m echani s m s off ai l ur e ar e di s cus s ed and r ecom m endat i on f or pr event i on ofr eoccur r ence ofs uch f ai l ur es ar e pr ovi ded. Case - I Fai l ed boi l er t ubes of Al Khobar pl ant wer er ecei ved. The t ubes had ci r cum f er ent i al cr acks and bl own up por t i ons . Al lt he f ai l ur es wer e det ect ed on t he f i r es i de s ur f aces of t he t ubes . Pr es ence ofs ul f ur i nt he oi las h depos i t s on t he f i r es i de oft he t ubes appear s t o be t he m ai n caus e off ai l ur e ofboi l er t ubes . The cr acki ng oft he t ube att he wel dm ent was due t o t he com bi ned ef f ect of Si nduced cor r os i on and wel di ng s t r es s es . Ci r cum f er ent i al f i s s ur es i ni t i at ed by t he m ol t en as h wer e enhanced gr eat l y due t o wel di ng s t r es s es and r es ul t ed i n t he cr acki ng of t ube at t he wel dm ent . I ti s o m ai nt ai nal ow m et alt em per at ur e r ecom m ended t o avoi d hi gh s ul f ur i nt he f ueland t

over heat i ng pr obl em s . For avoi di ng r eoccur r ence ofs uch f ai l ur es i ti sr ecom m ended t o car r y out r egul ar i ns pect i on of s cal e depos i t i on on t he s t eam / wat er s i de s ur f ace and m eas ur em entofdet er i or at i on i nt he boi l er t ube t hi cknes s .I ft he am ountoft he depos i t s has cr os s ed t he al l owabl e l i mi t , cl eani ng of t he t ubes s houl d be car r i ed out at el y. i m m edi I N TR O D U C TI ON The failure of industrial boilers has been a prominent feature in fossil fuel fired power plants. The contribution of one or several factors appear to be responsible for failures, culminating in the partial or complete shutdown of the plant. The use of high sulfur

or/and vanadium-containing fuel, exceeding the design limit of temperature and pressure during operation, and poor maintenance are some of the factors which have a detrimental effect on the performance of materials of construction. A survey of the literature [1-8] pertaining to the performance of steam boilers during the last 30 years shows that abundant cases have been referred to, concerned with the failure of boilers due to fuel ash corrosion, overheating, hydrogen attack, carburization and decarburization, corrosion fatigue cracking, stress corrosion cracking, caustic embrittlement, erosion, etc. Oil ash corrosion which is quite common in utility boilers is originated from the vanadium present in the oil. Vanadium reacts with sodium, sulfur, and chlorine during combustion to produce low melting point ash compositions. These molten ash deposits on the boiler tube surfaces dissolve protective oxides and scales, causing accelerated tube wastage [3]. Corrosion problems in boiler tubes arisen due to overheating are quite common. This mode of failure is predominantly found in

superheaters, reheaters, and water wall tubes, and in the result of operating conditions in which tube metal temperature exceeds the design limits for periods ranging from days to

about 12 years service, resulted in deposition of carbon coke and soot particles on the tube surface and introduced a carburization process in the steel matrix [11].

Gabrielle [12] overviewed the water related tube failures in industrial boilers. The causes of the majority of failures are attributed to the upset in water quality and/or steam purity. The mechanisms of failures due to overheating (short term and long term), water-side corrosion, general surface attack, stress-assisted corrosion, caustic embrittlement, hydrogen damage, and chelant corrosion have been discussed in detail.

This paper presents the results of two separate investigations carried out to determine the causes of failure of boiler tubes of Al-Khobar and Al-Khafji Power and Desalination Plants. The main aim of this investigation is to acquaint the operation and maintenance personnel with the different corrosion modes involved in failures, and to suggest some measures for preventing the recurrence of such failures. C A SE -I : SU LFU R I N D U C ED C O R R O SI ON AND STR ESS

EN H A N C ED C O R R O SI ON G EN ER A L D ESC R I PTI ON Failed tubes, designated as A and B of Al-Khobar plant were from the tertiary superheater area. All the tubes were first examined by nacked eyes and then under a stereo microscope and the failed area were marked by arrow (Fig. 1 a. and b). Following were the as received conditions of the above tubes. Tube A. : This tube (OD 45 mm thickness 6 mm) was cracked circumferentially at the HAZ of the weld and was found in two pieces. The fire-side surface was covered with a

In addition to this burst, large number of circumferential cracks, originating at the fireside surface of the tube and going deep into metal matrix, were also observed. M at eri alA nal ys i s Materials of A and B tubes were analyzed with the help of EDAX and their carbon level was determined by Carbon-sulfur analyzer. The composition of Tube A was found similar to 1 Cr 0.5 Mo steel (ASTM grade A213 T12) and tube B as 2 Cr 1.0 Mo steel (ASTM grade A 213 T22). Mi cros t ruct uraland El em ent alA nal ys es A small cross-section of the failed area was taken from the failed zone of the tube and mounted in conductive resins. Mounted specimens were abraded, polished, etched, dried and their metallographic studies were carried out under the metallurgical microscope. Metallographs of the tube A revealed that on fire-side surface of the tube thickness of oxide scale is not uniform and the corrosion is intergranular in nature (Fig.3 On fireside surface of the tube B, many grooves starting from the surface and going deep into the matrix were revealed by optical metallography. One of the grooves showing corrosion product within the canal of the groove is shown in the Figure 4. On the fireside surface the oxide scale were very fragile in nature and, therefore, were broken during polishing of the sample.

In order to understand the chemistry of oxide scales, metal matrix and inclusions found inside the cracks, EDAX and EPMA techniques were used. Figure 5 is the

characteristic EPMA composition profile of the oxide scale formed on the fireside surface of the boiler tube A. In these images sulfur is recognized in the innermost layer

Bunker-C oil is used for fuel in power plants. During the distillation process, virtually all the metallic compounds and a large part of the sulfur are concentrated in the residual fuel oil.

The fuel oil constituents that are reported to have the maximum effect on oil ash corrosion are vanadium, sodium, sulfur and chlorine. According to chemical analysis of deposits, formed on superheater tubes (Table - 1), sulfur content increases when vanadium content is reduced in the deposits [13]. Our EDX analysis and EPMA results showing no vanadium and considerable amount of sulfur in the corrosion product is in consistent with the findings of Tomozuchi et. al., [13].

Microscopic studies of the corroded areas of the boiler tubes have revealed selective corrosion of the grain boundaries of the tubes (Fig. 3). Chemical analysis of the

corrosion products indicates that sulfur is one of the major causes of the failure of the fire-side surfaces of the boiler tubes. Sul f urI nduced C orros i on Sulfur typically is found as sodium sulfate in fuel ash. dissociates according to the following reaction [14]. At high temperature it

Na2SO4

Na2O + SO3

The reaction products will alter the basicity of the molten ash deposits. Sulfur reacts with sodium in the melt altering the concentration of Na2O, and thereby changing the corrosion rates. The melting of deposits depends on the Na + S/V ratio and it ranges

increases the mechanical properties of the tube metal deteriorates.

Under these

circumstances if the temperature and pressure of the tube elevate abnormally due to some reason, the tube will burst.

Figure 6 is the EPMA sulfur print of the grooving. Existence of abundant sulfur at the tip of the groove proves that the reaction by alkali sulfate compounds play an important role in the grooving corrosion. During this corrosion the end of the corroded part grows deep into the metal matrix. St res s Enhanced C orros i on In the case of tube A it appears that the weldment was not stress relieved. When corrosive conditions are prevalent, the current flow between the anodic and cathodic half cells (stressed and unstressed regions respectively) is greatly enhanced. The

welding stresses of tube A, therefore, might have enhanced the growth of the fissures caused by sulfur induced corrosion and this resulted into the cracking of the tube at the weldment.

C A SE -I I : LO N G TER M O V ER H EA TI NG G EN ER A L D ESC R I PTI ON The strength of carbon steel remain nearly constant up to about 454 oC. Above this temperature, steel begins to loose its strength rapidly. If the tube metal temperate is gradually increased beyond this temperature, it will plastically deform and then rupture. The approximate time to rupture is a function of the hoop stress (related to internal

As the local regions develop hot spots, bulging of the tube occurs which results into the rupturing of the tube (Fig. 7). I D EN TI FI C A TI ON Overheating failures caused by the insulating effect of deposits can invariably be

recognized by the formation of blisters in the tube. These blisters represent a localized area of the tube that underwent creep deformation. Presence of thick, brittle, dark oxide layers on both internal and external surfaces indicate the occurrence of long-term overheating. Reduction in wall thickness and increase in OD of the tube (Fig 8) show the extent of oxide scale formation and bulging of the tube. Bulging usually causes spalling of deposits at the bulged site, which reduces the thickness of the wall tube. Due to prolonged thermal oxidation and thinning of the tube wall a hole appeared on the fireside (Fig. 7a). Superheater tubes shown in Figure 7b, were ruptured longitudinally due to high pressure and thinning of the tube wall. Here the broad mouth of the rupture indicates that the ruptured tubes remained in the furnace for long period during which its lip were heavily oxidized at high temperature and corrosion products were eroded due to flow of steam. Presence of S and V has been identified by EDAX in the oxide scales on the fireside surface of these tubes (Fig. 9 and 10). DI SC U SSI ON Long-term overheating is a chronic problem. It is the result of long-term deposition and/or long-term system operating problem. Heavy deposition on steam and fireside surfaces of water wall or superheater tubes insulates the tube wall from the cooling effect of water or steam. Deposits on superheater tubes caused by carryover and/or contaminated water can produce overheating. Heavy deposition on the steam-side

cleaning. Also firing procedures, and furnace temperature near the overheated areas should be checked. C O N C LU SI O NS 1. Presence of sulfur in the oil ash deposited on the fireside surfaces of the tube appears to be the main cause of the failure of the boiler tubes at Al-Khobar Power Plant.

2.

The mode of failure is intergranular corrosion attack induced by molten ash deposits when the tube metal temperature was raised above normal working temperature, i.e., 480 oC.

3. Cracking of the tube A of Al-Khobar plant at the weldment is due to the combined effect of sulfur-induced corrosion and welding stresses. Circumferential fissures initiated by the molten ash were enhanced greatly due to the welding stresses and resulting into the cracking of the tube at the weldment.

4. Rupturing of superheater tubes of boiler # 100 and 200 at Al-Khafji plant and hole formation in the superheater tube of boiler # 200 are the results of long-term overheating of the tubes.

5.

Thinning of the tube walls is due to localized deposits and overheating problem.

6. Ruptured tubes of boiler # 100 and # 200 remained unattended in failed condition for a long period due to which most of its lip portion were burned.

3. SWCC should establish its specification for the maximum amount of the sulfur and vanadium in the fuel oil and stable zone of gas and metal temperature.

4. All the operation parameters of the boiler should be strictly maintained and monitored properly.

5.

Scale deposition on the steam/water side surface and thickness of the boiler tubes should be inspected as soon as possible. If the amount of the deposits has crossed the allowable limit, cleaning of the tubes should be carried out at the earliest.

R EFER EN C ES 1. Reid, W. T. External Corrosion and Deposits - Boilers and Gas Turbines. New York :Elsvier, 1971. 2. Stringer, J. High Temperature Problems in the Electric Power Industry and their Solutions, in High Temperature Corrosion. Ed., R. A. Rapp. Houston : National Association of Corrosion Engineers, 1983, p. 389. 3. French, D. N. Liquid Ash Corrosion Problems in Fossil Fuel Boilers, Porc, Electrochem Soc., (1983), 83-85, p. 68. 4. Corrosion in Fossil Fuel Power Plants, in Metal Handbook, Vol. 13 ed. B. C. Syratt, Metals, Park, Ohio : American Society for Metals, 1987, p. 985. 5. Porta R. D. and H. M. Herro, The Nalco Guide to Boiler Failure Analysis. New York : McGrawll Hill, 1991. 6. Dooley, R B. Boiler Tube Failures - A Perspective and Vision, Proceedings International Conference on Boiler Tube Failures in Fossil Plants, Palo Alto, California : EPRI, 1992.

10. Lopez-Lopz, D., Wong-Noreno, and L. Martinez, Usual Superheater Tube Wastage Associated with Carburization, Materials Performance, (1994), 33(12), p. 45. 11. Paul, L. D. and R. R. Seeley, Oil Ash Corrosion - a Review of Utility Boiler, Corrosion, (1991), 47, p. 152. 12. Gabrielli, F. An Overview of Water-Related Tube Failure in Industrial Boilers, Materials Performance, (1988), 27(6), p. 51. T. Kawamura and Yoshio Harada, Control of Gasside Corrosion in Oil Fired Boilers, Mitsubishi Tech. Bulletin, No. 139, May, 1980. L. D. Paul and R. R. Seelay, Oil Ash Corrosion - A Review of Utility Boiler Experience, Corrosion, Feb. 1991, p. 152.

13.

14.

Tabl e 1. C hem i cal A nal ys i s ofD epos i t s Form ed on Superheat er Tubes ( A ts t eam t em perat ure 571 oC )[ R ef .13]

Fuel / Sul f ur ( % ) ppm ) V 2O 5 ( pH 1g/ 100 ml H2O Acid Insol. Matt Total C as C Total S as SO3 Total Fe as Fe2O3 Total V as V2O5 Total Ni as NiO Total Na as Na2O Total Ca as CaO Total Mg as MgO (%) (%) (%) (%) (%) (%) (%) (%) (%)

0. 2 -0. 3 13 6.5 0.86 0.50 51.8 4.70 0.85 3.38 34.4 2.06 1.92 87.1

2. 7 -2. 8 4565 3.5 3.90 0.66 24.4 13.0 30.0 6.42 17.6 2.25 1.41 72.0

1. 6 -1. 8 130150 3.8 2.54 0.44 21.6 11.2 49.7 2.24 17.8 1.17 0.88 72.0

2. 42. 5 200250 4.1 0.88 0.05 0.89 6.48 83.0 7.45 2.69 0.22 0.20 86.6

SO3 + V2O5 + Na2O (%)

Fi gure 1.Boi l er t ube - A of A l K hobar pl ant s how i ng crack at t he w el dm ent

Fi gure 3. M agni f i ed vi ew ofFi g. 6s how i ng i nt ergranul ar corros i on by m ol t en as h ( X 800)

Fi gure 5. EPM A m i crograph and com pos i t i on prof i l e of oxi de s cal ef orm ed on f i res i de s urf ace of t he boi l er t ubeA

Fi gure 8. A s recei ved condi t i on of t he boi l er t ubeC