Materials Science and Engineering A 415 (2006) 118125

Study of the degradation of power generation combustion components at elevated temperature

J. Castrejon a , S. Serna a, , A. Wong-Moreno b , A. Fragiel c , D. L pez-L pez b o o
Centro de Investigaci n en Ingeniera y Ciencias Aplicadas-UAEM, Av. Universidad 1001, C.P. 62209, Cuernavaca, Mor., M xico, Mexico o e b Instituto Mexicano del Petr leo, Eje Central No. 152, Col. San. Bartolo Atepehuacan, C.P. 07730, M xico, DF, Mexico o e c Centro de Ciencias de la Materia Condensada-UNAM, Km 7 Carretera Tijuana-Ensenada, C.P. 22800, Ensenada, Baja California, Mexico Received in revised form 31 August 2005; accepted 20 September 2005
a

Abstract Elevated temperature combustion of fuel oil that contains large amounts of vanadium, asphaltenes and mostly sulfur, presents a major challenge for materials selection and design of combustion components for the electric power generation. The combustion system, which consists of air nozzles and air swirlers, plays a key role in the performance of electric power plants. Air nozzles and air swirlers, which were operated for one year in a 350 MW boiler, were analyzed, presenting accelerated degradation. The particular features of corrosion behavior of these components made by stainless steels: 304, 446 and HH, are presented. The results obtained after optical, metallographic, and microprobe analysis revealed that the components ame contact at very high operating temperature promoted all materials degradation mechanisms. Under this scenario, it is very difcult to nd a material resistant to such accelerated wastage conditions. So, the solution of the problem must be oriented to re-design and improve the efciency of the ame contact with these components. 2005 Elsevier B.V. All rights reserved.
Keywords: Combustion system; High temperature; Oxidation; Corrosion; Stainless steel; Fuel oil

1. Introduction Conditions in which the fuel oil combustion take place, play a key role in the boiler materials performance. High air excess during the combustion process enhances high temperature oxidation of superheaters and reheaters, accelerated by vanadium and sulfur compounds. This condition also increases the generation of SO3 and hence the corrosion by sulfuric acid in the low temperature zone of the boiler. By other side, operation at low air excess is possible if the combustion system is well designed and in good conditions, otherwise a lot of partially burnt particles could be generated, impairing the efciency of the boiler and favoring the degradation of boiler materials due to carburization process [1]. Degradation of combustion system components displaces up the minimum oxygen excess required for its operation under good conditions, favoring the high temperature and low temperature corrosion of boiler materials. The problem increases as

the viscosity, asphaltene, sulfur and vanadium content increases. Mexican experience in burning heavy fuel oil shows that degradation of the combustion system has been an old problem even using better alloys with higher chromium content. Materials have been upgraded from 18Cr8Ni stainless steel to 309, 310, 446 and HH steels. The purpose of this research work was to nd evidence of the degradation mechanisms involved in several corroded burner components that were operating during a year. 2. Experimental procedure The present work is focused on the corrosion characteristics of ame swirlers and air nozzles from a tangential combustion system of a 350 MW boiler. A schematic representation of the boiler is shown in Fig. 1. The boiler has 16 burners distributed in the corners in four levels. Combustion system components were exposed during 1 year to ue gases. Typical operating conditions of this boiler are: full load during the day and 6070% during night. Material of ame swirlers is 18Cr8Ni stainless steel (304-type). Air nozzles were built from Fe25Cr alloy (446type) and Fe35 Cr25Ni (HH-type). Boiler uses a residual fuel

Corresponding author. Tel.: +52 777 3297084x6241; fax: +52 777 3297084. E-mail address: aserna@uaem.mx (S. Serna).

0921-5093/$ see front matter 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.msea.2005.09.080

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Fig. 1. Longitudinal scheme of the studied 350 MW boiler. A detail of the tangential combustion system is shown schematically.

oil with high sulfur, vanadium and asphaltene content. Table 1 shows the physical properties and typical composition of the fuel oil used in the boiler. A typical high sulfur fuel oil analysis is included for comparison. For the study of its degradation, the pieces that present more damage were selected (pieces in fourth level), in some cases, the components were almost consumed meanwhile in most of them a little portion of the component was wasted. Selected pieces of ame swirlers and air nozzles were cut and prepared in order to perform metallographic analysis, microhardness test and grain size measurements according to standards ASTM E384 [2] and ASTM E112 [3], respectively. The morphology, structure and composition of corrosion products as well as the subjacent metal were analyzed with a scanning electron microscope (SEM) Zeiss DSM 960 that is equipped with an energy-dispersive X-ray (EDX) analyzer Prime 60. Then, corrosion products of boiler components were manually extracted and analyzed by means of X-ray diffraction in a Siemens D-500 Difractometer.

3. Results 3.1. Damage description of combustion system components In Fig. 1, the burner levels disposition are shown. The most damaged air nozzles and ame swirlers were in the upper burners level (fourth level), three of the four burners of this level were seriously damaged. First and second burner levels were in very good conditions, third burner level were lightly corroded in some places. A general view of ame swirlers and air nozzles that were analyzed is shown in Figs. 2 and 3. Fig. 2 presents a ame swirler in an advanced degradation state with deposit accumulation inside of the internal ring, between the air swirler and fuel gun, also, it could be seen details of the damage developed in annular and blade sections. Considering an initial blade thickness of 3.5 mm, the corrosion rate was over 1.75 mm/yr. In the case of air nozzles, material was also consumed, considering an initial plate thickness of 10 mm the corrosion rate was over 5 mm/yr. However, the corrosion rate could be even greater if the damage had occurred during a shorter time period. The air nozzle built of 446-type steel shows clear deformation as can be seen in Fig. 3. Considering that the load this piece has to support is only its own weight, this deformation suggests that temperature was too high [4], probably near to the fusion temperature of the material, which is in the range 1400 1455 C. Damage in both air nozzles and ame swirlers were very localized: some places show a thickness near the original and at 2 cm distant from them, thickness reduction is very high as can be observed in Fig. 3. Damage is similar to the reported case for non-cooled boiler components in the same boiler [5]. 3.2. Corrosion products analysis Corrosion products are constituted basically by iron and chromium oxides with minor quantities of Ni, Si and V. X-ray analysis of corrosion products (Table 2), showed that Fe2 O3 and FeCr2 O4 are the main compounds. These results indicate that high temperature oxidation played a key role in the degradation

Table 1 Physical and chemical properties of the residual fuel oil Property API gravity Viscosity Fuel oil used in the boiler 11.26 535 ssf at 50 C, 83 ssf at 82.2 C 17.3b 16.4 0.069 3.95 276 26 25 60 3 High sulfur fuel oila 17.0 3138 ssu at 38 C (equiv. to 314 ssf) 10.33c 12.51 0.08 2.2 350 25 41 Not reported Not reported

Asphaltene (wt.%) Carbon Conradsond (wt.%) Ash (wt.%) Sulfur (wt.%) Vanadium (pure) Sodium (ppm) Nickel (ppm) Calcium (ppm) Potassium (ppm)
a b c d

Source: EPRI Report GS-67 14, February 1990. n-pentane insoluble. n-hexane insoluble. Standard ASTM D-189-88.

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Fig. 2. Air swirler after 1-year operation in the tangential ring system of a 350 MW oil-red boiler. Details are shown at right.

of the components, which is consistent with exposure at high temperatures [6]. 3.3. Fused zone during operation of 304-type ame swirler Samples from 304-type ame swirlers taken from the most corroded zone revealed the existence of zones with a consider-

able reduction of the grain size. Fig. 4 shows an optical image from a swirler blade. There is a change in microstructure in the zone near to the corrosion front (1 cm width). Grain size in the less affected zone is 17 m. Two zones are clearly depicted in the corrosion front: a sensitized austenitic structure with light grain size growth (22 m) and, a 150250 m narrow band with an extremely small grain size (4 m). This zone showed massive

Fig. 3. Air nozzles after one-year operation in the tangential ring system of a 350 MW oil-red boiler. Details of the corroded zones are presented besides scale gures.

J. Castrejon et al. / Materials Science and Engineering A 415 (2006) 118125 Table 2 Chemical compounds identied by X-ray diffraction Steel sample E2M1(304) E2M2(304) C1M2(446) C2M1(HH) Intensity: high medium low ! trace. Fe2 O3 FeCr2 O4 Cr2 O3 NiFe2 O4 ! ! !

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3.4. Grain growth process Grain growth processes occur at very high temperatures. In austenitic stainless steel, grain growth begins at 950 C with slow kinetics [8]. In the case of 304-type and 446-type steels, both produced by a wrought process with grain boundaries very well dened, the grain growth was clearly detected. Degradation front in the 304-type ame swirler was different in different places: fused zone was observed in some cases while in others a grain growth was detected even when a fused zone was not detected. Fig. 6 shows evidence of grain growth in the most corroded zone of a ame swirler blade. In the case of 446-type air nozzle, corroded zones revealed obvious grain growth and growth of high-chromium phases. The grain growth process was severe in the deformed zone of the material, as observed in the upper left photograph of Fig. 3. Fig. 7 shows an example from this zone, where the grain growth was at least from 20 to 1000 m. The precipitation of chromium rich phases was detected only near the corrosion front at the zones where the grains grew. EDX-analysis of these phases shows high chromium, nitrogen and carbon contents (74, 13 and 4.6 wt.%, respectively), minor quantities of vanadium and iron were also detected (2 and 6 wt.%). Vanadium was also detected in the matrix of the non-corroded zone and even when this element is not considered in the specication for this alloy, it has been detected in other samples of new 446-type material [9].

phases precipitation as can be seen in Fig. 5. Microprobe analysis revealed that this phase is an oxygen and silicon-rich phase with chromium, manganese, iron and vanadium (Fig. 5). Most of these phases are smaller than 1 m but some are until 25 m. Detail of the biggest phases reveals that they have a chromium rich dendritic structure as can be seen in Fig. 5. The presence of ne grain structure and the existence of dendritic structure containing oxygen and vanadium are indicators that this zone was fused during operation. Fine grain structure can be explained by a heterogeneous solidication process [7] promoted by silicon-rich phases. The presence of oxygen and vanadium indicate the absorption of these elements during the fused metal stage. The presence of silicon could have resulted from a segregation process during the fusion. The absence of grain growth in the zone adjacent to the fused zone is indicative that the high temperatures were present for a short time period.

Fig. 4. Air swirler blade analysis: (a) on the opposite place to degradation front (8 cm distant from c) (70); (b) at 1 cm from the degradation front showed in c (70); (c) at the degradation front (70); (d) detail from c (280).

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Fig. 5. SEM images of fusion zone. Upper: backscattering image. Lower: secondary electron image showing a detail of a bigger one phase, a dendritic structure is revealed. EDX-spectrum shows the composition of inter-dendritic zone (upper) and composition of dendrites (lower).

3.5. HH-type air nozzle phase transformation Corroded zones in the HH cast-type air nozzle revealed an altered microstructure as observed in Fig. 8. EDX-microanalysis revealed a transformation of the phases. They are very similar in chromium and iron contents but have higher silicon and carbon contents. Microhardness measurements revealed that transformed phase was notably harder than non-transformed phases, hardness increases from 180 to 1100 Vickers. It is important to observe how phases near to corrosion front change approaching to the edge; at 0.5 cm from the edge, the zone shows coalescence and at 0.1 cm it clearly shows that a volubility process of phases occurred. The differences in the precipitation state in a short distance indicate that a high thermal gradient was present. 3.6. Occurrence of high temperature oxidation, and oilash corrosion Analysis of the corrosion front of materials revealed that high temperature oxidation, oilash corrosion and carburization

mechanisms were in the degradation of the combustion system components. In 446 and HH-type alloys, a silicon oxide layer in the metal oxide interface was frequently observed (Fig. 9). It is well known that protective chromium oxide scales are commonly developed by alloys containing chromium and silicon at temperatures below 1000 C [10]. However, at higher temperatures silicon oxide is preferentially formed in the metal interface. Vanadium attack under oxidizing conditions was observed particularly in the 304-type ame swirler as can be seen in Fig. 10. The laminated structure of oxides is characteristic of an accelerated degradation process typical of high temperature vanadium attack [9]. Evidence of carburization was observed in some cases but not as frequently as the observed evidence of oxidation. Fig. 11 shows a carburization front in the same sample that exhibited vanadium attack (Fig. 10). The zones where both processes occurred are approximately 1 cm distant. This sample shows clearly that oxidation and carburization conditions might alternate. In this gure, the grain size was near to 200 m (almost

Fig. 6. Metallography of a 304-ame swirler blade, from the most corroded zone (left) and from the less corroded zone. Both images have the same magnication (70). These zones are 8 cm distant. A clear grain grow is observed indicating exposition to high temperatures.

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Fig. 7. Grain and phases growth in 446 steel air nozzle. Metallography of coolest zone: (a) shows a ne grain structure compared with grain size near to corroded front; in (b) images are at same magnication (70); (c) is a metallography (70) nearer than (b) from corroded front. (b) and (c) show precipitation of phases. Detail of one precipitate is shown in (d) (SEM image). EDX spectrum from the precipitate is shown in (d).

one order of magnitude bigger than that of the non-corroded zone). This grain growth suggests that the material was exposed to temperatures higher than 1000 C. 4. Discussion 4.1. Exposure to extremely high temperatures High temperatures due to ame contact, causing local fusion, probably caused the accelerated material degradation. These fused spots imply that temperatures in this zone were over 1400 C, causing severe oxidation, fusion and undesirable alloy transformation, due to segregation processes and absorption by the alloy of foreign elements. Fused areas will be consumed quickly by corrosion during and after the ame contact. Combustion components are cooled by the input of primary or secondary air at temperatures near to 100 C required by the combustion system. When ame contact is happening by the side of pieces facing the ame, ame swirler and air nozzles are exposed to a very high thermal gradient, with zones at temperatures over 1000 C (and probably over 1200 C), grain growth occurs. These conditions produce catastrophic corrosion rates and alternate materials are not likely to resist these conditions. The deposits formed with this type of fuel oil in boilers are very corrosive between 600 and 850 C, above this temperature most of them are decomposed lowering its corrosiveness and leaving the oxidation mechanism as the principal cause for the degradation of the components. According to this the analysis of corrosion products revealed that these were principally oxides,

as shown in Table 2, which is indicative that the main degradation mechanism was high temperature oxidation [9], then this behavior is a consequence to the exposure to elevated temperatures, which is consistent with the ame contact hypothesis. In addition, when the temperature is excessively high, this alloys could suffer catastrophic oxidation (in stainless steels this could happen above 1150 C [11]). 4.2. Exposition to variable oxidizingreducing conditions The components are subject to variable oxidizing and reducing conditions, as was observed in the sample from Figs. 10 and 11, which may result from the presence of a frequent ame impingement process. This type of process could explain the existence of alternating environment and also gives place to a frequent thermal shock avoiding the formation of protective oxide scales [1214]. 4.3. Corrosion rate and operating conditions The corrosion rates previously described are at least 1.75 mm/yr for the ame swirlers, and 0.5 mm/yr for the air nozzles. It is clear that degradation was not continuous and the corrosion rates could be negligible sometimes and higher for portions of the operating period. Under conditions of ame contact a piece of plate could probably be consumed in some hours or days. Most of the air nozzles and ame swirlers of the rst to third burner levels showed a negligible corrosion rate, suggesting that normal operating conditions do not cause rapid corrosion.

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Fig. 8. Metallography images from HH alloy air nozzle, c is a SEM image. Upper images show the microstructure from the less exposed zone to high temperatures. Below images shows microstructure from corroded zone, a (70), b (280) and c are 30 cm distant from corroded zone, d (70) is 1.5 cm distant from corrosion front, e (280) is 0.5 cm and f (280) is 0.1 cm distant from corrosion front. EDX spectra were obtained from phases in c (left) and e (right).

4.4. Operating conditions that favor the degradation process Flame contact with the combustion system components can occur if:

1. A back movement of the ame due to the presence of an undesirable air recirculation zone in the burner. This problem must be related to the combustion system design or to operating conditions out of design conditions. 2. Fuel leaks in the burner gun that produces small tires in the ame swirler zone.

Fig. 9. SEM image of corrosion front in 446-air nozzle in the corroded zone. The steel developed a high temperature thin layer of silicon oxide. EDX-spectrum of SiO2 is shown.

Fig. 10. SEM images of a corrosion front related to vanadium attack in the 304-ame swirler blade. (b) Detail of the corrosion front in (a). Spectrum was obtained from the deposit in (b).

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Under this condition, a resistant material is not available. Solution to the problem must be directed to solve the ame contact problem. Even the cooled components are subject to exposures to high temperatures. Catastrophic high temperature oxidation played a key role in the degradation mechanism. Oilash corrosion, carburization and alternating high temperature oxidizing and reducing environments contributed to the acceleration of metallic degradation of components. Acknowledgments This work was supported by the IIE through the project 10105. Thanks are given to the personnel of Villa de Reyes Utility Plant of CFE Mexico for their valuable cooperation.Uncited reference References The deposit accumulation inside the internal ring, between the ame swirler and the gun (Fig. 2) suggests that fuel leaks were involved in the degradation process or contributed to the initial stage. Considering the location of damaged components (at the fourth burner level) and that during night, the boiler works with lower load, probably with the fourth burner levels off, a ame contact to the burners of the fourth level might have occurred because air (protection air) is going into the combustion chamber through burners creating an oxygen-rich zone, which is attractive to the ame core which could be poor in oxygen. This condition could have been favored if the combustion system is unbalanced. There are many factors that can contribute to the degradation of the combustion system. The boiler needs a complete study of the possible design or operative conditions that contribute to ame contact of the equipment. 5. Conclusions From this study, the following conclusions are made: Accelerated degradation of combustion system components was related to the exposure of materials at very high temperature. The most probable root cause of the problem is ame contact due to events of irregular ame impingement process, which were associated to design, or operation conditions.
[1] D. L pez-L pez, A. Wong-Moreno, A. Ter n Sarabia, A. Velasco-T llez, o o a e L. Martnez, Mater. Corros. 49 (1998) 272277. [2] ASTM Designation E-384-84, Standard test method for microhardness of materials, American Society for Testing and Materials. [3] ASTM Designation E-112-96, Standard test methods for determining average grain size, American Society for Testing and Materials. [4] Metals Handbook, 9th ed. Elevated-temperature failures, vol. 11, ASM International, 1987, pp. 263277. [5] D. L pez-L pez, A. Wong-Moreno, L. Martinez. Corrosion and caro o burization of non-cooled boiler components, Corrosion95, Paper 464, Houston, TX, NACE International (1995). [6] D.B. Meddowcroft, Mater. Sci. Eng. 88 (1987) 320331. [7] G. Guy, Physical Metallurgy for Engineers, Addison-Wesley Publishing Company, USA, 1970, 9293. [8] F. B. Pickering, Physical metallurgy of stainless steel developments, International Metals Review, Review 211, December 1976. [9] A. Wong-Moreno, Corrosi n de Aleaciones Resistentes a Altas Temo peraturas por Dep sitos de Ceniza de Combustoleo Pesado, Doctoral o Thesis, Universidad Nacional Aut noma de M xico, 1998. o e [10] H.W. Grunling, R. Bauer, Thin Solid Films 95 (1982) 320. [11] Rundell R. Gene, Met. Prog. (1985), April. [12] W. T. Bakker, R.A. Perkins, J.B.M. Kip, Carburization in coal gasier environments, Corrosion91, Paper 63, (Houston, TX, NACE International, 1995). [13] H.J. Grabke, I. Wolf, Mater. Sci. Eng. 87 (1987) 2333. [14] A. Ter n-Sarabia, A. Wong-Moreno, D. L pez-L pez, L. Mariaca, A. a o o Peraza, Oxidaci n de Aceros Inoxidables Carburizados bajo Condio ciones de Ciclado T rmico, in: Proceedings of the XIV Congress of e the Academia National de Ingenieria A.C, (ANIAC), M xico, 1988, pp. e 305309.

Fig. 11. SEM-image depicting a carburization process in a corrosion front in the 304-ame swirler.