Supercritical Fluids - ACS Publications - American Chemical Society

Chapter 17

Degradation in Supercritical Water Oxidation Systems

Downloaded by CORNELL UNIV on September 27, 2016 | http://pubs.acs.org Publication Date: October 1, 1997 | doi: 10.1021/bk-1997-0670.ch017

D. B. Mitton, E.-H. Han, S.-H. Zhang, Κ. E. Hautanen, and R. M. Latanision H. H. Uhlig Corrosion Laboratory, Department of Materials Science and Engineering, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA 02139-4307 Supercritical water oxidation (SCWO) can effectively destroy various civilian and military wastes; however, the system will generally need to withstand a corrosive environment. To improve our understanding of degradation within such systems, exposure testing is being carried out in conjunction with analysis of failed components. Various alloys have been exposed to environments rangingfromdeionized water to highly chlorinated organic compounds and to temperatures as high as 600°C. Although, not surprisingly, high corrosion rates are encountered for the chlorinated feed streams, even deionized water can be aggressive at these conditions. In chlorinated feed streams, Hastelloy C-276 exhibits premature failure at subcritical conditions as a result of dealloying and cracking. At supercritical conditions (600C) in chlorinated environments, both high-nickel alloys and stainless steel exhibited significant corrosion. Analysis suggests that it may be possible to alter feed characteristics to reduce degradation to an acceptable level. This may permit the use of less costly materials for construction º

At a time when public opposition to landfills and incineration is increasing, the clean up of military and civilian hazardous wastes is gaining national importance (i). Supercritical water oxidation (SCWO) is one promising technology applicable to many organic wastes (2-4), including dilute aqueous solutions, which are difficult to treat by conventional methods. SCWO capitalizes on the properties of water characteristic of supercritical conditions, (374°C and 221 atm for pure water), where water is a fluid possessing properties between those of a liquid and a gas. As the solvation properties of supercritical water resemble those of a low polarity organic (2) hydrocarbons exhibit a significant increase in solubility concurrent with a reduced solubility of inorganic salts. Unfortunately, corrosion of the materials of fabrication is a significant concern in the context of the development of scaled-up systems for supercritical water oxidation (5-7) and may ultimately be the deciding factor in the commercial application of this technology. Although high nickel alloys may be employed for severe service (8), they are apparentiy unable to withstand certain conditions associated with SCWO (5, 9-14) as ihey tend to exhibit both significant weight loss and localized effects 242

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including stress corrosion cracking (SCC) and dealloying in chlorinated environments. In addition, selective dissolution of various alloying components from the high nickel alloys has been observed in SCWO systems. The loss of Cr and Mo for Inconel-625 (15) has been reported while, for Hastelloy C-276, the loss of either Cr, Mo and W (15) or Ni, Fe and Mo (16) is observed. Exposure studies were previously carried out in deionized water during commissioning of the corrosion test facility at ΜΓΓ to provide a base-line assessment of the materials of construction. The results (6,13) of a preliminary short term exposure (24 - 96 hours) at 300, 400 and 500°C indicate varying degrees of film formation and localized corrosion for the three alloys tested (Inconel-625, Hastelloy C-276 and stainless steel type 316). The effect of exposuretime(up to 240 hours), in deionized water at 500°C (22) was interpreted to indicate the formation of a protective oxide for both Inconel-625 and Hastelloy C-276 and a non-protective film for the stainless steel. During tests with methylene chloride (CH2O2)* axial throughwall ruptures have occurred in a number of Hastelloy C-276 preheater tubes of a tubular plug-flow reactor (PFR) system employed for kinetic studies at ΜΓΓ. Failures occurred in a region of the preheater which was at a high subcritical temperature and preliminary analysis revealed a dealloyed layer in which Ni (the major component of Hastelloy C-276) was lost leaving primarily a chromium oxide (10,16). Results and Discussion. Exposure Studies. A series of experiments conducted in deionized water revealed the possibility of pit initiation in high nickel alloys such as Inconel-625 and Hastelloy C-276 (12). Figure 1 reveals a recent scanning confocal laser micrograph of a pit on Inconel-625 after 10 days at 500°C in deionized water. The surface profile reveals that the depth of the pit is 2.64 μχη and its width is slighdy more than 6 μπι. Similar localized phenomena were observed on Hastelloy C-276; however, the pits tended to be covered by a reaction product cap (12). Although these pits are not large and exhibit a penetration rate of approximately 4 mils per year (mpy), the development of localized phenomena in such an innocuous environment is of interest. This suggests the possibility of the development of localized corrosion during system down-time (if die system is flushed with water) or during passivation treatments which employ water. Such discrete regions are potential stress concentration sites and mayresultin problems during subsequent runs with aggressive feed solutions. Recendy various alloys have been exposed to a highly chlorinated organic feed stream at 600°C. Figure 2 presents the corrosion rate based on weight loss for an exposure time of 66.2 hours. The feed stream contained approximately 3000 mg/kg chloride and 6 wt% O2. Based on weight loss data, C-276 and Inconel 625 exhibit similar corrosion rates of about 700 mpy while stainless steel type 316-Lrevealsa rate in excess of 2000 mpy. Figures 3 (a-c) present the cross section of U-bend samples after exposure. The weight loss data is corroborated by the stainless steel sample (Figure 3(a)), which has lost a significant portion of the cross section. Both Inconel-625 (Figure 3(b)) and Hastelloy C-276 (Figure 3(c)) exhibit a lower loss of cross section than the stainless steel, which again agrees with the weight loss data. The loss of cross section is, however, less on the Inconel-625 sample than on the Hastelloy C-276 coupon. This finding is in agreement with previously reported results indicating that Inconel-625 is more corrosion resistant than C-276 at temperatures above 350*C (J). Microscopic examination of the U-bend samples revealed no indication of stress corrosion cracking (SCC) for either of the nickel alloys; however, cracks were observed for the stainless steel sample. At high subcritical (10) and low supercritical (5) temperatures, Hastelloy may exhibit cracking. When exposed at 580°C to a feed stock of methylene chloride and isopropyl alcohol (neutralized with NaOH), Inconel 625 exhibited SCC; however,



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Figure 1. Scanning confocal laser micrograph of a pit on Inconel-625 after 10 days at 500°C in deionized water.


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Figure 2. The corrosion rate based on weight loss for an exposure time of 66.2 hours. The feed stream contained approximately 3000 mg/kg chloride and 6 wt% O2.




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Figure 3. The cross section of (a) 316-L stainless steel, (b) Inconel-625 and (c) Hastelloy C-276 U-bend samples after exposure for 66.2 hours to a feed stream contained approximately 3000 mg/kg chloride and 6 wt% Ο2·


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cracking was not observed for an Inconel-625 reactor exposed to a variety of feed streams even after 3000 hours of service (J). Failure Analysis. Premature failure of two preheater tubes from an experimental system (Figure 4) employed to study the kinetics of destruction in SCWO at ΜΓΓ have resulted during experiments which included ambient methylene chloride (CH2CI2) feed concentrations ranging from 0.017-0.04 Mol/1. The total time of exposure to the CI" containing feed solution prior to failure was 104 hours for the first and 45 hours for the second preheater. The Hastelloy C-276 preheaters were 250 300 cm long had an outside diameter (OD) of 1.6 mm and a wall thickness of 0.254 mm. Although, ultimately, failure took the form of an axial intergranular crack (20), elemental depletion (Ni, Mo, Fe) of the corroded layer and elevated Ni concentrations in the effluent in conjunction with no observable change in the dimensions of the corroded and non-corroded regions of the same tube confirmed that dealloying was also occurring for this alloy at these conditions (26). Although different conditions (temperature, feed type and composition) were employed during the various experiments, failures were restricted to a 20 cm length of tube near the inlet end of the preheater (Figure 4). Experimental conditions were designed for temperatures within the reactor section of the system to be between about 450 and 600°C; however, in the preheater, temperature varies between ambient and the test condition. Although at supercritical temperatures, the outiet of each preheater suffered minimal degradation (10) amounting to approximately 20 mpy. The lack of any appreciable corrosion at the exit to the preheater, which experienced significant HC1 concentrations at supercritical conditions, in conjunction with the proximity of the failures (within 20 cm of each other) suggested that failures were occurring within a region of the tube which was at subcritical temperatures. This was confirmed by heat transfer calculations indicating that the failure site was at a high but subcritical temperature (76). More recendy a preliminary investigation of the cool-down heat exchanger from this system (Figure 4) has provided some insight into corrosion within these facilities. Although the supercritical exit to the preheater suffered minimal attack, significant corrosion was subsequendy observed near the inlet to the cool-down heat exchanger. The form of attack in this region (Figure 5) is very similar to that seen within the subcritical region of the preheater (10, 16). Again intergranular dealloying is apparent and grain boundaries are obvious in the dealloyed layer. This is an important observation suggesting that there is a relatively restricted temperature region, apparendy corresponding to the temperature transition between subcritical and supercritical, within which corrosion is most severe. This situation is presented in Figure 6 which schematically reveals the rate of corrosion as a function of temperature within the preheater and cool-down heat exchanger. In the preheater the corrosion rate echoes the temperature as it increases into the high subcritical range; however, a further increase in temperature to supercritical, results in a dramatic decrease in the rate of degradation. The type and extent of corrosion within the reactor is not known as this unit has never been removed from service. It seems likely, however, that degradation relative to the preheater, is insignificant as this unit has exhibited no problems while, during the same time period, a number of preheaters have failed. In addition, the exit to the preheater and inlet to the cool-down heat exchanger, which are at supercritical conditions, both reveal low rates of corrosion. This suggests a similar condition within the supercritical reactor , which is located between these two points. A short distance into the cool down heat exchanger the corrosion rate increases again at a point which is assumed to be at a high subcritical value. Finally, beyond this maximum the corrosion rate decreases as a function of decreasing temperature. From the corrosion standpoint, this suggests the possibility



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of a design which could incorporate an easily replaced inexpensive section located at the two corrosion maxima. E-pH Diagrams. One of the main tools employed during an initial assessment of the possible behavior of a metal is the E-pH (Pourbaix) diagram. These maps graphically present the correlation between the solution oxidizing strength (potential) and acidity (pH) for the various stable phases possible for a system. Normally these diagrams are relevant for ambient conditions; however, data are available for some systems at higher temperatures (17, 18). These diagrams are constructed by using thermodynamic data available in the literature and the Nernst equation. It is, thus, possible to delineate regions in which specific species are most stable. This can be simplified further into regions which thermodynamically favor (i) immunity (no corrosion), (ii) passivity (reduced corrosion as a result of a protective film) and (iii) corrosion. By employing these diagrams the thermodynamically favored condition can be observed for a given pH and potential. It is possible to incorporate a number of such diagrams for various temperatures into one E-pH-T diagram, which can then be used to provide information on the trends in thermodynamic stability as a function of temperature. This is particularly valuable in die case of supercritical water oxidation as although the main reactor is at a higher temperature, some system components will experience lower temperatures ranging between ambient and the temperature of operation. As previously discussed, these systems can exhibit severe corrosion, which may be intensified within a restricted temperature zone. Figures 7 (a) and (b) present the chromium and nickel E-pH-T diagrams respectively. In all cases a molar activity of lxlO" was selected for calculation of the equilibrium line between soluble and insoluble species. Calculations were accomplished using the AG° values available for the individual temperatures in the literature (17) or through private communication (19). Figure 7(c) presents the region within which both chromium and nickel are stable over the temperature range 100°C to 300°C. If this region could be maintained during supercritical water oxidation it would minimize the likelihood of dealloying. This could have a significant impact on the use of alloys such as Hastelloy C-276 and may obviate the need for exotic liners (20). Although they do provide valuable information, the limitations of E-pH diagrams must be recognized; in general, they refer to pure, defect free, unstressed metals in pure water. While they indicate reactions which are thermodynamically possible, they do not provide any information on the reactionrate.They must, therefore, be utilized with great caution in predicting potential corrosion behavior. 6

Conclusions. Examination of U-bend samples (316-L stainless steel, Inconel-625 and Hastelloy C276) revealed no indication of stress corrosion cracking for the nickel alloys after exposure at 600°C for 66.2 hours to a feed stream contained approximately 3000 mg/kg chloride and 6 wt% O2. The stainless steel sample, however, exhibited cracking. Weight loss data from the same experiment indicate a very high corrosion rate (2000 mpy) for the stainless steel. Although the two high nickel alloys exhibit lower corrosion rates (700 mpy) than the stainless steel, the rate is still very high. Two corrosion maxima were observed during a failure analysis of Hastelloy C276 tubing employed in a PFR system at ΜΓΓ. These maxima apparendy correspond to the temperature transition between subcritical and supercritical, within which corrosion is most severe. Potentially this result indicates the possibility of a system design which could incorporate an easily replaced inexpensive section located at the two corrosion maxima.



Figure 7. E-pH-T diagrams for (a) chromium, (b) nickel, and (c) the region of stability for both chromium and nickel.


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E-pH-T diagrams were developed which reveal the region of stability for Cr and Ni over the temperature range between 100 and 300°C. The ability to maintain this region within SCWO systems could obviate the need for exotic liners and possibly permit the use of high nickel alloys as materials of fabrication. Acknowledgments.


The support of the Army Research Office for this project is much appreciated. The assistance of Glenn T. Hong of MODAR and Ron E. Mizia of INEL is gratefully acknowledged. K.E. Hautanen is supported by an AASERT award. E-H Han is supported, in part, by a Distinguished Senior Visiting Fellowship from the Chinese Academy of Science. Literature Cited. 1. Swallow, K.C. and Ham, D., The Nucleus, 1993, 11, p. 11. 2. Tester, J.W.; Holgate, H.R.; Armellini, F.J.; Webley, P.A.; Killilea, W.R.; Hong, G T. and Barner, H.E., in Emerging Technologies for Waste Management III, ACS Symposium Series, 518, ACS, Washington, DC 1993 p.35. 3. Modell, M., Standard Handbook of Hazardous Waste Treatment and Disposal, McGraw Hill, New York NY 1989 p. 8.153. 4. Franck, E.U. High Temperature, High Pressure Electrochemistry in Aqueous Solutions, NACE, Houston TX 1976 p. 109. 5. Latanision, R. M. and Shaw, R.W., Co-Chairs, "Corrosion in Supercritical Water Oxidation System - Workshop Summary"; 1993, Massachusetts Institute of Technology Energy Laboratory, MIT-EL 93-006. 6. Mitton, D.B.; Orzalli, J.C.; and Latanision, R.M., in Proceedings of the Third International Symposium on Supercritical Fluids , ISASF, Nancy France, 1994 Vol.3, p.43. 7. Thomas, A.J. and Gloyna, E.F. "Corrosion Behavior of High Grade Alloys in the Supercritical Water Oxidation of Sludges," 1991, University of Texas at Austin, Technical Report CRWR 229. 8. Asphahani, Α., Metals Handbook 9th Edition; ASM International: Metals Park, OH, 1987, Vol. 13p641-655. 9. Norby, Brad C. "Supercritical Water Oxidation Benchscale Testing Metallurgical Analysis Report," 1993, Idaho National Engineering Laboratory Report, EGGWTD-10675 10. Latanision, R.M., Corrosion, 1995, 51, p. 270. 11. Mitton, D.B.; Orzalli, J.C.; and Latanision, R.M., in Innovations in Supercritical Fluids: Science and Technology, ACS Symposium Series, 608, ACS, Washington, DC 1995 p. 327. 12. Mitton, D.B.; Orzalli, J.C.; and Latanision, R.M., in Physical Chemistry of Aqueous Systems-Meeting the Needs of Industry, Proc. 12th ICPWS, Begell House New York, NY 1995, p.638. 13. Orzalli, J.C., "Preliminary Corrosion Studies of Candidate Materials for Supercritical Water Oxidation Reactor Systems" 1994, Master's Thesis, Massachusetts Institute of Technology. 14. Kane, R.D. and Cuellar, D., "Literature and Experience Survey on Supercritical Water Corrosion," 1994,CLIInternational Report, No L941079K. 15. Bramlette, T.T.; Mills, B.E.; Hencken, K.R.; Brynildson, M.E.; Johnston, S.C.; Hruby, J.M.; Feemster, H.C.; Odegard, B.C.; and ucdd, M., "Destruction of DOE/DP Surrogate Wastes with Supercritical Water Oxidation Technology", 1990, Sandia National Laboratories, Livermore, CA, Sand 90-8229. 16. Mitton, D.B.; Marrone, P.A.; and Latanision, R.M., J. Electrochem Soc. 1996,Vol. 143 pp. L59.


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17. Lee, J.B., Corrosion, 1981, 37, p. 467. 18. Kriksunov, L. B. and Macdonald, D.D. "Development of Pourbaix Diagrams for Metals in Supercritical Aqueous Media," presented at The First International Workshop on Supercritical Water Oxidation, Amelia Island Plantation, Jacksonville Florida, February 6-9 1995. 19. Kriksunov, L. B., private communication 1995. 20. Hazlebeck, D.A.; Downey, K.W.; Jensen, D.D.; and Spritzer, M.H., in Physical Chemistry of Aqueous Systems-Meeting the Needs of Industry, Proc. 12th ICPWS, Begell House New York, NY 1995, p.632.3.


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