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1 Zairyo-to-Kankyo, High Temperature Corrosion in Environmental and Energy Conversion Equipments Yuuzou Kawahara Yokohama R&D Center, Mitsubishi Heavy Industries, Ltd. Wastage of materials manufactured by much effort is social loss, also, prevention of corrosion is important issue to effective use of energy and prevention of pollution. Furthermore, the corrosion can be directly related to safety life on recent people living contact with many machines and plants. High temperature corrosion arise on the social base equipments supporting human life such as energy conversion plants, chemical reactor,. pollution prevention equipment and transportation system, and corrosion phenomenas are somewhat complicated due to influencing man kinds of environmental and material factors. This paper describes basics of main corrosion reactions, mixed oxidant corrosion, molten salts corrosion and hot corrosion in actual equipments etc. aiming of easy understanding in students and non-professional people. Keywards : high temperature corrosion, chlorination, sulfidation, oxidation, molten salt corrosion, fossile fuel boiler, waste-to-energy boiler, gas turbine, mixed oxidant corrosion, protective oxide scale, corrosion mechanisms, corrosion prevention method Ni 5 ( ) (12, Nishiki-chyo, Naka-ku, Yokohama, Japan) CO 2 1 1) (1) (2) 100 2
2 1 1) () ( ) 3 O S Cl 3 1
3 Zairyo-to-Kankyo 2 3 () (Mixed Oxidants Corrosion) (O) O 2 H 2 O CO 2 2 () (P O2 ) Fe 2 O 3 Fe 3 O 4 FeO 3 P O2 Fe 2) 3 3)
4 1 2 (1273 K) 3 Fe Cr 3) / Cr 2 O 3 Fe 4 G 0 O 2 ( ) 4) Al, Si P O2 Cr 5 (Break-away) 6 5) 9Cr 1Mo 4 4)
5 Zairyo-to-Kankyo Cl V 2 O 5 PbO a) b) P S2, P Cl2 / 6 5) (FeS) a) b) ( Cr 40 ) (Ni 3 S 2 /Ni) c) P S2 (Fe Cr Al ) H 2 S S P O2 SO 2 S HCl Cl 2 a) 100 6) b) H 2 O HCl Na K Zn SOx HCl Na K V Zn Pb 2 10 O 2 O 2 ( NOx) / / O 2 SOx HCl Cl/S/O / MPa
6 7 Ni (Alloy 625) HCl 7 7) 1) 8 8) 2) ( ) 9 9) 3) Na, K Zn, Pb ) 4) HCl, SO 2,O 2 HC, CO 8) a)
7 Zairyo-to-Kankyo 11 13) 8 b) c) d) a) c) 11) 12) 9 Na, K, Fe Cl 1) (K, Na) 2 Fe(SO 4 ) 3 ( ) 11 13) 2) NOx( O 2 ) H 2 S HC () 14) ( kgf/cm 2 g) ( kgf/cm 2 g) () 12 15) P O2 P S2 H 2 S Cr Ni ) 10 NaCl/KCl/Na 2 SO 4 /Al 2 O 3 () Na 2 SO 4 V 2 O 5
8 12 15) 13 (2.25Cr 1Mo ) 19) Na 2 SO 4 P O2 P S2 17) S Mg(Ca) 18) ( O 2 H 2 S) 13 19) O ) () Ni Co (800) 14 20) Na 2 SO 4 (NaCl) 21) 15 22) TBC (Thermal Barrier Coating) 15 Ni (Inconel 751, 800, 90 Na 2 SO 4 /10 NaCl) 22) ZrO 2 (
9 Zairyo-to-Kankyo 16 V 2 O 5 (20 40 ) 23) ) 17 (Alloy 625) () Cl/S/O 1) / O 2 2) () 3) 4) In-situ 7) 16 V 2 O 5 Na 2 SO 4 23) 10) 1) 2) 3) P Cl2 P S2 P O2 (Molten Salts Induced Corrosion) C. Wagner 24) 17 (Alloy 625) EPMA 11) Cl, S, K / P Cl2 P S2 P O2 18 ( ) Cl S O Fe Cl O Fe S O 1)
10 Fe Cl 2 HCl Fe Cl 2 FeCl 2 (mp 667bp 1012 ) (1) 2FeCl 2 Cl 2 Fe 2 Cl 6 (mp 308bp 315 ) (2) Fe 2HCl FeCl 2 H 2 (3) HCl 1 atm HCl P Cl2 500 P Cl FeCl 2 O 2 (4) Deacon P Cl2 25) 2HCl 1/2O 2 H 2 Cl 2 (4) HCl 0.1 (1000ppm) 19 CrMo P Cl2 Fe 2 Cl 6 (5) (7) HCl, Cl 2 Cl 2 1) P O2 P H2O P Cl2 P Cl2 2) / () 28) 3) Cl 2 (Deacon ) 4FeCl 2 3O 2 2Fe 2 O 3 4Cl 2 (5) 2Fe 2 Cl 6 3O 2 2Fe 2 O 3 6Cl 2 (6) 4) Cl 2 ( 2Fe 2 Cl 6 4H 2 O 4FeO 8HCl 2Cl 2 (7) 3Fe 2 Cl 6 4O 2 2Fe 3 O 4 9Cl 2 ) 19 CrMo 26) P O2 P Cl2 P O2 O 2 Cl 2 O 2,Cl 2 2), 3), 4) 20 Fe Cl O P O2 P Cl2 27) (1), (3) Fe S P O2 P S2 FeCl 2 P Cl2 Fe 2 Cl 6 Fe 2 Cl 6 (2) Fe 2 Cl 6 18 Fe Cr Fe Cl O P O2 P Cl2
11 Zairyo-to-Kankyo 21 P O2 P S2 SOx(SO 2,SO 3 ) H 2 S P S2 P O2 S H 2 S, S P S2 1) Sulfidation H 2 S H 2 O 29), 30) ( Ni 3 S 2 /Ni ) 2) Acidic/Basic Fluxing Na 2 SO 4 O 2 (Basic Fluxing) O 2 M,O 2 (Acidic Fluxing) 31) 3) 32) P O2 (P O atm) FeS FeS 2 O 2 SO 2 ppm(p S atm) FeS P O2 P S2 Na 2 SO 4 3R Na 2 O 3RO S (R ) P O2, P S2 S P Cl2 P S2 FeCl 2 Fe 2 Cl 6 FeS 21 26) S Cl 12)
12 1) JSCE, High-Temperature Oxidation and Hot Corrosion of Metals(Jpn.), Maruzen(1982). 2) C. Wagner, J. Electrochem. Soc.,, 369 (1952). 3) 3, p.375 (1995). 4) F. D. Richardson and J. H. E. Jaffee, J. Iron Steel Inst.,, 261 (1948). 5) J. E. Truman, Corrosion, Vol.1, 2nd Ed. by L. L. Shreir, Newnes-Butterworths, p. 767 (1976). 6) K. Fujita, H. Onoue and K. Sakiyama, Boshoku-Gijutsu (presently Zairyo-to-Kankyo),, 340 (1970). 7) U. Kawahara, J. Soc. Mater. Sci. Jpn., (2000). 8) Y. Kawahara and M. Kira, Corrosion, (1997). 9) Y. Kawahara, et al., Corrosion, (1998). 10) Y. Kawahara and M. Kira, Zairyo-to-Kankyo, 1 8 (1997). 11) Y. Kawahara, Corrosion Science,, 223 (2002). 12) Y. Kawahara et al., CORROSION/2001, Paper No.1173, Houston TX, NACE, (2001). 13) K. Nakagawa, S. Kihara, T. Kawamoto and A. Ootomo, Boshoku-Gijutsu (presently Zairyo-to-Kankyo), 149 (1986). 14) /2001p.25 (2001). 15) (1996). 16) K. Natesan, Proc. Int. Conf. on Corrosion CONCORW 97, Mumbai, India, p.24 (1997). 17) Y. Harada, Boshoku-Gijutsu (presently Zairyo-to-Kankyo) (1977). 18) Y. Harada and M. Nakamori, Boshoku-Gijutsu (presently Zairyo-to-Kankyo), (1980). 19) Y. Harada, T. Kawamura, Mitsubishi Technical Bulletin, No.139 (1980). 20) Ch. Just, Conf. High. Temp. Alloys Gas Turbine, 147 (1978). 21), p.257 (1984). 22) M. Yoshiba, T. Miyagawa and T. Hamanaka, Boshoku- Gijutsu (presently Zairyo-to-Kankyo),, 39 (1990). 23) Y. Harada, MITSUBISHI JUKO GIHO, 6 17 (1980). 24) C. Wagner, Z. Phys. Chem.(B),, 25 (1933). 25) R. Huch, Breunst.-Wa()rme-Kraft, 2 76 (1966). 26) 1 2 p.34 (2001). 27) p.39 (2001). 28) K. Sakiyama and Y. Ihara, Proc. 25th Symposium, JSCE (1979). 29) J. A. Goebel and F. S. Pettit, Metall-Trans.,, 2875 (1971). 30) /2001p.1 (2001). 31) M. Kawakami, K. Goto, R. A. Rapp and F. Kajiyama, Tetsuto-Hagane,, 811 (1979). 32) J. B. Johnson, J. R. Nicholls, R. C. Hurst and P. Haucock, Corrosion Science,, 527 (1978)
Application of Solid Electrolyte Sensors to Hot Corrosion Studies Nobuo Otsuka* *Iron & Steel Research Laboratories, Sumitomo Metal Industries, Ltd. C
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