전이 금속 산화물이 담지된 La/Al 복합산화물 촉매상에서의 메탄 연소반응

서정권; 하백현; 고재천; 이정민

HWAHAK KONGHAK, Vol.31, No.6, 667-674, December, 1993

Export Citation

전이 금속 산화물이 담지된 La/Al 복합산화물 촉매상에서의 메탄 연소반응

Methane Combustion on Transition Metal Oxide Impregnated La/Al Oxide Catalysts

서정권, 하백현, 고재천, 이정민

초록

La/Al 복합산화물(Al₂O₃/La₂O₃=19)에 한종의 전이금속을 담지시킨 후 대기중에서 소성처리하여 연소촉매를 제조하고 메탄 연소반응을 실시하였다. X선 회절 분석결과 La/Al 복합산화물은 1200℃이상에서 무정형으로부터 La-β-Al₂O₃로 상전이가 일어났다. 구리가 담지된 경우에는 결정성장이 촉진되는 반면에 크롬이 담지된 경우에는 결정성장이 억제되었다. 소성온도의 증가에 따라 촉매 표면에서의 구리의 조성은 점차 감소하여 고용체(solid solution)가 형성되는 것으로 보이며, 크롬은 Cr₂O₃의 상태로 대부분 표면에 존재하는 것으로 나타났다. 메탄연소반응에 대한 촉매활성은 1200℃에서 소성퍼리한 시료에서는 구리, 크롬>철>망간>코발트>니켈이 담지된 순으로 활성을 나타내었다. 구리가 담지된 La/Al 복합산화물은 소성온도의 증가에 따라 활성이 감소하였으나 크롬이 담지된 경우에는 1400℃까지 촉매활성이 거의 일정하게 유지되었다.

Combustion catalysts were prepared by the impregnation of transition metal oxide on La/Al oxide(Al₂O₃/La₂O₃=19), and then calcined in air. Methane combustion was carried out using these catalysts. X-ray diffraction analysis indicates that La/Al oxide was crystallized from amorphous form into La-β-Al₂O₃phase above 1200℃. Crystallization was accelerated by the addition of copper on La/Al oxide, but it was retarded by the addition of chromium on La/Al oxide. The copper content of the surface of CuO-La/Al oxide decreased as the calcination temperature increased. This result indicates the formation of solid solution. In case of Cr₂O₃-La/Al oxide, Cr₂O₃ mainly existed on the catalyst surface. The activities of catalysts calcined at 1200℃ appeared as the following order; CuO, Cr₂O₃>Fe₂O₃>MnO>CoO>NiO. The catalytic activity of CuO-La/Al oxide decreased as the calcination temperature increased. However the catlytic activity of Cr₂O₃-La/Al oxide was still maintained after calcination at 1400℃.

[References]

Dwyer FG, Catal. Rev.-Sci. Eng., 6, 261 (1972)
Shelef M, Catal. Rev.-Sci. Eng., 11, 1 (1975)
Trim DL, Appl. Catal., 7, 249 (1983)
Prasad R, Kennedy La, Ruckenstein R, Catal. Rev.-Sci. Eng., 26, 1 (1984)
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Pfefferle Ld, Pfefferle WC, Catal. Rev.-Sci. Eng., 29, 219 (1987)
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[Referenced By]

[1] Dwyer FG, Catal. Rev.-Sci. Eng., 6, 261 (1972)

[2] Shelef M, Catal. Rev.-Sci. Eng., 11, 1 (1975)

[3] Trim DL, Appl. Catal., 7, 249 (1983)

[4] Prasad R, Kennedy La, Ruckenstein R, Catal. Rev.-Sci. Eng., 26, 1 (1984)

[5] Enga BE, Thompson DT, Plast. Metals Rev., 23, 134 (1979)

[6] Pfefferle Ld, Pfefferle WC, Catal. Rev.-Sci. Eng., 29, 219 (1987)

[7] Matsuda S, Kato S, Mizumoto M, Yamashita H, "Proceedngs, 8th Interational Congress on Catalysis, Berlin, vol. 4, p. 879, Dechema Frankfurt (1984)

[8] Machida M, Eguchi K, Arai H, J. Catal., 103, 385 (1987)

[9] Voorhoeve RJH, "Advanced Materials in Catalysis," (Burton, J.J. and Garten, R.L., eds.), p. 129, Academic Press, New York (1977)

[10] Zhang HM, Shimizu Y, Teraoka Y, Miura N, Yamazoe N, J. Catal., 121, 432 (1990)

[11] Kesselring JP, Krill WV, Chu EK, Kendall RM, Symp. Mew Fuels Adv. Comb. Technol., p. 433 (1979)

[12] Rutham R, Sanders MK, J. Catal., 27, 287 (1972)

[13] Ropp RC, Carroll B, J. Am. Ceram. Soc., 63, 416 (1980)

[14] Fritsche ET, Tensmeyer LG, J. Am. Ceram. Soc., 50, 167 (1967)

[15] Lowell S, Shields JE, "Powder Surface Area and Porosity," Champman and Hall, New York, p. 62 (1984)