알칼리 금속이 첨가된 silica-alumina 촉매에 의한 메탄올의 탈수소반응의 연구

곽종운; 박진남; 이호인

Journal of the Korean Industrial and Engineering Chemistry, Vol.7, No.4, 698-706, August, 1996

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알칼리 금속이 첨가된 silica-alumina 촉매에 의한 메탄올의 탈수소반응의 연구

A Study on the Dehydrogenation of Methanol by Alkali-doped Silica-alumina Catalyst

곽종운, 박진남, 이호인

초록

메탄올로부터 HCHO를 생성하기 위하여 연속흐름 장치하에서 알칼리금속이 혼입된 여러가지 실리카-알루미나 촉매상에서 메탄올 탈수소반응을 수행하였다. HCHO의 생성은 촉매상의 Br nsted산보다는 Lewis산에 의존하였다. 이를 통해 메탄올의 탈수소촉매반응은 전자반응임을 알았고, 실리카-알루미나상의 Br nsted산은 알칼리금속의 혼입에 의해서 중화되었으며, Br nsted산의 중화효과는 혼입된 알칼리금속의 전자주게능력(electron-donating capacity)에 따라 다르게 나타났다. 그리고 메탄올 탈수소반응의 활성화에너지는 촉매의 Br nsted산점이 K에 의해 중화되었을 때 감소하는 경향을 보여주었다.

Dehydrogenation of methanol to produce formaldehyde was carried out over various silica-alumina catalysts doped with alkali metals in a continuous flow system. The reaction was rather dependent on Lewis acid than Br nsted acid suggesting that dehydrogenation of methanol was an electronic reaction. The Br nsted acid sites on silica-alumina were neutralized by doping with alkali metals, and the neutralization effect of Br nsted acid was dependent on the electron-donating capacity of the dopant metals. Activation energy for dehydrogenation of methanol decreased when Br nsted acid was neutralized by doping with K.

[References]

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[1] Walker JF, "Formaldehyde," Reinhold, New York (1964)

[2] Mark HF, Othmer DF, Overberger CG, Seaborg GT, "Kirk-Othmer Encyclopedia of Chemical Technology," 3rd Ed., Vol. 11, John Wiley & Sons, New York (1984)

[3] Mann RS, Hahn KW, J. Catal., 15, 329 (1969)

[4] Wachs IE, Madix RJ, J. Catal., 53, 208 (1978)

[5] Neilson A, Catal. Rev.-Sci. Eng., 23, 171 (1981)

[6] Richler H, Schultz H, Chem. Eng. Technol., 42, 1162 (1970)

[7] Shah YT, Perrotta AZ, Ind. Eng. Chem. Prod. Res. Dev., 15, 123 (1966)

[8] Huang CP, Richardson JT, J. Catal., 51, 1 (1978)

[9] Wainwright MS, Forster NR, Catal. Rev.-Sci. Eng., 19, 211 (1979)

[10] Allen JA, Clerk AJ, Pure Appl. Chem., 21, 145 (1971)

[11] Villadsen I, Livbjerg H, Catal. Rev.-Sci. Eng., 17, 203 (1978)

[12] Mross WD, Catal. Rev.-Sci. Eng., 25, 591 (1983)

[13] Chen I, Chen FL, Ind. Eng. Chem. Res., 29, 534 (1990)

[14] Demicheli MC, Duprez D, Barbier J, Ferretti OA, Ponzi EN, J. Catal., 145(2), 437 (1994)

[15] Vordonis L, Koutsoukos PG, Lycourbhiotis A, J. Catal., 101, 186 (1986)

[16] Bridger GW, Ammonia Plant Saf., 18, 24 (1976)

[17] Anderson JR, Boudart M, Catal. Sci. Tech., 2, 244 (1981)

[18] Jones CA, Leonard JJ, Sofranko JA, J. Catal., 103, 311 (1987)

[19] Weast RC, "Handbook of Chemistry and Physics," 56th. ed., CRC Press, F224 (1975)

[20] Taylor WJ, Wagman DD, Williams MG, Pitzer KS, Rossini RD, J. Res. Nat. Bur., 37, 95 (1946)