헤테로폴리산 촉매에 의한 에탄올 전환반응

홍성수; 이상기; 이호인

Journal of the Korean Industrial and Engineering Chemistry, Vol.4, No.3, 549-557, September, 1993

Export Citation

헤테로폴리산 촉매에 의한 에탄올 전환반응

Conversion of Ethanol over Heteropoly Acids

홍성수, 이상기, 이호인

초록

헤테로폴리산 촉매에 의한 에탄올 전환반응에서, 반응성, 반응 메카니즘, 반응물과 함께 주입된 유기염기의 효과 및 금속염 촉매의 산의 세기와 촉매활성과의 관계를 연구하였다. 에탄을 전환반응은 촉매의 의액상에서 일어났고, 이러한 성질 때문에 아주 높은 촉매활성을 보여 주었으며, SiO₂에 담지 시켜 표면적을 증가시킨 촉매에서도 활성이 그다지 증가하지 않았다. 에틸렌과 에테르가 생성되는 반응 메카니즘은 서로 다른 것으로 관찰되었으며, 알루미늄 이온에 의해 부분적으로 이온 교환된 여러 가지 12-텅스토인산염들은 서로 다른 촉매활성을 보여주었다.

In the conversion of ethanol over heteropoly acids, we have studied catalytic reactivity, reaction mechanism, effect of organic bases added to reactant, and relation between acid strength of ion-exchanged catalysts and catalytic activities. The conversion of ethanol proceeded in the pseudoliquid phase of heteropoly acid. Due to this novel behavior, area increased by supporting with SiO₂. The reaction mechanism of ethylene production was different from that of ether production, and various partially substituted Al salts of 12-tungstophosphoric acid showed different catalytic activities.

[References]

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[1] Brey WS, Krieger KA, J. Am. Chem. Soc., 71, 3637 (1949)

[2] vanAlphen J, Rec. Trav. Chim., 49, 754 (1930)

[3] Whitmore FC, J. Am. Chem. Soc., 54, 2986 (1932)

[4] Ono Y, Ind. J. Tech., 21, 335 (1983)

[5] Urabe K, Fujita K, Izumi Y, Shokubai, 22, 223 (1980)

[6] Hong SS, Lee HI, J. Korean Ind. Eng. Chem., 2(4), 363 (1991)

[7] Hong SS, Lim KC, Lee HI, J. Korean Ind. Eng. Chem., 4(2), 335 (1993)

[8] McVicker GB, Vannice MA, J. Catal., 63, 25 (1980)

[9] Baily JC, Inorg. Synth., 1, 132 (1939)

[10] Hammett LP, Deyrup AJ, J. Am. Chem. Soc., 54, 2721 (1932)

[11] Tanabe K, "Solid Acids and Bases," Academic Press, New York, 12 (1970)

[12] Muraue M, Shokubai, 5, 192 (1963)

[13] deBoer JH, Fahin RB, Lisen BG, Visseren WJ, deVleesschauwer WFNM, J. Catal., 7, 163 (1967)

[14] Okuhara T, Hashimoto T, Misono M, Yoneda Y, Chem. Lett., 573 (1983)

[15] Saito Y, Cook PN, Niyama H, Echigoya E, J. Catal., 95, 49 (1985)

[16] Okuhara T, Kasai A, Hayakawa N, Misono M, Yoneda Y, Chemosphere, 391 (1981)

[17] Raman G, Raman SK, World Cong. IV of Chem. Eng., Tokyo, 318 (1986)

[18] Furuta M, Sakata K, Misono M, Yoneda Y, Chemosphere, 31 (1979)

[19] Okuhara T, Hayakawa N, Kasai A, Misono M, Yoneda Y, Shokubai, 22, 226 (1980)

[20] Othmer K, "Eneyclopedia of Chem. Tech.," 2nd ed., John Wiley & Sons, New York, Vol. 16, 869 (1967)

[21] Misono M, Proc. 4th Int. Conf. Chem. and Uses of Molybdenum, 289 (1982)

[22] Niiyama H, Saito Y, Echigoya E, Proc. 7th Int. Cong. Catal., 1416 (1980)

[23] Baba T, Watanabe H, Ono Y, J. Phys. Chem., 87, 2406 (1983)

[24] Ai M, J. Catal., 8, 1 (1967)