고체산 촉매에 의한 가솔린 옥탄가 향상제인 ETBE(Ethyl tert-Butyl Ether) 합성

박남국; 김재승; 서성규; 오영열

Journal of the Korean Industrial and Engineering Chemistry, Vol.4, No.1, 162-170, March, 1993

Export Citation

고체산 촉매에 의한 가솔린 옥탄가 향상제인 ETBE(Ethyl tert-Butyl Ether) 합성

Solid Acid Catalyzed Formation of ETBE(Ethyl tert-Butyl Ether) as an Octane Enhancer for Gasoline

박남국, 김재승, 서성규, 오영열

초록

TBA(tert-butyl alcohol)와 ethanol로부터 고체산 촉매상에서 가솔린 옥탄가 향상제인 ETBE(ethyl tert-butyl ether)의 기상 합성반응에 관하여 연구하였다. 헤테로폴리산 촉매가 제올라이트계 촉매보다 활성이 우수하였으며, H₄SiW₁₂O₄₀촉매는 현재 공업적으로 이용되고 있는 Amberlyst-15 수지촉매의 대체가능성을 보였다. 또한 전이금속 양이온으로 교환된 헤테로폴리산 촉매는 수소환원에 의한 새로운 산점의 생성 및 증가에 따라 촉매활성이 크게 증가되었다. 이러한 수소환원 효과는 촉매의 환원특성과 관계되며, 환원 용이성은 Ag₊＞Cu₂₊＞Fe₂₊의 순서였다.

Vapor-phase ETBE(ethyl tert-butyl ether) synthesis from TBA(tert-butyl alcohol) and ethanol was carried over solid acid catalysts such as heteropoly acids and proton type zeolites. Heteropoly acids were more active than proton type zeolites and H₄SiW₁₂O₄₀ catalyst showed about the same activity as Amberlyst-15 ion exchange resin catalyst used as an industrial catalyst in ETBE synthesis. The catalytic activity of transition metal exchanged heteropoly acids was greatly enhanced, because new acid site was generated with hydrogen reduction. This effect of hydrogen reduction was related to the reduction characteristics of catalysts and the order of reducibility was Ag₊>Cu₂₊>Fe₂₊.

[References]

Tau LM, Davis BH, Appl. Catal., 53, 263 (1980)
Chem. J., 1, 9 (1991)
Jose MI, Javier FI, Cunill TE, Chem. Tech., Feb., 120 (1988)
Keggin JF, Proc. Roy. Soc. Ser., A144, 75 (1934)
Okuhara T, Kasai A, Hayakawa N, Yoneda Y, Misono M, J. Catal., 83, 121 (1983)
Kim JS, Seo SG, HWAHAK KONGHAK, 24(6), 485 (1986)
Kim JS, Park NC, Seo SG, HWAHAK KONGHAK, 26(6), 664 (1988)
Kim JS, Park NC, Seo SG, HWAHAK KONGHAK, 29(4), 440 (1991)
Misono M, Mizuno N, Katamura K, Kasai A, Konishi Y, Sakata K, Okuhara T, Yoneda Y, Bull. Chem. Soc. Jpn., 55, 400 (1982)
Rocchiccioli-Deltcheff C, Thouvenot R, Frank R, Spectrochim. Acta, 32A, 587 (1976)
Eguchi K, Yamazone N, Seiyama T, J. Chem. Soc. Jpn., 3, 336 (1981)
Kim JS, Kim JM, Seo SG, Park NC, Niiyama H, Appl. Catal., 37, 44 (1988)
Basila MR, Kantner TR, Rhee KH, J. Phys. Chem., 68, 3197 (1964)
Parry EP, J. Catal., 2, 371 (1962)
Yoshida S, Niiyama H, Echigoya E, J. Phys. Chem., 86, 3150 (1982)
Baba T, Watanabe H, Ono Y, J. Phys. Chem., 87, 2406 (1983)

[Referenced By]

[1] Tau LM, Davis BH, Appl. Catal., 53, 263 (1980)

[2] Chem. J., 1, 9 (1991)

[3] Jose MI, Javier FI, Cunill TE, Chem. Tech., Feb., 120 (1988)

[4] Keggin JF, Proc. Roy. Soc. Ser., A144, 75 (1934)

[5] Okuhara T, Kasai A, Hayakawa N, Yoneda Y, Misono M, J. Catal., 83, 121 (1983)

[6] Kim JS, Seo SG, HWAHAK KONGHAK, 24(6), 485 (1986)

[7] Kim JS, Park NC, Seo SG, HWAHAK KONGHAK, 26(6), 664 (1988)

[8] Kim JS, Park NC, Seo SG, HWAHAK KONGHAK, 29(4), 440 (1991)

[9] Misono M, Mizuno N, Katamura K, Kasai A, Konishi Y, Sakata K, Okuhara T, Yoneda Y, Bull. Chem. Soc. Jpn., 55, 400 (1982)

[10] Rocchiccioli-Deltcheff C, Thouvenot R, Frank R, Spectrochim. Acta, 32A, 587 (1976)

[11] Eguchi K, Yamazone N, Seiyama T, J. Chem. Soc. Jpn., 3, 336 (1981)

[12] Kim JS, Kim JM, Seo SG, Park NC, Niiyama H, Appl. Catal., 37, 44 (1988)

[13] Basila MR, Kantner TR, Rhee KH, J. Phys. Chem., 68, 3197 (1964)

[14] Parry EP, J. Catal., 2, 371 (1962)

[15] Yoshida S, Niiyama H, Echigoya E, J. Phys. Chem., 86, 3150 (1982)

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