헤테로폴리산 촉매를 이용한 TAME, ETBE 및 MTBE 합성반응의 연구

박진화; 이용우

Journal of the Korean Industrial and Engineering Chemistry, Vol.8, No.4, 582-588, August, 1997

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헤테로폴리산 촉매를 이용한 TAME, ETBE 및 MTBE 합성반응의 연구

Synthesis of TAME, ETBE, and MTBE Using Heteropolyacid Catalyst

박진화, 이용우

초록

고체산 촉매인 헤테로폴리상 촉매를 이용하여 대기오염 방지를 위한 옥탄가 향상제인 TAME, ETBE 및 MTBE 합성반응에 대한 실험을 고정층 상압유통식 반응장치에서 수행하였다. 일반적으로 TAME, ETBE 및 MTBE 합성반응에서 헤테로폴리산에 hetero원자와 poly원자를 치환시켜 비교한 결과, 배위된 poly원자가 W, hetero원자가 Si인 H₄SiW₁₂O₄₀ 촉매의 활성이 가장 우수하였고, 또한 치환된 금속에 따라 촉매의 활성이 달랐으며 이는 촉매의 산성질과 관련이 있음을 알 수 있었다. 헤테로폴리산 촉매를 이용한 합성반응에서 TAME 경우는 FeHPW₁₂O₄₀과 K₃PMo₁₂O₄₀이 비교적 활성이 좋았으나, ETBE나 MTBE 경우에 비해서는 다소 활성이 낮았다. 그리하여 본 연구에서는 활성이 좋은 헤테로폴리산 촉매들을 선정하여 각각에 대하여 1:1로 다음과 같이 혼합하여 H₄SiW₁₂O₄₀:Sr₂SiW₁₂O₄₀, H₄SiW₁₂O₄₀:NaH₂PW₁₂O₄₀, Fe_1.5PW₁₂O₄₀:Mg₂SiW₁₂O₄₀ 및 Mg₂SiW₁₂O₄₀:Ba₂SiW₁₂O₄₀ 실험한 결과, 혼합촉매들이 각각의 단일성분 촉매때보다 TBA의 전화율과 ETBE나 MTBE의 선택율이 더욱 향상되었음을 알 수 있었다

Synthetic reaction of TAME, ETBE, and MTBE compounds used largely for gasoline octane number enhancer to prevent air pollution was investigated using heteropolyacid catalyst in a fixed bed flow reactor. In the synthetic reaction of TAME, ETBE and MTBE, after hetero atom being replaced with poly atom, the activity of the catalyst, H₄SiW₁₂O₄₀ with coordinated bond with W and an hetero atom of Si was the highest among the catalysts tested. Also the activity depended upon the metals replaced which are related to the catalyst acidity. FeHPW₁₂O₄₀ and K₃PMo₁₂O₄₀ catalysts showed high activity in TAME synthesis, while they were not effective in ETBE and MTBE synthesis. In this study catalysts showing high activity were selected and mixed with equal weight combination of H₄SiW₁₂O₄₀ and Sr₂SiW₁₂O₄₀;H₄SiW₁₂O₄₀ and NaH₂PW₁₂O₄₀;Fe_1.5PW₁₂O₄₀ and Mg₂SiW₁₂O₄₀; Mg₂SiW₁₂O₄₀ and Ba₂SiW₁₂O₄₀. The mixed heteropolyacid catalysts showed higher TBA conversion rate and better selectivity of ETBE and MTBE than the single catalysts.

[References]

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

[2] 전학제, "촉매개론," 383-393 (1992)

[3] Igarashi A, Matsuda T, Ogino Y, J. Jpn. Petrol. Inst., 22, 30 (1980)

[4] Nomiya K, Sara S, Miwa M, Chem. Lett., 1075 (1980)

[5] Otake M, Onoda T, J. Catal., 38, 494 (1975)

[6] Ono Y, Mori T, Keii T, Int. Congr. Cata., Proc. 7th, 755 (1980)

[7] Hayashi H, Moffat JB, J. Catal., 83, 192 (1983)

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

[9] Okuhara T, Kasai A, Hayakawa N, Misono M, Yoneda Y, Chem. Lett., 391 (1981)

[10] Basila MR, Kantner TR, Rhee KH, J. Phys. Chem., 68, 3179 (1964)

[11] Ward JW, J. Catal., 9, 225 (1967)

[12] Takesono T, Fujiwara Y, U.S. Patent, 4,182,913 (1980)

[13] Bailer JC, Inorg. Synth., 1, 127 (1939)

[14] Booth HS, McGraw-Hill, Inorganic Synthesis (1939)

[15] Park JH, Cho HG, Shin JS, Park NC, Kim JS, HWAHAK KONGHAK, 33(1), 19 (1995)

[16] Misono M, Mizuno N, Katamura K, Kasai A, Konishi Y, Sakata K, Okuhara T, Yoneda Y, Bull. Chem. Soc. Jpn., 55, 440 (1982)

[17] Rocchiccioli C, Thouvenot DR, Frank R, Spectrochim. Acta, 32A, 587 (1976)

[18] Park NC, Kim JS, Seo SG, Oh YY, J. Korean Ind. Eng. Chem., 4(1), 162 (1993)

[19] Morrison RT, Body RN, 유기화학(상), 3rd, ed., 청문각, pp. 187 ~ 192 (1976)

[20] Padmanabhen VR, J. Catal., 24, 88 (1972)

[21] Ancillott F, Mauri MM, Pescarollo E, J. Catal., 46, 49 (1977)

[22] Colombo F, Corl L, Dalloro L, Delogu P, Ind. Eng. Chem. Fundam., 22, 219 (1983)

[23] Dean JA, Lange's Handbook of Chemistry, 13th ed., McGraw-Hill, New York (1985)

[24] 박진화, 박사학위논문, 전남대학교 일반대학원 (1995)