이온교환수지 촉매를 이용한 옥탄가 향상제인 TAME 합성반응의 연구

박진화

Journal of the Korean Industrial and Engineering Chemistry, Vol.7, No.5, 832-842, October, 1996

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이온교환수지 촉매를 이용한 옥탄가 향상제인 TAME 합성반응의 연구

A Study over Catalytic Behavior Octane Enhancer, TAME Synthesis with Ion Exchange Resin Catalysts

박진화

초록

성질이 서로 다른 그물 구조형 이온교환수지인 Amberlyst-15, Amberlyst-15(wet)와 Amberlyst XN-1010을 가지고 고정층 상압 유통식 반응장치에서 옥탄가 향상제인 TAME 합성반응을 행하였다. Amberlyst-15가 Amberlyst-15(wet)와 Amberlyst XN-1010에 비해 활성이 좋았는데 그 이유는 겔형 미세입자 내부 활성점의 반응참여 정로가 크기 때문으로 생각되며, TAME 합성반응의 최적 조건들은, 반응온도=135℃, 반응물 몰비(MeOH/I.A.A.)=1.0∼4.0, W/F=2.0∼4.0 gr.-cat. hr/gr.-mole일 때이었다. X-ray 회절 분석결과 2θ=20에서 styrene divinyl benzene이 가교결합을 나타냈으며, DSC 분석결과 열적 안정성의 순서로는 Amberlyst-15, Amberlyst-15(wet) 및 Amberlyst XN-1010이였다. 본 실험에서 구한 TAME 합성의 겉보기 활성화 에너지 값은 Amberlyst-15:Ea=12.36 kcal/mole, Amberlyst-15(wet):Ea=12.46 kcal/mole 및 Amberlyst XN-1010:Ea=14.72 kcal/nole이였다.

TAME synthesis was studied in a fixed bed reactor with 3 different types of exchanged resins i.e, Amberlyst-15, Amberlyst-15(wet) and Amberlyst XN-1010. Amberlyst-15 has highest activity, presumably due to the higher reaction participation of the inner active sites of gel shape microparticular resin structure. The optimum reaction conditions for TAME synthesis were found as follows ; reaction temperature of 135℃, molar ratio(MeOH/I.A.A) of 1.0∼4.0 and W/F of 2.0∼4.0 gr.-cat. hr/gr.-mole. The cross-linking bond of styrene divinyl benzene was observed at 2θ=20 in XRD pattern. The DSC analysis showed that the thermal stability was in order of Amberlyst-15>Amberlyst-15(wet) > Amberlyst XN-1010. The apparent activation energies of TAME synthesis reaction with Amberlyst-15, Amberlyst-15(wet) and Amberlyst XN-1010 were 12.36, 12.46 and 14.72 kcal/mole, respectively.

[References]

Adams BA, Holmes EL, J. Soc. Chem. Ind., 54, 1 (1935)
Hodge P, Sherrington DC, "Polymer-Supported Reactions in Organic Synthesis," John Wiley & Sons, New York (1980)
Tamura SJ, Shokubai, 34, 249 (1992)
Pitochelli AR, "Ion Exchange Catalysis & Matrix Effects," Rohm & Hass Co., Philadelphia (1975)
Kunin R, "Catalysis with IonExchange Resins," No. 135, Rohm and Hass Co., Philadelphia, July (1973)
Jarrel MS, Gates BC, Drench WJ, Catalysis, 47, 269 (1977)
Hanson DL, Katzer JR, Gates BC, Schwit GCA, J. Catal., 32, 204 (1972)
Gates BC, Scheab GW, J. Catal., 15, 430 (1969)
Dimer RB, Dooley KM, Gates BC, Albright RL, J. Catal., 74, 373 (1982)
Hennico A, Leonard J, Chodorge JA, Nocca JL, Institut Francais du Petrole, "IFP Etherification Technology: the MTBE and TAME Processes," 127-129 (1973)
Ancillotti R, Maur MM, Pescarollo E, J. Catal., 46, 49 (1977)
Herwig J, Schleppinghoff B, Schulwitz S, Hydrocarb. Process., June, 86 (1984)
Bothe N, Widdecke H, Polymer, 20, 850 (1979)
Wheato RM, Harrington EF, Ind. Eng. Chem., 44 (1976)
Helfferich F, "Ion Exchange," McGraw-Hill, New York (1962)
Rodriguez O, Setinek K, J. Catal., 39, 449 (1975)
Ihm SK, Chung MJ, Park KY, Ind. Eng. Chem. Res., 27, 41 (1988)
Lee MY, Ihm SK, HWAHAK KONGHAK, 25(6), 607 (1987)
Lee GH, "MTBE Cracking over the Macroreticular Resin Catalysts," KAIST, M.S. Thesis (1986)
Thornton R, Gates BC, J. Catal., 34, 275 (1974)
Anchillotti F, Mauri MM, Pescarolb E, J. Catal., 46, 49 (1977)
Gates BC, Johanson LN, AIChE J., 17, 981 (1974)
Gicquel A, Torck B, J. Catal., 83, 9 (1983)
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[1] Adams BA, Holmes EL, J. Soc. Chem. Ind., 54, 1 (1935)

[2] Hodge P, Sherrington DC, "Polymer-Supported Reactions in Organic Synthesis," John Wiley & Sons, New York (1980)

[3] Tamura SJ, Shokubai, 34, 249 (1992)

[4] Pitochelli AR, "Ion Exchange Catalysis & Matrix Effects," Rohm & Hass Co., Philadelphia (1975)

[5] Kunin R, "Catalysis with IonExchange Resins," No. 135, Rohm and Hass Co., Philadelphia, July (1973)

[6] Jarrel MS, Gates BC, Drench WJ, Catalysis, 47, 269 (1977)

[7] Hanson DL, Katzer JR, Gates BC, Schwit GCA, J. Catal., 32, 204 (1972)

[8] Gates BC, Scheab GW, J. Catal., 15, 430 (1969)

[9] Dimer RB, Dooley KM, Gates BC, Albright RL, J. Catal., 74, 373 (1982)

[10] Hennico A, Leonard J, Chodorge JA, Nocca JL, Institut Francais du Petrole, "IFP Etherification Technology: the MTBE and TAME Processes," 127-129 (1973)

[11] Ancillotti R, Maur MM, Pescarollo E, J. Catal., 46, 49 (1977)

[12] Herwig J, Schleppinghoff B, Schulwitz S, Hydrocarb. Process., June, 86 (1984)

[13] Bothe N, Widdecke H, Polymer, 20, 850 (1979)

[14] Wheato RM, Harrington EF, Ind. Eng. Chem., 44 (1976)

[15] Helfferich F, "Ion Exchange," McGraw-Hill, New York (1962)

[16] Rodriguez O, Setinek K, J. Catal., 39, 449 (1975)

[17] Ihm SK, Chung MJ, Park KY, Ind. Eng. Chem. Res., 27, 41 (1988)

[18] Lee MY, Ihm SK, HWAHAK KONGHAK, 25(6), 607 (1987)

[19] Lee GH, "MTBE Cracking over the Macroreticular Resin Catalysts," KAIST, M.S. Thesis (1986)

[20] Thornton R, Gates BC, J. Catal., 34, 275 (1974)

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

[22] Gates BC, Johanson LN, AIChE J., 17, 981 (1974)

[23] Gicquel A, Torck B, J. Catal., 83, 9 (1983)

[24] Ancillotti F, MassiMauri M, Pescarello E, Romagnoni L, J. Mol. Catal., 4, 37 (1978)