Mo/SiO2촉매상에서 t-Butyl hydroperoxide에 의한 염화알릴의 에폭시화반응에 관한 속도론적 연구

김성우; 박대원; 정종식; 박대철

Journal of the Korean Industrial and Engineering Chemistry, Vol.3, No.4, 649-656, December, 1992

Export Citation

Mo/SiO2촉매상에서 t-Butyl hydroperoxide에 의한 염화알릴의 에폭시화반응에 관한 속도론적 연구

Kinetic Study on the Epoxidation of Allyl Chloride by t-Butyl hydroperoxide over Mo/SiO₂ Catalyst

김성우, 박대원, 정종식, 박대철

초록

t-Butyl hydroperoxide(TBHP)에 의한 염화알릴의 에폭시화에 의해서 에피클로로히드린을 합성하는데 실리카에 담지된 몰리브데늄 촉매를 사용하였다. 속도론적 연구는 회분 반응기를 사용하여 60-80℃, 10기압에서 TBHP/염화알릴의 농도비를 0.01-0.1의 범위내에서 수행하였다. t-butyl alcohol(TBA)에 의해서 염화알릴의 에폭시화 반응이 억제되었고, 반응속도는 Michaelis-Menten 형태의 속도식으로 표현할 수 있었다. 반응기구는 TBHP와 TBA의 가역흡착과 Mo/SiO₂에 흡착된 TBHP와 염화알릴의 표면반응으로 설명할 수 있었다.

The synthesis of epichlorohydrin was carried out by the epoxidation of allyl chloride with tert-butyl hydroperoxide(TBHP) over silica supported molybdenum catalyst. Kinetic study was perfomed at 60-80℃ and 10 atm with the molar ratio of TBHP/Allyl chloride between 0.01 and 0.1 in a batch reactor. The epoxidation of allyl chloride was inhibited by tert-butyl alcohol and kinetic data could be represented by Michaelis-Meten type rate equation. The reaction mechanism could be explained by the combination of reversible adsorption of TBHP and tert-butyl alcohol accompanied by reaction of allyl chloride with TBHP adsorbed on Mo/SiO₂ catalyst.

[References]

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[1] Hatch LF, Matar S, "From Hydrocarbons to Petrochemicals," Gulf Publishing Co., Houston, 190 (1981)

[2] Simmrock KH, Hydrocarb. Process., 105 (1978)

[3] Polaczek J, Bobinski J, Int. Chem. Eng., 83 (1971)

[4] Gould ES, Rado M, J. Catal., 13, 238 (1969)

[5] Sheldon RA, Kochi JK, Adv. Catal., 25, 272 (1976)

[6] Sheldon RA, J. Mol. Catal., 7, 107 (1980)

[7] Sheldon RA, Kochi JK, "Metal-Catalyzed Oxidations of Organic Compounds," Academic Press, N.Y., Chapt. 3 (1981)

[8] Sheldon RA, VanDoorn JA, J. Catal., 31, 427 (1973)

[9] Eur. Patent, 1,248,079 (1971)

[10] Eur. Patent, 1,248,709 (1971)

[11] Eur. Patent, 1,249,082 (1971)

[12] Eur. Patent, 87100625 (1987)

[13] Baker TN, Mains MJ, Sheng MN, Zajacek JG, J. Org. Chem., 38, 1145 (1973)

[14] Kaloustian J, Raffi E, Lena L, Metzger J, Bull. Soc. Chem. Fr., 4415 (1971)