프로필렌 선택산화반응에서 a-Bi2Mo3O12와 SnO2의 상간협동 I.기계적 혼합촉매

박대원; 김경훈; 김종화; 나석은

Journal of the Korean Industrial and Engineering Chemistry, Vol.6, No.4, 571-578, August, 1995

Export Citation

프로필렌 선택산화반응에서 a-Bi2Mo3O12와 SnO2의 상간협동 I.기계적 혼합촉매

Phase Cooperation between α-Bi₂Mo₃O₁₂ and SnO₂ for the Selective Oxidation of Propylene Ⅰ. Mechanically Mixed Catalyst

박대원, 김경훈, 김종화, 나석은

초록

본 연구는 프로필렌의 선택산화반응에서 α-Bi2Mo3O12(BM) 와 SnO2의 기계적 혼합촉매의 상승효과에 관한 메카니즘을 규명하기 위한 것이다. 촉매의 물리적 성질 및 구조를 관찰하기 위하여 BET, XRD, SEM 등을 사용하였고, 촉매의 산화-환원 특성은 승온탈착(TPD), 승온환원(TPR), 승온재산화(TPROX) 실험으로 조사하였다. BM과 SnO2의 기계적 혼합촉매의 프로필렌 전화율과 아크롤레인 및 아크릴산의 수율이 각각의 BM과 SnO2의 산술 평균값보다 높았다. 이와 같은 상승효과는 두 상간의 협동에 의한 것으로 추측된다. 즉 SnO2의 산소 빈자리에 흡수된 산소이온이 경계면을 통하여 BM 상에 전달되어 이의 재산화를 촉진시키기 때문으로 판단된다.

The present study was aimed to elucidate the mechanism of synergistic effect in the mechanically mixed catalysts of α-Bi2Mo3O12(BM) and SnO2 for the selective oxidation of propylene. Physical and structural properties of catalysts were characterized by BET, XRD and SEM. Reduction and oxidation behaviors of catalysts were studied using TPD, TPR and TPROX. Reaction test showed that the catalyst mixture had higher conversion of propylene and higher yield of acrolein and acrylic acid than either of the each metal oxide. The origin of the synergy is attributed to the cooperation of the two metal oxide catalysts. Oxygen ions formed at the oxygen vacancies of SnO2 move to BM and promote its reoxidation.

[References]

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[1] French Patent DE 2,397,229 (1979)

[2] Japan Patent, 86-11, 211 (1986)

[3] Grasselli RK, Burrington JD, Adv. Catal., 30, 133 (1981)

[4] Hucknall DJ, "Selective Oxidation of Hydrocarbons," 23, Academic Press, New York (1974)

[5] Gates BC, Katzer JR, Schuit GC, "Chemistry of Catalytic Process," McGraw-Hill, London (1979)

[6] Carson D, Coudurier G, Forissier M, Verdine JC, J. Chem. Soc.-Faraday Trans., 1, 79 (1983)

[7] Weng LT, Delmon B, Appl. Catal., 81, 141 (1992)

[8] Ozkan US, Schrader GL, J. Catal., 95, 120 (1985)

[9] Qiu FY, Weng LT, Ruiz P, Delmon B, Appl. Catal., 47, 115 (1989)

[10] Ozkan US, Schrader GL, Appl. Catal., 23, 327 (1985)

[11] Ozkan US, Gill RC, Smith MR, Appl. Catal., 62, 105 (1990)

[12] Zhou B, Chuang KT, Guo X, J. Chem. Soc.-Faraday Trans., 87, 3695 (1991)

[13] Liu ZX, Bao QX, Wu NJ, J. Catal., 113, 45 (1988)

[14] Park DW, Na SE, Kim KH, Lee WH, HWAHAK KONGHAK, 32(2), 213 (1994)

[15] Synder TP, Hill CG, Catal. Rev.-Sci. Eng., 31, 43 (1989)

[16] Chung YS, M.S. Dissertation, POSTECH (1993)

[17] Park DW, Na SE, Kim KH, Lee WH, Chung JS, J. Korean Ind. Eng. Chem., 5(2), 295 (1994)

[18] Weng LT, Spitaels N, Yasse B, Ladriere J, Ruiz P, Delmon B, J. Catal., 132, 319 (1991)

[19] Bielanski A, Haber J, Catal. Rev.-Sci. Eng., 19, 1 (1979)