2차세공이 형성된 모더나이트와 알루미나를 혼합한 촉매상에서 Triphenylmethane의 분해반응

이경환; 최준우; 하백현

Journal of the Korean Industrial and Engineering Chemistry, Vol.8, No.6, 1048-1053, December, 1997

Export Citation

2차세공이 형성된 모더나이트와 알루미나를 혼합한 촉매상에서 Triphenylmethane의 분해반응

Catalytic Cracking of Triphenylmethane on Alumina Mixed with Mordenite Formed Secondary Pore

이경환, 최준우, 하백현

초록

수소형 모더나이트를 불화수소산처리하여 실리카/알루미나의 비가 다른 변형된 모더나이트를 만들고 이를 γ-알루미나와 혼합한 촉매를 제조하여 미소반응기에서 triphenylmethane (TPM)의 분해반응을 실시하였다. 미세공 구조인 수소형 모더나이트를 불화수소산처리로 탈알루미늄하면 산량은 감소하지만 2차 세공인 중세공이 형성되어 TPM의 분해활성과 2차 분해생성물인 벤젠의 선택성이 향상되었다. 그러나 더욱 불화수소산처리된 모더나이트는 산량 감소와 일부 세공구조의 파괴에 의한 미세공막힘 현상에 의해 분해활성이 저하되었다. 따라서 전처리된 모더나이트상에서 TPM의 분해활성과 벤젠의 선택성은 모더나이트의 실리카/알루미나 비가 17 정도에서 가장 우수하였다. 이들 전처리된 모더나이트를 알루미나와 혼합한 촉매는 순수한 모더나이트 촉매보다 TPM의 분해활성이 더욱 우수하였다. 이는 알루미나의 큰 중세공에서 TPM이 1차 분해반응하고 다음에 모더나이트의 중세공과 미세공에서 분해되는 단계적인 분해반응이 일어나기 때문이다.

Modified mordenites by HF treatement, which have different SiO₂/Al₂O₃ ratio, and those mixed with γ-alumina are prepared and used for catalytic cracking of triphenylmethane(TPM) in micro-activity tester(MAT). Dealumination of mordenites decreased the acid content but developed secondary mesopores. The conversion and the selectivity of benzene over modified mordenites with the mesopores were increased. However, for the further dealuminated mordenites, they decreased due to the destruction of pore structure and low acid amount. Accordingly, the maximum cracking activity and the maximum selectivity of benzene were obtained about 17 SiO₂/Al₂O₃ ratio of modified mordenites. The modified mordenites mixed with alumina enhanced the cracking activity of TPM compared with the pure mordenites. It can be explained that TPM is cracked at active sites with in large pores of alumina firstly and further cracked into small molecules in zeolite pores as step mechanism of catalytic cracking.

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[1] Biswas J, Maxwell IE, Appl. Catal., 63, 197 (1990)

[2] Bertolacini RJ, Cutberlet LC, Kim DK, Robbinson KK, Am. Chem. Soc. Div. Fuel Chem. Prepr., 23, 1 (1978)

[3] Stiegel CJ, Tischer RE, Polinski LM, Ind. Eng. Chem. Fundam., 25, 330 (1986)

[4] Shimura J, Shiroto Y, Takeuchi C, Ind. Eng. Chem. Fundam., 25, 330 (1986)

[5] Raatz F, Freund E, Marcilly C, J. Chem. Soc.-Faraday Trans., 79, 229 (1983)

[6] Van Geem PC, Scholle KFM, vander Velden GPM, Veeman WS, J. Phys. Chem., 92, 1585 (1988)

[7] Goovaerts F, Vansant EF, Pilippaerts J, J. Chem. Soc.-Faraday Trans., 85, 3675 (1989)

[8] Ghosh AK, Kydd RA, Catal. Rev.-Sci. Eng., 27, 539 (1985)

[9] Choudhary VR, Ind. Eng. Chem. Prod. Res. Dev., 16, 12 (1997)

[10] Jaras S, Appl. Catal., 2, 207 (1982)

[11] Biswas J, Maxwell IE, Appl. Catal., 58, 1 (1990)

[12] Weisz PB, Pure Appl. Chem., 52, 2091 (1980)

[13] Corma A, Monton JB, Orchilles AV, Appl. Catal., 16, 59 (1985)

[14] Jacobs PA, Tielen M, Proceedings of the 8th International Congress on Catalysis, Berlin, July 2-6, 1984, Vol. IV, Verlag Chemie, Weinheim, p. 357 (1984)

[15] Hernandez F, Moudafi L, Fajula F, Figueras F, Proceedings of the 8th International Congress on Catalysis, Berlin, July 2-6, 1984, Vol. II, Verlag Chemie, Weinheim, p. 447 (1984)

[16] Nace DM, Ind. Eng. Chem. Prod. Res. Dev., 2, 203 (1970)

[17] Lee KH, Ph.D. Dissertation, Hanyang Univ., Seoul, Korea (1996)

[18] Lee KH, Ha BH, HWAHAK KONGHAK, 34(1), 28 (1996)

[19] Lok BM, Gortsema FP, Messina CA, Rastelli H, Izod TPJ, Am. Chem. Soc. Div. Petrochem. Prepr., 27, 470 (1982)

[20] Abbot J, Guerzoni FN, Appl. Catal., 85, 173 (1992)