Titanium silicalite I 촉매의 제조 및 n-hexane의 액상 산화반응 특성

김정규; 고용식; 김태진; 안화승

HWAHAK KONGHAK, Vol.33, No.4, 511-520, August, 1995

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Titanium silicalite I 촉매의 제조 및 n-hexane의 액상 산화반응 특성

Preparation of a Titanium Silicalite I Catalyst and Its Liquid Phase n-Hexane Oxidation Characteristics

김정규, 고용식, 김태진, 안화승

초록

티타늄 실리카라이트 I 촉매를 다양한 방법으로 수열합성하고 제반 합성인자들의 촉매입자 형태에 대한 영향을 구체적으로 검토하였다. XRD, SEM, IR, ²⁹Si MAS NMR, UV-VIS DRS 및EXAFS 분석을 통하여 물리화학적 특성를 살펴보았으며, 과산화수소를 산화제로 n-헥산의 액상 산화반응을 수행하여 제조한 촉매의 반응특성을 고찰하였다. 적당량의 TPAOH, 알콕사이드 실리카, 수화과정 중의 연속적인 물 보충, 그리고 빠른 수열합성 반응기의 가열이 작은 제올라이트 결정을 얻느데 유리하였다. n-핵산의 산화반응에서는 2,3-알콜과 함께 2,3-케톤이 연속적인 산화 경로를 통하여 생성되었고, 2-헥산올이 3-헥산올 보다 빠르게 산화되었다. 메탄올과 아세톤이 용매로서 우수하였고, 적당량의 용매하에서 과산화수소/n-헥산의 물비가 2 정도에서 반응이 우수하였다.

Titanium silicalite 1 catalysts were prepared using various hydrothermal synthesis methods and the effects of synthesis parameters on the catalyst morphology were investigated. XRD, SEM, IR, 29Si MAS NMR, UV-VIS DRS, and EXAFS analysis were then performed to evaluate its physico-chemical properties. For its catalytic property study, liquid phase n-hexane oxidation using H2O2 as oxidant was carried out. It was established that an adequate amount of TPAOH, alkoxide silicon source, continuous water replenishment during the hydrolysis process and fast heating of the hydrothemal reactor vessel are necessary in order to obtain small zeolite crystals. In the n-hexane oxidation, 2,3-hexanol and 2,3-hexanone were produced via successive oxidation sequences, and 2-hexanol was found to be more quickly oxidized to ketone than 3-hexanol. Methanol and acetone were superior as a solvent, and under non-excess solvent condition, n-hexane/H₂O₂ mole ratio of 2 was found adequate for the better conversion.

[References]

Taramasso M, Perego G, Notari B, U.S. Patent, 4,410,501 (1983)
Thangaraj A, Kumar R, Ratnasamy P, Appl. Catal., 57, L1 (1990)
Thangaraj A, Kumar R, Ratnasamy P, J. Catal., 131, 294 (1991)
Tatsumi T, Nakamura M, Taminaga H, "Catalytic Science Technology," Vol. 1, S. Yoshida et al. (Editors), Kodansha, Tokyo, 213 (1991)
Clerici MG, Bellussi G, Romano U, J. Catal., 129, 159 (1991)
Tvaruzkova Z, Habersberger K, Zilkova N, Jiru P, Appl. Catal. A: Gen., 79, 105 (1991)
Thangaraj A, Sivasanker S, Ratnasamy P, J. Catal., 131, 394 (1991)
Tvaruzkova Z, Petras M, Habersberger K, Jiru P, Catal. Lett., 13, 117 (1992)
Niwa M, Yamazaki K, Murakami Y, Chem. Lett., 441 (1989)
Huybrechts DRC, Buskens PL, Jacobs PA, "New Developments in Selective Oxidation by Heterogeneous Catalysts," Ruiz, P. and Delmon, B.(Editors), Elsevier Science Publishers, Amsterdam, 21 (1992)
Padovan M, Genoni F, Leofanti G, Petrini G, Trezza G, Zecchina A, "Preparation of Catalysts V," Poncelet, G. et al. (Editors), Elsevier Science Publishers, Amsterdam, 431 (1991)
Skeels GW, Planigan EM, "Zeolite Synthesis," Occelli, M.L., and Robson, H.E. (Editors), ACS, Washington D.C., 421 (1989)
Huybrechts DRC, Vaesen I, Li HX, Jacobs PA, Catal. Lett., 8, 237 (1991)
Notari B, "Structure-Activity and Selectivity Relationships in Heterogeneous Catalysis," Grasselli, R.K. and Sleight, A.W. (Editors), Elsevier Science Publishers, Amsterdam, 243 (1991)
Huybrechts DRC, Buskens PL, Jacobs PA, J. Mol. Catal., 71, 128 (1992)
Bellussi G, Fattore V, "Zeolite Chemistry and Catalysis," Jacobs, P.A. et al. (editors), Elsevier Science Publishers, Amsterdam, 78 (1991)
Geobaldo F, Bordiga S, Zeocchina A, Giamello E, Leofanti G, Petrini G, Catal. Lett., 16, 109 (1992)
Kraushaar B, Van Hooff JHC, Catal. Lett., 1, 81 (1988)
Boccuti MR, Rao KM, Zecchina A, Leofanti G, Petrini G, Stud. Surf. Sci. Catal., 48, 133 (1989)
Zecchina A, Spoto G, Bordiga S, Ferrero A, Petrini G, Leofanti G, Padovan M, "Zeolite Chemistry and Catalysis," Elsevier Science Publishers, Amsterdam, 251 (1991)
Tangaraj A, Eapen MJ, Sivasanker S, Ratnasamy P, Zeolites, 12, 943 (1992)
VanderPol AJHP, VanHooff JHC, Appl. Catal., 92, 93 (1992)
Perego G, Bellussi G, Corno C, Taramasso M, Buonomo F, Esposito A, "Proceedings of the 7th Int. Zeolite Conference," Tokyo, 129 (1986)
Clerici MG, Appl. Catal., 68, 249 (1991)
Schultz E, Ferrini C, Prins R, Catal. Lett., 221 (1992)
Behrens P, Felsche J, Vetter S, Schults-Ekloff G, Jaeger NI, Nieman W, J. Chem. Soc.-Chem. Commun., 678 (1991)
Tatsumi T, Nakamura M, Yuasa K, Tominaga H, Catal. Lett., 10, 259 (1991)

[Referenced By]

[1] Taramasso M, Perego G, Notari B, U.S. Patent, 4,410,501 (1983)

[2] Thangaraj A, Kumar R, Ratnasamy P, Appl. Catal., 57, L1 (1990)

[3] Thangaraj A, Kumar R, Ratnasamy P, J. Catal., 131, 294 (1991)

[4] Tatsumi T, Nakamura M, Taminaga H, "Catalytic Science Technology," Vol. 1, S. Yoshida et al. (Editors), Kodansha, Tokyo, 213 (1991)

[5] Clerici MG, Bellussi G, Romano U, J. Catal., 129, 159 (1991)

[6] Tvaruzkova Z, Habersberger K, Zilkova N, Jiru P, Appl. Catal. A: Gen., 79, 105 (1991)

[7] Thangaraj A, Sivasanker S, Ratnasamy P, J. Catal., 131, 394 (1991)

[8] Tvaruzkova Z, Petras M, Habersberger K, Jiru P, Catal. Lett., 13, 117 (1992)

[9] Niwa M, Yamazaki K, Murakami Y, Chem. Lett., 441 (1989)

[10] Huybrechts DRC, Buskens PL, Jacobs PA, "New Developments in Selective Oxidation by Heterogeneous Catalysts," Ruiz, P. and Delmon, B.(Editors), Elsevier Science Publishers, Amsterdam, 21 (1992)

[11] Padovan M, Genoni F, Leofanti G, Petrini G, Trezza G, Zecchina A, "Preparation of Catalysts V," Poncelet, G. et al. (Editors), Elsevier Science Publishers, Amsterdam, 431 (1991)

[12] Skeels GW, Planigan EM, "Zeolite Synthesis," Occelli, M.L., and Robson, H.E. (Editors), ACS, Washington D.C., 421 (1989)

[13] Huybrechts DRC, Vaesen I, Li HX, Jacobs PA, Catal. Lett., 8, 237 (1991)

[14] Notari B, "Structure-Activity and Selectivity Relationships in Heterogeneous Catalysis," Grasselli, R.K. and Sleight, A.W. (Editors), Elsevier Science Publishers, Amsterdam, 243 (1991)

[15] Huybrechts DRC, Buskens PL, Jacobs PA, J. Mol. Catal., 71, 128 (1992)

[16] Bellussi G, Fattore V, "Zeolite Chemistry and Catalysis," Jacobs, P.A. et al. (editors), Elsevier Science Publishers, Amsterdam, 78 (1991)

[17] Geobaldo F, Bordiga S, Zeocchina A, Giamello E, Leofanti G, Petrini G, Catal. Lett., 16, 109 (1992)

[18] Kraushaar B, Van Hooff JHC, Catal. Lett., 1, 81 (1988)

[19] Boccuti MR, Rao KM, Zecchina A, Leofanti G, Petrini G, Stud. Surf. Sci. Catal., 48, 133 (1989)

[20] Zecchina A, Spoto G, Bordiga S, Ferrero A, Petrini G, Leofanti G, Padovan M, "Zeolite Chemistry and Catalysis," Elsevier Science Publishers, Amsterdam, 251 (1991)

[21] Tangaraj A, Eapen MJ, Sivasanker S, Ratnasamy P, Zeolites, 12, 943 (1992)

[22] VanderPol AJHP, VanHooff JHC, Appl. Catal., 92, 93 (1992)

[23] Perego G, Bellussi G, Corno C, Taramasso M, Buonomo F, Esposito A, "Proceedings of the 7th Int. Zeolite Conference," Tokyo, 129 (1986)

[24] Clerici MG, Appl. Catal., 68, 249 (1991)

[25] Schultz E, Ferrini C, Prins R, Catal. Lett., 221 (1992)

[26] Behrens P, Felsche J, Vetter S, Schults-Ekloff G, Jaeger NI, Nieman W, J. Chem. Soc.-Chem. Commun., 678 (1991)

[27] Tatsumi T, Nakamura M, Yuasa K, Tominaga H, Catal. Lett., 10, 259 (1991)