알루미늄 함유 티타늄 실리카라이트-1 촉매의 합성 및 특성 연구

고용식; 홍석봉; 김건중; 안화승

Journal of the Korean Industrial and Engineering Chemistry, Vol.9, No.5, 639-647, October, 1998

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알루미늄 함유 티타늄 실리카라이트-1 촉매의 합성 및 특성 연구

Synthesis and Characterization of Al-containing Titanium Silicalite-1 Catalysts

고용식, 홍석봉, 김건중, 안화승

초록

알루미늄 함유 티타늄 실리카라이트-1 ([Al]-TS-1) 촉매를 수열합성하고 실리카원, 알루미늄원, SiO₂/TiO₂ 몰비, 및 숙성처리와 같은 합성인자들의 영향을 살펴 보았다. 제조한 촉매의 구조, 결정의 크기 및 모양은 X-선 회절분석 및 주사전자 현미경으로 살펴보았으며, UV-vis DRS 분석으로 제올라이트 구조 내로 치환된 티타늄의 상태를 확인하였다. [Al]-TS-1의 합성에 있어서는 약 24시간의 숙성과정이 필수적이었으며, Cab-O-Sil을 실리카원으로 사용한 경우가 Ludox 및 TEOS를 사용한 경우보다 더욱 빠른 결정화 속도를 나타내었다. 알루민산나트륨을 알루미늄원으로 사용한 경우가 질산알루미늄을 사용한 경우보다 더 높은 결정화도를 나타내었고 결정화 시간도 단축되었다. 합성한 촉매의 산화/환원 특성은 과산화수소를 산화제로 2-butanol의 액상 산화를 모델 반응으로 선택하여 검토하였다. 산촉매반응으로 톨루엔 알킬화반응을 수행한 결과, [Al]-TS-1의 산세기는 구조내에 존재하는 티타늄에 기인하여 약해졌으며 para-에틸톨루엔의 선택도는 향상됨을 알 수 있었다.

Al-containing titanium silicalite-1 ([Al]-TS-1) catalyst was prepared hydrothermally, and the effects of synthesis parameters such as silica/alumina sources, SiO₂/TiO₂ ratio, and aging treatment were investigated. The structure, crystal size, and shape were examined by XRD and SEM, and the extent of titanium incorporation into the zeolite framework was examined using UV-vis DRS spectroscopy. For [Al]-TS-1 catalyst preperation, aging of ca. 24h was essential, and the faster crystallization rates were achieved with Cab-O-Sil than with Ludox or TEOS as a silica source. In addition, the higher crystallinity and faster crystallization rate were obtained using sodium aluminate as an aluminum source. 2-butanol oxidation using H₂O₂ as an oxidant was carried out to confirm the redox property of the [Al]-TS-1. Acid sites catalyzed toluene alkylation study indicated that lattice titanium species in [Al]-TS-1 weakened the acid strength, and the para-ethyltoluene selectivity was enhanced as a results.

Keywords:[Al]-TS-1;Hydrogen Peroxide;Liquid Oxidation Reaction;Ethyl Toluene

[References]

Hoelderich WF, "Zeolites: Facts, Figures, Futures," P.A. Jacobs and R.A. van Santen (Eds.), Elsevier Science Publishers, Amsterdam, 69 (1989)
Kaeding WW, Young LB, Chu CC, J. Catal., 89, 267 (1984)
Kim JH, Namba S, Yashima T, Zeolites, 11, 59 (1991)
Borade RB, Malgeri AB, Paasada Rao TSR, "New Development in Zeolite Science and Technology," Proc. 7th Int. Zeolite Conf., Tokyo, 851 (1986)
Taramasso M, Perego G, Notari B, U.S. Patent, 4,410,501 (1983)
Huybrechts DRC, Buskens PL, Jacobs PA, "New Development in Selective Oxidation by Heterogeneous Catalysts," P. Ruiz and B. Delmon (Eds.), Elsevier Science Publishers, Amsterdam, 21 (1992)
Tvaruzkova Z, Petras M, Habersberger K, Jiru P, Catal. Lett., 13, 117 (1992)
Thangaraj A, Sivasanker S, Ratnasamy P, J. Catal., 131, 294 (1991)
Nemeth LT, Hyatt EM, Malloy TP, U.S. Patent, 5,233,097 (1993)
Bellussi G, Carati A, Clerici MG, Esposito A, "Preparation of Catalysts V," G. Poncelet, P.A. Jacobs, P. Grange and B. Delmon (Eds.), Elsevier Science Publishers, Amsterdam, 421 (1991)
Thangaraj A, Kumar R, Sivasanker S, Zeolites, 12, 135 (1992)
Reddy JS, Kumar R, Csicsery SM, J. Catal., 145(1), 73 (1994)
Szostak R, "Molecular Sieves: Principles of Synthesis and Identification," Van Nostrand Reinhold, New York, 206 (1989)
Inui H, Yamase O, Nagata H, Fukuda K, Ukawa T, Mayamito A, Meier WM, "Molecular Sieves," Society of the Chemical Industries, London, 10 (1968)
Szostak R, "Molecular Sieves: Principles of Synthesis and Identification," Van Nostrand Reinhold, New York, 119 (1989)
Snel R, Appl. Catal., 11, 271 (1984)
Barrer RM, Chem. Ind., 1203 (1968)
Huybrechts DRC, Buskens PL, Jacobs PA, J. Mol. Catal., 71, 128 (1992)
Zecchina A, Spoto A, Bordiga G, Ferrero S, Petrini A, Leofanti G, Padovan M, "Zeolite Chemistry and Catalysis," Elsevier Science Publishers, Amsterdam, 251 (1991)
Boccuti MR, Rao KM, Zecchina A, Leofanti G, Petrini G, Stud. Surf. Sci. Catal., 48, 133 (1989)
Khouw CB, Davis ME, J. Catal., 151(1), 77 (1995)
Topsoe NY, Pederson K, Deroune EG, J. Catal., 70, 41 (1981)
Chen NC, Chu SJ, Chang NS, Chen PY, Chung TK, Chen LY, "Catalysis," Elsevier Science Publishers, Amsterdam, 253 (1987)

[Referenced By]

[1] Hoelderich WF, "Zeolites: Facts, Figures, Futures," P.A. Jacobs and R.A. van Santen (Eds.), Elsevier Science Publishers, Amsterdam, 69 (1989)

[2] Kaeding WW, Young LB, Chu CC, J. Catal., 89, 267 (1984)

[3] Kim JH, Namba S, Yashima T, Zeolites, 11, 59 (1991)

[4] Borade RB, Malgeri AB, Paasada Rao TSR, "New Development in Zeolite Science and Technology," Proc. 7th Int. Zeolite Conf., Tokyo, 851 (1986)

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

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

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

[8] Thangaraj A, Sivasanker S, Ratnasamy P, J. Catal., 131, 294 (1991)

[9] Nemeth LT, Hyatt EM, Malloy TP, U.S. Patent, 5,233,097 (1993)

[10] Bellussi G, Carati A, Clerici MG, Esposito A, "Preparation of Catalysts V," G. Poncelet, P.A. Jacobs, P. Grange and B. Delmon (Eds.), Elsevier Science Publishers, Amsterdam, 421 (1991)

[11] Thangaraj A, Kumar R, Sivasanker S, Zeolites, 12, 135 (1992)

[12] Reddy JS, Kumar R, Csicsery SM, J. Catal., 145(1), 73 (1994)

[13] Szostak R, "Molecular Sieves: Principles of Synthesis and Identification," Van Nostrand Reinhold, New York, 206 (1989)

[14] Inui H, Yamase O, Nagata H, Fukuda K, Ukawa T, Mayamito A, Meier WM, "Molecular Sieves," Society of the Chemical Industries, London, 10 (1968)

[15] Szostak R, "Molecular Sieves: Principles of Synthesis and Identification," Van Nostrand Reinhold, New York, 119 (1989)

[16] Snel R, Appl. Catal., 11, 271 (1984)

[17] Barrer RM, Chem. Ind., 1203 (1968)

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

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

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

[21] Khouw CB, Davis ME, J. Catal., 151(1), 77 (1995)

[22] Topsoe NY, Pederson K, Deroune EG, J. Catal., 70, 41 (1981)

[23] Chen NC, Chu SJ, Chang NS, Chen PY, Chung TK, Chen LY, "Catalysis," Elsevier Science Publishers, Amsterdam, 253 (1987)