Synthesis and Crystallization Process of Polymorph A Enriched Beta Zeolite in the Presence of Two New Quaternary Ammonium Bases†

doi:10.7503/cjcu20140340

Abstract

Abstract:

In the presence of trimethyl-cyclohexyl ammonium hydroxide or ethyl-dimethyl-cyclohexyl ammo-nium hydroxide, chiral polymorph A enriched Beta zeolites were synthesized. The products were further cha-racterized by X-ray powder diffraction(XRD), scanning electron microscope(SEM), ²⁹Si magic-angle spinning nuclear magnetic resonance(²⁹Si MAS NMR) and nitrogen adsorption-desorption analyses. The crystallization process of the polymorph A enriched Beta zeolite in the presence of trimethyl-cyclohexyl ammonium hydroxide and the influence of the water content in the initial mixture on the enrichment of the polymorph A were investigated. The results showed that the appropriate water content in the initial mixture was critical for the formation of polymorph A enriched Beta zeolite, the enrichment of chiral polymorph A occurred in the early stage of crystallization and the degree of the enrichment of polymorph A did not change during the crystallization.

Key words: Beta zeolite, Polymorph A, Chiral zeolite

CLC Number:

O611.4

TrendMD:

GUO Wen, YAN Wenfu, XU Ruren, WANG Yongrui, MU Xuhong. Synthesis and Crystallization Process of Polymorph A Enriched Beta Zeolite in the Presence of Two New Quaternary Ammonium Bases^†[J]. Chem. J. Chinese Universities, 2014, 35(7): 1363.

Figures/Tables 7

Fig.1 Powder XRD patterns of polymorph A enriched Beta zeolites a. SDA=ethyl-dimethyl-cyclohexyl ammonium hydroxide; b. SDA=trimethyl-cyclohexyl ammonium hydroxide. * Denotes the characteristic diffraction peaks of polymorph A.

Fig.2 Simulated powder XRD patterns of the Beta zeolite with different polymorph ratios of A/B and the experimental powder XRD patterns of the polymorph A enriched Beta zeolite and the normal Beta zeolite a. SDA=ethyl-dimethyl-cyclohexyl ammonium hydroxide; b. SDA=trimethyl-cyclohexyl ammonium hydroxide.

Fig.3 As-synthesized polymorph A enriched Beta zeolite with truncated bipyramidal morphology(A, B) and cubic morphology(C, D) SDA=trimethyl-cyclohexyl ammonium hydroxide.

Fig.4 29Si MAS NMR spectra of polymorph A enriched Beta zeolite SDA=trimethyl-cyclohexyl ammonium hydroxide.

Fig.5 Nitrogen adsorption-desorption isotherms of calcined polymorph A enriched Beta zeolite SDA=trimethyl-cyclohexyl ammonium hydroxide.

Fig.6 XRD patterns of the samples from the gels dried for different time at 80 ℃ SDA=trimethyl-cyclohexyl ammonium hydroxide. Drying treatment time/h: a. 120; b. 168; c. 216; d. 288.

Fig.7 XRD patterns of the samples isolated throughout the hydrothermal treatment period for polymorph A enriched Beta zeolite Hydrothermal treatment time/h: a. 24; b. 48; c. 72; d. 96; e. 120; f. 168; g. 216.

References 29

[1]	Kulprathipanja S.(Ed.), Zeolites in Industrial Separation and Catalysis, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, 2010
[2]	Cejka J., Corma A., Zones S., (Eds.), Zeolites and Catalysis: Synthesis, Reactions and Applications, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, 2010
[3]	Broach R. W., Kirchner R. M., Micropor. Mesopor. Mater., 2011, 143(2/3), 398—400
[4]	Rajic' N., Logar N. Z., Kaucic V., Zeolites, 1995, 15, 672—678
[5]	Song X. W., Li Y., Lin. G., Wang Z. P., Yu J. H., Xu R. R., Angew. Chem. Int. Ed., 2009, 48(2), 314—317
[6]	Sun J. L., Díaz-Cabanas M. J., Moliner M., Zhang D. L., Li M. R., Zou X. D., Nature, 2009, 458(7242), 1154—1157
[7]	Tang L. Q., Shi L., Bonneau C., Sun J. L., Yue H. J., Ojuva A., Lee B. L., Kritikos M., Bell R. G., Bacsik Z., Mink J., Zou X. D., Nat. Mater., 2008, 7(5), 381—385
[8]	Chen N. Y., Recent Advances in Shape-selective Catalysis and Its Industrial Applications in Shape-selective Catalysis, ACS Symposium SeriesAmerican Chemical Society, Washington, 1999, 738, 39—63
[9]	Cantín Á., Corma A., Díaz-Cabanas M. J., Jordá J. L., Moliner M., Rey F., Angew. Chem. Int. Ed., 2006, 45(47), 8013—8015
[10]	Wadlinger R. L., Kerr G. T., Rosinski E. J., Catalytic Composition of a Crystalline Zeolite, US3308069A,196703-07
[11]	Newsam J. M., Treacy M. M. J., Koetsier W. T., Degruyter C. B., Proc. R. Soc. London, Ser. A,1988, 420(1859), 375—405
[12]	Higgins J. B., Lapierre R. B., Schlenker J. L., Rohrman A. C., Wood J. D., Kerr G. T., Rohrbaugh W. J., Zeolites,1988, 8(6), 446—452
[13]	Treacy M. M. J., Newsam J. M., Deem M. W., Proc. R. Soc. London, Ser., 1991, 433(1889), 499—520
[14]	Liu Z., Ohsuna T., Terasaki O., Camblor M. A., Diaz-Cabanas M. J., Hiraga K., J. Am. Chem. Soc., 2001, 123(22), 5370—5371
[15]	Corma A., Navarro M. T., Rey F., Rius J., Valencia S., Angew. Chem. Int. Ed., 2001, 40(12), 2277—2280
[16]	Kadgaonkar M. D., Kasture M. W., Bhange D. S., Joshi P. N., Ramaswamy V., Kumar R., Micropor. Mesopor. Mater., 2007, 101(1/2), 108—114
[17]	Kadgaonkar M. D., Kasture M. W., Bhange D. S., Joshi P. N., Ramaswamy V., Gupta N. M., Kumar R., Micropor. Mesopor. Mater., 2007, 105(1/2), 82—88
[18]	Corma A., Moliner M., Cantin A., Diaz-Cabanas M. J., Lorda J. L., Zhang D. L., SunJ. L., Jansson K., Hovmoller S., Zou X. D., Chem. Mater., 2008, 20(9), 3218—3223
[19]	Taborda F., Willhammar T., Wang Z., Montes C., Zou X. D., Micropor. Mesopor. Mater., 2011, 143(1), 196—205
[20]	Taborda F., Wang Z. Y., Willhammar T., Montes C., Zou X. D., Micropor. Mesopor. Mater., 2012, 150(1), 38—46
[21]	Davis M. E., Lobo R. F., Chem. Mater., 1992, 4(4), 756—768
[22]	Tong M. Q., Yan W. F., Yu J. H.,Xu R. R., Chem. J. Chinese Universities, 2013, 34(3),494—498(童明全, 闫文付, 于吉红, 徐如人. 高等学校化学学报, 2013, 34(3), 494—498)
[23]	Yan W. F., Tong M. Q., Yu J. H., Xu R. R., The Preparation of Chiral Polymorph A Enriched β Zeolite, CN102190314A, 2011-09-21(闫文付, 童明全, 于吉红, 徐如人. 手性多形体A过量的β沸石分子筛的制备方法, CN102190314A, 2011-09-21)
[24]	Camblor M.A., Corma A., Valencia S.,Chem. Commun., 1996, (20), 2365—2366
[25]	Takagi Y., Komatsu T., Kitabata Y., Micropor. Mesopor. Mater., 2008, 109(1—3), 567—576
[26]	Tian D. Y., Yan W. F., Cao X. J., Yu J. H., Xu R. R., Chem. Mater., 2008, 20(6), 2160—2164
[27]	Harris R. K., Newman R. H., J. Chem. Soc., Faraday Trans. 2, 1977, 73(7), 1204—1215
[28]	Wright P. A., Zhou W. Z., Pérez-Pariente J., Arranz M., J. Am. Chem. Soc., 2005, 127(2), 494—495
[29]	Camblor M. A., Corma A., Valencia S., J. Mater. Chem., 1998, 8(9), 2137—2145
	(Ed.: F, K, M)