Abstract
Zeolites β, Y and mordenite are modified with organic and inorganic cupric salts using a liquid phase deposit method, and their catalytic performance and the dispersion states of copper on the zeolites are characterized by using naphthalene isopropylation reaction and 129Xe NMR, respectively. The experimental results indicate that naphthalene conversion on the catalysts decreases in the order of HY>H β >HMCM-22>HM. The performance of the zeolites has been largely improved after the modification. Naphthalene conversion rate reaches 97% and 60%, and ββ ∼-selectivity 66% and 70% for CuHY and CuH β, respectively. Metal surfactants, such as hexanoic and octanoic copper, play a positive role in modifying the external surface and pore structure of zeolitesβ and Y. 129 Xe NMR results demonstrate that the two types of the pore channels in CuH β are unimpeded for xenon atoms, and there is a fast chemical exchange between two xenon atoms located in different adsorption sites; Cu2+ ion is a strong adsorption site for xenon atoms and it is a strong active center as well; Cu2+ and Cu++ ions coexist in channels of zeolites, which are in agreement with the conclusions from ab iniiio quantum chemical calculations.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Frank, H. -G., Stadelhofer, J. W., Industrial Aromatic Chemistry, Berlin, Heidelberg, New York, London, Paris, Tokyo: Springer-Verlag, 1987, 317–329.
Olah, G. A., Olah, J. A., Aromatic substitution, XXXII. Stannic and aluminum chloride catalyzed Friedel-Crafts alkylation of naphthalene with halides, Differentiation of kinetically and thermodynamically controlled product compositions and the isomerization of alkylnaphthalene, J. Am. Chem. Soc, 1976, 98: 1839–1842.
Moreau, P., Finiels, A., Geneste, P. et al., Selective isopropylation of naphthalene over zeolites, J. Catal., 1992, 136: 487–492.
Horsley, J. A., Fellmann, J. D., Derouane, E. G. et al., Computer-assisted screening of zeolite catalysts for the selective isopropylation of naphthalene, J. Catal., 1994, 147: 231–240.
Schmitz, A. D., Song, C., Shape-selective isopropylation of naphthalene over dealuminated mordenites, increasing β-substitution selectivity by adding water, Catal. Letter, 1996, 40: 59–65.
Zhang, M. J., Chen, S. Y., Shen, S. D. et al., Catalytic performance of zeolite catalysts for shape selective isopropylation of naphthalene, Chin. J. Catal., 2000, 2: 145–148.
Zhang, M. J., Chen, S. Y., Sun, Y. H. et al., Shape selective isopropylation of coal tar naphthalene over molecular sieve catalysts, in Proceedings for Coal Science in 21st Century, Vol II (eds. Li, B. Q., Liu, Z. Y.), Taiyuan: Shanxi Sei. Technol. Press, 1999, 1017–1020.
Liu, Z., Moreau, P., Fajula, F., Liquid phase selective alkylation of naphthalene with t-butanol over large pore zeolites, Appl. Catal., 1997, 159: 305–316.
Wang, H., Zhang, H., Liu, Z. M., Shape-selective synthesis of 2,6-di(tert-butyl)naphthalene over HY zeolite, Chin. J. Catal., 2002, 2: 137–139.
Armengol, E., Corma, A., Garcia, H. et al., Acid zeolites as catalysts in organic reactions, tert-butylation of anthracene, naphthalene and thianthrene, Appl. Catal. A, 1997, 149: 411–423.
Chen, F., Deng, F., Ye, C. H. et al., Preferential occupation of Xenon in MCM-22 as revealed by 129Xe NMR, J. Phys. Chem. B, 2001, 105: 9426–9432.
Benslama, R., Fraissard, J., Albizane, A. et al., An example of the technique of studying absorbed xenon by 129Xe n.m.r.: Approximate determination of the internal void space of zeolite beta, Zeolites, 1988, 8: 196–198.
Sayle, D. C., Richard, C., Catlow, A. et al., A refined model for the active site within the NO decomposition catalyst, Cu-ZSM-5, Micropor. Mesopor. Mater., 1998, 20: 259–267.
Gedeon, A., Bonardet, J. L., Fraissard, J. et al., Application of 129Xe nuclear magnetic resonance to the study of Cu-Y zeolites: dehydration andredox effects, Solid State Nuclear Resonance, 1995, 5: 201–212.
Author information
Authors and Affiliations
Corresponding authors
Rights and permissions
About this article
Cite this article
Mingjin, Z., Anmin, Z., Feng, D. et al. Surface chemical modification of zeolites and their catalytic performance for naphthalene alkylation. Sc. China Ser. B-Chem. 46, 216–223 (2003). https://doi.org/10.1360/03yb9030
Received:
Issue Date:
DOI: https://doi.org/10.1360/03yb9030