van Miltenburg, A., Pawlesa, J., Bouzga, A. M., Žilková, N., Čejka, J., and Stöcker, M.
Modification of HMCM-22 zeolite by alkaline treatment was investigated by various characterization techniques and in toluene disproportionation and alkylation with isopropyl alcohol. This ‘desilication’ process led for mild alkaline concentrations (~0.10–0.20 M NaOH at 323 K for 45 min) to the partial destruction of the zeolite framework, but also to the formation of additional mesoporosity. Furthermore, the accessibility/availability of Lewis acid sites, investigated by d3-acetonitrile and pyridine adsorption using FTIR spectroscopy, increased for these mild alkaline treatments, while the Brønsted acidity decreased. Higher alkaline concentrations (up to 0.50 M NaOH) led to a too severe framework and pore destruction and a decrease of both the Lewis and Brønsted acid site concentration. Decomposition and deconvolution of 29Si MAS-NMR spectra confirmed the Si extraction and partial framework destruction, since more Q3 SiOH groups were formed at the expense of the Q4 T-atoms in the framework. Furthermore, the T6 and T7 Si-atoms were preferentially extracted, which would indicate that an interconnection between the intralayer and the interlayer and/or outer surface is formed. The toluene conversion in its disproportionation reaction increased for the mildly treated sample, while the selectivity to xylene isomers (and cymene and n-propyltoluene isomers in the alkylation reaction with isopropyl alcohol) was similar to the thermodynamic equilibrium, suggesting that the reaction primarily occurs at outer surface cups of the HMCM-22 zeolite. [ABSTRACT FROM AUTHOR]