Aromatization of n-hexane over zinc-modified ZSM-5 zeolites was investigated. It was shown that incorporation of zinc by ion exchange into cationic positions of NH4-ZSM-5 zeolite causes acid-site strength redistribution and generation of new relatively strong Lewis acid sites in zeolite increasing the selectivity of n-hexane aromatization in comparison with the parent NH4-ZSM-5 zeolite. Simultaneous presence of Lewis and Broensted acid sites in ZSM-5 zeolite does not affect the strength of Broensted acid sites in zeolite. For the activity/selectivity of aromatization of n-hexane on Zn-modified ZSM-5 zeolites, the amount of Zn and its localization in the cationic positions are decisive. The reaction of n-hexane can be also initiated by the Zn species alone in the cationic positions. ZnO species alone as an extraframework phase was found inactive in the catalyst for aromatization of n-hexane. The influence of ZnO addition on the performance of pure ammonium forms of ZSM-5 zeolites in n-hexane conversion is a result of partial migration of zinc into cationic positions of zeolite by solid-state ion exchange.
Adsorption properties determined by physical adsorption of nitrogen for a series of ZSM-5 zeolite samples with various Si/Al ratios and different crystal size were compared. In addition to the BET method, the t-plot method was used to determine the microporosity of samples. Very small crystals of ZSM-5 zeolites, generally below 1 μm, with Si/Al ratio between 14 and 21 exhibit adsorption isotherms typical for purely microporous solids. Samples with Si/Al ratios larger than (about) 95 show low-pressure steps and hysteresis loops and, depending on crystal morphology, also high-pressure hysteresis loops. The low-pressure steps were associated with steps on t-plots which showed two linear parts. Small increase of adsorption up to relative pressure 0.2 is characteristic for samples with Si/Al ratios between 25 and 50.
Abs~aetAromatization of n-hexane and disproportionation of toluene over H-ZSM-5 and Zn-ZSM-5 prepared by ion-exchange with aqueous solution has been studied.Introduction of zinc into ZSM-5 does not si~ificantly affect the total acidity determined by TPDA, but causes redistribution in the strength and type of acid sites. From the results it was concluded that the first step in the aromatization of n-hexane on Zn-ZSM-5 is probably the formation of carbonium ions by hydride abstraction with acid sites in zeolite and that Zn species have a decisive role in oligomerization of cracking products and in dehydrogenation of cyclic intermediates.
The sorption properties of samples of H-ZSM-5 zeolite and their forms modified with P, B and Mg were determined by the physical adsorption of nitrogen and evaluated by BET isotherm and t-plot methods. The diffusivities of the samples were measured using a new flow gravimetric method involving the sorption of p- and o-xylenes. The BET specific surface area decreased from 358 m2/g to 35–90 m2/g mainly because of a decrease in micropore volume as determined by the t-plot method. The rate of sorption of p-xylene on all the samples investigated followed Fick's second law of diffusion, leading to an effective diffusivity of ca. 1.7 × 10−11 m2/s, irrespective of whether the H-form or the modified forms were investigated. The sorption isotherms for o-xylene showed some unusual steps. Values for the effective diffusivities decreased from 2.6 × 10−12 m2/s for the H-form to 2.0–2.3 × 10−12 m2/s for the modified forms. The equilibrium concentration of o-xylene at P/P0 = 0.1 was only 0.38–0.68 mol/unit cell, while that of p-xylene was 4.40–5.98 mol/unit cell.
Evaluation of microporosity by t-plot method of a series of NH4Y samples ~abilized by different hydrothermal treatments with subsequent HCI extraction shows the strong influence of stabilizing conditions on the solubility of extrafi'amework aluminhma species created.
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