Hierarchical AlSBA-15–zeolite materials were utilized as a supports for preparing hydroisomerization catalysts. Detailed consideration was given to: (i) the effect of the zeolite type introduced into AlSBA-15–zeolite composites (where zeolite is β, mordenite or ZSM-5) as well as (ii) the promotion effect of Pd addition. The composites showed higher activity in isomerization as compared to Pt/AlSBA-15. The enhanced isomerization efficiency were explained by the appropriate metallic and acidic function as well as suitable transport properties. The modification of the hydrogenating function by Pd incorporation increases the hydroisomerization efficiency of Pt-Pd/AlSBA-15–β catalyst. Over bimetallic Pt-Pd/AlSBA-15–β, the high yields of isomers (68 wt%) with respect to 50 wt% for a control catalyst. The most promising Pt-Pd/AlSBA-15–β catalyst allows to improve research octane number from 0 to the 74 value.
NiMo catalysts supported on mesoporous MCM-41 type materials shaped with binder were tested for activity in the hydrodesulfurization of 4,6-dimethyldibenzothiophene (4,6-DMDBT) and the diesel fuel fraction (0.92 wt% of sulfur). The aim of the investigation was to evaluate the effect of ion exchange with protons of Al- or Ti-substituted MCM-41 mesoporous supports. The subjected catalytic systems were NiMo/HAlMCM-41 and NiMo/HTiMCM-41, and for comparison purposes NiMo/AlMCM-41 and NiMo/TiMCM-41. The samples were characterized by N2 sorption (at 77 K), XRD, TEM, XPS, SEM and Py–IR. It was found that the functionalization of AlMCM-41 and TiMCM-41 with protons increased the conversion of 4,6-DMDBT and the pseudo-first-order rate constant. Correspondingly, 4,6-DMDBT HDS reactions over the NiMo/HTiMCM-41 catalyst proceeded to a similar extent via hydrogenation and direct desulfurization, whereas over the NiMo/HAlMCM-41 they proceeded mainly via direct desulfurization. Furthermore, the ion-exchanged catalysts displayed two-fold higher efficiency in direct desulfurization than their non-modified counterparts. The NiMo/HTiMCM-41 catalyst exhibited the highest catalytic efficiency in the HDS of 4,6-DMDBT and the diesel oil fraction. The high activity of the NiMo/HTiMCM-41 catalyst is mainly attributed to its appropriate acidity, as well as the metal–support interaction providing both the high dispersion of the active phase and the desirable multilayered stacking morphology of the active phase slabs.
Physicochemical and catalytic properties of H/ZSM-5 and Ni,H/ZSM-5 along with Ni,H/ZSM-5–Al2O3 (1 : 1) systems were examined. The systems with a binder were prepared by two different methods of mixing zeolite with aluminum hydroxide. The samples were characterized by N2 sorption (at 77 K), X-ray diffraction, 27Al magic-angle spinning (MAS) NMR spectroscopy, temperature-programmed desorption of ammonia and adsorption of pyridine. Preparation of the zeolite catalyst with aluminium hydroxide was made by two methods: (1) mixing of powders and (2) combining appropriate pastes. Regardless of the method used for mixing there was no blocking of zeolite channels by aluminum oxide. The method of mixing zeolite with aluminium hydroxide powders promotes migration of aluminum from aluminum hydroxide/oxide to the zeolite framework. The results of n-hexane conversion showed that with Ni,H/ZSM-5 a slightly lower conversion than with H/ZSM-5 catalyst was observed that can be explained by a reduced yield of cracking products. Ni,H/ZSM-5–Al2O3 (1 : 1) catalytic systems were insignificantly less efficient in n-hexane transformation than alumina free samples but at the same time they were less selective towards hydrocarbons with boiling temperatures higher than this of n-hexane, precursors of carbonaceous deposits.