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Metal-zeolite composite catalysts have found numerous applications in adsorption, gas separation, petroleum refining and chemical industry. The key issue in the design of these catalysts is localization of the metal within the zeolite structure. This paper focuses on a new approach to the synthesis of nickel-zeolite composite catalysts selectively containing metal nanoparticles inside the zeolite pores. In the catalysts prepared by conventional impregnation, metal particles from the external surface of the zeolites were selectively removed by extraction with bulky polymer molecules of poly-4-styrenesulfonic acid. The method is particularly suitable for the ZSM-5 zeolite with relatively narrow micropores. The nickel zeolite catalysts were tested in hydrogenation of toluene and 1,3,5-tri-isopropyl benzene (TIPB). The removal of nickel particles from the zeolite external surface leads to a considerable decrease in the hydrogenation rate of the bulky TIPB molecules, while toluene hydrogenation rate was affected to a much lesser extent and was almost proportional to the nickel content. The proposed methodology can be extended to other types of microporous catalysts. [ABSTRACT FROM AUTHOR]

Cobalt distribution between the external surface and micropores and acidity of the large pore BEA zeolite were controlled by choosing the sequence of impregnation and ion exchange procedures. Higher concentration of ion exchangeable cobalt was observed in the catalyst prepared by ion‐exchange of the zeolite proton form. The presence of Na+ instead of H+ ions in the exchange positions of zeolite favored deposition of cobalt on the external surface. The acid sites in the zeolite micropores can be then restored by subsequent ion exchange of sodium with ammonium nitrate and calcination. The catalytic performance of the cobalt zeolite catalysts prepared using different impregnation and ion exchange procedures was tested in the Fischer‐Tropsch synthesis. Higher reaction rates were observed over the catalysts, which did not contain cobalt ions in the cation sites of the zeolite. Lower methane selectivity, higher selectivity to long chain hydrocarbons and high fraction of isomerized products are observed when cobalt species are located on the zeolite outer surface and acid sites inside the BEA zeolite micropores. Ion launch sequence: Impregnation and ion exchange sequences control metal localization, acidity, diffusion and performance of cobalt‐BEA catalysts for Fischer‐Tropsch synthesis [ABSTRACT FROM AUTHOR]

Abstract: A series of nanosized ZSM‐5 samples was synthesized at 170, 150, 120, and 100 °C. Experimental data show that the decrease of crystallization temperature leads to significant changes in zeolite properties. Crystals synthesized at 100 °C exhibit many framework defects with lower acid‐site density, strength, and a larger external surface area. The selectivity to light olefins and the propylene‐to‐ethylene ratio increases as the crystallization temperature decreases. A propylene‐to‐ethylene ratio of above 6 with the highest selectivity to propylene of 53 % was obtained over ZSM‐5 catalyst prepared at 100 °C. The stability of the nanosized zeolite in methanol to olefins (MTO) was also improved compared to the industrial sample with a similar Si/Al ratio. This catalytic performance is a result of the decrease in the acid‐site density, strength, and the crystals’ size, providing a shorter diffusion path and larger external surface area. The presence of structural defects and a different external surface in the crystals has been shown to play an important role in the MTO catalyst performance. [ABSTRACT FROM AUTHOR]

This study focuses on the effects of the localization of Co species, zeolite structure, and acidity on the performance of Co bifunctional catalysts promoted with Pt for the direct synthesis of iso-paraffins from syngas. ZSM-5, MOR, and BEA were chosen as zeolites with different structures and pore diameters. The catalysts were prepared either by incipient wetness impregnation or by the mechanical mixing of the zeolite with a conventional silica-supported Co catalyst. The increase in the pore size and open character of the zeolite structure from ZSM-5 to BEA resulted in a higher fraction of Co located inside the pores of the catalysts prepared by impregnation. The catalytic performance was affected strongly by the zeolite acidity, pore structure, and Co distribution between the pores and the external surface. The selectivity to short-chain iso-paraffins is affected principally by the zeolite acidity, whereas the selectivity to long-chain branched hydrocarbons mostly depends on steric effects. [ABSTRACT FROM AUTHOR]

• We propose here the synthesis of dihydroxybenenzes by isomerization over Pt/ZSM-5. • Catalyst converts catechol and hydroquinone to each other with selectivity up to 74 %. • Isomerization proceeds via coke formed by quinone condensation and hydrogenolysis. Dihydroxybenzenes, including catechol, resorcinol and hydroquinone, have significant commercial value for a variety of applications such as adhesives, resins, pharmaceuticals, coatings etc. However, selective production of required isomers by phenol hydroxylation represents a considerable challenge. Here, we report a new approach for the synthesis of dihydroxybenzenes by their isomerization using a bifunctional Pt/ZSM-5 catalyst. The catalyst successfully facilitates the transformation of catechol and hydroquinone to each other with a selectivity of up to 74 % and yields up to 50 %. The investigation of the mechanism suggests that isomerization proceeds via a carbonaceous deposit (coke) formed by intermediate quinone condensation with subsequent hydrogenolysis to isomers. The proposed mechanism shows the way for the design of the efficient process for isomerization of dihydroxybenzenes. [ABSTRACT FROM AUTHOR]

Zeolite dealumination and desilication are common methods, which improve accessibility of the active sites located inside the zeolite crystallites and tune the zeolite acidity. The exact mechanism of these post-synthesis zeolite treatments remains under discussion. In this paper, a series of dealuminated and desilicated ZSM-5 zeolites are prepared using single or combined post-synthesis dealumination and desilication of large zeolite single crystals with oxalic acid and sodium hydroxide. The ZSM-5 zeolite has been synthesized using silica extracted from fly ash. Zeolite desilication results in the potholes, leaf-type structures and other clearly visible defects on the surface of zeolite crystallites, while the effect of dealumination is less pronounced. The low temperature nitrogen adsorption suggests the formation of mesopores in the zeolites formed by the voids between and in the irregular zeolite crystallites produced during post-synthesis treatments. 27Al and 29Si MAS NMR in combination with XRD data are indicative of only minor modifications of the bulk zeolite structure during dealumination and desilication. The total Brønsted acidity only slightly decreases and is not affected by the type of zeolite post-synthesis treatment. After desilication of large single crystals of ZSM-5, noticeable enhancement of the Brønsted acidity on the zeolite external surface has been detected by FTIR of adsorbed collidine. The zeolites with higher acidity on the external surface have shown higher activity in the anisole acylation with hexanoic acid. A combination of characterization techniques suggests that the dealumination and desilication of the large crystals of ZSM-5 zeolite using post-synthesis treatments respectively with acid and alkali selectively starts at the zeolite external surface. Image 1 • Desilication and dealumination strongly affect the surface of zeolite crystallites. • Potholes and other defects on the zeolite external surface contribute to mesoporosity. • Zeolite bulk structure is not altered at first stages of post synthesis treatments. • Higher acidity on the external surface enhances activity in the anisole acylation. [ABSTRACT FROM AUTHOR]