Search

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]

Different acidic heterogeneous catalysts like alumina, aluminosilicate, zirconium phosphate, niobic acid, ion-exchange resin Amberlyst-15, and zeolite MOR have been studied in fructose dehydration to 5-hydroxymethylfurfural (HMF). The acidity of these materials was characterized using temperature-programmed desorption of NH3 and IR spectroscopy of adsorbed pyridine. The nature and strength of acid sites was shown to play a crucial role in the selectivity towards HMF. Brønsted acid sites in the case of zeolites and ion-exchange resin led to high selectivities in the dehydration of fructose with an increase in selectivity with the addition of an organic phase. Lewis acidity in the case of phosphate and oxides resulted in the intensive production of humins from fructose at the initial stages of the process, whereas organic phase addition did not affect selectivity. [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]