Catalytic roles of the acid sites in different pore channels of H‐ZSM‐5 zeolite for methanol‐to‐olefins conversion

H‐ZSM‐5 zeolite is a typical catalyst for methanol‐to‐olefins(MTO)conversion.Although the performance of zeolite catalysts for MTO conversion is related to the actual location of acid sites in the zeolite framework,the catalytic roles of the acid sites in different pore channels of the H‐ZSM‐5 zeolite are not well understood.In this study,the MTO reaction network,involving the aromatic cycle,alkene cycle,and aromatization process,and also the diffusion behavior of methanol feedstock and olefin and aromatic products at different acid sites in the straight channel,sinusoidal channel,and intersection cavity of H‐ZSM‐5 zeolite was comparatively investigated using density functional theory calculations and molecular dynamic simulations.The results indicated that the aromatic cycle and aromatization process occurred preferentially at the acid sites in the intersection cavities with a much lower energy barrier than that at the acid sites in the straight and sinusoidal channels.In contrast,the formation of polymethylbenzenes was significantly suppressed at the acid sites in the sinusoidal and straight channels,whereas the alkene cycle can occur at all three types of acid sites with similar energy barriers and probabilities.Consequently,the catalytic performance of H‐ZSM‐5 zeolite for MTO conversion,including activity and product selectivity,can be regulated properly through the purposive alteration of the acid site distribution,viz.,the location of Al in the zeolite framework.This study helps to elucidate the relation between the catalytic performance of different acid sites in the H‐ZSM‐5 zeolite framework for MTO conversion,which should greatly benefit the design of efficient catalyst for methanol conversion.

ADSORPTION EQUILIBRIUM OF ETHYLENE-CARBON DIOXIDE MIXTURE ON ZEOLITE ZSM5 AND ITS CORRELATION

Binary gas mixture adsorption equilibrium data for the ethylene-carbon dioxide system were obtained for cation exchanged forms of ZSM5 (Li^+, Na^+, K^+, Rb^+, Mg^(+2), Ca^(+2), Sr^(+2), and Ba^(+2)) for the gas phase CO_2 mole fracion of 0.766 at 308K and 101. 3kPa. The experimental adsorption phase diagrams were obtained for CO_2-C_2H_4 on NaZSM5 and MgZSM5. Single component adsorption isotherms for CO_2 and C_2H_4 were also obtained for these two zeolites. The single component data were used to obtain parameters derived in the vacancy solution model (VSM) and the statistical thermodynamic model(STM). These parameters were, in turn, used to predict binary mixture isotherms for these two zeolites. The agreement between experimental data and predicted value is generally good.

External surface modification of as-made ZSM-5 and their catalytic performance in the methanol to propylene reaction

Post-synthetic treatment of high-silica as-made ZSM-5 with organic template in the micropores was explored to reduce/remove the external surface acid density of ZSM-5. It is found that Na_2H_2 EDTA treatment can selectively remove the surface Al atoms, but generates new acid sites（likely silanol nests） on the external surface. H_3PO_4 treatment is unable to remove surface Al atoms, while small amount of P is left on the external surface, which effectively decreases the acid density. The catalytic performance of the resultant materials is evaluated in the methanol conversion reaction. H_3PO_4 treatment can effectively improve both the catalytic lifetime and the stability of propene selectivity.This occurs due to a combination of the increased tolerance to the external coke deposition and the depressed coking rate（reduced side reactions）. Na_2H_2 EDTA treatment only prolongs the catalytic lifetime, resulting from the improved tolerance to the external coke deposition. Under the optimized H_3PO_4 treatment condition, the resultant ZSM-5 gives a catalytic lifetime of about 1.5 times longer than the precursor. Moreover, the propene selectivity is improved, showing a slight increasing trend until the deactivation.

Gas-Phase Beckmann Rearrangement of Cyclohexanone Oxime over B-ZSM-5 Derived Titanosilicalite

Four different ZSM 5 zeolites are tested for the gas phase Beckmann rearrangement of cyclohexanone oxime (CHO) into lactam. B ZSM 5 derived titanosilicalite (Ti ZSM 5) exhibits catalytic performances comparable to hydrothermally synthesized titanosilicalite (TS 1), much better than B ZSM 5 and Al ZSM 5. The effect of reaction conditions (solvent, feed space velocity, and water) on the catalytic performance of Ti ZSM 5 is studied. It is found that a quantitative relationship exists among the feed space velocity, the reaction time, and the CHO constant conversion. Ethanol or methanol as solvent shows higher activity, lactam selectivity, and stability than benzene and n hexanol. The addition of water to the rearrangement with a maximum amount of 1.0 mole per mole CHO results in the increase of CHO conversion while no meaningful changes in lactam selectivity and stability are observed.