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 framewor...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.展开更多
With the aim of achieving a high 5-hydroxymethylfurfural(HMF)yield from glucose with H-ZSM-5 catalyst at low cost,three inexpensive biphasic reaction systems,H2O?tetrahydrofuran(THF),H2O?2-methyltetrahydrofuran(MeTHF)...With the aim of achieving a high 5-hydroxymethylfurfural(HMF)yield from glucose with H-ZSM-5 catalyst at low cost,three inexpensive biphasic reaction systems,H2O?tetrahydrofuran(THF),H2O?2-methyltetrahydrofuran(MeTHF)and H2O?2-butanol,were discovered and proved to be particularly effective in promoting the formation of HMF from glucose over H-ZSM-5 zeolite.In order to determine the optimal process conditions,the effects of various experimental variables,such as reaction temperature,reaction time,catalyst dosage,volume of organic solvent,as well as inorganic salt type on glucose conversion to HMF in three systems were investigated in detail.It was found that under optimal reaction conditions,H2O?THF,H2O?2-butanol and H2O?MeTHF allowed the glucose dehydration process to achieve HMF yields of up to 61%,59%,and 50%,respectively.Moreover,in the three biphasic systems,the H-ZSM-5 catalyst was also demonstrated to maintain excellent stability.Thus,the catalytic approach proposed in this paper can be believed to have potential prospects for industrially efficient and low-cost production of HMF.展开更多
The porosity of H‐ZSM‐5zeolite is known to facilitate the diffusion of molecules in the methanol‐to‐aromatics(MTA)reaction.The activity and selectivity of the H‐ZSM‐5catalyst in the MTAreaction has been studied ...The porosity of H‐ZSM‐5zeolite is known to facilitate the diffusion of molecules in the methanol‐to‐aromatics(MTA)reaction.The activity and selectivity of the H‐ZSM‐5catalyst in the MTAreaction has been studied as a function of crystal size.ZSM‐5zeolites with different crystal sizeswere successfully synthesized by conventional hydrothermal methods.Tailoring ZSM‐5particle sizewas easily controlled by changes to the sol‐gel composition,and in particular,the deionized waterto tetrapropylammonium hydroxide ratio,and crystallization time.The structure of the H‐ZSM‐5zeolites were characterized by X‐ray diffraction and the morphology of the zeolite particles wasdetermined by scanning electron microscopy.N2adsorption‐desorption measurements establishedchanges to the textural properties,and compositional properties were characterized by X‐ray fluorescencespectroscopy.Acidity measurements of the catalysts were measured by pyridine‐adsorbedFourier transform infrared spectroscopy and the temperature‐programmed desorption of ammonia.After subjecting the catalysts to the MTA reaction,the total amount of coke formed on the spentdeactivated catalysts was determined by thermal gravimetric analysis.The results show that theSiO2/Al2O3molar ratios and acidic properties of the H‐ZSM‐5samples are similar,however,thenano‐sized hierarchical ZSM‐5zeolite with an additional level of auxiliary pores possesses a higher展开更多
文摘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.
基金Project(3207049713)supported by the Scientific Research Foundation of Graduate School of Southeast University,China
文摘With the aim of achieving a high 5-hydroxymethylfurfural(HMF)yield from glucose with H-ZSM-5 catalyst at low cost,three inexpensive biphasic reaction systems,H2O?tetrahydrofuran(THF),H2O?2-methyltetrahydrofuran(MeTHF)and H2O?2-butanol,were discovered and proved to be particularly effective in promoting the formation of HMF from glucose over H-ZSM-5 zeolite.In order to determine the optimal process conditions,the effects of various experimental variables,such as reaction temperature,reaction time,catalyst dosage,volume of organic solvent,as well as inorganic salt type on glucose conversion to HMF in three systems were investigated in detail.It was found that under optimal reaction conditions,H2O?THF,H2O?2-butanol and H2O?MeTHF allowed the glucose dehydration process to achieve HMF yields of up to 61%,59%,and 50%,respectively.Moreover,in the three biphasic systems,the H-ZSM-5 catalyst was also demonstrated to maintain excellent stability.Thus,the catalytic approach proposed in this paper can be believed to have potential prospects for industrially efficient and low-cost production of HMF.
基金supported by the National Natural Science Foundation of China (21676300)~~
文摘The porosity of H‐ZSM‐5zeolite is known to facilitate the diffusion of molecules in the methanol‐to‐aromatics(MTA)reaction.The activity and selectivity of the H‐ZSM‐5catalyst in the MTAreaction has been studied as a function of crystal size.ZSM‐5zeolites with different crystal sizeswere successfully synthesized by conventional hydrothermal methods.Tailoring ZSM‐5particle sizewas easily controlled by changes to the sol‐gel composition,and in particular,the deionized waterto tetrapropylammonium hydroxide ratio,and crystallization time.The structure of the H‐ZSM‐5zeolites were characterized by X‐ray diffraction and the morphology of the zeolite particles wasdetermined by scanning electron microscopy.N2adsorption‐desorption measurements establishedchanges to the textural properties,and compositional properties were characterized by X‐ray fluorescencespectroscopy.Acidity measurements of the catalysts were measured by pyridine‐adsorbedFourier transform infrared spectroscopy and the temperature‐programmed desorption of ammonia.After subjecting the catalysts to the MTA reaction,the total amount of coke formed on the spentdeactivated catalysts was determined by thermal gravimetric analysis.The results show that theSiO2/Al2O3molar ratios and acidic properties of the H‐ZSM‐5samples are similar,however,thenano‐sized hierarchical ZSM‐5zeolite with an additional level of auxiliary pores possesses a higher
