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
Hierarchical ZSM-5 zeolite was hydrothermally synthesized by a novel silicone quaternary ammonium salt surfactant as a mesopore director.The crystallinity and the morphology of sample were characterized by X-ray diffr...Hierarchical ZSM-5 zeolite was hydrothermally synthesized by a novel silicone quaternary ammonium salt surfactant as a mesopore director.The crystallinity and the morphology of sample were characterized by X-ray diffraction(XRD),field-emission scanning electron microscope(FE-SEM),and transmission electronic microscope(TEM).Results indicated that the prepared ZSM-5 zeolites had good crystallinity,ellipsoid structure morphology and rough surface.Moreover,the pore size was enlarged to about 4 nm measured by nitrogen sorption,which indicated positive function of the synthesized template.展开更多
Synthesis of ZSM-5 zeolite typically utilizes small molecule polyamines or quaternary ammonium salts as organic structure guiding agent(OSDA).By contrast,the OSDA-free hydrothermal synthesis system eliminates the use ...Synthesis of ZSM-5 zeolite typically utilizes small molecule polyamines or quaternary ammonium salts as organic structure guiding agent(OSDA).By contrast,the OSDA-free hydrothermal synthesis system eliminates the use of organic templates and the subsequent calcination procedure.This not only reduces the cost of synthesis,but also prevents environmental pollution from the combustion of organic templates,representing an eco-friendly approach.Despite this,literature suggests that even so-called template-free synthesis systems often involve trace amount of organic substances like alcohol.In the present work,a calcined commercial ZSM-5 zeolite was served as seed,with sodium aluminate as aluminum source and silica sol as silicon source,ensuring an entirely template-free synthesis system.Polycrystalline ZSM-5 aggregates consisted of rod-like nanocrystals were successfully prepared in the completely OSDA-free system.Effects of the Si/Al ratio in ZSM-5 seed,dosage and crystallization conditions such as crystallization temperature and crystallization time on ZSM-5 synthesis were investigated.The results show that a highly crystallinity ZSM-5 aggregate consisting of primary nano-sized crystals less than 100 nm is produced from a gel precursor with 5.6%(in mass)seed after hydrothermal treatment for 48 h.Furthermore,the Si/Al ratio in ZSM-5 seed has little effect on the topological structure and pore structure of the synthesized samples.However,the seeds with a low Si/Al ratio facilitate faster crystallization of zeolite and enhance the acidity,especially the strong acid centers,of the catalyst.The catalytic performance of the synthesized polycrystalline ZSM-5 was evaluated during dehydration of methanol and compared with a commercial reference ZSM-5r.The results exhibit that as compared with the reference catalyst,the fabricated sample has a longer catalytic lifetime(16 h vs 8 h)attributed to its hierarchical pores derived from the loosely packed primary nanoparticles.Additionally,the prepared polycrystalline catalyst also exhibits a higher aromatics selectivity(28.1%-29.8%vs 26.5%).展开更多
Developing hierarchical and nanoscale ZSM-5 catalysts for diffusion-limited reactions has received ever-increasing attention. Here, ZSM-5 architecture integrated with hierarchical pores and nanoscale crystals was succ...Developing hierarchical and nanoscale ZSM-5 catalysts for diffusion-limited reactions has received ever-increasing attention. Here, ZSM-5 architecture integrated with hierarchical pores and nanoscale crystals was successfully prepared via in situ self-assembly of nanoparticles-coated silicalite-1. First, the oriented attachment of amorphous nanoparticles on external surface of silicalite-1 was achieved by controlling the alkalinity of Si-Al coating solution. The partial exposure of the external surface of silicalite-1 ensured the uniform removal of silicon in the bulk phase for the creation of hierarchical pores during the subsequent desilication-recrystallization. The uniform removal of silicon species in the bulk phase was mainly due to the synergistic effect of surface protection and alkaline etching, which could be balanced by regulating the relative amount of tetrapropylammonium cation and OH– in desilication-recrystallization solution. Importantly, the removed silicon from silicalite-1 recrystallized and in situ assembled into final ZSM-5 nanocrystals induced by surface Si-Al nanoparticles. The hierarchical pores and nanoscale crystals on this integrated architecture not only promoted the removal of coke precursors from micropores but also provided large external specific surface (91 m^(2)·g^(-1)) for coke deposition. Consequently, a much longer catalytic lifetime was achieved for methanol-to-aromatics reaction compared to conventional hollow structure ZSM-5 (84 h vs 46 h), with relatively high stability.展开更多
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
基金National Natural Science Foundation of China(No.21676053)
文摘Hierarchical ZSM-5 zeolite was hydrothermally synthesized by a novel silicone quaternary ammonium salt surfactant as a mesopore director.The crystallinity and the morphology of sample were characterized by X-ray diffraction(XRD),field-emission scanning electron microscope(FE-SEM),and transmission electronic microscope(TEM).Results indicated that the prepared ZSM-5 zeolites had good crystallinity,ellipsoid structure morphology and rough surface.Moreover,the pore size was enlarged to about 4 nm measured by nitrogen sorption,which indicated positive function of the synthesized template.
基金National Natural Science Foundation of China(U19B2003,21706177,21975174)Foundation Supported by China Petroleum&Chemical Corporation(121014-2)。
文摘Synthesis of ZSM-5 zeolite typically utilizes small molecule polyamines or quaternary ammonium salts as organic structure guiding agent(OSDA).By contrast,the OSDA-free hydrothermal synthesis system eliminates the use of organic templates and the subsequent calcination procedure.This not only reduces the cost of synthesis,but also prevents environmental pollution from the combustion of organic templates,representing an eco-friendly approach.Despite this,literature suggests that even so-called template-free synthesis systems often involve trace amount of organic substances like alcohol.In the present work,a calcined commercial ZSM-5 zeolite was served as seed,with sodium aluminate as aluminum source and silica sol as silicon source,ensuring an entirely template-free synthesis system.Polycrystalline ZSM-5 aggregates consisted of rod-like nanocrystals were successfully prepared in the completely OSDA-free system.Effects of the Si/Al ratio in ZSM-5 seed,dosage and crystallization conditions such as crystallization temperature and crystallization time on ZSM-5 synthesis were investigated.The results show that a highly crystallinity ZSM-5 aggregate consisting of primary nano-sized crystals less than 100 nm is produced from a gel precursor with 5.6%(in mass)seed after hydrothermal treatment for 48 h.Furthermore,the Si/Al ratio in ZSM-5 seed has little effect on the topological structure and pore structure of the synthesized samples.However,the seeds with a low Si/Al ratio facilitate faster crystallization of zeolite and enhance the acidity,especially the strong acid centers,of the catalyst.The catalytic performance of the synthesized polycrystalline ZSM-5 was evaluated during dehydration of methanol and compared with a commercial reference ZSM-5r.The results exhibit that as compared with the reference catalyst,the fabricated sample has a longer catalytic lifetime(16 h vs 8 h)attributed to its hierarchical pores derived from the loosely packed primary nanoparticles.Additionally,the prepared polycrystalline catalyst also exhibits a higher aromatics selectivity(28.1%-29.8%vs 26.5%).
基金financial support from the National Natural Science Foundation of China(Nos.22278292,21978191).
文摘Developing hierarchical and nanoscale ZSM-5 catalysts for diffusion-limited reactions has received ever-increasing attention. Here, ZSM-5 architecture integrated with hierarchical pores and nanoscale crystals was successfully prepared via in situ self-assembly of nanoparticles-coated silicalite-1. First, the oriented attachment of amorphous nanoparticles on external surface of silicalite-1 was achieved by controlling the alkalinity of Si-Al coating solution. The partial exposure of the external surface of silicalite-1 ensured the uniform removal of silicon in the bulk phase for the creation of hierarchical pores during the subsequent desilication-recrystallization. The uniform removal of silicon species in the bulk phase was mainly due to the synergistic effect of surface protection and alkaline etching, which could be balanced by regulating the relative amount of tetrapropylammonium cation and OH– in desilication-recrystallization solution. Importantly, the removed silicon from silicalite-1 recrystallized and in situ assembled into final ZSM-5 nanocrystals induced by surface Si-Al nanoparticles. The hierarchical pores and nanoscale crystals on this integrated architecture not only promoted the removal of coke precursors from micropores but also provided large external specific surface (91 m^(2)·g^(-1)) for coke deposition. Consequently, a much longer catalytic lifetime was achieved for methanol-to-aromatics reaction compared to conventional hollow structure ZSM-5 (84 h vs 46 h), with relatively high stability.
基金Key Research and Development Plan of Shaanxi Province(2023-YBGY-290)Research Project of Shaanxi Yanchang Petroleum(Group)Co.,Ltd.(No.ycsy2023ky-B-81)。
