Template-free nanosized ZSM-5 seeds with an average size of 15 nm were prepared from a synthesis solution with the composition 12Na2O∶100SiO2∶2Al2O3∶2500H2O. By the use of these seeds, thin ZSM-5 zeolite membranes ...Template-free nanosized ZSM-5 seeds with an average size of 15 nm were prepared from a synthesis solution with the composition 12Na2O∶100SiO2∶2Al2O3∶2500H2O. By the use of these seeds, thin ZSM-5 zeolite membranes were prepared on the outer surface of a porous α-alumina tube with a pore size of 2 μm in a gel system by varying-concentration synthesis with organic-free template. The first composition synthesis sol-gel was the same as seeds of molar composition and the second one was 12Na2O∶100SiO2∶2Al2O3∶5000H2O at 180 ℃ for 10 h, respectively. XRD shows that the film consists of well-crystallized ZSM-5 zeolite. SEM investigation indicats that the zeolite films on the supports are defect free and the film thickness is approximately 8 μm. The permeances for H2, N2, CH4 and CO2 are 8.94×10-7, 3.27×10-7, 3.9×10-7, 3.14×10-7 and 0.874×10-7 mol·m2·s-1·Pa-1, respectively. The ideal selectivity of membrane at room temperature for H2/CO2, H2/N2, H2/CH4 are 2.84, 2.73 and 2.29, respectively.展开更多
Various metal-modified ZSM-5 zeolite adsorbents prepared by the impregnation method were applied to the removal of organic chlorides from model naphtha.The adsorption performance and regeneration stability were invest...Various metal-modified ZSM-5 zeolite adsorbents prepared by the impregnation method were applied to the removal of organic chlorides from model naphtha.The adsorption performance and regeneration stability were investigated by static adsorption experiments.The morphologies,structural features,and physicochemical properties of the adsorbents were characterized by X-ray diffraction,Brunauer-Emmett-Teller analysis,NH3 temperature-programmed desorption,scanning electron microscopy,transmission electron microscopy,and pyridine adsorption infrared spectroscopy.The Mg/ZSM-5 zeolite adsorbent possessed a relatively high specific surface area and good metal dispersion and exhibited the best dechlorination and regeneration performance.The characterization results revealed that introduction of the metal exerted a significant influence on the acidic properties of the catalyst surface.A decrease in the ratio of Brønsted acidic sites to Lewis acidic sites and an increase in the amount of moderately acidic sites were confirmed to be responsible for the excellent adsorption performance of the Mg-modified ZSM-5 zeolite.Furthermore,the Langmuir adsorption isotherm model was applied to study the adsorption equilibrium and thermodynamics of the Mg/ZSM-5 adsorbent under mild conditions.The results revealed that the removal of 1,2-dichloroethane by the Mg/ZSM-5 adsorbent was endothermic,spontaneous,disordered,and primarily involved physical adsorption.展开更多
Nanosized Ga-containing ZSM-5 zeolites were prepared via isomorphous substitution and impregnation followed by characterized using various techniques. The catalytic performance of the zeolites for the aromatization of...Nanosized Ga-containing ZSM-5 zeolites were prepared via isomorphous substitution and impregnation followed by characterized using various techniques. The catalytic performance of the zeolites for the aromatization of 1-hexene was investigated. The results indicate that isomorphous substitution promotes the incorporation of Ga heteroatoms into the framework along with the formation of extra-framework GaO^+species([GaO^+]a) that have stronger interactions with the negative potential of the framework. In addition, based on the Py-IR results and catalytic performance, the [GaO^+]aspecies with stronger Lewis acid sites produced a better synergism with moderate Br?nsted acid sites and thus improved the selectivity to aromatic compounds. However, the impregnation results in the formation of Ga_2O_3 phase and small amounts of GaO^+species that are mainly located on the external surface([GaO^+]~b), which contribute to weaker Lewis acid sites due to weaker interactions with the zeolite framework. During 1-hexene aromatization, the nanosized Ga isomorphously substituted ZSM-5 zeolite samples(Gax-NZ5) exhibited better catalytic performance compared to the impregnated samples, and the highest aromatic yield(i.e.,65.4 wt%) was achieved over the Ga4.2-NZ5 sample, which contained with the highest Ga content.展开更多
By optimizing the orystallization condition, a procedure for the synthesis of small crystallite zeolite ZSM-5 was developed. Compared with the larger crystallite ZSM-5. the smaller one exhibits higher catalytic perfor...By optimizing the orystallization condition, a procedure for the synthesis of small crystallite zeolite ZSM-5 was developed. Compared with the larger crystallite ZSM-5. the smaller one exhibits higher catalytic performance in aromatization reaction of propane.展开更多
The pore sizes of traditional zeolites are in the range of0. 3-1. 5 nm,which strongly hinder the diffusion of large reactant and product molecules within the zeolite pores. To compensate for it,we tried to create meso...The pore sizes of traditional zeolites are in the range of0. 3-1. 5 nm,which strongly hinder the diffusion of large reactant and product molecules within the zeolite pores. To compensate for it,we tried to create mesopores in traditional microporous zeolites and retain all advantages of microporous zeolites. Mesoporous Zeolite Socony Mobile-Five( ZSM-5) zeolite was synthesized by a new double ester base long carbon chains organosilane quaternary ammonium salt as the soft template agent in hydrothermal method.The structure of the acquired zeolite crystals was confirmed by fieldemission scanning electron microscopy( FE-SEM), transmission electron microscopy( TEM), nitrogen adsorption-desorption measurements and X-ray diffraction( XRD),which indicated that their structure had the same characteristics as traditional ZSM-5 zeolites. Compared with traditional ZSM-5 zeolite,there were 4 nm and 15 nm mesopores in the crystal. The prepared hierarchical porous ZSM-5 zeolite was expected to be effective catalytic materials for chemical reactions involving large molecules.展开更多
First,the hierarchical ZSM-5 zeolite was prepared by hydrothermal method using mesoporous template cetyltrimethylammonium bromide(CTAB).The physical and chemical properties of the hierarchical ZSM-5 zeolite were chara...First,the hierarchical ZSM-5 zeolite was prepared by hydrothermal method using mesoporous template cetyltrimethylammonium bromide(CTAB).The physical and chemical properties of the hierarchical ZSM-5 zeolite were characterized by X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FT-IR)and N2 adsorption-desorption and Scanning electron microscope(SEM).Then,the as-prepared hierarchical ZSM-5 zeolite and ion exchange resin were used as catalysts to evaluate the reaction performance of the synthesis of tributyl citrate.Compared with the ion exchange resin,the as-prepared ZSM-5 has a microporous and mesoporous composite structure and a large specific surface area,so that significantly improving the catalytic performance of synthesizing tributyl citrate and increasing the esterification rate of the reaction 8.7%.展开更多
A series of core-shell zeolites with a ZSM-5 zeolite core and a MCM-41 shell with varying shell thicknesses were successfully fabricated via a cetyltrimethylammonium bromide(CTAB)-directed sol-gel coating method in an...A series of core-shell zeolites with a ZSM-5 zeolite core and a MCM-41 shell with varying shell thicknesses were successfully fabricated via a cetyltrimethylammonium bromide(CTAB)-directed sol-gel coating method in an ultradilute solution. Extensive characterization techniques, including XRD, TEM, N_(2) adsorption-desorption, NH_(3)-TPD, and IR measurements, confirmed the successful coating of a microporous ZSM-5 core with a mesoporous MCM-41 shell layer and were further employed to explore the textural properties and acidic properties of the samples. The hexane cracking results revealed a significant enhancement in olefin yields after introducing the MCM-41 shell to ZSM-5. Interestingly, a volcanic trend in olefin yields was observed with the increase in the shell thickness. In particular, the highest olefin yield of 51.5%, exceeding that of the core catalyst by 17.1%, was achieved when the shell thickness was controlled at 40 nm.Moreover, the catalyst lifetime investigation revealed that the core-shell composite catalyst exhibited a minimal reduction in hexane conversion of merely 3.8% over a 120 h reaction period, significantly outperforming the 11.3% reduction exhibited by the core catalyst. This remarkable catalytic performance was attributed to the passivation of external acid sites and the introduction of more developed pore channels by the shell, which effectively mitigated unwanted side reactions. The successful synthesis of these core-shell structured catalysts presents a novel strategy for improving catalytic performance in hexane cracking, in addition to serving as a solid foundation for the design of industrial catalysts for light naphtha cracking.展开更多
ZSM-5 zeolite membrane reactor was used in ethylbenzene dehydrogenation to styrene under the circumstances of commercial production.The experimental results indicated that the conversion of ethylbenzene in the membran...ZSM-5 zeolite membrane reactor was used in ethylbenzene dehydrogenation to styrene under the circumstances of commercial production.The experimental results indicated that the conversion of ethylbenzene in the membrane reactor increased with increasing pressure of the membrane tube.Using the inert sweep gas instead of vacuumizing, the result of long term steady operation under the same condition showed that the selectivity of styrene increased and the conversion of ethylbenzene in the membrane reactor increased by 7.52% in comparison with the fixed-bed reactor.展开更多
High-permeance ZSM-5 zeolite membrane was prepared on porous tubular α-Al 2O 3 support by varying-temperature hydrothermal synthesis. XRD patterns show that the membrane consists of ZSM-5 zeolite crystals. SEM analys...High-permeance ZSM-5 zeolite membrane was prepared on porous tubular α-Al 2O 3 support by varying-temperature hydrothermal synthesis. XRD patterns show that the membrane consists of ZSM-5 zeolite crystals. SEM analysis indicates that few defects exist in the membrane and the thickness of the membrane is about 9 μm. The hydrogen permeance through the membrane is about 2.4×10 -6 mol/(m 2·s·Pa), and the separation factor for n-C 4H 10/i-C 4H 10 mixture (volume ratio 1∶1) is 40, which indicates that it has a high quality with high permeance and selectivity. Repeated nucleation and re-growth of the crystals on the support result in the dense membrane formation.展开更多
Zeolite ZSM 5 membrane, whose permeance was up to 10 -6 mol/(m 2·s·Pa) and a magnitude higher than that of other groups, was prepared on α Al 2O 3 support by multi in situ hydrothermal treatments, using opt...Zeolite ZSM 5 membrane, whose permeance was up to 10 -6 mol/(m 2·s·Pa) and a magnitude higher than that of other groups, was prepared on α Al 2O 3 support by multi in situ hydrothermal treatments, using optimized sol prescription and cheap n butane as the structure directing agent. The membrane was characterized by means of XRD, SEM and single gas permeances measurements, which showed that it was dense and integral without large intercrystal pores and cracks. The permeance of H 2, N 2, C 3H 8 and n C 4H 10 was up to 2.35×10 -6 , 1.0×10 -6 , 1.13×10 -7 and 4.9×10 -8 mol/(m 2·s·Pa), respectively. Ideal selectivity of H 2/N 2, H 2/C 3H 8 and H 2/ n C 4H 10 was 2.45, 20.8 and 48, respectively. [WT5HZ]展开更多
基金This work was financially supported by the Specialized Research Fund for the Doctoral Program of High Education (SRFDP)(No.B20020288015).
文摘Template-free nanosized ZSM-5 seeds with an average size of 15 nm were prepared from a synthesis solution with the composition 12Na2O∶100SiO2∶2Al2O3∶2500H2O. By the use of these seeds, thin ZSM-5 zeolite membranes were prepared on the outer surface of a porous α-alumina tube with a pore size of 2 μm in a gel system by varying-concentration synthesis with organic-free template. The first composition synthesis sol-gel was the same as seeds of molar composition and the second one was 12Na2O∶100SiO2∶2Al2O3∶5000H2O at 180 ℃ for 10 h, respectively. XRD shows that the film consists of well-crystallized ZSM-5 zeolite. SEM investigation indicats that the zeolite films on the supports are defect free and the film thickness is approximately 8 μm. The permeances for H2, N2, CH4 and CO2 are 8.94×10-7, 3.27×10-7, 3.9×10-7, 3.14×10-7 and 0.874×10-7 mol·m2·s-1·Pa-1, respectively. The ideal selectivity of membrane at room temperature for H2/CO2, H2/N2, H2/CH4 are 2.84, 2.73 and 2.29, respectively.
基金This work was financially supported by the Natural Science Foundation of Shandong Province(ZR2021MB134 and ZR2022MB019)the National Natural Science Foundation of China(22008131)+1 种基金the Talent Fund for Province and Ministry Co-construction Collaborative Innovation Center of Eco-chemical Engineering(STHGYX2220)the Opening Fund of State Key Laboratory of Heavy Oil Processing(SKLOP202002002).
文摘Various metal-modified ZSM-5 zeolite adsorbents prepared by the impregnation method were applied to the removal of organic chlorides from model naphtha.The adsorption performance and regeneration stability were investigated by static adsorption experiments.The morphologies,structural features,and physicochemical properties of the adsorbents were characterized by X-ray diffraction,Brunauer-Emmett-Teller analysis,NH3 temperature-programmed desorption,scanning electron microscopy,transmission electron microscopy,and pyridine adsorption infrared spectroscopy.The Mg/ZSM-5 zeolite adsorbent possessed a relatively high specific surface area and good metal dispersion and exhibited the best dechlorination and regeneration performance.The characterization results revealed that introduction of the metal exerted a significant influence on the acidic properties of the catalyst surface.A decrease in the ratio of Brønsted acidic sites to Lewis acidic sites and an increase in the amount of moderately acidic sites were confirmed to be responsible for the excellent adsorption performance of the Mg-modified ZSM-5 zeolite.Furthermore,the Langmuir adsorption isotherm model was applied to study the adsorption equilibrium and thermodynamics of the Mg/ZSM-5 adsorbent under mild conditions.The results revealed that the removal of 1,2-dichloroethane by the Mg/ZSM-5 adsorbent was endothermic,spontaneous,disordered,and primarily involved physical adsorption.
基金supported by the National Natural Science Foundation of China(Nos.21276067 and 21676074)Programs of International S&T cooperation(No.2014DFR41110)
文摘Nanosized Ga-containing ZSM-5 zeolites were prepared via isomorphous substitution and impregnation followed by characterized using various techniques. The catalytic performance of the zeolites for the aromatization of 1-hexene was investigated. The results indicate that isomorphous substitution promotes the incorporation of Ga heteroatoms into the framework along with the formation of extra-framework GaO^+species([GaO^+]a) that have stronger interactions with the negative potential of the framework. In addition, based on the Py-IR results and catalytic performance, the [GaO^+]aspecies with stronger Lewis acid sites produced a better synergism with moderate Br?nsted acid sites and thus improved the selectivity to aromatic compounds. However, the impregnation results in the formation of Ga_2O_3 phase and small amounts of GaO^+species that are mainly located on the external surface([GaO^+]~b), which contribute to weaker Lewis acid sites due to weaker interactions with the zeolite framework. During 1-hexene aromatization, the nanosized Ga isomorphously substituted ZSM-5 zeolite samples(Gax-NZ5) exhibited better catalytic performance compared to the impregnated samples, and the highest aromatic yield(i.e.,65.4 wt%) was achieved over the Ga4.2-NZ5 sample, which contained with the highest Ga content.
文摘By optimizing the orystallization condition, a procedure for the synthesis of small crystallite zeolite ZSM-5 was developed. Compared with the larger crystallite ZSM-5. the smaller one exhibits higher catalytic performance in aromatization reaction of propane.
基金National Natural Science Foundation of China(No.21676053)
文摘The pore sizes of traditional zeolites are in the range of0. 3-1. 5 nm,which strongly hinder the diffusion of large reactant and product molecules within the zeolite pores. To compensate for it,we tried to create mesopores in traditional microporous zeolites and retain all advantages of microporous zeolites. Mesoporous Zeolite Socony Mobile-Five( ZSM-5) zeolite was synthesized by a new double ester base long carbon chains organosilane quaternary ammonium salt as the soft template agent in hydrothermal method.The structure of the acquired zeolite crystals was confirmed by fieldemission scanning electron microscopy( FE-SEM), transmission electron microscopy( TEM), nitrogen adsorption-desorption measurements and X-ray diffraction( XRD),which indicated that their structure had the same characteristics as traditional ZSM-5 zeolites. Compared with traditional ZSM-5 zeolite,there were 4 nm and 15 nm mesopores in the crystal. The prepared hierarchical porous ZSM-5 zeolite was expected to be effective catalytic materials for chemical reactions involving large molecules.
文摘First,the hierarchical ZSM-5 zeolite was prepared by hydrothermal method using mesoporous template cetyltrimethylammonium bromide(CTAB).The physical and chemical properties of the hierarchical ZSM-5 zeolite were characterized by X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FT-IR)and N2 adsorption-desorption and Scanning electron microscope(SEM).Then,the as-prepared hierarchical ZSM-5 zeolite and ion exchange resin were used as catalysts to evaluate the reaction performance of the synthesis of tributyl citrate.Compared with the ion exchange resin,the as-prepared ZSM-5 has a microporous and mesoporous composite structure and a large specific surface area,so that significantly improving the catalytic performance of synthesizing tributyl citrate and increasing the esterification rate of the reaction 8.7%.
基金sponsored financially by the National Natural Science Foundation of China (Grant No. 21776076)the Fundamental Research Funds for the Central Universities (Grant No. JKA01211710)。
文摘A series of core-shell zeolites with a ZSM-5 zeolite core and a MCM-41 shell with varying shell thicknesses were successfully fabricated via a cetyltrimethylammonium bromide(CTAB)-directed sol-gel coating method in an ultradilute solution. Extensive characterization techniques, including XRD, TEM, N_(2) adsorption-desorption, NH_(3)-TPD, and IR measurements, confirmed the successful coating of a microporous ZSM-5 core with a mesoporous MCM-41 shell layer and were further employed to explore the textural properties and acidic properties of the samples. The hexane cracking results revealed a significant enhancement in olefin yields after introducing the MCM-41 shell to ZSM-5. Interestingly, a volcanic trend in olefin yields was observed with the increase in the shell thickness. In particular, the highest olefin yield of 51.5%, exceeding that of the core catalyst by 17.1%, was achieved when the shell thickness was controlled at 40 nm.Moreover, the catalyst lifetime investigation revealed that the core-shell composite catalyst exhibited a minimal reduction in hexane conversion of merely 3.8% over a 120 h reaction period, significantly outperforming the 11.3% reduction exhibited by the core catalyst. This remarkable catalytic performance was attributed to the passivation of external acid sites and the introduction of more developed pore channels by the shell, which effectively mitigated unwanted side reactions. The successful synthesis of these core-shell structured catalysts presents a novel strategy for improving catalytic performance in hexane cracking, in addition to serving as a solid foundation for the design of industrial catalysts for light naphtha cracking.
文摘ZSM-5 zeolite membrane reactor was used in ethylbenzene dehydrogenation to styrene under the circumstances of commercial production.The experimental results indicated that the conversion of ethylbenzene in the membrane reactor increased with increasing pressure of the membrane tube.Using the inert sweep gas instead of vacuumizing, the result of long term steady operation under the same condition showed that the selectivity of styrene increased and the conversion of ethylbenzene in the membrane reactor increased by 7.52% in comparison with the fixed-bed reactor.
文摘High-permeance ZSM-5 zeolite membrane was prepared on porous tubular α-Al 2O 3 support by varying-temperature hydrothermal synthesis. XRD patterns show that the membrane consists of ZSM-5 zeolite crystals. SEM analysis indicates that few defects exist in the membrane and the thickness of the membrane is about 9 μm. The hydrogen permeance through the membrane is about 2.4×10 -6 mol/(m 2·s·Pa), and the separation factor for n-C 4H 10/i-C 4H 10 mixture (volume ratio 1∶1) is 40, which indicates that it has a high quality with high permeance and selectivity. Repeated nucleation and re-growth of the crystals on the support result in the dense membrane formation.
文摘Zeolite ZSM 5 membrane, whose permeance was up to 10 -6 mol/(m 2·s·Pa) and a magnitude higher than that of other groups, was prepared on α Al 2O 3 support by multi in situ hydrothermal treatments, using optimized sol prescription and cheap n butane as the structure directing agent. The membrane was characterized by means of XRD, SEM and single gas permeances measurements, which showed that it was dense and integral without large intercrystal pores and cracks. The permeance of H 2, N 2, C 3H 8 and n C 4H 10 was up to 2.35×10 -6 , 1.0×10 -6 , 1.13×10 -7 and 4.9×10 -8 mol/(m 2·s·Pa), respectively. Ideal selectivity of H 2/N 2, H 2/C 3H 8 and H 2/ n C 4H 10 was 2.45, 20.8 and 48, respectively. [WT5HZ]
