ITQ-2 zeolites were prepared by sequential alkali-swelling and ultrasonic-delamination of precursor MCM-22 and characterized by X-ray powder diffraction, scanning electron microscopy, nitrogen adsorption-desorption, a...ITQ-2 zeolites were prepared by sequential alkali-swelling and ultrasonic-delamination of precursor MCM-22 and characterized by X-ray powder diffraction, scanning electron microscopy, nitrogen adsorption-desorption, ammonia temperature-programmed desorption and in-situ Fourier-transform infrared spectroscopy. The delamination induced a change in the morphology of ITQ-2 zeolites from aggregated thin platelets to scattered platelets, together with a significant increase in external specific surface area, which reached a plateau at the ultrasonic treatment time of 3 h. The catalytic cracking of n-dodecane over ITQ-2 zeolites was evaluated with ITQ-2 coated on the inside wall of a tubular reactor at 550 ℃ and 4 MPa. The sample obtained by ultrasonic treatment of 3 h （ITQ-2-3） gave the highest initial conversion of n-dodecane, whereas those of 5 h and I h gave the conversion even lower than MCM-22, which was in agreement with the trend of the ratio of strong Lewis acid to the total acid amount. Although the amount of cokes deposited on ITQ-2-3 was larger than that on MCM-22, the former deactivated slowly, suggesting that a large external specific surface area benefits the stability of zeolite coatings,展开更多
A series of phosphorus-modified PITQ-13 catalysts was prepared by wet impregnation of NH4H2PO4 solution into an HITQ-13 parent. The catalysts were characterized using XRD, N2 adsorption, MAS NMR and NH3-TPD. Their cat...A series of phosphorus-modified PITQ-13 catalysts was prepared by wet impregnation of NH4H2PO4 solution into an HITQ-13 parent. The catalysts were characterized using XRD, N2 adsorption, MAS NMR and NH3-TPD. Their catalytic performance in 1-butene catalytic cracking was evaluated in a fixed fluidized bed reactor. The results showed that the crystallinity, surface area and pore volume of P-modified PITQ-13 catalysts decreased with the increasing amounts of P. The number of weak acid sites increased, whereas that of strong acidity decreased. The selectivity to propylene in 1-butene cracking reactions increased because of the decrease in strong acidity. The yield of propylene achieved 41.6% over PITQ-13-2 catalyst with a P content of 1.0 wt%, which was 5.1% greater than that achieved over HITQ-13 catalyst.展开更多
Using silica gel as the precursor, MCM-22(p) was synthesized under the static conditions. Then ITQ-2 zeolite was obtained by using n-cetyltrimethylammonium bromide (CTAB) and tetrapro- pylammonium hydroxide (TPAOH) as...Using silica gel as the precursor, MCM-22(p) was synthesized under the static conditions. Then ITQ-2 zeolite was obtained by using n-cetyltrimethylammonium bromide (CTAB) and tetrapro- pylammonium hydroxide (TPAOH) as the swelling agents to swell the pores of MCM-22(p). The ob- tained zeolite was characterized by XRD, SEM, BET, NH3-TPD. The results show that the zeolite had the best swelling when MCM-22(p):CTAB:TPAOH=1:4:1. The synthesis duration and temperature did not influence significantly the pore swelling. Except TPAOH, CTAB can also be used together with tetrabuthylammonium hydroxide (TBAOH) as the pore swelling agent. There was contribution of sur- face area and pore volume from the mesoporous pores in the ITQ-2 zeolite and it also showed weaker acidity than MCM-22. However, the ITQ-2 supported NiW catalyst showed higher activity and selec- tivity to the middle distillates in the hydrocracking of vacuum gasoil (VGO) than MCM-22 supported catalyst. This implied that the diffusion of large molecules of heavy oil in the catalyst was facilitated due to the presence of the mesoporous pores and hence higher activity and selectivity to middle dis- tillates.展开更多
Exploring the native defects of zeolites is highly important for understanding the properties of zeolites, such as catalysis and optics. Here, ITQ-16 films were prepared via the secondary growth method in the presence...Exploring the native defects of zeolites is highly important for understanding the properties of zeolites, such as catalysis and optics. Here, ITQ-16 films were prepared via the secondary growth method in the presence of Ge atoms. Various intrinsic defects of ITQ-16 films were fully studied through photoluminescence and FTIR characterizations. It was found that both the as-synthesized and calcined ITQ-16 films displayed multicolor photolumines- cence including ultraviolet, blue, green and red emissions by exciting upon appropriate wavelengths. The results in- dicate that Si--OH and non-bridging oxygen hole centers（NBOHCs） are responsible for the origin of green and red emissions at 540--800 nm, while according to a variety of emission bands of calcined ITQ-16 film, blue emission bands at around 446 and 462 nm are attributed to peroxy free radicals（≡SiO2＊）, ultraviolet emissions ranging from 250 nm to 450 nm are suggested originating from a singlet-to-triplet transition of two-fold-coordinated Si and Ge, respectively.展开更多
Continuous ITQ-16 and ITQ-17 films on silicon wafer were prepared in fluoride media using TEAOH asorganic structure-directing agent. The proportion ofpolymorph C in the as-synthesized ITQ-16 and ITQ-17 films wasdeterm...Continuous ITQ-16 and ITQ-17 films on silicon wafer were prepared in fluoride media using TEAOH asorganic structure-directing agent. The proportion ofpolymorph C in the as-synthesized ITQ-16 and ITQ-17 films wasdetermined via X-ray diffraction characterization. The proportion of polymorph C in the ITQ-16 and 1TQ-17 filmswas controlled via optimizing the compositions of the reaction mixtures and reaction conditions, such as varyingthe Si/Ge molar ratio and adding n-propyl alcohol as a solvent in the reaction mixture, The Ge atoms in the reactionmedia strongly increased the crystallization of polymorph C in ITQ-16 and ITQ-17 films. Moreover, the stabilizingand buffering effect of n-propyl alcohol on crystal growth further enhanced the proportion of polymorph C in theITQ-16 and ITQ-17 films. For potential catalytic applications, A1 was incorporated into the framework ofpolymorphC, and a pure phase of polymorph C in Al-ITQ-17 film was achieved from the synthesis gel in the n-propyl alcohol phase.展开更多
文摘ITQ-2 zeolites were prepared by sequential alkali-swelling and ultrasonic-delamination of precursor MCM-22 and characterized by X-ray powder diffraction, scanning electron microscopy, nitrogen adsorption-desorption, ammonia temperature-programmed desorption and in-situ Fourier-transform infrared spectroscopy. The delamination induced a change in the morphology of ITQ-2 zeolites from aggregated thin platelets to scattered platelets, together with a significant increase in external specific surface area, which reached a plateau at the ultrasonic treatment time of 3 h. The catalytic cracking of n-dodecane over ITQ-2 zeolites was evaluated with ITQ-2 coated on the inside wall of a tubular reactor at 550 ℃ and 4 MPa. The sample obtained by ultrasonic treatment of 3 h （ITQ-2-3） gave the highest initial conversion of n-dodecane, whereas those of 5 h and I h gave the conversion even lower than MCM-22, which was in agreement with the trend of the ratio of strong Lewis acid to the total acid amount. Although the amount of cokes deposited on ITQ-2-3 was larger than that on MCM-22, the former deactivated slowly, suggesting that a large external specific surface area benefits the stability of zeolite coatings,
基金supported by PetroChina Company Limited(12-09-01-01)the National Basic Research Program of China(973 Program,2012CB215001)
文摘A series of phosphorus-modified PITQ-13 catalysts was prepared by wet impregnation of NH4H2PO4 solution into an HITQ-13 parent. The catalysts were characterized using XRD, N2 adsorption, MAS NMR and NH3-TPD. Their catalytic performance in 1-butene catalytic cracking was evaluated in a fixed fluidized bed reactor. The results showed that the crystallinity, surface area and pore volume of P-modified PITQ-13 catalysts decreased with the increasing amounts of P. The number of weak acid sites increased, whereas that of strong acidity decreased. The selectivity to propylene in 1-butene cracking reactions increased because of the decrease in strong acidity. The yield of propylene achieved 41.6% over PITQ-13-2 catalyst with a P content of 1.0 wt%, which was 5.1% greater than that achieved over HITQ-13 catalyst.
文摘Using silica gel as the precursor, MCM-22(p) was synthesized under the static conditions. Then ITQ-2 zeolite was obtained by using n-cetyltrimethylammonium bromide (CTAB) and tetrapro- pylammonium hydroxide (TPAOH) as the swelling agents to swell the pores of MCM-22(p). The ob- tained zeolite was characterized by XRD, SEM, BET, NH3-TPD. The results show that the zeolite had the best swelling when MCM-22(p):CTAB:TPAOH=1:4:1. The synthesis duration and temperature did not influence significantly the pore swelling. Except TPAOH, CTAB can also be used together with tetrabuthylammonium hydroxide (TBAOH) as the pore swelling agent. There was contribution of sur- face area and pore volume from the mesoporous pores in the ITQ-2 zeolite and it also showed weaker acidity than MCM-22. However, the ITQ-2 supported NiW catalyst showed higher activity and selec- tivity to the middle distillates in the hydrocracking of vacuum gasoil (VGO) than MCM-22 supported catalyst. This implied that the diffusion of large molecules of heavy oil in the catalyst was facilitated due to the presence of the mesoporous pores and hence higher activity and selectivity to middle dis- tillates.
基金Supported by the Postdoctoral Science Foundation of China（No.2013M541716）, the Postdoctoral Science Foundation of Jiangsu Province, China（No.1301055C） and the Scientific Research Foundation for the Returned Overseas Chinese Scholars Sponsored by the Ministry of Education of China（No.K510900314）.
文摘Exploring the native defects of zeolites is highly important for understanding the properties of zeolites, such as catalysis and optics. Here, ITQ-16 films were prepared via the secondary growth method in the presence of Ge atoms. Various intrinsic defects of ITQ-16 films were fully studied through photoluminescence and FTIR characterizations. It was found that both the as-synthesized and calcined ITQ-16 films displayed multicolor photolumines- cence including ultraviolet, blue, green and red emissions by exciting upon appropriate wavelengths. The results in- dicate that Si--OH and non-bridging oxygen hole centers（NBOHCs） are responsible for the origin of green and red emissions at 540--800 nm, while according to a variety of emission bands of calcined ITQ-16 film, blue emission bands at around 446 and 462 nm are attributed to peroxy free radicals（≡SiO2＊）, ultraviolet emissions ranging from 250 nm to 450 nm are suggested originating from a singlet-to-triplet transition of two-fold-coordinated Si and Ge, respectively.
文摘Continuous ITQ-16 and ITQ-17 films on silicon wafer were prepared in fluoride media using TEAOH asorganic structure-directing agent. The proportion ofpolymorph C in the as-synthesized ITQ-16 and ITQ-17 films wasdetermined via X-ray diffraction characterization. The proportion of polymorph C in the ITQ-16 and 1TQ-17 filmswas controlled via optimizing the compositions of the reaction mixtures and reaction conditions, such as varyingthe Si/Ge molar ratio and adding n-propyl alcohol as a solvent in the reaction mixture, The Ge atoms in the reactionmedia strongly increased the crystallization of polymorph C in ITQ-16 and ITQ-17 films. Moreover, the stabilizingand buffering effect of n-propyl alcohol on crystal growth further enhanced the proportion of polymorph C in theITQ-16 and ITQ-17 films. For potential catalytic applications, A1 was incorporated into the framework ofpolymorphC, and a pure phase of polymorph C in Al-ITQ-17 film was achieved from the synthesis gel in the n-propyl alcohol phase.
