Carbon deposition during methanol to hydrocarbons leads to the quick deactivation of ZSM-5 catalyst and it is one of the major problems for this technology. Decreasing the crystal size or introducing mesopores into ZS...Carbon deposition during methanol to hydrocarbons leads to the quick deactivation of ZSM-5 catalyst and it is one of the major problems for this technology. Decreasing the crystal size or introducing mesopores into ZSM-5 zeolites can improve its diffusion property and decrease the coke formation. In this paper, nano-sized ZSM-5 zeolite with intercrystalline mesopores combining the mesoporous and nano sized structure was fabricated. For comparison, the mesoporous ZSM-5 and nano-sized ZSM-5 were also prepared. These catalyst samples were characterized by XRD, BET, NH3-TPD, TEM, Py-IR and TG techniques and used on the conversion of methanol to gasoline in a fixed-bed reactor at T=405 degrees C, WHSV =4.74 h(-1) and P=1.0 MPa. It was found that the external surface area of the nano-sized ZSM-5 zeolite with intercrystalline mesopores reached 104 m(2)/g, larger than that of mesoporous ZSM-5 (66 m(2)/g) and nano sized ZSM-5 (76 m(2)/g). Catalytic lifetime of the nano-sized ZSM-5 zeolite with intercrystalline mesopores was 93 h, which was only longer than that of mesoporous ZSM-5 (86 h), but shorter than that of nano sized ZSM-5 (104 h). Strong acidity promoted the coke formation and thus decreased the catalytic lifetime of the nano-sized ZSM-5 zeolite with intercrystalline mesopores though it presented large external surface that could improve the diffusion property. The special zeolite catalyst was further dealuminated to decrease the strong acidity. After this, its coke formation rate was slowed and catalytic lifetime was prolonged to 106 h because of the large external surface area and decreased weak acidity. This special structural zeolite is a potential catalyst for methanol to gasoline reaction. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.展开更多
Co/SiO2 and zirconium promoted Co/Zr/SiO2 catalysts were prepared using dielectric-barrier discharge （DBD） plasma instead of the conventional thermal calcination method. Fischer-Tropseh Synthesis （FTS） performance...Co/SiO2 and zirconium promoted Co/Zr/SiO2 catalysts were prepared using dielectric-barrier discharge （DBD） plasma instead of the conventional thermal calcination method. Fischer-Tropseh Synthesis （FTS） performances of the catalyst were evaluated in a fixed bed reactor. The results indicated that the catalyst treated by DBD plasma shows the higher FTS activity and yield of heavy hydrocarbons as compared with that treated by the conventional thermal calcination method. Increase in CO conversion was unnoticeable on the Co/SiO2 catalyst, but significant on the Co/Zr/SiO2 catalyst, both prepared by DBD plasma. On the other hand, heavy hydrocarbon selectivity and chain growth probability （a value） were enhanced on all the catalysts prepared by the DBD plasma. In order to study the effect of the DBD plasma treatment on the FTS performance, the catalysts were characterized by N2-physisorption, H2-temperature programed reduction （H2-TPR）, H2-temperature- programmed desorption （H2-TPD） and oxygen titration, transmission electron microscope （TEM） and X-ray diffraction （XRD）. It was proved that, compared with the traditional calcination method, DBD plasma not only could shorten the precursor decomposition time, but also could achieve better cobalt dispersion, smaller Co304 cluster size and more uniform cobalt distribution. However, cobalt reducibility was hindered to some extent in the Co/SiO2 catalyst prepared by DBD plasma, while the zirconium additive prevented significantly the decrease in cobalt reducibility and increased cobalt dispersion as well as the FTS performance.展开更多
Two-step conversion of methanol to aromatics via light hydrocarbons can significantly improve the conversion stability compared with direct aromatization of methanol,but it remains a challenge to achieve a high p-xyle...Two-step conversion of methanol to aromatics via light hydrocarbons can significantly improve the conversion stability compared with direct aromatization of methanol,but it remains a challenge to achieve a high p-xylene(PX)selectivity.Herein,silica coating was firstly used to passivate external acid sites of ZSM-5 catalyst for the aromatization of light hydrocarbons by the chemical liquid deposition method.With the increase of SiO_(2) deposition,the density of the external acid sites of the catalyst was decreased from 0.1 to 0.03 mmol·g^(-1),which inhibited the surface secondary reactions and increased the PX/X from 34.6% to 60.0%.In view of the fact that the aromatization process in the second step was partly inhibited as methanol was consumed in advance in the upper methanol-to-light hydrocarbons catalyst layer,part of methanol was directly introduced into the lower aromatization catalyst layer to promote the alkylation process during the aromatization,which decreased the toluene selectivity from 34.5% to 14.3% but increased the xylene selectivity from 40.0%to 55.3%.It was also found that an appropriate external acid density was needed for aromatization catalyst to strengthen the alkylation process and improve the selectivity of xylene under the conditions of methanol introduction.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the Science and Technology Foundation Platform Construction Project of Shanxi Province(No.2015091009)the National Science Foundation for Young Scientists of China(No.21606160)+1 种基金the Qualified Personnel Foundation of Taiyuan University of Technology(No.tyut-rc201454a)School Fund of Taiyuan University of Technology(Nos.1205-04020202 and 1205-04020102)
文摘Carbon deposition during methanol to hydrocarbons leads to the quick deactivation of ZSM-5 catalyst and it is one of the major problems for this technology. Decreasing the crystal size or introducing mesopores into ZSM-5 zeolites can improve its diffusion property and decrease the coke formation. In this paper, nano-sized ZSM-5 zeolite with intercrystalline mesopores combining the mesoporous and nano sized structure was fabricated. For comparison, the mesoporous ZSM-5 and nano-sized ZSM-5 were also prepared. These catalyst samples were characterized by XRD, BET, NH3-TPD, TEM, Py-IR and TG techniques and used on the conversion of methanol to gasoline in a fixed-bed reactor at T=405 degrees C, WHSV =4.74 h(-1) and P=1.0 MPa. It was found that the external surface area of the nano-sized ZSM-5 zeolite with intercrystalline mesopores reached 104 m(2)/g, larger than that of mesoporous ZSM-5 (66 m(2)/g) and nano sized ZSM-5 (76 m(2)/g). Catalytic lifetime of the nano-sized ZSM-5 zeolite with intercrystalline mesopores was 93 h, which was only longer than that of mesoporous ZSM-5 (86 h), but shorter than that of nano sized ZSM-5 (104 h). Strong acidity promoted the coke formation and thus decreased the catalytic lifetime of the nano-sized ZSM-5 zeolite with intercrystalline mesopores though it presented large external surface that could improve the diffusion property. The special zeolite catalyst was further dealuminated to decrease the strong acidity. After this, its coke formation rate was slowed and catalytic lifetime was prolonged to 106 h because of the large external surface area and decreased weak acidity. This special structural zeolite is a potential catalyst for methanol to gasoline reaction. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.
基金supported by the National Natural Science Foundation of China(No.21076151)
文摘Co/SiO2 and zirconium promoted Co/Zr/SiO2 catalysts were prepared using dielectric-barrier discharge （DBD） plasma instead of the conventional thermal calcination method. Fischer-Tropseh Synthesis （FTS） performances of the catalyst were evaluated in a fixed bed reactor. The results indicated that the catalyst treated by DBD plasma shows the higher FTS activity and yield of heavy hydrocarbons as compared with that treated by the conventional thermal calcination method. Increase in CO conversion was unnoticeable on the Co/SiO2 catalyst, but significant on the Co/Zr/SiO2 catalyst, both prepared by DBD plasma. On the other hand, heavy hydrocarbon selectivity and chain growth probability （a value） were enhanced on all the catalysts prepared by the DBD plasma. In order to study the effect of the DBD plasma treatment on the FTS performance, the catalysts were characterized by N2-physisorption, H2-temperature programed reduction （H2-TPR）, H2-temperature- programmed desorption （H2-TPD） and oxygen titration, transmission electron microscope （TEM） and X-ray diffraction （XRD）. It was proved that, compared with the traditional calcination method, DBD plasma not only could shorten the precursor decomposition time, but also could achieve better cobalt dispersion, smaller Co304 cluster size and more uniform cobalt distribution. However, cobalt reducibility was hindered to some extent in the Co/SiO2 catalyst prepared by DBD plasma, while the zirconium additive prevented significantly the decrease in cobalt reducibility and increased cobalt dispersion as well as the FTS performance.
基金financial support from the National Natural Science Foundation of China(21978191 and 22278292)Key Research and Development Project of Shanxi Province(International Science and Technology Cooperation Program)(201803D421011)。
文摘Two-step conversion of methanol to aromatics via light hydrocarbons can significantly improve the conversion stability compared with direct aromatization of methanol,but it remains a challenge to achieve a high p-xylene(PX)selectivity.Herein,silica coating was firstly used to passivate external acid sites of ZSM-5 catalyst for the aromatization of light hydrocarbons by the chemical liquid deposition method.With the increase of SiO_(2) deposition,the density of the external acid sites of the catalyst was decreased from 0.1 to 0.03 mmol·g^(-1),which inhibited the surface secondary reactions and increased the PX/X from 34.6% to 60.0%.In view of the fact that the aromatization process in the second step was partly inhibited as methanol was consumed in advance in the upper methanol-to-light hydrocarbons catalyst layer,part of methanol was directly introduced into the lower aromatization catalyst layer to promote the alkylation process during the aromatization,which decreased the toluene selectivity from 34.5% to 14.3% but increased the xylene selectivity from 40.0%to 55.3%.It was also found that an appropriate external acid density was needed for aromatization catalyst to strengthen the alkylation process and improve the selectivity of xylene under the conditions of methanol introduction.
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.
