The cracking and aromatization of n hexane over H ZSM 5 modified by various rare earths were investigated by means of continuous flow micro reactor. The surface properties of modified H ZSM 5 catalysts were obta...The cracking and aromatization of n hexane over H ZSM 5 modified by various rare earths were investigated by means of continuous flow micro reactor. The surface properties of modified H ZSM 5 catalysts were obtained from IR, XRD and XPS. The results show that the rare earths enhance the aromatizing properties of the catalysts which are prepared by mechanical mixture method. The results of n hexane cracking and aromatization are correlated with the acidity. The Brnsted acidic sites are the active sites of n hexane aromatization, while Lewis acid site plays an important role in n hexane cracking.展开更多
Methanol to gasoline reaction was investigated on two prepared ZSM-5 catalysts. The first one was a conventional catalyst denoted as ZSM-5（C） and the other was a hierarchical catalyst-ZSM-5（S） which was prepared b...Methanol to gasoline reaction was investigated on two prepared ZSM-5 catalysts. The first one was a conventional catalyst denoted as ZSM-5（C） and the other was a hierarchical catalyst-ZSM-5（S） which was prepared by incorporation of table sugar in catalyst gel during the synthesis procedure. The catalysts were characterized by FTIR, XRD, FE-SEM, N2 adsorption-desorption, NH3-TPD and TGA analytical technics. The proposed material showed pore modification as well as acidity moderating properties in ZSM-5 catalyst. The methanol to gasoline reaction was conducted in a fixed bed reactor with a WHSV of 1.5 h-1.Methanol conversions, gasoline yield and selectivity in production for the synthesized catalysts were determined by gas chromatography method. The sugar modified catalyst converted more methanol than the conventional one and an enhancement in catalyst’s life time was observed. The selectivity to aromatics and durene were reduced compared to the conventional catalyst, so the gasoline quality was also further improved. The coking rate of catalysts was calculated employing TGA method. A reduction in coking rate and an increase in coke capacity of the modified catalyst were observed.展开更多
The catalytic decomposition of NO over Ag-ZSM-5 catalyst prepared by ion-exchange was investigated. The exchanged silver in the zeolite was reduced and it collected in the course of the reaction to form silver particl...The catalytic decomposition of NO over Ag-ZSM-5 catalyst prepared by ion-exchange was investigated. The exchanged silver in the zeolite was reduced and it collected in the course of the reaction to form silver particles of about 20 nm. The catalytic reaction induced a pronounced restructuring of the Ag particles through preferential formation of the (111) facets. These facets were shown to hind a tightly bound oxygen species (O-gamma). The O-gamma species occupies the active sites for NO adsorption resulting in catalyst deactivation. It could be removed by appropriate reducing agents, such as CO, to recover the active sites at elevated temperatures.展开更多
A non-phosgene route for the synthesis of hexamethylene-1,6-diisocyanate(HDI) was developed via catalytic decomposition of hexamethylene-1,6-dicarbamate(HDC) over Zn–Co bi-metallic supported ZSM-5 catalyst.The cataly...A non-phosgene route for the synthesis of hexamethylene-1,6-diisocyanate(HDI) was developed via catalytic decomposition of hexamethylene-1,6-dicarbamate(HDC) over Zn–Co bi-metallic supported ZSM-5 catalyst.The catalyst was characterized by FTIR and XRD analyses. Three solvents dioctyl sebacate(DOS), dibutyl sebacate(DBS) and 1-butyl-3-methylimidazolium tetrafluoroborate(BMIMBF_4) were investigated and compared; DOS gave better performance. The catalytic performances for thermal decomposition of HDC to HDI using DOS as solvent were then investigated, and the results showed that, under the optimized reaction conditions, i.e.,10 wt%concentration of HDC in DOS, 250 °C temperature, 60 min reaction time, 83.8% yield of HDI had been achieved over Zn–Co/ZSM-5. Decomposition of the intermediate hexamethylene-1-carbamate-6-isocyanate(HMI) over Zn–Co/ZSM-5 in DOS solvent was further studied and the results indicated that yield of HDI from HMI reached to 69.6%(98.6% HDI selectively) at 270 °C, which further increased the yield of the total HDI(HDI_(tol)) to as high as 95.0%. Recycling of catalyst showed that HDI and HMI yield slightly decreased, and by-product yield increased after the catalyst was reused for 4 times. At last possible reaction mechanism was proposed.展开更多
The influences of binder and molding method on the catalytic performance of methane aromatization in the absence of O2 over MoO3/ZSM-5 catalysts were investigated.SEM,NH3-TPD,FT-IR of adsorbed pyridine,N2 adsorption-d...The influences of binder and molding method on the catalytic performance of methane aromatization in the absence of O2 over MoO3/ZSM-5 catalysts were investigated.SEM,NH3-TPD,FT-IR of adsorbed pyridine,N2 adsorption-desorption,cyclohexane adsorption and XPS were employed to characterize the physical and chemical properties of the catalysts.It was found that SiO2 was a suitable binder for the catalyst due to its appropriate weak acidity.The laminar catalyst comprising of an inert spherical core and a MoO3/ZSM-5 laminar shell with 0.1 0.2 mm in thickness showed a better catalytic performance than the extruded catalyst.The improved activity of the laminar catalyst could be attributed to the easy carbonization of Mo species and the quick removal of reaction products from the catalyst surface.展开更多
The Cu-Mo/ZSM-5 catalysts with different Cu/Mo ratios were prepared by wetimpregnation method, and their catalytic performance for selective catalytic reduction of NO_x wasstudied. The results showed that Cu-Mo/ZSM-5 ...The Cu-Mo/ZSM-5 catalysts with different Cu/Mo ratios were prepared by wetimpregnation method, and their catalytic performance for selective catalytic reduction of NO_x wasstudied. The results showed that Cu-Mo/ZSM-5 is a very effective catalyst for NO_x catalyticreduction with ammonia, especially when Cu/Mo molar ratio is about 1.5. It not only exhibited theextremely high catalytic activity, but also showed good stability for O_2. The bulk phase structureof Cu-Mo/ZSM-5 catalysts was determined by XRD technique, and the results indicated that there is amaximum dispersion for Cu species when Cu/Mo molar ratio is 1.5, and an interaction between Cu andMo along with HZSM-5 may be present in Cu-Mo/ZSM-5, which may possibly result in a special structurefavorable for the catalytic reduction of NO_x over Cu-Mo/ZSM-5 catalyst.展开更多
A ZSM-5/MAPO composite catalyst was prepared by adding ZSM-5 zeolite powder to a conventional molecular sieve synthesis system, followed by modification with NH_4H_2PO_4. The samples were characterized by XRD, SEM, IR...A ZSM-5/MAPO composite catalyst was prepared by adding ZSM-5 zeolite powder to a conventional molecular sieve synthesis system, followed by modification with NH_4H_2PO_4. The samples were characterized by XRD, SEM, IR, NH_3-TPD, and BET analyses. The catalytic property of the samples toward the methanol-to-olefin(MTO) reaction was evaluated in a connected in series two-stage unit equipped with a continuous flow(once-through) fixed-bed tubular reactor similar to an industrial reactor. The first reactor mainly converted methanol into dimethyl ether and water, followed by being subject to continuous reaction in the second reactor, in which DME was converted to hydrocarbons. The composites exhibited the typical framework topology of MFI, AEI and AFI, which represented the ZSM-5 zeolite, the molecular sieves AlPO-18 or SAPO-18, AlPO-5 or SAPO-5, respectively. The composites showed several advantages for optimizing the zeolite acidity, enhancing the mass transfer, and restraining the side reactions. Catalytic reaction results showed that the composites exhibited higher selectivity to light olefins(84.0%) and lower selectivity to C_2―C_4 alkanes and C_5^+ hydrocarbons than pure ZSM-5. Moreover, the composite zeolite loaded with 3% of P demonstrated improved catalytic activity and stability for the conversion of methanol to propylene, because the coking rate was obviously suppressed.展开更多
It is useful for practical operation to study the rules of production of propylene by the catalytic conversion of heavy oil in FCC （fluid catalytic cracking）. The effects of temperature and C/O ratio （catalyst to o...It is useful for practical operation to study the rules of production of propylene by the catalytic conversion of heavy oil in FCC （fluid catalytic cracking）. The effects of temperature and C/O ratio （catalyst to oil weight ratio） on the distribution of the product and the yield of propylene were investigated on a micro reactor unit with two model catalysts, namely ZSM-5/Al2O3 and USY/Al2O3, and Fushun vacuum gas oil （VGO） was used as the feedstock. The conversion of heavy oil over ZSM-5 catalyst can be comparable to that of USY catalyst at high temperature and high C/O ratio. The rate of conversion of heavy oil using the ZSM-5 equilibrium catalyst is lower compared with the USY equilibrium catalyst under the general FCC conditions and this can be attributed to the poor steam ability of the ZSM-5 equilibrium catalyst. The difference in pore topologies of USY and ZSM-5 is the reason why the principal products for the above two catalysts is different, namely gasoline and liquid petroleum gas （LPG）, repspectively. So the LPG selectivity, especially the propylene selectivity, may decline if USY is added into the FCC catalyst for maximizing the production of propylene. Increasing the C/O ratio is the most economical method for the increase of LPG yield than the increase of the temperature of the two model catalysts, because the loss of light oil is less in the former case. There is an inverse correlation between HTC （hydrogen transfer coefficient） and the yield of propylene, and restricting the hydrogen transfer reaction is the more important measure in increasing the yield of propylene of the ZSM-5 catalyst. The ethylene yield of ZSM-5/A1203 is higher, but the gaseous side products with low value are not enhanced when ZSM-5 catalyst is used. Moreover, for LPG and the end products, dry gas and coke, their ranges of reaction conditions to which their yields are dependent are different, and that of end products is more severe than that of LPG. So it is clear that maximizing LPG and propylene and restricting dry gas and coke can be both achieved via increasing the severity of reaction conditions among the range of reaction conditions which LPG yield is sensitive to.展开更多
The isomerization of light paraffin over HZSM-5-Ni-Mo-F synthetic zeolite catalysts was studied, and the effects of reaction conditions on the isomerization were investigated. The results show that the optimum reactio...The isomerization of light paraffin over HZSM-5-Ni-Mo-F synthetic zeolite catalysts was studied, and the effects of reaction conditions on the isomerization were investigated. The results show that the optimum reaction condition can be obtained to enhance the research octane number (RON) of product and the liquid yield. The optimum experimental condition is: HZSM-5 catalyst with 1.5wt% of Ni, 2wt% of Mo and 0.4wt% of F, at a temperature of 345℃ and a reaction mass hourly space velocity (MHSV) of 0.2 h-1. The isomerization reaction of light paraffin from Tarim refinery was studied and the research octane number (RON) of gasoline product could be enhanced by 20 units under the condition of nonhydrogenization and optimum experimental status.展开更多
文摘The cracking and aromatization of n hexane over H ZSM 5 modified by various rare earths were investigated by means of continuous flow micro reactor. The surface properties of modified H ZSM 5 catalysts were obtained from IR, XRD and XPS. The results show that the rare earths enhance the aromatizing properties of the catalysts which are prepared by mechanical mixture method. The results of n hexane cracking and aromatization are correlated with the acidity. The Brnsted acidic sites are the active sites of n hexane aromatization, while Lewis acid site plays an important role in n hexane cracking.
基金the Petrochemical Research and Technology Company, Tehran, Iran for financial support of this research
文摘Methanol to gasoline reaction was investigated on two prepared ZSM-5 catalysts. The first one was a conventional catalyst denoted as ZSM-5（C） and the other was a hierarchical catalyst-ZSM-5（S） which was prepared by incorporation of table sugar in catalyst gel during the synthesis procedure. The catalysts were characterized by FTIR, XRD, FE-SEM, N2 adsorption-desorption, NH3-TPD and TGA analytical technics. The proposed material showed pore modification as well as acidity moderating properties in ZSM-5 catalyst. The methanol to gasoline reaction was conducted in a fixed bed reactor with a WHSV of 1.5 h-1.Methanol conversions, gasoline yield and selectivity in production for the synthesized catalysts were determined by gas chromatography method. The sugar modified catalyst converted more methanol than the conventional one and an enhancement in catalyst’s life time was observed. The selectivity to aromatics and durene were reduced compared to the conventional catalyst, so the gasoline quality was also further improved. The coking rate of catalysts was calculated employing TGA method. A reduction in coking rate and an increase in coke capacity of the modified catalyst were observed.
文摘The catalytic decomposition of NO over Ag-ZSM-5 catalyst prepared by ion-exchange was investigated. The exchanged silver in the zeolite was reduced and it collected in the course of the reaction to form silver particles of about 20 nm. The catalytic reaction induced a pronounced restructuring of the Ag particles through preferential formation of the (111) facets. These facets were shown to hind a tightly bound oxygen species (O-gamma). The O-gamma species occupies the active sites for NO adsorption resulting in catalyst deactivation. It could be removed by appropriate reducing agents, such as CO, to recover the active sites at elevated temperatures.
基金Supported by the National Natural Science Foundation of China(21476244,21406245)Transformational Technologies for Clean Energy and Demonstration,Strategic Priority Research Program of the Chinese Academy of Sciences,(XDA 21030600)the Youth Innovation Promotion Association CAS(2016046)
文摘A non-phosgene route for the synthesis of hexamethylene-1,6-diisocyanate(HDI) was developed via catalytic decomposition of hexamethylene-1,6-dicarbamate(HDC) over Zn–Co bi-metallic supported ZSM-5 catalyst.The catalyst was characterized by FTIR and XRD analyses. Three solvents dioctyl sebacate(DOS), dibutyl sebacate(DBS) and 1-butyl-3-methylimidazolium tetrafluoroborate(BMIMBF_4) were investigated and compared; DOS gave better performance. The catalytic performances for thermal decomposition of HDC to HDI using DOS as solvent were then investigated, and the results showed that, under the optimized reaction conditions, i.e.,10 wt%concentration of HDC in DOS, 250 °C temperature, 60 min reaction time, 83.8% yield of HDI had been achieved over Zn–Co/ZSM-5. Decomposition of the intermediate hexamethylene-1-carbamate-6-isocyanate(HMI) over Zn–Co/ZSM-5 in DOS solvent was further studied and the results indicated that yield of HDI from HMI reached to 69.6%(98.6% HDI selectively) at 270 °C, which further increased the yield of the total HDI(HDI_(tol)) to as high as 95.0%. Recycling of catalyst showed that HDI and HMI yield slightly decreased, and by-product yield increased after the catalyst was reused for 4 times. At last possible reaction mechanism was proposed.
基金supported by the National Basic Research Program of China(Grant 2005CB 221405)
文摘The influences of binder and molding method on the catalytic performance of methane aromatization in the absence of O2 over MoO3/ZSM-5 catalysts were investigated.SEM,NH3-TPD,FT-IR of adsorbed pyridine,N2 adsorption-desorption,cyclohexane adsorption and XPS were employed to characterize the physical and chemical properties of the catalysts.It was found that SiO2 was a suitable binder for the catalyst due to its appropriate weak acidity.The laminar catalyst comprising of an inert spherical core and a MoO3/ZSM-5 laminar shell with 0.1 0.2 mm in thickness showed a better catalytic performance than the extruded catalyst.The improved activity of the laminar catalyst could be attributed to the easy carbonization of Mo species and the quick removal of reaction products from the catalyst surface.
文摘The Cu-Mo/ZSM-5 catalysts with different Cu/Mo ratios were prepared by wetimpregnation method, and their catalytic performance for selective catalytic reduction of NO_x wasstudied. The results showed that Cu-Mo/ZSM-5 is a very effective catalyst for NO_x catalyticreduction with ammonia, especially when Cu/Mo molar ratio is about 1.5. It not only exhibited theextremely high catalytic activity, but also showed good stability for O_2. The bulk phase structureof Cu-Mo/ZSM-5 catalysts was determined by XRD technique, and the results indicated that there is amaximum dispersion for Cu species when Cu/Mo molar ratio is 1.5, and an interaction between Cu andMo along with HZSM-5 may be present in Cu-Mo/ZSM-5, which may possibly result in a special structurefavorable for the catalytic reduction of NO_x over Cu-Mo/ZSM-5 catalyst.
基金financially supported by the National International Cooperation S & T Project of China (No.2015DFA40660)
文摘A ZSM-5/MAPO composite catalyst was prepared by adding ZSM-5 zeolite powder to a conventional molecular sieve synthesis system, followed by modification with NH_4H_2PO_4. The samples were characterized by XRD, SEM, IR, NH_3-TPD, and BET analyses. The catalytic property of the samples toward the methanol-to-olefin(MTO) reaction was evaluated in a connected in series two-stage unit equipped with a continuous flow(once-through) fixed-bed tubular reactor similar to an industrial reactor. The first reactor mainly converted methanol into dimethyl ether and water, followed by being subject to continuous reaction in the second reactor, in which DME was converted to hydrocarbons. The composites exhibited the typical framework topology of MFI, AEI and AFI, which represented the ZSM-5 zeolite, the molecular sieves AlPO-18 or SAPO-18, AlPO-5 or SAPO-5, respectively. The composites showed several advantages for optimizing the zeolite acidity, enhancing the mass transfer, and restraining the side reactions. Catalytic reaction results showed that the composites exhibited higher selectivity to light olefins(84.0%) and lower selectivity to C_2―C_4 alkanes and C_5^+ hydrocarbons than pure ZSM-5. Moreover, the composite zeolite loaded with 3% of P demonstrated improved catalytic activity and stability for the conversion of methanol to propylene, because the coking rate was obviously suppressed.
文摘It is useful for practical operation to study the rules of production of propylene by the catalytic conversion of heavy oil in FCC （fluid catalytic cracking）. The effects of temperature and C/O ratio （catalyst to oil weight ratio） on the distribution of the product and the yield of propylene were investigated on a micro reactor unit with two model catalysts, namely ZSM-5/Al2O3 and USY/Al2O3, and Fushun vacuum gas oil （VGO） was used as the feedstock. The conversion of heavy oil over ZSM-5 catalyst can be comparable to that of USY catalyst at high temperature and high C/O ratio. The rate of conversion of heavy oil using the ZSM-5 equilibrium catalyst is lower compared with the USY equilibrium catalyst under the general FCC conditions and this can be attributed to the poor steam ability of the ZSM-5 equilibrium catalyst. The difference in pore topologies of USY and ZSM-5 is the reason why the principal products for the above two catalysts is different, namely gasoline and liquid petroleum gas （LPG）, repspectively. So the LPG selectivity, especially the propylene selectivity, may decline if USY is added into the FCC catalyst for maximizing the production of propylene. Increasing the C/O ratio is the most economical method for the increase of LPG yield than the increase of the temperature of the two model catalysts, because the loss of light oil is less in the former case. There is an inverse correlation between HTC （hydrogen transfer coefficient） and the yield of propylene, and restricting the hydrogen transfer reaction is the more important measure in increasing the yield of propylene of the ZSM-5 catalyst. The ethylene yield of ZSM-5/A1203 is higher, but the gaseous side products with low value are not enhanced when ZSM-5 catalyst is used. Moreover, for LPG and the end products, dry gas and coke, their ranges of reaction conditions to which their yields are dependent are different, and that of end products is more severe than that of LPG. So it is clear that maximizing LPG and propylene and restricting dry gas and coke can be both achieved via increasing the severity of reaction conditions among the range of reaction conditions which LPG yield is sensitive to.
文摘The isomerization of light paraffin over HZSM-5-Ni-Mo-F synthetic zeolite catalysts was studied, and the effects of reaction conditions on the isomerization were investigated. The results show that the optimum reaction condition can be obtained to enhance the research octane number (RON) of product and the liquid yield. The optimum experimental condition is: HZSM-5 catalyst with 1.5wt% of Ni, 2wt% of Mo and 0.4wt% of F, at a temperature of 345℃ and a reaction mass hourly space velocity (MHSV) of 0.2 h-1. The isomerization reaction of light paraffin from Tarim refinery was studied and the research octane number (RON) of gasoline product could be enhanced by 20 units under the condition of nonhydrogenization and optimum experimental status.
