This study employed a wet impregnation method to synthesize five types of Cu/HZSM-5 adsorbents with Si/Al ratios of 25,50,85,200,and 300,used for the removal of H_(2)S in lowtemperature,low-oxygen environments.The imp...This study employed a wet impregnation method to synthesize five types of Cu/HZSM-5 adsorbents with Si/Al ratios of 25,50,85,200,and 300,used for the removal of H_(2)S in lowtemperature,low-oxygen environments.The impact of different Si/Al ratios on the adsorption oxidative performance of Cu_(30)/HZSM-5–85 adsorbents was investigated.According to the performance test results,Cu_(30)/HZSM-5–85 exhibited the highest breakthrough capacity,reaching 231.75 mg H_(2)S/g_(sorbent).Cu/HZSM-5 sorbent maintains a strong ability to remove H_(2)S even under humid conditions and shows excellent water resistance.XRD,BET,and XPS results revealed that CuO is the primary active species,with Cu_(30)/HZSM-5–85 having the largest surface area and highest CuO content,providing more active sites for H_(2)S adsorption.H_(2)-TPR and O_(2)-TPD results confirmed that Cu_(30)/HZSM-5–85 sorbent exhibits outstanding redox properties and oxygen storage capacity,contributing to excellent oxygen transferability in the molecular sieve adsorption-oxidation process.With notable characteristics such as a large surface area,high desulfurization efficiency,and water resistance,Cu_(30)/HZSM-5–85 sorbents hold significant importance for industrial applications.展开更多
Shape-selective methylation of 2-methylnaphthalene (2-MN) was carried out over NH 4 F and Pt modified HZSM-5 (SiO 2 /Al 2 O 3 = 83) catalysts in a fixed-bed down-flow reactor using methanol as methylating agent and 1,...Shape-selective methylation of 2-methylnaphthalene (2-MN) was carried out over NH 4 F and Pt modified HZSM-5 (SiO 2 /Al 2 O 3 = 83) catalysts in a fixed-bed down-flow reactor using methanol as methylating agent and 1,3,5-trimethylbenzene (1,3,5-TMB) as a solvent. Pt promoted HZSM-5 catalysts showed low concentration of coke-like polycondensed aromatics, NH 4 F modification decreased non-shape-selective acid sites. After Pt and NH 4 F co-modification, both conversion of 2-MN and selectivity to 2,6-DMN were improved. 6%NH 4 F/0.5%Pt/HZSM-5 catalyst exhibited 13.8% of 2-MN conversion with 6.2% of 2,6-DMN yield after 7 h time on stream (TOS), and 2,6-/2,7-DMN ratio of 1.7 after 10 h of TOS.展开更多
A series of composite catalysts were prepared by the wet mixing method, and the mass ratio of CuO-ZnO-Al2O3-ZrO2 component to HZSM-5 zeolite （molar ratio of SiO2 to Al2O3 being 25） was 2：1. The CuO-ZnO-Al2O3-ZrO2 ...A series of composite catalysts were prepared by the wet mixing method, and the mass ratio of CuO-ZnO-Al2O3-ZrO2 component to HZSM-5 zeolite （molar ratio of SiO2 to Al2O3 being 25） was 2：1. The CuO-ZnO-Al2O3-ZrO2 （CuO/ZnO/Al2O3=3/6/1 by weight） component was prepared by a modified ＇two-step＇ co-precipitation method. The effects of ZrO2 on the performance of CuO-ZnO-Al2O3/HZSMo5 catalyst for dimethyl ether synthesis from CO2 hydrogenation were investigated. It was found that ZrO2 improved the properties of CuO-ZnO-Al2O3/HZSM-5 as a structural promoter.展开更多
Chlorobenzene removal was investigated in a non-thermal plasma reactor using CeO2/HZSM-5catalysts.The performance of catalysts was evaluated in terms of removal and energy efficiency.The decomposition products of chlo...Chlorobenzene removal was investigated in a non-thermal plasma reactor using CeO2/HZSM-5catalysts.The performance of catalysts was evaluated in terms of removal and energy efficiency.The decomposition products of chlorobenzene were analyzed.The results show that CeO2/HZSM-5 exhibited a good catalytic activity,which resulted in enhancements of chlorobenzene removal,energy efficiency,and the formation of lower amounts of by-products.With regards to CO2 selectivity,the presence of catalysts favors the oxidation of by-products,leading to a higher CO2 selectivity.With respect to ozone,which is considered as an unavoidable by-product in air plasma reactors,a noticeable decrease in its concentration was observed in the presence of catalysts.Furthermore,the stability of the catalyst was investigated by analyzing the evolution of conversion in time.The experiment results indicated that CeO2/HZSM-5 catalysts have excellent stability：chlorobenzene conversion only decreased from 78%to 60%after 75 hr,which means that the CeO2/HZSM-5 suffered a slight deactivation.Some organic compounds and chlorinated intermediates were adsorbed or deposited on the catalysts surface as shown by the results of Fourier Transform Infrared（FT-IR） spectroscopy,scanning electron microscope（SEM） and energy dispersive X-ray spectroscopy（EDS） analyses of the catalyst before and after the reaction,revealing the cause of catalyst deactivation.展开更多
The conversion of CO_(2) into specific aromatics by modulating the morphology of zeolites is a promising strategy.HZSM-5 zeolite with hollow tubular morphology is reported.The morphology of zeolite was precisely contr...The conversion of CO_(2) into specific aromatics by modulating the morphology of zeolites is a promising strategy.HZSM-5 zeolite with hollow tubular morphology is reported.The morphology of zeolite was precisely controlled,and the acid sites on its outer surface were passivated by steam-assisted crystallization method,so that the zeolite exhibits higher aromatic selectivity than sheet HZSM-5 zeolite and greater p-xylene selectivity than chain HZSM-5 zeolite.The tandem catalyst was formed by combining hollow tubular HZSM-5 zeolites with ZnZrO_(x)metal oxides.The para-selectivity of p-xylene reached 76.2%at reaction temperature of 320℃,pressure of 3.0 MPa,and a flow rate of 2400 mL g^(-1)h^(-1)with an H_(2)/CO_(2) molar ratio of 3/1.Further research indicates that the high selectivity of p-xylene is due to the pore structure of hollow tubular HZSM-5 zeolite,which is conducive to the formation of p-xylene.Moreover,the passivation of the acid site located on the outer surface of zeolite effectively prevents the isomerization of p-xylene.The reaction mechanism of CO_(2) hydrogenation over the tandem catalyst was investigated using in-situ diffuse reflectance Fourier transform infrared spectroscopy and density functional theory.The results showed that the CO_(2) to p-xylene followed a methanol-mediated route over ZnZrO_(x)/hollow tubular HZSM-5 tandem catalysts.In addition,the catalyst showed no significant deactivation in the 100 h stability test.This present study provides an effective strategy for the design of catalysts aimed at selectively preparing aromatics through CO_(2)hydrogenation.展开更多
基金supported by the National Natural Science Foundation of China(Nos.52270106 and 22266021)Yunnan Major Scientific and Technological Projects(No.202202AG050005)Yunnan Fundamental Research Projects(No.202201AT070116).
文摘This study employed a wet impregnation method to synthesize five types of Cu/HZSM-5 adsorbents with Si/Al ratios of 25,50,85,200,and 300,used for the removal of H_(2)S in lowtemperature,low-oxygen environments.The impact of different Si/Al ratios on the adsorption oxidative performance of Cu_(30)/HZSM-5–85 adsorbents was investigated.According to the performance test results,Cu_(30)/HZSM-5–85 exhibited the highest breakthrough capacity,reaching 231.75 mg H_(2)S/g_(sorbent).Cu/HZSM-5 sorbent maintains a strong ability to remove H_(2)S even under humid conditions and shows excellent water resistance.XRD,BET,and XPS results revealed that CuO is the primary active species,with Cu_(30)/HZSM-5–85 having the largest surface area and highest CuO content,providing more active sites for H_(2)S adsorption.H_(2)-TPR and O_(2)-TPD results confirmed that Cu_(30)/HZSM-5–85 sorbent exhibits outstanding redox properties and oxygen storage capacity,contributing to excellent oxygen transferability in the molecular sieve adsorption-oxidation process.With notable characteristics such as a large surface area,high desulfurization efficiency,and water resistance,Cu_(30)/HZSM-5–85 sorbents hold significant importance for industrial applications.
基金Supported by the Program for New Century Excellent Talents in University (NCET-04-0268)the Expertise-Introduction Project for Disciplinary Innovation of Universities
文摘Shape-selective methylation of 2-methylnaphthalene (2-MN) was carried out over NH 4 F and Pt modified HZSM-5 (SiO 2 /Al 2 O 3 = 83) catalysts in a fixed-bed down-flow reactor using methanol as methylating agent and 1,3,5-trimethylbenzene (1,3,5-TMB) as a solvent. Pt promoted HZSM-5 catalysts showed low concentration of coke-like polycondensed aromatics, NH 4 F modification decreased non-shape-selective acid sites. After Pt and NH 4 F co-modification, both conversion of 2-MN and selectivity to 2,6-DMN were improved. 6%NH 4 F/0.5%Pt/HZSM-5 catalyst exhibited 13.8% of 2-MN conversion with 6.2% of 2,6-DMN yield after 7 h time on stream (TOS), and 2,6-/2,7-DMN ratio of 1.7 after 10 h of TOS.
文摘A series of composite catalysts were prepared by the wet mixing method, and the mass ratio of CuO-ZnO-Al2O3-ZrO2 component to HZSM-5 zeolite （molar ratio of SiO2 to Al2O3 being 25） was 2：1. The CuO-ZnO-Al2O3-ZrO2 （CuO/ZnO/Al2O3=3/6/1 by weight） component was prepared by a modified ＇two-step＇ co-precipitation method. The effects of ZrO2 on the performance of CuO-ZnO-Al2O3/HZSMo5 catalyst for dimethyl ether synthesis from CO2 hydrogenation were investigated. It was found that ZrO2 improved the properties of CuO-ZnO-Al2O3/HZSM-5 as a structural promoter.
基金supported by the Program for Changjiang Scholars and Innovative Research Team in University(No.IRT13096)the International S&T Cooperation Program of China(No.2011DFA92660)+2 种基金the National Natural Science Foundation of China(No.21276239)the Zhejiang Province Natural Science Foundation of China(No.LY14E080009)the International Cooperation Program of Zhejiang province(No.2013C24003)
文摘Chlorobenzene removal was investigated in a non-thermal plasma reactor using CeO2/HZSM-5catalysts.The performance of catalysts was evaluated in terms of removal and energy efficiency.The decomposition products of chlorobenzene were analyzed.The results show that CeO2/HZSM-5 exhibited a good catalytic activity,which resulted in enhancements of chlorobenzene removal,energy efficiency,and the formation of lower amounts of by-products.With regards to CO2 selectivity,the presence of catalysts favors the oxidation of by-products,leading to a higher CO2 selectivity.With respect to ozone,which is considered as an unavoidable by-product in air plasma reactors,a noticeable decrease in its concentration was observed in the presence of catalysts.Furthermore,the stability of the catalyst was investigated by analyzing the evolution of conversion in time.The experiment results indicated that CeO2/HZSM-5 catalysts have excellent stability：chlorobenzene conversion only decreased from 78%to 60%after 75 hr,which means that the CeO2/HZSM-5 suffered a slight deactivation.Some organic compounds and chlorinated intermediates were adsorbed or deposited on the catalysts surface as shown by the results of Fourier Transform Infrared（FT-IR） spectroscopy,scanning electron microscope（SEM） and energy dispersive X-ray spectroscopy（EDS） analyses of the catalyst before and after the reaction,revealing the cause of catalyst deactivation.
基金financially supported by the National Natural Science Foundation of China(22268039)the Natural Science Foundation for Distinguished Young Scholars of Gansu Province(23JRRA682)。
文摘The conversion of CO_(2) into specific aromatics by modulating the morphology of zeolites is a promising strategy.HZSM-5 zeolite with hollow tubular morphology is reported.The morphology of zeolite was precisely controlled,and the acid sites on its outer surface were passivated by steam-assisted crystallization method,so that the zeolite exhibits higher aromatic selectivity than sheet HZSM-5 zeolite and greater p-xylene selectivity than chain HZSM-5 zeolite.The tandem catalyst was formed by combining hollow tubular HZSM-5 zeolites with ZnZrO_(x)metal oxides.The para-selectivity of p-xylene reached 76.2%at reaction temperature of 320℃,pressure of 3.0 MPa,and a flow rate of 2400 mL g^(-1)h^(-1)with an H_(2)/CO_(2) molar ratio of 3/1.Further research indicates that the high selectivity of p-xylene is due to the pore structure of hollow tubular HZSM-5 zeolite,which is conducive to the formation of p-xylene.Moreover,the passivation of the acid site located on the outer surface of zeolite effectively prevents the isomerization of p-xylene.The reaction mechanism of CO_(2) hydrogenation over the tandem catalyst was investigated using in-situ diffuse reflectance Fourier transform infrared spectroscopy and density functional theory.The results showed that the CO_(2) to p-xylene followed a methanol-mediated route over ZnZrO_(x)/hollow tubular HZSM-5 tandem catalysts.In addition,the catalyst showed no significant deactivation in the 100 h stability test.This present study provides an effective strategy for the design of catalysts aimed at selectively preparing aromatics through CO_(2)hydrogenation.
