KIT-5/Beta composite supports were synthesized using an in situ self-assembly hydrothermal method,and NiW/KIT-5/Beta catalysts were prepared by impregnation.A series of characterization techniques were utilized to eva...KIT-5/Beta composite supports were synthesized using an in situ self-assembly hydrothermal method,and NiW/KIT-5/Beta catalysts were prepared by impregnation.A series of characterization techniques were utilized to evaluate the influence of varying hydrothermal synthesis temperatures on the physicochemical properties of both the KIT-5/Beta supports and the resulting catalysts.The catalytic performances of catalysts were evaluated under reaction conditions of 320℃,4 MPa H_(2)pressure,and a weight hourly space velocity(WHSV)of 4.8 h^(-1)for hydrodenitrogenation(HDN)of quinoline.The results indicated that the specific surface area and pore structure of the materials could be effectively regulated by adjusting the hydrothermal synthesis temperature,which in turn influenced the number of active sites on the catalyst.The NiW/KB-125 catalyst,synthesized at 125℃,presented the highest quinoline HDN efficiency(96.8%),which can be attributed to its favorable pore channel structure,greater Brønsted acid number,higher degree of metal sulfidation(80.12%)and appropriate metal-support interaction(MSI).展开更多
The structure-performance relationship of Cu/Al_(2)O_(3) catalysts in the hydrogenation of diethyl oxalate(DEO)for the synthesis of alcohol ether esters has been investigated by various characterization techniques inc...The structure-performance relationship of Cu/Al_(2)O_(3) catalysts in the hydrogenation of diethyl oxalate(DEO)for the synthesis of alcohol ether esters has been investigated by various characterization techniques including XRD,XPS,N2O titration,and 27Al MAS-NMR.The results showed that when the crystal configurations of Al_(2)O_(3) were the same,increasing the specific surface area could effectively refine the size of copper nanoparticles(Cu NPs),and ultimately improve the conversion of DEO.Meanwhile,the smaller size ofγ-Al_(2)O_(3)(HSAl and SBAl)loaded Cu NPs promotes the reaction towards the deep hydrogenation to produce ethanol(EtOH)and ethylene glycol(EG).Besides,the larger size of Cu NPs on the surface of amorphous Al_(2)O_(3)(HTAl and SolAl)resulted in a lower conversion rate,where ethyl glycolate(Egly)is the main product.Despite there are differences in Al^(3+)ionic coordination in Al_(2)O_(3) with different crystal structures,the experimental data showed that the differences in Al^(3+)ionic coordination did not significantly affect the catalytic performance in the hydrogenation reaction.The formation of alcohol-ether ester chemicals is critically dependent on the interactions between Cu sites and acidic sites.Among them,EG and EtOH were dehydrated to form 2-ethoxyethanol via the SN2 mechanism,while Egly and EtOH were reacted to form ethyl ethoxyacetate(EEA)via the SN2 mechanism.This study provides a theoretical basis for the optimization of the coal-based glycol processes to achieve a diversified product portfolio.展开更多
基金Supported by the Autonomous Research Project of SKLCC(2024BWZ003)Strategic Priority Research Program of the Chinese Academy of Sciences(XDA0390401)the Doctoral Research Start-up Funding of Shanxi Institute of Technology(026012).
文摘KIT-5/Beta composite supports were synthesized using an in situ self-assembly hydrothermal method,and NiW/KIT-5/Beta catalysts were prepared by impregnation.A series of characterization techniques were utilized to evaluate the influence of varying hydrothermal synthesis temperatures on the physicochemical properties of both the KIT-5/Beta supports and the resulting catalysts.The catalytic performances of catalysts were evaluated under reaction conditions of 320℃,4 MPa H_(2)pressure,and a weight hourly space velocity(WHSV)of 4.8 h^(-1)for hydrodenitrogenation(HDN)of quinoline.The results indicated that the specific surface area and pore structure of the materials could be effectively regulated by adjusting the hydrothermal synthesis temperature,which in turn influenced the number of active sites on the catalyst.The NiW/KB-125 catalyst,synthesized at 125℃,presented the highest quinoline HDN efficiency(96.8%),which can be attributed to its favorable pore channel structure,greater Brønsted acid number,higher degree of metal sulfidation(80.12%)and appropriate metal-support interaction(MSI).
文摘The structure-performance relationship of Cu/Al_(2)O_(3) catalysts in the hydrogenation of diethyl oxalate(DEO)for the synthesis of alcohol ether esters has been investigated by various characterization techniques including XRD,XPS,N2O titration,and 27Al MAS-NMR.The results showed that when the crystal configurations of Al_(2)O_(3) were the same,increasing the specific surface area could effectively refine the size of copper nanoparticles(Cu NPs),and ultimately improve the conversion of DEO.Meanwhile,the smaller size ofγ-Al_(2)O_(3)(HSAl and SBAl)loaded Cu NPs promotes the reaction towards the deep hydrogenation to produce ethanol(EtOH)and ethylene glycol(EG).Besides,the larger size of Cu NPs on the surface of amorphous Al_(2)O_(3)(HTAl and SolAl)resulted in a lower conversion rate,where ethyl glycolate(Egly)is the main product.Despite there are differences in Al^(3+)ionic coordination in Al_(2)O_(3) with different crystal structures,the experimental data showed that the differences in Al^(3+)ionic coordination did not significantly affect the catalytic performance in the hydrogenation reaction.The formation of alcohol-ether ester chemicals is critically dependent on the interactions between Cu sites and acidic sites.Among them,EG and EtOH were dehydrated to form 2-ethoxyethanol via the SN2 mechanism,while Egly and EtOH were reacted to form ethyl ethoxyacetate(EEA)via the SN2 mechanism.This study provides a theoretical basis for the optimization of the coal-based glycol processes to achieve a diversified product portfolio.
