To prepare a highly efficient NiMo/Al_(2)O_(3) hydrodesulfurization catalyst,the combined effects of specific organic functional groups and alumina surface characteristics were investigated.First,the correlation betwe...To prepare a highly efficient NiMo/Al_(2)O_(3) hydrodesulfurization catalyst,the combined effects of specific organic functional groups and alumina surface characteristics were investigated.First,the correlation between the surface characteristics of four different alumina and the existing Mo species states was established.It was found that the Mo equilibrium adsorption capacity can be used as a specific descriptor to quantitatively evaluate the changes in surface characteristics of different alumina.A lower Mo equilibrium adsorption capacity for alumina means weaker metal-support interaction and the loaded Mo species are easier to transform into MoS2.However,the Mo-O-Al bonds still exist at the metal-support interface.The introduction of cationic surfactant hecadecyl trimethyl ammonium bromide(CTAB)can further improve Mo species dispersion through electrostatic attraction with Mo anions and interaction of its alkyl chain with the alumina surface;meanwhile,the introduction of ethylenediamine tetraacetic acid(EDTA)can complex with Ni ions to enhance the Ni-promoting effect on Mo.Therefore,the NiMo catalyst designed using alumina with lower Mo equilibrium adsorption capacity and the simultaneous addition of EDTA and CTAB exhibits the highest hydrodesulfurization activity for 4,6-dimethyl dibenzothiophene because of its proper metal-support interaction and more well-dispersed Ni-Mo-S active phases.展开更多
Yolk-shell SiO2 particles(YP)with center-radial meso-channels were fabricated through a simple and effective method.Al-containing YP-supported NiMo catalysts with different Al amounts(NiMo/AYP-x,x=Si/Al molar proporti...Yolk-shell SiO2 particles(YP)with center-radial meso-channels were fabricated through a simple and effective method.Al-containing YP-supported NiMo catalysts with different Al amounts(NiMo/AYP-x,x=Si/Al molar proportion)were prepared and dibenzothiophene(DBT)and 4,6-dimethyl-dibenzothiophene(4,6-DMDBT)were employed as the probes to evaluate the hydrodesulfurization(HDS)catalytic performance.The as-prepared AYP-x carriers and corresponding catalysts were characterized by some advanced characterizations to obtain deeper correlations between physicochemical properties and the HDS performance.The average pore sizes of series AYP-x supports are above 6.0 nm,which favors the mass transfer of organic sulfides.The cavity between the yolk and the shell is beneficial for the enrichment of S-containing compounds and the accessibility between reactants and active metals.Aluminum embedded into the silica framework could facilitate the formation of Lewis(L)and Brønsted(B)acid sites and adjust the metal-support interaction(MSI).Among all the as-synthesized catalysts,NiMo/AYP-20 catalyst shows the highest HDS activities.The improved HDS activity of NiMo/AYP-20 catalyst is attributed to the perfect combination of excellent structural properties of the yolk-shell mesoporous silica,enhanced acidity,moderate MSI,and good accessibility/dispersion of active components.展开更多
A three-lumping Langmuir-Hinshelwood kinetic model was established based on the structures and reactivities of sulfur compounds.This model described the ultra-deep hydrodesulfurization(UDHDS)performance of diesel,redu...A three-lumping Langmuir-Hinshelwood kinetic model was established based on the structures and reactivities of sulfur compounds.This model described the ultra-deep hydrodesulfurization(UDHDS)performance of diesel,reducing sulfur content from 10000μg/g to less than 10μg/g,with experimental and predicted data showing a discrepancy of less than 10%.The diesel UDHDS reaction was simulated by combining the mass transfer,reaction kinetics model,and physical properties of diesel.The results showed how the concentrations of H2S,hydrogen,and sulfur in the gas,liquid,and solid phases varied along the reactor length.Moreover,the study discussed the effects of each process parameter and impurity concentrations(H2S,basic nitrogen and,non-basic nitrogen)on diesel UDHDS.展开更多
Herein,we designed and constructed a mesoporous LaAlOx via a solvent evaporation induced self-assembly protocol.The structure and physicochemical property of the corresponding NiMo supported catalyst was analyzed by a...Herein,we designed and constructed a mesoporous LaAlOx via a solvent evaporation induced self-assembly protocol.The structure and physicochemical property of the corresponding NiMo supported catalyst was analyzed by a set of characterizations,and its catalytic activity was investigated for hydrodesulfurization(HDS)of 4,6-dimethyldibenzothiophene.It has confirmed that the incorporation of La profoundly facilitate the generation of“Type II”NiMoS phase by weakening the interaction of Mo–O–Al leakage and promoting the sulfidation of both Ni and Mo oxides as well as changing the morphology of Ni promoted MoS2 slabs,thereafter boosting the HDS performance substantially.The finding here may contribute to the fundamental understanding of structure-activity in ultra-deep desulfurization and inspire the advancement of highly-efficient HDS catalyst in future.展开更多
A highly active sulfided NiPMo/MCM-41(NiPMo-S/M41)hydrodesulfurization(HDS)catalyst was successfully synthesized using Keggin-type phosphomolybdic acid as the phosphorus and molybdenum source and thioacetamide as the ...A highly active sulfided NiPMo/MCM-41(NiPMo-S/M41)hydrodesulfurization(HDS)catalyst was successfully synthesized using Keggin-type phosphomolybdic acid as the phosphorus and molybdenum source and thioacetamide as the sulfur source.The supported catalysts NiPMo/M41,Ni_(2)P-Mo/M41,and Ni_(2)P/M41 were also prepared to investigate the effects of Mo,S,and the Keggin structure on the HDS performance.The HDS activities of NiPMo/M41 and NiPMo-S/M41 toward dibenzothiophene were much higher than that of Ni_(2)P-Mo/M41,demonstrating that the active phases in the Keggin-structured catalysts were significantly superior to the Mo-modified Ni_(2)P phase.The HDS activities of the catalysts followed the order NiPMo-S/M41(96.7%)>NiPMo/M41(89.9%)>Ni_(2)P-Mo/M41(53.5%)>Ni_(2)P/M41(48.9%).For Ni_(2)P/M41,Ni_(2)P-Mo/M41,and NiPMo/M41,cyclohexylbenzene(CHB)was formed in low concentrations(<21.0%),indicating that direct desulfurization was the favored reaction route and that this did not change for Keggin-structured NiPMo/M41.By contrast,the CHB selectivity of NiPMo-S/M41 increased to 44.6%,much higher than that of NiPMo/M41(17.6%),demonstrating that sulfidation enhanced the hydrogenation ability,which was ascribed to a metal-acid synergistic effect.展开更多
A H_(2)O_(2)etching strategy was adopted to introduce coordinatively unsaturated sites(CUS)on MoS_(2)-based catalysts for dibenzothiophene(DBT)hydrodesulfurization(HDS).The CUS concentrations on MoS_(2) slabs were fin...A H_(2)O_(2)etching strategy was adopted to introduce coordinatively unsaturated sites(CUS)on MoS_(2)-based catalysts for dibenzothiophene(DBT)hydrodesulfurization(HDS).The CUS concentrations on MoS_(2) slabs were finely regulated by changing the concentrations of H_(2)O_(2)solution.With the increasing H_(2)O_(2)concentrations(0.1–0.3 mol/L),The CUS concentrations on MoS_(2) slabs increased gradually.However,the high-concentration H_(2)O_(2)etching(0.5 mol/L)increased the MoOxSy and MoO_(3) contents on MoS_(2) slabs compared to etching with the H_(2)O_(2)concentration of 0.3 mol/L,which led to the less CUS concentration in the sulfided Mo–H-0.5 catalyst than in the sulfided Mo–H-0.3 catalyst.A microstructure-activity correlation indicated that the CUS introduced by H_(2)O_(2)etching on MoS_(2) slabs significantly enhanced DBT HDS.Different Co loadings were further introduced into Mo–H-0.3,which had the most CUS concentration,and the corresponding 0.2-CoMo catalyst with the highest CoMoS content(3.853 wt%)exhibited the highest reaction rate constant of 6.95×10^(−6)mol g^(−1)s^(−1)among these CoMo catalysts.展开更多
A novel composite material(TD)composed of TS-1 microcrystalline and dendritic mesoporous silica nanospheres(DMSNs)was successfully prepared.The TD composite material had open pore structure and large specific surface ...A novel composite material(TD)composed of TS-1 microcrystalline and dendritic mesoporous silica nanospheres(DMSNs)was successfully prepared.The TD composite material had open pore structure and large specific surface area,which was conducive to the mass transfer of reactants and products.The Ti element in TS-1 could be used as an electron assistant,and the spillover d-electrons were conducive to the improvement of the sulfidation and dispersion of MoS_(2),thereby forming more type II MoS_(2) active phases.The incorporation of Ti could bring more Brønsted(B)and Lewis(L)acid,which was conducive to the hydrogenation pathway(HYD)selectivity(41.2%)of dibenzothiophene(DBT)hydrodesulfurization(HDS)and isomerization(ISO)route selectivity(21.9%)of 4,6-dimethyldibenzothiophene(4,6-DMDBT)HDS,thus improve the HDS activity of DBT and 4,6-DMDBT.NiMo/TD-70(Aging temperature=70℃)had the best HDS activities of DBT(99.0%)and 4,6-DMDBT(93.7%)due to its large open pore structure,good acidity,suitable metal-support interaction(MSI)and perfect dispersion of the metallic active sites.展开更多
基金funding of the National Key Research and Development Plan(Grant 2017YFB0306600)the Project of SINOPEC(NO.117006).
文摘To prepare a highly efficient NiMo/Al_(2)O_(3) hydrodesulfurization catalyst,the combined effects of specific organic functional groups and alumina surface characteristics were investigated.First,the correlation between the surface characteristics of four different alumina and the existing Mo species states was established.It was found that the Mo equilibrium adsorption capacity can be used as a specific descriptor to quantitatively evaluate the changes in surface characteristics of different alumina.A lower Mo equilibrium adsorption capacity for alumina means weaker metal-support interaction and the loaded Mo species are easier to transform into MoS2.However,the Mo-O-Al bonds still exist at the metal-support interface.The introduction of cationic surfactant hecadecyl trimethyl ammonium bromide(CTAB)can further improve Mo species dispersion through electrostatic attraction with Mo anions and interaction of its alkyl chain with the alumina surface;meanwhile,the introduction of ethylenediamine tetraacetic acid(EDTA)can complex with Ni ions to enhance the Ni-promoting effect on Mo.Therefore,the NiMo catalyst designed using alumina with lower Mo equilibrium adsorption capacity and the simultaneous addition of EDTA and CTAB exhibits the highest hydrodesulfurization activity for 4,6-dimethyl dibenzothiophene because of its proper metal-support interaction and more well-dispersed Ni-Mo-S active phases.
文摘针对室内全球导航卫星系统(Global navigation satellite system,GNSS)信号受遮挡时,农用车辆协同定位精度低、稳定性差、信号丢包等问题,本文开展面向超宽带(Ultra-wideband,UWB)调频技术的室内外农用车辆协同定位算法研究。首先,搭建三基站多边测距定位模型,实现主基站绝对位置标定以及辅助基站绝对位置坐标的变换求解;其次,提出全质心加权最小二乘的高速双边双向(Weighted least squares high double sided two-way ranging,WLS-HDS-TWR)农机协同定位算法,基于泰勒级数展开的WLS估计算法,求解主车位置。同时,提出面向室内环境的多状态基站组合的UWB定位模块布设模式,并验证其可行性;通过飞行时间法(Time of flight,TOF)获取主从车距离信息,融合GNSS标定位置信息、主车坐标信息以及测距信息,实现主从车协同定位。最后,基于Prescan/Simulink搭建联合仿真平台,验证提出算法的可靠性;通过农用履带车辆开展室内及室外协同定位实车试验,试验结果表明:全质心WLS-HDS-TWR协同定位算法可有效解决室内GNSS信号缺失问题,室内环境下,定位精度较HDS-TWR及全质心LS-HDS-TWR算法分别提高26.98%和22.03%,满足智能农机协同定位作业需求。
基金The authors acknowledge the financial supports from the National Science Foundation of China(U1908204,91845201,and 22002093)the funds that Central Government Guides Local Science and Technology Development(2022JH6/100100052)Scientific Research Project of Education Department of Liaoning Province(LQN202006).
文摘Yolk-shell SiO2 particles(YP)with center-radial meso-channels were fabricated through a simple and effective method.Al-containing YP-supported NiMo catalysts with different Al amounts(NiMo/AYP-x,x=Si/Al molar proportion)were prepared and dibenzothiophene(DBT)and 4,6-dimethyl-dibenzothiophene(4,6-DMDBT)were employed as the probes to evaluate the hydrodesulfurization(HDS)catalytic performance.The as-prepared AYP-x carriers and corresponding catalysts were characterized by some advanced characterizations to obtain deeper correlations between physicochemical properties and the HDS performance.The average pore sizes of series AYP-x supports are above 6.0 nm,which favors the mass transfer of organic sulfides.The cavity between the yolk and the shell is beneficial for the enrichment of S-containing compounds and the accessibility between reactants and active metals.Aluminum embedded into the silica framework could facilitate the formation of Lewis(L)and Brønsted(B)acid sites and adjust the metal-support interaction(MSI).Among all the as-synthesized catalysts,NiMo/AYP-20 catalyst shows the highest HDS activities.The improved HDS activity of NiMo/AYP-20 catalyst is attributed to the perfect combination of excellent structural properties of the yolk-shell mesoporous silica,enhanced acidity,moderate MSI,and good accessibility/dispersion of active components.
文摘A three-lumping Langmuir-Hinshelwood kinetic model was established based on the structures and reactivities of sulfur compounds.This model described the ultra-deep hydrodesulfurization(UDHDS)performance of diesel,reducing sulfur content from 10000μg/g to less than 10μg/g,with experimental and predicted data showing a discrepancy of less than 10%.The diesel UDHDS reaction was simulated by combining the mass transfer,reaction kinetics model,and physical properties of diesel.The results showed how the concentrations of H2S,hydrogen,and sulfur in the gas,liquid,and solid phases varied along the reactor length.Moreover,the study discussed the effects of each process parameter and impurity concentrations(H2S,basic nitrogen and,non-basic nitrogen)on diesel UDHDS.
基金financial support of the National Natural Science Foundation of China(22002050,22178154)the Project of Jiangsu University Senior Talents Foundation(20JDG35)+1 种基金Postdoctoral Science Foundation of China(2022T150765,2020M683154)National Engineering Laboratory for Mobile Source Emission Control Technology(NELMS2020B01).
文摘Herein,we designed and constructed a mesoporous LaAlOx via a solvent evaporation induced self-assembly protocol.The structure and physicochemical property of the corresponding NiMo supported catalyst was analyzed by a set of characterizations,and its catalytic activity was investigated for hydrodesulfurization(HDS)of 4,6-dimethyldibenzothiophene.It has confirmed that the incorporation of La profoundly facilitate the generation of“Type II”NiMoS phase by weakening the interaction of Mo–O–Al leakage and promoting the sulfidation of both Ni and Mo oxides as well as changing the morphology of Ni promoted MoS2 slabs,thereafter boosting the HDS performance substantially.The finding here may contribute to the fundamental understanding of structure-activity in ultra-deep desulfurization and inspire the advancement of highly-efficient HDS catalyst in future.
基金National Natural Science Foundation of China(Grant No.52006225).
文摘A highly active sulfided NiPMo/MCM-41(NiPMo-S/M41)hydrodesulfurization(HDS)catalyst was successfully synthesized using Keggin-type phosphomolybdic acid as the phosphorus and molybdenum source and thioacetamide as the sulfur source.The supported catalysts NiPMo/M41,Ni_(2)P-Mo/M41,and Ni_(2)P/M41 were also prepared to investigate the effects of Mo,S,and the Keggin structure on the HDS performance.The HDS activities of NiPMo/M41 and NiPMo-S/M41 toward dibenzothiophene were much higher than that of Ni_(2)P-Mo/M41,demonstrating that the active phases in the Keggin-structured catalysts were significantly superior to the Mo-modified Ni_(2)P phase.The HDS activities of the catalysts followed the order NiPMo-S/M41(96.7%)>NiPMo/M41(89.9%)>Ni_(2)P-Mo/M41(53.5%)>Ni_(2)P/M41(48.9%).For Ni_(2)P/M41,Ni_(2)P-Mo/M41,and NiPMo/M41,cyclohexylbenzene(CHB)was formed in low concentrations(<21.0%),indicating that direct desulfurization was the favored reaction route and that this did not change for Keggin-structured NiPMo/M41.By contrast,the CHB selectivity of NiPMo-S/M41 increased to 44.6%,much higher than that of NiPMo/M41(17.6%),demonstrating that sulfidation enhanced the hydrogenation ability,which was ascribed to a metal-acid synergistic effect.
基金support of the National Natural Science Foundation of China(Grant Nos.21978323 and 22108145).
文摘A H_(2)O_(2)etching strategy was adopted to introduce coordinatively unsaturated sites(CUS)on MoS_(2)-based catalysts for dibenzothiophene(DBT)hydrodesulfurization(HDS).The CUS concentrations on MoS_(2) slabs were finely regulated by changing the concentrations of H_(2)O_(2)solution.With the increasing H_(2)O_(2)concentrations(0.1–0.3 mol/L),The CUS concentrations on MoS_(2) slabs increased gradually.However,the high-concentration H_(2)O_(2)etching(0.5 mol/L)increased the MoOxSy and MoO_(3) contents on MoS_(2) slabs compared to etching with the H_(2)O_(2)concentration of 0.3 mol/L,which led to the less CUS concentration in the sulfided Mo–H-0.5 catalyst than in the sulfided Mo–H-0.3 catalyst.A microstructure-activity correlation indicated that the CUS introduced by H_(2)O_(2)etching on MoS_(2) slabs significantly enhanced DBT HDS.Different Co loadings were further introduced into Mo–H-0.3,which had the most CUS concentration,and the corresponding 0.2-CoMo catalyst with the highest CoMoS content(3.853 wt%)exhibited the highest reaction rate constant of 6.95×10^(−6)mol g^(−1)s^(−1)among these CoMo catalysts.
基金This research was supported by the Science Foundation of China University of Petroleum-Beijing(No.2462023QNXZ002)the National Key R&D Program of China(2021YFA1501201)+2 种基金the National Natural Science Foundation of China(No.22278174)Independent research project of State Key Laboratory of heavy oil(2021–01)Shandong Excellent Young Scientists Fund Program(Overseas,2022HWYQ-082).
文摘A novel composite material(TD)composed of TS-1 microcrystalline and dendritic mesoporous silica nanospheres(DMSNs)was successfully prepared.The TD composite material had open pore structure and large specific surface area,which was conducive to the mass transfer of reactants and products.The Ti element in TS-1 could be used as an electron assistant,and the spillover d-electrons were conducive to the improvement of the sulfidation and dispersion of MoS_(2),thereby forming more type II MoS_(2) active phases.The incorporation of Ti could bring more Brønsted(B)and Lewis(L)acid,which was conducive to the hydrogenation pathway(HYD)selectivity(41.2%)of dibenzothiophene(DBT)hydrodesulfurization(HDS)and isomerization(ISO)route selectivity(21.9%)of 4,6-dimethyldibenzothiophene(4,6-DMDBT)HDS,thus improve the HDS activity of DBT and 4,6-DMDBT.NiMo/TD-70(Aging temperature=70℃)had the best HDS activities of DBT(99.0%)and 4,6-DMDBT(93.7%)due to its large open pore structure,good acidity,suitable metal-support interaction(MSI)and perfect dispersion of the metallic active sites.