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
A series of sulfided tertiary NiMoP/ γ Al 2O 3 catalysts with different contents of MoO 3 were prepared by using molybdophosphoric acid of Keggin structure(H 3PMo 12 O 40 ) and nickel nitrate as origins of active pha...A series of sulfided tertiary NiMoP/ γ Al 2O 3 catalysts with different contents of MoO 3 were prepared by using molybdophosphoric acid of Keggin structure(H 3PMo 12 O 40 ) and nickel nitrate as origins of active phase components of molybdenum, phosphorus and nickel, and characterized by TPR technique, with their HDS activity being investigated with thiophene as a model substrate. For the sulfided Mo 0 catalyst containing no nickel as promoter, the only hydrogen sulfide evolution peak Ⅰ is observed at 462 K and attributed to the hydrogenation of the so called edge sulfur atoms chemisorbed on coordinatively unsaturated(cus) Mo x+ sites on the MoS 2 phase(MoS 2 slab). With the introduction of nickel into the active phase of the sulfided Mo 0 catalyst and with the increase of the molybdenum loading, a new hydrogen sulfide evolution peak Ⅱ gradually develops at the low temperature side of the peak Ⅰ, at the same time accompanied by both the increase of the area ratio of the peak Ⅱ to the peak Ⅰ and the shift of the hydrogen sulfide evolution maximum rate to lower temperatures, which may imply the existence of two kinds of active centers related to molybdenum and nickel respectively and the synergic action between the two centers above. It should be noted that for the sulfided NiMoP/ γ Al 2O 3 catalysts, the thiophene HDS rate and the quantity of hydrogen sulfide evolved during TPR process increase monotonously with the atomic ratio of molybdenum to nickel in the form of [ n (Ni)+ n (Mo)]/ n (Ni). On the basis of the results here, the conclusion may be reached that the two kinds of vacancies can be formed on the edge of Ni Mo S slab due to the loss of S during TPR process and vacancies or sites related to the H 2S evolution peak II should be regarded as the mainly active reaction centers of thiophene HDS.展开更多
A series of sulfided PtMo/ γ Al 2O 3 catalysts[ w (Mo)=9.0%] with different contents of Pt were characterized by using low temperature FTIR spectroscopy of adsorbed CO, while their HDS activity was investigated with ...A series of sulfided PtMo/ γ Al 2O 3 catalysts[ w (Mo)=9.0%] with different contents of Pt were characterized by using low temperature FTIR spectroscopy of adsorbed CO, while their HDS activity was investigated with thiophene as a model substrate. Experimentally, it was found that no existence of the bands related to the surface complexes of Al 3+ ←CO and Pt 0←CO→Pt 0 was observed at 77 K and that the rate of the thiophene HDS reaction(573 K) is well linearly proportional to the area of the Pt 0←CO band at 2 093 cm -1 with a higher extrapolated HDS rate compared to that of sulfided Mo/ γ Al 2O 3 catalyst at the zero content of platinum. On the basis of the results here, the conclusion may be made that the active monolayer phase of Pt Mo S may be formed over sulfided PtMo/ γ Al 2O 3 catalysts during the sulfidation process and that both Mo 2+ and Pt 0 sites for CO adsorption should be the active reaction centers of thiophene HDS.展开更多
A sulfided Mo/γ-Al2O3 catalyst was characterized by low-temperature FTIR spectroscopy of adsorbed carbon monoxide, with its HDS activity being investigated with thiophene as a mold substrate. On the basis of the resu...A sulfided Mo/γ-Al2O3 catalyst was characterized by low-temperature FTIR spectroscopy of adsorbed carbon monoxide, with its HDS activity being investigated with thiophene as a mold substrate. On the basis of the results here, the conclusion may be obtained that the sites for CO adsorption should be the active reaction centers of thiophene HDS.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.
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.
文摘A series of sulfided tertiary NiMoP/ γ Al 2O 3 catalysts with different contents of MoO 3 were prepared by using molybdophosphoric acid of Keggin structure(H 3PMo 12 O 40 ) and nickel nitrate as origins of active phase components of molybdenum, phosphorus and nickel, and characterized by TPR technique, with their HDS activity being investigated with thiophene as a model substrate. For the sulfided Mo 0 catalyst containing no nickel as promoter, the only hydrogen sulfide evolution peak Ⅰ is observed at 462 K and attributed to the hydrogenation of the so called edge sulfur atoms chemisorbed on coordinatively unsaturated(cus) Mo x+ sites on the MoS 2 phase(MoS 2 slab). With the introduction of nickel into the active phase of the sulfided Mo 0 catalyst and with the increase of the molybdenum loading, a new hydrogen sulfide evolution peak Ⅱ gradually develops at the low temperature side of the peak Ⅰ, at the same time accompanied by both the increase of the area ratio of the peak Ⅱ to the peak Ⅰ and the shift of the hydrogen sulfide evolution maximum rate to lower temperatures, which may imply the existence of two kinds of active centers related to molybdenum and nickel respectively and the synergic action between the two centers above. It should be noted that for the sulfided NiMoP/ γ Al 2O 3 catalysts, the thiophene HDS rate and the quantity of hydrogen sulfide evolved during TPR process increase monotonously with the atomic ratio of molybdenum to nickel in the form of [ n (Ni)+ n (Mo)]/ n (Ni). On the basis of the results here, the conclusion may be reached that the two kinds of vacancies can be formed on the edge of Ni Mo S slab due to the loss of S during TPR process and vacancies or sites related to the H 2S evolution peak II should be regarded as the mainly active reaction centers of thiophene HDS.
文摘A series of sulfided PtMo/ γ Al 2O 3 catalysts[ w (Mo)=9.0%] with different contents of Pt were characterized by using low temperature FTIR spectroscopy of adsorbed CO, while their HDS activity was investigated with thiophene as a model substrate. Experimentally, it was found that no existence of the bands related to the surface complexes of Al 3+ ←CO and Pt 0←CO→Pt 0 was observed at 77 K and that the rate of the thiophene HDS reaction(573 K) is well linearly proportional to the area of the Pt 0←CO band at 2 093 cm -1 with a higher extrapolated HDS rate compared to that of sulfided Mo/ γ Al 2O 3 catalyst at the zero content of platinum. On the basis of the results here, the conclusion may be made that the active monolayer phase of Pt Mo S may be formed over sulfided PtMo/ γ Al 2O 3 catalysts during the sulfidation process and that both Mo 2+ and Pt 0 sites for CO adsorption should be the active reaction centers of thiophene HDS.
文摘A sulfided Mo/γ-Al2O3 catalyst was characterized by low-temperature FTIR spectroscopy of adsorbed carbon monoxide, with its HDS activity being investigated with thiophene as a mold substrate. On the basis of the results here, the conclusion may be obtained that the sites for CO adsorption should be the active reaction centers of thiophene HDS.
