The effect of support calcination temperature on the benzene selective hydrogenation performance of the Ru-Ce-B/ZrO2 catalysts was investigated.It was found that with increasing calcination temperature,the surface are...The effect of support calcination temperature on the benzene selective hydrogenation performance of the Ru-Ce-B/ZrO2 catalysts was investigated.It was found that with increasing calcination temperature,the surface area decreased,on the contrary,the pore size and the amount of monoclinic phase increased.With increasing support calcination temperature,the activity of the catalyst roughly decreased and cyclohexene selectivity increased.The activity decreased due to the decrease of the surface areas.The increase of the cyclohexene selectivity was correlated not only with the decrease of the surface areas but also with the increase of monoclinic phases,rich in surface hydroxyl,and the enlarged pore size of zirconia.This suggests the monoclinic zirconia with a medium surface area,rather than a big one,and a mesoporous structure,even including some macropores,is an ideal support of the catalyst for benzene selective hydrogenation.展开更多
Ru-Ce catalysts were prepared by a co-precipitation method.The effects of Ce precursors with different valences and Ce contents on the catalytic performance of Ru-Ce catalysts were investigated in the presence of ZnSO...Ru-Ce catalysts were prepared by a co-precipitation method.The effects of Ce precursors with different valences and Ce contents on the catalytic performance of Ru-Ce catalysts were investigated in the presence of ZnSO4.The Ce species in the catalysts prepared with different valences of the Ce precursors all exist as CeO2 on the Ru surface.The promoter CeO2alone could not improve the selectivity to cyclohexene of Ru catalysts.However,almost all the CeO2 in the catalysts could react with the reaction modifier ZnSO4 to form(Zn(OH)2)3(ZnSO4)(H2O)3 salt.The amount of the chemisorbed salt increased with the CeO2 loading,resulting in the decrease of the activity and the increase of the selectivity to cyclohexene of Ru catalyst.The Ru-Ce catalyst with the optimum Ce/Ru molar ratio of 0.19 gave a maximum cyclohexene yield of 57.4%.Moreover,this catalyst had good stability and excellent reusability.展开更多
A novel nanosized amorphous Ru-Fe-B/ZrO2 alloy catalyst for benzene selective hydrogenation to cyclohexene was investigated. The superior properties of this catalyst were attributed to the combination of the nanosize ...A novel nanosized amorphous Ru-Fe-B/ZrO2 alloy catalyst for benzene selective hydrogenation to cyclohexene was investigated. The superior properties of this catalyst were attributed to the combination of the nanosize and the amorphous character as well as to its textural character. In addition, the concentration of zinc ions, the content of ZrO2 in the slurry, and the pretreatment of the catalyst were found to be effective in improving the activity and the selectivity of the catalyst.展开更多
A Ru-La/ZrO2 catalyst was prepared by the precipitation method, in which Ru was an active component, La was a promoter and ZrO2 was a dispersant. Comparing with the catalyst prepared by the chemical reduction method, ...A Ru-La/ZrO2 catalyst was prepared by the precipitation method, in which Ru was an active component, La was a promoter and ZrO2 was a dispersant. Comparing with the catalyst prepared by the chemical reduction method, the Ru-La/ZrO2 exhibited higher activity and better selectivity. At 140 ℃ and hydrogen pressure of 5 MPa, the C6H10 selectivity reached 70% at a C6H6 conversion of 35% for a reaction time was 5 min and the total La/Ru loading was 10%. Textural parameters of the catalyst were obtained by physical adsorption, BET surface area and specific pore volume measurements. The catalyst sample gave a BET area of 41 m2/g and a specific pore volume of 1.1 cm^3/g, and the most probable pore distribution was located at 5 to 10 nm. H2-TPR measurements showed that ruthenium oxide could be reduced to its metallic state at about 403 K. XRD determinations indicated that ruthenium and lanthanum were highly dispersed on the zirconia. A significant advantage of the Ru-La/ZrO2 catalyst is that it can be used directly in its unreduced state for the selective hydrogenation of benzene.展开更多
Ru-based catalysts promoted with Mn and Zn were prepared by a co-precipitation method. In liquid-phase hydrogenation of benzene, the Ru-Mn-Zn catalysts exhibited superior catalytic performance to the catalysts promote...Ru-based catalysts promoted with Mn and Zn were prepared by a co-precipitation method. In liquid-phase hydrogenation of benzene, the Ru-Mn-Zn catalysts exhibited superior catalytic performance to the catalysts promoted with Zn or Mn alone. The optimum Mn/Zn molar ratio was determined to be 0.3. With the addition of 0.5 g NaOH, the Ru-Mn-Zn-0.3 catalyst, which was reduced at 150 ？ C, afforded a cyclohexene selectivity of 81.1% at a benzene conversion of 60.2% at 5 min and a maximum cyclohexene yield of 59.9% at 20 min. Based on characterizations, the excellent performance of Ru-Mn-Zn catalyst was ascribed to the suitable pore structure, the appropriate reducibility and the homogenous chemical environment of the catalyst.展开更多
Selective hydrogenation of benzene is an atom economic green route to produce cyclohexene. The control of Zn species is the key to the catalytic performance of Ru–Zn catalysts. The influences of ZnO crystals on selec...Selective hydrogenation of benzene is an atom economic green route to produce cyclohexene. The control of Zn species is the key to the catalytic performance of Ru–Zn catalysts. The influences of ZnO crystals on selective hydrogenation of benzene were explored. A series of Ru–Zn catalysts with different Zn contents and ZnO morphologies were prepared by changing the amount of NaOH in the co-precipitation process. The catalysts were characterized by N_2 physisorption, X-ray powder diffraction(XRD), inductively coupled plasma optical emission spectrometer(ICP-OES), scanning electron microscope(SEM), temperature-programmed reduction(H_2-TPR)and Malvern laser particle size analyzer. It is found that with increasing the amount of NaOH, the Zn content first increased then decreased, and the ZnO crystals changed from relatively thicker pyramidal-shaped crystals to slimmer needle-shaped crystals. The catalyst had the highest Zn content(22.1%) and strongest interaction between ZnO crystals and Ru particles at pH 10.6 of the solution after reduction. As a result, it had the lowest activity. The activity of Ru–Zn catalysts is affected by both the Zn content and the interaction between ZnO crystals and Ru particles. The effect of reduction time was also investigated. Prolonging the reduction time caused no significant growth of ZnO crystals but the aggregation of catalyst particles and growth of Ru nanocrystals, thus resulting in the decrease of catalytic activity.展开更多
The effect of La on the performance of a supported RuB amorphous alloy catalyst for benzene selective hydrogenation was studied by means of activity and selectivity tests, such as HRTEM, SAED, XPS, and XRD. The result...The effect of La on the performance of a supported RuB amorphous alloy catalyst for benzene selective hydrogenation was studied by means of activity and selectivity tests, such as HRTEM, SAED, XPS, and XRD. The results show that the addition of La to RuB amorphous alloy catalyst can evidently increase the activity and improve the thermal stability of RuB amorphous alloy to refrain its crystallization. The promoting effect of La on the activity of RuB amorphous alloy catalyst is because of the high dispersion of the active components.展开更多
The monometallic Ru catalysts with the CeO2 without calcination and ZnSO4 as co-modifiers gave a cyclohexene yield of 58.5% at the optimum nominal CeO2/Ru molar ratio of 0.15. Moreover, this catalyst had a good stabil...The monometallic Ru catalysts with the CeO2 without calcination and ZnSO4 as co-modifiers gave a cyclohexene yield of 58.5% at the optimum nominal CeO2/Ru molar ratio of 0.15. Moreover, this catalyst had a good stability. The chemisorbed （Zn（OH）2）3（ZnSOa）（H20）3 salt on Ru surface, which was formed by the CeO2 reacting with ZnSO4, created the new Ru active sites suitable for the formation of cyclohexene and improved the selectivity to cyclohexene. In addition, the Zn2＋ in the aqueous phase could form a stable complex with cyclohexene, stabilizing the cyclohexene in the liquid phase and improving the selectivity to cyclo- hexene. The calcination treatment of CeO2 was not beneficial for the enhancement of the selectivity to cyclohexene since it is difficult for the CeO2 calcinated to react with ZnSO4 to form the （Zn（OH）2）3（ZnSO4）（H20）3 salt.展开更多
A series of Ru/FeOx catalysts were synthesized for the selective hydrogenation of CO2to CO.Detailed characterizations of the catalysts through X‐ray diffraction,X‐ray photoelectron spectroscopy,transmission electron...A series of Ru/FeOx catalysts were synthesized for the selective hydrogenation of CO2to CO.Detailed characterizations of the catalysts through X‐ray diffraction,X‐ray photoelectron spectroscopy,transmission electron microscopy,and temperature‐programmed techniques were performed to directly monitor the surface chemical properties and the catalytic performance to elucidate the reaction mechanism.Highly dispersed Ru species were observed on the surface of FeOx regardless of the initial Ru loading.Varying the Ru loading resulted in changes to the Ru coverage over the FeOx surface,which had a significant impact on the interaction between Ru and adsorbed H,and concomitantly,the H2activation capacity via the ability for H2dissociation.FeOx having0.01%of Ru loading exhibited100%selectivity toward CO resulting from the very strong interaction between Ru and adsorbed H,which limits the desorption of the activated H species and hinders over‐reduction of CO to CH4.Further increasing the Ru loading of the catalysts to above0.01%resulted in the adsorbed H to be easily dissociated,as a result of a weaker interaction with Ru,which allowed excessive CO reduction to produce CH4.Understanding how to selectively design the catalyst by tuning the initial loading of the active phase has broader implications on the design of supported metal catalysts toward preparing liquid fuels from CO2.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences toward preparing liquid fuels from CO2.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.展开更多
Series of carbon nanotube supported Ru-based catalysts were prepared by impregnation method and applied successfully for complete removal of CO by CO selective methanation from H2-rich gas stream conducted in a fixed-...Series of carbon nanotube supported Ru-based catalysts were prepared by impregnation method and applied successfully for complete removal of CO by CO selective methanation from H2-rich gas stream conducted in a fixed-bed quartz tubular reactor at ambient pressure. It was found that the metal promoter, reduction temperature and metal loading affected the catalytic properties significantly. The most excellent performance was presented by 30 wt% Ru-Zr/CNTs catalyst reduced at 350 ℃. Since it decreased CO concentration to below 10 ppm from 12000 ppm by CO selective methanation at the temperature range of 180-240 ℃, and kept CO selectivity higher than 85% at the temperature below 200 ℃. Characterization using XRD, TEM, H2-TPR and XPS suggests that Zr modification of Ru/CNTs results in the weakening of the interaction between Ru and CNTs, a higher Ru dispersion and the oxidization of surface Ru. Amorphous and high dispersed Ru particles with small size were obtained for 30 wt% Ru-Zr/CNTs catalyst reduced at 350 ℃, leading to excellent catalytic performance in CO selective methanation.展开更多
Amorphous Ni-Ru-B/ZrO2 catalysts were prepared by chemical reduction method. The effects of Ni-Ru-B loading and Ru/Ni mole ratio on the catalytic performance for selective CO methanation from reformed fuel were studie...Amorphous Ni-Ru-B/ZrO2 catalysts were prepared by chemical reduction method. The effects of Ni-Ru-B loading and Ru/Ni mole ratio on the catalytic performance for selective CO methanation from reformed fuel were studied, and the catalysts were characterized by BET, ICP, XRD and TPD. The results showed that Ru strongly affected the catalytic activity and selectivity by increasing the thermal stability of amorphous structure, promoting the dispersion of the catalyst particle, and intensifying the CO adsorption. For the catalysts with Ru/Ni mole ratio under 0.15, the CO methanation conversion and selectivity increased significantly with the increasing Ru/Ni mole ratio. Among all the catalysts investigated, the 30 wt% Ni-Ru-B loading amorphous Ni61Ru9B30/ZrO2 catalyst with 0.15 Ru/Ni mole ratio presented the best catalytic performance, over which higher than 99.9% of CO conversion was obtained in the temperature range of 230℃-250℃, and the CO2 conversion was kept under the level of 0.9%.展开更多
氮化硅是一种良好的载体,具有较高的水热稳定性和机械稳定性,其表面的氨基基团能够较好地锚定金属,显著提高金属分散度。但是,商品氮化硅比表面积较低,对金属分散作用仍然有限。因此,以自制的高比表面积氮化硅(Si_(3)N_(4))为载体,通过...氮化硅是一种良好的载体,具有较高的水热稳定性和机械稳定性,其表面的氨基基团能够较好地锚定金属,显著提高金属分散度。但是,商品氮化硅比表面积较低,对金属分散作用仍然有限。因此,以自制的高比表面积氮化硅(Si_(3)N_(4))为载体,通过浸渍法制备了不同Ru负载量(质量分数分别为0.5%、1.0%和2.0%)的催化剂(分别为0.5%Ru/Si_(3)N_(4)、1.0%Ru/Si_(3)N_(4)和2.0%Ru/Si_(3)N_(4)),并以商品氮化硅(Si_(3)N_(4)-C)为载体制备了2.0%Ru/Si_(3)N_(4)-C催化剂作为对照组。表征了催化剂的理化性质,测试了其在300℃、0.1 MPa下的CO_(2)加氢反应活性。结果显示,与Si_(3)N_(4)-C相比,Si_(3)N_(4)的比表面积较高(502 m^(2)/g),Si_(3)N_(4)作为载体显著提高了金属分散度,降低了金属粒径,催化剂暴露出更多的活性位点。0.5%Ru/Si_(3)N_(4)的金属粒径较小,展现出强的H_(2)吸附能力,H难以解吸,抑制了中间物种CO加氢生成CH_(4)。随着Ru负载量增加,金属粒径增大,催化剂的CH_(4)选择性更好。Ru/Si_(3)N_(4)系列催化剂中,2.0%Ru/Si_(3)N_(4)的CH_(4)选择性较高(98.8%)。空速为10000 m L/(g·h)时,0.5%Ru/Si_(3)N_(4)的CO选择性为88.2%。与2.0%Ru/Si_(3)N_(4)相比,2.0%Ru/Si_(3)N_(4)-C的金属粒径更大,活性位点较少,活性更低。2.0%Ru/Si_(3)N_(4)和2.0%Ru/Si_(3)N_(4)-C的CO_(2)转化率分别为53.1%和9.2%。Si_(3)N_(4)有效提高了金属分散度,提高了催化剂的CO_(2)加氢反应活性;通过调控Ru负载量控制催化剂金属粒径,可实现对产物CO或CH_(4)选择性的调控。展开更多
Ru-B/γ-Al2O3 catalyst was prepared by reductant impregnation method,which was applied in the selective hydrogenation of ethyl 1H-indole-2-carboxylate for producing ethyl 2,3,3a,7a-tetrahydro-1H-indole-2-carboxylate w...Ru-B/γ-Al2O3 catalyst was prepared by reductant impregnation method,which was applied in the selective hydrogenation of ethyl 1H-indole-2-carboxylate for producing ethyl 2,3,3a,7a-tetrahydro-1H-indole-2-carboxylate with hydrogen as reductant.Furthermore,we discussed the influences of substrate concentration,reaction solvent,hydrogenation temperature,initial hydrogen pressure and reaction time on the catalytic performance of the as-prepared catalyst.The obtained Ru-B/γ-Al2O3 catalyst showed a high-efficiency for the selective hydrogenation of ethyl 1H-indole-2-carboxylate（＞99％ conversion and selectivity） in i-propanol used as solvent at a concentration of 10％（mass fraction） of ethyl 1H-indole-2-carboxylate,a pressure of hydrogen of 6 MPa and a reaction temperature of 373 K.展开更多
文摘The effect of support calcination temperature on the benzene selective hydrogenation performance of the Ru-Ce-B/ZrO2 catalysts was investigated.It was found that with increasing calcination temperature,the surface area decreased,on the contrary,the pore size and the amount of monoclinic phase increased.With increasing support calcination temperature,the activity of the catalyst roughly decreased and cyclohexene selectivity increased.The activity decreased due to the decrease of the surface areas.The increase of the cyclohexene selectivity was correlated not only with the decrease of the surface areas but also with the increase of monoclinic phases,rich in surface hydroxyl,and the enlarged pore size of zirconia.This suggests the monoclinic zirconia with a medium surface area,rather than a big one,and a mesoporous structure,even including some macropores,is an ideal support of the catalyst for benzene selective hydrogenation.
基金supported by the National Nature Science Foundation of China(21273205)the Innovation Found for Technology Based Firms of China(10C26214104505)+1 种基金the Chinese Post-doctorate Science Fund 51th batch of surface subsidizes(2012M511125)the Scientific Research Foundation of Graduate School of Zhengzhou University
文摘Ru-Ce catalysts were prepared by a co-precipitation method.The effects of Ce precursors with different valences and Ce contents on the catalytic performance of Ru-Ce catalysts were investigated in the presence of ZnSO4.The Ce species in the catalysts prepared with different valences of the Ce precursors all exist as CeO2 on the Ru surface.The promoter CeO2alone could not improve the selectivity to cyclohexene of Ru catalysts.However,almost all the CeO2 in the catalysts could react with the reaction modifier ZnSO4 to form(Zn(OH)2)3(ZnSO4)(H2O)3 salt.The amount of the chemisorbed salt increased with the CeO2 loading,resulting in the decrease of the activity and the increase of the selectivity to cyclohexene of Ru catalyst.The Ru-Ce catalyst with the optimum Ce/Ru molar ratio of 0.19 gave a maximum cyclohexene yield of 57.4%.Moreover,this catalyst had good stability and excellent reusability.
文摘A novel nanosized amorphous Ru-Fe-B/ZrO2 alloy catalyst for benzene selective hydrogenation to cyclohexene was investigated. The superior properties of this catalyst were attributed to the combination of the nanosize and the amorphous character as well as to its textural character. In addition, the concentration of zinc ions, the content of ZrO2 in the slurry, and the pretreatment of the catalyst were found to be effective in improving the activity and the selectivity of the catalyst.
文摘A Ru-La/ZrO2 catalyst was prepared by the precipitation method, in which Ru was an active component, La was a promoter and ZrO2 was a dispersant. Comparing with the catalyst prepared by the chemical reduction method, the Ru-La/ZrO2 exhibited higher activity and better selectivity. At 140 ℃ and hydrogen pressure of 5 MPa, the C6H10 selectivity reached 70% at a C6H6 conversion of 35% for a reaction time was 5 min and the total La/Ru loading was 10%. Textural parameters of the catalyst were obtained by physical adsorption, BET surface area and specific pore volume measurements. The catalyst sample gave a BET area of 41 m2/g and a specific pore volume of 1.1 cm^3/g, and the most probable pore distribution was located at 5 to 10 nm. H2-TPR measurements showed that ruthenium oxide could be reduced to its metallic state at about 403 K. XRD determinations indicated that ruthenium and lanthanum were highly dispersed on the zirconia. A significant advantage of the Ru-La/ZrO2 catalyst is that it can be used directly in its unreduced state for the selective hydrogenation of benzene.
文摘Ru-based catalysts promoted with Mn and Zn were prepared by a co-precipitation method. In liquid-phase hydrogenation of benzene, the Ru-Mn-Zn catalysts exhibited superior catalytic performance to the catalysts promoted with Zn or Mn alone. The optimum Mn/Zn molar ratio was determined to be 0.3. With the addition of 0.5 g NaOH, the Ru-Mn-Zn-0.3 catalyst, which was reduced at 150 ？ C, afforded a cyclohexene selectivity of 81.1% at a benzene conversion of 60.2% at 5 min and a maximum cyclohexene yield of 59.9% at 20 min. Based on characterizations, the excellent performance of Ru-Mn-Zn catalyst was ascribed to the suitable pore structure, the appropriate reducibility and the homogenous chemical environment of the catalyst.
基金Supported by the National Natural Science Foundation of China(no.U1162129)
文摘Selective hydrogenation of benzene is an atom economic green route to produce cyclohexene. The control of Zn species is the key to the catalytic performance of Ru–Zn catalysts. The influences of ZnO crystals on selective hydrogenation of benzene were explored. A series of Ru–Zn catalysts with different Zn contents and ZnO morphologies were prepared by changing the amount of NaOH in the co-precipitation process. The catalysts were characterized by N_2 physisorption, X-ray powder diffraction(XRD), inductively coupled plasma optical emission spectrometer(ICP-OES), scanning electron microscope(SEM), temperature-programmed reduction(H_2-TPR)and Malvern laser particle size analyzer. It is found that with increasing the amount of NaOH, the Zn content first increased then decreased, and the ZnO crystals changed from relatively thicker pyramidal-shaped crystals to slimmer needle-shaped crystals. The catalyst had the highest Zn content(22.1%) and strongest interaction between ZnO crystals and Ru particles at pH 10.6 of the solution after reduction. As a result, it had the lowest activity. The activity of Ru–Zn catalysts is affected by both the Zn content and the interaction between ZnO crystals and Ru particles. The effect of reduction time was also investigated. Prolonging the reduction time caused no significant growth of ZnO crystals but the aggregation of catalyst particles and growth of Ru nanocrystals, thus resulting in the decrease of catalytic activity.
文摘The effect of La on the performance of a supported RuB amorphous alloy catalyst for benzene selective hydrogenation was studied by means of activity and selectivity tests, such as HRTEM, SAED, XPS, and XRD. The results show that the addition of La to RuB amorphous alloy catalyst can evidently increase the activity and improve the thermal stability of RuB amorphous alloy to refrain its crystallization. The promoting effect of La on the activity of RuB amorphous alloy catalyst is because of the high dispersion of the active components.
基金Project supported by National Natural Science Foundation of China （21273205）, and the Innovation Fund for Technology Based Firms of China （10C26214104505）
文摘The monometallic Ru catalysts with the CeO2 without calcination and ZnSO4 as co-modifiers gave a cyclohexene yield of 58.5% at the optimum nominal CeO2/Ru molar ratio of 0.15. Moreover, this catalyst had a good stability. The chemisorbed （Zn（OH）2）3（ZnSOa）（H20）3 salt on Ru surface, which was formed by the CeO2 reacting with ZnSO4, created the new Ru active sites suitable for the formation of cyclohexene and improved the selectivity to cyclohexene. In addition, the Zn2＋ in the aqueous phase could form a stable complex with cyclohexene, stabilizing the cyclohexene in the liquid phase and improving the selectivity to cyclo- hexene. The calcination treatment of CeO2 was not beneficial for the enhancement of the selectivity to cyclohexene since it is difficult for the CeO2 calcinated to react with ZnSO4 to form the （Zn（OH）2）3（ZnSO4）（H20）3 salt.
基金supported by the National Natural Science Foundation of China(21476145,91645117)China Postdoctoral Science Foundation(2016M600221)~~
文摘A series of Ru/FeOx catalysts were synthesized for the selective hydrogenation of CO2to CO.Detailed characterizations of the catalysts through X‐ray diffraction,X‐ray photoelectron spectroscopy,transmission electron microscopy,and temperature‐programmed techniques were performed to directly monitor the surface chemical properties and the catalytic performance to elucidate the reaction mechanism.Highly dispersed Ru species were observed on the surface of FeOx regardless of the initial Ru loading.Varying the Ru loading resulted in changes to the Ru coverage over the FeOx surface,which had a significant impact on the interaction between Ru and adsorbed H,and concomitantly,the H2activation capacity via the ability for H2dissociation.FeOx having0.01%of Ru loading exhibited100%selectivity toward CO resulting from the very strong interaction between Ru and adsorbed H,which limits the desorption of the activated H species and hinders over‐reduction of CO to CH4.Further increasing the Ru loading of the catalysts to above0.01%resulted in the adsorbed H to be easily dissociated,as a result of a weaker interaction with Ru,which allowed excessive CO reduction to produce CH4.Understanding how to selectively design the catalyst by tuning the initial loading of the active phase has broader implications on the design of supported metal catalysts toward preparing liquid fuels from CO2.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences toward preparing liquid fuels from CO2.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.
文摘Series of carbon nanotube supported Ru-based catalysts were prepared by impregnation method and applied successfully for complete removal of CO by CO selective methanation from H2-rich gas stream conducted in a fixed-bed quartz tubular reactor at ambient pressure. It was found that the metal promoter, reduction temperature and metal loading affected the catalytic properties significantly. The most excellent performance was presented by 30 wt% Ru-Zr/CNTs catalyst reduced at 350 ℃. Since it decreased CO concentration to below 10 ppm from 12000 ppm by CO selective methanation at the temperature range of 180-240 ℃, and kept CO selectivity higher than 85% at the temperature below 200 ℃. Characterization using XRD, TEM, H2-TPR and XPS suggests that Zr modification of Ru/CNTs results in the weakening of the interaction between Ru and CNTs, a higher Ru dispersion and the oxidization of surface Ru. Amorphous and high dispersed Ru particles with small size were obtained for 30 wt% Ru-Zr/CNTs catalyst reduced at 350 ℃, leading to excellent catalytic performance in CO selective methanation.
基金supported by the National Natural Science Foundation of China (No: 20576023)the Guangdong Province Natural Science Foundation(No: 06025660)the Natural Science Foundation of Zhongkai University of Agriculture and Engineering (G3100026)
文摘Amorphous Ni-Ru-B/ZrO2 catalysts were prepared by chemical reduction method. The effects of Ni-Ru-B loading and Ru/Ni mole ratio on the catalytic performance for selective CO methanation from reformed fuel were studied, and the catalysts were characterized by BET, ICP, XRD and TPD. The results showed that Ru strongly affected the catalytic activity and selectivity by increasing the thermal stability of amorphous structure, promoting the dispersion of the catalyst particle, and intensifying the CO adsorption. For the catalysts with Ru/Ni mole ratio under 0.15, the CO methanation conversion and selectivity increased significantly with the increasing Ru/Ni mole ratio. Among all the catalysts investigated, the 30 wt% Ni-Ru-B loading amorphous Ni61Ru9B30/ZrO2 catalyst with 0.15 Ru/Ni mole ratio presented the best catalytic performance, over which higher than 99.9% of CO conversion was obtained in the temperature range of 230℃-250℃, and the CO2 conversion was kept under the level of 0.9%.
文摘氮化硅是一种良好的载体,具有较高的水热稳定性和机械稳定性,其表面的氨基基团能够较好地锚定金属,显著提高金属分散度。但是,商品氮化硅比表面积较低,对金属分散作用仍然有限。因此,以自制的高比表面积氮化硅(Si_(3)N_(4))为载体,通过浸渍法制备了不同Ru负载量(质量分数分别为0.5%、1.0%和2.0%)的催化剂(分别为0.5%Ru/Si_(3)N_(4)、1.0%Ru/Si_(3)N_(4)和2.0%Ru/Si_(3)N_(4)),并以商品氮化硅(Si_(3)N_(4)-C)为载体制备了2.0%Ru/Si_(3)N_(4)-C催化剂作为对照组。表征了催化剂的理化性质,测试了其在300℃、0.1 MPa下的CO_(2)加氢反应活性。结果显示,与Si_(3)N_(4)-C相比,Si_(3)N_(4)的比表面积较高(502 m^(2)/g),Si_(3)N_(4)作为载体显著提高了金属分散度,降低了金属粒径,催化剂暴露出更多的活性位点。0.5%Ru/Si_(3)N_(4)的金属粒径较小,展现出强的H_(2)吸附能力,H难以解吸,抑制了中间物种CO加氢生成CH_(4)。随着Ru负载量增加,金属粒径增大,催化剂的CH_(4)选择性更好。Ru/Si_(3)N_(4)系列催化剂中,2.0%Ru/Si_(3)N_(4)的CH_(4)选择性较高(98.8%)。空速为10000 m L/(g·h)时,0.5%Ru/Si_(3)N_(4)的CO选择性为88.2%。与2.0%Ru/Si_(3)N_(4)相比,2.0%Ru/Si_(3)N_(4)-C的金属粒径更大,活性位点较少,活性更低。2.0%Ru/Si_(3)N_(4)和2.0%Ru/Si_(3)N_(4)-C的CO_(2)转化率分别为53.1%和9.2%。Si_(3)N_(4)有效提高了金属分散度,提高了催化剂的CO_(2)加氢反应活性;通过调控Ru负载量控制催化剂金属粒径,可实现对产物CO或CH_(4)选择性的调控。
文摘Ru-B/γ-Al2O3 catalyst was prepared by reductant impregnation method,which was applied in the selective hydrogenation of ethyl 1H-indole-2-carboxylate for producing ethyl 2,3,3a,7a-tetrahydro-1H-indole-2-carboxylate with hydrogen as reductant.Furthermore,we discussed the influences of substrate concentration,reaction solvent,hydrogenation temperature,initial hydrogen pressure and reaction time on the catalytic performance of the as-prepared catalyst.The obtained Ru-B/γ-Al2O3 catalyst showed a high-efficiency for the selective hydrogenation of ethyl 1H-indole-2-carboxylate（＞99％ conversion and selectivity） in i-propanol used as solvent at a concentration of 10％（mass fraction） of ethyl 1H-indole-2-carboxylate,a pressure of hydrogen of 6 MPa and a reaction temperature of 373 K.
