HNO 3 -pretreated CNTs were employed as supports, and a special ultrasound-assisted impregnation method was designed to prepare supported Cu-Co catalysts for higher-alcohol synthesis from syngas. The catalysts used in...HNO 3 -pretreated CNTs were employed as supports, and a special ultrasound-assisted impregnation method was designed to prepare supported Cu-Co catalysts for higher-alcohol synthesis from syngas. The catalysts used in this work were characterized by N 2 adsorption-desorption, TEM, XRD, H 2 -TPR, CO-TPD techniques. It was found that the pre-treatment procedure of CNTs remarkably promoted the catalytic properties of the Cu-Co/CNTs catalysts. For the Cu-Co catalyst supported on CNTs pre-treated by 68 wt% HNO 3 , some active components were introduced into the CNTs channels, their dispersions and the amount of strongly adsorbed CO-species were improved. The CO conversion and alcohol yield on the HNO 3 -pretreated Cu-Co/CNTs catalyst were increased by ～21% and ～69%, respectively, compared with those on the normal Cu-Co/CNTs catalyst.展开更多
The biggest challenging issue in photocatalysis is efficient separation of the photoinduced carriers and the aggregation of photoexcited electrons on photocatalyst’s surface.In this paper,we report that double metall...The biggest challenging issue in photocatalysis is efficient separation of the photoinduced carriers and the aggregation of photoexcited electrons on photocatalyst’s surface.In this paper,we report that double metallic co-catalysts Ti3C2 MXene and metallic octahedral(1T)phase tungsten disulfide(WS2)act pathways transferring photoexcited electrons in assisting the photocatalytic H2 evolution.TiO2 nanosheets were in situ grown on highly conductive Ti3C2 MXenes and 1T-WS2 nanoparticles were then uniformly distributed on TiO2@Ti3C2 composite.Thus,a distinctive 1T-WS2@TiO2@Ti3C2 composite with double metallic co-catalysts was achieved,and the content of 1T phase reaches 73%.The photocatalytic H2 evolution performance of 1T-WS2@TiO2@Ti3C2 composite with an optimized 15 wt%WS2 ratio is nearly 50 times higher than that of TiO2 nanosheets because of conductive Ti3C2 MXene and 1T-WS2 resulting in the increase of electron transfer efficiency.Besides,the 1T-WS2 on the surface of TiO2@Ti3C2 composite enhances the Brunauer–Emmett–Teller surface area and boosts the density of active site.展开更多
Effects of carbon nanotubes （CNT） and alumina （γ-Al2O3） supports on the catalytic activities of hydrodesulfurization （HDS） process over Co- Mo catalyst have been studied. XRD results indicated that the main act...Effects of carbon nanotubes （CNT） and alumina （γ-Al2O3） supports on the catalytic activities of hydrodesulfurization （HDS） process over Co- Mo catalyst have been studied. XRD results indicated that the main active phases in CNT and γ-Al2O3 supported Co-Mo catalysts are MoO2 and MOO3, respectively. The TPR results reveal that the reduction peak temperatures of the active species on CNT supported Co-Mo catalyst is lower than those on alumina supported Co-Mo catalyst, indicating that the CNT supports favor the reduction of active species. Catalytic evaluation results displayed that the sulfur content in the reaction products on the CNT supported Co-Mo catalyst is lower than that on the alumina supported Co-Mo catalyst if the HDS reaction was carried out at a temperature above 583 K.展开更多
Co-Mo-based catalysts supported on mixed oxide supports MgO-Al2O3 with different Mg/Al atom ratios for water gas shift reaction were studied by means of TPR, Raman, XPS and ESR. It was found that the octahedral Mo spe...Co-Mo-based catalysts supported on mixed oxide supports MgO-Al2O3 with different Mg/Al atom ratios for water gas shift reaction were studied by means of TPR, Raman, XPS and ESR. It was found that the octahedral Mo species in oxidized Co-Mo/MgO（x）-Al2O3 catalyst and the contents of Mo^5＋, Mo^4＋, S^2- and S^2-2 species in the functioning catalysts increased with increasing the Mg/Al atom ratio of the support under the studied experimental conditions. This is favorable for the formation of the active Co-Mo-S phase of the catalysts. Catalytic performance testing results showed that the catalysts Co-Mo/MgO-Al2O3 with the Mg/Al atom ratio of the support in the range of 0.475-0.525 exhibited optimal catalytic activity for the reaction.展开更多
Ni-Co bimetallic catalysts with different Ni/Co content were derived from cold plasma jet decomposition and reduction of hydrotalcite-like compounds containing Ni,Co,Mg and Al,and their catalytic performance was inves...Ni-Co bimetallic catalysts with different Ni/Co content were derived from cold plasma jet decomposition and reduction of hydrotalcite-like compounds containing Ni,Co,Mg and Al,and their catalytic performance was investigated with dry reforming of methane.Experimental results showed that the hydrotalcite-like precursors could be completely decomposed and partly reduced by cold plasma jet,and the Nicontained catalysts exhibited much higher activity than the catalyst without Ni.Especially,the catalyst with Ni/Co ratio of 8/2 achieved not only the highest conversions of 80.3%and 69.3%for CH4 and CO2,respectively,but also the best stability in 100 h testing.The catalysts were characterized by XRD,XPS,TEM and N2 adsorption techniques,and the results showed that the better performance of the 8Ni2Co bimetallic catalyst was attributed to its higher metal dispersion,smaller metal particle size,as well as the interaction effect between Ni and Co,which were brought by the special catalyst preparation method.展开更多
The Co-incorporated Ce1-xZrxO2 catalysts were prepared by co-precipitation for carbon dioxide reforming of methane.The ratio of Ce to Zr was varied to optimize the performances of co-precipitated Co-Ce-Zr-Ox catalysts...The Co-incorporated Ce1-xZrxO2 catalysts were prepared by co-precipitation for carbon dioxide reforming of methane.The ratio of Ce to Zr was varied to optimize the performances of co-precipitated Co-Ce-Zr-Ox catalysts.The prepared catalysts were characterized by various physico-chemical characterization techniques including TPR,X-ray diffraction,N2 adsorption at low temperature,XPS and CO2-TPSR.The co-precipitated Co-Ce0.8Zr0.2O2 sample containing 16% CoO exhibited a higher catalytic activity among the five catalysts,and the activity was maintained without significant loss during the reaction for 60 h.Under the conditions of 750 ℃,0.1 MPa,36000 ml/（h gcat）,and CO2/CH4 molar ratio of 1：1,the CO2 conversion over this catalyst was 75% while the CH4 conversion was 67%.The cubic Ce0.8Zr0.2O2 facilitated a higher dispersion and a higher reducibility of the cobalt component,and the apparent activation energy for Co-Ce0.8Zr0.2O2 sample was 49.1 kJ/mol in the CO2/CH4 reforming reaction.As a result,the Co-Ce0.8Zr0.2O2 sample exhibited a higher activity and stability for the reforming of CH4 with CO2.展开更多
The activation of adsorbed CO is an important step in CO hydrogenation. The results from TPSR of pre-adsorbed CO with H2 and syngas suggested that the presence of H2 increased the amount of CO adsorption and accelerat...The activation of adsorbed CO is an important step in CO hydrogenation. The results from TPSR of pre-adsorbed CO with H2 and syngas suggested that the presence of H2 increased the amount of CO adsorption and accelerated CO dissociation. The H2 was adsorbed first, and activated to form H＊ over metal sites, then reacted with carbonaceous species. The oxygen species for CO2 formation in the presence of hydrogen was mostly OH^＊, which reacted with adsorbed CO subsequently via CO^＊＋OH^＊ → CO2^＊＋H^＊; however, the direct CO dissociation was not excluded in CO hydrogenation. The dissociation of C-O bond in the presence of H2 proceeded by a concerted mechanism, which assisted the Boudourd reaction of adsorbed CO on the surface via CO^＊＋2H^＊ → CH^＊＋OH^＊. The formation of the surface species （CH） from adsorbed CO proceeded as indicated with the participation of surface hydrogen, was favored in the initial step of the Fischer-Tropsch synthesis.展开更多
A novel Co-B amorphous alloy catalyst in the form of ultrafine particles was prepared by chemical reduction of CoCl2 with aqueous NaBH4, which exhibited excellent activity and selectivity during the hydrogenation of c...A novel Co-B amorphous alloy catalyst in the form of ultrafine particles was prepared by chemical reduction of CoCl2 with aqueous NaBH4, which exhibited excellent activity and selectivity during the hydrogenation of cinnamaldehyde to cinnamyl alcohol in liquid phase. The optimum yield of cinnamyl alcohol was 87.6%, much better than the yield of using Raney Ni, Raney Co and other Co-based catalysts.展开更多
The effects of Ce on reduction of non-chromium iron based CO shift catalyst were studied by XRD, TPR, SEM and XPS. The results show that Ce refines Fe2O3 grains and riches on the surface of catalyst in the process of ...The effects of Ce on reduction of non-chromium iron based CO shift catalyst were studied by XRD, TPR, SEM and XPS. The results show that Ce refines Fe2O3 grains and riches on the surface of catalyst in the process of reduction, which leads to decrease of the initial reductive temperature and increase of the final reductive temperature.展开更多
The product distributions of Fischer-Tropsch synthesis over Co/AC catalyst are investigated under different reaction conditions in an integral fixed bed reactor.It is found that the product distributions deviate from ...The product distributions of Fischer-Tropsch synthesis over Co/AC catalyst are investigated under different reaction conditions in an integral fixed bed reactor.It is found that the product distributions deviate from the ASF distribution.The deviation from ASF distribution is analyzed by taking the readsorption of alkenes and the following secondary reaction into consideration.It is noted that the contents of alcohol,alkene and alkane decline with the increasing carbon number,showing a slighter declining tendency of alkanes than those of alkenes and alcohols.It is also found that high temperature,space velocity,H2/CO in feed gas and low pressure are preferential for light hydrocarbons and alcohols while against the chain propagation.The effect of space velocity on the product distributions especially on the light products is not obvious.It is noticed that low temperature,space velocity,H2/CO and high pressure lead to high contents of alcohols;high temperature,H2/CO and low space velocity lead to high contents of alkanes.The effect of pressure on the amounts of alkanes is not significant;high space velocity and low temperature,pressure,H2/CO are preferential for alkenes.展开更多
The correlation between phase structures and surface acidity of Al2O3 supports calcined at different temperatures and the catalytic performance of Ni/Al2O3 catalysts in the production of synthetic natural gas(SNG) via...The correlation between phase structures and surface acidity of Al2O3 supports calcined at different temperatures and the catalytic performance of Ni/Al2O3 catalysts in the production of synthetic natural gas(SNG) via CO methanation was systematically investigated. A series of 10 wt% NiO/Al2O3 catalysts were prepared by the conventional impregnation method, and the phase structures and surface acidity of Al2O3 supports were adjusted by calcining the commercial γ-Al2O3 at different temperatures(600–1200 C). CO methanation reaction was carried out in the temperature range of 300–600 C at different weight hourly space velocities(WHSV = 30000 and 120000 mL·g-1h-1) and pressures(0.1 and 3.0 MPa). It was found that high calcination temperature not only led to the growth in Ni particle size, but also weakened the interaction between Ni nanoparticles and Al2O3 supports due to the rapid decrease of the specific surface area and acidity of Al2O3 supports. Interestingly, Ni catalysts supported on Al2O3 calcined at 1200 C(Ni/Al2O3-1200) exhibited the best catalytic activity for CO methanation under different reaction conditions. Lifetime reaction tests also indicated that Ni/Al2O3-1200 was the most active and stable catalyst compared with the other three catalysts, whose supports were calcined at lower temperatures(600, 800 and 1000 C). These findings would therefore be helpful to develop Ni/Al2O3 methanation catalyst for SNG production.展开更多
The nanosheets structured K–Co–MoS_2 catalyst was prepared through a one-step hydrothermal synthesis combined with the wetness impregnation. The fresh catalyst has a high dispersion of Co–Mo–S active phase and no ...The nanosheets structured K–Co–MoS_2 catalyst was prepared through a one-step hydrothermal synthesis combined with the wetness impregnation. The fresh catalyst has a high dispersion of Co–Mo–S active phase and no Co_9S_8 is found. The pure H_2 activated catalyst shows a higher intrinsic activity, especially the C_(2+) OH selectivity for the higher alcohol synthesis compared to the one activated by 5% H_2/N_2 atmosphere. The reason is attributed to that the pure H_2 activation more effectively suppresses the formation of Co_9S_8 and stabilizes the Co–Mo–S active phase during the reaction due to the formation of SH species.展开更多
The influence of La loading on Zr-Co/activated carbon （AC） catalysts has been studied for Fischer-Tropsch synthesis. The catalyst samples were characterized by XRD, TPR, CO-TPD, and temperature programmed CO hydroge...The influence of La loading on Zr-Co/activated carbon （AC） catalysts has been studied for Fischer-Tropsch synthesis. The catalyst samples were characterized by XRD, TPR, CO-TPD, and temperature programmed CO hydrogenation. The catalytic property was evaluated in a fixed bed reactor. The experimental results showed that CO conversion increased from 86.4% to 92.3% and the selectivity to methane decreased from 14.2% to 11.5% and C5＋ selectivity increased from 71.0% to 74.7% when low La loading （La = 0.2wt%） was added into the Zr-Co/AC catalyst. However, high loadings of La （La = 0.3-1.0 wt%） would decrease catalyst activity as well as the C5＋ selectivity and increase methane selectivity. XRD results displayed that La-modified Zr-Co/AC catalyst had little effect on the dispersion of Co catalyst. But, the results of TPR, CO-TPD, and temperature programmed CO hydrogenation techniques indicated that the extent of cobalt reduction was found to greatly influence the activity and selectivity of the catalyst. The addition of a small amount of La increased the reducibility of the Zr-Co/AC catalyst and restrained the formation of methane and improved the selectivity to long chain hydrocarbons. However, excess of La led to the decrease of the reducibility of Co catalyst thus resulted in higher methanation activity.展开更多
The ultrafine particles of a new style Fe-Cu-based catalysts for CO hydrogenation were prepared by impregnating the organic sol of Fe（OH）3 and Cu（OH）2 onto the activated Al2O3, in which the organic sol of Fe（OH）...The ultrafine particles of a new style Fe-Cu-based catalysts for CO hydrogenation were prepared by impregnating the organic sol of Fe（OH）3 and Cu（OH）2 onto the activated Al2O3, in which the organic sol of Fe（OH）3 and Cu（OH）2 were prepared in the microemulsion of dodecylbenzenesulfonic acid sodium（S）/n-butanol（A）/toluene（O）/water with V（A）/V（O） = 0.25 and W（A）/W（S） = 1.50. This catalyst was characterized by particle size analysis, XRD and TG. The results of particle size analysis showed that Fe（OH）3 particles with a mean size of 17.1 nm and Cu（OH）2 particles with an average size of 6.65 um were obtained. TG analysis and XRD patterns suggested that 673 K is the optimal calcination temperature. CO hydrogenation produced C＋OH with a high selectivity above 58 wt% by using the ultrafine particles as catalyst, and the total alcohol yield of 0.250 g·ml^-1 ·h^-1 was obtained when the contents of Al2O3 and K were 88.61 wt% and 1.60 wt%, respectively.展开更多
基金supported by the Foundation of Shaanxi Educational Committee (2010JK608)the Research Foundation of XATU (204-000092)supported by the National Natural Science Foundation of China (205903603)
文摘HNO 3 -pretreated CNTs were employed as supports, and a special ultrasound-assisted impregnation method was designed to prepare supported Cu-Co catalysts for higher-alcohol synthesis from syngas. The catalysts used in this work were characterized by N 2 adsorption-desorption, TEM, XRD, H 2 -TPR, CO-TPD techniques. It was found that the pre-treatment procedure of CNTs remarkably promoted the catalytic properties of the Cu-Co/CNTs catalysts. For the Cu-Co catalyst supported on CNTs pre-treated by 68 wt% HNO 3 , some active components were introduced into the CNTs channels, their dispersions and the amount of strongly adsorbed CO-species were improved. The CO conversion and alcohol yield on the HNO 3 -pretreated Cu-Co/CNTs catalyst were increased by ～21% and ～69%, respectively, compared with those on the normal Cu-Co/CNTs catalyst.
基金fundings from the National Natural Science Foundation of China (Nos. 51872173 and 51772167)Taishan Scholarship of Young Scholars (No. tsqn201812068)+2 种基金Natural Science Foundation of Shandong Province (No. ZR2017JL020)Taishan Scholarship of Climbing Plan (No. tspd20161006)Key Research and Development Program of Shandong Province (No. 2018GGX102028)
文摘The biggest challenging issue in photocatalysis is efficient separation of the photoinduced carriers and the aggregation of photoexcited electrons on photocatalyst’s surface.In this paper,we report that double metallic co-catalysts Ti3C2 MXene and metallic octahedral(1T)phase tungsten disulfide(WS2)act pathways transferring photoexcited electrons in assisting the photocatalytic H2 evolution.TiO2 nanosheets were in situ grown on highly conductive Ti3C2 MXenes and 1T-WS2 nanoparticles were then uniformly distributed on TiO2@Ti3C2 composite.Thus,a distinctive 1T-WS2@TiO2@Ti3C2 composite with double metallic co-catalysts was achieved,and the content of 1T phase reaches 73%.The photocatalytic H2 evolution performance of 1T-WS2@TiO2@Ti3C2 composite with an optimized 15 wt%WS2 ratio is nearly 50 times higher than that of TiO2 nanosheets because of conductive Ti3C2 MXene and 1T-WS2 resulting in the increase of electron transfer efficiency.Besides,the 1T-WS2 on the surface of TiO2@Ti3C2 composite enhances the Brunauer–Emmett–Teller surface area and boosts the density of active site.
文摘Effects of carbon nanotubes （CNT） and alumina （γ-Al2O3） supports on the catalytic activities of hydrodesulfurization （HDS） process over Co- Mo catalyst have been studied. XRD results indicated that the main active phases in CNT and γ-Al2O3 supported Co-Mo catalysts are MoO2 and MOO3, respectively. The TPR results reveal that the reduction peak temperatures of the active species on CNT supported Co-Mo catalyst is lower than those on alumina supported Co-Mo catalyst, indicating that the CNT supports favor the reduction of active species. Catalytic evaluation results displayed that the sulfur content in the reaction products on the CNT supported Co-Mo catalyst is lower than that on the alumina supported Co-Mo catalyst if the HDS reaction was carried out at a temperature above 583 K.
文摘Co-Mo-based catalysts supported on mixed oxide supports MgO-Al2O3 with different Mg/Al atom ratios for water gas shift reaction were studied by means of TPR, Raman, XPS and ESR. It was found that the octahedral Mo species in oxidized Co-Mo/MgO（x）-Al2O3 catalyst and the contents of Mo^5＋, Mo^4＋, S^2- and S^2-2 species in the functioning catalysts increased with increasing the Mg/Al atom ratio of the support under the studied experimental conditions. This is favorable for the formation of the active Co-Mo-S phase of the catalysts. Catalytic performance testing results showed that the catalysts Co-Mo/MgO-Al2O3 with the Mg/Al atom ratio of the support in the range of 0.475-0.525 exhibited optimal catalytic activity for the reaction.
基金supported by the National Natural Science Foundation of China(11075113)
文摘Ni-Co bimetallic catalysts with different Ni/Co content were derived from cold plasma jet decomposition and reduction of hydrotalcite-like compounds containing Ni,Co,Mg and Al,and their catalytic performance was investigated with dry reforming of methane.Experimental results showed that the hydrotalcite-like precursors could be completely decomposed and partly reduced by cold plasma jet,and the Nicontained catalysts exhibited much higher activity than the catalyst without Ni.Especially,the catalyst with Ni/Co ratio of 8/2 achieved not only the highest conversions of 80.3%and 69.3%for CH4 and CO2,respectively,but also the best stability in 100 h testing.The catalysts were characterized by XRD,XPS,TEM and N2 adsorption techniques,and the results showed that the better performance of the 8Ni2Co bimetallic catalyst was attributed to its higher metal dispersion,smaller metal particle size,as well as the interaction effect between Ni and Co,which were brought by the special catalyst preparation method.
文摘The Co-incorporated Ce1-xZrxO2 catalysts were prepared by co-precipitation for carbon dioxide reforming of methane.The ratio of Ce to Zr was varied to optimize the performances of co-precipitated Co-Ce-Zr-Ox catalysts.The prepared catalysts were characterized by various physico-chemical characterization techniques including TPR,X-ray diffraction,N2 adsorption at low temperature,XPS and CO2-TPSR.The co-precipitated Co-Ce0.8Zr0.2O2 sample containing 16% CoO exhibited a higher catalytic activity among the five catalysts,and the activity was maintained without significant loss during the reaction for 60 h.Under the conditions of 750 ℃,0.1 MPa,36000 ml/（h gcat）,and CO2/CH4 molar ratio of 1：1,the CO2 conversion over this catalyst was 75% while the CH4 conversion was 67%.The cubic Ce0.8Zr0.2O2 facilitated a higher dispersion and a higher reducibility of the cobalt component,and the apparent activation energy for Co-Ce0.8Zr0.2O2 sample was 49.1 kJ/mol in the CO2/CH4 reforming reaction.As a result,the Co-Ce0.8Zr0.2O2 sample exhibited a higher activity and stability for the reforming of CH4 with CO2.
基金The National Key Project for Basic Research of China(973 Project)(No.2005CB221402)China National Petroleum Corporation
文摘The activation of adsorbed CO is an important step in CO hydrogenation. The results from TPSR of pre-adsorbed CO with H2 and syngas suggested that the presence of H2 increased the amount of CO adsorption and accelerated CO dissociation. The H2 was adsorbed first, and activated to form H＊ over metal sites, then reacted with carbonaceous species. The oxygen species for CO2 formation in the presence of hydrogen was mostly OH^＊, which reacted with adsorbed CO subsequently via CO^＊＋OH^＊ → CO2^＊＋H^＊; however, the direct CO dissociation was not excluded in CO hydrogenation. The dissociation of C-O bond in the presence of H2 proceeded by a concerted mechanism, which assisted the Boudourd reaction of adsorbed CO on the surface via CO^＊＋2H^＊ → CH^＊＋OH^＊. The formation of the surface species （CH） from adsorbed CO proceeded as indicated with the participation of surface hydrogen, was favored in the initial step of the Fischer-Tropsch synthesis.
基金This work was supported by the National Natural Science Foundation of China (29973025) and the Natural Science Foundation of Shanghai Science and Technology Committee (98QMA11402).
文摘A novel Co-B amorphous alloy catalyst in the form of ultrafine particles was prepared by chemical reduction of CoCl2 with aqueous NaBH4, which exhibited excellent activity and selectivity during the hydrogenation of cinnamaldehyde to cinnamyl alcohol in liquid phase. The optimum yield of cinnamyl alcohol was 87.6%, much better than the yield of using Raney Ni, Raney Co and other Co-based catalysts.
文摘The effects of Ce on reduction of non-chromium iron based CO shift catalyst were studied by XRD, TPR, SEM and XPS. The results show that Ce refines Fe2O3 grains and riches on the surface of catalyst in the process of reduction, which leads to decrease of the initial reductive temperature and increase of the final reductive temperature.
基金supported by the National High Technology Research and Development Plan of China(863 plan)(Project No.2006AA05A111)
文摘The product distributions of Fischer-Tropsch synthesis over Co/AC catalyst are investigated under different reaction conditions in an integral fixed bed reactor.It is found that the product distributions deviate from the ASF distribution.The deviation from ASF distribution is analyzed by taking the readsorption of alkenes and the following secondary reaction into consideration.It is noted that the contents of alcohol,alkene and alkane decline with the increasing carbon number,showing a slighter declining tendency of alkanes than those of alkenes and alcohols.It is also found that high temperature,space velocity,H2/CO in feed gas and low pressure are preferential for light hydrocarbons and alcohols while against the chain propagation.The effect of space velocity on the product distributions especially on the light products is not obvious.It is noticed that low temperature,space velocity,H2/CO and high pressure lead to high contents of alcohols;high temperature,H2/CO and low space velocity lead to high contents of alkanes.The effect of pressure on the amounts of alkanes is not significant;high space velocity and low temperature,pressure,H2/CO are preferential for alkenes.
基金supported by the Hundred Talents Program of the Chinese Academy of Sciences (CAS),State Key Laboratory of Multiphase Complex Systems of China (No.MPCS-2009-C-01)the National Key Technology R&D Program of China (No.2010BAC66B01)the Knowledge Innovation Program of the CAS (No.KGCX2-YW-396)
文摘The correlation between phase structures and surface acidity of Al2O3 supports calcined at different temperatures and the catalytic performance of Ni/Al2O3 catalysts in the production of synthetic natural gas(SNG) via CO methanation was systematically investigated. A series of 10 wt% NiO/Al2O3 catalysts were prepared by the conventional impregnation method, and the phase structures and surface acidity of Al2O3 supports were adjusted by calcining the commercial γ-Al2O3 at different temperatures(600–1200 C). CO methanation reaction was carried out in the temperature range of 300–600 C at different weight hourly space velocities(WHSV = 30000 and 120000 mL·g-1h-1) and pressures(0.1 and 3.0 MPa). It was found that high calcination temperature not only led to the growth in Ni particle size, but also weakened the interaction between Ni nanoparticles and Al2O3 supports due to the rapid decrease of the specific surface area and acidity of Al2O3 supports. Interestingly, Ni catalysts supported on Al2O3 calcined at 1200 C(Ni/Al2O3-1200) exhibited the best catalytic activity for CO methanation under different reaction conditions. Lifetime reaction tests also indicated that Ni/Al2O3-1200 was the most active and stable catalyst compared with the other three catalysts, whose supports were calcined at lower temperatures(600, 800 and 1000 C). These findings would therefore be helpful to develop Ni/Al2O3 methanation catalyst for SNG production.
基金supported by the National Natural Science Foundation of China(21673214,U1732272)
文摘The nanosheets structured K–Co–MoS_2 catalyst was prepared through a one-step hydrothermal synthesis combined with the wetness impregnation. The fresh catalyst has a high dispersion of Co–Mo–S active phase and no Co_9S_8 is found. The pure H_2 activated catalyst shows a higher intrinsic activity, especially the C_(2+) OH selectivity for the higher alcohol synthesis compared to the one activated by 5% H_2/N_2 atmosphere. The reason is attributed to that the pure H_2 activation more effectively suppresses the formation of Co_9S_8 and stabilizes the Co–Mo–S active phase during the reaction due to the formation of SH species.
基金National Key Fundamental Research Development Plan ("973"Plan,No.2005CB221400)
文摘The influence of La loading on Zr-Co/activated carbon （AC） catalysts has been studied for Fischer-Tropsch synthesis. The catalyst samples were characterized by XRD, TPR, CO-TPD, and temperature programmed CO hydrogenation. The catalytic property was evaluated in a fixed bed reactor. The experimental results showed that CO conversion increased from 86.4% to 92.3% and the selectivity to methane decreased from 14.2% to 11.5% and C5＋ selectivity increased from 71.0% to 74.7% when low La loading （La = 0.2wt%） was added into the Zr-Co/AC catalyst. However, high loadings of La （La = 0.3-1.0 wt%） would decrease catalyst activity as well as the C5＋ selectivity and increase methane selectivity. XRD results displayed that La-modified Zr-Co/AC catalyst had little effect on the dispersion of Co catalyst. But, the results of TPR, CO-TPD, and temperature programmed CO hydrogenation techniques indicated that the extent of cobalt reduction was found to greatly influence the activity and selectivity of the catalyst. The addition of a small amount of La increased the reducibility of the Zr-Co/AC catalyst and restrained the formation of methane and improved the selectivity to long chain hydrocarbons. However, excess of La led to the decrease of the reducibility of Co catalyst thus resulted in higher methanation activity.
文摘The ultrafine particles of a new style Fe-Cu-based catalysts for CO hydrogenation were prepared by impregnating the organic sol of Fe（OH）3 and Cu（OH）2 onto the activated Al2O3, in which the organic sol of Fe（OH）3 and Cu（OH）2 were prepared in the microemulsion of dodecylbenzenesulfonic acid sodium（S）/n-butanol（A）/toluene（O）/water with V（A）/V（O） = 0.25 and W（A）/W（S） = 1.50. This catalyst was characterized by particle size analysis, XRD and TG. The results of particle size analysis showed that Fe（OH）3 particles with a mean size of 17.1 nm and Cu（OH）2 particles with an average size of 6.65 um were obtained. TG analysis and XRD patterns suggested that 673 K is the optimal calcination temperature. CO hydrogenation produced C＋OH with a high selectivity above 58 wt% by using the ultrafine particles as catalyst, and the total alcohol yield of 0.250 g·ml^-1 ·h^-1 was obtained when the contents of Al2O3 and K were 88.61 wt% and 1.60 wt%, respectively.
