The partial oxidation of ethanol to hydrogen was investigated over Ni/Fe/La catalysts prepared by the co precipitation method. The effects of introduction of La promoter and the reaction temperature on the catalytic ...The partial oxidation of ethanol to hydrogen was investigated over Ni/Fe/La catalysts prepared by the co precipitation method. The effects of introduction of La promoter and the reaction temperature on the catalytic performance were studied. It was found that the introduction of La into Ni/Fe catalysts is helpful to increase the selectivity to hydrogen and the stability of the catalysts. The results of XRD and XPS characterization show that the structure of the catalyst was changed during the reaction. The existence of LaFeO 3 species is possibly the main reason of the increase of the catalyst stability.展开更多
MgH_(2) is considered one of the most promising hydrogen storage materials because of its safety,high efficiency,high hydrogen storage quantity and low cost characteristics.But some shortcomings are still existed:high...MgH_(2) is considered one of the most promising hydrogen storage materials because of its safety,high efficiency,high hydrogen storage quantity and low cost characteristics.But some shortcomings are still existed:high operating temperature and poor hydrogen absorption dynamics,which limit its application.Porous Ni_(3)ZnC_(0.7)/Ni loaded carbon nanotubes microspheres(NZC/Ni@CNT)is prepared by facile filtration and calcination method.Then the different amount of NZC/Ni@CNT(2.5,5.0 and 7.5 wt%)is added to the MgH_(2) by ball milling.Among the three samples with different amount of NZC/Ni@CNT(2.5,5.0 and 7.5 wt%),the MgH_(2)-5 wt%NZC/Ni@CNT composite exhibits the best hydrogen storage performances.After testing,the MgH_(2)-5 wt%NZC/Ni@CNT begins to release hydrogen at around 110℃ and hydrogen absorption capacity reaches 2.34 wt%H_(2) at 80℃ within 60 min.Moreover,the composite can release about 5.36 wt%H_(2) at 300℃.In addition,hydrogen absorption and desorption activation energies of the MgH_(2)-5 wt%NZC/Ni@CNT composite are reduced to 37.28 and 84.22 KJ/mol H_(2),respectively.The in situ generated Mg_(2)NiH_(4)/Mg_(2)Ni can serve as a"hydrogen pump"that plays the main role in providing more activation sites and hydrogen diffusion channels which promotes H_(2) dissociation during hydrogen absorption process.In addition,the evenly dispersed Zn and MgZn2 in Mg and MgH_(2) could provide sites for Mg/MgH_(2) nucleation and hydrogen diffusion channel.This attempt clearly proved that the bimetallic carbide Ni_(3)ZnC_(0.7) is a effective additive for the hydrogen storage performances modification of MgH_(2),and the facile synthesis of the Ni_(3)ZnC_(0.7)/Ni@CNT can provide directions of better designing high performance carbide catalysts for improving MgH_(2).展开更多
Among challenges implicit in the transition to the post-fossil fuel energetic model,the finite amount of resources available for the technological implementation of CO_(2) revalorizing processes arises as a central is...Among challenges implicit in the transition to the post-fossil fuel energetic model,the finite amount of resources available for the technological implementation of CO_(2) revalorizing processes arises as a central issue.The development of fully renewable catalytic systems with easier metal recovery strategies would promote the viability and sustainability of synthetic natural gas production circular routes.Taking Ni and NiFe catalysts supported over g-Al_(2)O_(3) oxide as reference materials,this work evaluates the potentiality of Ni and NiFe supported biochar catalysts for CO_(2) methanation.The development of competitive biochar catalysts was found dependent on the creation of basic sites on the catalyst surface.Displaying lower Turn Over Frequencies than Ni/Al catalyst,the absence of basic sites achieved over Ni/C catalyst was related to the depleted catalyst performances.For NiFe catalysts,analogous Ni_(5)Fe_(1) alloys were constituted over both alumina and biochar supports.The highest specific activity of the catalyst series,exhibited by the NiFe/C catalyst,was related to the development of surface basic sites along with weaker NiFe-C interactions,which resulted in increased Ni0:NiO surface populations under reaction conditions.In summary,the present work establishes biochar supports as a competitive material to consider within the future low-carbon energetic panorama.展开更多
To study the modification mechanism of activated carbon(AC)by Fe and the low-temperature NH_(3)-selective catalytic reduction(SCR)denitration mechanism of Fe/AC catalysts,Fe/AC catalysts were prepared using coconut sh...To study the modification mechanism of activated carbon(AC)by Fe and the low-temperature NH_(3)-selective catalytic reduction(SCR)denitration mechanism of Fe/AC catalysts,Fe/AC catalysts were prepared using coconut shell AC activated by nitric acid as the support and iron oxide as the active component.The crystal structure,surface morphology,pore structure,functional groups and valence states of the active components of Fe/AC catalysts were characterised by X-ray diffraction,scanning electron microscopy,nitrogen adsorption and desorption,Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy,respectively.The effect of Fe loading and calcination temperature on the low-temperature denitration of NH_(3)-SCR over Fe/AC catalysts was studied using NH_(3)as the reducing gas at low temperature(150℃).The results show that the iron oxide on the Fe/AC catalyst is spherical and uniformly dispersed on the surface of AC,thereby improving the crystallisation performance and increasing the number of active sites and specific surface area on AC in contact with the reaction gas.Hence,a rapid NH_(3)-SCR reaction was realised.When the roasting temperature remains constant,the iron oxide crystals formed by increasing the amount of loading can enter the AC pore structure and accumulate to form more micropores.When the roasting temperature is raised from 400 to 500℃,the iron oxide is mainly transformed fromα-Fe_(2)O_(3)toγ-Fe_(2)O_(3),which improves the iron oxide dispersion and increases its denitration active site,allowing gas adsorption.When the Fe loading amount is 10%,and the roasting temperature is 500℃,the NO removal rate of the Fe/AC catalyst can reach 95%.According to the study,the low-temperature NH_(3)-SCR mechanism of Fe/AC catalyst is proposed,in which the redox reaction between Fe~(2+)and Fe~(3+)will facilitate the formation of reactive oxygen vacancies,which increases the amount of oxygen adsorption on the surface,especially the increase in surface acid sites,and promotes and adsorbs more reaction gases(NH_(3),O_(2),NO).The transformation from the standard SCR reaction to the fast SCR reaction is accelerated.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
Characteristics of carbon deposition of CH 4 and C 2H 4 decomposition over supported Ni and Ni Ce catalysts were studied by using a pulse reaction as well as BET, TPR, XPS and hydrogen chemisorption techniques. It...Characteristics of carbon deposition of CH 4 and C 2H 4 decomposition over supported Ni and Ni Ce catalysts were studied by using a pulse reaction as well as BET, TPR, XPS and hydrogen chemisorption techniques. It is found that there is a metal semiconductor interaction (MScI) in the Ni Ce catalyst, and the effect of MScI on the carbon deposition of CH 4 decomposition is opposite to that of C 2H 4. A novel model of carbon deposition of CH 4 or C 2H 4 decomposition was proposed.展开更多
In this paper, Ni/Zr–Yb–O catalysts with different sodium contents are prepared by a co-precipitation method, using aqueous Na2CO3 solution as a precipitant, and the effect of sodium on the catalyst structure and ca...In this paper, Ni/Zr–Yb–O catalysts with different sodium contents are prepared by a co-precipitation method, using aqueous Na2CO3 solution as a precipitant, and the effect of sodium on the catalyst structure and catalytic performance for syngas methanation is extensively investigated using five Ni/Zr–Yb–O catalysts, containing 0, 0.5, 1.5,4.5 and 13.5 wt% Na^+, those are denoted as Cat-1, Cat-2, Cat-3, Cat-4 and Cat-5 respectively. It is found that the interaction between Ni and support determines the catalytic performance of Ni/Zr–Yb–O and the residual sodium content negatively affects the interaction between Ni and support. Cat-1 exhibits an excellent catalytic performance.During a long run time of 380 h, no deactivation is observed and both CO conversion and CH4 selectivity maintain a level above 90%. However, Cat-3 and Cat-5 suffer rapid deactivation under the same reaction condition. The characterization results indicate the strong interaction between Ni and support enables Cat-1 to possess well dispersed Ni species, resistance to sintering and carbon deposition and thus the excellent catalytic performance. However, the presence of sodium ions over Ni/Zr–Yb–O degrades the interaction between Ni and support and the catalytic performance, especially for the stability. The relative weak interaction between Ni and support results in severe sintering of both ZrO2 and Ni under the reaction condition, carbon deposition and the poor catalytic performance.展开更多
Six Ni-Mo catalysts with different metal contents were prepared and characterized by N2 adsorption and X-ray diffractometry. The active phase microstructure of these catalysts was examined by the Raman spectroscopy, t...Six Ni-Mo catalysts with different metal contents were prepared and characterized by N2 adsorption and X-ray diffractometry. The active phase microstructure of these catalysts was examined by the Raman spectroscopy, temperatureprogrammed reduction(TPR), X-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy. Hydrodesulfurization(HDS) activity of catalyst samples were analyzed in a flow fixed-bed microreactor. The sulfidation degree of Mo and the length of the MoS2 slab slightly increased with the amount of metal loaded following sulfidation. This small change is attributed to polymolybdate species observed in all the oxidized catalysts. Weak metal-support interactions, as determined by the TPR technique, increased the NiSx sulfidation phase and MoS2 slab stacking. The HDS activity of the catalyst samples increased with the number of active sites. For high metal loading catalysts, their HDS activity was nearly identical because the sulfur atoms cannot easily approach active sites. This change is caused by the large number of stacked layers in the MoS2 slabs as well as the decrease in the specific surface area and pore volume of the catalyst samples with an increasing metal loading.展开更多
Methane decomposition reaction has been studied at three different activation temperatures(500°C,800°C and950°C)over mesoporous alumina supported Ni–Fe and Mn–Fe based bimetallic catalysts.On co-impre...Methane decomposition reaction has been studied at three different activation temperatures(500°C,800°C and950°C)over mesoporous alumina supported Ni–Fe and Mn–Fe based bimetallic catalysts.On co-impregnation of Ni on Fe/Al_2O_3the activity of the catalyst was retained even at the high activation temperature at 950°C and up to180 min.The Ni promotion enhanced the reducibility of Fe/Al_2O_3oxides showing higher catalytic activity with a hydrogen yield of 69%.The reactivity of bimetallic Mn and Fe over Al_2O_3catalyst decreased at 800°C and 950°C activation temperatures.Regeneration studies revealed that the catalyst could be effectively recycled up to 9times.The addition of O_2(1 ml,2 ml,4 ml)in the feed enhanced substantially CH_4conversion,the yield of hydrogen and the stability of the catalyst.展开更多
基金Supported by the 973project of China(G2 0 0 0 0 2 6 4 )
文摘The partial oxidation of ethanol to hydrogen was investigated over Ni/Fe/La catalysts prepared by the co precipitation method. The effects of introduction of La promoter and the reaction temperature on the catalytic performance were studied. It was found that the introduction of La into Ni/Fe catalysts is helpful to increase the selectivity to hydrogen and the stability of the catalysts. The results of XRD and XPS characterization show that the structure of the catalyst was changed during the reaction. The existence of LaFeO 3 species is possibly the main reason of the increase of the catalyst stability.
基金supported by research programs of National Natural Science Foundation of China(52101274,51731002)Natural Science Foundation of Shandong Province(No.ZR2020QE011)Youth Top Talent Foundation of Yantai University(2219008).
文摘MgH_(2) is considered one of the most promising hydrogen storage materials because of its safety,high efficiency,high hydrogen storage quantity and low cost characteristics.But some shortcomings are still existed:high operating temperature and poor hydrogen absorption dynamics,which limit its application.Porous Ni_(3)ZnC_(0.7)/Ni loaded carbon nanotubes microspheres(NZC/Ni@CNT)is prepared by facile filtration and calcination method.Then the different amount of NZC/Ni@CNT(2.5,5.0 and 7.5 wt%)is added to the MgH_(2) by ball milling.Among the three samples with different amount of NZC/Ni@CNT(2.5,5.0 and 7.5 wt%),the MgH_(2)-5 wt%NZC/Ni@CNT composite exhibits the best hydrogen storage performances.After testing,the MgH_(2)-5 wt%NZC/Ni@CNT begins to release hydrogen at around 110℃ and hydrogen absorption capacity reaches 2.34 wt%H_(2) at 80℃ within 60 min.Moreover,the composite can release about 5.36 wt%H_(2) at 300℃.In addition,hydrogen absorption and desorption activation energies of the MgH_(2)-5 wt%NZC/Ni@CNT composite are reduced to 37.28 and 84.22 KJ/mol H_(2),respectively.The in situ generated Mg_(2)NiH_(4)/Mg_(2)Ni can serve as a"hydrogen pump"that plays the main role in providing more activation sites and hydrogen diffusion channels which promotes H_(2) dissociation during hydrogen absorption process.In addition,the evenly dispersed Zn and MgZn2 in Mg and MgH_(2) could provide sites for Mg/MgH_(2) nucleation and hydrogen diffusion channel.This attempt clearly proved that the bimetallic carbide Ni_(3)ZnC_(0.7) is a effective additive for the hydrogen storage performances modification of MgH_(2),and the facile synthesis of the Ni_(3)ZnC_(0.7)/Ni@CNT can provide directions of better designing high performance carbide catalysts for improving MgH_(2).
文摘Among challenges implicit in the transition to the post-fossil fuel energetic model,the finite amount of resources available for the technological implementation of CO_(2) revalorizing processes arises as a central issue.The development of fully renewable catalytic systems with easier metal recovery strategies would promote the viability and sustainability of synthetic natural gas production circular routes.Taking Ni and NiFe catalysts supported over g-Al_(2)O_(3) oxide as reference materials,this work evaluates the potentiality of Ni and NiFe supported biochar catalysts for CO_(2) methanation.The development of competitive biochar catalysts was found dependent on the creation of basic sites on the catalyst surface.Displaying lower Turn Over Frequencies than Ni/Al catalyst,the absence of basic sites achieved over Ni/C catalyst was related to the depleted catalyst performances.For NiFe catalysts,analogous Ni_(5)Fe_(1) alloys were constituted over both alumina and biochar supports.The highest specific activity of the catalyst series,exhibited by the NiFe/C catalyst,was related to the development of surface basic sites along with weaker NiFe-C interactions,which resulted in increased Ni0:NiO surface populations under reaction conditions.In summary,the present work establishes biochar supports as a competitive material to consider within the future low-carbon energetic panorama.
基金Project(51974048) supported by the National Natural Science Foundation of ChinaProject(CQBX202225) supported by Postdoctoral Innovation Talent Program of Chongqing,ChinaProject(CSTB2023NSCQ-BHX0166) supported by Natural Science Foundation of Chongqing,China。
基金Funded by the General Project of Science and Technology Plan of Yunnan Science and Technology Department(Nos.202001AT070029,2019FB077)Open Fund of Key Laboratory for Ferrous Metallurgy and Resources Utilization of Ministry of Education(No.FMRUlab-20-4)。
文摘To study the modification mechanism of activated carbon(AC)by Fe and the low-temperature NH_(3)-selective catalytic reduction(SCR)denitration mechanism of Fe/AC catalysts,Fe/AC catalysts were prepared using coconut shell AC activated by nitric acid as the support and iron oxide as the active component.The crystal structure,surface morphology,pore structure,functional groups and valence states of the active components of Fe/AC catalysts were characterised by X-ray diffraction,scanning electron microscopy,nitrogen adsorption and desorption,Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy,respectively.The effect of Fe loading and calcination temperature on the low-temperature denitration of NH_(3)-SCR over Fe/AC catalysts was studied using NH_(3)as the reducing gas at low temperature(150℃).The results show that the iron oxide on the Fe/AC catalyst is spherical and uniformly dispersed on the surface of AC,thereby improving the crystallisation performance and increasing the number of active sites and specific surface area on AC in contact with the reaction gas.Hence,a rapid NH_(3)-SCR reaction was realised.When the roasting temperature remains constant,the iron oxide crystals formed by increasing the amount of loading can enter the AC pore structure and accumulate to form more micropores.When the roasting temperature is raised from 400 to 500℃,the iron oxide is mainly transformed fromα-Fe_(2)O_(3)toγ-Fe_(2)O_(3),which improves the iron oxide dispersion and increases its denitration active site,allowing gas adsorption.When the Fe loading amount is 10%,and the roasting temperature is 500℃,the NO removal rate of the Fe/AC catalyst can reach 95%.According to the study,the low-temperature NH_(3)-SCR mechanism of Fe/AC catalyst is proposed,in which the redox reaction between Fe~(2+)and Fe~(3+)will facilitate the formation of reactive oxygen vacancies,which increases the amount of oxygen adsorption on the surface,especially the increase in surface acid sites,and promotes and adsorbs more reaction gases(NH_(3),O_(2),NO).The transformation from the standard SCR reaction to the fast SCR reaction is accelerated.
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.
文摘Characteristics of carbon deposition of CH 4 and C 2H 4 decomposition over supported Ni and Ni Ce catalysts were studied by using a pulse reaction as well as BET, TPR, XPS and hydrogen chemisorption techniques. It is found that there is a metal semiconductor interaction (MScI) in the Ni Ce catalyst, and the effect of MScI on the carbon deposition of CH 4 decomposition is opposite to that of C 2H 4. A novel model of carbon deposition of CH 4 or C 2H 4 decomposition was proposed.
基金Supported by the National Natural Science Foundation of China(21673187,21336009,21576228)National Key Technology Support Program of China(2014BAC10B01).
文摘In this paper, Ni/Zr–Yb–O catalysts with different sodium contents are prepared by a co-precipitation method, using aqueous Na2CO3 solution as a precipitant, and the effect of sodium on the catalyst structure and catalytic performance for syngas methanation is extensively investigated using five Ni/Zr–Yb–O catalysts, containing 0, 0.5, 1.5,4.5 and 13.5 wt% Na^+, those are denoted as Cat-1, Cat-2, Cat-3, Cat-4 and Cat-5 respectively. It is found that the interaction between Ni and support determines the catalytic performance of Ni/Zr–Yb–O and the residual sodium content negatively affects the interaction between Ni and support. Cat-1 exhibits an excellent catalytic performance.During a long run time of 380 h, no deactivation is observed and both CO conversion and CH4 selectivity maintain a level above 90%. However, Cat-3 and Cat-5 suffer rapid deactivation under the same reaction condition. The characterization results indicate the strong interaction between Ni and support enables Cat-1 to possess well dispersed Ni species, resistance to sintering and carbon deposition and thus the excellent catalytic performance. However, the presence of sodium ions over Ni/Zr–Yb–O degrades the interaction between Ni and support and the catalytic performance, especially for the stability. The relative weak interaction between Ni and support results in severe sintering of both ZrO2 and Ni under the reaction condition, carbon deposition and the poor catalytic performance.
基金SINOPEC for its financial support(No.108012/No.108041)
文摘Six Ni-Mo catalysts with different metal contents were prepared and characterized by N2 adsorption and X-ray diffractometry. The active phase microstructure of these catalysts was examined by the Raman spectroscopy, temperatureprogrammed reduction(TPR), X-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy. Hydrodesulfurization(HDS) activity of catalyst samples were analyzed in a flow fixed-bed microreactor. The sulfidation degree of Mo and the length of the MoS2 slab slightly increased with the amount of metal loaded following sulfidation. This small change is attributed to polymolybdate species observed in all the oxidized catalysts. Weak metal-support interactions, as determined by the TPR technique, increased the NiSx sulfidation phase and MoS2 slab stacking. The HDS activity of the catalyst samples increased with the number of active sites. For high metal loading catalysts, their HDS activity was nearly identical because the sulfur atoms cannot easily approach active sites. This change is caused by the large number of stacked layers in the MoS2 slabs as well as the decrease in the specific surface area and pore volume of the catalyst samples with an increasing metal loading.
基金the Deanship of Scientific Research at King Saud University for its funding this research group No.(RG-1436-119)
文摘Methane decomposition reaction has been studied at three different activation temperatures(500°C,800°C and950°C)over mesoporous alumina supported Ni–Fe and Mn–Fe based bimetallic catalysts.On co-impregnation of Ni on Fe/Al_2O_3the activity of the catalyst was retained even at the high activation temperature at 950°C and up to180 min.The Ni promotion enhanced the reducibility of Fe/Al_2O_3oxides showing higher catalytic activity with a hydrogen yield of 69%.The reactivity of bimetallic Mn and Fe over Al_2O_3catalyst decreased at 800°C and 950°C activation temperatures.Regeneration studies revealed that the catalyst could be effectively recycled up to 9times.The addition of O_2(1 ml,2 ml,4 ml)in the feed enhanced substantially CH_4conversion,the yield of hydrogen and the stability of the catalyst.
