The Mo modified Ni/Al_2O_3 catalysts were prepared and sulfided at different temperatures, and their catalytic activity for thioetherification of mercaptans and olefins(or dienes), hydrogenation of dienes and olefins ...The Mo modified Ni/Al_2O_3 catalysts were prepared and sulfided at different temperatures, and their catalytic activity for thioetherification of mercaptans and olefins(or dienes), hydrogenation of dienes and olefins in the thioetherification process using fluidized catalytic cracking(FCC) naphtha as the feedstock was investigated. In order to disclose the correlation between the physicochemical characteristics of catalysts and their catalytic activity, the surface structures and properties of the catalysts sulfided at different temperatures were characterized by the high resolution transmission electronic microscopy(HRTEM), X-ray photoelectron spectroscopy(XPS) and H2-temperature programmed reduction(H_2-TPR) technique. The results showed that an increase of sulfurization temperature not only could promote the sulfurization degree of active metals on the catalysts, but also could adjust the micro-morphology of active species. These changes could improve the catalytic performance of thioetherification, and hydrogenation of dienes and olefins. However, an excess sulfurization temperature was more easily to upgrade the ability of the catalyst for hydrogenation of olefins, which could lead to a decrease of the octane number of the product. It was also showed that a moderate sulfurization temperature not only could improve the catalytic performance of thioetherification and hydrogenation of dienes but also could control hydrogenation of olefins.展开更多
Coral reef-like Ni/Al2O3 catalysts were prepared by co-precipitation of nickel acetate and aluminium nitrate with sodium carbonate aqueous solution in the medium of ethylene glycolye.Methanation of syngas was carried ...Coral reef-like Ni/Al2O3 catalysts were prepared by co-precipitation of nickel acetate and aluminium nitrate with sodium carbonate aqueous solution in the medium of ethylene glycolye.Methanation of syngas was carried out over coral reef-like Ni/Al2O3 catalysts in a continuous flow type fixed-bed reactor.The structure and properties of the fresh and used catalysts were studied by SEM,N2 adsorption-desorption,XRD,H2-TPR,O2-TPO,TG and ICP-AES techniques.The results showed that the coral reef-like Ni/Al2O3 catalysts exhibited better activity than the conventional Ni/Al2O3-H2O catalysts.The activities of coral reef-like catalysts were in the order of Ni/Al2O3-673Ni/Al2O3-573Ni/Al2O3- 473Ni/Al2O3-773.Ni/Al2O3-673-EG catalyst showed not only good activity and improved stability but also superior resistance to carbon deposition,sintering,and Ni loss.Under the reaction conditions of CO/H2（molar ratio）=1：3,593 K,atmospheric pressure and a GHSV of 2500 h-1,CH4 selectivity was 84.7%,and the CO conversion reached 98.2%.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
The preferential oxidation of CO(CO-PROX)reaction is a cost-effective method for eliminating trace amounts of CO from the fuel H2.Pt-based catalysts have been extensively studied for COPROX,with their activity influen...The preferential oxidation of CO(CO-PROX)reaction is a cost-effective method for eliminating trace amounts of CO from the fuel H2.Pt-based catalysts have been extensively studied for COPROX,with their activity influenced by the morphology of the support.Hydrothermal synthesis was employed to produce different morphologies ofγ-Al_(2)O_(3):flower-likeγ-Al_(2)O_(3)(f)exposing(110)crystal faces,sheet-likeγ-Al_(2)O_(3)(s)revealing(100)crystal faces,and rod-likeγ-Al_(2)O_(3)(r)displaying(111)crystal faces,followed by loading PtCo nanoparticles.The exposed crystal faces of the support impact the alloying degree of the PtCo nanoparticles,and an increase in the alloying degree correlates with enhanced catalyst reactivity.Pt_(3)Co intermetallic compounds were identified onγ-Al_(2)O_(3)(f)exposing(110)crystal faces,and PtCo/γ-Al_(2)O_(3)(f)showed high catalytic activity in the CO-PROX reaction,achieving 100%CO conversion across a broad temperature range of 50−225°C.In contrast,only partial alloying of PtCo was observed onγ-Al_(2)O_(3)(s).Furthermore,no alloying between Pt and Co occurred in PtCo/γ-Al_(2)O_(3)(r),resulting in a reaction rate at 50°C that was merely 11%of that of PtCo/γ-Al_(2)O_(3)(f).The formation of Pt3Co intermetallic compounds led to a more oxidized state of Pt,which significantly diminished the adsorption of CO on Pt and augmented the active oxygen species,thereby facilitating the selective oxidation of CO.展开更多
This work synthesized a series of Ni/CeO_(2)/Al_(2)O_(3) catalysts with varying CeO_(2) doping amounts to enhance low-temperature CO_(2) methanation.The introduction of CeO_(2) weakens the interaction between Ni and A...This work synthesized a series of Ni/CeO_(2)/Al_(2)O_(3) catalysts with varying CeO_(2) doping amounts to enhance low-temperature CO_(2) methanation.The introduction of CeO_(2) weakens the interaction between Ni and Al_(2)O_(3),leading to the formation of Ni-CeO_(2) active sites.This results in a high dispersion of Ni and CeO_(2),improved catalyst reducibility,increased number of active sites,and enhanced the CO_(2) methanation.This work further investigated the impact of WHSV and catalyst stacking configuration to enhance the reaction.When the catalyst is stacked into three segments with a temperature gradient of 330℃,300℃,and 250℃under WHSV=9000 ml·h^(-1)·g^(-1),the CO_(2) conversion significantly increases to 95%,which is remarkably close to the thermodynamic equilibrium(96%).展开更多
High-temperature experiments were carried out for the slag systems of“FeO”−SiO_(2)−CaO−Al_(2)O_(3)and“FeO”−SiO_(2)−CaO−MgO at 1200℃and p(O_(2))of 10^(−7)kPa.The equilibrated samples were quenched,and the phase co...High-temperature experiments were carried out for the slag systems of“FeO”−SiO_(2)−CaO−Al_(2)O_(3)and“FeO”−SiO_(2)−CaO−MgO at 1200℃and p(O_(2))of 10^(−7)kPa.The equilibrated samples were quenched,and the phase compositions were measured by electron probe microanalysis(EPMA).A series of pseudo-ternary and pseudo-binary phase diagrams are constructed to demonstrate their applications in copper smelting process and evaluation of the thermodynamic database.Spinel and tridymite are identified to be the major primary phases in the composition range related to the copper smelting slags.It is found that the operating window of the smelting slag is primarily determined by w_(Fe)/w_(SiO_(2))ratio in the slag.Both MgO and Al_(2)O_(3)in the slag reduce the operating window which requires extra fluxing agent to keep the slag to be fully liquid.Complex spinel solid solutions cause inaccurate predictions of the current thermodynamic database.展开更多
基金support provided by the National Natural Science Foundation of China(Granted No.21276276)
文摘The Mo modified Ni/Al_2O_3 catalysts were prepared and sulfided at different temperatures, and their catalytic activity for thioetherification of mercaptans and olefins(or dienes), hydrogenation of dienes and olefins in the thioetherification process using fluidized catalytic cracking(FCC) naphtha as the feedstock was investigated. In order to disclose the correlation between the physicochemical characteristics of catalysts and their catalytic activity, the surface structures and properties of the catalysts sulfided at different temperatures were characterized by the high resolution transmission electronic microscopy(HRTEM), X-ray photoelectron spectroscopy(XPS) and H2-temperature programmed reduction(H_2-TPR) technique. The results showed that an increase of sulfurization temperature not only could promote the sulfurization degree of active metals on the catalysts, but also could adjust the micro-morphology of active species. These changes could improve the catalytic performance of thioetherification, and hydrogenation of dienes and olefins. However, an excess sulfurization temperature was more easily to upgrade the ability of the catalyst for hydrogenation of olefins, which could lead to a decrease of the octane number of the product. It was also showed that a moderate sulfurization temperature not only could improve the catalytic performance of thioetherification and hydrogenation of dienes but also could control hydrogenation of olefins.
基金financially supported by Independent Research Subject from Ministry of Science and Technology of China(No.2008BWZ005)
文摘Coral reef-like Ni/Al2O3 catalysts were prepared by co-precipitation of nickel acetate and aluminium nitrate with sodium carbonate aqueous solution in the medium of ethylene glycolye.Methanation of syngas was carried out over coral reef-like Ni/Al2O3 catalysts in a continuous flow type fixed-bed reactor.The structure and properties of the fresh and used catalysts were studied by SEM,N2 adsorption-desorption,XRD,H2-TPR,O2-TPO,TG and ICP-AES techniques.The results showed that the coral reef-like Ni/Al2O3 catalysts exhibited better activity than the conventional Ni/Al2O3-H2O catalysts.The activities of coral reef-like catalysts were in the order of Ni/Al2O3-673Ni/Al2O3-573Ni/Al2O3- 473Ni/Al2O3-773.Ni/Al2O3-673-EG catalyst showed not only good activity and improved stability but also superior resistance to carbon deposition,sintering,and Ni loss.Under the reaction conditions of CO/H2（molar ratio）=1：3,593 K,atmospheric pressure and a GHSV of 2500 h-1,CH4 selectivity was 84.7%,and the CO conversion reached 98.2%.
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(22376063,21976057)the Fund of the National Engineering Laboratory for Mobile Source Emission Control Technology(NELMS2020A05)Fundamental Research Funds for the Central Universities.
文摘The preferential oxidation of CO(CO-PROX)reaction is a cost-effective method for eliminating trace amounts of CO from the fuel H2.Pt-based catalysts have been extensively studied for COPROX,with their activity influenced by the morphology of the support.Hydrothermal synthesis was employed to produce different morphologies ofγ-Al_(2)O_(3):flower-likeγ-Al_(2)O_(3)(f)exposing(110)crystal faces,sheet-likeγ-Al_(2)O_(3)(s)revealing(100)crystal faces,and rod-likeγ-Al_(2)O_(3)(r)displaying(111)crystal faces,followed by loading PtCo nanoparticles.The exposed crystal faces of the support impact the alloying degree of the PtCo nanoparticles,and an increase in the alloying degree correlates with enhanced catalyst reactivity.Pt_(3)Co intermetallic compounds were identified onγ-Al_(2)O_(3)(f)exposing(110)crystal faces,and PtCo/γ-Al_(2)O_(3)(f)showed high catalytic activity in the CO-PROX reaction,achieving 100%CO conversion across a broad temperature range of 50−225°C.In contrast,only partial alloying of PtCo was observed onγ-Al_(2)O_(3)(s).Furthermore,no alloying between Pt and Co occurred in PtCo/γ-Al_(2)O_(3)(r),resulting in a reaction rate at 50°C that was merely 11%of that of PtCo/γ-Al_(2)O_(3)(f).The formation of Pt3Co intermetallic compounds led to a more oxidized state of Pt,which significantly diminished the adsorption of CO on Pt and augmented the active oxygen species,thereby facilitating the selective oxidation of CO.
基金financial support of the National Natural Science Foundation of China(22178265)Tianjin Science and Technology Project(21JCYBJC00400)Open Project for Ningbo Key Laboratory of Green Petrochemical Carbon Emission Reduction Technology and Equipment(ZITJU2023-ZYDK001).
文摘This work synthesized a series of Ni/CeO_(2)/Al_(2)O_(3) catalysts with varying CeO_(2) doping amounts to enhance low-temperature CO_(2) methanation.The introduction of CeO_(2) weakens the interaction between Ni and Al_(2)O_(3),leading to the formation of Ni-CeO_(2) active sites.This results in a high dispersion of Ni and CeO_(2),improved catalyst reducibility,increased number of active sites,and enhanced the CO_(2) methanation.This work further investigated the impact of WHSV and catalyst stacking configuration to enhance the reaction.When the catalyst is stacked into three segments with a temperature gradient of 330℃,300℃,and 250℃under WHSV=9000 ml·h^(-1)·g^(-1),the CO_(2) conversion significantly increases to 95%,which is remarkably close to the thermodynamic equilibrium(96%).
文摘High-temperature experiments were carried out for the slag systems of“FeO”−SiO_(2)−CaO−Al_(2)O_(3)and“FeO”−SiO_(2)−CaO−MgO at 1200℃and p(O_(2))of 10^(−7)kPa.The equilibrated samples were quenched,and the phase compositions were measured by electron probe microanalysis(EPMA).A series of pseudo-ternary and pseudo-binary phase diagrams are constructed to demonstrate their applications in copper smelting process and evaluation of the thermodynamic database.Spinel and tridymite are identified to be the major primary phases in the composition range related to the copper smelting slags.It is found that the operating window of the smelting slag is primarily determined by w_(Fe)/w_(SiO_(2))ratio in the slag.Both MgO and Al_(2)O_(3)in the slag reduce the operating window which requires extra fluxing agent to keep the slag to be fully liquid.Complex spinel solid solutions cause inaccurate predictions of the current thermodynamic database.
