The reduction of carbon emissions in the steel industry is a significant challenge,and utilizing CO_(2) from carbon intensive steel industry off-gases for methanol production is a promising strategy for decarbonizatio...The reduction of carbon emissions in the steel industry is a significant challenge,and utilizing CO_(2) from carbon intensive steel industry off-gases for methanol production is a promising strategy for decarbonization.However,steelwork off-gases typically contain various impurities,including H_(2)S,which can deactivate commercial methanol synthesis catalysts,Cu/ZnO/Al_(2)O_(3)(CZA).Reverse water-gas shift(RWGS)reaction is the predominant side reaction in CO_(2) hydrogenation to methanol which can occur at ambient pressure,enabling the decouple of RWGS from methanol production at high pressure.Then,a series of activated CZA catalysts has been in-situ pretreated in 400 ppm H_(2)S/Ar at 250℃and tested for both RWGS reaction at ambient pressure and CO_(2) hydrogenation to methanol at high pressure.An innovative decoupling strategy was employed to isolate the RWGS reaction from the methanol synthesis process,enabling the investigation of the evolution of active site structures and the poisoning mechanism through elemental analysis,X-ray Diffraction,X-ray Photoelectron Spectroscopy,Fourier Transform Infrared Spectroscopy,Temperature Programmed Reduction and CO_(2) Temperature Programmed Desorption.The results indicate that there are different dynamic migration behaviors of ZnO_(x) in the two reaction systems,leading to different poisoning mechanisms.These interesting findings are beneficial to develop sulfur resistant and durable highly efficient catalysts for CO_(2) hydrogenation to methanol,promoting the carbon emission reduction in steel industry.展开更多
The lime-Cu^(2+)-xanthate process is commonly used for the flotation separation of sphalerite from pyrite.In this process,lime is added to the pulp to inhibit the floatability of pyrite.However,the excessive use of li...The lime-Cu^(2+)-xanthate process is commonly used for the flotation separation of sphalerite from pyrite.In this process,lime is added to the pulp to inhibit the floatability of pyrite.However,the excessive use of lime can result in pipeline blockage and inadequate recovery of associated precious metals.Therefore,it is necessary to develop new flotation process that minimizes or eliminates the use of lime.In this paper,a novel Fe^(3+)-Cu^(2+)-butyl xanthate process was developed as an alternative to lime for separating of sphalerite from pyrite.The flotation results indicated that with the artificially-mixed minerals,the flotation recovery of pyrite was lower than 16%and that of sphalerite was higher than 47%at pH 5.0−10.0.The zeta potential measurements revealed that ferric ion preferred to adsorb on pyrite,and copper ion displaced with zinc ion from the lattice at the interface of sphalerite.The wettability analyses indicated that the hydrophobicity of sphalerite surface increased apparently after being treated with Fe^(3+)-Cu^(2+)-BX,while the hydrophobicity of pyrite surface remained nearly unchanged.With XPS analysis,Cu-S bond and hydrophilic ferric hydroxide were detected separately on the surface of sphalerite and pyrite after conditioning with Fe^(3+)-Cu^(2+)-BX,which facilitated the flotation separation of sphalerite from pyrite with butyl xanthate collector.展开更多
A series of composite catalysts were prepared by the wet mixing method, and the mass ratio of CuO-ZnO-Al2O3-ZrO2 component to HZSM-5 zeolite （molar ratio of SiO2 to Al2O3 being 25） was 2：1. The CuO-ZnO-Al2O3-ZrO2 ...A series of composite catalysts were prepared by the wet mixing method, and the mass ratio of CuO-ZnO-Al2O3-ZrO2 component to HZSM-5 zeolite （molar ratio of SiO2 to Al2O3 being 25） was 2：1. The CuO-ZnO-Al2O3-ZrO2 （CuO/ZnO/Al2O3=3/6/1 by weight） component was prepared by a modified ＇two-step＇ co-precipitation method. The effects of ZrO2 on the performance of CuO-ZnO-Al2O3/HZSMo5 catalyst for dimethyl ether synthesis from CO2 hydrogenation were investigated. It was found that ZrO2 improved the properties of CuO-ZnO-Al2O3/HZSM-5 as a structural promoter.展开更多
An effective catalytic transfer hydrogenation (CTH) process of bio-based levulinate esters into γ-valerolactone (GVL) was explored over ternary Cu/ZnO/Al2O3 catalyst which was prepared by coprecipitation method and c...An effective catalytic transfer hydrogenation (CTH) process of bio-based levulinate esters into γ-valerolactone (GVL) was explored over ternary Cu/ZnO/Al2O3 catalyst which was prepared by coprecipitation method and could be sustainably used. As a result, quantitative conversion of ethyl levulinate (EL) and 99.0% yield of GVL were obtained in the CTH process using i-PrOH as hydrogen donor. The Cu/ZnO/Al2O3 catalyst with high-surface-area could be reused at least four times without the loss of catalytic activity. Furthermore, the structure and properties of Cu/ZnO/Al2O3 catalyst was characterized through XRD, BET, SEM, TEM and H2-TPR. Also, the influence of different support oxides and calcination temperatures was investigated.展开更多
In this study,the thermal stability of a Fe2 O3 catalyst for mercury oxidation was significantly improved by doping with Al2 O3.After 1 hr,the catalyst doped with 10 wt.%Al2 O3 still exhibited a mercury conversion eff...In this study,the thermal stability of a Fe2 O3 catalyst for mercury oxidation was significantly improved by doping with Al2 O3.After 1 hr,the catalyst doped with 10 wt.%Al2 O3 still exhibited a mercury conversion efficiency of 70.9%,while the undoped sample even lost its catalytic activity.Doping with Al2 O3 retarded the collapse of the catalyst mesoporous structure during high-temperature calcination,and the doped samples maintained a higher specific surface area,smaller pore size,and narrower pore size distribution.Transmission electron microscope images revealed that after calcination at 350℃,the average size of the catalyst grains in Fe2 O3 was 23.4 nm;however,the corresponding values for 1%Al2 O3/Fe2 O3,3%Al2 O3/Fe2 O3,and 10%Al2 O3/Fe2 O3 were only 13.3,7.1,and 4.7 nm,respectively.Results obtained from X-ray diffraction and thermogravimetry coupled with differential scanning calorimetry confirmed that doping with Al2 O3 also retards the crystallization of the catalysts at high temperature,constraining catalyst grains to a smaller size.展开更多
Given the difficulties of degrading benzotriazole(BTA),this study used a one-pot hydrothermal method to prepareα-Fe_(2)O_(3)/Cu_(2)O(FC)composites for photoelectrocatalytic(PEC)degradation of BTA.The characterization...Given the difficulties of degrading benzotriazole(BTA),this study used a one-pot hydrothermal method to prepareα-Fe_(2)O_(3)/Cu_(2)O(FC)composites for photoelectrocatalytic(PEC)degradation of BTA.The characterization of FC structure showed that Cu_(2)O in cubic crystals was loaded with circular sheets of Fe_(2)O_(3).Owing to this structure,FC showed efficient PEC degradation of BTA when exposed to ultraviolet light.The experimental results demonstrated that FC efficiently degraded BTA.When the PEC degradation continued for 60 min,100%degradation of BTA was achieved because FC enhanced the photoelectron-hole separation and the separation and transfer of articulated carriers.High per-formance liquid chromatography-mass spectrometry showed that intermediates formed during the PEC degradation of BTA.Finally,various pathways for degradation of BTA were postulated.This FC-based PEC system provides a harmless and effective method for degradation of BTA.展开更多
A La-modified Al2O3 catalyst was prepared with deposition-precipitation method. The effect of calcination temperature on the reactivity for vapor phase hydrofluorination of acetylene to vinyl fluoride. The catalysts c...A La-modified Al2O3 catalyst was prepared with deposition-precipitation method. The effect of calcination temperature on the reactivity for vapor phase hydrofluorination of acetylene to vinyl fluoride. The catalysts calcined at different temperatures were characterized using NH3-TPD, pyridine-FTIR, X-ray diffraction, and Raman techniques. It was found that the calcination process could not only change the structure of these catalysts but also modify the amount of surface acidity on the catalysts. The catalyst calcined at 400 ℃ exhibited the highest conversion of acetylene （94.6%） and highest selectivity to vinyl fluoride （83.4%） and lower coke deposition selectivity （0.72%）. The highest activity was related to the largest amount of surface acidity on the catalyst, and the coke deposition was also related to the total amount of surface acidic sites.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22276060 and 21976059)Guangdong Basic and Applied Basic Research Foundation(No.2024A1515012636)China Scholarship Council Scholarship(No.201906155006)。
文摘The reduction of carbon emissions in the steel industry is a significant challenge,and utilizing CO_(2) from carbon intensive steel industry off-gases for methanol production is a promising strategy for decarbonization.However,steelwork off-gases typically contain various impurities,including H_(2)S,which can deactivate commercial methanol synthesis catalysts,Cu/ZnO/Al_(2)O_(3)(CZA).Reverse water-gas shift(RWGS)reaction is the predominant side reaction in CO_(2) hydrogenation to methanol which can occur at ambient pressure,enabling the decouple of RWGS from methanol production at high pressure.Then,a series of activated CZA catalysts has been in-situ pretreated in 400 ppm H_(2)S/Ar at 250℃and tested for both RWGS reaction at ambient pressure and CO_(2) hydrogenation to methanol at high pressure.An innovative decoupling strategy was employed to isolate the RWGS reaction from the methanol synthesis process,enabling the investigation of the evolution of active site structures and the poisoning mechanism through elemental analysis,X-ray Diffraction,X-ray Photoelectron Spectroscopy,Fourier Transform Infrared Spectroscopy,Temperature Programmed Reduction and CO_(2) Temperature Programmed Desorption.The results indicate that there are different dynamic migration behaviors of ZnO_(x) in the two reaction systems,leading to different poisoning mechanisms.These interesting findings are beneficial to develop sulfur resistant and durable highly efficient catalysts for CO_(2) hydrogenation to methanol,promoting the carbon emission reduction in steel industry.
基金Project(52204363)supported by the National Natural Science Foundation of ChinaProject(2024JJ8042)supported by the Hunan Natural Science Foundation,ChinaProject(22C0220)supported by the Education Department of Hunan Province,China。
文摘The lime-Cu^(2+)-xanthate process is commonly used for the flotation separation of sphalerite from pyrite.In this process,lime is added to the pulp to inhibit the floatability of pyrite.However,the excessive use of lime can result in pipeline blockage and inadequate recovery of associated precious metals.Therefore,it is necessary to develop new flotation process that minimizes or eliminates the use of lime.In this paper,a novel Fe^(3+)-Cu^(2+)-butyl xanthate process was developed as an alternative to lime for separating of sphalerite from pyrite.The flotation results indicated that with the artificially-mixed minerals,the flotation recovery of pyrite was lower than 16%and that of sphalerite was higher than 47%at pH 5.0−10.0.The zeta potential measurements revealed that ferric ion preferred to adsorb on pyrite,and copper ion displaced with zinc ion from the lattice at the interface of sphalerite.The wettability analyses indicated that the hydrophobicity of sphalerite surface increased apparently after being treated with Fe^(3+)-Cu^(2+)-BX,while the hydrophobicity of pyrite surface remained nearly unchanged.With XPS analysis,Cu-S bond and hydrophilic ferric hydroxide were detected separately on the surface of sphalerite and pyrite after conditioning with Fe^(3+)-Cu^(2+)-BX,which facilitated the flotation separation of sphalerite from pyrite with butyl xanthate collector.
文摘A series of composite catalysts were prepared by the wet mixing method, and the mass ratio of CuO-ZnO-Al2O3-ZrO2 component to HZSM-5 zeolite （molar ratio of SiO2 to Al2O3 being 25） was 2：1. The CuO-ZnO-Al2O3-ZrO2 （CuO/ZnO/Al2O3=3/6/1 by weight） component was prepared by a modified ＇two-step＇ co-precipitation method. The effects of ZrO2 on the performance of CuO-ZnO-Al2O3/HZSMo5 catalyst for dimethyl ether synthesis from CO2 hydrogenation were investigated. It was found that ZrO2 improved the properties of CuO-ZnO-Al2O3/HZSM-5 as a structural promoter.
基金the financial support from the State Key Program of the National Natural Science Foundation of China(No.21436007)the support from the central laboratory of SESE in SJTU
文摘An effective catalytic transfer hydrogenation (CTH) process of bio-based levulinate esters into γ-valerolactone (GVL) was explored over ternary Cu/ZnO/Al2O3 catalyst which was prepared by coprecipitation method and could be sustainably used. As a result, quantitative conversion of ethyl levulinate (EL) and 99.0% yield of GVL were obtained in the CTH process using i-PrOH as hydrogen donor. The Cu/ZnO/Al2O3 catalyst with high-surface-area could be reused at least four times without the loss of catalytic activity. Furthermore, the structure and properties of Cu/ZnO/Al2O3 catalyst was characterized through XRD, BET, SEM, TEM and H2-TPR. Also, the influence of different support oxides and calcination temperatures was investigated.
基金supported by the National Key Research and Development Program of China(No.2017YFC0210501)National Natural Science Foundation of China(No.21607009)National Engineering Laboratory for Flue Gas Pollutants Control Technology and Equipment(No.NEL-KF-201902)
文摘In this study,the thermal stability of a Fe2 O3 catalyst for mercury oxidation was significantly improved by doping with Al2 O3.After 1 hr,the catalyst doped with 10 wt.%Al2 O3 still exhibited a mercury conversion efficiency of 70.9%,while the undoped sample even lost its catalytic activity.Doping with Al2 O3 retarded the collapse of the catalyst mesoporous structure during high-temperature calcination,and the doped samples maintained a higher specific surface area,smaller pore size,and narrower pore size distribution.Transmission electron microscope images revealed that after calcination at 350℃,the average size of the catalyst grains in Fe2 O3 was 23.4 nm;however,the corresponding values for 1%Al2 O3/Fe2 O3,3%Al2 O3/Fe2 O3,and 10%Al2 O3/Fe2 O3 were only 13.3,7.1,and 4.7 nm,respectively.Results obtained from X-ray diffraction and thermogravimetry coupled with differential scanning calorimetry confirmed that doping with Al2 O3 also retards the crystallization of the catalysts at high temperature,constraining catalyst grains to a smaller size.
基金supported by the Open Program of the Tianjin Key Laboratory of Green Chemical Engineering Process Engineering,Tiangong University,Tianjin(Grant No.GCEPE20190108)the Inner Mongolia Natural Science Foundation(Grant No.2020MS02015)the Regional Science Foundation Project of the National Natural Science Foundation of China(Grant No.42167029)
文摘Given the difficulties of degrading benzotriazole(BTA),this study used a one-pot hydrothermal method to prepareα-Fe_(2)O_(3)/Cu_(2)O(FC)composites for photoelectrocatalytic(PEC)degradation of BTA.The characterization of FC structure showed that Cu_(2)O in cubic crystals was loaded with circular sheets of Fe_(2)O_(3).Owing to this structure,FC showed efficient PEC degradation of BTA when exposed to ultraviolet light.The experimental results demonstrated that FC efficiently degraded BTA.When the PEC degradation continued for 60 min,100%degradation of BTA was achieved because FC enhanced the photoelectron-hole separation and the separation and transfer of articulated carriers.High per-formance liquid chromatography-mass spectrometry showed that intermediates formed during the PEC degradation of BTA.Finally,various pathways for degradation of BTA were postulated.This FC-based PEC system provides a harmless and effective method for degradation of BTA.
基金supported by the National Natural Science Foundation of China(20976162,21103149,20906079)Natural Science Foundation of Zhejiang Province,China(R5100266)Significant Science and Technology Project of Zhejiang Province,China(2010C13001)~~
基金ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China （No.20873125）,
文摘A La-modified Al2O3 catalyst was prepared with deposition-precipitation method. The effect of calcination temperature on the reactivity for vapor phase hydrofluorination of acetylene to vinyl fluoride. The catalysts calcined at different temperatures were characterized using NH3-TPD, pyridine-FTIR, X-ray diffraction, and Raman techniques. It was found that the calcination process could not only change the structure of these catalysts but also modify the amount of surface acidity on the catalysts. The catalyst calcined at 400 ℃ exhibited the highest conversion of acetylene （94.6%） and highest selectivity to vinyl fluoride （83.4%） and lower coke deposition selectivity （0.72%）. The highest activity was related to the largest amount of surface acidity on the catalyst, and the coke deposition was also related to the total amount of surface acidic sites.
