Electrolytic reduction is a crucial process during the pyroprocessing of oxide spent fuel.This paper investigates the effects of different concentrations of Li2O on the properties of the LiCl-UCl3-Li2O mol...Electrolytic reduction is a crucial process during the pyroprocessing of oxide spent fuel.This paper investigates the effects of different concentrations of Li2O on the properties of the LiCl-UCl3-Li2O molten salt system during electrolytic reduction using first-principles molecular dynamics simulations.The study reveals that increasing Li2O concentration lowers the ion diffusion coefficients of Li+,Cl-,and O2-in the electrolyte,which has negative effect on the transport property of the system.A thorough analysis of the ligand structures formed by various components in the molten salt was conducted,including radial distribution functions and angular distribution functions.The analysis reveals that oxygen ions compete with chloride ions for coordination with cations.This competitive interaction has a significant impact on the coordination between Li-Cl and U-Cl elements,thereby influencing the microstructure.The analysis of electronic structures shows that the addition of Li2O affects the charge transfer among lithium,uranium,and chlorine,impacting the bond strength between anions and cations.Finally,the calculation of redox potential shows that an appropriate concentration of Li2O is beneficial to the electrochemical reduction process.The research results provide a theoretical basis for the design of molten salts in the electrolytic reduction process.展开更多
Composite supports CeO2-ZrO2-Al2O3(CZA) and CeO2-ZrO2-Al2O3-La2O3(CZALa) were prepared by co-precipitation method. Palladium catalysts were prepared by impregnation and their purification ability for CH4, CO and N...Composite supports CeO2-ZrO2-Al2O3(CZA) and CeO2-ZrO2-Al2O3-La2O3(CZALa) were prepared by co-precipitation method. Palladium catalysts were prepared by impregnation and their purification ability for CH4, CO and NOx in the mixture gas simulated the exhaust from natural gas vehicles (NGVs) operated under stoichiometric condition was investigated. The effect of La2O3 on the physicochemical properties of supports and catalysts was characterized by various techniques. The characterizations with X-ray diffraction (XRD) and Raman spectroscopy revealed that the doping of La2O3 restrained effectively the sintering of crystallite particles, maintained the crystallite particles in nanoscale and stabilized the crystal phase after calcination at 1000 ℃. The results of N2-adsorption, H2-temperatnre-programmed reduction (H2-TPR) and oxygen storage capacity (OSC) measurements indicated that La2O3 improved the textural properties, reducibility and OSC of composite supports. Activity testing results showed that the catalysts exhibit excellent activities for the simultaneous removal of methane, CO and NOx in the simulated exhaust gas. The catalysts supported on CZALa showed remarkable thermal stability and catalytic activity for the three pollutants, especially for NOx. The prepared palladium catalysts have high ability to remove NOx, CH4 and CO, and they can be used as excellent catalysts for the purification of exhaust from NGVs operated under stoichiometric condition. The catalysts reported in this work also have significant potential in industrial application because of their high performance and low cost.展开更多
The catalytic behaviors of Pd(1.4 wt%)catalysts supported on CeO2-ZrO2-La2O3 mixed oxides with different Ce/Zr molar ratios were investigated for methanol decomposition.Nitrogen adsorption-desorption(BET),X-ray photoe...The catalytic behaviors of Pd(1.4 wt%)catalysts supported on CeO2-ZrO2-La2O3 mixed oxides with different Ce/Zr molar ratios were investigated for methanol decomposition.Nitrogen adsorption-desorption(BET),X-ray photoelectron spectroscopy(XPS),H2 temperature-programmed reduction(H2-TPR),X-ray diffraction(XRD)and Pd dispersion analysis were used for their characterization.Pd/Cc0.76Zro.18 La0.06O1.97 catalyst showed the highest BET surface area,best Pd dispersion capability and strongest metal-support interaction.Moreover,XPS showed that there was lattice defect oxygen or mobile oxygen.According to the result of O 1s measurements the lattice defect oxygen or mobile oxygen helped to maintain Pd in a partly oxidized state and increased the activity for methanol decomposition.The Pd/Ce0.76Zr0.18La0.0601.97 catalyst exhibited the best activity.A 100%conversion of methanol was achieved at around 260°C,which was about 20-40°C lower than other catalysts.展开更多
The sulfation of CeO2/γ-Al2O3 sorbent in simulated flue gas was studied. A series of CeO2/γ-Al2O3 sorbents with different CeO2 loadings were prepared by impregnation and characterized by X-ray diffraction. Thermogra...The sulfation of CeO2/γ-Al2O3 sorbent in simulated flue gas was studied. A series of CeO2/γ-Al2O3 sorbents with different CeO2 loadings were prepared by impregnation and characterized by X-ray diffraction. Thermogravimetric technique was used to study the sulfation of CeO2/γ-Al2O3 sorbents, mainly on the CeO2 loading, sulfation cycles, and intrinsic kinetics. The study revealed that monolayer coverage of CeO2 supported on γ-Al2O3 was 0. 125 g CeO2/g (γ-Al2O3). Below monolayer coverage, CeO2 was highly dispersed on γ-Al2O3. The optimal CeO2 loading on sulfation was 0.03 g CeO2/g (γ-Al2O3). CeO2/γ-Al2O3 sorbent was recyclable by controlling sulfation time. Intrinsic kineticd equation was R = 1. 1394×10^-4×exp ( - 1,508.39/T) mg·mg^-1·s^-1 Activation energy and reaction order were 12.54 kJ·mol^-1 and first order, respectively.展开更多
A solid ternary mixture consisting of NaF,silicon and one metal oxide such as La2O3,CeO2,Pr6O11,Nd2O3,and Y2O3 was prepared and usedas de-fluorinated reagent for CF4 decomposition.The results show that 90% conversion ...A solid ternary mixture consisting of NaF,silicon and one metal oxide such as La2O3,CeO2,Pr6O11,Nd2O3,and Y2O3 was prepared and usedas de-fluorinated reagent for CF4 decomposition.The results show that 90% conversion of CF4 can be reached initially over NaF-Si-La2O3,NaF-Si-CeO2,NaF-Si-Nd2O3,and NaF-Si-Y2O3 at 850 C.The fresh and used reagents were characterized using XRD and XPS techniques.It was found that the active components of NaF and metal oxides in NaF-Si-CeO2,NaF-Si-Pr6O11,NaF-Si-Nd2O3,and NaF-Si-Y2O3 weretransformed into inert phases of mixed metal fluorides and silicates,respectively,resulting in an ineffective utilization of these de-fluorinatedreagents,whereas no inert phases from NaF and La2O3 can be observed in the used NaF-Si-La2O3,indicating the NaF-Si-La2O3 reagent couldbe utilized more efficiently than the other reagents in CF4 decomposition.展开更多
基金financial support provided by the National Natural Science Foundation of China(22476130 and 12205190)。
摘要Electrolytic reduction is a crucial process during the pyroprocessing of oxide spent fuel.This paper investigates the effects of different concentrations of Li2O on the properties of the LiCl-UCl3-Li2O molten salt system during electrolytic reduction using first-principles molecular dynamics simulations.The study reveals that increasing Li2O concentration lowers the ion diffusion coefficients of Li+,Cl-,and O2-in the electrolyte,which has negative effect on the transport property of the system.A thorough analysis of the ligand structures formed by various components in the molten salt was conducted,including radial distribution functions and angular distribution functions.The analysis reveals that oxygen ions compete with chloride ions for coordination with cations.This competitive interaction has a significant impact on the coordination between Li-Cl and U-Cl elements,thereby influencing the microstructure.The analysis of electronic structures shows that the addition of Li2O affects the charge transfer among lithium,uranium,and chlorine,impacting the bond strength between anions and cations.Finally,the calculation of redox potential shows that an appropriate concentration of Li2O is beneficial to the electrochemical reduction process.The research results provide a theoretical basis for the design of molten salts in the electrolytic reduction process.
基金supported by the National Natural Science Foundation of China (No. 20773090, 20803049)the National High Technology Researchand Development Program of China (863 Program, No. 2006AA06Z347)the Specialized Research Fund for the Doctoral Program of Higher Education(20070610026)
摘要Composite supports CeO2-ZrO2-Al2O3(CZA) and CeO2-ZrO2-Al2O3-La2O3(CZALa) were prepared by co-precipitation method. Palladium catalysts were prepared by impregnation and their purification ability for CH4, CO and NOx in the mixture gas simulated the exhaust from natural gas vehicles (NGVs) operated under stoichiometric condition was investigated. The effect of La2O3 on the physicochemical properties of supports and catalysts was characterized by various techniques. The characterizations with X-ray diffraction (XRD) and Raman spectroscopy revealed that the doping of La2O3 restrained effectively the sintering of crystallite particles, maintained the crystallite particles in nanoscale and stabilized the crystal phase after calcination at 1000 ℃. The results of N2-adsorption, H2-temperatnre-programmed reduction (H2-TPR) and oxygen storage capacity (OSC) measurements indicated that La2O3 improved the textural properties, reducibility and OSC of composite supports. Activity testing results showed that the catalysts exhibit excellent activities for the simultaneous removal of methane, CO and NOx in the simulated exhaust gas. The catalysts supported on CZALa showed remarkable thermal stability and catalytic activity for the three pollutants, especially for NOx. The prepared palladium catalysts have high ability to remove NOx, CH4 and CO, and they can be used as excellent catalysts for the purification of exhaust from NGVs operated under stoichiometric condition. The catalysts reported in this work also have significant potential in industrial application because of their high performance and low cost.
基金the National Natural Science Foundation of China(20773090)the Specialized Research Fund for the Doctoral Program of Higher Education of China(20070610026,200806100009)
摘要The catalytic behaviors of Pd(1.4 wt%)catalysts supported on CeO2-ZrO2-La2O3 mixed oxides with different Ce/Zr molar ratios were investigated for methanol decomposition.Nitrogen adsorption-desorption(BET),X-ray photoelectron spectroscopy(XPS),H2 temperature-programmed reduction(H2-TPR),X-ray diffraction(XRD)and Pd dispersion analysis were used for their characterization.Pd/Cc0.76Zro.18 La0.06O1.97 catalyst showed the highest BET surface area,best Pd dispersion capability and strongest metal-support interaction.Moreover,XPS showed that there was lattice defect oxygen or mobile oxygen.According to the result of O 1s measurements the lattice defect oxygen or mobile oxygen helped to maintain Pd in a partly oxidized state and increased the activity for methanol decomposition.The Pd/Ce0.76Zr0.18La0.0601.97 catalyst exhibited the best activity.A 100%conversion of methanol was achieved at around 260°C,which was about 20-40°C lower than other catalysts.
基金Project supported bythe National Natural Science Foundation of China (90210003) Natural Science Foundation of Bei-jing City (2012010)
摘要The sulfation of CeO2/γ-Al2O3 sorbent in simulated flue gas was studied. A series of CeO2/γ-Al2O3 sorbents with different CeO2 loadings were prepared by impregnation and characterized by X-ray diffraction. Thermogravimetric technique was used to study the sulfation of CeO2/γ-Al2O3 sorbents, mainly on the CeO2 loading, sulfation cycles, and intrinsic kinetics. The study revealed that monolayer coverage of CeO2 supported on γ-Al2O3 was 0. 125 g CeO2/g (γ-Al2O3). Below monolayer coverage, CeO2 was highly dispersed on γ-Al2O3. The optimal CeO2 loading on sulfation was 0.03 g CeO2/g (γ-Al2O3). CeO2/γ-Al2O3 sorbent was recyclable by controlling sulfation time. Intrinsic kineticd equation was R = 1. 1394×10^-4×exp ( - 1,508.39/T) mg·mg^-1·s^-1 Activation energy and reaction order were 12.54 kJ·mol^-1 and first order, respectively.
基金supported by the National Natural Science Foundation of China (No. 20976149)
摘要A solid ternary mixture consisting of NaF,silicon and one metal oxide such as La2O3,CeO2,Pr6O11,Nd2O3,and Y2O3 was prepared and usedas de-fluorinated reagent for CF4 decomposition.The results show that 90% conversion of CF4 can be reached initially over NaF-Si-La2O3,NaF-Si-CeO2,NaF-Si-Nd2O3,and NaF-Si-Y2O3 at 850 C.The fresh and used reagents were characterized using XRD and XPS techniques.It was found that the active components of NaF and metal oxides in NaF-Si-CeO2,NaF-Si-Pr6O11,NaF-Si-Nd2O3,and NaF-Si-Y2O3 weretransformed into inert phases of mixed metal fluorides and silicates,respectively,resulting in an ineffective utilization of these de-fluorinatedreagents,whereas no inert phases from NaF and La2O3 can be observed in the used NaF-Si-La2O3,indicating the NaF-Si-La2O3 reagent couldbe utilized more efficiently than the other reagents in CF4 decomposition.