The kinetics and the difference for Pr(Ⅲ)and Nd(Ⅲ)extraction from nitrate aqueous solution using trialkylmethylammonium nitrate([A336][NO3])as extractant were investigated by the single drop technique.The dependence...The kinetics and the difference for Pr(Ⅲ)and Nd(Ⅲ)extraction from nitrate aqueous solution using trialkylmethylammonium nitrate([A336][NO3])as extractant were investigated by the single drop technique.The dependence of the extraction rate of Pr(Ⅲ)and Nd(Ⅲ)on the concentrations of free Pr(Ⅲ)and Nd(Ⅲ)ions,the concentrations of Na NO3 and H+in aqueous solutions,and the concentrations of[A336][NO3]in kerosene solutions were discussed and the corresponding extraction rate equations for Pr(Ⅲ)and Nd(Ⅲ)were obtained.These equations demonstrated that the reaction rate constant of Pr(Ⅲ)with[A336][NO3]was double than that of Nd(Ⅲ).The effect of the addition of diethylenetriaminepentaacetic acid(DTPA)on the difference in the extraction rate of Pr(Ⅲ)and Nd(Ⅲ)by[A336][NO3]was also investigated.It was revealed that the difference in the complex formation rates of Pr(Ⅲ)and Nd(Ⅲ)with DTPA made a significant impact on the difference in the extraction rates of Pr(Ⅲ)and Nd(Ⅲ)with[A336][NO3].The ratio of extraction rates of Pr(Ⅲ)to Nd(Ⅲ)with[A336][NO3]was in proportion to the ratio of complex formation rates of Pr(Ⅲ)to Nd(Ⅲ)with DTPA.The extraction rate difference for Pr(Ⅲ)and Nd(Ⅲ)with[A336][NO3]increased due to a higher complex formation rate constant of DTPA with the free and un-complexed Nd(Ⅲ)ions in the aqueous nitrate solution than that with Pr(Ⅲ)ions.Therefore,the addition of DTPA in the aqueous nitrate solution is an effective method to intensify the separation of Pr(Ⅲ)and Nd(Ⅲ)in kinetics.The study on the extraction mechanism indicated that both the extraction of Pr(Ⅲ)and Nd(Ⅲ)by[A336][NO3]were diffusion controlled,and the reactions obeyed SN2 mechanism.The present work highlights a possible approach to strengthen the kinetic separation of Pr(Ⅲ)and Nd(Ⅲ).展开更多
A new approach was suggested in present work for improving the separation between Pr(Ⅲ) and Nd(Ⅲ)by a so-called kinetic "push and pull" system consisting of [A336][NO3] and DTPA in a column extractor.It is...A new approach was suggested in present work for improving the separation between Pr(Ⅲ) and Nd(Ⅲ)by a so-called kinetic "push and pull" system consisting of [A336][NO3] and DTPA in a column extractor.It is revealed that,when organic extractant [A336][NO3] is continuously pumped into the column extractor in the form of dispersed oil droplets and at the same time DTPA was injected into the aqueous feed solution whet the extraction was just started,the separatiot factor of Pr(Ⅲ) to Nd(Ⅲ),βPr/Nd,increased obviously with the time,and could even achieve 21.7.Such an amazing increase in βPr/Nd value might be due to the extraction rate of Pr(Ⅲ) by [A336][NO3] oil droplets being faster than that of Nd(Ⅲ),while the complexing rate of Nd(Ⅲ) with DTPA in the aqueous solutions being faster than that of Pr(III).The opposite order of the two rates for Pr(Ⅲ) and Nd(Ⅲ) result in their kinetic "push and pull" separation.In contrast,the βPr/Nd value in traditional thermodynamic separation reported in previous literatures is only around 5 or even less,even though using the same extractant [A336][NO3] and DTPA but by previously adding DTPA into the aqueous feed solutions for pre-complexing of Pr(Ⅲ) and Nd(Ⅲ).Various effects from the pH and addition amount of DTPA aqueous solutions,LiNO3 concentrations in initial aqueous feed solutions,the initial concentration ratios of Pr(Ⅲ) to Nd(Ⅲ) ions,the initial pH of aqueous feed solutions,and the concentrations of [A336][NO3] in organic phases,on the kinetic separatiot of Pr(Ⅲ) and Nd(Ⅲ) are discussed.The present work highlights a promising approach for separation of rare earths or other targets with extreme similarity in physicochemical properties.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.51574213,51074150)the Key Project of Chinese National Programs for Fundamental Research and Development(973 Program No.2012CBA01203)。
文摘The kinetics and the difference for Pr(Ⅲ)and Nd(Ⅲ)extraction from nitrate aqueous solution using trialkylmethylammonium nitrate([A336][NO3])as extractant were investigated by the single drop technique.The dependence of the extraction rate of Pr(Ⅲ)and Nd(Ⅲ)on the concentrations of free Pr(Ⅲ)and Nd(Ⅲ)ions,the concentrations of Na NO3 and H+in aqueous solutions,and the concentrations of[A336][NO3]in kerosene solutions were discussed and the corresponding extraction rate equations for Pr(Ⅲ)and Nd(Ⅲ)were obtained.These equations demonstrated that the reaction rate constant of Pr(Ⅲ)with[A336][NO3]was double than that of Nd(Ⅲ).The effect of the addition of diethylenetriaminepentaacetic acid(DTPA)on the difference in the extraction rate of Pr(Ⅲ)and Nd(Ⅲ)by[A336][NO3]was also investigated.It was revealed that the difference in the complex formation rates of Pr(Ⅲ)and Nd(Ⅲ)with DTPA made a significant impact on the difference in the extraction rates of Pr(Ⅲ)and Nd(Ⅲ)with[A336][NO3].The ratio of extraction rates of Pr(Ⅲ)to Nd(Ⅲ)with[A336][NO3]was in proportion to the ratio of complex formation rates of Pr(Ⅲ)to Nd(Ⅲ)with DTPA.The extraction rate difference for Pr(Ⅲ)and Nd(Ⅲ)with[A336][NO3]increased due to a higher complex formation rate constant of DTPA with the free and un-complexed Nd(Ⅲ)ions in the aqueous nitrate solution than that with Pr(Ⅲ)ions.Therefore,the addition of DTPA in the aqueous nitrate solution is an effective method to intensify the separation of Pr(Ⅲ)and Nd(Ⅲ)in kinetics.The study on the extraction mechanism indicated that both the extraction of Pr(Ⅲ)and Nd(Ⅲ)by[A336][NO3]were diffusion controlled,and the reactions obeyed SN2 mechanism.The present work highlights a possible approach to strengthen the kinetic separation of Pr(Ⅲ)and Nd(Ⅲ).
基金supported by the National Natural Science Foundation of China(51574213,51074150)the Key Project of Chinese National Programs for Fundamental Research and Development(973 Program)(2012CBA01203).
文摘A new approach was suggested in present work for improving the separation between Pr(Ⅲ) and Nd(Ⅲ)by a so-called kinetic "push and pull" system consisting of [A336][NO3] and DTPA in a column extractor.It is revealed that,when organic extractant [A336][NO3] is continuously pumped into the column extractor in the form of dispersed oil droplets and at the same time DTPA was injected into the aqueous feed solution whet the extraction was just started,the separatiot factor of Pr(Ⅲ) to Nd(Ⅲ),βPr/Nd,increased obviously with the time,and could even achieve 21.7.Such an amazing increase in βPr/Nd value might be due to the extraction rate of Pr(Ⅲ) by [A336][NO3] oil droplets being faster than that of Nd(Ⅲ),while the complexing rate of Nd(Ⅲ) with DTPA in the aqueous solutions being faster than that of Pr(III).The opposite order of the two rates for Pr(Ⅲ) and Nd(Ⅲ) result in their kinetic "push and pull" separation.In contrast,the βPr/Nd value in traditional thermodynamic separation reported in previous literatures is only around 5 or even less,even though using the same extractant [A336][NO3] and DTPA but by previously adding DTPA into the aqueous feed solutions for pre-complexing of Pr(Ⅲ) and Nd(Ⅲ).Various effects from the pH and addition amount of DTPA aqueous solutions,LiNO3 concentrations in initial aqueous feed solutions,the initial concentration ratios of Pr(Ⅲ) to Nd(Ⅲ) ions,the initial pH of aqueous feed solutions,and the concentrations of [A336][NO3] in organic phases,on the kinetic separatiot of Pr(Ⅲ) and Nd(Ⅲ) are discussed.The present work highlights a promising approach for separation of rare earths or other targets with extreme similarity in physicochemical properties.
