Abstract A new mixer-settler-mixer three chamber integrated extractor is proposed in this work for liquid-liquid- liquid three phase countercurrent and continuous extraction. Experiments revealed the influences of the structural design of the three-liquid-phase extractor and some key operational parameters on three-phase partition of two phenolic isomers, p-nitrophenol （p-NP） and o-nitrophenol （o-NP）. The model three-liquid-phase extraction system used here is nonane （organic top-plaase）-polyethylene glycol （PEG 20UU） （polymer mlddle-phase）-（NH4）2SO4 aqueous solution （aqueous bottom-phase）. It is indicated that agitating speed and retention time in three-phase mixer are key parameters to extraction fraction of nitrophenol. Dispersion band behavior is related to agitating intensity, and its occurrence does not affect the extraction fraction of target compounds. The present work highlights the possibility of a feasible approach of scaling up of the proposed three-phase extraction apparatus for future in- dustrial-aimed applications.
A new method by liquid-liquid-liquid three phase system, consisting of acidified primary amine N1923 （abbreviated as A-N1923）, poly（ethylene glycol） （PEG） and （NH4）2S04 aqueous solution, was suggested for the separation and simultaneous extraction of Ⅴ（Ⅴ） and Cr（Ⅵ） from the acidic leach solutions of high- chromium vanadium-titanium magnetite. Experimental results indicated that Ⅴ（Ⅴ） and Cr（Ⅵ） could be selectively enriched into the A-N1923 organic top phase and PEG-rich middle phase, respectively, while AI（Ⅲ） and other co-existing impurity ions, such as Si（Ⅳ）, Fe（Ⅲ）, Ti（Ⅳ）, Mg（Ⅱ） and Ca（Ⅱ） in acidic leach solutions, could be enriched in the （NH4）2SO4 bottom aqueous phase. During the process for extraction and separation of Ⅴ（Ⅴ） and Cr（Ⅵ）, almost all of impurity ions could be removed. The separation factors between Ⅴ （Ⅴ） and Cr（Ⅵ） could reach 630 and 908, respectively in the organic top phase and PEG middle phase, and yields of recovered Ⅴ（Ⅴ） and Cr（Ⅵ） in the top phase and middle phase respectively were all above 90%. Various effects including aqueous pH, A-N1923 concentration, PEG added amount and （NH4）2SO4 concentration on three-phase partitioning of Ⅴ（Ⅴ） and Cr（Ⅵ） were discussed. It was found that the partition of Cr（Ⅵ） into the PEG-rich middle phase was driven by hydrophobic interaction, while extraction of Ⅴ（Ⅴ） by A-N1923 resulted of anion exchange between NO; and H2V10O4-28. Stripping of Ⅴ（Ⅴ） and Cr（Ⅵ） from the top organic phase and the middle PEG-rich phase were achieved by mixing respectively with NANO3 aqueous solutions and NaOH-（NH4）2SO4 solutions. The present work highlights a new approach for the extraction and purification of V and Cr from the complex multi-metal co-existing acidic leach solutions of high-chromium vanadium-titanium magnetite.
Pan SunKun HuangXiaoqin WangNa SuiJieyuan LinWenjuan CaoHuizhou Liu
Acco rding to the tetrad-effect,14 elements of lanthanides can be divided into four groups.In our previous study,a new approach was proposed for the kinetic separation of four rare earth ions La(Ⅲ),Gd(Ⅲ),Ho(Ⅲ) and Lu(Ⅲ) coming from four groups.In that study,four rare-earth ions were kinetically separated from their coexisting mixed aqueous solutions,by performing liquid-column elution using the aqueous solution containing four lanthanide rare-earth ions as the stationary phase and the dispersed organic oil droplets containing HEHEHP(2-ethyl hexyl phosphonic acid mono 2-ethyl hexyl ester) extractant as the mobile phase.The study of extraction kinetics is very important for understanding the kinetic separation of rare earth ions,which was carried out in this paper.The extraction kinetics of La(Ⅲ),Gd(Ⅲ),Ho(Ⅲ) and Lu(Ⅲ) by HEHEHP diluted in heptane were investigated using single drop method.The different parameters affecting the extraction rate such as column length,specific interfacial area,rare earth ion concentration,extractant concentration,hydrogen ion concentration and temperature were separately studied and the rate equations are deduced.It is first order with respect to rare earth ion and HEHEHP concentrations,and negative first order with respect to hydrogen ion concentrations.The rate constants at 293.15 K are 10-6.23,10-5.73,10-5.58 and 10-5.43,respectively.The experimental results demonstrate that the extraction rate of La(Ⅲ), Gd(Ⅲ),Ho(Ⅲ) or Lu(Ⅲ) is diffusion-controlled,and the extraction reaction takes place at the interface rather than in the bulk phase.The extraction model was proposed.Besides,the kinetic separation of rare earth ions by HEHEHP oil drops was discussed.
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.
Xiaoqin WangKun HuangWenjuan CaoPan SunNa SuiWeiyuan SongHuizhou Liu
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).
Xiaoqin WangKun HuangWenjuan CaoPan SunWeiyuan SongHuizhou Liu
A new approach was proposed for grouping separation of 14 lanthanide rare-earth ions from their coexisting mixed aqueous solutions, by performing liquid-column elution using the aqueous solution containing 14 lanthanide rare-earth ions as the stationary phase and the dispersed organic oil droplets containing P507 extractant as the mobile phase. It was revealed that 14 lanthanide rare-earth ions could be separated into four groups, according to the lanthanide tetrad effect, respectively eluting out from the liquid column at different time in a certain order. Various effects including the saponification degree of P507, the concentration of P507 in organic phase, the length and inner diameter of the extraction column on the performance of grouping separation of rare-earth ions were discussed. The changes of the mass transfer coefficients were also investigated. The separation efficiency of the four groups of rareearth elements(REEs) was evaluated based on the elution resolution, Rs, of the elution peaks of La(Ⅲ),Gd(Ⅲ), Ho(Ⅲ) and Lu(Ⅲ), the four representative elements respectively from each of the four groups of REEs. Experimental results demonstrated that the separation of REEs by liquid-column elution mainly depended on the competitive adsorption of different rare-earth groups onto the surface of ascending P507 oil droplets. The affinity of different rare-earth groups with P507 extractant and a limited adsorption capacity of P507 molecules at the surface of the oil droplets ascending in liquid column play the important role. The present work highlights a promising technique for grouping separation of multiple lanthanide elements co-existing complex systems.
