Interactions between trivalent rare earth oxides and mixed [Hbet][Tf2N]:H2O systems in the development of a one-step process for the separation of light from heavy rare earth elements


The factors, including ionic liquid: water ratios, temperature, solvent: solute contact times, and the effect of dissolved rare earth metal ions on the [Hbet][Tf2N]:H2O thermometric phase change are determined to develop a process for separating the light from the heavy rare earth metal oxides in [Hbet][Tf2N]:H2O mixtures. The relative solubility data for three light (La2O3, Nd2O3, and Eu2O3), two heavy (Y2O3 and Yb2O3) rare earth metal oxides (REOs), and Gd2O3 at different temperatures and different solute: solvent contact times are reported for 1:1 [Hbet][Tf2N]:H2O. The light REOs dissolve easily at 57 degrees C with the La and Eu reaching maximum solubility within minutes while the heavy REOs have very low solubilities at this temperature with negligible amounts being dissolved for contact times less than 80 min. Gd2O3 dissolves more slowly than the La, Eu, and Nd oxides at 57 degrees C reaching maximum solubility only after 160 min. Changing the [Hbet][Tf2N]:H2O ratio from 1:1 to 16:1 increases the time required to dissolve the REOs. The times taken to reach maximum solubility decrease for all of the REOs up to 95 degrees C, resulting in the separations between the light and heavy rare earth elements, and Gd becoming less distinct. The presence of rare earth metal ions in [Hbet][Tf2N]:H2O results in a reduction in the upper critical solution temperature (UCST) of the solvent from 55.6 degrees C to as low as 31.8 degrees C with Gd3+. The best separation of light from heavy REOs is achieved at 57 degrees C but better separation of Gd from the light REOs is achieved at 40 degrees C, below the solvent UCST. The best conditions for a one-step separation of light from heavy REOs in [Hbet][Tf2N]:H2O mixtures is achieved with 1:1 [Hbet][Tf2N]:H2O at 57 degrees C using short contact oxide: solvent times (maximum 5 min). Separations of light from heavy REOs, in waste phosphor samples, containing La2O3, CeO2, Eu2O3, Gd2O3, Tb3O4 and Y2O3, are also achieved even in the presence of high concentrations of heavy REOs using short contact times. The use of [Hbet][Tf2N]:H2O as a means of separating light and heavy REOs is aided by the ease of recycling the solvent which can be recycled and reused at least five times with little loss of solvent quality or efficiency. (C) 2015 Elsevier B. V. All rights reserved.



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Schaeffer, N; Grimes, S; Cheeseman, C

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We wish to acknowledge an EPSRC DTA Scholarship for N.S., The Royal Academy of Engineering for equipment funding and Balcan Engineering Ltd. UK for samples of waste phosphor powder, and Dr Geoff Fowler for his help and advice.

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