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Rare earth separations by selective borate crystallization.

ABSTRACT: Lanthanides possess similar chemical properties rendering their separation from one another a challenge of fundamental chemical and global importance given their incorporation into many advanced technologies. New separation strategies combining green chemistry with low cost and high efficiency remain highly desirable. We demonstrate that the subtle bonding differences among trivalent lanthanides can be amplified during the crystallization of borates, providing chemical recognition of specific lanthanides that originates from Ln³⁺ coordination alterations, borate polymerization diversity and soft ligand coordination selectivity. Six distinct phases are obtained under identical reaction conditions across lanthanide series, further leading to an efficient and cost-effective separation strategy via selective crystallization. As proof of concept, Nd/Sm and Nd/Dy are used as binary models to demonstrate solid/aqueous and solid/solid separation processes. Controlling the reaction kinetics gives rise to enhanced separation efficiency of Nd/Sm system and a one-step quantitative separation of Nd/Dy with the aid of selective density-based flotation.

SUBMITTER: Yin X

PROVIDER: S-EPMC5355876 | biostudies-literature | 2017 Mar

REPOSITORIES: biostudies-literature

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Rare earth separations by selective borate crystallization.

Yin Xuemiao X Wang Yaxing Y Bai Xiaojing X Wang Yumin Y Chen Lanhua L Xiao Chengliang C Diwu Juan J Du Shiyu S Chai Zhifang Z Albrecht-Schmitt Thomas E TE Wang Shuao S

Nature communications 20170314

Lanthanides possess similar chemical properties rendering their separation from one another a challenge of fundamental chemical and global importance given their incorporation into many advanced technologies. New separation strategies combining green chemistry with low cost and high efficiency remain highly desirable. We demonstrate that the subtle bonding differences among trivalent lanthanides can be amplified during the crystallization of borates, providing chemical recognition of specific la ...[more]

PMID: 28290448

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Project description:Abstract The interaction between rare earth element (REE)‐rich (La, Pr, Nd, Dy) aqueous solutions, dolomite (CaMg(CO3)2), and aragonite (CaCO3) at low temperature hydrothermal conditions (25–220 °C) is studied. The experiments result in the solvent‐mediated surface precipitation and subsequent pseudomorphic mineral replacement of the dolomite and aragonite seeds by newly formed REE‐carbonates. The host grains are replaced from periphery inward. The newly formed REE‐bearing carbonates in La‐, Pr‐, and Nd‐doped systems follow the crystallization sequence: lanthanite [REE2(CO3)3·8H2O] → kozoite [orthorhombic REECO3(OH)] → hydroxylbastnasite [hexagonal REECO3(OH)]. The interaction of Dy‐bearing solutions with dolomite results only in the crystallization of kozoite [orthorhombic DyCO3(OH)]. However, experiments with aragonite reveal a two‐step crystallization pathway: tengerite [Dy2(CO3)3·2‐3(H2O)] → kozoite [orthorhombic DyCO3(OH)]. The temperature, the dissolution rate of the host mineral, and the ionic radii of the REE3+ in question are found to control the kinetics of the replacement reaction, the polymorph selection, and the crystallization pathways toward bastnasite. The findings allow to gain a more in‐depth understanding of the formation REE‐bearing carbonates, particularly the mineral bastnasite, which is the main source of REEs for industry. This knowledge can be used to improve REE separation, exploration, exploitation methods, as well to produce carbonate minerals with tailored structures. The interaction of rare earth element (REE)‐bearing solutions and dolomite/aragonite results in solvent‐mediated surface precipitation and subsequent pseudomorphic mineral replacement of the host carbonate seeds by newly formed rare earth carbonates, following the crystallization sequence: lanthanite → kozoite → hydroxylbastnasite. The reaction is controlled by the temperature, ionic radii of the REE3+, and the solubility and dissolution rate of the host mineral.

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Rare earth separations by selective borate crystallization.

Publications

Rare earth separations by selective borate crystallization.

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