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Mechanism of Li+/Na+ separation by crown ether and butyrate acid root

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Abstract

Lithium is critical for economic growth since it is the primary component of batteries. Na+ is one of the main impurity ions in solution during the separation and enrichment of Li+. According to the size-matching effect between the cavities of crown ethers and Li+, crown ethers can selectively adsorb Li+. Herein, 1,8-dihydroxyl-4,4,5,5-tetramethylbenzo-14-crown-4 was synthesized and used to extract lithium from a Li+/Na+ mixed solution. Density functional theory (DFT) was used to explore the properties of complexes with M062X. The results show that the interactions between crown ethers and metal ions are due to electrostatic attraction. Hydroxyl functional groups can synergistically extract Li+/Na+ from solutions with the oxygen atom in the crown ether ring. The stability of the complex is also enhanced by van der Waals interactions between the butyrate acid root and crown ether. 1,8-dihydroxyl-4,4,5,5-tetramethylbenzo-14-crown-4 has a stronger interaction with lithium butyrate than with sodium butyrate for most conformations. The adsorption selectivity for Li+ is proportional to the number of ether oxygen atoms that interact with Li+. The Li+ extraction efficiency increases from 3.93% to 20.93% in lithium hydroxide solution with the presence of butyrate acid root. When the butyrate acid root is added to the mixed Li+/Na+ solution, the Li+ extraction efficiency increases from 6.54% to 31.20%, while the Li+/Na+ separation coefficient decreases from 33.25 to 1.32.

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摘要:

锂作为电池的主要成分, 对经济增长至关重要。Na+是Li+分离和富集过程中的主要杂质离子之一。根据冠醚的空腔与Li+之间的尺寸匹配效应, 冠醚对Li+具有选择性的吸附能力。本文合成了1,8-dihydroxyl-4,4,5,5-tetramethylbenzo-14-crown-4, 用于从Li+/Na+混合溶液中提取锂。利用密度泛函理论 (M062X) 研究了络合机理, 结果表明冠醚与金属离子之间的相互作用是静电吸引作用。羟基官能团中的氧原子可以与冠醚环中的氧原子协同提取溶液中的Li+/Na+, 丁酸根与冠醚之间的范德华相互作用也增强了配合物的稳定性。1,8-dihydroxyl-4,4,5,5-tetramethylbenzo-14-crown-4构象与丁酸锂的相互作用强于与丁酸钠的相互作用, 且冠醚对Li+的选择性吸附能力与醚氧原子的数量成正比。在丁酸根的存在下, LiOH溶液中Li+的萃取效率从3.93%提高到20.93%。Li+和Na+的混合溶液中加入丁酸根时, Li+的萃取效率从6.54%提高到31.20%, 但Li+/Na+的分离系数从33.25下降到1.32。

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Acknowledgements

This study was financially supported by the National Natural Science Foundation of China (Nos. 51704011, U1703130 and 51904003).

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  1. School of Metallurgical Engineering, Anhui University of Technology, Ma’anshan, 243002, China

    Yong-Pan Tian, Cheng-Cheng Wang, Fan Zhang, Sen Huang, Liang Xu, Zhuo Zhao & Bi-Hai Tong

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Tian, YP., Wang, CC., Zhang, F. et al. Mechanism of Li+/Na+ separation by crown ether and butyrate acid root. Rare Met. 42, 1238–1248 (2023). https://doi.org/10.1007/s12598-022-02201-z

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