Fujian Key Laboratory of Pollution Control and Resource Reuse, School of Environmental and Resource Sciences, Fujian Normal University, Fuzhou 350117, Fujian, China.
Longyan Rare Earth Development Limited Company, Longyan 364000, China.
Environ Sci Technol. 2024 Jun 4;58(22):9612-9623. doi: 10.1021/acs.est.3c10653. Epub 2024 May 21.
In this study, a sample of 2-methylimidazole zinc salt (ZIF-8) demonstrated high selectivity for the recovery of heavy rare earth elements (REEs) from real rare earth mining wastewater. Results show that the distribution coefficient values of Y (4.02 × 10 mL·g), Gd (7.8 × 10 mL·g), and Dy (6.8 × 10 mL·g) are orders of magnitude higher than those of K (359.51 mL·g), Mn (266.67 mL·g), Ca (396.42 mL·g), and Mg (239.48 mL·g). Moreover, the desorption efficiency of heavy REEs exceeded 40%. Advanced characterizations and density functional theory (DFT) calculations were utilized to elucidate that the heavy REEs were more likely to bind to the nitrogen atoms of imidazole groups on ZIF-8 compared to non-REEs. Furthermore, the adsorption and desorption of heavy REEs primarily depend on the chemical interaction confirmed by adsorption kinetics, isotherm model, and thermodynamic analysis, which involves the dissociation of water and the formation of REE-O bonds. Finally, the ZIF-8 exhibits a remarkable recovery efficiency of over 40% for heavy REEs in column tests conducted over 7h. The findings reported here provide new insights into the selective recovery of heavy REEs from real mining wastewater.
在这项研究中,使用 2-甲基咪唑锌盐(ZIF-8)作为样本,证明了其对从实际稀土矿废水中回收重稀土元素(REEs)具有高选择性。结果表明,Y(4.02×10 mL·g)、Gd(7.8×10 mL·g)和 Dy(6.8×10 mL·g)的分配系数值是 K(359.51 mL·g)、Mn(266.67 mL·g)、Ca(396.42 mL·g)和 Mg(239.48 mL·g)的数量级。此外,重 REEs 的解吸效率超过 40%。先进的表征和密度泛函理论(DFT)计算表明,与非 REEs 相比,重 REEs 更有可能与 ZIF-8 上咪唑基团的氮原子结合。此外,吸附和解吸的主要取决于吸附动力学、等温模型和热力学分析所证实的化学相互作用,涉及水的离解和 REE-O 键的形成。最后,ZIF-8 在 7 小时的柱试验中对重 REEs 的回收效率超过 40%。本研究结果为从实际采矿废水中选择性回收重 REEs 提供了新的见解。