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Li /Mg2 选择性
ACS Applied Materials & Interfaces · 2021 · IF 9.229

Novel Positively Charged Metal-Coordinated Nanofiltration Membrane for Lithium Recovery

Li Wang,Danyal Rehman,Peng-Fei Sun,Akshay Deshmukh,Liyuan Zhang,Qi Han,Zhe Yang,Zhongying Wang,Hee-Deung Park,John H. Lienhard,Chuyang Y. Tang

Nanofiltration (NF) with high water flux and precise separation performance with high Li+/Mg2+ selectivity is ideal for lithium brine recovery. However, conventional polyamide-based commercial NF membranes are ineffective in lithium recovery processes due to their undesired Li+/Mg2+ selectivity. In addition, they are constrained by the water permeance selectivity trade-off, which means that a highly permeable membrane often has lower selectivity. In this study, we developed a novel nonpolyamide NF membrane based on metal-coordinated structure, which exhibits simultaneously improved water permeance and Li+/Mg2+ selectivity. Specifically, the optimized Cu–m-phenylenediamine (MPD) membrane demonstrated a high water permeance of 16.2 ± 2.7 LMH/bar and a high Li+/Mg2+ selectivity of 8.0 ± 1.0, which surpassed the trade-off of permeance selectivity. Meanwhile, the existence of copper in the Cu–MPD membrane further enhanced anti-biofouling property and the metal-coordinated nanofiltration membrane possesses a pH-responsive property. Finally, a transport model based on the Nernst–Planck equations has been developed to fit the water flux and rejection of uncharged solutes to the experiments conducted. The model had a deviation below 2% for all experiments performed and suggested an average pore radius of 1.25 nm with a porosity of 21% for the Cu–MPD membrane. Overall, our study provides an exciting approach for fabricating a nonpolyamide high-performance nanofiltration membrane in the context of lithium recovery.

研究领域: 材料科学 · 环境工程 · 化学工程
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SEPARATION AND PURIFICATION TECHNOLOGY · 2023 · IF 8.6

A remarkable improved Li+/Mg2+ selectivity and Li+ recovery simultaneously by adding crown ether to tributyl phosphate-ionic liquid extraction system as co-extractant

Junyuan Hua,Jintao He,Hongchang Pei,Jiahui Du,Xiaohua Ma,Jianxin Li

The high similarity in chemical properties between Li + and Mg 2+ poses a substantial challenge for their selective separation from salt lake brine with high Mg-Li (m/m) ratios. Herein, a highly efficient solvent extraction system was reported for Li + /Mg 2+ selective separation, with tributyl phosphate (TBP) and di(aminobenzo)-14-crown-4 (CE) as extractants, [C 4 mim][NTf 2 ] (IL) as co-extractant, and methylene chloride as a diluent. Simulated brines included 0.01 M LiCl and 0.01 and 0.2 M MgCl 2 with Mg/Li mass ratios of 3.5 and 70, respectively. Molecular dynamics (MD), density functional theory (DFT), and 1 H NMR analysis were employed to reveal the hydrogen bond interaction and compatibility between CE, TBP, and IL. Under the optimal extraction conditions containing a concentration of 20 mg/mL CE and 0.61 mmol/mL IL, the maximum single-stage Li + extraction rate of the TBP-CE-IL extraction system with Mg/Li mass ratios of 3.5 and 70 were 89.5 and 81.8 %, and the separation factor of Li to Mg were up to 515 and 422. Compared with the TBP-IL extraction system, the addition of CE effectively improved the extraction rate of Li + and the selectivity of Mg-Li, which was due to the hydrogen bond interaction between CE and TBP/IL and the cavity size effect between CE and Li + , improving CE coordination and endowing the complex generated in the organic phase with greater stability. The possible structure of the complex in the organic phase was determined to be 2TBP·Li·NTf 2 -CE·Li·NTf 2 through Li + extraction dynamic analysis. In summary, this work provides an efficient separation technology for Li + extraction from salt lake brine.

CAS / MDL: 174899-83-3 126-73-8
研究领域: 化学工程 · 材料科学 · 环境化学
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CHEMICAL ENGINEERING JOURNAL · 2022 · IF 16.744

Layer-by-layer assembly of cation exchange membrane for highly efficient monovalent ion selectivity

Jiadi Ying,Yuqing Lin,Yiren Zhang,Yan Jin,Hideto Matsuyama,Jianguo Yu

The development of cation exchange membranes (CEMs) with high monovalent/divalent cation selectivity has great potential for enhanced salt separation for wastewater reclamation, and layer-by-layer (LbL) self-assembly of polyelectrolyte films with high monovalent selectivities among cations has expanded the applications of such membranes. However, the structure–property relationship for constructing multilayered polyelectrolyte films with enhanced separation performance remains poorly understood. This study reports a novel CEM engineered by coating a [polyethyleneimine/polystyrene sulfonate (PEI/PSS)] n alternate electro-deposition multilayer on a polyacrylate substrate membrane. The newly developed CEM exhibited a monovalent selectivity of 4.59 for Li + /Mg 2+ with an optimal permeation of 0.16 mmol·cm −2 ·h −1 for Li + , demonstrating a competitive separation property compared to state-of-the-art permselective membranes. A detailed quantitative investigation provides the underlying insights into the monovalent selectivity for each polyelectrolyte layer. The results indicate negligible interface impedance toward monovalent cations but strengthened repulsion against divalent cations, thereby promoting a quick passage for monovalent cations while imposing temporal retardation on divalent cations during the electrodialysis (ED) process. Therefore, this study elucidates the characteristic reason for the enhanced monovalent ion permselectivity of LbL polyelectrolyte membranes in electro-driven separation processes.

CAS / MDL: 97-90-5 9002-98-6
研究领域: 材料科学 · 化学工程 · 环境工程
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LANGMUIR · 2025 · IF 3.9

Surfactant Interlayer-Tuned Positively Charged Nanofiltration Membranes via Kinetics-Enhanced Interfacial Polymerization for Ultrahigh Li+/Mg2+Selectivity in Salt-Lake Brines

Yu Tang,Shengde Dong,Junjie Shan,Ping Li,Ying Cheng,Leya Guo,Yin Xiang,Yanxia Sun,Qi Xu,Chunxi Hai,Haijiao Xie,Yuan Zhou

The burgeoning energy sector exhibits a demand for lithium resources. Notably, salt lakes, rich in lithium, challenge due to the high Mg2+/Li+ ratios encountered. Nanofiltration, characterized by its simplicity, environmental sustainability, holds promising prospects for Mg2+/Li+ separation in salt lakes. Density functional theory (DFT) simulations reveal that sodium dodecyl sulfate (SDS) surfactant layers significantly lower the energy barrier for polyethylenimine (PEI) transfer, which fundamentally enhances the interfacial polymerization kinetics. This study activates polysulfone (PSF) ultrafiltration (UF) membrane surfaces with SDS surfactants to form a negatively charged surface-active interlayers, the hydrophilicity of the membrane surface was increased and then accelerating polymerization at the PEI/TMC interface. Under optimized conditions, the membranes achieve 98.6% MgCl2 retention and ultrahigh selectivity (S(Li/Mg) = 118.75) with a Mg2+/Li+ ratio of 50:1, showing sustained performance in a 44 h test. This work provides efficient separation method for high-performance lithium extraction from salt lake brines.

研究领域: 膜科学 · 化学工程 · 材料科学 · 分离技术 · 计算化学
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