SEPARATION AND PURIFICATION TECHNOLOGY
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2024
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IF 8.1
Chenxi Tian,Da Lei,Yongchao Qian,Xiang-Yu Kong,Zhong Liu
The development of advanced membranes with precise ion selectivity is essential for efficient Li + /Mg 2+ separation. In this study, we synthesized a novel Lys-TMC membrane via a nucleophilic addition reaction between Lysine and trimesoyl chloride (TMC), yielding in a negatively charged surface interconnected by amide bonds. We systematically investigated the effects of varying Lys:TMC ratios on the membrane’s chemical structure, surface morphology, and ion separation performance. Our results revealed that the degree of cross-linking increases initially with the Lysine content, reaching an optimum at a Lys:TMC ratio of 10:1, where the membrane exhibited prominent Turing patterns on its surface. These patterns were critical for achieving effective ion separation. In contrast, excessive Lysine led to spontaneous polymerization, resulting in irregular ‘stone-like’ structures and the loss of Turing patterns. The optimally cross-linked Lys-TMC membrane displayed superior Li + /Mg 2+ separation performance, highlighting the crucial role of controlled cross-linking and Turing structure formation in enhancing ion selectivity. This work provides a mechanistic understanding of the relationship between Turing structure formation and ion sieving performance, offering a promising strategy for designing advanced separation membranes.
研究领域:
材料科学
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化学工程
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膜技术
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离子分离
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产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
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2023
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IF 8.6
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.
研究领域:
化学工程
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材料科学
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环境化学
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产品关联
DOI
高影响因子
LANGMUIR
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2025
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IF 3.9
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
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化学工程
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材料科学
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分离技术
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计算化学
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产品关联
DOI
PubMed
高影响因子
ACS Applied Materials & Interfaces
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2021
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IF 9.229
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
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环境工程
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化学工程
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DOI
高影响因子
Engineering
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2022
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IF 12.834
Wenguang Wang,Yanqiu Zhang,Xiaobin Yang,Haixiang Sun,Yadong Wu,Lu Shao
Monovalent cation exchange membranes (M-CEMs) have been extensively applied in environmental remediation and energy harvesting such as the extraction of Na + or Li + from brine and seawater. However, owing to the limitations of membrane structures and materials, M-CEMs have a low perm-selectivity issue. Herein, we proposed a facile approach to construct a novel M-CEM with a Janus-charged structure, consisting of a positively-charged trimesic acid/polyethylenimine surface thin layer and a negatively charged commercial cation exchange membrane (CEM). Selectrodialysis results indicated that the Janus-charged M-CEMs could effectively suppress the migration of anions, which often occurred in porous CEMs, thereby enabling the novel Janus-charged M-CEMs to possess high perm-selectivity and high total cation fluxes. Compared with state-of-the-art M-CEMs, the Janus-charged M-CEM exhibited the highest perm-selectivity of 145.77 for Na + /Mg 2+ beyond the contemporary “Upper Bound” plot as well as the excellent perm-selectivity of 14.11 for Li + /Mg 2+ , indicating its great potentials in ion separation. This study can provide novel insights into the design of Janus-charged M-CEMs for ion separation in diverse environmental and energy applications.
研究领域:
环境科学
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能源材料
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膜技术
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF MEMBRANE SCIENCE
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2024
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IF 8.4
Yanna Wu,Mengmeng Jia,Shuming Li,Zong Lu,Yanying Wei,Haihui Wang
Lithium extraction from salt lake is important for carbon neutrality, while obtaining both high Li + /Mg 2+ selectivity and high water permeance is still challenging. The burgeoning two-dimensional (2D) material membranes in decade show enormous potential to solve above problem due to its highly designable lamellar structure. In this work, a kind of positively charged laminated membranes using MXene nanosheets as building blocks with decoration of poly (diallyl dimethyl ammonium chloride) (PDDA) were proposed. Benefiting from the well–intercalated PDDA between MXene nanosheets, the interlayer spacing between neighboring nanosheets was greater than 2 nm, which was conductive to enhance water permeance. Simultaneously, the introduction of PDDA endowed the membrane with positive charge, which exhibited sharply improved Li + /Mg 2+ selectivity by an order of magnitude due to enhanced Donnan effect. The prepared MXene/PDDA membrane with a modification mass ratio of 1:10 exhibited high Li + /Mg 2+ selectivity of 29.3 with MgCl 2 saline solution permeance of 9.8 L m −2 h −1 ·bar −1 and pure water permeance of 32.3 L m −2 h −1 ·bar −1 , which was promising for lithium extraction. Such membrane constructing concept could be expanded to other kinds of membranes based on 2D nanosheets for effective ion sieving.
研究领域:
材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2022
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IF 16.744
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.
研究领域:
材料科学
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化学工程
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环境工程
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF MEMBRANE SCIENCE
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2020
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IF 7.183
Zhao Yang,Wangxi Fang,Zhenyi Wang,Ruolin Zhang,Yuzhang Zhu,Jian Jin
The wide application of lithium batteries in consumer electronics and electric vehicles bring about ever-rising demand of lithium resources globally. Nanofiltration (NF) membranes with high Mg 2+ /Li + selectivity could achieve highly efficient separation of lithium from natural brines, which provides a good alternative for steady lithium supply. In this work, we developed a dual-skin layer nanofiltration membrane comprised of a polyethylene-imine (PEI) layer grafted on a polyamide layer. The polyamide layer was prepared via interfacial polymerization to endow the NF membrane with sub-nm pores, while the PEI layer was grafted on the polyamide surface via amidation reaction to further equip the membrane with enhanced positive charge. With the synergistic effect of size sieving from the polyamide layer and electrostatic exclusion from the PEI layer, the dual-skin layer NF membrane exhibits a high rejection of 98.5% to MgCl 2 and a low rejection of 46.2% to LiCl, suggesting a high Mg 2+ /Li + selectivity. As using this dual-skin layer NF membrane for separating Li + from a simulated brine, a high Mg 2+ /Li + separation factor (S Mg , Li ) up to 33.4 was achieved, which is the highest value among the pressure-driven polymeric nanofiltration membranes reported so far.
研究领域:
材料科学
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环境工程
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
DESALINATION
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2023
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IF 9.9
Tingyu Li,Xinzhu Zhang,Yu Zhang,Jixiao Wang,Zhi Wang,Song Zhao
Selective lithium recovery from salt lake brine using emerging nanofiltration membranes is expected to solve the insufficient supply of lithium resources. In this work, 1,4,7,10-tetraazacyclododecane (Cyclen) was employed as a novel structural regulator through interfacial polymerization of polyethyleneimine (PEI) and trimesoyl chloride (TMC) to develop polyamide NF membrane with efficient Li + /Mg 2+ separation performance. After the introduction of Cyclen to aqueous phase , the PEI/Cyclen-TMC selective layer was confirmed to possess a higher crosslinking degree and larger d-spacing than PEI-TMC layer, endowing a dedicated channel for Li + transport. The water permeance of PEI/Cyclen-TMC composite membrane reached 14.0 L·m −2 ·h −1 ·bar −1 , about 3.8 times higher than PEI-TMC composite membrane, and meanwhile the separation factor ( S Li,Mg ) could be stabilized as 8.7 to realize a considerable reduction of Mg 2+ /Li + mass ratio from 20 to 2.3. Additionally, PEI/Cyclen-TMC composite membrane was utilized to operate a three-stage nanofiltration treatment procedure of a simulated salt lake brine (Mg 2+ /Li + mass ratio: 40). The results indicated that Li + could be efficiently retracted to obtain a solution with 19.5 mg·L −1 Li + and Mg 2+ /Li + mass ratio of 0.3. After the subsequent precipitation and filtration, the obtained Li 2 CO 3 purity could reach 93 %, indicating the potential application of nanofiltration for lithium recovery.
研究领域:
材料科学
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环境工程
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF MEMBRANE SCIENCE
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2024
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IF 8.4
Zhiyuan Zha,Tingyu Li,Ismail Hussein,Ying Wang,Song Zhao
The scarcity of lithium can be effectively addressed by extracting it from salt-lake brines. In this work, aza-crown ether (diazo-18-crown-6, DA18C6) was coupled into a polyamide (PA) network interfacial polymerized by trimesoyl chloride and polyethyleneimine (PEI) for efficient Li + /Mg 2+ separation. The embedment of DA18C6 molecule into PA network was confirmed by structural characterization and density functional theory simulation, which enhanced crosslinking degree and reduced average pore size of PA selective layer. In addition, the strong interaction between DA18C6 and Li + was proven through molecular dynamics simulation. The resulting PEI@DA18C6-PA membrane displayed a high pure water permeance of 10.4 L⋅m − 2 ⋅h − 1 ⋅bar − 1 and an excellent Li + /Mg 2+ separation factor ( S Li,Mg ) of 11.2, which was comparable with most reported Li + /Mg 2+ separation membranes . Furthermore, the PEI@DA18C6-PA membrane was employed in a three-stage NF treatment process to filtrate simulated brines containing a high Mg 2+ /Li + ratio of 57. The results demonstrated that Li + can be effectively concentrated and extracted through the membrane to obtain a permeate with an ultralow Mg 2+ /Li + ratio of only 0.03, suggesting that PEI@DA18C6-PA membrane has great application potential in lithium extraction from salt-lake brines.
研究领域:
材料科学
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环境工程
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
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2024
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IF 8.3
Jia-Shuai Chen,Jing Wang,Ji-Hong Zhang,Zhi-Yuan Guo,Pan-Pan Zhang,Xiao-Fu Guo,Jie Liu,Zhi-Yong Ji
Achieving separation of lithium and magnesium with similar radii is crucial for the current lithium extraction technology from salt lakes, which usually possess a high lithium-to-magnesium ratio. Herein, we proposed the facile sequential interfacial polymerization (SIP) approach to construct electronanofiltration membranes (ENFMs) with a bilayer charged structure consisting of a high positively charged surface and a negatively charged sublayer. The trimesoyl chloride (TMC) concentration was adjusted to enhance the −COOH content and negative charge of the polyamide sublayer to promote Li+ migration, and then the quaternized polyethylenimine was introduced to the membrane surface by the SIP process to increase the positive charge density on the surface of the ENFMs, which would block the migration of Mg2+ and enhance the Li+/Mg2+ selectivity of the ENFMs. The optimal quaternary-modified ENFMs achieved outstanding selectivity for Li+/Mg2+ (49.85) and high Li+ flux (4.10 × 10–8 mol cm–2 s–1) at a current density of 10 mA cm–2. Moreover, in simulated brines with low lithium concentration and high Mg2+/Li+ ratio, the optimal ENFMs also displayed elevated Li+/Mg2+ selectivity (>45), highlighting the substantial promise of the membranes for practical applications.
研究领域:
材料科学
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化学工程
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环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of Environmental Chemical Engineering
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2024
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IF 7.4
Yufei Yan,Jin Wang,Wubin Wang,Chao Han,Kaili Huo,Qingyun Zhang,Ning Wang
Positively charged nanofiltration (NF) membranes are widely used to separate Li + and Mg 2+ , which play an important role in extracting lithium from salt lakes. Despite its widespread use, the polyethyleneimine-trimesoyl chloride (PEI-TMC) membrane has attracted attention due to its limited permeance and separation efficiency. To address these challenges, we introduced amine-functionalized titanium dioxide (TiO 2 -NH 2 ) nanoparticles into the interfacial polymerization (IP) reaction. The introduction of TiO 2 -NH 2 reduced the diffusion rate of PEI and formed nanoscale water channels in the polyamide (PA) layer. This modification effectively modulated the structure of the NF membrane. The NF membrane exhibited high water permeance (9.65 L·m −2 ·h −1 ·bar −1 ) and Li + /Mg 2+ selectivity ( S Li, Mg = 16.31) when 0.03 wt% TiO 2 -NH 2 was used. The DLVO theory and transition state theory showed that the introduction of TiO 2 -NH 2 improved the rejection of Li + and Mg 2+ by the membrane. Furthermore, the optimized NF membranes demonstrated excellent stability during long-term filtration and in the mixed salt solutions with varying Mg 2+ /Li + mass ratios. This work is of great significance for designing and advancing membrane materials that facilitate the efficient separation of lithium from salt lakes with high Mg 2+ /Li + mass ratios.
研究领域:
材料科学
·
环境工程
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）