DESALINATION
·
2025
·
IF 9.8
Shishuo Wang,Fei Guo,Xuemei Wu,Yuandong Jia,Gaohong He,Xiaobin Jiang
Lithium and its compounds are critical strategic resources with wide-ranging applications. This study developed a bipolar membrane precipitation coupled electrodialysis enrichment (BMp-EDe) process for extracting lithium from brines with an Mg/Li ratio of 20. The method is based on phase separation achieved through precipitation-coupled ion permeation and a synergistic mechanism for ion enrichment, resulting in significant process intensification. Key factors such as current density, molar ratio between diluate and base chambers, and base chamber concentration were optimized to control nucleation and prevent membrane fouling. Under conditions of current density ranging from 200 to 400 A·m −2 and a molar ratio of the diluate chamber to the base chamber between 13 and 16, the magnesium removal rate in the BMp-EDe process is found to exceed 99.90 %, with a separation factor greater than 20,000. The optimal separation factor is observed to reach 40,244, with a magnesium removal rate as 99.96 % and a lithium recovery rate as 95.32 %. With optimized operation conditions, the energy consumption of magnesium precipitation decreased from 11.89 kWh·kg −1 (Mg 2+ ) to 7.97 kWh·kg −1 (Mg 2+ ). Thus, an alternative method is presented that employs commercial bipolar membranes to achieve ultra-high magnesium‑lithium separation efficiency. Additionally, a mechanism for the continuous operation of the magnesium precipitation chamber is validated, which can effectively prevent membrane fouling.
研究领域:
化学工程
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材料科学
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产品关联
DOI
高影响因子
FLUID PHASE EQUILIBRIA
·
2017
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IF 2.473
Xu Zhao,Haihong Wu,Mengshan Duan,Xiaocui Hao,Qiwei Yang,Qi Zhang,Xiping Huang
Ionic liquids (ILs) have been proposed as promising extractants to broaden the potential utility of liquid–liquid extraction process for lithium, but developing an attractive IL from numerous available ILs remains challenging. In this work, a rapid preliminary predicting and screening method based on COSMO-RS was proposed. The design strategy was to collocate anions that had intensive affinity to lithium ion with high hydrophobic cations. Based on it, a series of candidate ILs were prepared and characterized by 1 H and 13 C NMR spectroscopy, including [P 4444 ]-based and [N 4444 ]-based ILs with phosphate, phosphinate and long-chain carboxylate anions. The further extraction experiments indicated that the tetrabutylammonium mono-2-ethylhexyl(2-ethylhexyl)phosphate ([N 4444 ][EHPMEH]) had the highest Li + extraction efficiency. The extraction mechanism was investigated by slope analysis method and ATR-IR spectroscopy. It was determined that every Li + associated with 1.33 molecule [N 4444 ][EHPMEH] to form the extracted species. The stripping study showed that the Li + was able to be stripped by only 0.5 mol/L HCl without additional agents. The extraction experiments of Li + from multi-metal-ion solution were also carried out, and the distribution ratio of Li + was nearly twice those of Na + , K + , and Rb + , indicating that [N 4444 ][EHPMEH] was available to separate lithium ion from the other alkali metal ions.
研究领域:
化学工程
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材料科学
✓ 已验证
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DOI
高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2023
·
IF 9.5
Huawen Peng,Yongjin Hu,Shaoping Li,Jingyi Rao,Qiang Zhao
High performance Mg 2+ /Li + separation membranes are needed to meet the rising demands for lithium supply, yet state-of-the-art polyamide nanofiltration membranes show limited permeance due to relatively dense structures. This work exploited sulfonium salts for the first time to modify nanofiltration membranes , leading to sulfonium-polyamide membranes with high Mg 2+ /Li + separation performance. The occurrence and competition of three types of reactions during the surface modification process were studied and correlated to properties of resultant membranes. Both the positive charge and loose structures of polyamide membranes were enhanced as a result of sulfonium modification, leading to ∼4.3 times improved permeance. The modified membrane exhibited water permeance (∼26.4 L m -2 h -1 bar -1 ) that is one of the top tier values among recent membranes, coupled with good Mg 2+ /Li + selectivity (∼11) in separating high Mg 2+ /Li + ratio feed (∼103). Moreover, the modified membrane showed good stability during one-month continuous operation. This work shows the promising potential of sulfoniums for engineering advanced lithium extraction membranes.
研究领域:
材料科学
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环境工程
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产品关联
DOI
高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2024
·
IF 8.4
Keting Li,Yufan Hao,Na Yang,Longfei Zhang,Luhong Zhang,Yongli Sun,Bin Jiang
Polyethyleneimine (PEI) nanofiltration (NF) membranes demonstrate remarkable effectiveness in separating lithium and magnesium from salt lakes, attributed to their positively charged surface. However, undesired permeability resulting from densely cross-linked structures limits the further industrial applications and development of PEI NF membranes. Herein, a high permeable Mg 2+ /Li + separation NF membrane with stronger internal and surface positive charge was fabricated using 1-Aminopyridinium iodide (1-AI) for the first time through a capping-grafting synergistic strategy. On the one hand, the monoamine character of 1-AI can realize the end-capping (EC) effect on the acyl chloride monomers in the interfacial polymerization process, which can contribute to a reduction in the cross-linking degree of the membrane. On the other hand, 1-AI with a quaternary ammonium group as the surface grafting (SG) agent can significantly improve the surface positive charge property of the membrane. The synergistic effect of capping-grafting not only rendered the membrane looser and effectively enhanced the surface positive charge of the membrane, but also increased the depth of grafting modification, leading to a notable rise in the internal positive charge of the membrane. After the capping-grafting treatment, the water permeance of the PEI-EC/SG membrane reached 19.8 L·m −2 ·h −1 ·bar −1 , approximately 4.5 times that of the original PEI membrane, while keeping an ideal MgCl 2 rejection rate (97.1%) and exhibiting good Mg 2+ /Li + selectivity (27.7). This work demonstrates the advantages of the capping-grafting synergistic method in regulating membrane structure for improving permeability as well as the surface and internal charge properties of the membrane for enhancing ion selectivity.
研究领域:
材料科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
Nature Communications
·
2023
·Vol. 14
·期 1
·1-11
·
IF 16.6
Peng Huawen,Yu Kaicheng,Liu Xufei,Li Jiapeng,Hu Xiangguo,Zhao Qiang
Current polyamide lithium extraction nanofiltration membranes are susceptible to chlorine degradation and/or low permeance, two problems that are hard to reconcile. Here we simultaneously circumvented these problems by designing a quaternized-spiro piperazine monomer and translating its beneficial properties into large-area membranes (1 × 2 m 2 ) via interfacial polymerization with trimesoyl chloride. The quaternary ammonium and spiral conformation of the monomer confer more positive charge and free volume to the membrane, leading to one of the highest permeance (~22 L m −2 h −1 bar −1 ) compared to the state-of-the-art Mg 2+ /Li + nanofiltration membranes. Meanwhile, membrane structures are chlorine resistant as the amine–acyl bonding contains no sensitive N-H group. Thus the high performance of membrane is stable versus 400-h immersion in sodium hypochlorite, while control membranes degraded readily. Molecular simulations show that the high permeance and chlorine resistance, which were reproducible at the membrane module level, arise from the spiral conformation and secondary amine structures of the monomer.
研究领域:
材料科学
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化学工程
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环境科学
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产品关联
DOI
PubMed
高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2024
·
IF 8.4
Yingyao He,Guiliang Li,Haibo Lin,Qiu Han,Yinlu Ye,Jianqiang Wang,Fu Liu
Selective separation property enhancement is quite important for membranes separations, especially for high mass ratio Mg 2+ /Li + separations. Low selectivity and unclear separation mechanism are the challenges for current membranes. In this study, we designed 4-aminophenyl-15-crown-5 incorporated polyamide nanofiltration membranes through interfacial polymerization for Li + enrichment. The electrochemical tests and energy barrier calculations using transition state theory confirmed that the crown ether in nanofiltration membrane is responsible for governing Mg 2+ transportation, resulting in a substantial energy barrier impeding its transport. Furthermore, a two-stage nanofiltration process was employed to enhance Li + enrichment in simulated brine and achieved 35-fold increase in Li + enrichment using as-fabricated membranes. These results demonstrate the substantial potential for Li + extraction from brine with a high Mg 2+ /Li + mass ratio using the crown ether incorporated membrane. Meanwhile, the proposed strategy incorporating transport barriers presents a novel approach for designing ion-selective channels within membranes.
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
JOURNAL OF MEMBRANE SCIENCE
·
2024
·
IF 8.4
Faizal Soyekwo,Changkun Liu,Xin Mao,Ruixin Nie
Efficient magnesium-lithium separation is key to extracting lithium resources from salt lake brines. However, efficient magnesium-lithium separation is constrained by the high magnesium-to-lithium ratios on the nanofiltration separation performance due to the weakened Donnan effect and inherent permeability-selectivity trade-off behaviour. To address this challenge, a dual methylpiperidinium ionic liquid was designed in this work and incorporated into polyamide networks to manipulate the structural properties of polyamide membrane for improved magnesium/lithium separation. We demonstrate that the piperidinium modification of polyamide networks not only modulated and enhanced the morphology, hydrophilicity , free volume and electropositivity, but also synergized the steric hindrance differentiation inside the membrane nanochannels . These structural advantages enabled the modified membrane to achieve high-separation performance with enhanced water permeance of 37.3 L m −2 h −1 bar −1 and Mg 2+ /Li + selectivity of 30.6 (for Mg/Li mass ratio of 31.2). Molecular dynamics simulations further confirmed that the fast water transport and the difference in the ion separation behaviour are strongly correlated to the enhanced structural properties of membranes. We expect this work to provide insightful guidance for engineering high-performance membranes and make contributions in the application of nanofiltration in lithium mining from high Mg/Li ratio brines.
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
SEPARATION AND PURIFICATION TECHNOLOGY
·
2025
·
IF 9
Yaoxian Hu,Hui Su,Wensen Liu,Zhaowu Zhu,Tao Qi
Effective lithium extraction from magnesium-rich brines is crucial to meet the increasing lithium demand. Traditional solvent extraction using tributyl phosphate (TBP) as the main extractant exhibits limited Li/Mg separation and dissolution losses during long-term operation. Herein, a novel ionic liquid-assisted lithium extraction system (2-Ethylhexyl diphenyl phosphate (DPOP)/1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide [Emim][NTf 2 ]) using organophosphate containing rigid phenyl groups was proposed. The phenyl group increased the steric hindrance of the extractant, enhancing the system efficiency for separating Li + from impurities. Results demonstrated that introducing the phenyl group into phosphate considerably improved the Li/Mg and Li/Ca separation factors, reaching 4,641 and 93, respectively, under optimal conditions, with a single-stage Li + extraction efficiency of 67%. After washing and stripping, a LiCl solution (purity = 99.68%) was obtained. Electrospray ionization mass spectrometry confirmed that the molecular formula of the extracted Li + complex was [Li·2DPOP][NTf 2 ]. Subsequent density functional theory calculations on the complexes revealed shorter bond lengths for the DPOP/[Emim][NTf 2 ] system with Li + than those with Mg 2+ and more negative binding energy and Gibbs free energy change during Li + extraction. Therefore, this system preferentially extracts Li + with tighter and more stable binding than Mg 2+ , exhibiting excellent Li selectivity.
研究领域:
化学工程
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
·
IF 8.1
Guoke Zhao,Ying Wan,Guoyuan Pan,Hao Yu,Gongqing Tang,Xiaozhi Gong,Yang Zhang,Jie Sun,Yiqun Liu
Lithium extraction from brine sources such as salt lakes, seawater, and produced water from oil/gas fields is garnering increasing interests from the academic and industrial sectors due to its cost-effectiveness and reduced environmental impact. A critical technological challenge is the efficient separation of Mg 2+ and Li + ions. Many researchers have reported the preparation of positively charged nanofiltration membranes with quaternary ammonium groups, yet investigations about quaternary phosphonium groups are scarce. In this work, positively charged nanofiltration membranes were prepared utilizing polyethyleneimine as the aqueous phase monomer, trimesoyl chloride as the organic phase monomer, and 3-bromopropyl triphenyl phosphonium bromide as the functionalizing monomer. The TFC-P + membranes, enriched with a high density of quaternary phosphonium groups and an enhanced Donnan effect, achieve a MgCl 2 rejection of 98.9 %, a Mg 2+ /Li + selectivity of 81.6, and a water flux of 50 LMH under 0.5 MPa. The membranes possess an enhanced comprehensive separation capability that exceeds that of the majority of nanofiltration membranes documented in scholarly articles. Additionally, the membranes exhibit outstanding anti-fouling and anti-bacterial characteristics, essential for their industrial applications. The preparation method proposed herein is simple and conducive to continuous production processes. In light of the abundant produced water reserves from oil and gas extraction, future work will focus on pilot-scale lithium extraction experiments.
研究领域:
化学工程
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材料科学
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产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
·
IF 8.1
Bingqin Li,Liangxing Jiang,Nan Xiao,Siliang Liu,Zongliang Zhang,Fangyang Liu,Michael L. Free
Traditional technologies of lithium extraction from salt lakes suffer the low efficiency of Li + /Mg 2+ separation and high energy consumption. We introduce a novel electrodialysis process that leverages Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP, one of lithium superionic conductors) and incorporates an aided charge balance (ACB) system, all under low voltage and ultra-low current conditions. The remarkable ion selectivity of LATP, coupled with the enhanced recovery ratio facilitated by ACB, collectively empower this technology to achieve extremely high separation efficiency and remarkably low energy consumption. In a simulated pristine brine, the average Li/Mg separation coefficient reached 5924, accompanied by an exceptionally low energy consumption of only 0.80 kWh·kg −1 Li . Furthermore, this technique enabled the production of battery-grade Li 2 CO 3 with an outstanding purity of 99.93 %, achieved through a streamlined process comprising only two stages.
研究领域:
材料科学
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环境工程
✓ 已验证
DOI
高影响因子
Journal of Water Process Engineering
·
2023
·
IF 7
Lei Ma,Qiuyan Bi,Wanji Zhou,Xingliang Liu,Fuju Qi,Hao Zhang,Yifan Gao,Shiai Xu
Nanofiltration (NF) membrane with high selectivity and permeance is important for recovering lithium from salt lake brine. In this work, sandwich-like NF membranes were prepared using polyamide (PA) as the interfacial polymerization (IP) layer, dopamine (DA) and zwitterion-g-C 3 N 4 as the composite interlayer and polyethersulfone (PES) ultrafiltration (UF) membrane as the substrate. Three NF membranes were prepared with different zwitterion-g-C 3 N 4 : M3 membrane modified with C 5 H 12 ClNO 2 -g-C 3 N 4 , M4 membrane modified with C 12 H 24 N 2 O 4 S-g-C 3 N 4 and M5 membrane modified with C 19 H 39 NO 2 -g-C 3 N 4 , and their physical and chemical properties, separation capacity, and antifouling behaviour were analyzed. The zwitterion-g-C 3 N 4 composite interlayer improves the hydrophilicity and pore structure of NF membranes. The water contact angle (CA) of M5 membrane is 25.5°and its pore size is 0.49 nm. M5 membrane shows a high retention rate of 96.66 % for Mg 2+ in mixed salt solution (Mg 2+ /Li + = 84) and performs well in salt lake brine with a rejection of 97.90 % to Mg 2+ . The flux recovery ratio (FRR) can be kept above 93 %. This study may give ideas for the preparation of composite NF membrane for water softening and lithium utilization.
研究领域:
材料科学
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环境科学
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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
·
2023
·
IF 9.5
Yifan Zhang,Yaru Fan,Guoli Zhou,Yijun Cao,Jingtao Wang,Xiaobin Jiang,Ning Zhang,Shaohua Yin
With the rapid development of Li-ion batteries (LiBs), the demand for lithium sharply increased. Salt lakes contribute to major extractable lithium in the world, however, the efficient separation of Mg 2+ and Li + remains a challenge. The PEI-based nanofiltration (NF) membrane shows great potential for Mg 2+ /Li + separation in recent studies, due to its positively charged surface and tunable pore size. In this work, ethylenediamine-terminated polyethyleneimine (EDA@PEI) was utilized as the aqueous monomer reacting with trimesoyl chloride (TMC) via interfacial polymerization (IP) to fabricate a new class of PEI-based NF membranes. This work explored critical membrane fabrication parameters and characterizations of EDA@PEI NF membranes. Additionally, this work compared EDA@PEI-TMC and PEI-TMC membranes on their physicochemical properties and NF performance. The results show that PEI containing EDA groups at ends provides the probability for connection of the backbone via TMC, thus enhancing the cross-linking degree (DNC) of EDA@PEI NF membranes. Meanwhile, the presence of EDA groups enhances the Zeta potential of membranes. The best-performing EDA@PEI-TMC membrane exhibits the highest rejection for Mg 2+ of 99.21 %, and excellent Mg 2+ /Li + separation that S Li/Mg reaches 69.20, 80.62 and 46.79 at Mg 2+ /Li + mass ratios of 40:1, 60:1, and 120:1, respectively. During a 48-h NF test, EDA@PEI-TFC membrane shows consistent performance and steady flux. This work demonstrates the great application potential of EDA@PEI NF membranes for Mg 2+ /Li + separation, and provides a candidate for fabricating PEI-based NF membranes.
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
危险品化学品经营许可证（带存储）