SEPARATION AND PURIFICATION TECHNOLOGY
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2024
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IF 8.1
Yanan Wei,Qian Zhang,Yuan Han,Xinyu Xu,Wenmeihui Zhao,Ying Hu,Rongmei Liu,Guixiang Qian,Zhongliang Tian,Chao Yang
In China, 80 % of lithium resources are in the salt lakes of the Tibetan Plateau, although the Mg 2+ /Li + ratios in them are too high, limiting the development of China’s lithium extraction industry from the salt lakes. This study investigates the potential of the LiMn 2 O 4 -Zn cell system for lithium extraction from brines with high Mg 2+ /Li + ratios. The system demonstrates excellent selectivity for Li + and efficiently extracts Li + even in brines with Mg 2+ /Li + ratios as high as 100:1 (wt%). The system operates stably at various brine concentrations, particularly in high-salinity environments. The study also investigates the kinetic performance of the LMO-Zn system, revealing optimal performance at high Li + concentrations and moderate current densities. The LiMn 2 O 4 -Zn cell system presents a promising approach for lithium extraction from brines, offering high selectivity, reversibility, and adaptability.
研究领域:
材料科学
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能源工程
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环境科学
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产品关联
DOI
高影响因子
HYDROMETALLURGY
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2022
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IF 4.217
Ruibing Bai,Junfeng Wang,Daoguang Wang,Junjie Cui,Yanqiang Zhang
In view of the complex problems for the ionic liquids (ILs) recovery with the system containing ILs and TBP, this work proposed a NaNTf 2 -based synergistic extraction system, NaNTf 2 + TBP, which could realize the effective reutilization of the extraction system without reducing the lithium separation ability. Under the optimal extraction parameters, the extraction efficiency of Li + exceeded 98%, while that of Mg 2+ was only ~1%. The results of mass spectrometry (ESI-MS) and slope analysis showed that two TBP molecules involved in the extraction process of Li + , and the Li + extraction mechanism obeyed the cation-exchange process. According to the red shift of the FT − IR peak of P O in TBP and the chemical shift changes of P in 31 P NMR, the interaction strength between TBP and different metal ion followed the sequence: E TBP−H >> E TBP−Li > E TBP−Mg > E TBP−K > E TBP−Na . It was also found that after a three−stage countercurrent extraction process, [Li + ] org was 0.42 g L −1 , and the total recovery efficiency of Li + was about 98%. The saturated extraction capacity for Li + could be as high as 5.4 g L −1 , and Li + could be stripped with the aqueous solution containing 0.2 mol L -1 HCl. In addition, the extraction efficiency of Li + was almost not attenuated after 6 extraction cycles. This new extraction system shows a certain industrial application prospect for Li + separation from the salt lake bine with high Mg/Li ratio.
研究领域:
化学工程
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材料科学
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DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2017
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IF 2.843
Peng Chen,Siyang Tang,Hairong Yue,Changjun Liu,Chun Li,Bin Liang
A new method coupling CO2 mineralization and solvent extraction was proposed and investigated to precipitate magnesium from high Mg/Li ratio brine. Organic amine was employed to extract HCl formed during the CO2 mineralization process and to realize continuous conversion of MgCl2 to precipitated MgCO3, thereby removing the magnesium contained in the brine. The effects of brine concentration, extractant, diluents, extractant concentration, phase ratio, and reaction temperature were systematically investigated. A blend of trioctylamine and isoamyl alcohol was used as the extractant and diluent, and the reaction parameters were optimized. The mechanism was proposed, and a stripping process was designed. Under the optimal conditions, the conversion of magnesium was as high as 67.41%, and the Mg/Li ratio of the raffinate decreased from 20 to 5.4.
研究领域:
化学工程
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环境科学
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产品关联
DOI
高影响因子
Journal of Energy Chemistry
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2024
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IF 14
Yameng Wang,Zi-Yu Liu,Yubei Su,Yu Liu,Aoqun Liu,Xiaoye Zhang,Yugang Huang,Liyun Zhang,Haisheng Chen,Wancheng Zhu
In light of the burgeoning energy technology sector and the ever-growing demand for lithium across diverse industrial domains, conventional lithium extraction methods have been proven inadequate due to their limited production capacity and high operational costs. This work introduces a novel approach to the manganese-titanium based composite HMTO (Mn:Ti=1:4) lithium ion-sieve (LIS) nanospheres, employing lithium acetate dihydrate, manganese carbonate and titanium dioxide P25 as the primary materials. These nanospheres exhibit relatively uniform spherical morphology, narrow size distribution, small average particle size ( ca. 55 nm), large specific surface area (43.58 m 2 g −1 ) and high surface O 2− content (59.01%). When utilized as the adsorbents for Li + ions, the HMTO (Mn:Ti=1:4) LIS demonstrates a fast adsorption rate, approaching equilibrium within 6.0 h with an equilibrium adsorption capacity ( q e ) of 79.5 mg g −1 and a maximum adsorption capacity ( q m ) of 87.26 mg g −1 (initial concentration C 0 : 1.8 g L −1 ). In addition, the HMTO (Mn:Ti=1:4) also delivers a high lithium extraction from the simulated high magnesium-lithium molar ratio salt lake brine (Mg:Li=103), achieving a q e of 33.85 mg g −1 along with a remarkable selectivity ( α Mg Li = 2192.76 ). Particularly, the HMTO (Mn:Ti=1:4) LIS showcases a satisfactory recycling adsorption performance. The adsorption capacity remains at a high level, even that determined after the 5 th cycle (55.45 mg g −1 ) surpasses that of the most recently reported adsorbents. Ultimately, the fantastic synergistic lithium adsorption mechanism is deliberately uncovered by leveraging the ion exchange principles and molecular dynamics (MD) simulations.
研究领域:
材料科学
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能源技术
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化学工程
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纳米技术
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环境科学
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产品关联
DOI
高影响因子
DESALINATION
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2025
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IF 9.8
Qibiao Chen,Chao Qian,Shaodong Zhou
Global demand for lithium necessitates efficient extraction technologies, especially from low-quality brines with high magnesium-to‑lithium (Mg/Li) ratios, where conventional methods falter. This study presents a novel, quantum chemistry-guided methodology for the rational design of solvent extraction systems to address this challenge. By evaluating lithium binding affinities, triisopropylphenyl phosphate (TiPPP) was identified as a superior extractant. When formulated into an TiPPP-FeCl 3 system, it demonstrated exceptional performance under optimized conditions (90 % vol extractant, Fe/Li molar ratio of 1.2, O/A ratio of 1). In a single stage, the system achieved a lithium extraction efficiency of 92.8 %, corresponding to a remarkable Li/Mg separation factor of 1699. After scrubbing and stripping, the Mg/Li mass ratio in the final product was reduced to 0.0199, a 4156-fold decrease from the initial brine (82.7), outperforming the conventional tributyl phosphate (TBP)-FeCl 3 system. A combination of DFT calculations and spectroscopic analyses (Infrared spectroscopy, Ultraviolet spectroscopy, Raman spectroscopy, and electrospray ionization mass spectrometry) confirmed that the high selectivity is governed by both the electronic environment of the phosphoryl (P=O) group and the steric hindrance effects. This study not only presents a high-performance system for direct lithium extraction but also establishes a rational design paradigm for developing advanced extractants for challenging separation tasks.
研究领域:
无机化学
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分离科学
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资源加工工程
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环境化学
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材料化学
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计算化学
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产品关联
DOI
高影响因子
Surfaces and Interfaces
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2025
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IF 6.3
Guoke Zhao,Jie Sun,Gongqing Tang,Yang Zhang,Guoyuan Pan,Yiqun Liu
To address the critical challenge of lithium extraction from high Mg 2+ /Li + ratio brines, this study develops a high-performance separation membrane through synergistic regulation of binary and ternary acyl chloride monomers combined with a bis-quaternary ammonium salt surface modification strategy. Optimizing the ratio of terephthaloyl chloride (TPC) to trimesoyl chloride (TMC) facilitates the formation of a periodic stripe Turing structure on the piperazine-based polyamide membrane's surface, markedly increasing the effective permeation area and water flux. The study reveals that adjusting the TPC ratio finely tunes the polyamide network's crosslinking density, thereby affecting the size exclusion effect. Additionally, TPC incorporation, by diminishing surface carboxyl density, enhances the membrane's surface positive charge, significantly improving its Li + permeability and Mg 2+ rejection capabilities. The optimized TPC-20 membrane demonstrates exceptional ion selectivity, achieving a MgCl 2 rejection of 91.3 %, a LiCl rejection of 11.3 %, and a water flux of 61 LMH. Further enhancement via amino-terminated bis-quaternary ammonium salt (ATBAS) grafting achieves 98.7 % Mg 2+ rejection, a record Li + negative rejection of -37.3 %, and a Mg 2+ /Li + selectivity of 105.1. Extended testing for 120 h verifies the membrane's reliable performance, highlighting its potential for industrial application. This research provides an efficient and energy-saving membrane separation solution for lithium extraction from brines.
研究领域:
膜科学
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材料工程
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分离技术
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化学工程
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环境科学
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纳米技术
✓ 已验证
产品关联
DOI
高影响因子
Journal of Materials Chemistry A
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2025
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IF 9.5
Fei Guo,Lingfeng Wang,Huixin Dong,Pengyu Yan,Shishuo Wang,Qingquan Li,Shaohua Yin,Guoli Zhou,Ning Zhang,Xiao Wu,Yuandong Jia,Gaohong He,Xiaobin Jiang
High ion-selectivity and robust long-term stability are critical performance metrics for nanofiltration (NF) membranes targeting lithium extraction from high-salinity brines with impurities and high magnesium lithium ratios. Herein, a positive and negative heterostructure dual-layer NF membrane with sub-10 nanometer PA layer on 2D Zn-TCPP nanosheets through interfacial polymerization method coupled with vacuum assisted filtration was constructed. PA layer with positively charge on the top performed as the ‘shield’ that effectively retains Mg2+, while negatively charged Zn-TCPP coupled with uniform pores performed as the ‘accelerator’ to facilitate Li+ permeate. The addition of Zn-TCPP can increase the membrane free volume fraction and construct effective screening channels. An appropriate amount of Zn-TCPP nanosheets can construct PA layers as thin as 5 nm and lead to the best Li/Mg separation performance. (Water permeance of 6.79 L⋅m−2⋅h−1 bar−1 over 360 hours continuous operation when Mg/Li ratio is 50:1, and Li+/Mg2+ separation factor is 80.79). In the ternary metal ions solution tests (Li⁺, Mg²⁺, X⁺, where X = Na⁺ or K⁺ with doubled concentration), Li+/Mg2+ separation factor remains still above 40. The DFT simulations and molecular dynamics reveal The transmembrane energy barrier for Mg²⁺ significantly exceeds that for Li⁺ across the membrane. The adsorption heights of ions on Zn-TCPP in a stable state, the different ion perforation energy and ion diffusion rate furtherly explain the reason for the membrane with excellent separation performance.
研究领域:
材料科学
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膜技术
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分离科学
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能源材料
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环境工程
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
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2018
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IF 6.14
Yong Wang,Haotian Liu,Jiahui Fan,Xueting Liu,Yafei Hu,Yulei Hu,Zhiyong Zhou,Zhongqi Ren
A fluoride-free ionic liquid 1-butyl-3-methylimidazolium phosphotungstate ([Bmim]3PW12O40) was synthesized and first used as co-extraction reagent for recovery of lithium ions from salt lake brine with a high Mg/Li ratio. Fourier transform infrared spectra (FT-IR), nuclear magnetic resonance (NMR) and thermogravimetric analysis (TGA) were used for characterizations of the prepared ionic liquid. Tributyl phosphate (TBP), [Bmim]3PW12O40, and dimethyl phthalate (DMP) were used as extractant, co-extraction reagent, and diluent, respectively. Effects of molar ratio of [Bmim]3PW12O40 to Li+, O/A phase ratio, volume fraction of TBP,and carbon chain length of ionic liquid on extraction efficiency and separation factor of Li+ were investigated. The overall extraction efficiency of Li+ was 99.23% after five stages cross-current extraction experiments under optimal conditions. The washing and stripping experiments of the organic phase were conducted, and the parameters were optimized. The reusability of the organic phase was investigated. A total of 10 regeneration cycles of extraction processes showed that the organic phase was highly stable for selective extraction of Li+. Finally, the extraction mechanism using the proposed extraction system was also explored. The results showed that the highly selective extraction of lithium ion was realized by cation exchange and coordination between TBP and Li+.
研究领域:
化学工程
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材料科学
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环境科学
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产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
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2021
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IF 7.312
Rujie Li,Wanhang Wang,Yangyang Wang,Xiaoyu Wei,Ziqi Cai,Zhiyong Zhou
A novel ionic liquid named 1-butyl-3-methylimidazolium tetraphenylboron ([Bmim]Bph 4 ) containing a stereo symmetric structure of Bph 4 - was synthesized and used as co-extractants with TBP and CH 2 BrCl as extractant and diluent for selective extraction of lithium ions from salt lake brines with high molar ratio of magnesium to lithium. The effects of extraction conditions containing molar ratio of co-extractant to lithium ion, volume percentage of TBP and O/A phase ratio on extraction performance were investigated. Under the optimal extraction conditions, the maximum separation factor of lithium to magnesium reached up to 2754 after one single-stage extraction process. After four stages of counter-current extraction process, the extraction efficiency of Li + reached up to 99.47%. Then the washing and stripping conditions were optimized with the combination of LiCl and NaCl solution as the washing agent and Na 2 CO 3 solution as the stripping agent. After that, 10 cycles of the whole extraction experiments were carried out and the organic phase exhibited excellent reusability and stability. Since no acid and alkaline were used throughout the extraction process, the novel extraction process is greener and more environmentally friendly than the traditional solvent extraction process.
研究领域:
化学工程
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材料科学
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环境科学
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DOI
高影响因子
DESALINATION
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2022
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IF 11.211
Yangyang Wang,Wenjing Duan,Rujie Li,Fan Zhang,Shichao Tian,Zhongqi Ren,Zhiyong Zhou
The novel heteropolyacid ionic liquid 1-methylimidazolium silicotungstate ([Mmim] 4 SiW 12 O 40 ) was synthesized using a one-step method and subsequently characterized. This compound was then employed as a co-extractant for the removal of lithium from salt lake brine having a high Mg/Li molar ratio , in conjunction with tributyl phosphate (TBP) and γ-heptanolide as the extractant and diluent, respectively. The optimal extraction conditions gave a single-stage lithium ion extraction efficiency of approximately 60 %. More environmentally friendly and efficient processes were also developed. In one approach, a portion of the aqueous phase containing only HCl and LiCl after stripping was used for washing along with an aqueous HCl solution as the stripping agent and Mg(OH) 2 for regeneration. In the alternative method, NaCl and LiCl were used as washing agents while Na 2 CO 3 was employed for stripping and regeneration, reducing the time required without the need for strong acids or bases. This system showed good extraction efficiency stability over 10 consecutive cycles. The mechanism of this process was explored using Fourier transform infrared spectroscopy and 31 P nuclear magnetic resonance spectroscopy and the binding capacity of TBP for the metals was found to decrease in the order of Li + > Na + > Mg 2+ > K + .
研究领域:
化学
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材料科学
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环境科学
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分析化学
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产品关联
DOI
高影响因子
JOURNAL OF MEMBRANE SCIENCE
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2025
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IF 9
Ting Qi,Xiaona Wei,Xianfu Chen,Tiandan Lu,Dongliang Jin,Jing Zhong
Nanofiltration (NF) membranes are emerging as promising candidates for lithium extraction. However, their performance is challenged by the comparable physicochemical characteristics of Li + and Mg 2+ . In this work, a dual-reinforcement strategy is proposed to simultaneously enhance both selectivity and permeability by combining the densification of the polyamide (PA) network and the construction of Li + -selective transport channels. During the interfacial polymerization of piperazine (PIP) and trimesoyl chloride (TMC), the cross-linking density of the PA layer is increased by adding sodium dodecyl sulfate (SDS), while Li + -selective transport nanochannels are constructed by incorporating 15-crown-5 ether (CE). This synergistic modification enhances Mg 2+ rejection via intensified size exclusion and facilitates Li + permeation through ion-specific recognition. The resulting PIP/SDS/CE-PA membrane exhibits a high cross-linking degree of 91.26 %, a reduced pore size of 0.70 nm, and a narrow pore size distribution (σ = 1.22). Molecular dynamics simulations confirm the preferential complexation of CE with Li + , and that Li + exhibits faster and more favourable translocation in the PIP/SDS/CE-PA membranes, thereby facilitating its selective transport. Experimentally, the membrane achieves a high MgCl 2 rejection of 97.1 % and a low LiCl rejection of 56.7 %, yielding an exceptional Li + /Mg 2+ selectivity of 30 in a MgCl 2 /LiCl binary system, while maintaining a water permeance of 5 L m −2 h −1 bar −1 . These findings demonstrate the strong potential of the PIP/SDS/CE-PA membrane for the direct treatment of high Mg 2+ /Li + ratio salt-lake brines and offer a versatile strategy for designing next-generation NF membranes for selective ion separations.
研究领域:
材料科学
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膜技术
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分离科学
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环境工程
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能源材料
✓ 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）