SEPARATION AND PURIFICATION TECHNOLOGY
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2024
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IF 8.1
Hemin Li,Yuefeng Deng,Ji Chen
Lithium is becoming one of the most eye-catching metal elements in modern industry, mainly because of its crucial role in manufacturing lithium-ion batteries. The demand for lithium in the new energy market is burgeoning significantly, while enormous lithium resources reserved in salt lakes in northwest China are not exploited effectively, due to the high Mg/Li mass ratio. Although the TBP extraction system has been applied in lithium extraction from salt lake brines, there are still some problems to be solved, such as its high solubility, easy degradation, and so on. In this work, a novel low dissolution loss extraction system was developed, with DEHEHP and FeCl 3 serving as extractant and co-extractant, respectively. A real brine from Da Qaidam Lake was used to prove its practicality and effectiveness. After studying the detailed conditions of each process, a whole countercurrent process was performed, including eight stages of extraction, two stages of scrubbing, three stages of stripping, and regeneration. It was found that 99.4% of Li + was successfully recovered from the brine, and the stripping liquor contained 22.74 g/L Li + , 0.51 g/L Mg 2+ , and 3.16 g/L B. The concentration of Li + increased approximately 20-fold while the Mg/Li mass ratio decreased by a factor of 3900, from real brine to stripping liquor. High-purity (>98.5%) lithium carbonate products were prepared from the stripping liquor by precipitation. The dissolution loss of the organic phase in the raffinate was only 22.5 ppm, much lower than published works. Finally, the mechanism of extraction and co-extraction were systematically studied and the structure of the complex formed during extraction was revealed as LiFeCl 4 ·2DEHEHP.
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
Separations
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2022
·Vol. 10
·期 1
·24
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IF 3.344
Huifang Li,Lijuan Li,Wu Li
Lithium extraction from salt lake brine with a high mass ratio of Mg/Li by counter-current method using TBP-DIBK extraction system was investigated in this study. In the extraction process, TBP and DIBK acted as extractant, kerosene was used as diluent, and FeCl3was used as co-extractant. The operation conditions of extraction, scrubbing, stripping, and regeneration were investigated. In this study, 5.5 mol/L LiCl + 0.5 mol/L HCl was used as a scrubbing solution for purifying products, and 6 mol/L HCl solution was used as a stripping agent to transfer Li+from organic phase to aqueous phase. Furthermore, 2 mol/L NaOH and saturated MgCl2were used as the regeneration agent to remove H+from organic phase. The counter-current extraction experiments of 3-1-1-3 stages were carried out. After 10 cycles, the lithium extraction efficiency reached 99.90%; the separation factor of Li/Mg, Li/K, Li/Na, and Li/Ca was 5.215 × 104, 2.159 × 103, 3.659 × 102, and 3.104 × 102, respectively. The results indicated that the TBP-DIBK extraction system was effective at extracting lithium from salt lake brine with a high mass ratio of Mg/Li. Furthermore, the study of extraction thermodynamics suggested that lithium extraction was an exothermic process and that lower temperature promoted lithium extraction.Keywords:lithium extraction;salt lake brine;TBP-DIBK;extraction thermodynamics
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
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2024
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IF 8.1
Qing Liu,Huifang Xing,Yan Zhang,Yunze Zhao,Meng Rong,Huizhou Liu,Liangrong Yang
The metatitanic acid H 2 TiO 3 (HTO) with high selectivity shows potential in lithium extraction from salt lake brine. Nevertheless, the sluggish adsorption kinetics and unsatisfying actual adsorption capacity hinder H 2 TiO 3 industrial application. Herein, a rare earth element Nd-doped H 2 TiO 3 (Nd-HTO-1 %) was synthesized. The crystallinity, morphology, hydrophilicity, adsorption property and mechanism of Nd-HTO-1 % were systematically characterized by a series of techniques. Interestingly, Nd-doping promotes the generation of oxygen vacancies, thereby increasing the density of surface hydroxyl groups and making the surface high-hydrophilic and particle size decreased. After 1 % Nd-doping, high-hydrophilic HTO was obtained with a contact angle of 16.5°. The adsorption capacity of Nd-HTO-1 % increased by 12.5 % compared with HTO, and the equilibrium time of adsorption reduced by half to 4 h. After eight cycles, Nd-HTO-1 % still showed a considerable adsorption capacity of 39.69 mg·g −1 . In the meantime, the dissolution loss of titanium is merely 0.14 %, showing excellent cycling stability. Combined with the considerable selectivity exhibiting in Qarhan salt lake brine, it demonstrates potential in utilization of Nd-doped H 2 TiO 3 for lithium extraction from salt lake brine.
研究领域:
材料科学
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化学工程
✓ 已验证
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DOI
高影响因子
Journal of Sustainable Metallurgy
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2023
·Vol. 9
·期 4
·1456-1465
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IF 2.4
Li Hui-Fang,Li Li-Juan,Ji Lian-Min,Shi Dong
To develop a more stable and more efficient extraction system, a novel amide extraction system, containing extractant N , N -bis(2-ethylhexyl) acetamide (N523) and diluent diisobutyl ketone (DIBK), was proposed in this work. A series of operation conditions, such as the concentration of initial lithium in aqueous phase, the volume ratio of N523 and DIBK, phase ratio of O / A , the molar ratio of Fe/Li, were carried out. The lithium extraction rate reached up to 92% under the optimal extraction conditions. Considering the mass transfer of two phases and consumption of extractant, the three-stage counter-current extraction experiment was conducted. After 6 cycles experiment of the three stage counter-current extraction, the lithium extraction rate reached 99.89% and the separation factor of Li/Mg, Li/Na, Li/K, and Li/Ca were 103,300, 5288, 5233, and 760.4, respectively. The stoichiometry of the complex was LiFeCl 4 ·N523 by the slope method. The results indicated that N523-DIBK extraction system was effective to recovery of lithium from salt lake brine with high mass ratio of Mg/Li. Furthermore, the extraction thermodynamics study revealed lithium extraction was an exothermic process, which meant lower temperature promoted lithium extraction. Graphical Abstract
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
JOURNAL OF CHEMICAL AND ENGINEERING DATA
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2023
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IF 2.6
Tingting Zhou,Xueli Huang,Baharguli Hadeerbieke,Fangning Yan,Xueying Wang,Qinglong Luo
The phase diagram can guide the comprehensive utilization of salt lake brine, particularly lithium extraction. In this paper, the study on phase equilibria of the quinary system Li+, Na+, K+, Mg2+//Cl––H2O saturated with NaCl·2H2O and its subsystem Li+, Na+, Mg2+//Cl––H2O at 258.15 K were carried out using the isothermal dissolution equilibrium method. Based on the experimental data, equilibrium diagrams for stable phases were plotted. For the equilibrium diagram of the quaternary system Li+, Na+, Mg2+//Cl––H2O at 258.15 K, there are two invariant points, five univariant curves, and four crystallization fields. The quinary system Li+, Na+, K+, Mg2+//Cl––H2O saturated with NaCl·2H2O at 258.15 K contains three invariant points, seven univariant curves, and five crystallization fields. Comparing the phase diagram of the system at 258.15 K to that at 298.15 K reveals that, except KCl, all crystallization zones have decreased, and LiCl·MgCl2·7H2O has the smallest crystallization zone compared to the other salts in the systems. This fundamental research could be valuable for promoting comprehensive utilization of the lithium-containing salt lake brine.
研究领域:
化学
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材料科学
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DOI
高影响因子
DESALINATION
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2025
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IF 9.8
Yifan Shao,Chao Hu,Ruirui Liu,Bingxin Liu,Yongquan Zhou,Jianming Pan
The design of adsorbents with high recognition activity, high site density and high mass transfer efficiency is the significant to the removal of specific non-metallic ions from Salt Lake brines. Here we report the fabrication of ZIF-67-derived hollow Co 3 S 4 nanoadsorbent for the adsorption and separation of boron (B) in complex water from concentrated salt solutions. The adsorption experiments displayed that the B adsorption capacity of the hollow Co 3 S 4 material exhibited substantial B adsorption capacity, reaching 283.3 mg·g −1 , which represents an impressive 7.3-fold improvement over ZIF-67. On these grounds, a series of kinetic and thermodynamic studies were conducted, and the results revealed that the adsorption process is more consistent with the spontaneous exothermic reaction of the Langmuir adsorption isothermal model (R 2 = 0.999). The results of the charge density and density of states depicted that Co atoms strongly interact before and after adsorption, and that Co atoms are tend to react spontaneously with H 3 BO 3 , which serves as the primary adsorption site. The interaction including electrostatic and hydrogen bonds jointly realizes in B adsorption performance with high selectivity and excellent cycle stability. This study highlighted the high adsorption performance of the hollow Co 3 S 4 for boron in real water of the Salt Lake brine and provided a new idea for the design of other ZIFs derived hollow nanoadsorbent for practical applications.
研究领域:
材料科学
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环境科学
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化学工程
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高影响因子
Materials
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2025
·Vol. 18
·期 10
·2373
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IF 3.2
Jing Zhu,Xiyun Yang,Yongqiang Huang,Rongzheng Yao
With the depletion of solid lithium ore, extracting lithium from salt lake brine has become a critical focus for future endeavors. A four-step method was used to synthesize high-purity H1.6Mn1.6O4for extracting Li+. Porous cubic Mn2O3was hydrothermally synthesized with carbon spheres and surfactants as templates. Then, it was converted to LiMnO2by calcining with Li2CO3. After roasting and acid pickling, H1.6Mn1.6O4was successfully synthesized. The impacts of calcination temperature, Li/Mn molar ratio and glucose addition on LiMnO2composition, loss percentage of dissolved Mn in precursor, and the adsorption characteristics of the lithium ion sieve were studied. Glucose inhibited the formation of LiMn2O4and promoted the formation of pure LiMnO2. The resulting precursor without impurities showed porous structure. After acid pickling, H1.6Mn1.6O4showed a high-adsorption performance and excellent cycle performance. After five cycles, adsorption capacity remained above 30 mg/g, and the loss percentage of dissolved Mn stabilized at about 1%. The Li+–H+exchange conformed to pseudo-second-order adsorption dynamics and the Langmuir adsorption isotherm equation, indicating that the adsorption process can be classified as monolayer chemical adsorption.
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
CHEMICAL ENGINEERING JOURNAL
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2025
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IF 13.2
Qing Liu,Huifang Xing,Yunze Zhao,Qingfen Liu,Qiyu Meng,Huizhou Liu,Liangrong Yang
Titanium (Ti)-based lithium ion sieves (LISs) have advantages such as structural stability and environmental friendliness, making them promising for lithium extraction from salt lake brine. However, the adsorption kinetics and capacity of granulated Ti-based LISs are very limited, which restricts their industrial applications. Inspired by biomimetic channels for Li transport, herein, a Ti-based LISs membrane with fast kinetics and high adsorption capacity has been proposed. Firstly, a flower-shaped Li 2 TiO 3 (LTO) assembled by nanosheets with a superhydrophilic surface was prepared for the first time. Thereafter, the LTO was compounded into poly (oligo (ethylene glycol) methacrylate) (POEGMA) through UV-curing to obtain the PP@POEGMA/LTO membrane. Due to the lithiophilic properties of oligoethers in POEGMA, Li + ions could pass through the inner pathway preferentially and rapidly. Furthermore, the abundant hydroxyl functional groups in POEGMA enhanced the hydrophilicity of membrane, facilitating the mass transfer of ad/desorption. After 0.1 mol·L −1 HCl elution to obtain PP@POEGMA/HTO composite membrane, the adsorption equilibrium of membrane was found to achieve within 4 h, as fast as that of the powders HTO. Meanwhile, the equilibrium adsorption capacity reached 32.19 mg·g −1 . Dynamic adsorption experiments revealed that the composite membrane maintained a lithium removal rate of over 80 % within 30 min, with the adsorption capacity stabilizing at 20 mg·g −1 after five cycles. As for selective adsorption experiments in the Qarhan salt-lake brine and natural seawater, PP@POEGMA/HTO membrane showed a Li/Mg separation factor of 86.4 in spite of the Mg/Li as high as 249, and Li/Na separation factor of 14,508 in spite of the Na/Li as high as 60674, respectively. This work provides a straightforward approach for LISs membrane to achieving high-efficiency recovery, promoting their application in practical industries.
研究领域:
材料科学
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环境工程
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DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
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2024
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IF 8.1
Chi Ma,Jianfeng Zhang,Yinting Liu,Liquan Sun,Qingfen Liu
A novel integrated separation process for boron (B), lithium (Li), and magnesium (Mg) is developed using precipitation and three-liquid-phase extraction (TLPE) methods from salt lake brine with high Mg-Li ratio. Simulated brine is precipitated using (NH 4 ) 2 SO 4 and subsequently extracted through the three-liquid-phase system, which comprises 2-ethyl-1,3-hexanediol (BEPD) dissolved in butyl acetate (BA), polyethylene glycol with average molecular weight of 2000 (PEG2000), and brine. After optimizing the experimental conditions, the process achieves a precipitation of 95.6 % for Mg 2+ and extraction rates of 87.2 % for B 3+ , 73.5 % for Li + , and 91.9 % for Mg 2+ . The separation performance for actual brine demonstrates that the extraction rates of B 3+ , Li + , and Mg 2+ are 84.9, 74.8, and 91.5 %, respectively, which are similar to the results obtained from simulated brine. Moreover, TLPE mechanism is analyzed that B is combined with polyhydroxy compounds in the top phase as H 3 BO 3 , while Li + is extracted by the electrostatic interaction of oxygen atom active groups in the middle phase, and Mg 2+ is remained in the bottom phase due to hydration. Our precipitation and TLPE methods show apparent advantages in achieving integrated separation with high efficiency for B, Li, and Mg in the brine.
研究领域:
化学工程
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材料科学
✓ 已验证
DOI
高影响因子
HYDROMETALLURGY
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2024
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IF 4.8
Xinyu Cheng,Dong Shi,Yuze Zhang,Xiaowu Peng,Shaolei Xie,Lijuan Li,Yong Niu,Yuxuan Wang,Fugen Song
Cesium is an important strategic resource, and solvent extraction is the most frequently used technology for its extraction from various minerals and brines. However, this common method faces operational and cost problems owing to large alkali consumption. A synergistic extraction system consisting of 4- tert -butyl-2-(α-methylbenzyl) phenol (t-BAMBP) and di-(2-ethylhexyl) phosphoric acid (D2EHPA) was designed and used to extract Cs + from an alkali-free solution. The effects of variables such as: (i) pH, (ii) concentration of t-BAMBP and D2EHPA, (iii) temperature, (iv) Cs + concentration, and (v) coexisting cations, on the Cs + extraction performance of the synergistic system were investigated. The most suitable organic phase composition was 1.0 mol/L t-BAMBP and 0.1 mol/L D2EHPA in kerosene, and the synergistic coefficient was up to 57 at 25 °C and an organic/aqueous phase volume ratio of 1/1. The extraction sequence of cations using the t-BAMBP–D2EHPA synergistic system followed the descending order Cs + > Rb + > Ca 2+ > K + > Li + > Mg 2+ > Na + . The chemical formula of the extracted species was determined as [CsA(HA)(ROH) 2 ] using the slope method. The Cs + extraction process is an exothermic reaction with an enthalpy ( ΔH o ) of −55.3 kJ mol −1 , confirmed by the thermodynamic study. After three-stage countercurrent extraction, the extraction efficiency of Cs + was 92.6%, demonstrating excellent selectivity from coexisting cations. The t-BAMBP–D2EHPA synergistic system showed outstanding economic and environmental advantages and a good application prospect to develop a conceptual process flowsheet for extraction with this system and stripping with HCl to separate cesium salt from salt-lake brine.
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
HYDROMETALLURGY
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2025
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IF 5.3
Minxiu Zhou,Hui Su,Yaoxian Hu,Wensen Liu,Zhaowu Zhu,Tao Qi,Daoyong Lin
The increasing adoption of lithium-ion batteries in new energy sectors has substantially increased lithium consumption. Chilean salt lakes consist of high concentrations of Li + , (1.14 g/L) and Ca 2+ (>10 g/L) and low concentration of Cl − (<200 g/L). The TBP-FeCl 3 system can efficiently extract lithium from high Mg brine, but the system has not yet been studied in low chloride and high calcium brine. In this paper, the effect of different extraction, scrubbing, and stripping conditions on the lithium extraction percentage from this type of brine was investigated using a TBP-FeCl 3 system. The results indicated that 100 % TBP mixed with brine containing 15–20 g/L Fe 3+ and 0.05 mol/L HCl at O/A = 1:1, extracted 52.9 % of Li + and produced an organic phase of 0.72 g/L Li + , accompanied by Ca 2+ and Na + concentrations of 2.82 g/L and 2.47 g/L, respectively. The extraction percentage of Li + reached 74.2 % after a four-stage extraction process. The loaded organic phase was scrubbed with 4 mol/L LiCl solution at O/A = 1:1, and the scrubbing percentage of the impurity ions was >90 %. The scrubbed organic phase was stripped by simulated counter-current stripping by 2.5 mol/L HCl at O/A = 15:1 for ten stages, and the recovery of Li + was 80.3 %. The stripping solution had a Li + concentration of 25.3 g/L and an impurity ion concentration of <1 g/L and the loss of Fe 3+ was <100 mg/L. The TBP-FeCl 3 extraction system offers the efficient and direct extraction of lithium from Chilean brine and provides technical support for the clean mining of lithium resources in South American salt lakes.
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
CHEMICAL ENGINEERING JOURNAL
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2023
·
IF 15.1
Xuezhen Wang,Xiaotong Jiang,Junmin Wu,Kaiyu Zhao,Yafei Guo,Tianlong Deng,Xiaoping Yu
With the development of new energy industry, the extraction of lithium from liquid minerals has attracted extensive attention. Herein, a novel phenolic resin-supported H 2 TiO 3 foam (RF/UF-HTO) was developed for Li + recovery from aqueous solutions. It was found that when the thermosetting phenolic resin was modified with urea and then foamed by petroleum ether with boiling points of 60 ∼ 90 °C under the assistance of 1.5% Tween 80 + 3% sodium dodecyl sulfate, the material presented a porous 3D network structure with a high specific surface area and porosity. The maximum adsorption capacity of the material reached 52.41 mg·g −1 . The adsorption rate was controlled by the particle diffusion, and the adsorption was proven to be an endothermic process by the microcalorimetry. The material exhibited high adsorption performance for low-concentration Li + in geothermal water with a low degree of mineralization. The adsorption capacity reached 21.50 mg·g −1 after only 6 h, and the attenuation of adsorption capacity was only 1.96 mg·g −1 after 10 cycles. Because of the high Mg 2+ concentration and high degree of mineralization, the adsorption capacity for Li + in salt lake brine was low. This problem was successfully solved by regeneration with Ba(OH) 2 , by which the adsorption capacity was enhanced from 0.54 to 20.72 mg·g −1 . Even for the fixed-bed adsorption, the adsorption capacity still reached 8.5 mg·g −1 . Based on these excellent properties, the material and method developed in this work can be used for Li + recovery from brine with different degrees of mineralization and composition.
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
危险品化学品经营许可证（带存储）