SEPARATION AND PURIFICATION TECHNOLOGY
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2024
·
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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产品关联
DOI
高影响因子
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
·
2019
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IF 3.131
Guotai Zhang,Jingze Zhang,Yuan Zhou,Guicai Qi,Yongmin Wu,Chunxi Hai,Weiping Tang
Al-doped lithium manganese oxides Li 1.6 Al x Mn 1.6- x O 4 were successfully prepared by sol–gel synthesis and solid state reactions . Protonated samples were obtained by further acid treatment. Experiments were performed to study the effects of physical properties including the Al 3+ doping content x and calcination temperature for optimizing the synthesis of H 1.6 Al x Mn 1.6-x O 4 ion-sieve pursing nice performance such as enlarging the adsorption capacity and minimizing dissolution loss of manganese. The characteristics of a series of Al-doped ion-sieve were studied by XRD , SEM and EDS . The crystal structure was kept well after Al doping from XRD analysis. SEM and EDS showed that Al was uniformly distributed in the sample. The valence state of Mn in Al-doped ion-sieve precursor was analyzed by XPS . Adsorption/desorption experiments were carried out to evaluate the amounts of lithium extraction, lithium adsorption capacity and the manganese and aluminum dissolution loss of the ion-sieve. The results showed that the Al-doped H 1.6 Mn 1.6 O 4 ion-sieve exhibited higher absorption capacity (which approached 32.6 mg g −1 while the undoped one reached only 27.6 mg g −1 ). Furthermore, the dissolution loss of manganese and aluminum from the Al-doped ion-sieve were the most impressive among the ones. Importantly, the Al-doped ion-sieve still preserve a high adsorption capacity (26.8 mg g −1 ) and pretty low manganese dissolution loss (1.92%) after performing up to 4 cycles of adsorption/desorption experiments, indicating an enhanced stability of the Al-doped H 1.6 Mn 1.6 O 4 ion-sieve.
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
DESALINATION
·
2024
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IF 8.3
Li Wang,Jianfeng Zhang,Shixin Meng,Huiyong Wu,Yunze Zhao,Zhen Meng,Lei Feng,Huanting Wang,Yuan Cheng,Liangrong Yang,Huizhou Liu
The dissolution loss of extractant into aqueous solution during lithium solvent extraction from salt lakes poses a significant issue. We found that branched chains of neutral organophosphorus extractants provide suitable steric hindrance, enhancing lithium extraction efficiency and Li/Mg selectivity. Additionally, increasing the number of alkyl chains in organophosphorus extractants increases their hydrophobicity, thereby reducing extractant dissolution loss during the extraction process. Based on these findings, a novel extraction system comprising tri(2-ethylhexyl) phosphate (TOP), FeCl 3 , and 4-methyl-2-pentanone (MIBK) was explored. The extraction conditions, including the Fe/Li molar ratio, diluents, phase ratio, and stripping conditions, were thoroughly investigated and optimized. The extraction mechanism was elucidated at the molecular level using FT-IR, Raman, NMR, and density functional theory (DFT) calculations. The results demonstrated that the TOP-FeCl 3 -MIBK system achieved an 85 % extraction efficiency for Li + in a single stage, with a Li + /Mg 2+ separation factor reaching 5842, surpassing previously reported data in the literature. 31 P NMR and 7 Li NMR analyses revealed that the TOP and tributyl phosphate (TBP) complexes existed in different forms within the organic phase. Slope analysis indicated that the stoichiometric ratio of the extraction complex involving Li + , TOP, and MIBK was LiFeCl 4 ·TOP·MIBK. Furthermore, DFT calculations indicated that the TOP complex was more stable than the TBP complex after extraction. We anticipate that our findings will pave the way for the development of a series of novel extractants with higher Li/Mg selectivity by enhancing steric hindrance and incorporating longer alkyl chains to minimize dissolution loss. We expect this research to inspire the development of similar neutral organophosphorus extractants.
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
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
·
2023
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IF 4.5
Jun Gu,Guolang Zhou,Linlin Chen,Xiaowei Li,Guiling Luo,Linjing Fan,Yanhong Chao,Haiyan Ji,Wenshuai Zhu
With the unprecedented heat of lithium resources, it has been a hot topic to find an effective, low-energy-consumption, and eco-friendly method for extracting lithium from salt lakes. As an electrochemically active material, LiMn 2 O 4 (LMO) is widely used in electrochemical lithium extraction. In order to reduce the Mn dissolution loss and improve the cycle stability of LMO, we designed octahedral LMO with controllable particle size by adjusting the water/ethanol volume ratio of the precursor solution. Through the electrochemical performance test, it was found that with the increase in particle size, the cycle stability of LMO and the lithium ion transport performance also improved. The Mn dissolution loss per 30 cycles of LMO (B-LMO) was 0.187%, and the capacity was maintained at the initial 86.9%. The electrochemical lithium extraction system of B-LMO//Ag exhibits excellent lithium extraction performance. After 1 h of extraction, the lithium extraction capacity is 20.6 mg/g, and the energy consumption is 15.2 Wh/mol.
研究领域:
材料科学
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电化学工程
✓ 已验证
产品关联
DOI
高影响因子
Gels
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2024
·Vol. 10
·期 11
·710
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IF 5
Yujie Zhang,Yang Wang,Le Guo,Chenzhengzhe Yan,Long Li,Shuyun Cui,Yujie Wang
In recent years, with the development of the new energy industry, lithium resources need to be supplied in large quantities. The lithium-ion sieve (LIS) is regarded as an ideal adsorbent for recovering lithium resources from brine because of its excellent lithium adsorption capacity and structural stability. However, because it is powdery after molding, and there will be problems such as dissolution loss of manganese, which limits its industrial development. In this study, in the process of preparing hydrogels of acrylic acid (AA), acrylamide (AM) and chitosan (CS), an LIS hydrogel with high mechanical properties, strong adsorption capacity and low dissolution loss was prepared by doping LIS and Al ions. Among them, the stress of the prepared chitosan–acrylic acid–acrylamide hydrogel (PASA-1) with an Al doping content of 1% reached 603 KPa, and the maximum strain reached 189%, which showed excellent damage resistance. In addition, the adsorption performance of PASA-1 reached 43.2 mg/g, which was excellent, which was attributed to the addition of Al ions, which inhibited the dissolution loss of manganese ions. This idea has great potential in the direction of lithium resource recovery and provides a new method for the use of hydrogel in the direction of lithium-ion sieves.
研究领域:
材料科学
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环境科学
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能源科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
RSC Advances
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2024
·Vol. 14
·期 28
·19795-19805
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IF 3.9
Longyan Song,Minxia Liu,Min Nian,Gang Yang
Manganese-based lithium-ion sieves have become some of the promising adsorbents for extracting Li+ from brines. However, manganese dissolution loss (MDL) severely impairs the stability and cyclicity of ion sieves. A novel ozone eluent was first developed to extract Li+ from lithium manganese oxides, which decreased MDL decreased from 5.89% to 0.11%, and after ten regeneration cycles, the adsorption capacity retained 85.39% of the initial value, which was better than 55.15% when only hydrochloric acid (HCl) was used as the eluent. Based on these phenomena, the mechanism for the O3 lowering of MDL was investigated. First, the catalytic decomposition reaction of O3 competed with the disproportionation reaction, and the involvement of O3 inhibited the occurrence of the disproportionation reaction. Additionally, the presence of O3 and reactive oxygen species provided a preferential electron acceptor compared to Mn3+ during the migration of electrons from the bulk phase to the surface. In this study, MDL was greatly reduced with a very simple strategy, and the cycling stability of the adsorbent was improved.
研究领域:
材料科学
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化学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of Environmental Chemical Engineering
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2024
·
IF 7.4
Qian Liu,Li Zhang,Xuna Liu,Zhongquan Zhong,Wei Deng,Ping Yang
Lithium ion-sieve with selective adsorption capacity is an important research direction in the field of recovering lithium from brine. The lithium ion-sieve precursor Li 1.6 Mn 1.6 O 4 was efficiently prepared using a combination of the hydrothermal method and solid-phase calcination. Subsequently, a highly adsorbent with high adsorption capacity was obtained through a process involving pickling and Li leaching. The impact of different preparation routes and conditions on both the intermediate product LiMnO 2 and the ion-sieve precursor Li 1.6 Mn 1.6 O 4 were investigated. Under conditions of 25 °C, pH 9, and an initial Li + concentration of 100 mg/L, the initial adsorption capacity and Mn dissolution loss are relatively optimal. After 10 cycles, the adsorption capacity stabilizes at 25–30 mg/g, However, Mn dissolution loss is unavoidable, it stabilizes between 2.0 % and 2.5 %. The selective adsorption of Li + remains effective even in the presence of Ca 2+ , Mg 2+ , Na + , and K + interference. Li desorption and Mn dissolution loss were investigated using density functional theory, Fukui function, electron orbital theory, and density of states. The introduction of H + during the pickling process induced structural modifications in the ion-sieve precursor Li 1.6 Mn 1.6 O 4 , leading to a decrease in Mn-Mn bonds, Mn-O bonds, and Li-O distances. Initially, Li + at each site of Li 1.6 Mn 1.6 O 4 had an equal probability of being replaced by H + . Subsequent desorption occurred far away from the desorption point. The loss of Mn 3+ in Li 1.6 Mn 1.6 O 4 resulted in an increased electrophilic attack index at the H + substitution site, and the 3d orbital electrons of Mn 3+ migrate to the 4d and 2p orbitals to seek stability.
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
MICROPOROUS AND MESOPOROUS MATERIALS
·
2023
·
IF 5.2
Yuwen Gao,Shougui Wang,Fei Gao,Changqing Guo,Jipeng Dong,Guanghui Chen
The Li 1.6 Mn 1.6 O 4 driven lithium ion-sieve (LIS) is considered as a potential adsorbents for recovering Li + ions from brines owing to their good theoretical adsorption performance and excellent adsorption selectivity. However, the poor cycle stability and the decrease of adsorption capacity resulting from the manganese dissolution loss limit its practical applications. In this work, to mitigate this issue, several novel Al and Cr co-doped manganese LISs were prepared by a facile hydrothermal synthesis method, followed by the acid treatment. The characterization results show that Al and Cr ions are uniformly doped into the spinel crystal structure of LIS, and the introduction of Al and Cr ions can cause the crystal shrinkage, decrease the Mn 3+ content, and raise the mean valence of manganese in the co-doped samples, effectively improving their structural stability. Compared with un-doped ion-sieve H 1.6 Mn 1.6 O 4 , the optimal co-doped ion-sieve H 1.6 Mn 1.54 Al 0.02 Cr 0.04 O 4 with 2% Al doping and 4% Cr doping possesses a higher lithium adsorption capacity, lower manganese dissolution loss, and stronger cyclic stability. Additionally, the H 1.6 Mn 1.54 Al 0.02 Cr 0.04 O 4 possesses a high adsorption selectivity of Li + over Mg 2+ , Ca 2+ , K + and Na + . Furthermore, the lithium adsorption is determined to be a chemical and monolayer adsorption process on the prepared LIS. The good lithium adsorption capacity and adsorption selectivity as well as the good recyclability make the prepared Al and Cr co-doped LIS a promising adsorbent for the efficient lithium recovery form 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
危险品化学品经营许可证（带存储）