MINERALS ENGINEERING
·
2021
·
IF 4.765
Hongxiang Xu,Li Zhang,Zengrui Pang,Zhenlei Wang,Weichao Li,Jiushuai Deng
Ionic liquids were extensively used in many extraction and separation processes for metal ions because of excellent dissolving and selecting ability. The COSMO-RS method was applied for selecting suitable ionic liquid from 80 kinds of ionic liquids. Hydrophilicity, solvent solubility, distribution ratio were considered as important factors for selecting suitable ionic liquids. [N1888][P507] was suitable ionic liquid for extracting and separating heavy rare earths. A solvent extraction system containing ionic liquid [N1888][P507] and molecular extractant TRPO to separate heavy rare earths was studied. The results showed that the mixture of the [N1888][P507] and TRPO contributed to high extractabilities and selectivities of heavy rare earths. The abilities to form third phase and product emulsification phenomenon decreased with the concentration ratio of TRPO and [N1888][P507] increasing. The extraction mechanism of HREEs was deduced as ion association. The quantitative stripping of HREEs from loaded organic phase could be achieved with deionized water and low concentration of hydrochloric acid. The article showed that the mixture of [N1888][P507] and TRPO might be an effective and environmentally friendly extractant for extraction and separation of heavy rare earths.
研究领域:
化学工程
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环境科学
✓ 已验证
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2025
·
IF 9
Meiying Xie,Fan Yang,Luyao Yang,Rong Liu,Jinming Du,Qinghao Zhao,Xiaojing Li
To date, no extractants have shown good heavy rare earth elements (HREEs) extraction and separation performance within a large acidity window. Herein, a strategy to introduce benzene and tertiary amine functional groups with both an electron donation effect and large steric hindrance effect into the structure of phosphonic acid was proposed, and a new extractant, ((dioctylamino)methyl)phenylphosphonic acid (DOAM-PPA), has been successfully synthesized by a simple one-step process. The pK a value of DOAM-PPA is higher than those of 2-ethylhexylphosphoric acid mono-2-ethylhexyl ester (P507), di-(2,4,4′-trimethylpentyl)phosphinic acid (Cyanex 272), and bis(2-ethylhexyl)phosphate (P204). DOAM-PPA exhibited good separation of HREEs. DOAM-PPA enabled efficient extraction and separation of HREEs at initial pH = 4.00–1.25 and 0.1–2 mol/L HCl. Its operating window in the acidic region was much larger than those of P507, Cyanex 272 and P204. Under 0.5 mol/L HCl and 0.1 mol/L NaCl, the separation factor (β Lu/Y ) of DOAM-PPA for Lu and Y reached 53.55, which was much greater than those of P507, Cyanex 272 and P204. The saturation capacity of DOAM-PPA for Lu is 2.45 times greater than that of P204 at 0.5 mol/L HCl. When DOAM-PPA was used to directly extract LYSO leachate, although the concentrations of Lu and Y reached 15.5 g/L and 0.75 g/L, respectively, the β Lu/Y still reached 20.22, the β Lu/Ce was 59.37–116.25, and the extraction percentages of Lu were all >86%. Considering the synthetic conditions, separation performance, saturation capacity, stripping performance, recycling performance and operating window in the acidic region, we believe that DOAM-PPA has great potential for HREEs separation and recovery applications.
研究领域:
化学工程
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2018
·
IF 3.927
Junlian Wang,Xinyu Liu,Jiashuai Fu,Meiying Xie,Guoyong Huang,Huajun Wang
Scientists have always been seeking more efficient extractants for rare earths extraction and separation, especially for heavy rare earths. In this paper, a novel extractant (2,4-dimethylheptyl)(2,4,4′-trimethylpentyl)phosphinic acid (USTB-2) was synthesized. The structures of the intermediate and USTB-2 were characterized by 31 P NMR, 1 H NMR, FT-IR and ESI-MS. Its p K a was 5.62. Its extraction ability was between Cyanex 272 and P507. Its extraction mechanism was cation exchange. Its extraction capacity was larger than that of Cyanex 272 and lower than that of P507. Its solubility in 3 mol/L HCl and deionized water was 11.2 mg/L and 19.0 mg/L, respectively. The Lu(III) loaded in USTB-2 solution can be easily stripped by HCl, HNO 3 and H 2 SO 4 . It has good separation performance for heavy rare earths. Its average separation factor ( β ¯ ) for adjacent heavy REs from Gd to Lu was 2.18. For some heavy RE couples like Er/Ho, Yb/Tm and Lu/Yb (especially for Lu/Yb), USTB-2 possesses even better separation performance than Cyanex 272. Its extraction efficiency for nonferrous metal ions was in the order Al > Gd > Zn > Nd > La > Co > Cu. The separation factors of Al/Gd, Gd/Zn, Zn/Nd, La/Co by USTB-2 were 2.67, 5.39, 3.35 and 26.67, respectively.
研究领域:
化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF RARE EARTHS
·
2017
·
IF 2.429
Junlian Wang,Meiying Xie,Juanjuan Ma,Huajun Wang,Shengming Xu
(2,3-Dimethylbutyl)(2,4,4′-trimethylpentyl)phosphinic acid (INET-3) was impregnated onto dry macroporous resins XAD-16 and pretreated XAD-16 with ethyl alcohol and HCl (Pre-XAD-16) to prepare the solvent impregnated resins SIRs-INET-3/XAD-16 and SIRs-INET-3/Pre-XAD-16. The molecular weight distribution of the low molecular weight (LMW) polymers washed off by ethyl alcohol during XAD-16 pretreatment was determined by gel permeation chromatography (GPC). The macroporous resins (XAD-16 & Pre-XAD-16), the corresponding solvent impregnated resins (SIRs-INET-3/XAD-16 & SIRs-INET-3/Pre-XAD-16) and the PVA coated SIRs-INET-3/Pre-XAD-16 with boric acid as cross-linking agent were characterized by FT-IR, SEM-EDS and TGA . The effects of XAD-16 pretreatment and PVA coating technology on RE(III) adsorption equilibrium time, INET-3 losses during extraction and adsorption capacity were investigated. The adsorption kinetics , selectivity and stripping behaviors of SIRs-INET-3/XAD-16 were further studied. The washed off LMW polymers had the Mn of 36,656, Mw of 40,310 and polydispersity coefficient of 1.10. The SIRs-INET-3/XAD-16 had shorter equilibrium time, less INET-3 loss and more Tm(III) adsorption capacity than the SIRs-INET-3/Pre-XAD-16. The PVA coated SIRs-INET-3/Pre-XAD-16 had less INET-3 loss and more Tm(III) adsorption capacity but longer equilibrium time than the uncoated SIRs-INET-3/Pre-XAD-16. The adsorption of RE(III) on the SIRs-INET-3/XAD-16 followed the pseudo-second-order kinetic model . The Tm(III) accumulative adsorption amounts onto SIRs-INET-3/XAD-16 after eight extraction stages was 23.6 mg/g. The separation factors of adjacent heavy RE(III) β Er/Ho , β Tm/Er , β Yb/Tm and β Lu/Yb values were 1.76, 2.59, 2.56 and 1.19, respectively. The adsorbed Lu(III) onto the SIRs-INET-3/XAD-16 can be stripped completely by 1.0 mol/L H 2 SO 4 .
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
JOURNAL OF MEMBRANE SCIENCE
·
2020
·
IF 7.183
Yitan Wang,Li Chen,Yongsheng Yan,Ji Chen,Jiangdong Dai,Xiaohui Dai
Adjacent rare earth separation has always been one of the hardest separation tasks around world. In this article, a task-specific ionic liquid Cyphos IL 104 embedded polymer inclusion membrane (PIM) was fabricated to realize the adsorption and separation of adjacent heavy rare earth elements Lutetium (III) and Ytterbium (III). Chemical composition of the PIM was verified by attenuated total reflectance Fourier transformed infrared spectroscopy and X-ray photoelectron spectroscopy. And results confirmed only P O and P–O groups participated in the formation of Rare Earth (III)-Cyphos IL 104 complex. A typical thumb-like asymmetric structure was observed by scanning electron microscopy. And the addition of Cyphos IL 104 promoted the hydrophilicity of the PIM as the water contact angle became smaller. Static adsorption and dynamic transport performances were studied in details to get the optimum separation condition. The permeability coefficients of Yb(III) and Lu(III) were 156 μm s −1 and 114.82 μm s −1 , respectively; And the initial membrane fluxes were 90.17 μm m −2 s −1 and 65.61 μm m −2 s −1 , respectively. The separation factor between Yb(III) and Lu(III) was calculated as 1.37 under the optimized transport condition. All these would provide promising developments of adjacent heavy rare earth separation with an efficient and practical membrane strategy.
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
HYDROMETALLURGY
·
2016
·
IF 2.29
Junlian Wang,Meiying Xie,Huajun Wang,Shengming Xu
Nonsymmetric (2,3-dimethylbutyl)(2,4,4′-trimethylpentyl)phosphinic acid (INET-3) may be a superior extractant for extraction and separation of heavy rare earths (REs), as its extraction ability falls between that of P507 and Cyanex 272. Its purity and pK a were determined using potentiometric titration methods. The extraction mechanism and extraction equilibrium constants of INET-3 for heavy REs from chloride media were studied. The effects of the anion types (Cl − , NO 3 − and SO 4 2 − ) and concentrations (0.1, 0.5 and 1.0 mol/L) on RE(III) extraction were investigated. The extraction capacity and separation factors of INET-3 for heavy REs were determined. The stripping behaviours of heavy RE complexes with INET-3 by HCl , HNO 3 and H 2 SO 4 were examined. The results showed that the pK a of INET-3 was 5.45. The extraction capacity of INET-3 was approximately twice that of Cyanex 272 and only one-third that of P507. Loaded heavy RE(III) extracted by INET-3 was completely stripped out by HCl, HNO 3 and H 2 SO 4 solutions when the pH was at or below 1.2. Among the three inorganic acids , H 2 SO 4 was the most effective stripping agent. INET-3 can separate heavy RE(III) efficiently, and the separation factors of adjacent heavy RE(III) β Er/Ho , β Tm/Er , β Yb/Tm and β Lu/Yb were 3.25, 2.73, 2.96 and 1.53, respectively, when extracted from a Ho/Er/Tm/Yb/Lu quinary system.
研究领域:
化学工程
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF RARE EARTHS
·
2025
·
IF 7.2
Yuhe Ran,Ru’an Chi,Zhenyue Zhang,Yuting Shi,Wendou Chen,Fei Long,Hanjun Wu
Weathered rare earth ores are an important strategic mineral resource in China, and they are the primary source of medium and heavy rare earths (MHRE). The efficient recovery of MHRE is of great significance from an industrial standpoint. In this study, fulvic acid (FA) is employed as a precipitant to investigate the precipitation of rare earth (RE). The results indicate that the precipitation rates ( w ) of RE range from 89.69 wt% to 99.86 wt% with the pH of 9, the molar ratio of 2, and the temperature of 40 °C, except for Lu 3+ , the w reaches 97.33 wt% with the pH of 9, the molar ratio of 3, and the temperature of 25 °C. The w of RE in the ammonium acetate rare earth leaching solution ranges from 95.99 wt% to 98.54 wt%, with the MH/L of the rare earth distribution after precipitation increasing from 0.77 to 0.80. The use of FA as a precipitant is demonstrated to yield effective precipitation of RE, particularly those of MHRE. FA complexes with RE 3+ , where deprotonation of COO – increases the surface electron density of oxygen atoms, creating additional active sites for electron-deficient RE 3+ . The mechanism provides a theoretical basis for using carboxylic acid compounds as new precipitants. Further, a novel technology for FA complexation precipitation of RE from lignite extract is proposed.
研究领域:
化学工程
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矿物加工
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环境科学
✓ 已验证
DOI
高影响因子
RARE METALS
·
2020
·Vol. 40
·期 9
·2633-2644
·
IF 2.161
Yang Bin,Wu Suo-Zhi,Liu Xin-Yu,Yan Zeng-Xin,Liu Yu-Xue,Li Qi-Song,Yu Feng-Shan,Wang Jun-Lian
Abstract A solid-phase extraction resin SIRs-P227/XAD-7HP was prepared by impregnating extractant P227 onto macroporous resin XAD-7HP beads. SIRs-P227/XAD-7HP beads were characterized by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) equipped with energy-dispersive spectroscopy (EDS). The adsorption kinetics, particle size effect, adsorption isotherm, pH equilibrium –lg D relationship (where D is distribution coefficient), desorption, adsorption selectivity for heavy rare earths, and impurity ions were studied. The results showed that the adsorption kinetics of Lu(III) on the SIRs-P227/XAD-7HP beads fitted the Morris–Weber model best. The adsorbance decreased as the particle size increased. The pH equilibrium –lg D relationship fitted well with a straight line, and the slope was 1.56. The experimental data fitted well with Langmuir adsorption. The calculated maximum adsorption capacity was 23.8 mg·g −1 , while the experimental datum was 22.7 mg·g −1 at the given conditions. The adsorbed Lu(III) can be easily stripped by 0.1 mol·L −1 HCl. The adsorption selectivity of SIRs-P227/XAD-7HP for heavy REs exhibited the following order: Lu > Yb > Tm > Er > Ho. The adjacent heavy rare earth (RE) separation factors β Lu/Yb , β Yb/Tm , β Tm/Er , and β Er/Ho were 1.57, 3.00, 3.03, and 2.23, respectively, at liquid/solid ratio (L/S) equal to 3:20. The adsorption selectivity for impurity ions exhibited the following order: Fe > Lu > Tm > Zn > Mg > Ca > Ho > Co > Ni > Cu > Al. Graphic abstract
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
HYDROMETALLURGY
·
2015
·
IF 1.933
Li Chen,Ji Chen,Yu Jing,Deqian Li
Several novel extraction systems were reported since 2-ethylhexyl phosphonic acid mono-(2-ethylhexyl) ester (P507) had been confronted with low selectivity and incomplete stripping for heavy rare earths (HREs). This paper makes a comprehensive appraisal of P507, bis (2,4,4-trimethylpentyl) phosphinic acid (Cyanex272), mixture of P507 and Cyanex272, P507 adding isooctanol and bifunctional ionic liquid extractant (Bif-ILE) [trialkylmethyl-ammonium][di-(2-ethylhexyl)orthophosphinate] ([A336][P507]). Thermodynamics study, apparent kinetics study and theoretical calculation for the cascade extraction are all included. We put forward coordination equilibrium effect for the first time to illustrate the inner and outer environment during the coordination. It could be useful to explain the extraction ability and selectivity of different extractants. All these would provide separation of HREs with more feasible and informative understanding and guidance.
研究领域:
化学工程
·
稀有金属提取
✓ 已验证
产品关联
DOI
高影响因子
MINERALS ENGINEERING
·
2020
·
IF 3.795
Li Chen,Hailian Li,Ji Chen,Deqian Li,Tianchi Liu
Incomplete stripping and high acidity consumption were the major drawbacks for the separation of heavy rare earth elements (HREEs) by the popular extractant 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (P507). This article studied di-(2-ethylhexyl) phosphinic acid (P227) from thermodynamics and kinetics theoretical researches to cascade extraction simulations for the separation of HREEs. P227 was capable of complete stripping for HREEs with low acidity, and had high organic REE loading with clear and fast phase separation. Constant interfacial area cell with laminar flow was implemented to reveal the different kinetics mechanisms for the extraction and stripping of Lu 3+ . The multi-stages of cascade extraction simulation designed for the separation between Er 3+ /Tm 3+ could be of great significance for practical application. Corresponding products with high purity at both exits obtained successfully via the simulation. All these will provide the promising industrial applications of P227 with more fundamental data and guidance.
研究领域:
化学工程
·
稀有金属提取
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF RARE EARTHS
·
2022
·
IF 4.632
Junlian Wang,Guodong Xu,Wen Xu,Jianguo Cui,Yufu Chen,Ziyong Chang
The relationship between dialkylphosphinic acid structure and their loading capacity for HREEs and emulsification phenomena has rarely been studied. In this paper, we took Lu extraction as an example to study the effect of β , γ , δ -substituents of dialkylphosphinic acids on their loading capacity and anti-emulsification performance for HREEs. To discuss conveniently, the dialkylphosphinic acids were classified into two groups: β -substituent group (P208, INET-1, P218, USTB-1 and P227) and γ , δ -substituent group (P218, P2132 and Cyanex 272). For β -substituent group extractants, their loading capacities are in the order P208 (299.7 mg/L) ≈ INET-1 (299.5 mg/L) > P218 (270.8 mg/L) >> USTB-1 (163.1 mg/L) > P227 (151.4 mg/L), while their anti-emulsification/gelation performances are just in the opposite order P227 > USTB-1 > P218 > P208 ≈ INET-1 under the studied conditions. For γ , δ -substituent group extractants, their loading capacities are in the order P218 (270.8 mg/L) > P2132 (192.3 mg/L) > Cyanex 272 (131.7 mg/L), while the anti-emulsification performance of P218 is better than those of P2132 and Cyanex 272. The loading capacity data given in the parentheses are obtained through repeatedly extracting Lu from ∼4 × 10 −4 mol/L of Lu aqueous feed solution with initial pH of 2.40 by 0.01 mol/L extractant at phase ratio A/O of 1:1.
研究领域:
化学工程
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF RARE EARTHS
·
2022
·
IF 4.632
Junlian Wang,Wen Xu,Jianguo Cui,Guodong Xu,Yufu Chen,Peilong Wang,Ziyong Chang
Heavy rare earth element (HREE) separation has always been a great challenge. The kind of dialkylphosphinic acids is recognized as the third generation of organophosphorous acid extractants. However, detailed relationship between β -substituent (especially when it changes from H to methyl, and further to ethyl) and their extraction behaviors and selectivity for HREEs have rarely been reported. Besides, there are also few reports on effect of γ , δ -substituent on HREE extraction and separation. In this paper, we synthesized five and collected two dialkylphosphinic acids with different β , γ , δ -substituents (from H to ethyl). These extractants were divided into two groups to discuss their extraction behaviors and selectivity for HREEs: β -substituent group (P208, INET-1, P218, USTB-1 and P227) and γ , δ -substituent group (P218, P2132 and Cyanex 272). To evaluate and compare their extractabilities, P507 was used as a reference and Tm, Yb, Lu were extracted with 0.01 mol/L of these extractants from single Tm, Yb and Lu solutions (∼4 × 10 −4 mol/L) at different initial pH. Besides, pH 0.5 Tm , pH 0.5 Yb and pH 0.5 Lu values and their differences (ΔpH 0.5 Tm–Yb , ΔpH 0.5 Yb–Lu , ΔpH 0.5 Tm–Lu ) for each extractant were given to roughly evaluate their separation performance for Tm, Yb and Lu. To further investigate the selectivity of these extractants for HREEs, Tb, Dy, Ho, Er, Tm, Yb and Lu were extracted from their mixed solution with initial pH of 4.00 at phase ratio A/O of 2:1, 1:1 or 1:2. Their HREE separation performance is mainly discussed based on the adjacent HREE separation factors ( β N+1/N ) and their average value ( β T b − L u ¯ ).
研究领域:
化学
·
材料科学
✓ 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）