The adjustable synergistic effects between acid–base coupling bifunctional ionic liquid extractants for rare earth separation

Two of the most widely used industrial extractants for rare earth elements (REEs), that is, di(2‐ethylhexyl)phosphoric acid (HDEHP) and 2‐ethyl(hexyl) phosphonic acid mono‐2‐ethylhexyl ester (HEH[EHP]) were developed into [DEHP]^? type acid–base coupling bifunctionalized ionic liquids (ABC‐BILs) and [EHEHP]^? type ABC‐BILs, respectively. The combinations of ABC‐BIL extractants revealed synergistic effects for REEs. Seven different combinations of ABC‐BILs and five kinds of REEs confirmed the novel synergistic extraction. Some synergy coefficients of the combined ABC‐BILs were bigger than those of mixed HDEHP and HEH[EHP] by two orders of magnitude. The first synergistic extraction produced by ionic liquid extractants in the field of solvent extraction was reported in this article. The novel synergistic extraction from combined ABC‐BILs extractants revealed highly efficient and environmentally friendly potential in both of academic research and industrial application for REEs separation. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3859–3868, 2014     

Synergistic extraction and separation study of rare earth elements from nitrate medium by mixtures of sec‐nonylphenoxy acetic acid and 2,2′‐bipyridyl

BACKGROUND: Synergistic extraction has been proven to enhance extractability and selectivity. Numerous types of synergistic extraction systems have been applied to rare earth elements, among which sec‐nonylphenoxyacetic acid (CA100) has proved to be an excellent synergistic extractant. In this study, the synergistic enhancement of the extraction of holmium(III) from nitrate medium by mixtures of CA100 (H₂A₂) with 2,2′‐bipyridyl (bipy, B) in n‐heptane has been investigated. The extraction of all other lanthanides (except polonium) and yttrium by the mixtures in n‐heptane has also been studied. RESULTS: Mixtures of CA100 and bipy have significant synergistic effects on all rare earth elements, for example holmium(III) is extracted as Ho(NO₃)₂HA₂B with the mixture instead of HoH₂A₅, which is extracted by CA100 alone. The thermodynamic functions, ΔH^o, ΔG^o, and ΔS^o have been calculated as 2.96 kJ mol^?1, ? 6.23 kJ mol^?1, and 31.34 J mol^?1 K^?1, respectively. CONCLUSION: Methods of slope analysis and constant molar ratio have been successfully applied to study the synergistic extraction stoichiometries of holmium(III) by mixtures of CA100 and bipy. Mixtures of these extractants have also shown various synergistic effects with other rare earth elements, making it possible to separate them. Thus CA100 + bipy may be used to separate yttrium from other lanthanides at appropriate ratios of the extractants. Copyright © 2011 Society of Chemical Industry     

Synergistic separation of yttrium ions in lanthanide series from rare earths mixture via hollow fiber supported liquid membrane

Separation of yttrium ions from the mixture of rare earths in lanthanide series has been examined by a microporous hydrophobic hollow fiber supported liquid membrane. Cyanex 272 and TBP in kerosene are used separately as an extractant. Nitric acid solution is used as a stripping solution. Increasing the concentration of Cyanex 272 increases the percentages of extraction and stripping of yttrium from rare earths but slightly percentages are obtained by TBP. Interestingly, when TBP is added with Cyanex 272, the percentages of extraction and stripping increases. This is due to the synergistic effect of the extractants. Moreover, yttrium can be selectively extracted and stripped more than other lanthanide ions because the equilibrium constant decreases with an increase in atomic number or decreases with the ionic radius of the lanthanides. In other words, yttrium is separated selectively due to the smallest ionic radius while other lanthanides are separated with a decrease in ionic radius or an increase in atomic number.     

Recovery of rare earth elements from simulated fluorescent powder using bifunctional ionic liquid extractants (Bif‐ILEs)

BACKGROUND: Numerous high purity ammonium‐type ionic liquid extractants have been prepared for engineering purposes. Bifunctional ionic liquid extractants (Bif‐ILEs) have been widely applied to separate and extract rare earths and metal ions with high extraction efficiencies and selectivities. In the present study, new Bif‐ILEs [A336][P204] and [A336][P507] have been used to extract rare earths from a simulated solution of a fluorescent powder in a high concentration of Al(NO₃)₃. RESULTS: Bif‐ILEs were prepared from Aliquat336 (A336) and the commercial organophosphorus acid extractants, P204 and P507. These extractants [A336][P204] and [A336][P507] have similar characteristics to neutral organophosphorus extractants. When these Bif‐ILEs were used to extract RE(III) from a simulated waste fluorescent powder system a third phase appeared which could be eliminated by the addition of 10% isopropanol modifier. The coexisting Al₂O₃ in the fluorescent powder was changed to a salting‐out agent (Al(NO₃)₃) in the extraction process and promoted the extraction efficiency of RE(III). Using a countercurrent extraction process at a phase ratio V_o:V_w = 4:1 and pH = 0.56, the RE(III) recovery reached 95.2% in 5–7 stages. Finally, the extractabilities of these bifunctional extractants were compared with the neutral organophosphorus extractants P350, TBP and Cyanex923 at different concentrations, initial pHs and temperatures. CONCLUSIONS: By comparison with other neutral organophosphorus extractants, Bif‐ILEs [A336][P204] and [A336][P507] can be considered efficient potential extractants for separating and recycling REEs and Al₂O₃ from waste fluorescent powder. Copyright © 2011 Society of Chemical Industry     

Analysis of the Interaction between Organophosphorus Acid and Tertiary Amine Extractants in the Binary Mixtures by Fourier Transform Infrared Spectroscopy (FT-IR)

In the synergistic solvent extraction of rare earth elements by binary mixtures of organophosphorus acid and tertiary amine extractants, the extraction reaction depends on the nature and strength of the interaction between the two extractants in the mixtures. In order to correlate qualitatively the interaction in different mixtures, the FT-IR spectra for organophosphorus acid (D2EHPA, PC88A, and Cyanex 272) and tertiary amine (Alamine 336 and TEHA) extractants and their mixtures have been analyzed. The primary focus was on investigating the changes in the characteristic functional groups of acidic and amine extractants in the binary mixtures as the strength and concentration of these extractants varied. IR spectroscopy of the organics confirmed the interaction in the binary mixtures, and strength of the interaction increased with the increase in the acidity of acidic extractant and the basicity of the amine extractant.     

Solvent extraction studies of Sm(III) from nitrate medium and separation factors of rare earth elements with mixtures of sec‐octylphenoxyacetic acid and 1,10‐phenthroline

BACKGROUND: Liquid–liquid extraction is widely used for the separation of rare earths, among which synergistic extraction has attracted more and more attention. Numerous types of synergistic extraction systems have been applied to rare earths with high extraction efficiency and selectivities. In the present study, mixtures of sec‐octylphenoxyacetic acid (CA12, H₂A₂) and 1,10‐phenanthroline (phen, B) have been used for the extraction of rare earths from nitrate medium. The stoichiometry of samarium(III) extraction has been studied using the methods of slope analysis and constant molar ratio. The possibility of using synergistic extraction effects to separate rare earths has also been studied. RESULTS: Mixtures of CA12 and phen display synergistic effects in the extraction of rare earth elements giving maximum enhancement coefficients of 5.5 (La); 13.7 (Nd); 15.9 (Sm); 24.5 (Tb); 45.4 (Yb) and 12.3 (Y). Samarium(III) is extracted as SmHA₄B₃ with mixtures of CA12 and phen instead of SmHA₄ when extracted with CA12 alone. The calculated logarithm of the equilibrium constant is 6.0 and the thermodynamic functions, ΔH, ΔG, and ΔS, have been calculated as 4.3 kJ mol^?1, ? 33.7 kJ mol^?1 and 129.7 J mol^?1 K^?1, respectively. CONCLUSION: Mixtures of CA12 and phen exhibit synergistic effects on rare earth elements. Graphical and numerical methods have been successfully used to determine their stoichiometries. The different synergistic effects may provide the possibility of separating yttrium from heavy lanthanoids at an appropriate ratio of CA12 and phen. Copyright © 2010 Society of Chemical Industry     

Rare Earth Metal Extraction by Liquid Surfactant Membranes Containing a Calixarene Carboxylate Derivative: Permeation Acceleration Effect of Sodium Ions

ABSTRACT

Calixarene carboxylate derivatives were used as a mobile carrier for rare earth permeation in a liquid surfactant membrane (LSM) system. The effect of alkali metal ions on the extraction behavior of rare earth metals in both liquid-liquid extraction and LSM systems has been studied. The addition of sodium ions considerably enhanced the extraction ability of rare earth metals in the extraction equilibrium. Furthermore, the presence of alkali metal ions in the material solution affected the rate of rare earth permeation in LSMs. The most accelerative transport of rare earth metals by LSMs was achieved by the addition of sodium ions. This acceleration effect of sodium ions was predominant in a tetracarboxylate calixarene whose cavity size just fits the ionic diameter of sodium ions. The sodium-loaded calix[4]arene derivative showed good performance as an effective mobile carrier for rare earth metals in the presence of sodium ions.     

萃取法在盐湖卤水提硼中的研究进展

硼资源的开发利用对现代工业的发展具有重要作用。硼镁矿作为传统的硼资源,其储量和品位逐渐降低;而盐湖卤水中含有丰富的硼,占我国总储量的30%以上,盐湖硼资源的高效开发是解决我国高度依赖进口的有效途径。采用溶剂萃取法从盐湖卤水中提硼具有选择性好、效率高、成本低等特点,应用前景广阔。溶剂萃取的关键是萃取体系的选择,因此针对不同类型的盐湖,优选萃取性能好、水溶性小的萃取体系成为当前研究的热点。针对目前萃取工艺的应用以及近期研究开发的新型萃取体系,本工作综述了不同体系萃取硼的特点,包括脂肪醇(一元脂肪醇、二元脂肪醇和混合醇)、含羟基的芳香族化合物、含羟基的胺类化合物和离子液体四类萃取体系,重点总结了各类萃取体系萃取硼的机理,并概述了萃取剂结构对萃取性能的影响规律,分析了共存离子对萃取过程的影响,探讨了新型硼萃取剂的研发方向。其中脂肪醇中的一元醇需要在高酸度、强盐析下实现对硼酸的高效萃取。二元醇较一元醇的萃取效率更高,但二元醇黏度大、溶损高、反萃困难,萃取剂循环性能相对较差。混合醇体系能够降低有机相的黏度和水溶性,并且具有一定的协同萃取效应,成本低,适用于工业化应用。其他体系,如含羟基的芳香类和胺类化合物在碱性条件下对硼有较好的萃取效果,但一般价格较高,工业应用较为困难。离子液体由于其不易挥发、化学稳定性好、结构可设计性等优点应用于盐湖卤水萃取提硼,同时可作稀释剂,具有一定的应用前景。分析表明,混合醇作为经济高效的萃取体系在酸性盐湖卤水提硼中更具优势,有望大规模工业化应用。     

疏水性离子液体-中性磷氧萃取剂萃取稀土元素的应用

液液萃取广泛应用于稀土元素的分离回收,为了便于相的分离,通常采用疏水性萃取剂。基于液液萃取的特性,通过微波辅助法合成了疏水性离子液体1-丁基-3-甲基咪唑六氟磷酸盐（[BMIM][PF₆]）。分别探究了[BMIM][PF₆]搭配不同中性磷氧萃取剂对稀土元素中Nd³⁺和Pr³⁺的萃取研究。结果表明1-丁基-3-甲基咪唑六氟磷酸盐-三正辛基氧化磷（[BMIM][PF₆]-TOPO）为最适宜萃取体系。在最适宜萃取体系下,探究了时间、温度、pH值、V（A）/V（O）（水相稀土离子/有机相萃取体系）和萃取组分体积比对萃取效率的影响。结果表明：萃取时间为20 min、温度为25℃、pH值=6.0、V（A）/V（O）=1.0、V_[BMIM][PF6]：V_TOPO=1：1,体系对于Nd³⁺的萃取效果最佳,萃取率可达97.8%;萃取时间为25 min、温度为25℃、pH值=6.0、V（A）/V（O）=1.0、V_[BMIM][PF6]：V_TOPO=1：1,体系对于Pr³⁺的萃取效果最佳,萃取率可达94.2%;萃取过程为放热反应,反应焓变分别为ΔH（Nd³⁺）=-38.43 kJ·mol^-1,ΔH（Pr³⁺）=-28.76 kJ·mol^-1。     

脱芳复合萃取剂的研究进展

复合萃取剂包括传统复合溶剂和新型复合溶剂。前者是有机溶剂与有机溶剂或无机盐的复配,后者则是不同种类的离子液体复配,它们不仅具有对芳烃的溶解性好、选择性高的优点,而且萃取后,萃余油的收率相对较高,已经成为继单一萃取剂用于油品（石脑油、重整汽油和模拟油等）脱芳烃研究之后又一新的研究热点。本文综述了国内外脱芳烃复合萃取剂的研究进展,重点介绍了两类复合萃取剂（萃取剂与醇类、胺类溶剂或无机盐复配和离子液体复配）在油品萃取脱芳烃中的应用;根据复合萃取剂中助萃取剂的种类不同,对用于萃取脱芳烃的复合萃取剂进行了分类总结;介绍了不同种类的萃取剂复配与不同种类的离子液体复配的研究进展;最后指出复合萃取剂在分离芳烃应用中具有选择性高、分配系数高、操作工艺简单有效且成本低廉等优点,是工业上萃取脱芳烃今后的发展趋势。     

Synergistic extraction of rare earths(III) from chloride medium with mixtures of 1‐phenyl‐3‐methyl‐4‐benzoyl‐pyrazalone‐5 and di‐(2‐ethylhexyl)‐2‐ethylhexylphosphonate

The synergistic effect of 1‐phenyl‐3‐methyl‐4‐benzoyl‐pyrazalone‐5 (HPMBP, HA) and di‐(2‐ethylhexyl)‐2‐ethylhexylphosphonate (DEHEHP, B) in the extraction of rare earths (RE) from chloride solutions has been investigated. Under the experimental conditions used, there was no detectable extraction when DEHEHP was used as a single extractant while the amount of RE(III) extracted by HPMBP alone was also low. But mixtures of the two extractants at a certain ratio had very high extractability for all the RE(III). For example, the synergistic enhancement coefficient was calculated to be 9.35 for Y³⁺, and taking Yb³⁺ and Y³⁺ as examples, RE³⁺ is extracted as RE(OH)A₂.B. The stoichiometry, extraction constants and thermodynamic functions such as Gibbs free energy change ΔG (?17.06 kJ mol^?1), enthalpy change ΔH (?35.08 kJ mol^?1) and entropy change ΔS (?60.47 J K^?1 mol^?1) for Y³⁺ at 298 K were determined. The separation factors (SF) for adjacent pairs of rare earths were calculated. Studies show that the binary extraction system not only enhances the extraction efficiency of RE(III) but also improves the selectivity, especially between La(III) and the other rare earth elements. Copyright © 2006 Society of Chemical Industry     

Comparison in the extraction behavior of uranium(VI) from nitric acid medium using CHON based extractants,monoamide, malonamide,and diglycolamide,dissolved in piperidinium ionic liquid

Liquid-liquid extraction of U(VI) from nitric acid medium was carried out using three different class of CHON based molecular extractants namely monoamide, malonamide, and diglycolamide present in 1-butyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide ([C₄mpip][NTf₂]) ionic liquid. The extractants investigated were di-n-hexyloctanamide (DHOA), N,N-dimethyl-N,N-di-octyl-2-(2-hexyloxylethyl)malonamide (DMDOHEMA) and N,N,N’,N’-tetra(ethylhexyl)diglycolamides (T2EHDGA). The extraction behavior of uranium(VI) in ionic liquid medium was investigated as a function of various parameters, such as the duration and temperature of equilibration, aqueous phase concentrations of feed acid, extractant, NaNO₃, and ionic liquid cation, etc. The extraction of U(VI) observed in these systems were compared with each other and the distribution ratios of U(VI) decreased in the order T2EHDGA > DMDOHEMA > DHOA. The slope analysis of the extraction data was carried out to understand the mechanistic aspects of extraction. The extraction of U(VI) observed in [C₄mpip][NTf₂] ionic liquid was also compared with pyrrolidinium ([C₄mpyr][NTf₂]) and imidazolium ([C₄mim][NTf₂]) based ionic liquids under identical experimental condition.     

Rare-earth separation based on the differences of ionic magnetic moment via quasi-liquid strategy

The separation of rare earth elements is particularly difficult due to their similar physicochemical properties. Based on the tiny differences of ionic radius, solvent extraction has been developed as the “mass method” in industry with hundreds of stages, extremely intensive chemical consumption and large capital investments. The differences of the ionic magnetic moment among rare earths are greater than that of ionic radius. Herein, a novel method based on the large ionic magnetic moment differences of rare earth elements was proposed to promote the separation efficiency. Rare earths were firstly dissolved in the ionic liquid, then the ordering degree of them was improved with the Z-bond effect, and finally the magnetic moment differences between paramagnetic and diamagnetic rare earths in quasi-liquid system were enhanced. Taking the separation of Er/Y, Ho/Y and Er/Ho as examples, the results showed that Er(III) and Ho(III) containing ionic liquids had obvious magnetic response, while ionic liquids containing Y(III) had no response. The separation factors of Er/Y and Ho/Y were achieved at 9.0 and 28.82, respectively. Magnetic separation via quasi-liquid system strategy provides a possibility of the novel, green, and efficient method for rare earth separation.     

Synergistic Extraction of Rare Earth Elements from Phosphoric Acid Medium using a Mixture of Surfactant AOT and DEHCNPB

We describe here the formulation of a new synergistic extractant system for the extraction of rare earth elements from aqueous phosphoric acid solution containing large quantities of impurities currently found in urban mines and secondary deposits. This new synergistic system is original in its concept as it contains the association of the bifunctional extractant amido-phosphonate, known for its high efficiency in the recovery of uranium from phosphate rocks, with the(Bis(2-ethylhexyl) sulfosuccinate sodium) (AOT) surfactant molecule known to form reverse micelles in aliphatic diluents. The mixture was found to extract synergistically rare earth elements with high distribution coefficients (D), and exhibits a high separation factor (S.F.) toward iron (III) from phosphoric acid solution. A complete thermodynamic study of its extraction properties is also presented, showing this system has the ability to extract Rare Earth Elements (REEs) from a wide range of phosphoric acid concentrations, which is often the case in industrial processes.     

Synergistic Effects in the Extraction of Uranium(VI) by Di-4-octylphenyl Phosphoric Acid

Abstract

The extraction of uranium(VI) from sulfuric acid solutions by di-4-octylphenyl phosphoric acid (DOPPA) is enhanced by the addition of neutral organophosphorus compounds due to synergistic action. The effect of tri-n-butyl phosphate (TBP), dibutylbutyl phosphonate (DBBP), and tri-n-octyl phosphine oxide (TOPO) was studied. The synergistic effect increased in this order. In the case of TBP and DBBP the extraction coefficient for U(VI) decreased with increasing concentration of synergistic agent after reaching a maximum. With TOPO, on the other hand, there was an increase even after this limit. This was because of the extraction of uranium by TOPO itself. The effect of uranium loading in the organic phase on the synergistic behavior was studied and the results were compared with those obtained with di-2-ethylhexyl phosphoric acid (DEHPA) in the presence of the same synergistic agents. The results with these two extractants indicate that with TOPO the synergism is mainly due to the formation of substitution products of the type UO₂A₂B₂ and with TBP addition products of the type UO₂(HA₂)₂B.     

液膜对不同酸度磷矿浸出液中稀土的提取

用浓盐酸溶解富含镧、铈等稀土离子的织金磷矿,得到含稀土离子的磷矿浸出液,以P204为载体、Span80或T154作表面活性剂、磺化煤油作溶剂、盐酸作内水相解析剂制成的乳状液膜对酸解液中镧、铈等稀土离子进行提取,考察了流动载体浓度、表面活性剂种类及浓度对稀土提取率的影响及磷矿浸出液中不同浓度稀土离子在不同酸度下的分离提取情况. 结果表明,液膜中最佳载体浓度为12%(j),最佳表面活性剂浓度为4%(j),随外水相pH值增大,液膜对稀土离子的提取率提高,外水相稀土离子浓度为100 mg/L,pH=1时,其提取率可达79.93%.     

Extraction of Rare Earth Metals Using Liquid Surfactant Membranes Prepared by a Synthesized Surfactant

Abstract

Three surfactants, l-glutamic acid dioleyl ester ribitol (nonionic, 2C ₁₈Δ⁹ GE), l-glutamic acid dioleyl ester quaternary ammonium chloride (cationic, 2C ₁₈Δ⁹ GEC ₂ QA), and dioleyl dimethyl quaternary ammonium chloride (cationic, 2C ₁₈Δ⁹ QA) were synthesized for potential use in liquid membrane operations. These surfactants have strongly hydrophobic, twin oleyl chains as the hydrophobic moiety. Using the synthesized surfactants, extraction of rare earth metals was carried out by liquid surfactant membranes in a stirred tank. The extraction behavior of 12 kinds of rare earth metals was systematically studied with 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester (commercial name: PC-88A) as a carrier. Different surfactants having an identical hydrophobic moiety can have significantly different behaviors in rare earth extractions by liquid surfactant membranes, where extraction efficiency appears to be governed by the nature of the interfacial microenvironment between oil and water. An interfacial reaction model which takes into account the adsorption of a surfactant at the interface has been proposed to evaluate the permeation rate of rare earth metals by liquid surfactant membranes. It was found that a cationic surfactant strongly enhances the extraction rate of rare earth metals compared with the conventional surfactant, Span 80. The cationic surfactant 2C ₁₈Δ⁹ GEC ₂ QA appears to be one of the best surfactants currently available for rare earth extraction by liquid surfactant membranes.     

盐湖提锂萃取剂及萃取体系研究进展

中国盐湖中蕴藏着丰富的锂资源,溶剂萃取法提锂是目前研究较多且较深入的方法之一。大量研究表明,萃取剂分子的结构是决定萃取效率的关键因素。对近年来盐湖卤水提锂萃取剂及萃取体系的研究进展做了综述,着重综述了醇+酮、有机磷、季胺盐-偶氮离子螯合-缔合、冠醚和离子液体等不同类型萃取剂及萃取体系的研究现状,分析了各类萃取剂在提锂过程中的机理、特点及存在的问题,并在此基础上对溶剂萃取法盐湖提锂萃取剂的发展方向做了展望。     

含氮杂环化合物与有机酸协同体系在镍、钴萃取分离中的应用

近年来开发了多种含氮杂环化合物与有机酸类萃取剂的协同体系,明显提高了镍、钴的萃取性能,同时增强了对杂质元素的分离效果,具有较大的实际应用价值。本工作综述了一些具有代表性的含氮杂环化合物与有机酸类萃取剂组成的协同萃取体系,探讨了萃取体系对镍、钴的协同萃取效果及与常见杂质元素的分离,并讨论了协同萃取体系潜在的工业应用。协同体系对镍、钴的萃取及对杂质元素的分离主要是由酸性萃取剂本身性质和含氮杂环协萃剂的影响共同决定,有机磺酸、羧酸、膦酸等萃取剂与含氮杂环化合物组成的协同萃取体系在萃取镍、钴的过程中对金属杂质元素分离的选择性不同,在镍、钴的提取及生产过程中也展现出不同的应用价值。     

离子液体在稀土萃取分离中的应用

稀土元素萃取分离是获得高纯单一稀土的关键步骤之一,开发对稀土元素具有高效分离能力的新材料和新过程是全球科技工作者研究的热点。离子液体作为一类代表性的新材料,因具有不挥发、不易燃、稳定性好、结构性质可调等独特的物理化学性质,近年来在稀土元素萃取分离领域的应用受到广泛关注。在稀土元素萃取分离过程中,离子液体不仅可用作萃取剂,也可作为稀释剂、协萃剂或同时作为萃取剂和稀释剂。系统评述了离子液体在稀土元素萃取分离中的研究进展,对非功能化离子液体和功能化离子液体在稀土元素萃取分离中的萃取行为和萃取机理进行了分析。同时,对该领域的发展所面临的主要问题和进一步的研究工作进行了探讨。