Extraction of rare earth elements from nitrate solution using novel unsymmetrical diglycolamide

A novel unsymmetrical diglycolamide (DGA), namely N,N-dihexyl-N’,N’-didecyldiglycolamide (DHD²DGA), was synthesized for the extraction of Nd(III), Sm(III), Gd(III), Dy(III), Ho(III) and Er(III) in nitric acid solutions. The effects of HNO₃, HCl or H₂SO₄ on the distribution ratio of the investigated metal ions were investigated. A systematic investigation was carried out using DHD²DGA in n-dodecane from nitric acid solutions. The main extracted species of Nd(III), Sm(III), Gd(III), Dy(III), Ho(III) and Er(III) were studied at different nitric acid concentrations by the slope analysis method and the enthalpy change of the extraction reactions was determined. The IR spectra of the extracted species were also investigated. The values of thermodynamic functions for the extraction of the lanthanides were calculated. The obtained results indicated that the effective separation of Ln(III) from Fe(III), Ni(II), Co(II) and Cs(I) can be obtained.     

New Insight into the Americium/Curium Separation by Solvent Extraction using Diglycolamides

The liquid–liquid extraction process called EXAm was developed by the CEA to allow the recovery of Americium alone from a PUREX raffinate. Americium is extracted from a highly acidic feed solution (HNO₃ 4–6 M) by a mixture of two extractants: DMDOHEMA and HDEHP. The Am/Cm selectivity is improved using a specific diglycolamide (TEDGA) as a selective aqueous complexing agent which retains preferentially Cm and heavier lanthanides in the aqueous phase. In this study, the impact of the lipophilicity and steric hindrance of several diglycolamides on the Am/Cm selectivity was investigated in order to understand the enhancement brought by TEDGA. For this purpose, liquid–liquid extraction and partitioning experiments were performed under various conditions.     

Silica-based solvent impregnated adsorbents for separation of rare earth metals

Silica-based solvent impregnated adsorbents are prepared, employing 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester as an extractant. Two kinds of silica particles are used as supports; (i) those whose surface is coated by a styrene/divinylbenzene copolymer and (ii) those whose hydroxyl-terminated pentadimethyl siloxane group is immobilized on the surface. The adsorbent based on silica particles coated by styrene/divinylbenzene can be repeatedly used for adsorption–elution processing, while the adsorption capacity of the adsorbent based on silica particles modified by the siloxane group is decreased by repeated cycles. The adsorbent is applicable to chromatographic operation for Dy/Nd, and quantitative adsorption–elution is achieved.     

Extraction of some Hexavalent Actinide Ions from Nitric Acid Medium using Several Substituted Diglycolamides

Several substituted diglycolamides, namely TPDGA, THDGA, TODGA, and TDDGA, were evaluated in a comparative study on the extraction of hexavalent actinide ions such as UO₂²⁺, NpO₂²⁺, and PuO₂²⁺ from nitric acid medium. The acid extraction constants (K_H) for the diglycolamides were determined to be 3.8 ± 0.6, 1.6 ± 0.1, 4.1 ± 0.4, and 1.4 ± 0.2 for TPDGA, THDGA, TODGA, and TDDGA, respectively. Though metal ion extraction generally increased with increasing the feed acid concentration, the nature of the extracted species changed with aqueous-phase acidity. While complexes of the type MO₂(NO₃)₂·nL (where L is the diglycolamide extractant and n is 1 and 2) were found to be extracted at 1 M HNO₃, the average number of ligand molecules associated with the complex decreased to ?1 when the nitric acid concentration increased to 3 M. These results have great significance from the actinide separation point of view, as the actinides ions can be made virtually inextractable by adjusting their oxidation state. The thermodynamic parameters were also calculated, which indicated spontaneous reactions with large exothermicities.     

Extraction of gold from cyanide or chloride media by Cyanex 923

A new phosphine oxide extractant, commercially known as Cyanex 923, has been studied in order to be applied in the recovery of gold from either cyanide or chloride aqueous media. Au(CN)₂⁻ is extracted by this reagent throughout the whole pH range. The presence of lithium salts in the media improves the extraction. The extraction mechanism proposed can be explained in terms of a solvating reaction, the species formed in the organic phase being the following: Li⁺Au(CN)₂⁻3(R₃PO). The stripping can be performed by low ionic strength solutions such as dilute KCN solutions, and the reaction is enhanced by an increase in temperature. In chloride media, the extractant is able to extract gold (III) in the entire range of acid concentrations. The amount of extraction agent required, to achieve the same level of extraction, in this medium is much lower than in the cyanide media. The temperature has a negative effect on the extraction. Another difference observed between the two media, is that the presence of ionic salts in chloride media has no influence on the extraction, which may be attributed to the fact that the extracted species, HAuCl₄, is a protonated instead of an ionic species. © 1998 SCI     

Economics of rare earth elements in ceramic capacitors

Ceramic capacitors are an indispensable component in electronic circuits, since they are used in various applications such as timing, filtering, and decoupling. These capacitors are doped with REEs that improve their operating life and electrical properties. In this paper, the economics of rare earth elements (REEs) are reviewed in light of their importance in ceramic capacitors. The developing rare earth element supply and demand crisis that can negatively impact the ceramic capacitor industry and, hence, the global economy, is explained. The cause of this crisis and the response of the world are also discussed.     

ICP-MS在稀土元素分析中的应用与作用

稀土元素是指周期表中IIIB族,原子序数21的钪(Sc)、39的钇(Y)和57的镧(La)至71的镥(Lu)共17元素,具有独特的电子构型、特殊的物理、化学性质,使稀土元素在我国工业、国防、医疗、农业等多个不同领域得到广泛应用,稀土元素的分析测试是应用的基础。与其他的分析仪器相比,ICP-MS具有多元素快速分析、精度好、准确度高、低检出限等分析优势,目前,这一技术已在稀土元素分析过程中得到广泛实践应用。     

Magneto-optical properties of rare earth metals substituted Co-Zn spinel nanoferrites

Cobalt–zinc ferrite nanoparticles (NPs) substituted with three different metals, Co_0.5Zn_0.5Re_xFe_2-xO₄ (RE = Ce, Dy, and Y; 0.00?≤?x?≤?0.05) were prepared hydrothermally. Fourier Transform-Infrared (FT-IR) Spectroscopy, X-ray powder diffraction (XRD), Field-Emission Scanning Electron Microscope (FESEM) coupled with energy-dispersive X-ray spectroscopy (EDX) and Vibrating Sample Magnetometry (VSM) analyzed the products. The formation of cubic phase of spinel Co-Zn ferrite NPs were confirmed through XRD, FT-IR and FE-SEM techniques. The structural investigation of NPs by XRD revealed that the lattice parameter "a" decreases with the introduction of the RE in the ferrite structure by the substitution of Fe³⁺ by RE ions. The different magnetic parameters of Co_0.5Zn_0.5Re_xFe_2-xO₄ (RE = Ce, Dy, and Y; 0.00?≤?x?≤?0.05) NPs such as the saturation magnetization, coercivity, remanence, and magnetic moment were calculated and discussed in relation to structure and microstructure properties. M (H) hysteresis curves indicated that the samples exhibit superparamagnetic nature at room temperature. A slight improvement in the magnetization was obtained especially for the Ce- and Y-substituted Co_0.5Zn_0.5Fe₂O₄ (CZF) NPs at a certain RE level. However, the case Dy-substituted CZF products showed a sharp decrease in the magnetization with x?>?0.01. The results are mostly ascribed to the substitution of smaller Fe³⁺ ions with larger RE³⁺ ions.     

稀土改性固体超强酸催化制备生物柴油的研究

以SO42-/ZrO2为母体,引入稀土元素La、Ce对其进行改性,制备出一系列稀土固体超强酸催化剂,用X射线衍射、红外光谱和BET手段表征了催化剂的物化性能。研究了催化剂合成生物柴油的催化性能,系统考察了n(甲醇):n(脂肪酸甘油三酯)、催化剂用量、反应温度、反应时间等因素对生物柴油产率的影响。结果表明:稀土的引入使活性四方相ZrO2更加稳定;催化剂中形成了固体超强酸结构,且改性后酸强度增大,催化剂活性中心数目增加。SO42-/ZrO2-La2O3的催化活性较高,n(甲醇)∶n(脂肪酸甘油三酯)=10∶1、m(催化剂)∶m(原料油)=4∶100、反应温度250℃、反应时间9 h,此时甲酯的产率可达到73.46%。该催化剂活性较高,重复使用3次后生物柴油产率仍在60%之上。     

High temperature phase transition behavior of schorl particles modified with rare earth

In this study, rare earth/schorl composites were prepared using co-precipitation technique with Xinjiang schorl and cerium nitrate as raw materials. The phase transitions and the lattice parameters were investigated simultaneously during the heat treatment process utilizing a high temperature X-ray diffraction. The microstructures of the composites treated at 800, 850, 900 and 950 °C were characterized by scanning electron microscope, transmission electron microscope and high resolution transmission electron microscope. The results clearly indicate that the cerium ions exchanged the interfacial structure of schorl particles, which led to the reduction in phase transition temperature. The interfacial migration and mass transfer were promoted during the phase transformation, rendering a better transformation of mullite crystals from schorl.     

Effects of rare earth elements doping on gas sensing properties of ZnO nanowires

The effects of rare earth elements (Ce, Eu, and Er) doping on the microstructure and gas sensing properties of ZnO nanowires were investigated. The Ce, Eu, Er-doped ZnO nanowires and pristine ZnO nanowires were synthesized via a solvothermal route. The structure of the prepared samples was studied and compared by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron microscopy. The gas sensors were fabricated by coating the prepared samples on aluminum oxides tube-based Au sensing electrode, with Ni-Cr heating wire to control the operating temperature. The operating temperature of all sensors was determined to be 300 °C with consideration of ethanol response. At this temperature, all sensors showed good ethanol sensing performance, with the 1%Ce-doped ZnO nanowires-based sensor exhibited the highest ethanol response over the other sensors. The mechanism for the microstructure and gas sensing behavior difference of various samples was discussed.     

Extraction of protactinium from acid media using Aliquat 336

Solvent extraction studies on protactinium were carried out from hydrofluoric acid, hydrochloric acid, and a mixture of hydrochloric and hydrofluoric acids using Aliquat 336 and ²³¹Pa. The extraction of protactinium from hydrofluoric acid (0.025–10 M) decreased with increasing acid concentration and was less than 10% above 5 M. The extraction from hydrochloric acid (0.5–8 M) started only above 4 M and increased with increasing acid concentration. The extraction of protactinium from a mixture containing hydrochloric acid (0.5–8 M) and 0.03 M hydrofluoric acid decreased with increasing acid concentration reached to a minimum at about 2 M and then increased with increasing acid concentration. At low acidity, extraction of protactinium from hydrofluoric acid was higher compared to hydrochloric acid and the mixture of hydrochloric and hydrofluoric acids. Nitric acid (10 M) and hydrofluoric acid (10 M) were suitable for quantitative recovery of protactinium from organic phase. The extraction of ²³¹Pa from real thorium lean raffinate of thorium–uranium extraction process was studied using optimized extraction conditions.     

The selective adsorption of rare earth elements by modified coal fly ash based SBA-15

Rare earth elements (REE) are strategic resources and the recycling of REE in alternative resources is urgent and gets increasingly attention. However, the separation of REE in these alternative resources is still a challenge due to the low concentration of REE and multi coexisted ions in acidic system. In this study, the species distribution of REE within the pH 0-8.0 was calculated. The SBA-15 originated from coal fly ash was modified by two steps with (3-aminopropyl) triethoxysilane (APTES) and diethylenetriaminepentaacetic dianhydride (DTPADA) to obtain DTPADA-SBA-15 adsorbent, which was applied to the selective adsorption of REE. The results showed that DTPADA-SBA-15 possessed excellent adsorption performance on the selective adsorption of REE, including Eu, Gd, Tb, Nd and Sm, in acidic solution (pH 2) with multi competing ions. The FT-IR and Zeta potential characterization verified that the chemical adsorption through the coordination of O in DTPADA-SBA-15 with REE was dominant at lower pH value. The study of adsorption kinetics indicated that the adsorption of rare earth metal ions followed pseudo-second-order kinetic, of which the adsorption process followed the Langmuir isotherm model.     

Shungite/poly(vinyl alcohol) hybrid hydrogels: An efficient adsorption material for rare earth metals in aqueous media

Rare earth elements play a pivotal role in modern technologies, thereby driving an escalating demand for their procurement. To effectively extract these elements from aqueous solutions, it is imperative to explore innovative sorbent materials. In this context, a hydrogel sorbent material was developed by employing poly(vinyl alcohol) (PVA) and shungite—an economical, naturally occurring, easily processable, and sustainable material. This was achieved through the freezing–thawing method, employing sodium borate as a crosslinking agent. The physicochemical characteristics of the hydrogels were determined through scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), Fourier-transform infrared spectroscopy (FTIR), Brunauer–Emmett–Teller (BET) analysis, Zetasizer analysis, and elemental analysis. The shungite-incorporated PVA hydrogels displayed notable characteristics, including a substantial swelling capacity of 61% and a specific surface area of 32.8 m²/g. Most significantly, these hydrogels exhibited a remarkable affinity for La³⁺ ions, with an uptake ratio of 134 mg/g. This was followed by Nd³⁺, Dy³⁺, and Er³⁺ ions, which displayed uptake ratios of 79, 74, and 73 mg/g, respectively.     

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     

Extraction and separation of molybdenum(VI) from acidic media by fatty hydrazides

BACKGROUND: The increasing demand for molybdenum has encouraged the development of low‐cost and environmentally friendly extractants to recycle and recover this metal. In the present study, solvent extraction of Mo(VI) from acidic media using a mixture of fatty hydrazides synthesised from palm olein as the extractant was carried out. The effects of various parameters such as acid, diluent, contact time, extractant concentration, metal ion concentration and stripping agent and the separation of Mo(VI) from other metal ions such as Co(II), Ni(II), Al(III) and Mn(II) were investigated. RESULTS: It was found that the extraction of Mo(VI) into the organic phase involved the formation of 1:3 complexes. Mo(VI) was successfully separated from commonly associated metal ions such as Ni(II), Co(II), Al(III) and Mn(II). Mo(VI) stripping from the loaded organic phase was studied using different acidic and alkaline solutions and was found to be optimal with ammonium hydroxide solution. CONCLUSION: These results are useful for the development of a method to recover Mo(VI) from acidic media utilising fatty hydrazides as the extractant. Copyright © 2008 Society of Chemical Industry     

Effect of rare earth additives on properties of silicon nitride ceramics

Abstract

Silicon nitride ceramics with rare earth (Re) compound (5 wt-%) and MgO (3 wt-%) additives were fabricated by spark plasma sintering and following heat treatment. The Re compounds included two groups: ReF₃ ((Re?=?La,Nd,Gd) and Re₂O₃ (Re?=?La,Nd,Gd). Specimens show the same tendency in the sintering shrinkage rate, relative density, grain size and bending strength with the increasing Re cation (Re³⁺) radius both in ReF₃ and Re₂O₃ added samples. However, as to aspect ratios and thermal conductivity, the change rules are completely opposite between the two groups of specimens.     

气液液微分散萃取强化低浓度稀土离子富集回收

我国稀土矿产资源分布广泛,种类丰富齐全。但稀土开采过程中的酸沉、浸出等流程会产生大量富含低浓度稀土离子等污染物的废水,该部分废水若排放进入地下水体或河流,会对生态环境和人民的身体健康造成严重的影响。萃取技术在稀土离子分离领域应用广泛,然而传统的萃取技术和设备若在大相比下操作将存在萃取剂耗量大、溶剂夹带损失严重、萃取效率低、易乳化等弊端。气液液微分散技术近年来成为微流控、微化工、微分析等领域的重要研究内容。其应用于萃取过程具有传质速度快、分相时间短的独特优势。本文介绍了气液液微分散萃取技术在低浓度稀土离子富集回收领域的研究进展,具体包括气液液微分散体系的微流控制备方法和调控规律、多相微分散体系的流型、气液液微分散萃取技术在低浓度稀土离子萃取回收领域的应用及其过程放大研究。已有的研究结果表明气液液微分散萃取技术在低浓度稀土离子富集回收领域展现出了独特的优势,有望解决稀土浸矿尾液处理的难题。本文主要针对以上几个方面的研究进展进行综述,并对其未来的发展方向进行了展望。     

Extraction of rare earth metals with a multistage mixer-settler extraction column

Extraction behavior of rare earth metals within a mixer-settler extraction column has been analyzed with the stage efficiency calculated from mass transfer coefficients and interfacial area. The mass transfer coefficient within the dispersed drops is determined from a rigid sphere model by taking into account the residence time distribution of drops, and the coefficient around the drops is calculated by Ranz-Marshall's correlation with the terminal settling velocity of a rigid sphere. The interfacial area of dispersed drops is calculated by the use of correlations for the drop diameter and the holdup of dispersed phase in the mixer-settler extraction column. The calculated results for the separation of samarium and gadolinium with a five-stage mixer-settler extraction column are compared with the experimental results at various agitation speeds and flow ratios between two phases. The extraction behavior in the multistage column is explained by a model based on the hydrodynamics and the mass transfer within the mixer. Effects of the pH value in aqueous phase, the extractant concentration in organic phase and the number of stages on the extraction behavior in the mixer-settler column are also shown.     

Competitive foam separation of rare earth elements from aqueous solutions using a cationic collector

ABSTRACT

Competitive foam separation of two rare earth elements (REEs), Eu(III) and Tb(III), are investigated in this study in presence of ethylenediaminetetraacetic acid (edta) using cetylpyridinium chloride (CPC). The effects of pH, [edta]/Σ[REEs] and [CPC]/[edta] molar ratio, frother concentration, ionic strength and air-flow rate on the foam separation efficiency are also evaluated. At the optimal experimental condition, Eu(III)/Tb(III) separation factor of 141.56 is obtained. The kinetic data obtained at all the studied parameters are analyzed by the flotation first-order and second-order kinetic models. Eventually, a schematic flow-sheet for Eu(III)/Tb(III) separation is proposed.