Rare Earth Ions Adsorption onto Graphene Oxide Nanosheets

Graphene oxide (GO) was synthesized and used as a coagulant of rare earth elements (REEs) from aqueous solution. Stability and adsorption capacities were exhibited for target REEs such as La(III), Nd(III), Gd(III), and Y(III). The parameters influencing the adsorption capacity of the target species including contact time, pH, initial concentration, and temperature were optimized. The adsorption kinetics and thermodynamics were studied. The method showed quantitative recovery (99%) upon desorption using HNO₃ acid (0.1 M) after a short contact time (15 min).     

白云鄂博稀土共生矿超重力梯级分离稀土元素的工艺研究

我国白云鄂博矿稀土储量居世界首位,其稀土矿物以轻稀土为主,Ce, La, Pr, Nd占稀土氧化物总量的97%以上,具有重要的工业价值。由于四种稀土元素具有极其相似的物化性质,因此在目前的处理工艺中很难实现不同稀土元素的彼此分离。本工作基于稀土精矿的矿相演变及元素迁移规律,在降温熔析过程中不同温度区间内会析出不同稀土相：在1400～1500℃的温度区间只有氧化稀土相析出,随着温度降至1200～1400℃,铁酸稀土相开始析出,当温度降至1100～1200℃时铈磷灰石相析出。利用超重力技术进行氧化稀土相、铁酸稀土相、铈磷灰石相的梯级分离实验,结果表明,98.38%的Ce元素优先以氧化稀土相形式析出并实现分离,97.70%的La元素进入铁酸稀土相作为第二相被分离,而Pr和Nd元素最终以铈磷灰石相的形式分离,以此实现了稀土精矿中Ce, La, Pr, Nd的梯级分离。     

Mechanochemical synthesis of LaCrO3 by grinding constituent oxides

Hydrous amorphous chromium oxide (Cr₂O₃·nH₂O) and crystalline one (Cr₂O₃) powders prepared by heating Cr(OH)₃·nH₂O at different temperatures were separately ground with La₂O₃ powder using a planetary ball mill at room temperature to investigate mechanochemical synthesis of LaCrO₃. Hydrous amorphous chromium oxide prepared reacts with La₂O₃ to form LaCrO₃ and the reaction proceeds with an increase in grinding time. No reaction takes place in the case of crystalline Cr₂O₃. The ground sample consists of agglomerates and large particles with size up to around 100 μm and shows low specific surface area of about 5 m²/g. The mechanochemical method can be also used to synthesize other chromium rare earth complex oxides by grinding the mixture of hydrous chromium oxide and rare earth (Pr, Nd and Sm) oxides.     

Comparative Evaluation of Tri-n-butyl Phosphate (TBP) and Tris(2-ethylhexyl) Phosphate (TEHP) for the Recovery of Uranium from Monazite Leach Solution

Separation of U(VI) from Th(IV) and rare earth elements (REEs) present in monazite leach solution (nitric acid medium) has been studied using tris(2-ethylhexyl) phosphate (TEHP) and tri-n-butyl phosphate (TBP) dissolved in n-paraffin as solvents under varying experimental conditions such as nitric acid, extractant and metal ion concentrations etc. There is an increase in distribution ratio of U(VI) (D _U ) with increase in aqueous phase acidity up to 5 M HNO₃ beyond which a decrease is observed. Typically for 1 × 10^?3 M U(VI), the D_U values increase from 8 (0.5 M HNO₃) to 80 (5 M HNO₃) for 1.1 M TEHP, and from 2 (0.5 M HNO₃) to 43 (5 M HNO₃) for 1.1 M TBP in n-paraffin. The separation factors of U(VI) (β: D_U/D_M) over metal ions (M) such as Th(IV) and Y(III) (chosen as a representative of heavy REEs) are better for TEHP than TBP at all nitric acid concentrations. Batch solvent extraction data have been used to construct the McCabe-Thiele diagrams for the recovery of U(VI) employing TEHP as the extractant. A process flow sheet has been proposed with 0.2 M TEHP in n-paraffin as solvent for the recovery of U(VI) from simulated monazite leach solution in HNO₃ medium.     

Separation of La(III), Eu(III), and Ho(III) with Sorbents Impregnated by Mixtures of Acidic Phosphoryl Podands and Amines in Nitric Acid Solutions

ABSTRACT

The possibility of separation of La(III), Eu(III), and Ho(III) as respective individual representatives of light, medium, and heavy rare earth elements was studied using sorbents impregnated by mixtures of acidic phosphoryl podands derived from diethylene glycol and octyl, dioctyl, and trioctyl amines from nitric acid solutions of various concentrations. The influence of the phosphoryl podands structure, their percentage content, and proportion in a sorbent and the nature of an acid on the efficiency of separation of La(III), Eu(III), Ho(III) was studied. It is shown that the greater is the concentration of HNO₃, the smaller are the separation factors of REEs, and remarkably so. The most efficient separation is achieved with the concentration of HNO₃ not over 0.04 mol/L. The optimal conditions of separation of La(III), Eu(III), and Ho(III) with the developed sorbent were found. Repeated use of the sorbent for the separation of La(III), Eu(III), and Ho(III) after its regeneration with 0.04 mol/L HNO₃ was estimated. It was found that the efficiency of separation of REEs with the sorbents impregnated by a mixture of 1,5-bis(2-oxyethoxyphosphoryl-4-ethylphenoxy)-3-oxapentane and trioctylamine (TOA) exceeds markedly that made of a mixture of di-(2-ethylhexyl)phosphoric acid (DEHPA) and TOA.     

扬州古运河沉积物中稀土元素形态分布特征

采用ICP-MS和BCR连续提取法检测了扬州古运河三湾段沉积物中稀土元素含量和形态分布,并与参考值(中国东部上地壳、江苏省表层A层土壤、黄河沉积物和长江沉积物)稀土元素含量进行对比,研究了稀土元素的富集与亏损状况、不同赋存形态的分布特征及沉积物中稀土元素物质来源。研究结果表明:样品中稀土元素Ce、Pr、Nd、Sm四种稀土元素的含量分别高于四个参考值,其中以Ce的超标较为严重。沉积物中轻稀土元素存在一定的富集现象,异常系数δEu值达1.2。Gd的[(F_1+F_2+F_3)/T)]值均高于其它元素,导致Gd元素由沉积物中向上覆水体迁移能力较强,潜在生态危害性较大。物源指示分析,扬州古运河三湾段沉积物中的稀土元素物质来源与黄河沉积物相似。     

In situ separation and characterization of britholite crystals in RE-bearing slag via supergravity

Bayan Obo ore has abundant rare earth (RE) reserves, and RE elements (REEs) are mainly transferred into the RE-bearing slag. However, the utilization of RE-bearing slag is greatly limited due to the serious lack and ambiguity of RE crystals. In this study, in situ separation of RE crystals from RE-bearing slag via supergravity was developed, and the high-purity crystals of britholite with various REEs contents were selectively separated from the CaO–SiO₂–CaF₂–P₂O₅–Ce₂O₃ system with a high REEs recovery ratio of 95.58%–98.65%. On this basis, the chemical formula, the crystal structure, and the formation mechanism of britholite were characterized from the high-purity crystals through a combination of the Rietveld refinement and DFT calculation. It was found that the britholite was verified to be evolved from Ca₅(PO₄)₃F, there would be an SiO₄⁴⁻ instead of a PO₄³⁻ when a Ce³⁺ replaced a Ca²⁺, the chemical formula changed from Ca₅(PO₄)₃F to Ca_4.377Ce_0.623Si_0.6P_2.4O₁₂F, Ca_3.956Ce_1.044Si_1.01P_1.99O₁₂F, and Ca_3.176Ce_1.824Si_1.93P_1.07O₁₂F with the increase of REEs content, and the substitution range of REEs was between 0 and 2. This study supplements some necessary basic data of RE crystals, which provides the theoretical reference for efficient recovery of RE resources and sustainable utilization of RE-bearing slag.     

Thermodynamics and crystallization kinetics of REEs in CaO–SiO2–Ce2O3 system

Rare earth elements (REEs) have become increasingly important as ceramic materials. The RE-bearing slags contain massive REEs resources, whereas the lack of thermodynamic and kinetic data of REEs has brought great difficulties to efficient recovery of REEs from RE-bearing slags and the application in ceramics. According to the compositions of the RE-bearing slags in industrial production, the isothermal phase equilibria of CaO–SiO₂–Ce₂O₃ system at 1500°C and 1300°C were constructed by means of liquid-quenching method combined with a series of analyses, which provides the thermodynamic data for the equilibria of REEs. On this basis, the crystallization behaviors of the RE phase (Ce_9.33−xCa_x(SiO₄)₆O_2−0.5x) was investigated, and the temperature range in which the RE phase crystallized singly in RE-bearing slags with a selected compositions was acquired. CCT and TTT diagrams for CaO–SiO₂–Ce₂O₃ system were established to characterize the crystallization kinetics of the RE phase, and the favorable conditions for its crystallization and growth in RE-bearing slags were determined. In this study, the complete thermodynamic and kinetic basic data of REEs in CaO–SiO₂–Ce₂O₃ system are provided for RE-bearing slags.     

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 elements leaching from Chadormalu apatite concentrate: Laboratory studies and regression predictions

The extraction of rare earth elements from apatite concentrate of Chadormalu plant of Iran was studied with the dissolution of ore in nitric acid. The parameters of acidity: 60%, solid to liquid ratio: 30%, leaching time: 30 minute, agitation rate: 200 rpm, temperature: 60 °C and particle size (d₈₀): 50 microns were determined as the optimum operational conditions. The recoveries of lanthanum, cerium, neodymium and yttrium were achieved at 74, 59, 72 and 73%, respectively, in the optimized conditions. Multivariable regression was used to predict La, Ce, Nd, Y and total REEs (Y+Nd+Ce+La) leaching recoveries, using experimental data from laboratory studies. It was achieved quite satisfactory correlations of 0.93, 0.98, 0.99, 0.97 and 0.99 for the prediction of Y, Nd, Ce, La and total REEs recoveries, respectively. It was shown that the proposed equations accurately reproduce the effects of operational variables on the different REEs recoveries, and can be used to optimize the REEs leaching plant.     

Rare earth silicate environmental barrier coatings for SiC/SiC composites and Si3N4 ceramics

Rare earth silicates have been investigated to evaluate their potential as an advanced environmental barrier coating (EBC) having higher temperature capability than current EBCs. Volatility data in high steam environments indicate that rare earth monosilicates (RE₂SiO₅; RE: rare earth element) have lower volatility than the current barium strontium aluminum silicate (BSAS) EBC top coat in combustion environments. Rare earth silicates also exhibit superior chemical compatibility compared to BSAS. The superior chemical compatibility and low volatility are key attributes to achieve higher temperature capability. The chemical compatibility is especially critical for EBCs on Si₃N₄ because of the high chemical reactivity of some of the oxide additives in Si₃N₄. In simulated combustion environments, EBCs with a rare earth monosilicate top coat exhibit superior temperature capability and durability compared to the current state-of-the art EBCs with a BSAS top coat.     

The separation of europium from a middle rare earth concentrate by combined chemical reduction,precipitation and solvent-extraction methods

The chemical reduction of pure europium(III) chloride solutions was investigated using reagents comprising reactive metals (Zn and Mg), metal amalgams (Zn-Hg, Na-Hg and Eu-Hg), metal hydride (NaBH₄) and nitrogenous reductants (N₂H₄ and NH₂OH). Using 100% excess of reducing agent and of ammonium sulphate, efficient precipitation of europium(II) sulphate was obtained with the metal amalgams (99·7–99·9%) and with zinc metal (99·8%), whereas only partial precipitation was obtained with magnesium metal (69%), and no precipitation was observed with the other reagents. Application of the method to synthetic rare earth chloride solutions containing europium 7·5, neodymium 5, samarium 35 and gadolinium 20 g dm⁻³ gave efficient precipitation of europium(II) sulphate with zinc and europium amalgams, but no selective precipitation with sodium amalgam. Reduction of an authentic middle rare earth chloride solution with zinc amalgam gave 97·5% recovery of europium(II) sulphate containing (as a percentage of the total rare earths) europium 92, samarium 3·5, neodymium 2, cerium 1, praseodymium 0·6 and gadolinium 0·5%. Conversion of the europium(II) sulphate to europium(II) chloride, followed by re-precipitation of the sulphate increased the europium content only to 96·5%, whereas replacement of the re-precipitation by solvent extraction of the trivalent rare earth impurities into solutions of commercial organophosphorus or carboxylic acids in xylene increased the europium content to > 99·98%. The zinc ions introduced into the middle rare earth mother liquor during the reduction procedure can be removed by solvent extraction into a commercial phosphine oxide (Cyanex 925), without loss of rare earth values.     

Use of a liquid chemical waste to produce a clay–carbon adsorbent

The feasibility of producing an adsorbent from an alkaline aqueous tarry industrial waste has been investigated in this study. The inherent disadvantages of producing a solid carbonaceous material from a waste with its organic content in a dissolved state were overcome by neutralising the waste liquor to pH<2 in the presence of fuller's earth, filtering and producing a solid cake more suitable for thermal treatment. Optimisation of this procedure, followed by ZnCl₂ activation, produced clay–carbon adsorbents with surface areas of up to 225 m² g⁻¹ capable of adsorbing 28% of phenol and 35% of 4-nitrophenol from 10 mM aqueous solution. The potential of this procedure in a beneficial waste reduction and re-use context are highlighted. © 1998 SCI     

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     

Ellipsometric measurements of the barrier layer in composite aluminum oxide films

The composite oxide film (hydrous + anodic) formed on aluminum foil was chemically stripped to remove only the outer hydrous layer. Ellipsometry of the remaining barrier film showed it to be thinner and have a higher refractive index than conventional anodic barrier films grown to the same voltage. Reanodization to improve film stability gave a further increase in refractive index which indicated that the barrier film had contained some voids. The barrier film is almost entirely crystalline γ-Al₂O₃ and the higher field strength compared with conventional amorphous anodic films on aluminum is believed to be a characteristic of the denser oxide.     

Random copolymerization of ϵ-caprolactone and trimethylene carbonate with rare earth catalysts

Random copolymerization of trimethylene carbonate (TMC) with ϵ-caprolactone (CL) catalyzed by rare earth chloride-epoxide or rare earth isopropoxide has been investigated for the first time. It was found that in the presence of epoxide, rare earth chlorides have high activities for the copolymerization, giving high-molecular-weight random copolymer P(CL-co-TMC) with a narrow molecular weight distribution. Light rare earth chloride-propylene oxide systems are more effective for the copolymerization than heavy rare earth chloride-propylene oxide systems. For the rare earth chloride-epoxide catalyst system, epoxide is the requisite component, and its amount affects the catalytic activity; while rare earth isopropoxide can catalyze the copolymerization alone. The preparative conditions of the copolymer with NdCl₃-5PO system were studied. The reactivity ratios of CL and TMC copolymerization with NdCl₃-5PO determined by Fineman-Ross method are 1.60 for r_TMC and 0.72 for r_CL, respectively. The copolymers were characterized by ¹H- and ¹³C-NMR, GPC, and DSC. The mechanism study shows that the rare earth alkoxide is the active species that initiates the ring opening copolymerization of CL and TMC with acyl-oxygen bond cleavages of the monomers. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 2131–2139, 1997     

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.     

Similar but Not the Same: First Kinetic and Structural Analyses of a Methanol Dehydrogenase Containing a Europium Ion in the Active Site

Since the discovery of the biological relevance of rare earth elements (REEs) for numerous different bacteria, questions concerning the advantages of REEs in the active sites of methanol dehydrogenases (MDHs) over calcium(II) and of why bacteria prefer light REEs have been a subject of debate. Here we report the cultivation and purification of the strictly REE‐dependent methanotrophic bacterium Methylacidiphilum fumariolicum SolV with europium(III), as well as structural and kinetic analyses of the first methanol dehydrogenase incorporating Eu in the active site. Crystal structure determination of the Eu‐MDH demonstrated that overall no major structural changes were induced by conversion to this REE. Circular dichroism (CD) measurements were used to determine optimal conditions for kinetic assays, whereas inductively coupled plasma mass spectrometry (ICP‐MS) showed 70 % incorporation of Eu in the enzyme. Our studies explain why bacterial growth of SolV in the presence of Eu³⁺ is significantly slower than in the presence of La³⁺/Ce³⁺/Pr³⁺: Eu‐MDH possesses a decreased catalytic efficiency. Although REEs have similar properties, the differences in ionic radii and coordination numbers across the series significantly impact MDH efficiency.     

Brønsted acid-free controlled polymerization of tetrahydrofuran catalyzed by recyclable rare earth triflates in the presence of epoxides

We report a series of novel, highly efficient, hydrolytically stable and recyclable Lewis acid rare earth triflate catalysts for the living/controlled bulk ring-opening polymerization (ROP) of tetrahydrofuran (THF) in the presence of epoxides. The rare earth triflates [RE(OTf)₃] include that of Sc, Y, La, Nd, Dy and Lu. Epoxides include propylene oxide (PO), cyclohexene oxide (CHO) or styrene oxide (SO). Especially RE(OTf)₃/PO shows high activities, producing PTHF with up to 62 percent conversion and relatively narrow molecular weight distributions (MWDs) (as low as 1.14). Molecular weights (MWs) can be readily controlled from 1.7 to 56.1 kDa by changing monomer to catalyst molar ratios. The Sc(OTf)₃/PO catalyst gives an α,ω-dihydroxyl telechelic PTHF with MWs close to calculated values and MWDs below 1.2. The rare earth catalysts are easily recovered by simple water extractions. For instance, Sc(OTf)₃ can be used at least six times without an obvious decrease of catalytic activity. A polymerization mechanism involving the first two propagation steps of the alkyltetrahydrofuranium cation is proposed to account for the induction periods observed.     

Agitation leaching of rare earth elements from phosphogypsum by weak sulfuric solutions

It has been shown that the processes of the recovering rare earth elements from phosphogypsum using agitation leaching by solutions that contain 2–10 wt % H₂SO₄ have poor economic prospects.