Extraction kinetics and kinetic separation of La(III), Gd(III), Ho(III) and Lu(III) from chloride medium by HEHEHP

According to the tetrad-effect, 14 elements of lanthanides can be divided into four groups. In our previous study, a new approach was proposed for the kinetic separation of four rare earth ions La(III), Gd(III), Ho(III) and Lu(III) coming from four groups. In that study, four rare-earth ions were kinetically separated from their coexisting mixed aqueous solutions, by performing liquid-column elution using the aqueous solution containing four lanthanide rare-earth ions as the stationary phase and the dispersed organic oil droplets containing HEHEHP (2-ethyl hexyl phosphonic acid mono 2-ethyl hexyl ester) extractant as the mobile phase. The study of extraction kinetics is very important for understanding the kinetic separation of rare earth ions, which was carried out in this paper. The extraction kinetics of La(III), Gd(III), Ho(III) and Lu(III) by HEHEHP diluted in heptane were investigated using single drop method. The different parameters affecting the extraction rate such as column length, specific interfacial area, rare earth ion concentration, extractant concentration, hydrogen ion concentration and temperature were separately studied and the rate equations are deduced. It is first order with respect to rare earth ion and HEHEHP concentrations, and negative first order with respect to hydrogen ion concentrations. The rate constants at 293.15 K are 10^−6.23, 10^−5.73, 10^−5.58 and 10^−5.43, respectively. The experimental results demonstrate that the extraction rate of La(III), Gd(III), Ho(III) or Lu(III) is diffusion-controlled, and the extraction reaction takes place at the interface rather than in the bulk phase. The extraction model was proposed. Besides, the kinetic separation of rare earth ions by HEHEHP oil drops was discussed.     

A novel method for synthesis of styryl phosphonate monoester and its application in La(III) extraction

Herein, styryl phosphonate monoester (SPE) was synthesized and first introduced as rare earth extractant. The solvent extraction of lanthanum (III) from nitrate solution using styryl phosphonate mono-iso-octyl ester (SPE108), di-2-ethylhexyl phosphoric acid (D2EHPA) and 2-ethylhexyl phosphonic acid-mono-2-ethylhexyl ester (EHEHPA) as extractants was investigated. The effects of experimental parameters including equilibrium time, extractant concentration, aqueous pH, phase ratio and salt concentration on the extraction process were studied. The results indicate that the extraction ability and capacity of the extractants follow the order: SPE108 > D2EHPA > EHEHPA. What's more, the extraction process is less affected by ammonium sulfate in the aqueous phase with SPE108. The results of the separation between lanthanum and adjacent lanthanides (Ce, Pr, Nd, Sm) show that SPE108 can separate lanthanides efficiently at low pH. The extraction mechanism of SPE108 is proved to be similar to D2EHPA, and the density functional theory (DFT) calculation results infer that SPE108 exhibits superior extraction ability due to its strong electron-accepting ability.     

Solvent extraction of Ce(III) and Pr(III) with P507 using SiC foam as a static mixer

Extraction reactor is a major research area of interest within the field of rare earths extraction and separation. SiC foam offers excellent material characteristics as well as three-dimensional (3-D) reticulated structure; however, very little research has been carried out on its application in extraction reactor so far. In this work, a static mixer reactor based on SiC foam was designed and demonstrated to extract and separate Ce(III) and Pr(III) from nitric acid media by using 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester (P507) as extractant. The structure–performance relationship between SiC foam and extraction performance was studied by experiment combined with computational fluid dynamics (CFD) simulation. The experiment data are in good agreement with the simulation results. Contrast experiment by using a Kenics mixer was carried out, and SiC foam shows better extraction and mass transfer performance. Using the optimal structural SiC foam (pore size D = 2.3 mm, open porosity ε = 85%, foam length L = 80 mm), high extraction efficiency η (Pr(III): 94.6%, Ce(III): 88.5%) and separation factor β (2.27) between Ce(III) and Pr(III) is achieved at a high total throughput of 200 mL/min. Besides, overall volumetric mass transfer coefficient K_La of Pr(III) and Ce(III) are 0.519 and 0.378 s^?1 at the residence time τ of 3.6 s, respectively, which reach the high level of microchannel reactors and are better than conventional extractors and other static mixers. SiC foam is found to be applicable as a static mixer for efficient and high-throughput extraction and separation of rare earths.     

Preparation of Nd(III) carbonate by precipitation stripping of Nd(III)-loaded VA10

The preparation of fine particles of Nd(III) carbonate from kerosene solution, from which Nd(III) was extracted with versatic acid 10 (VA10) by a precipitation stripping technique using an aqueous NH₃-(NH₄)₂CO₃ solution as stripping medium, was studied. In preliminary experiments, we were unable to recover simple Nd(III) carbonate from Nd(III)-loaded VA10 by CO₂ gas bubbling, when water, (NH₄)₂CO₃, NH₄HCO₃, NaHCO₃, or NA₂CO₃ solution saturated with CO₂ was used as the stripping solution. To obtain simple Nd(III) carbonate, it is necessary to use more than the stoichiometric amount of NH₃ compared to VA10 and about 10 times as much (NH₄)₂CO₃ as Nd(III). The solution mixture of NH₃-(NH₄)₂)CO₃ acts as a pH buffer, an adductor for VA10, and a CO ₃ ²⁻ ion source. Although it was concluded that the precipitates are Nd₂(CO₃)₃·xH₂O (x⊧4), their X-ray pattern does not coincide with that quoted by JCPDS. By heating these precipitates, cubic Nd₂O₃ was obtained at 823 K, while, at 973 K, hexagonal Nd₂O₃ was formed. Since the stripping solution consisting of NH₃-(NH₄)₂CO₃ was highly alkaline, VA10 was also stripped in the aqueous phase. To use a closed-circuit system for the precipitation stripping of Nd(III) carbonate from Nd(III)-loaded VA10, it is important to regenerate VA10 in the organic phase. For this purpose, evaporation of NH₃ by air bubbling was studied. By bubbling air into a stripping solution warmed at 333 K, almost all the VA10 can be transferred to the organic phase.     

Separation of trivalent rare earths from nitrate medium using solvent extraction with a novel extractant 2-ethylhexyl ((2-ethylhexylamino)methyl) phosphonic acid

By introducing the amine group into the structure of P227, a novel extractant 2-ethylhexyl ((2-ethylhexylamino)methyl) phosphonic acid (EEAMPA, abbreviated as HA) was synthesized for the extraction and separation of trivalent rare earths (REs) from nitrate medium. The influence factors including extractant concentration, equilibrium time, HNO₃ concentration, separation factors, cycle regeneration, stripping acidity, and actual leach liquor of metal ions, were studied systematically. The results show that the extraction ability of EEAMPA for REs decreases with increasing acidity. A possible extraction mechanism is proposed and the extracted species as REHA₃(NO₃) are confirmed by the slope analysis method. The extraction equilibrium can reach faster than P227. It shows good chemical stability and cycling regeneration. Stripping studies show that HCl is an excellent stripping agent and REs can be effectively stripped from the organic phase.     

Extraction of rare earth ions from phosphate leach solution using emulsion liquid membrane in concentrated nitric acid medium

It is very significant to recover rare earths (REs) from wet-process phosphoric acid, in terms of extraction rate and selectivity, the current carrier di(2-ethlhexly) phosphate (D2EHPA) out there is still inferior. Based on this question, our team modified D2EHPA to synthesize new extractants. This paper presents a comprehensive study on the extraction of rare earth ions (RE³⁺) from phosphate leach solution using emulsion liquid membrane (ELM) in concentrated nitric acid medium. The ELM system is made up of (RO)₂P(O)OPh-COOH as carrier, polyisocrotyl succinimide (T154) as surfactant, sulfonated kerosene as diluent, phosphoric acid (H₃PO₄) as stripping solution. Different chemical parameters such as type and concentration of carrier, surfactant, stripping solution, volume ratio of oil phase to internal phase, and volume ratio of emulsion ratio to external phase were analyzed. The extraction of RE³⁺ was evaluated by the yield of extraction. In addition, the demulsification process was also investigated. The proposed method of ELM using (RO)₂P(O)OPh-COOH as carrier can be expected to provide an efficient, simplify operation, and facilitated method for extracting RE³⁺.     

Solvent extraction-separation of La(III), Eu(III) and Er(III) ions from aqueous chloride medium using carbamoyl-carboxylic acid extractants

N,N-dibutyldiglycol amic acid(HLI) and N,N-dioctyldiglycol amic acid(HLII) were synthesized and characterized by conventional spectroscopic methods. These molecules were examined as extractants for extraction-separation of La(III), Eu(III) and Er(III), as representative ions of light, middle and heavy rare earths, from aqueous chloride solutions. The analysis of the extraction equilibria revealed that the extracted species of lanthanum and europium ions by both of the extractants had a 1:3 metal to ligand ratio. It was suggested that erbium ions were extracted into the organic phase via the formation of Er(LI or II)2Cl complexes. The effect of the organic diluents on the extraction-separation efficiency of the studied rare earths by HLI and HLII was investigated by comparing the results obtained in dichloromethane and carbon tetrachloride. Regardless to the diluent used, the order of selectivity presented by the investigated extractants was Er(III)Eu(III)La(III). It is noteworthy that, a significant enhancement in separation of the studied rare earths by the extractants was achieved in their competitive extraction experiments with respect to that obtained in single component extraction experiments. Applicability of the extractants for the removal of rare earth ions from spent Ni-MH batteries was tested by removal of La(III), Eu(III) and Er(III) ions from simulated leach solution of such batteries.     

新稀土显色剂偶氮溴膦─DBSN光度性能的研究及其应用

研究了新显色剂偶氮溴膦─ＤＢＳＮ（ＢＰＡ─ＤＢＳＮ）与稀土元素的显色反应。它能在强酸性介质中形成稳定的稀土络合物。显色酸度范围宽,铈、钇络合物的表观摩尔吸光系数分别为１３．２×１０４Ｌ·ｍｏｌ－１及１２．８×１０４Ｌ·ｍｏｌ－１·ｃｍ－１。比尔定律范围分别为０～５５μｇ／２５ｍｌ及０～３５μｇ／２５ｍｌ。大多数常见金属离子的允许量可达毫克级以上。     

Optical and electrical conductivity properties of rare earth elements (Sm,Y, La,Er) co-doped CeO2

In this research, un-doped CeO₂ and Ce_0.85La_0.10M_0.05O₂ (M: Sm, Er, Y) compounds were synthesized by hydrothermal method and the multi-functional properties are reported. Oxygen defects were created with the additives of rare earth ions. The electrical and luminescence behaviors of the synthesized compounds were investigated in accord with the types of additives. The synthesized products were characterized by X-ray diffraction (XRD) analysis, Brunauer–Emmett–Teller (BET) measurement, UV–vis diffuse reflectance spectroscopy (DRS), scanning electron microscopy (SEM), photoluminescence (PL) spectroscopy and electrochemical impedance spectroscopic (EIS). All synthesized compounds are found to be nano-structured and have cubic phase. The total conductivity of all samples was calculated. Hence, the total conductivity of un-doped CeO₂, Ce_0.85La_0.10Y_0.05O₂, Ce_0.85La_0.10Er_0.05O₂ and Ce_0.85La_0.10Sm_0.05O₂ is found to be 2.07 × 10^?10, 5.70 × 10^?4, 1.0 × 10^?3 and 0.0747 S/cm, respectively. Also, bandgap energy (E_g) of these samples calculated from UV visible absorption spectra is discussed, and the optical results show variation between 3.2 and 2.15 eV. Additionally, the luminescence properties of the compounds were investigated and different emissions occur depending on the additive type. Accordingly, photoluminescent emission spectra of Ce_0.85La_0.10Y_0.05O₂, Ce_0.85La_0.10Er_0.05O₂ and Ce_0.85La_0.10Sm_0.05O₂ phosphors indicate that these phosphors have red, green and orange-red colors, respectively.     

电解控制酸度萃取法研究HEH(EHP)从氯化稀土溶液中萃取La(Ⅲ)、Ce(Ⅲ)、Pr(Ⅲ)和Nd(Ⅲ)

首次提出电解控制酸度萃取法,探讨了该法萃取反应机理。并用该法研究了HEH(EHP)从氯化稀土混合溶液中萃取La( )、Ce( )、Pr( )和Nd( )过程中各元素在HEH(EHP)—酸性萃取体系中的分离系数(β)、萃取速率(r)和电流效率(η1)等的变化规律。     

Solvent extraction and separation of light rare earth elements (La,Pr and Nd) in the presence of lactic acid as a complexing agent by Cyanex 272 in kerosene and the effect of citric acid,acetic acid and Titriplex III as auxiliary agents

At present, the use of rare earth elements (REEs) has become an inevitable necessity in many modern industries. In general, liquid extraction is the best commercial method for extracting REEs due to its ability to control high volumes of liquids with electrical load. With the aim of improving a separation technology that would be superior to the existing extraction systems, the extraction behaviors of La(III), Pr(III), and Nd(III) from an HCl medium with Cyanex 272 in the presence of the complexing agent lactic acid (HLac) and auxiliary agents citric acid (H₃Cit), acetic acid (HAc), and Titriplex III have been reported. The effect of pH and lactic acid concentration has been examined. The use of lactic acid as a complexing agent leading to a high extraction of REEs with Cyanex 272 at pH = 5 was compared with systems without lactic acid. The results show that the use of acetic acid along with lactic acid leads to an increase in the extraction percentage of LREEs. While use of citric acid and Titriplex III reduces the extraction percentage of LREEs. Finally, the presence of Titriplex III together with lactic acid could lead to an increase in the separation factor of Pr and Nd.     

Theoretical elucidation of rare earth extraction and separation by diglycolamides from crystal structures and DFT simulations

Diglycolamides(DGAs) show excellent application prospects for the extraction and separation of rare earth metals from highly radioactive liquid wastes and rare earth ores.The extraction ability of DGAs for rare earth ions in nitrate or chloride media increases with increasing atomic number of the rare earth metal.To understand the origin of this phenomenon,three binuclear crystals [Ln(TEDGA)3][Ln(NO_3)_6] of N,N,N',N'-tetraethyldiglycolamide(TEDGA) with rare earth ions La(Ⅲ),Pr(Ⅲ) and Eu(III) were prepared and characterized crystallographically.The three complexes belong to the triclinic crystal system,P-1 space group.The bond lengths of Ln-O_(amide) are significantly shorter than those of Ln-O_(ether) in the same crystal.The Ln-O_(amide) and Ln-O_(enher) bond lengths gradually decrease with increasing atomic number of the rare earth ion.The dihedral angle formed by TEDGA and metal ions through the tridentate coordination gradually increases with increasing metal ion atomic number,tending toward the formation of sizeable planar coordination structures for the most massive rare earth ions.The structures of the compounds formed by the extractant and metal ion were optimized by means of DFT simulations.We find that the interaction between TEDGA and the rare earth ion is dominated by electrostatic interaction by analyzing binding energy,WBIs,Mulliken charge,natural electron configurations,and molecular orbital interaction.The covalent component of the Ln-O bonds of the complexes increases with increasing metal atomic number.The observed increase in extraction and separation capacity of diglycolamides for rare earth ions with increasing atomic number might be due to the formation of two fivemember rings by one tridentate ligand.The rare earth ions with large atomic numbers tend to form planar structures with large dihedral angles with DGA ligands.     

Electrical conductivity of REF_3-LiF(RE=La and Nd) molten salts

The electrical conductivity of REF3-LiF(RE=La and Nd) molten salts(xREF_3=5 mol%-40 mol%) was systematically measured over the temperature range from 1223 to 1423 K by using continuously varying cell constant(CVCC) method.Electrical conductivity values of LaF3-LiF and NdF_3-LiF molten salts within the studied ranges are 4.11-9.39 and 3.62-9.51 S/cm,respectively.The composition and temperature dependences of electrical conductivity and the factor of RE_2 O_3 on electrical conductivity were investigated.The electrical conductivity nonlinearly decreases with the increasing mole percent of REF_3 for the changing of structural ion in molten salts.A good linear relationship between the natural logarithm of electrical conductivity(lnκ) and the reciprocal of the absolute temperature(T~(-1)) can be interpreted by the trend that electrical conductivity linearly increases with increasing temperature.Although it is an important factor of RE_2 O_3 on electrical conductivity,the influence of RE_2 O_3 on conductivity is small for the very limited solubility of RE_2 O_3 in REF_3-LiF molten salts.The results of this work supplement the present electrical conductivity data of rare earth fluoride electrolyte.     

Comparative studies on Y(III) and Dy(III) extraction from hydrochloric and nitric acids by Cyanex 572 as a novel extractant

Extraction of Y(III) and Dy(III) from hydrochloric and nitric acids by Cy-572 in kerosene was studied. The factors affecting the extraction were separately investigated. The stoichiometry of the extracted species was deduced on the basis of slope analysis method. Evaluation of extraction equilibrium and stripping investigation was studied as well as saponification effect of Cy-572. The composition of the extracted metal species in the organic phase was found to be $\overline{{[\text{MA}}_3·{\left(\text{HA}\right)}_3]}$ for Y(III) or Dy(III) in both media. 1.0 mol/L HCl is the best stripping agent for each metal ion from the studied acidic media in one step. Saponified Cy-572 does not exhibit any selectivity towards the extraction of Y(III) or Dy(III) from both HCl and HNO₃ solutions. Based on the obtained results, the data were compared and the separation feasibility between lanthanides and Y(III) in the two media was discussed.     

水热法合成BaNd_xFe_（12－x）O_（19）铁氧体的研究

本文利用水热法合成了六角形磁铅石结构的ＢａＮｄｘＦｅ（１２－ｘ）Ｏ（１９）铁氧体，用Ｘ射线衍射仪、透射电子显微镜和振动样品磁强计等仪器对粉末的结构、形貌和磁学性能进行了研究，并讨论了Ｎｄ（３＋）对钡铁氧体磁学性能的影响。结果表明，Ｎｄ（３＋）可以明显提高ＢａＦｅ（１２）Ｏ（１９）粉末的矫顽力。     

Study on transport of Dy（III） by dispersion supported liquid membrane

The transport of Dy(III) through a dispersion supported liquid membrane (DSLM) consisting of polyvinylidene fluoride membrane (PVDF) as the liquid membrane support and dispersion solution including HCl solution as the stripping solution and 2-ethyl hexyl phosphonic acid-mono-2-ethyl hexyl ester (PC-88A) dissolved in kerosene as the membrane solution, was studied. The effects of pH value, initial concentration of Dy(III) and different ionic strength in the feed phase, volume ratio of membrane solution and stripping solution, concentration of HCl solution, concentration of carrier, different stripping agents in the dispersion phase on transport of Dy(III) were also investigated, respectively. As a result, when the concentration of HCl solution was 4.0 mol/L, concentration of PC-88A was 0.10 mol/L, and volume ratio of membrane solution and stripping solution was 40:20 in the dispersion phase, and pH value was 5.0 in the feed phase, the transport effect of Dy(III) was the best. Ionic strength had no obvious effect on transport of Dy(III). Under the optimum condition studied, when initial concentration of Dy(III) was 0.8 × 10^?4 mol/L, the transport rate of Dy(III) was up to 96.2% during the transport time of 95 min. The kinetic equation was developed in terms of the law of mass diffusion and the theory of interface chemistry. The diffusion coefficient of Dy(III) in the membrane and the thickness of diffusion layer between feed phase and membrane phase were obtained and the values were 1.99 × 10^?7 m²/s and 15.97 μm, respectively. The results were in good agreement with experimental results.     

Evaluation of toxicity profiles of rare earth elements salts (lanthanides)

The presented study aims to extend the knowledge of toxicological profile of rare earth elements salts(REEs).The basal toxicity test performed comprised assessment of cytotoxicity(3 T3 Balb/c Neutral Red Uptake Test)that allows for calculation of LD50(rats)on the basis of the concentration which leads to a50%reduction in cell growth(IC50).Environmental toxicity was addressed by the Tubifex tubifex(T.t.)express test.The in vitro skin irritation(OECD TG 439)and skin corrosion tests(OECD TG 431)utilizing the 3 D in vitro reconstructed human epidermal model EpiDerm(MatTek IVSL,SK)were used for assessment of skin irritation and corrosion potential hazard of REEs.Mutagenic effects were determined using the bacterial reverse mutation assay(Ames Test)on 5 Salmonella typhimurium strains with and without metabolic activation(OECD TG 471).Endocrine disruption was evaluated by means of a yeastbased assay YES/YAS(Xenometrix,CH).Skin sensitization was assessed using the LuSens assay,based on a genetically modified human keratinocyte cell line(OECD TG 442 D).The tested REEs have no potential of mutagenicity or skin sensitization,exhibit very weak endocrine disruption potential and only exceptional local irritation/corrosion effects for thulium(Ⅲ)chloride anhydrous,but have acute and chronic toxic effects on the aquatic environment.     

Research progress of rare earth separation methods and technologies

Strategical elements,such as rare earth elements,play a crucial role in the industry,especially in producing high-tech materials.Major global industries have developed a strong dependence on rare earth materials.Every year,there are innovations in industries such as modern technology,green energy,or communications technology,which need more strategic metals to improve investment profitability.This article reviews advances in rare earth separation methods and techniques to guide and recommend the...     

A novel extractant bis(2-ethylhexyl) ((2-ethylhexylamino)methyl) phosphine oxide for cerium(IV) extraction and separation from sulfate medium

By introducing the amine group into phosphorus extractant, a novel aminophosphine compound bis(2-ethylhexyl) ((2-ethylhexylamino)methyl) phosphine oxide (DEHAPO, abbreviated as A) was synthesized for the extraction of cerium (IV) (Ce(IV)) from sulfate medium (H₂SO₄). The influence factors including extractant concentration, H₂SO₄ concentration and temperature on the Ce(IV) extraction were investigated and discussed. It is found that the extraction ability of Ce(IV), thorium (IV) (Th(IV)) and rare earths (REs(III)) (La, Gd, Yb) decreases in sulphate medium in the following order: Ce(IV) > Th(IV) > REs(III). The extraction process is an exothermic reaction and the thermodynamic parameters were calculated. The extracted complex of Ce(HSO₄)₂SO₄·A in loaded organic solution was identified by the slope methods and further proved by FT-IR spectral analysis. Stripping studies indicate that Ce(IV) can be effectively stripped from the organic phase. The results of separation factors (β) and saturation loading capacity demonstrate that DEHAPO could be used to selectively extract Ce(IV) from sulphate medium with high separation efficiency and good extraction ability.     

Luminescence of halophosphate solid-solution Ca5(PO4)3(F0.8Cl0.2):Eu2+,Mn2+ for WLED

Solid-solution based luminescent materials have been widely explored due to their tunable optical properties in recent years. In this work, instead of more common cation-substitution approach, we investigated the luminescence properties of Eu~(2+) and Mn~(2+) co-doped halophosphate solid solution Ca_5(PO_4)_3(F_(0.8)Cl_(0.2)) via anion substitution synthesized by high temperature solid state reaction method.The formation of the solid solution was confirmed by X-ray diffraction(XRD) characterization, which indicates that the introduction of certain proportion of Cl~-will not make significant change on the Ca_5(PO_4)_3F lattice. We also studied the energy transfer from Eu~(2+) to Mn~(2+) in the host so as to obtain white light emission via adjusting the doping concentrations of Eu~(2+) and Mn~(2+). The white light emission was achieved through combination of Eu~(2+) blue emission and Mn~(2+) red-orange emission with appropriate proportions. The results suggest that Ca_5(PO_4)_3(F_(0.8)Cl_(0.2)):0.01Eu~(2+),0.18 Mn~(2+) could be a potential WLED phosphor working under ultraviolet excitation.