Synergistic extraction of rare earths by mixture of HDEHP and HEH/EHP in sulfuric acid medium

The extraction of RE（Ⅲ） （RE=La, Nd, Sm, Gd） in sulfuric acid medium using the mixture of HDEHP（H2B2） and HEH/EHP（H2L2） was investigated. The synergistic enhancement coefficient（R） was calculated for La （1.96）, Nd（3.52）, Sm（5.96）, and Gd（5.71）, respectively, at pH=2.0, and it was seen that the R increased with the increase of aqueous quilibrium pH. The configuration of the extracted complexes was considered to be RE（SOa）xH2x（HB2）3 with HDEHP, RE（SOa）xH2x（HL2）3 with HEH/EHP, and RE（HB2）2（HL2） with their mixture as the extractant with the slope method. The equilibrium constants and stability constants were calculated. A cation exchange mechanism was proposed as well.     

Solvent extraction and separation of light rare earths from chloride media using HDEHP-P350 system

Solvent extraction is the most important method for rare earth extraction and separation.Currently,di(2-ethylhexyl)phosphoric acid(HDEHP)and 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester(HEH/EHP)are widely used in industrial production,but there are still obvious deficiencies that require further research to resolve.In this paper,the unsaponification extraction of light rare earth ions in a hydrochloric acid medium by di(2-ethylhexyl)phosphoric acid-di(1-methyl-heptyl)methyl phosphonate(HDEHPP350)system was studied.The results show that the addition of P350 reduces the extraction capacity of HDEHP,and also greatly reduces the concentration of acidity required for the back-extraction.It still has a good separation factor for light rare earths without saponification,and the extractant is not easy to emulsify.With an aqueous phase of pH=2.85,and HDEHP mole fraction XHDEHP=0.9(compared with O/A=2),the separation effect of light rare earth is the best,resulting in the separation coefficientβCe/La=3.39,βPr/Ce=1.67 andβNd/Pr=1.45,respectively.The loaded light rare earth ions extracted by HDEHP-P350 can be easily stripped when 2 mol/L HCl is used as the stripping agent.Finally,the extraction mechanism is discussed using a slope method,and the final structure of the extracted complex is determined to be RECl[(DEHP)₂]₂P350_(o),based on a combination of infrared spectra and 1 H NMR and 31P NMR analyses.     

Solvent extraction and separation of light rare earths from chloride media using HDEHP-P350 system

Solvent extraction is the most important method for rare earth extraction and separation.Currently,di(2-ethylhexyl)phosphoric acid(HDEHP)and 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester(HEH/EHP)are widely used in industrial production,but there are still obvious deficiencies that require further research to resolve.In this paper,the unsaponification extraction of light rare earth ions in a hydrochloric acid medium by di(2-ethylhexyl)phosphoric acid-di(1-methyl-heptyl)methyl phosphonate(HDEHPP350)system was studied.The results show that the addition of P350 reduces the extraction capacity of HDEHP,and also greatly reduces the concentration of acidity required for the back-extraction.It still has a good separation factor for light rare earths without saponification,and the extractant is not easy to emulsify.With an aqueous phase of pH=2.85,and HDEHP mole fraction XHDEHP=0.9(compared with O/A=2),the separation effect of light rare earth is the best,resulting in the separation coefficientβCe/La=3.39,βPr/Ce=1.67 andβNd/Pr=1.45,respectively.The loaded light rare earth ions extracted by HDEHP-P350 can be easily stripped when 2 mol/L HCl is used as the stripping agent.Finally,the extraction mechanism is discussed using a slope method,and the final structure of the extracted complex is determined to be RECl[(DEHP)₂]₂P350_(o),based on a combination of infrared spectra and 1 H NMR and 31P NMR analyses.     

Solvent extraction of La（III） with 2-ethylhexyl phosphoric acid-2-ethylhexyl ester （EHEHPA） by membrane dispersion micro-extractor

The conventional rare earth solvent extraction equipments have many problems such as long mixing time, low processing capacity, large factory area occupation, high energy consumption and so on. In order to solve the problems, many types of equipments were brought out. In this work, studies were carried out on the La（III） extraction process with 2-ethylhexyl phosphoric acid-2-ethylhexyl ester （EHEHPA） by membrane dispersion micro-extractor. Equilibrium studies showed that the initial aqueous pH value 4.15 with the saponification rate 40%was the optimal operation condition. The effects of membrane dispersion micro-extractor operational conditions such as dispersion mode, bulk flow rate and organic phase flow rate on the extraction efficiency were studied. The results showed that when the organic solution was the dispersed phase, the extraction efficiency was higher than that of others. Increasing bulk flow ratio could enhance the extraction efficiency greatly. When the ratio of organic phase flow rate to that of aque-ous phase was 80：80, the extraction efficiency was over 95%. The effect of stripping phase acidity on the La（III） recovery was studied. The results showed that when the stripping phase pH was 2.0, organic phase flow rate to stripping phase flow rate was 20：80;the re-covery efficiency of La（III） can reach 82%.     

Study on thorium recovery from bastnaesite treatment process

Thorium (Th) stripping behavior from HEH/EHP (2-(ethylhexyl) phosphoric acid mono-2-ethylhexyl ester) with H2SO4, HCl and HNO3 were investigated. The results indicated that H2SO4 was the most effective stripping reagent compared with HCl and HNO3. Selecting H2SO4 as the stripping reagent, the effect of phase ratio, acidity, H2SO4 amount, HEH/EHP concentration and Th loading in HEH/EHP on Th stripping were systematically investigated. As a result, the optimum stripping conditions of Th(IV) were obtained as the concentration of H2SO4 solution was 3.50 mol/L, phase ratio was 4:1. Low HEH/EHP concentration was benefit for Th stripping. Based on the results, pilot test for new Bastnaesite treatment process was carried out and the recovery of Ce, F and Th were more than 99%, 98% and 95% separately.     

Synergistic extraction of heavy rare earths by mixture of α-aminophosphonic acid HEHAMP and HEHEHP

Synergistic extraction of heavy rare earths(REs) were investigated in chloride media by the mixture of(2-ethylhexylamino)methyl phosphonic acid mono-2-ethylhexyl ester(HEHAMP) and 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester(HEHEHP). The maximum synergistic enhancement coefficients(R) of Lu, Yb, Tm, Er, Y and Ho are 2.89, 2.76, 2.54, 2.14, 2.14 and 2.06, respectively, when the mole fraction X_(HEHAMP) is 0.5. The synergistic separation factors of the heavy REs are obtained(β_(Y/Ho)=1.31,β_(Er/Y)= 1.61,β_(Tm/Er)= 1.78, β_(Yb/Tm)= 1.76, β_(Lu/Yb) = 1.20). The extracted complex is determined to be RE[H(EHAMP)_2][H(EHEHP)_2]_2 by the slope analysis method. The loading capacities of the mixtures consisting of 15% HEHAMP and 15% HEHEHP for Y and Lu are about 26.59 g/L(Yb_2 O_3) and 27.25 g/L(Lu_2 O_3),respectively.     

New Environment-Friendly Approach for Bastnasite Metallurgic Treatment （Ⅰ）： Extraction of Tetravalent Cerium from Sulphuric Acid Medium with Di（2-ethylhexyl） Phosphoric Acid

The extraction of cerium （Ⅳ) from sulphuric acid medium with Di(2-ethylhexyl) phosphoric acid (DEHPA) was studied. The influence of sulphate ion, acidity, extractant concentration as well as the presence of fluoride ion on the extraction of Ce(Ⅳ) was investigated, and the extraction mechanism was also discussed. The results show that sulphate ion can inhibit the extraction of Ce(Ⅳ) significantly due to its complexation with Ce(Ⅳ). Fluoride ion can enhance Ce(Ⅳ) extraction dramatically by the formation of CeF2^2 and less amount of CeF^3 which can almost be extracted completely. Nevertheless, in the case as F/Ce(mole ratio) in the initial aqueous phase is approximately more than 1.5, the precipitate will be formed and the extraction can not be progressed smoothly.     

Thermodynamics and kinetics of lutetium extraction with HEH(EHP) in hydrochloric acid medium

Solvent extraction has been the most widely used technique for rare earths separation. In this study, thermodynamics and kinetics of lutetium extraction with HEH(EHP) in hydrochloric acid medium were investigated. The extraction mechanism and the relevant parameters were determined by experiment research which can guide the practical extraction process. The data indicated that chloride ion had no effect on lutetium extraction, the rate constant increased when stirring speed was enhanced. Effects of temperature, HEH(EHP) concentration, acidity, and chloride concentration were also studied. Thickness of the diffusion film was also calculated to be 4.66×10~(–3) cm at 150 r/min.     

Application of monodispersive anion exchangers in sorption and separation of Y^3＋ from Nd^3＋ and Sm^3＋ complexes with dcta

Rare earth complexes with trans-1,2-diaminocyclohexane-N,N,N ,N -tetraacetic acid （DCTA） of the Ln（dcta） type exhibited an unusual sequence of affinity on the polystyrene anion exchangers： pm^3＋〉Nd^3＋〉Sm^3＋〉Pr^3＋〉Ce^3＋〉Eu^3＋〉Gd^3＋〉La^3＋〉Sc^3＋〉Tb^3＋〉Dy^3＋〉 Ho^3＋〉Y^3＋〉Er^3＋〉Tm^3＋〉Yb3＋〉Lu^3＋[1]. Taking into account the position of Y^3＋, Sm^3＋, and Nd^3＋ in this affinity series, for the monodispersive polystyrene anion exchangers, Lewatit MonoPlus M 500, Lewatit MonoPlus M 600, Lewatit MonoPlus MP 500, Lewatit MonoPlus MP 64, and for the heterodispersive anion exchanger, Lewatit MP 62, the weight （Dg） and bed （Dv） distribution coefficients of these complexes and working ion exchange capacities （Cw） were determined. Based on these values, purifications of Y^3＋ from Nd^3＋ and Y^3＋ from Sm^3＋ in the macro-micro component system on these anion exchangers were studied. The application potential of this method was highlighted for the separation of Y^3＋ in the presence of Nd^3＋ and Sm^3＋. With 1 L of monodispersive and strongly basic polystyrene gel anion exchanger Lewatit MonoPlus M 500 in the acetate form, it is possible to obtain approximately 79 g Y2O3 purified from Nd2O3 and 70 g Y2O3 purified from Sm2O3 in the same process condition.     

Characteristic of synergistic extraction of oxalic acid with system from rare earth metallurgical wastewater

Large amount of high concentration acidic wastewater would be produced in the conversion process of chloride rare earth into oxide rare earth.It was a mixed solution of oxalic acid and hydrochloric acid,so the recycling use was very difficult.The method of liquid-liquid extraction was proposed in this paper to achieve wastewater treatment and reclamation.The mechanism of extraction of oxalic acid from the wastewater with the systems of 50% TOB+45% kerosene and 5% 2-ethyl hexanol was investigated.The composition and structure of the extracted species and the establishment of the mathematical model of the oxalic acid extraction were determined by the use of saturation method,equimolar series method.The results showed that extraction of oxalic acid by TOB was a neutral association extraction,oxalic acid existed mainly in a molecular form in the organic phase,and the extraction combination ratio was 2:1.The duality extraction system composed of extractant TOB and TOC had synergistic extraction effect on oxalic acid and chlorhydric acid,and the extraction dislribution ratio was improved greatly.The optimum volume fiaction of TOB was 0.6-0.8.     

Synergistic extraction of rare earth by mixtures of 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester and di-(2-ethylhexyl) phosphoric acid from sulfuric acid medium?

The extraction of Nd3 and Sm3 , including the extraction and stripping capability as well as the separation effect of Nd3 or Sm3 , from a sulfuric acid medium, by mixtures of di-(2-ethylhexyl) phosphoric acid (HDEHP, H2A2(0)) and 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester (HEH/EHP, H2L2(0)) were studied. The distribution ratios and synergistic coefficients of Nd3 and Sm3 in different acidities were also determined. A synergistic extractive effect was found when HDEHP and HEH/EHP were used as mixed extractants for Sm3 or Nd3 . The chemical compositions of the extracted complex were determined as Nd·(HA2)2·HL2 and Sm·(HA2)2·HL2. The extraction equilibrium constants, enthalpy change, and entropy change of the extraction reaction were also determined.     

Synergistic extraction of cerium from sulfuric acid medium using mixture of 2-ethylhexyl phosphonic acid mono 2-ethylhexyl ester and Di-（2-ethyl hexyl） phosphoric acid as extractant

Synergistic extraction of cerium(IV) from sulfuric acid medium using mixture of 2-ethylhexyl phosphonic acid mono 2-ethylhexyl ester(HEH/EHP, HL) and Di-(2-ethyl hexyl) phosphoric acid (HDEHP, HA) as extractant was investigated. The results indicated that the maximum synergistic enhancement coefficients were obtained at the mole fraction of HEH/EHP=0.6, and cerium(IV) was extracted into organic phase in the form of Ce(SO4)0.5HL2A2. A cation exchange mechanism was proposed for the synergistic extraction of Ce(IV). The equilibrium constants and thermodynamic functions such as △G, △H, and △S were determined in the extraction of Ce(IV) from sulfuric medium using mixture of HEH/EHP and HDEHP.     

P204萃取铒的热力学和动力学研究

用含萃取剂P204的磺化煤油对稀土离子Er~（3+）进行萃取平衡研究,得到了萃取平衡式和平衡常数。用恒界面槽测量稀土离子的萃取速率和反萃速率,考察了Er~（3+）浓度、H~+浓度、P204液度和络合物浓度对反应速率的影响,从而得到了反应速率的表达式。提出了界面反模型,用动力学及界面张力实验进行了验证。     

Solvent extraction of cadmium from sulfate solution with di-(2-ethylhexyl) phosphoric acid diluted in kerosene

In the present paper, solvent extraction process has been used for extraction of cadmium from sulfate solution using di-(2-ethylhexyl) phosphoric acid (D2EHPA) with 1% isodecanol in kerosene diluent expected from industrial effluents or leaching of ores/secondary materials. Different process parameters such as pH, contact time, extractant concentration, O/A ratio etc. were investigated. Results demonstrated that quantitative extraction of cadmium was feasible from 4.45 mM cadmium feed solution in single stage at equilibrium pH 4.5, time 2 min and O/A ratio 1:1 with 0.15 mM D2EHPA. The extraction mechanism of cadmium from sulfate solution by D2EHPA in kerosene could be represented at equilibrium by Cd²⁺ + 3/2 (H₂A₂)_org ⇔ CdA₂(HA)_org + 2H⁺. The loading capacity of 0.15 mM D2EHPA in sulfate solution was determined to be ∼ 8.9 mM cadmium. The loaded cadmium was effectively stripped using 180 g/L sulfuric acid. The metal or salt could be produced by electrolysis or crystallization from the stripped solution.     

Synthesis, characterization and fluorescence of N,N'-BIS (6-metyl-2-pyridine-carboxylamide-N-oxide)-1,2-ethane and corresponding rare earth (Ⅲ) complexes

A new ligand, N,N-BIS (6-metyl-2-pyridinecarboxylamide-N-oxide)-1,2-ethane (L) and six lanthanide(III) complexes (RE=La, Sm, Eu, Tb, Gd, Yb) were synthesized and characterized in detail. The results indicated that the composition of the binary complexes was determined as [REL(H₂O)(NO₃)₂]NO₃·nH₂O (n=0–2), and the Eu³⁺ complex had bright red fluorescence in solid state. Three complexes of Eu³⁺, Tb³⁺, and Gd³⁺ with 6-methylpicolinic acid N-oxide (L') were also synthesized. The relative intensity of sensitized luminescence for Eu³⁺ increased in the following order: L>L'. The phosphorescence spectra of the Gd³⁺ complexes at 77 K were measured. The energies of excited triplet state for the ligands were 20704 cm⁻¹ (L) and 20408 cm⁻¹ (L'). The facts that the ligands sensitized Eu³⁺ strongly and the order of the emission intensity for Eu³⁺ complexes were explained by ΔE(T-⁵D). This meant that the triplet energy level of the ligand was the main factor to influence RE³⁺ luminescence.     

Characterization of Y2O2S： Eu^3＋, Mg^2＋, Ti^4＋ Long-Lasting Phosphor Synthesized by Flux Method

Long-lasting phosphor Y₂O₂S: Eu³⁺, Mg²⁺, Ti⁴⁺ was synthesized by a flux method and their luminescence properties were investigated. The result indicates that the unit cell parameter c is linearly increased with the increase of Eu₂O₃ content in Y₂O₂S: Eu_x³⁺ (0.01 ≤ x ≤ 0.10). On the other hand, the change of unit cell parameter a is not linear dependence. In the Y₂O₂S: Eu³⁺ crystal structure, Eu³⁺ ions only replaced Y³⁺ ions' places in which it posited center position of c axis. With the increase of Eu₂O₃ content, the position of the strongest emission peak changed from 540 nm (⁵D₁→⁷F₂ transition) to 626 nm (⁵D₀→⁷F₂ transition), and the maximum intensity was obtained when x = 0.09 in Y₂O₂S: Eu_x³⁺ (0.01 ≤ x ≤ 0.10). This is due to the environment of trivalent europium in the crystal structure of Y₂O₂S. Doping with Mg²⁺ or Ti⁴⁺ ions alone cannot get the good long-lasting afterglow effect, whereas co-doping with Mg²⁺ and Ti⁴⁺ ions and excited with 365 nm ultraviolet light, a strong thermoluminesence peak appeared, red and orange long-lasting phosphorescence (LLP) was also observed and the phosphorescence lasted nearly 3 h in the light perception of the dark-adapted human eye (0.32 mcd · m⁻²). Thus the LLP mechanism was analyzed.     

Extraction of yttrium in the system Y(NO3)3-HNO3-H2O-Di(2-ethylhexyl) phosphoric acid

The extraction of yttrium from the system YCl₃-Di(2-ethylhexyl) phosphoric acid (D2EHPA) has been reported previously.^1,2 The extraction equilibrium in the system Y(NO₃)₃-HNO₃-H₂O-D2EHPA in Amsco as the solvent was studied as a function of the D2EHPA concentration, acidity and aqueous yttrium concentration, and the results were compared to the choride system. The ratio of the distribution ratios for nitrate and chloride system was found to vary from 0.5 to 7.0. Formerly Post-Doctoral Associate, Chemical Engineering Division, Ames Laboratory, U. S. Atomic Energy Commission, Iowa State University, Ames, Iowa. Formerly Deputy Director, Ames Laboratory, and Professor of Chemical Engineering, Iowa State University.     

The solvent extraction of lead from chloride solutions using di(2-ethylhexyl)phosphoric acid

Lead has been extracted from chloride solutions into kerosene containing excess di(2-ethylhexyl)phosphoric acid, using various concentrations of metal and extractant. Extraction proceeded readily, but the results indicated that 1.6 hydrogen ions were exchanged per atom of lead extracted, rather than 2.0 as would be expected for a divalent metal ion. Extraction was unaffected by metal concentration over the range studied (0.1–1.0 g l^?1), and the results were highly consistent. The unique log D vs. pH relation allowed simple collection of data for contact stage evaluation by rearrangement of the familiar solvent extraction equations and use of empirically derived constants. An S-shaped extraction isotherm resulted, which limits the ease with which aqueous lead concentrations may be reduced by extraction with di(2-ethylhexyl)phosphoric acid.     

Growth and Optical Spectra of Zn：Er：LiNbO3 Crystals Using Bridgman Method

The growth of LiNbO₃ single crystal with Er³⁺ and Zn²⁺ co-doped using Bridgman method and its characteristic absorption spectra and fluorescence spectra were reported. Large-size crystals initially containing Zn²⁺ (3%) and Er³⁺ (0.6%) with good optical quality were obtained using optimized conditions such as a growth rate of 0.8 1.5 mm·h⁻¹ and a temperature gradient of about 30 35 °C · cm⁻¹ across the solid-liquid interface and the sealed platinum crucible. X-ray diffraction and differential thermal analysis (DTA) were used to characterize the crystals. The results indicate that the concentration of Er³⁺ ions in crystals, their absorption intensity, and their fluorescence intensity decrease from the bottom to the top in the crystals. However, for the upper part of the crystal, the up-conversion fluorescence intensity is higher than that of the lower part excited by an 800 or 970 nm pump. The effects of the crystal lattice, their structural defect and their effective segregation of Er³⁺ ions were discussed with respect to the variations of the up-conversion fluorescence intensity.