Separation and recovery of rare earth from waste nickel-metal hydride batteries by phosphate based extraction-precipitation

A novel type of extraction-precipitation strategy based on phosphate was developed to recover rare earth (RE, i.e., La, Ce, Nd, and Pr) from waste nickel-metal hydride (NiMH) batteries. This method does not require saponification and organic solvents. The novel phosphates, i.e., dibenzyl phosphate (DBP), diphenyl phosphate (DPP), triphenyl phosphate (TPP) were studied as extraction-precipitants. DBP has high precipitation efficiencies for RE³⁺, which can reach 97.84%, 100%, 100% and 99.77%, respectively. In addition, the precipitation efficiencies of Mn²⁺, Co²⁺ and Ni²⁺ are less than 1.75%. DBP-RE has the largest particle size (D10 = 52.6 μm, D50 = 135.35 μm, D90 = 296.08 μm), which is much larger than the precipitations formed by NH₄HCO₃, H₂C₂O₄, CaO and MgO. The larger precipitation particle sizes contribute to improving the solid-liquid separation efficiency. With 3 mol/L hydrochloric acid, the stripping efficiency of DBP-RE reaches 98.60%, and the purity of recovered RE is 99.85%. The regenerated DBP can be directly used for the recycling extraction. Therefore, the novel extraction-precipitation strategy is a green and sustainable separation method.     

有机次膦酸在硝酸体系下提取稀土研究

本文采用溶剂萃取法,用有机次磷酸萃取剂从富含稀土元素镧(La）、钕(Nd）、钇(Y)、铈(Ce）的硝酸溶液中提取稀土。选择盐酸为反萃剂。考察了酸度、萃取剂浓度、相比和萃取时间对萃取率和反萃率的影响,结果表明,二异丁基膦酸萃取稀土的最佳条件为：室温,酸度0.2mol/l,萃取剂浓度40%,A/O比1:5,萃取时间15min,镧（La）、钕（Nd）,铈（Ce）和钇（Y）分别为41.68%、81.30%、81.29%和100%。当利用盐酸作为反萃实验的反萃剂时其最佳条件为：室温,初始水相稀土溶液为0.3 mol/L,反萃剂盐酸为6 mol/L,负载有机相与反萃剂盐酸溶液的体积比为1:6,将反萃的震荡时间改变为5min,应用上述条件的镧(La）、钕(Nd）、铈(Ce）、钇(Y)的反萃率分别为92.45%、94.88%、95.76%、93.34%。有机次膦酸对稀土元素（La）、钕（Nd）、铈（Ce）和钇（Y）的萃取效率不同。钇的提取率高于镧、钕和铈。它是一种有机次膦酸,对轻稀土元素亲和力低,对重稀土元素亲和力强。     

Recovery of rare earths from spent FCC catalysts by solvent extraction using saponified 2-ethylhexyl phosphoric acid-2-ethylhexyl ester(EHEHPA)

A process to recover rare earth(RE) metals from spent fluid catalytic cracking(FCC) catalysts by solvent extraction was studied, using saponified 2-ethylhexyl phosphoric acid-2-ethylhexyl ester(EHEHPA or P507). The recovery process involved three steps:(1) leaching REs(mainly lanthanum and cerium);(2) solvent extraction by applying saponified P507-kerosene system;(3) stripping. Experiments to assure optimal operating conditions were conducted. Results indicated that RE metals could be recovered effectively from spent catalyst with saponified P507-kerosene-HCl system. At room temperature of 25 oC, 10 g spent catalyst with 110 m L of HCl(1 mol/L) could achieve a leaching efficiency of 85%. For extraction, initial pH value of 3.17, organic/aqueous ratio(O/A ratio) of 2:1 with an extractants' saponification rate of 20% could obtain 100% efficiency. In the stripping process, 1 mol/L HCl with O/A ratio of 1:1 led to a stripping efficiency of 96%. In the present study, RE metals from spent FCC catalysts were effectively recovered, which avoided wasting a large amount of RE resources. It provides a theoretical support for commercial recycling of RE resources.     

Separation of aluminum from rare earth by solvent extraction with4-octyloxybenzoic acid

Leaching method is usually used to extract rare earth(RE) elements from ion adsorbed RE ores.In the leaching process,some impurities such as aluminum(Al) enter the leaching solution.The separation of Al from RE by carboxylic acid extractant 4-octyloxybenzoic acid(POOA) was studied in this article.By changing the pH value,temperature,solvent,saponification degree and other parameters,the extraction and separation performance of POOA in chloride system was systematically studied.Through specific e...     

用草酸溶液从负载钕的P204和P507有机相中直接反萃取沉淀钕的研究

介绍了用草酸溶液从负载钕的P204和P507有机相中直接反萃取沉淀钕的台架和半工业试验结果.用0.32～0.4 mol/L的草酸溶液从钕浓度为0.053 3～0.11 3 5 mol/L的有机相中直接反萃取沉淀钕,控制沉淀母液中剩余草酸浓度为0.2 mol/L,返回使用80%的母液.在接触时间10～40 min范围内,获得的Nd2O3纯度>99.88%,氯质量分数为1.0×10-2%,非稀土杂质含量符合99.9% Nd2O3产品质量要求.自行研制的三相反萃取槽结构合理,运行稳定,适应性强,级效率大于95%,运行过程中,倾斜板上无固体沉积,槽体内无固体结疤.     

萃取法提取铬(Ⅲ)分离铁(Ⅱ)的研究

采用皂化的P204+磺化煤油体系共萃铬、铁,选择性反萃分离铬、铁工艺,从电镀污泥硫酸浸出液中回收富集铬.考察皂化率、P204浓度、料液初始pH值、萃取时间、温度、相比等因素对于萃取效果的影响,考察反萃剂组成、浓度、相比等因素对反萃效果的影响.结果表明:P204皂化率及浓度是影响铬的萃取率重要因素.在萃取有机相组成为30 %P204+70 %磺化煤油,皂化率为70 %,料液pH=2.42,V_O/V_A=1/1,萃取温度28 ℃,振荡时间5 min条件下,经6级逆流萃取达到平衡之后,出口水相铬浓度为0.9 mg/L左右,铬萃取率为99.99 %.采用2段反萃工序有效的分离铬铁:采用2 mol/L硫酸反萃,相比V_O/V_A=5/1,温度32 ℃,振荡时间5 min,经过3级逆流反萃,铬反萃率为97.5 %,铬浓度富集到29.5 g/L,铁浓度为10 mg/L;反萃铬后负载有机相再用氢氧化钠溶液反萃铁.      

High-efficiency simultaneous extraction of rare earth elements and iron from NdFeB waste by oxalic acid leaching

Iron can not be recovered at high value because only rare earth elements are effectively recovered from NdFeB waste via oxidation roasting-hydrochloric acid leaching process.In this study,a new method for leaching NdFeB waste with oxalic acid was developed.The high-efficiency,simultaneous and high-value recovery of rare earth elements and iron was realized to simplify the process and improve the economic benefit.Results of the oxalic acid leaching experiments show that under the optimum leaching conditions at 90℃ for 6 h in the aqueous solution of oxalic acid(2 mol/L) with a liquid-solid ratio of60 mL/g,the iron leaching efficiency and precipitation rate of rare earth oxalate reach 93.89% and 93.17%,respectively.Rare earth oxalate and Fe(C₂O₄)3^3- were left in the residue and the leaching solution,respectively.The leaching mechanism was further analyzed by characterising the leach residues obtained through X-ray powder diffraction(XRD) and scanning electron microscopy-energy dispersive X-ray spectroscopy(SEM-EDS).Results of the leaching kinetics study indicate that the process of oxalic acid leaching follows the shrinking nucleus model,and the leaching kinetics model is controlled by the mixed factors of diffusion and chemical reaction.The leaching residue was calcined at 850℃ for 3 h and then decomposed into rare earth oxide,which can be directly used to prepare rare earth alloy via molten salt electrolysis.For the leaching solution,ferric oxalate solution was reduced using Fe powder to prepare the ferrous oxalate(FeC₂O₄-2H₂O).     

Preparation,luminescence and photofunctional performances of a hybrid layered gadolinium-europium hydroxide

The design and fabrication of rare earth ions incorporated into the inorganic/organic hybrid materials have attracted growing attention for seeking improved optical properties and photofunctional performances.In this paper,a novel hybrid composite based on the layered rare earth hydroxides was successfully prepared by the ion-exchange and intercalation chemical process.The rare earth elements in the composite contain gadolinium(Gd) and europium(Eu) and the molar ratio of Gd to Eu is kept constan...     

Behavior of phase transformation of Baotou mixed rare earth concentrate during oxidation roasting

Based on the new process named “Combination Method” for metallurgy and separation of Baotou mixed rare earth concentrate (BMREC), the aim of this paper is to clearly elucidate the phase change behavior of BMREC without additives during oxidative roasting at 450–800 °C. The results indicate that the bastnaesite in BMREC is decomposed at 450–550 °C, the weight loss is about 10.3 wt%, and the activation energy (E) is 144 kJ/mol. The bastnaesite in BMREC is decomposed into rare earth fluoride, rare earth oxides (La₂O₃, Ce₇O₁₂, Pr₆O₁₁ and Nd₂O₃), and CO₂, particularly, with the increase of roasting temperature, bastnaesite in BMREC is more completely decomposed into LaF₃, which causes a decrease in leaching rate of La during the HCl leaching process. Additionally, the maximum cerium oxidation efficiency reaches about 60 wt% when the roasting temperature is equal to or above 500 °C, and the oxidation reaction rate of cerium increases with the increasing roasting temperature.     

Coordination-reduction leaching process of ion-adsorption type rare earth ore with ascorbic acid

The magnesium sulfate(MgSO₄)-ascorbic acid(Vc) compound leaching technique can extract rare earth elements(REEs) existing in ion-exchangeable phase and colloidal phase from ion-adso rption type rare earth ore through the synergy effect of coordination and reduction,but its reaction process and mechanism remain unclear.In this paper,the coordination-reduction leaching mechanism was analyzed from the perspectives of leaching thermodynamics and kinetics,which provide theoretical guidance...     

稀土和铝在皂化氯代环烷酸体系中分配比及分离系数的研究

分别对萃取剂皂化值为0.35mol/L、0.40mol/L,不同料液酸度、铝浓度条件下氯化稀土溶液在皂化氯代环烷酸萃取体系中的稀土和铝分配比及分离系数进行研究,表明当料液中含有中、高浓度铝时,皂化值为0.35mol/L氯化环烷酸体系可以在较高酸度的条件下获得铝和稀土相对更高的分离系数及更好的分离效果.实际生产中可通过提高料液酸度实现铝和稀土的有效分离,同时抑制其它非稀土杂质的萃取,更有利于降低产品中杂质的含量.     

Extraction and separation of yttrium from other rare earths in chloride medium by phosphorylcarboxylic acids

Two phosphorylcarboxylic acids, 3-((bis(2-ethylhexyloxy))phosphoryl)propanoic acid (PPA) and 3-((bis(2-ethylhexyloxy))phosphoryl)-3-phenylpropanoic acid (PPPA), were synthesized for separating yttrium from other rare earths in the chloride feed of ion-adsorption type rare earth concentrate. The effect of the factors such as pH_1/2, temperature, saponification degree and phase modifiers was investigated. The separation efficiencies of PPA and PPPA are obviously better than the typical extractants such as sec-octylphenoxy acetic acid (CA-12) and naphthenic acid (NA). The extraction process of rare earths by PPA and PPPA is a cation exchanging reaction, which is similar to those of CA-12 and NA. The loaded rare earths in both PPA and PPPA systems can be effectively back-extracted by 0.5 mol/L HCl or higher concentration. A cascade extraction process for separating yttrium from other rare earths was developed using PPPA as the extractant. The yttrium product with the purity of 97.20 wt% was obtained by 35 stages of extraction and 12 stages of scrubbing.     

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.     

Extraction mechanism and separation behaviors of low-concentration Nd3+ and Al3+ in P507–H2SO4 system

In order to clarify the solvent extraction and separation behaviors of rare earths and impurity of Al during the extraction and enrichment of low-concentration leach solution of ion-adsorption rare earth ore, the extraction mechanism and separation behaviors of Nd³⁺ and Al³⁺ in the Nd₂(SO₄)₃–Al₂(SO₄)₃ mixed solution using P507 were studied in this work. The extraction of Nd³⁺ and Al³⁺ follows the cation exchange mechanism. With the increase of the equilibrium pH, β_Nd/Al in the extraction of the Nd₂(SO₄)₃–Al₂(SO₄)₃ mixed solution using P507 is always higher than that in the extraction of single Nd₂(SO₄)₃ and Al₂(SO₄)₃ solutions. It can be attributed to the fact that the extraction of Nd³⁺ using P507 is much faster than that of Al³⁺, and Al³⁺ is more prone to be hydrolyzed at lower pH. β_Nd/Al in the extraction of the Nd₂(SO₄)₃–Al₂(SO₄)₃ mixed solution decreases gradually with the increase of mixing time within the equilibrium pH range of 1.5–1.9. The extraction of Nd³⁺ using P507 is much faster than that of Al³⁺, but the stability of Al³⁺-loaded organic phase is better than that of Nd³⁺-loaded organic phase, thus Nd³⁺ in the Nd³⁺-loaded organic phase is gradually replaced by Al³⁺ in the aqueous phase with the increase of mixing time.     

Evaluating organic acids as alternative leaching reagents for rare earth elements recovery from NdFeB magnets

This study proposes an advanced leaching method using organic acids to recover rare earth elements (REEs) from NdFeB permanent magnets from end-of-life computers hard disk drives (HDDs). The end-of-life HDDs were first dismantled in order to recover NdFeB magnets, which were then thermally demagnetized at 350 °C during 30 min before crushing in a ball mill under inert atmosphere. Scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDS) analyses performed on the NdFeB magnets show the heterogeneous structure containing the major matric phase Nd₂Fe₁₄B and the REEs-rich phase containing Nd and Pr oxides. Additionally, X-ray diffraction (XRD) and Mössbauer spectroscopy (MS) analyses on the ground NdFeB magnet show that grinding NdFeB magnets under inert atmosphere helps to minimize its oxidation. Chemical analysis shows that the composition of the ground sample is Nd: 22.8 wt%, Pr: 3.3 wt%, Dy: 1.2 wt%, Fe: 62.6 wt%, Co: 1.5 wt%, B: 0.9 wt%, Ni: 0.6 wt%. Diagrams of speciation and equilibrium phases (E_h vs. pH) were calculated to determine the predominance of the formed species in the REEs–organic acids systems. The influence of the organic acid type (acetic acid, formic acid, citric acid and tartaric acid), the acid concentration (10 vol%, up to saturation), and the solid/liquid (S/L) ratio (0.5%–10%) on NdFeB magnets leaching was investigated employing an optimal experimental design conceived by the statistical software JMP. Acetic acid (CH₃COOH) shows the highest leaching performance of REEs, allowing leaching yields over 90% for Nd, Dy and Pr in the acid concentration range of 1.6–10 mol/L and the S/L ratio range of 0.5%–5% at a temperature of 60 °C. The results presented in this investigation suggest that REEs can be recovered from magnets of end-of-life HDDs using an eco-friendly method assisted by organic acids.     

Recycling rare earth from ultrafine NdFeB waste by capturing fluorine ions in wastewater and preparing them into nano-scale neodynium oxyfluoride

Ultrafine NdFeB waste is a relatively clean waste produced during NdFeB magnet processing. Fluorine-containing wastewater is a common type of industrial wastewater, such as stainless steel pickling wastewater. In this work, rare earth element neodynium was recycled from ultrafine NdFeB waste by capturing fluorine ions in the fluorine-containing wastewater and prepared into neodynium oxyfluoride. The reaction process was investigated through UV-Vis-NIR, thermogravimetry/differential thermogravimetry (TG/DTG), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The neodymium hydroxide in the ultrafine NdFeB waste reacted with fluorine ions to form Nd(OH)₂F, and Nd(OH)₂F was then transformed into neodymium oxyfluoride after decomposition. The formed neodymium oxyfluoride is found to be particles with rhombohedral structure and a particle size of around 50 nm. The reaction kinetics of forming Nd(OH)₂F was investigated. The reaction kinetic equation was established and the reaction activation energy was calculated. The effect of fluorine ion concentration on the reaction rate and products was evaluated. The results show that the reaction rate increases with the increase of fluorine ion concentration in the range of 0.01–1.5 mol/L, but it has little effect. In addition, the fluorine ion concentration affects the crystallinity of formed neodymium oxyfluoride. The recycling process not only realizes the sustainable utilization of rare earths, but also reduces the concentration of fluorine ions in the fluorine-containing wastewater, achieving two goals with one stone.     

环烷酸体系萃取分离稀土和铝的实验研究

在不改变料液酸度的条件下,研究了不同皂化值、相比和萃取级数对稀土和铝在环烷酸体系中的分配比和分离系数的影响.实验结果表明,环烷酸萃取体系分离稀土和铝的较优工艺参数为：皂化值0.25 mol/L、相比O/A=1.5,在此条件下,分配比DAl=4.035,DRE=0.111,分离系数βAl/RE=36.35,此外,随着萃取级数的增加,除铝率也会增加,当萃取级数大于2时,除铝率可达95%以上.     

Effects of iron and temperature on solubility of light rare earth sulfates in multicomponent system of Fe2(SO4)3-H3PO4-H2SO4 synthetic solution

Numerous light rare earth elements (LREE) minerals containing Fe and P were processed by sulfuric acid roasting method, and the leaching solution mainly comprises LREE sulfate, Fe₂(SO₄)₃, H₃PO₄, and H₂SO₄, however, the solubility data of LREE sulfates in this system is few. This work studies the solubility of LREE sulfates in independent LREE sulfate system RE₂(SO₄)₃-Fe₂(SO₄)₃-H₃PO₄-H₂SO₄ (RE = La, Ce, Pr or Nd) and mixed LREE sulfates system (La,Ce,Pr,Nd)₂(SO₄)₃-Fe₂(SO₄)₃-H₃PO₄-H₂SO₄ at different temperature (25–65 °C) and concentrations of Fe₂(SO₄)₃ (Fe₂O₃, 0–50.13 g/L), H₂SO₄ (0.5 mol/L), and H₃PO₄ (P₂O₅, 20.34 g/L) based on the industrial operating condition at low liquid and solid ratio 2:1. The solubility of each LREE sulfate in the independent system (La₂O₃, 12.25–20.88 g/L; CeO₂, 41.93–62.35 g/L; Pr₆O₁₁, 37.34–56.69 g/L; Nd₂O₃, 26.60–37.63 g/L) is much higher than that of the mixed system (La₂O₃, 6.95–11.03 g/L; CeO₂, 10.63–21.51 g/L; Pr₆O₁₁, 11.56–20.36 g/L; Nd₂O₃, 12.36–19.79 g/L) under the same other conditions. The results also indicate that, in the two systems, both Fe and the temperature have negative effects on the solubility of LREE sulfates. That may occur due to the complication reactions between the complexes of RESO₄⁺ and Fe(SO₄)₂^–. However, the influence degree of temperature and iron concentration on the LREE sulfates solubility varies in the two systems and among different LREE species. This research is of theoretical significance for optimizing the conditions of the sulfuric acid process for recovering the LREE from the mixed LREE bearing minerals as well as the single LREE containing secondary rare earth scraps.     

Energy transfer process of Nd3+/Ho3+ co-doped fluoride halide glasses with anion substituted multi-wavelength tunable mid-infrared luminescence

Ho³⁺ doped ZBLAN glass with 2.0 and 2.9 μm emission was prepared. In order to further improve the luminescence of Ho³⁺, halogen ions (Cl, Br, I) were introduced to reduce the maximum phonon energy and phonon state density of the sample. At the same time, Nd³⁺ was introduced to transfer the energy to Ho³⁺ pumped with a 793 nm laser (Nd³⁺:⁴F_5/2,⁴F_3/2→Ho³⁺:⁵I₆). The effect of different halogen ion on the luminescent properties of the fluoride halide glass was compared. The results show that the luminescent intensity of infrared increases with the introduction of different halogen ions. By comparison, it is found that the sample with I^– has the strongest luminescence of 1064 nm, 2.0 μm and 2.9 μm. This is consistent with the calculated J-O intensity parameters. In addition, the 2.0 and 2.9 μm emission of Ho³⁺ pumped with a 450 nm laser will not disappear. A mid-infrared sample with multi-wavelength excitation and multi-wavelength emission can be obtained. Nd³⁺/Ho³⁺ co-doped fluoride halide glasses with 1064 nm, 2.0 μm and 2.9 μm luminescence were prepared by melt quenching method. The luminescent mechanism and the energy transfer process between the two ions of Nd³⁺/Ho³⁺ co-doped fluoride halide glass were studied. The J-O parameters, luminescence lifetime and absorption emission cross-sectional area of Ho³⁺ and Nd³⁺ were calculated, respectively. It is found that the value of Ω₂ in the glass matrix increases with the introduction of different halogen ions, while Ω₄ and Ω₆ do not change obviously in different glass compositions. This is because the environment of the crystal field around the rare earth ions changes. The crystal phase and phonon energy of the sample were analyzed by X-ray diffraction pattern and a Fourier transform infrared spectrometer, respectively. Based on the above spectra and data (phonon energy is 634.71 cm⁻¹), it can be predicted that Nd³⁺/Ho³⁺ co-doped fluoride halide glass is a potential mid-infrared luminescent material.