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...     

Effective rare earth extraction from Nd-Fe-B waste by liquid cuprum extraction method

Recovery of rare earth (RE) elements from Nd-Fe-B waste is one of the ways to solve the problem of so-called RE-crisis. An alternative approach of extracting RE elements from Nd-Fe-B waste by molten Cu extraction based on liquid-solid diffusion and reaction is reported in this paper. The extraction process, product microstructure and extraction efficiency were systematically studied. The results show that the extraction rate of RE at 1200 °C is about 20% higher than that at 1100 °C. The enhanced extraction efficiency at 1200 °C results from the fact that the liquid Fe and Fe₂B are not co-soluble with Cu. Reducing the mass ratio of Cu to waste and the size of the waste scraps is also beneficial to enhancing the separation of RE and Fe elements. In addition, the extraction time should be well controlled, for example, less than 2 h at 1100 °C, in order to avoid the increased Fe content in the extracted product. Based on optimized process, the RE elements can be almost fully extracted from the waste. This work thus provides an effective method to recover the RE elements.     

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.     

Progress in green and efficient enrichment of rare earth from leaching liquor of ion adsorption type rare earth ores

Ion adsorption type rare earth ores (IATREOs) are a valuable strategic mineral resource in China, which feature a complete composition of fifteen rare earth elements and are rich in medium and heavy rare earth (RE) elements. In the leaching process for recovering rare earth elements from IATREOs, many impurities will be leached together with rare earth elements and enter the leaching liquor. An impurity removal-precipitation enrichment technique is currently applied to selectively recovery rare earth elements from the leaching liquor with the high content of impurities and low concentration of rare earth elements by using ammonium bicarbonate in the industry. However, a high loss of rare earth elements and severe ammonia nitrogen pollution are caused by this process. Therefore, more beneficial impurities removal technologies, mainly for aluminum, and green enrichment technologies with lower pollution are now urgently needed. For this purpose, this paper analyzed two aspects of research progress in recent decades: the green separation of rare earth elements and aluminum from leaching liquor and the green and efficient enrichment of rare earth elements. Finally, an approach for the high-efficiency and green enrichment of rare earth elements from leaching liquor of the IATREOs is proposed in several aspects, including impurity inhibition leaching, neutralization and impurity removal, alkaline calcium and magnesium salt precipitation enrichment, and centrifugal extraction enrichment.     

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...     

Migration behavior,separation and recycling of rare earth during thermal decomposition of Zhijin phosphorus ore

Zhijin phosphorus ore is a moderate and low-grade phosphorus rare-earth ore contained in mines. The separation and extraction of associated rare earth are important research topics. In this study,the migration behavior of rare earth during the thermal decomposition of Zhijin phosphorus ore and the separation and extraction of rare earth in phosphorus slag are discussed systematically. During the thermal decomposition process of phosphorus ore, almost all of the associated rare earth enters into the phosphorus slag phase but does not enter into the ferrophosphorus or gas phases. Amorphous calcium metasilicate and calcium fluosilicate are major components of phosphorus slag, and rare earth mainly exists as a calsil solid solution. Hydrochloric acid was used for acidolysis of the phosphorous slag.Under the following conditions, 96% of the rare earth in the phosphorous slag can be dissolved in the acidolysis solution: acid excess coefficient of 1.5, reaction time of 50 min and reaction temperature of 50℃. The rare earth in the acidolysis solution was separated and recycled using oxalic acid as a precipitator and NaOH as a pH modifier. At pH of 1.7, rare-earth-enriched matter with rare-earth content of 2.1 wt% was obtained, and the recovery of the rare earth was 88%.     

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.     

Flotation behavior and electronic simulations of rare earth minerals in the presence of dolomite supernatant using sodium oleate collector

Common rare earth (RE) minerals, such as bastnasite and monazite, may be formed in deposits associated with carbonate gangue, such as calcite and dolomite. Sodium oleate is a widely used collector for the flotation of both RE and gangue minerals, which might, therefore, be an inefficient process due to the lack of selectivity of this collector. Since these minerals are also sparingly soluble in solution, they could release their constituent ions into the solution, which could affect the floatability of other minerals. In this study, the interactions of sodium oleate with bastn(a|¨)site and monazite in the presence of dissolved dolomite species have been investigated. Micro flotation tests were carried out to explore the effects of these dissolved species on the floatability of the RE minerals. Zeta potential measurements and XPS characterization were carried out to understand how the species affect the collector adsorption. To complement these characterizations, density functional theory (DFT) simulations were conducted to investigate the collector-mineral and collector-adsorbed species (on the mineral surface) interactions.The results show that collector-dolomite interaction energy is greater than that of collector-adsorbed species, but lower than collector-monazite interaction energy, explaining the decrease in the minerals’recovery upon exposure to the dissolved mineral species. It is also shown that oleate ions (OI~-) have the strongest interaction with the minerals compared to other oleate species such as acid soap (HOI_2~-) and oleate dimer (Ol_2~(2-)). The behavior (strength and selectivity) of sodium oleate towards RE minerals and dolomite, as compared to other RE mineral collectors (such as aromatic hydroxamate), is attributed mainly to the collector's and the minerals'structure. The long hydrocarbon chain of sodium oleate which imparts hydrophobic characteristic to the minerals, makes it stronger collector than benzohydroxamate.Moreover, sodium oleate (with linear structure), unlike the aromatic hydroxamate, can approach the mineral easier due to lesser steric hindrance effect and higher reactivity of O involved in the interaction,making it less selective. In addition, it can interact easily with dolomite due to the presence of more exposed active sites than RE minerals.     

Luminescence and low temperature trap centers in mixed rare earth borate crystal

The single crystal of this compound has been grown from melt by using a conventional Czochralski technique. The temperature dependent luminescence spectra were measured using a 265 nm laser as an exciting source in the range of 10–300 K. The scintillation decay time profile was measured and found to have three components. The influence of the trap centers on the luminescence properties was studied by means of thermoluminescence (TL) glow peak analysis. Low temperature TL glow peaks were measured in the temperature range of 10–300 K at the heating rate of 0.1 K/s for X-ray irradiated sample. The TL glow peak consists of two dominant peaks at 88 and 109 K. Several glow peaks with a complex nature causes the decrease in the light yield at temperatures below 250 K, and along with long scintillation decay components were observed. The trap parameters such as activation energy (E), frequency factor (s) and order of kinetics (b) were calculated using various standard methods such as peak shape (PS), variable heating rate (VHR), initial rise (IR) and computerized glow curve deconvolution (CGCD).     

Effect of roasting activation of rare earth molten salt slag on extraction of rare earth,lithium and fluorine

A new process was proposed to extract rare earth elements(REEs),Li and F from electrolytic slag of rare earth molten salt by synergistic roasting and acid leaching.Firstly,the thermodynamic analysis of roasting reaction was carried out,then the effects of roasting factors on leaching REEs,Li and F in slag were investigated.In additions,the mineral phase and morphology of molten salt slag,roasting slag and acid leaching slag were characterized,and the migration mechanism of REES,Li and F minerals...     

Extraction and back-extraction behaviors of 14 rare earth elements from sulfuric acid medium by TODGA

The unique physical and chemical properties of rare earth elements lay the foundation for their extensive application. N,N,N',N' Tetra-octyl-3-oxopentanediamide(TODGA) is excellent in its ability of extracting rare earth elements and it is favored for green initiative. In this paper, the extraction and back-extraction of14 rare earth elements by TODGA were studied. Experiments show that in conditions of 6 mol/L sulfuric acid, the extraction temperature of 25 ℃,the phase ratio of 1:1 and 0.04 mol/LTODGA(aviation kerosene as the diluent), the extraction rates of 14 rare earth elements including lanthanum, cerium, praseodymium,neodymium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, and yttrium were 99.00%-99.73%. Mixed with hydrochloric acid and nitric acid(HCl 3.5 mol/L, HNO_30.5 mol/L), the recoveries of the 14 rare earth elements are 91.52%-99.91% when the extraction temperature is 25 ℃ and the ratio is 1:1. The following application is based on the optimum conditions above with practical samples(from the roasting production line of China North Rare Earth High-tech Company Limited) for extraction and back-extraction experiments. Experiments show that TODGA has excellent enrichment effect on 14 rare earth elements, the extraction rates are 91.36%-99.80%, the back-extraction rates are 87.29%-99.64% and the total recoveries are 81.19%-99.44%.     

Process mineralogy of Weishan rare earth ore by MLA

Mineral liberation analyser (MLA) was applied to quantitatively analyze the rare earth ore from Weishan in Shandong. Mineralogy parameters, such as mineral composition, occurrence states of rare earth elements (REEs) and valuable elements, mineral embedded grain size distribution, mineral association and liberation, are obtained. Results show that the contents of REEs and other valuable elements mainly contained in the ore were La 1.02 wt%, Ce 4.29 wt%, Pr 0.34 wt%, Nd 0.84 wt%, Sr 3.4 wt% and Ba 26.53 wt%, respectively. The REEs mainly occur in bastnaesite and carbocernaite in the form of independent mineral and the contents of bastnaesite and carbocernaite in the ore were 5.96 wt% and 12.30 wt%, respectively. 67.34% of strontium occurs in carbocernaite and the rest occurs in celestobarite and strontianite mineral. 92.71% of barium occurs in barite. Liberation of main rare-earth minerals such as bastnaesite and carbocernaite is more than 80% when the grinding fineness is 78.42% passing 74 μm. The research results could be employed to provide detailed basic theoretical data for further improvement of the beneficiation process flow and the processing index of rare earth ore, the recycling of other valuable minerals and the comprehensive utilization of tailings.     

从离子型稀土矿浸取液中提取稀土的技术现状与展望

综述了沉淀法、沉淀浮选法、溶剂萃取法、离子交换法、液膜分离法等方法从离子型稀土矿浸取液中提取稀土的技术研究进展.在提取稀土的各种方法中,碳酸沉淀法因成功实现了稀土母液无毒化,改善了矿山生态环境等特点,在今后很长的一段时期内仍将是从离子型稀土矿浸取液中提取稀土的主要方法.但溶剂萃取法由于可直接生产出可溶性稀土盐或稀土料液,还能对稀土进行萃取分组以制备稀土分组产品,从而改变了稀土矿山一直以来只能生产混合氧化稀土的不利局面,提高了矿山的经济效益等特点,且符合绿色化学提取稀土资源的要求,将会有很好的发展前景.     

碱熔预处理对废旧稀土荧光粉中稀土提取的影响

针对废旧稀土荧光粉特性,采用高温碱熔与酸浸相结合的方法处理废旧稀土荧光粉,考察碱熔温度、氢氧化钠用量、碱熔时间对稀土浸出率和铝回收率的影响,并对碱熔过程中的物相及形貌变化进行分析.结果表明,在碱熔温度为1050℃、氢氧化钠与废粉质量比为2.5∶1、碱熔时间为2 h 条件下,其稀土浸出率可达98%以上,铝回收率可达98%.通过对碱熔产物物相和形貌分析表明,废粉晶体结构被有效破坏,其中稀土以稀土氧化物形式存在,碱熔产物变成无定型云絮状.     

P507-N235体系稀土萃取分离性能研究

研究了P507-N235无皂化萃取体系稀土分离系数的变化规律。实验结果表明,P507中加入N235可提高La/Ce分离系数,且分离系数随N235加入量的增加而提高;相比O/A越大,La/Ce分离系数越高;萃取混合时间应控制在8 min较为合适;对比实验发现,P507-N235体系稀土元素间分离系数普遍高于现有的P507体系。     

Element migration and phase distribution characteristics during crystallization of rare earth phase in rare earth slag

The crystallization experiment of molten rare earth (RE) slag under different cooling rates was carried out. The characteristics of element migration and phase distribution during RE phase crystallization were studied by using different equipment. The experimental results show that there are two RE phases in the RE slag, namely (Ca, Ce, La)₅(SiO₄)₆F and (Ca,Ce,La,Mg)₃(Ti,Al,Nb)₂O₇. During the cooling crystallization process of molten RE slag, Ca and P elements in the RE phase of (Ca,Ce,La)₅(SiO₄)₆F migrate from inside to outside, and finally gather at the outer edge of the phase to form phase Ca₃(PO₄)₂. The RE phase (Ca,Ce,La)₅(SiO₄)₆F is distributed inside the furnace-cooled slag, and the RE phase (Ca,Ce,La,Mg)₃(Ti,Al,Nb)₂O₇ is distributed in the surface layer of the furnace-cooled slag. And based on the phase distribution characteristics, the central hollowing method is proposed to realize the preliminary enrichment of valuable elements Ti, Nb and RE in RE slag.     

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.     

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.     

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⁺.     

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.