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 socalled 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℃is about 20%higher than that at 1100℃.The enhanced extraction efficiency at 1200℃results from the fact that the liquid Fe and Fe2 B 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℃,in order to avoid the increased Fe content in the extracted product.Based on optimized process,the RE elements ca n be almost fully extracted from the waste.This work thus provides an effective method to recover the RE elements.

Component content distribution profile control in rare earth countercurrent extraction process

Considering that the on-line measurement and automatic control of element component content(ECC) are difficult to perform in rare earth cascade extraction process, the ECC distribution profile is dynamically regulated at all stages to assess the effect of product purity control. Focusing on the theory of countercurrent extraction, the technology parameters and pre-setting flow-rates during the extract process are designed. Under varying process parameters, a novel step by step model is also proposed for each stage to analyze the impact on the distribution profile change. Combining the mass balance model and ECC changing trend at the monitoring stage, the ECC distribution profile can be automatically regulated by dynamically compensating the related extract or scrubbing liquid flow-rate. To this end, the required product purity at the two outlets is achieved. Based on Wincc and Matlab dynamic simulators, a specific Pr/Nd cascade extraction process is used to illustrate and demonstrate the application of the present approach.

Studies on Expert System for Extraction of Rare Earths

An expert system has been developed,using LISP,for extraction of rare earths.The expert system was de- signed to mimic the deduction of chemists for rare earth separation.The knowledge base consists mainly of three parts:(1)the extractant solvents common use and the separations of the individual rare earths;(2)the recom- mendation of process for the separation of mixed rare earths with extraetant P507;(3)the evaluation of econo- my for planning to build a rare earth factory The knowledge base of this system was organized as files including frame files and rules.In addition,removing of the rules can be carried out in the file compiling window under the LISP environment.Both the forward-chaining and the reverse chaining were used simultaneously as the infer- ence strategies.The machine used was a microcomputer IBM PC-XT.

Breakthrough in the China's Separation Technology for Extraction of Rare Earth Elements

Separation technology of rare earth elements （REEs）, as the critical step in the separation process, had long been fraught with technical difficulty. A research project conducted by Baotou Shibo Rare Earth Extraction ＆ Equipment Co. Ltd., Baotou REE Research Institute, and Baotou Steel ＆ REE Group Hi-Tech Co. Ltd （Inner Mongolia）, has successfully solved the problem using a centrifugal extractor and advanced techniques to achieve a key breakthrough.

STUDY ON THE SEPARATION AND EXTRACTION MECHANISM OF RARE EARTH ELEMENTS BY MEANS OF REVERSED-PHASE PAPER CHROMATOGRAPHY

Reversed-phase paper chromatography technique is used for study on the extraction mechanism and sep- aration of rare earth elements.As the stationary phase,chromatographic paper strips are impregnated with a solution of monomyristyl phosphoric acid (MPA) in chloroform.Mineral acids are used as developers. The effect of concentration of acids and/or salts upon R_f has been investigated.According to the re- sults of R_f values for a given rare earth element in various acids,the order of extraction ability is HCl>HNO_3>H_2SO_4.A tetrad effect is clearly observed.for the R_f value of rare earth elements.The effects of other parameters on the R_f value,such as the quantities of extractant retained by the paper and the temperature are also examined.Based on the determination of the molar ratio of MPA to rare earth elements and the number of H^+ ions released in extraction reaction,a reasonable mechanism is proposed.The mutual separation of heavy rare earth elements will be better than that of the light rare earth group because of the larger separation coefficient of the former.A mixture of Ho-Er-Tm-Lu is successfully separated by the present method.

Quantum Chemical Calculation on the Structures and Electronic Properties of Phosphonate Ester as Rare Earth Extractants

Molecular mechanics, molecular dynamics and semi empirical quantum chemical method have been used to study the geometric and electronic structures of six phosphonate ester as rare earth extractants. The results show that the phosphorus atom exhibits sp 3 hybridization. The structures of the extractants are determined by the repulsion of the hydrocarbon groups. In the extractants that have two 2 ethyl hexyl groups, one 2 ethyl hexyl extends straight, and the other extends twistily. When the number of oxygen atom decreases, the negative charge of the phosphoryl oxygen atom increases, but the negative charge of oxygen atom and the positive charge of hydrogen of the hydroxyl group decreases, and the energies of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital(LUMO) increase. The energies of the occupied frontier orbitals are close to each other.

Solvent extraction kinetics of Sm(Ⅲ),Eu(Ⅲ) and Gd(Ⅲ) with 2-ethylhexyl phosphoric acid-2-ethylhexyl ester

Solvent extraction kinetics of Sm（Ⅲ）, Eu（Ⅲ） and Gd（Ⅲ） from hydrochloric acid have been focused on using 2-ethylhexyl phosphoric acid-2-ethylhexyl ester （P507） with Anordning for Kontinuerlig Undersokning av Fordelningsfaktore rid Vatske Extraction （AKUFVE）. Compared with the conventional set-up, some advantages emerge obviously, for example, fast phase separation, easy operation and convenience of kinetic data acquisition. First of all, the extraction mechanism was discussed based on the dimeric model of P507. Secondly, the effects of stirring speed were investigated and 420 r-min-1 was determined of the following experiments. The effects of pH, concentration of rare earth elements （REEs） and P507 on the extraction rate were analyzed. The results indicated that the extraction mechanism changed with the increasing concentration of P507. Then, the experiments with different temperature were carried out. It turned out that the values of apparent activation energy （Ea） for Sm（Ⅲ）, Eu（Ⅲ） and Gd（Ⅲ） extracted by P507 were 26.80 kJ-mol-1, 13.40 kJ.mol-1 and 1.10 kJ- mol- 1 respectively, the resistance of the entire process was limited by diffusion or both of diffusion and reaction. Finally, the correlation equations were obtained, and the theoretical results fit with the experimental data well, most relative error was within ± 30%.

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 distribution ratio was improved greatly. The optimum volume fraction of TOB was 0.6-0.8.

Extraction and separation of heavy rare earths from chloride medium byα-aminophosphonic acid HEHAPP

The extraction and separation of heavy rare earths（REs） using newly synthesized a-aminophosphonic acid extractant 2-ethylhexyl-3-（2-ethylhexylamino）pentan-3-yl phosphonic acid（HEHAPP, HA） in nheptane were investigated from chloride medium. The extraction stoichiometries of lanthanum, gadolinium, yttrium and lutetium are determined to be REA3 by the slope analysis method. The favorable separation factors of adjacent heavy REs（Ⅲ）,i.e. β（Y/Ho）, β（Er/Y）,β（Tm/Er）,β（Yb/Tm） and β（Lu/Yb）, are determined to be1.87,1.36, 3.21,3.22 and 1.93, respectively, when extracted from a binary system at proper condition. The loading capacities of HA for Ho, Er, Yb and Lu increase in the order Ho 〈 Er 〈 Yb 〈 Lu with the values being 0.201, 0.205, 0.216 and 0.229 mol/L, respectively. So HA would be a potential extractant for the separation of heavy REs（Ⅲ）. Among inorganic acids such as H2 SO4, HNO3 and HCl, HCl is tested to be the most effective stripping agent.

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 HCI medium with Cyanex 272 in the presence of the complexing agent lactic acid（HLac） and auxiliary agents citric acid（H3 Cit）, 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.

Solid-liquid extraction for yttrium recovery using porous polymeric resin(XAD-7) functionalized with D_(2)EHPA

The recovery of yttrium is proposed by applying a solid-liquid extraction process using di-2-ethyl hexylphosphoric acid(D2EHPA) as extracting agent.The extracting agents were supported on a macro porous polymeric resin XAD-7(solid phase).Yttrium ions extraction and discharge tests were performed,firstly from a synthetic aqueous solution of 100 mg/L Y(liquid phase) at 25℃ with stirring.The effects of pH of aqueous solutions bearing yttrium,volume fraction of extracting agents and the solid/liquid(S/L)ratio on the yttrium recovery were studied.The most favorable conditions for yttrium ions extraction are;20 vol% D_(2)EHPA functionalized resin,pH=1.5 and an S/L ratio of 10 mg/mL The discharge of yttrium ions was done under the same conditions of extraction stage,using a 2 mol/L [H_(2)SO_(4)] as stripping solution.Up to 80% yttrium is extracted,while 75% yttrium is recovered in the striping solution.In all experiments,the reaction equilibrium is reached after 20 min,and the kinetics for the extraction stage was determined as a second-order model.Also,experiments were carried out to discharge the yttriumloaded resins,and it has been determined that the best pH value to strip the Y ions is 1.5.Cyclic tests of extraction and discharge for yttrium ions show that the functionalized resin can work at least five cycles without decreasing its efficiency.Finally,the proposed process was tested in a real solution with Y ions fro m a waste fluorescent la mp powder leached in H_(2)SO_(4),demonstrating the ability to effectively recover yttrium,separating it from various metals from the studied residue.

Effects of organic acids on the leaching process of ion-adsorption type rare earth ore

To examine the activation of organic acids on the leaching process of ion-adsorption type rare earth ore（IRE-ore）, the leaching behavior of rare earth（RE） and zeta potential of IRE-ore were investigated in the absence and presence of carboxylic acids. The results show that all the tested organic acids（acetic acid,malonic acid, citric acid, tartaric acid, succinic acid, and malic acid） can promote RE extraction. At relatively high concentrations of organic acids, the activation efficiency of organic acids on RE extraction is generally consistent with their complexation ability; whereas at their low concentrations, the change of zeta potential on the IRE-ore surface with organic acid concentration and p H has a close association with RE extraction, which indicates that organic acids can impact the surface electrical property of IREore via their adsorption/desorption, and thereby increase/decrease the affinity of RE ions to IRE-ore.Therefore the influence of organic acids on the IRE-ore surface electrical property also plays an important role in RE extraction in addition to their complexation with RE ions.

Formation mechanism of micro emulsion on aluminum and lanthanum extraction in P507-HCl system

P507 solvent extraction is the main method to separate and purify the rare earth products.The emulsification may be caused by the impurities in process of extracting rare earths,and these result in huge economic loss and decrease the quality of rare earth products.In recent researches,the extractant was prone to emulsification,and aluminum content of rare earth products also increased,while aluminum concentration of feed was higher.Pointing to this problem,the structural change of saponification P507 extracting aluminum and lanthanum was investigated by infrared spectroscopy,and the results showed that Al ions exchanged with H of P-O-H to become P-O-Al.Because aluminum held the characteristic of hydrophilic after extracted in the form of hydroxyl polymer ions and this provided conditions for the formation of micro emulsion.The organic phase and aqueous phase were investigated by polarizing microscope after aluminum was extracted.The results showed that the organic phase was clear when the extraction capacity of Al was less than 5 g/L.If the extraction capacity of Al exceeded 5 g/L,it formed W/O of ME(micro emulsion),leading to form emulsion of the organic phase.When Al concentration of feed was less than 1 g/L,the aqueous phase would form O/W of ME.If aluminum was extracted by saponification P507 firstly,then the the organic phase loading aluminum extracted rare earth continually,the organic and aqueous phase formed emulsification easily.

A review on yttrium solvent extraction chemistry and separation process

This paper reviewed various systems such as neutral phosphorus and acid phosphorus, carboxylic acid and amine extractant for solvent extraction chemistry of yttrium, including thermodynamics, kinetics and yttrium extracting separation process containing the development course and new separation process.

Solution extraction of several lanthanides from nitric acid with isohexyl-BTP in [C_nmim][NTf_2] ionic liquid

The extraction behavior of several lanthanides（La^3＋, Eu^3＋, Lu^3＋） from nitric acid（HNO3） solution was studied using a novel extraction system based on 2,6-bis（5,6-dihexyl-1,2,4-triazin-3-yl） pyridine（isohexyl-BTP） as extractant in 1-alkyl-3-methylimidazolium bis（trifluoromethylsufonyl）imide（[Cnmim][NTf2]） ionic liquid. Isohexyl-BTP in ionic liquids exhibited remarkably better extraction performance for lanthanides than that in octanol-dodecane（3：7 v/v） system. Lower HNO3 concentration and short alkyl chain length of [Cnmim]^＋ were more favourable for removal of lanthanides. Besides, it was confirmed that isohexyl-BTP in ILs formed a 1：3 complex [Ln（BTP）3（NO3）n]^（3–n）＋（n=0, 1） by slope analysis. In addition, [C2mim][NTf2] preferred to extract lanthanides via a cation exchange mechanism at lower acidity, which was proved via UV-Vis measurement. It was speculated that extraction mechanism shifted from cation exchange to neutral species extraction with increase in HNO3 concentration and alkyl chain length of [Cnmim]^＋ due to the H^＋ completion, NO3^- inhibition and hydrophobicity of IL.

Study on separation technology of Pr and Nd in D_2EHPA-HCl-LA coordination extraction system

The separation coefficient of Nd/Pr was lower in D2EHPA-HCl system. Pointing to this problem,the effect of the acidity of feed and the concentration of lactic acid on the distribution ratio,separation coefficient and extraction capacity was investigated in unsaponified D2EHPA-HCl-LA system,and the regression equations were calculated in this paper. The results showed that the distribution ratio and separation coefficient both increased with decreasing of feed acidity and increasing of the lactic acid concentration,and the extraction capacity increased with increasing of lactic acid concentration in D2EHPA-HCl-LA system. When the pH value of the feed was 3.5 and lactic acid concentration was 0.6 mol/L,the max separation coefficient was 1.57,and the extraction capacity was 27.87 g/L.