Recovery of iron and rare earth elements from red mud through an acid leaching-stepwise extraction approach

A feasible approach to selectively recover iron and rare earth elements(REEs)from red mud through acid leaching-coordination-solvent extraction was proposed.The leaching efficiencies of Fe,Al,Ti,Sc,La,Ce,Nd and Y can reach up to 95.9%,82.1%,68.3%,93.3%,82.3%,96.9%,98.3%and 95.6%,respectively,under the optimal condition in the leaching process.Aliquat 336 showed excellent extraction performance of iron in chloride-rich solution,and the maximum extraction efficiency can reach over 96%in one time extraction while the loss of other metals was less than 10%,under the condition of Aliquat 336 concentration(v/v)of 30%,aqueous-organic ratio of 1.0 and extraction time of 20 min.Furthermore,P204 can effectively extract the scandium while Al and most other REEs remain in the aqueous phase.This approach may provide a new insight for the recovery of valuable resources from red mud.

Centrifugal extraction of rare earths from wet-process phosphoric acid

Phosphorite ore is a potential resource of rare earths （RE） as well as phosphate; therefore, the recovery of RE from wet-process phosphoric acid （WPA） is promising. This study investigated the influence of rotational speed, extractant concentration, flow ratio and phase contact time on the centrifugal extraction of RE from WPA and the separation of RE from impurities. The results indicate that higher rotational speed, higher extractant concentration and larger flow ratio are beneficial to the extraction of RE and impurities from phosphoric acid. It is found that the phase contact time for efficiently extracting RE and that for iron are of great difference, which provides an effective method for separating RE from iron using the non-equilibrium extraction process in centrifugal contactors. Compared with equilibrium extraction, the separation factor βRE/Fe is enhanced from 0.07 to 17.6.

Separation of middle rare earths by solvent extraction using 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester as an extractant

The extraction of the trivalent middle rare earths from chloride media by kerosene solutions of 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester as an extractant was studied. The separation factors between the elements using solution simulating wastes from NiMH spent batteries have been evaluated: the order of the extractive ability of extractant can be confirmed in Tb>Gd>Eu>Sm.

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 Nd^3＋ and Sm^3＋, including the extraction and stripping capability as well as the separation effect of Nd^3＋ or Sm^3＋, 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 Nd^3＋ and Sm^3＋ in different acidities were also determined. A synergistic extractive effect was found when HDEHP and HEH/EHP were used as mixed extractants for Sm^3＋ or Nd^3＋. 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.

Separation of Red (Y_2O_3: Eu^(3+)), Blue (Sr,Ca,Ba)_(10)(PO_4)_6Cl_2: Eu^(2+) and Green (LaPO_4:Tb^(3+),Ce^(3+)) Rare Earth Phosphors by Liquid/Liquid Extraction

A novel process for separation of red （Y2O3： Eu^3＋）, blue （Sr, Ca, Ba）10（PO4）6Cl2： Eu^2＋ and green （LaPO4： Tb^3＋, Ce^3＋） fine tricolor phosphor powders was established. First, the green phosphor was extracted and separated from three phosphor mixtures in heptane/DMF（N, N-Dimethylformamide） system using stearylamine or laurylamine （DDA） as the cationic surfactant. Then, after being treated with 99.5% ethanol, the blue and red phosphors could be separated in Heptane/DMF system in presence of 1-octanesulfonic acid sodium salt as the anionic surfactant. Satisfactory separation results have been achieved through two steps extractions with their artificial mixtures. The grades and recovery of separated products reached respectively as follows： red product was 95.3% and 90.9%, blue product was 90.0% and 95.2%, and green product was 92.2% and 91.8%.

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.

Component Content Soft-Sensor Based on Hybrid Models in Countercurrent Rare Earth Extraction Process

In consideration of the online measurement of the component content in rare earth countercurrent extraction separation process, the soft sensor method based on hybrid modeling was proposed to measure the rare earth component content. The hybrid models were composed of the extraction equilibrium calculation model and the Radial Basis Function (RBF) Neural Network (NN) error compensation model; the parameters of compensation model were optimized by the hierarchical genetic algorithms (HGA). In addition, application experiment research of this proposed method was carried out in the rare earth separation production process of a corporation. The result shows that this method is effective and can realize online measurement for the component content of rare earth in the countercurrent extraction.

Separation of Red (Y_2O_3:Eu^(3+)), Blue (BaMgAl_(10)O_(17):Eu^(2+)) and Green (CeMgAl_(10)O_(17):Tb^3) Rare Earth Phosphors by Liquid/Liquid Extraction

A novel process for separation of red （Y2O3：Eu^3＋）, blue（BaMgAl10O17：Eu^2＋） and green （CeMgAl10O17：Tb^3） rare earth fluorescent powders was proposed. At first, the blue powder can be extracted selectively from an aqueous solution using a chelating collector 2-thenoyltrifluoroacetone （TTA） dissolved in heptane at alkaline pH condition, then, chloroform was used for extracting the green powder into organic phase. The red phosphor remains in aqueous phase with potassium sodium tartrate depressant （PST）. Therefore, three phosphors can be separated successfully from their artificial mixtures by liquid/liquid extraction, and grades and recovery of separated products reach respectively as follows： red is 96.9% and 95.2%, blue is 82.7% and 98.8%, green is 94.6% and 82.6%.

Comparison of Economical and Technical Indices on Rare Earth Separation Processes of Bastnasite by Solvent Extraction

According to the composition of rare earth ores and the market, several feasible separation processes of bastnasite in Baotou of Inner Mongolia and Mianning of Sichuan by solvent extraction in HEH(EHP) HCl system were presented. The parameters of the processes such as stage numbers, volume of mixer settler, fixed investment of extractant and rare earths, consumption of chemical reagents including HCl and NH 3 were calculated and compared. The results show that the novel scheme can save cost more than 20% compared with those of others. By the economical analysis, the optimized separation process of bastnasite was obtained, which can be applied to the treatment of monazite too.

Neural Networks Based Component Content Soft-Sensor in Countercurrent Rare-Earth Extraction

The equilibrium model for multicomponent rare earth extraction is developed using neural networks, which combined with the material balance model could give online prediction of component content in countercurrent rare earth (extraction) production. Simulation experiments with industrial operation data prove the effectiveness of the hybrid soft-(sensor).

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.

Extraction Behavior of Rare Earths with 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 Using Solid-liquid Extraction Technique

The extraction behavior of rare earths was studied by using paraffin with ceresin as a diluent containing 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5.In solid phase,the composition of complexes is REP_3.The equilib- rium extraction constants and pH_(1/2) values of solid-liquid extraction are higher than those of normal liquid-liquid extraction.The extraction efficiency tends to maximum when the ratio of phases is 1:1.When the extraction temperature is higher than the melting point of paraffin and the extraction time is over 10 min,the extraction efficiency keeps constant.Moreover,the relationship among separation factor,equilibrium extrac- tion constant,pH_(1/2) value and atomic number was obtained.The mechanism of solid-liquid extraction is analogous to that of liquid-liquid extraction.

Situation and Developing Trend of Rare-Earth Countercurrent Extraction Processes Control

On the basis of the description of the rare-earth countercurrent extraction process, the on-line detecting method and equipments of rare-earth elements and the application in the process of the rare-earth countercurrent extraction are summarized. The procedure simulation of the computer, the automation control method and its current application are also mentioned in the process of rare-earth countercurrent extraction. The method of soft sensor is proposed. Optimal control method based on object-oriented rare-earth countercurrent extraction process and integrated automation system composed of process management system and process control system are presented, which are the developing direction of the automation of rare-earth countercurrent extraction process.

Component Content Soft-sensor Based on Neural Networks in Rare-earth Countercurrent Extraction Process

Throught fusion of the mechanism modeling and the neural networks modeling,a compo- nent content soft-sensor,which is composed of the equilibrium calculation model for multi-component rare earth extraction and the error compensation model of fuzzy system,is proposed to solve the prob- lem that the component content in countercurrent rare-earth extraction process is hardly measured on-line.An industry experiment in the extraction Y process by HAB using this hybrid soft-sensor proves its effectiveness.

Integrated Automation System for Rare Earth Countercurrent Extraction Process

Lower automation level in industrial rare-earth extraction processes results in high production cost, inconsistent product quality and great consumption of resources in China. An integrated automation system for extraction process of rare earth is proposed to realize optimal product indices, such as product purity,recycle rate and output. The optimal control strategy for output component, structure and function of the two-gradcd integrated automation system composed of the process management grade and the process control grade were discussed. This system is successfully applied to a HAB yttrium extraction production process and was found to provide optimal control, optimal operation, optimal management and remarkable benefits.

Application of ^(241)Am EDXRF to Determine Heavy Rare Earths in RE Separation Processes by Solvent Extraction

A fast EDXRF analysis by using radioisotope, 241 Am as an exciting source and high purity Ge as a planar detector in heavy rare earth separation processes by solvent extraction has been investigated Applying the method, heavy rare earth chloride aqueous samples in Er/Tm and Y/Er separation processes were off line analyzed The results show that the method can be used for a wide range of rare earth concentration(0 1 g/L～300 g/L) with high accuracy

Effect of Cycling Loaded Rare Earths on Stripping Process in P507 Extraction System

P507 （HEH [EHP]） is an important extractant for the separation of rare earth and is widely used in industry. Since the complexes of heavy rare earth ions with saponified P507 are so stable that the rare earth ions are difficult to be exchanged and stripped by H^＋ ions. Thus, the cycled extractant loads certain amount of heavy rare earth ion after stripped by acid. This amount of rare earth ions loaded in blank organic phase is named as the ＂cycling loaded rare earth ions （CLREs）＂. In the separation process of Tm^3＋, Yb^3 ＋, and Lu^3 ＋ , the amount of CLREs carl be more than 10% of the normal capacity of saponifiedorganic phase. In fact, CLREs affect the separation efficiency and decrease the purity of the products. Based on the extracting-stripping equilibrium and mass balance, the influence of different process parameters on the amount of CLREs was studied by computer simulation. The results indicate that higher acid consumption and more stripping stages are required to eliminate CLREs. For an industrial practice, however, the acid consumption and the number of stripping stage can be designed by choosing an economic process and controlling CLREs at a reasonable level.

Application of the Phase Transfer Catalysis in Rare Earth Solvent Extraction

In order to overcome the difficulty in stripping and reduce the equilibrium time in heavy rare earth separation with acidic organophosphorous extractants, the phase transfer catalysis (PTC) technique was introduced to the solvent extraction process, especially applied to the stripping section, which was called phase transfer catalysis stripping (PTCS) process. in the PTCS process, an acidic phosphorous extractant was mixed with another extractant which can transfer hydrogen ion from aqueous phase to organic phase and almost does not extract rare earth ions, so that the stripping efficiency can be improved and the stripping extraction equilibrium be accelerated. The reaction mechanism of the PTCS and the requisite properties for a feasible PTCS catalyst in rare earth extraction were studied. We selected D(2)EHPA as the extractant, Alamine 336 as the PTCS catalyst and mixed rare earth chlorides as the feed to test the PTCS phenomenon. Based on the experimental data, the applicability of PTCS technique in rare earth solvent extraction was discussed.

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.

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.