Decomposition of mixed rare earth concentrate by NaOH roasting and kinetics of hydrochloric acid leaching process

A new clean extraction technology for the decomposition of Bayan Obo mixed rare earth concentrate by NaOH roasting is proposed.The process mainly includes NaOH roasting to decompose rare earth concentrate and HCl leaching roasted ore.The effects of roasting temperature,roasting time,NaOH addition amount on the extraction of rare earth and factors such as HCl concentration,liquid-solid ratio,leaching temperature and leaching time on the dissolution kinetics of roasted ore were studied.The experimental results show that when the roasting temperature is 550℃and the roasting time is 60 min,the mass ratio of NaOH:rare earth concentrate is 0.60:1,the concentration of HCl is 6.0 mol/L,the ratio of liquid to solid(L/S)6.0:1.0,and the leaching temperature 90℃,leaching time 45 min,stirring speed 200 r/min,and the extraction of rare earth can reach 92.5%.The relevant experimental data show that the process of HCl leaching roasted ore conforms to the shrinking core model,but the control mechanism of the che mical reaction process is different when the leaching temperature is different.When the leaching temperature is between 40 and 70℃,the chemical reaction process is controlled by the diffusion of the product through the residual layer of the inert material.The average surface activation energy of the rare earth element is E_a=9.96 kJ/mol.When the leaching temperature is 75-90℃,the chemical reaction process is controlled by the interface transfer across the product layer(product layer interface mass transfer)and diffusion.The average surface activation energy of rare earth elements is E_a=41.65 kJ/mol.The results of this study have certain significance for the green extraction of mixed rare earth ore.

In-situ measurement of mineral phase transition and kinetics in roasting process of Bayan Obo mixed rare earth concentrate by sodium carbonate

In this study,the Bayan Obo rare earth concentrates mixed with Na_(2)CO_(3)were used for roasting research.The phase change process of each firing stage was analyzed.The kinetic mechanism model of the continuous heating process was calculated.This study aims to recover valuable elements and optimize the production process to provide a certain theoretical basis.Using X-ray diffraction(XRD),Fourier infrared spectroscopy,scanning electron microscopy with energy dispersive spectrometry,the reaction process and the existence of mineral phases were analyzed.The variable temperature XRD and thermogravimetric method were used to calculate the roasting kinetics.The phase transition results show that carbonate-like substances first decompose into fine mineral particles,and CaO,MgO,and SiO_(2)react to form silicates,causing hardening.Further,REPO_(4)and NaF can directly generate CeF_(3) and CeF_(4)at high temperatures,and a part of CeF_(4)and NaF forms a solid solution substance Na_(3)CeF_(7).Rare earth oxides calcined at a high temperature of 750℃were separated to produce Ce_(0.6)Nd_(0.4)O_(1.8),Ce_(4)O_(7),and LaPrO_(3+x).Then,BaSO_(4),Na_(2)CO_(3),and Fe_(2)O_(3)react to form barium ferrite BaFe_(12)O_(19);the kinetic calculation results show that during the continuous heating process,the apparent activation energy E reaches the minimum in the entire reaction stage in the temperature range of 440-524℃,and the reaction order n reaches the maximum,which indicates that the decomposition product REFO significantly impacts the reaction system and reduces the activation energy.The mechanism function is F(α)=[-In(1-α)]^(1/3).The reaction order n reaches the minimum in the temperature range of 680-757℃,and the apparent activation energy E is large.The difficulty of the reaction increases during the final stage.The reaction mechanism function is F(α)=[1-(1-α)^(1/3)]^(2).Observing the entire reaction stage,the step of controlling the reaction rate changes from random nucleation to three-dimensional diffusion(spherical symmetry).

Flotation-Calcination-Magnetic Separation Hybrid Process for Concentration of Rare Earth Minerals Contained in a Carbonatite Ore

A hybrid process consisting of flotation and magnetic separation has been developed to concentrate multi-phase rare earth minerals associated with a carbonatite ore that contains a significant amount of niobium. The deposit is known to contain at least 15 different rare earth minerals identified as silicocarbonatite, magnesiocarbonatite, ferrocarbonatites, calciocarbonatite, REE/Nb ferrocarbonatite, phosphates and niobates. Although no collector exists to float all the different rare earth minerals, the hydroxamic acid-based collectors have shown adequate efficiency in floating most of these minerals. 92% recovery of total rare earth oxide (TREO) and niobium in 45% mass was possible at d80 of <65 microns grind size. It was also possible to reduce the mass pull to 28%, but TREO and Nb’s recovery dropped to 85%. Calcination of the concentrate followed by quenching and fine grinding to <25 μm allowed upgrading the flotation concentrate by magnetic separation. It was demonstrated that at least 87% TREO and 85% Nb could be recovered in 16% of the feed mass. The paper discusses the overall concept of the flowsheet and the experimental strategies that led to this process.

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.

The Concentration Degree of Nationwide Rare Earth Industry Increased Significantly

Since the'Twelfth Five Year Plan'period,China has made considerable progress in the organization and setup of large rare earth groups,layout of rare earth industry has become more rational,the concentration degree has increased significantly,the previously small,scattered,and chaotic situation has basically been reversed.

Upconversion 32Nb_(2)O_(5)-10La_(2)O_(3)-16ZrO_(2) glass activated with Er^(3+)/Yb^(3+) and dye sensitized solar cell application

Er^(3+)/Yb^(3+)codoped niobium pentoxide glasses were fabricated by the aerodynamic levitation(ADL)method with rapid cooling rate.All samples with various doping concentrations showed good upconversion luminescence properties under 980 nm laser excitation.The structure,transmittance spectrum,and luminescence properties of the samples were systemically investigated by XRD,UV-Vis-NIR spectrophotometer,and upconversion spectra.All transparent samples exhibited green and red upconversion emissions centered at 532,547,and 670 nm.Experimental results showed that the sample codoped with 1 mol%Er^(3+)/Yb^(3+)has the strongest upconversion emissions,and the increase of the doped Yb^(3+)concentration results in the increased red emission and reduced green emission.The logI-logP plot of green emission indicated that the green emissions reach the saturation at high pump power excitation,deviating from the low-power regime.After one-photon energy transfer(ET)process,^(4)I_(11/2)+^(4)I_(11/2)→^(4)F_(7/2)+^(4)I_(15/2) process between the two neighboring Er^(3+)ions was responsible for the population of the 4S3/2/4H11/2 states.The niobium pentoxide codoped with Er^(3+)/Yb^(3+)bulk glasses could be used in the dye sensitized solar cell(DSSC)to improve the efficiency.