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

The magnesium sulfate(MgSO_(4))-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 for the compound leaching process.In the case of neodymium,about 45%of dissolved neodymium will exist as the complex species of NdVc_(()3(aq))in Nd-Vc-sulfate system.Based on this,it is deduced that the Gibbs free energy of the leaching reaction of ion-exchangeable phase REEs will change to a more negative value through the coordination of REEs cations and Vc anions in the MgSO_(4)leaching process.In addition,the E_(h)-pH diagrams of Ce-SO_(4)^(2-)-H_(2)O and Fe-SO_(4)^(2-)-H_(2)O together with the dissolution experiments confirm that the added Vc initiates the leaching process of colloidal phase REEs through reduction-dissolution reaction.Through the study of leaching kinetics,the leaching of REEs is controlled by diffusion and chemical reaction in the co mpound leaching system since colloidal phase REEs are leached.Therefore,the addition of Vc can shift the leaching equilibrium to a more favorable state and accelerate leaching process.The rare earth leaching efficiency of ion-exchangeable phase and colloidal phase can be effectively improved by increasing the reaction temperature,the conce ntrations of leaching agent and Vc,and the leaching agent acidity.

Wetting front migration model of ion-adsorption rare earth during the multi-hole unsaturated liquid injection

In the process of ion-adsorption rare earth ore leaching,the migration characteristics of the wetting front in multi-hole injection holes and the influence of wetting front intersection effect on the migration distance of wetting fronts are still unclear.Besides,wetting front migration distance and leaching time are usually required to optimize the leaching process.In this study,wetting front migration tests of ionadsorption rare earth ores during the multi-hole fluid injection(the spacing between injection holes was 10 cm,12 cm and 14 cm)and single-hole fluid injection were completed under the constant water head height.At the pre-intersection stage,the wetting front migration laws of ion-adsorption rare earth ores during the multi-hole fluid injection and single-hole fluid injection were identical.At the postintersection stage,the intersection accelerated the wetting front migration.By using the Darcy’s law,the intersection effect of wetting fronts during the multi-hole liquid injection was transformed into the water head height directly above the intersection.Finally,based on the Green-Ampt model,a wetting front migration model of ion-adsorption rare earth ores during the multi-hole unsaturated liquid injection was established.Error analysis results showed that the proposed model can accurately simulate the infiltration process under experimental conditions.The research results enrich the infiltration law and theory of ion-adsorption rare earth ores during the multi-hole liquid injection,and this study provides a scientific basis for optimizing the liquid injection well pattern parameters of ion-adsorption rare earth in situ leaching in the future.

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.

A two-parameter model for ion exchange process of ion-adsorption type rare earth ores

The establishment of a mathematical model for the ion exchange process is key to creating a theoretical basis for the mining of ion-adsorption type rare earth ores.Ore samples from Xinfeng,Xunwu and Anyuan were used as the test ore samples in the present study and equilibrium batch tests of ore sample leaching using various ammonium sulfate concentrations were performed.The results show that,after leaching,there is a negative exponential relationship between the ratio of the solid-phase rare earth ion concentration to the aqueous-phase rare earth ion concentration and the initial ammonium ion concentration.However,there is a linear relationship between the natural logarithm of the ratio of the solidphase ammonium ion concentration to the aqueous-phase ammonium ion concentration and the initial ammonium ion concentration.Based on the above two functional relationships,a two-parameter model for the equilibrium ion exchange process of ion-adsorption type rare earth ores was established.Using the established model to analyze the test data the model error for the Xunwu ore sample is found to be less than 5%.The proposed model is more accurate compared with the Kerr model.The two-parameter model proposed in this study provides theoretical support for the numerical simulation of column leaching(in-situ leaching)of ion-adsorption type rare earth ores.

Anti-adsorption mechanism of ion-adsorption type rare earth tailings

To investigate the process of RE^(3+)anti-adsorption on ion-adsorption type rare earth tailings,the thermodynamics,adsorption kinetics and infrared spectroscopy of these materials were investigated.The results indicate that the initial reaction rate of anti-adsorption of rare earth tailings is fast,but it reaches a balance in 6 min.The formula 1-2a/3-(1-a)2/3=k_2t(k represents rate constant of the reaction,a represents anti-adsorption rate of rare earth ore,t represents anti-adsorption time)of internal diffusion can be used to predict the kinetics of anti-adsorption in IATRE tailings.BecauseΔH<0,ΔG<0,ΔS>0(ΔH,ΔG,ΔS represent change of enthalpy,Gibbs free energy and entropy,respectively),the anti-adsorption of RE^(3+)on ion-adsorption type RE tailings is a spontaneous physical adsorption process.The effects of ligand exchange and strong chemical bond are not found in this process.Because the anti-adsorption process is exothermic,heating will inhibit the reaction and decrease the anti-adsorption performance.According to the infrared spectrum analysis,there are no significant changes in the mineral surface after anti-adsorption.Based on these findings,the anti-adsorption of rare earth tailings is physical adsorption.

Geochemical Characteristics of Rare Earth Elements in Guposhan Granite Complex and Their Petrogenetic Implication

In this paper the geochemical characteristics of rare earth elements in Guposhan granite complex in NanlingArea,South China,is systematically studied,and the balance of REE distribution in rock-forming minerals,which contain only 21.47～29.71 wt% of total REE in granites,is calculated.The petrogenetic relationship be-tween three different stages of the granites in the complex is discussed,and a geochemical model is suggested forthe formation of granitic magma in early stage by partial melting of the crustal basement rocks containing moreREE than that in the late stage.It shows that a ion-adsorption type of REE deposit could ocuur in the weath-ering crust on the early stage granite.Rb-Sr isotope isochron dating of the first stage medium-coarse-grainedK-feldspar granite shows that its age is 146.5 Ma and initial 87Sr/86Sr ratio is 0.71198.

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.

Molecular dynamics simulation of aluminum inhibited leaching during ion-adsorbed type rare earth ore leaching process

Molecular dynamics simulation was adopted to study the interaction between sulfosalicylic acid and aluminum,lanthanum and yttrium,and adsorption on kaolinite surfaces.A complexation reaction occurs between sulfosalicylic acid and aluminum,with an interaction energy of-10472.05 kJ/mol.O—Al covalent bonds are formed with a peak value of 7.93,while there is only weak adsorption between sulfosalicylic acid and rare earth ions.A hydrogen bonding reaction with 13605.82 kJ/mol energy occurs between sulfosalicylic acid and the surface of kaolinite(100).Thus,sulfosalicylic acid can form a complex with free aluminum ions,and can also be adsorbed on kaolinite by hydrogen bonding with aluminum in kaolinite(100)surfaces.Leaching of ion-adsorbed type rare earth ore was performed with aluminum inhibited,results show that when sulfosalicylic acid dosage increases from 0 to 0.15 wt%,aluminum ion concentration in the leaching solution decreases from 273.23 to 47.19 mg/L.And the effect of leaching pH value on the effect of sulfosalicylic acid on aluminum inhibition was studied,the result shows that,when the leaching pH value is 4.0—5.0,the rare earth leaching rate and the aluminum ion concentration basically remain unchanged.The molecular dynamics simulation results were verified by detection and analysis of XPS and SEM.

Non-ammonia enrichment of rare earth by magnesium oxide from rare earth leaching liquor in magnesium salt system

In order to solve the problem of ammonia-nitrogen pollution in the enrichment process of the ionadsorption type rare earth ore,the technology of non-ammonia precipitation with magnesium oxide precipitant was carried out.It is determined that the rare earth precipitation efficiency is 99.6%and the purity of rare earth concentrates is only 85.89 wt%under the optimum precipitation conditions.And the contents of MgO,SO3 and Al2O3 in the rare earth concentrates are 5.12 wt%,6.77 wt%and 1.78 wt%,respectively.Furthermore,the thermo-decomposition process of precipitates was investigated by TGDSC,XRD and FI-IR.The thermal decomposition process consists of two stages:the dehydration of rare earth hydroxide and alkaline rare earth sulfate within 900℃and the thermal decomposition of RE2O2SO4 at 900-1300℃.Therefore,a high-temperature calcinations method for removing SO3 from precipitates is proposed.When the precipitates are calcined at 1300℃for 2 h,the rare earth concentrates with a purity of 92.03 wt%can be acquired.Moreover,the content of SO3 in the concentrate is only 0.46 wt%.In the MgO precipitation and high-temperature calcinations process,the raw material cost is low and the quality of rare earth concentrates is acceptable.It could have great significance for nonammonia enrichment of rare earth from the rare earth leaching liquor,and finally solve the problem of ammonia nitrogen in the extraction process of the ion-adsorption type rare earth ore within magnesium salt system.

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.

Extraction mechanism and separation behaviors of low-concentration Nd^(3+) and Al^(3+) in P507-H_(2)SO_(4) 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 Nd^(3+)and Al^(3+)in the Nd_(2)(SO_(4))_(3)-AI_(2)(SO_(4))_(3) mixed solution using P507 were studied in this work.The extraction of Nd^(3+)and Al^(3+)follows the cation exchange mechanism.With the increase of the equilibrium pH,β_(Nd/Al) in the extraction of the Nd_(2)(SO_(4))_(3)-Al_(2)(SO_(4))_(3) mixed solution using P507 is always higher than that in the extraction of single Nd_(2)(SO_(4))_(3) and Al_(2)(SO_(4))_(3) solutions.It can be attributed to the fact that the extraction of Nd^(3+)using P507 is much faster than that of Al^(3+),and Al^(3+)is more prone to be hydrolyzed at lower pH.β_(Nd/Al) in the extraction of the Nd_(2)(SO_(4))_(3)-Al_(2)(SO_(4))_(3) mixed solution decreases gradually with the increase of mixing time within the equilibrium pH range of 1.5-1.9.The extraction of Nd^(3+)using P507 is much faster than that of Al^(3+),but the stability of Al^(3+)-Ioaded organic phase is better than that of Nd^(3+)-loaded organic phase,thus Nd^(3+)in the Nd^(3+)-loaded organic phase is gradually replaced by Al^(3+)in the aqueous phase with the increase of mixing time.