New Technology “Flotation to Form Agglomerates and Magnetic Separation” Allows Great Breakthrough for World Low-Grade Light Rare Earth Ores

Rare earth resources are relatively scarce worldwide, but their global consumption is increasing year-by-year. At present, China has about 36% of the global rare earth reserves, but provides 90% of the world＇s supply, which has generally met world demand and promoted the development of the world economy. In order to continuously and stably supply rare earths to international markets, the Chinese Government has financially supported the Institute of Multipurpose Utilization of Mineral Resources within the China Geological Survey to study the utilization of low-grade rare earth ores. Following many years of experimental research, the project has developed a new technology entitled ＂Flotation to Form Agglomerates and then Magnetic Separation＂, which will bring a technological revolution to the world＇s light rare earth ore dressing.

Partitioning properties of rare earth ores in China

The properties of rare earth partitioning in Chinese industrial rare earth ores were analyzed. Rare earth ores can be divided into the single-mineral type ore with bastnaesite, the multi-mineral type ore with bastnaesite and monazite, and the weathering crust type. Both the Bayan Obo rate earth ore and the Zhushan rate earth ore are a kind of mixed ore, consisting of basmaesite and monazite. Their rate earth partifionings are strongly enriched in light rate earths, where CeO2 is 50% and the light rate earth partitioning is totally over 95%. The Mianning rate earth ore as well as the Weishan rate earth is a kind of rate earth ore only having basmaesite. Their rare earth partitionings are also strongly enriched in light rate earths, in which CeO2 is 47% and the light rare earth partitioning is totally over 94%. For the weathering crust type rate earth ore, there are the Longnan rare earth ore, the Xunwu rare earth ore, and the middle yttrium and rich europium ore. In the Longnan rate earth ore, which is strongly enriched in heavy rate earths, Y2O3 is 64.83%, and the heavy and light rate earth partitionings are 89.40% and 10.53%, respectively. In the Xunwu rate earth ore, which is strongly enriched in light rate earths, CeO2 is 47.16%, and the light rate earth partitioning is totally 93.25%. Y and Eu are enriched in the middle yttrium and rich europium ore. Its middle rare earth partitioning is totally over 10%, and Eu2O3 and Y2O3 are over 0.5% and 20%, respectively, which are mainly industrial resources of the middle and the heavy rare earths.

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.

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.

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.

Swelling of clay minerals in ammonium leaching of weathered crust elution-deposited rare earth ores

The effect of hydrated radius, cation valence, pH and solution concentration on the zeta potential of clay minerals was investigated, and the relation between zeta potential of clay minerals and swelling was discussed in different leaching agents as well. The results show that the zeta potential of clay minerals decreases with the hydrated ionic radius increasing. It could be seen that the zeta potential of the clay minerals in AICl3 solution is positive,whereas that in NH4C1, KCl and MgCl2 solution is negative. And the zeta potential of clay minerals increases with the cation valence increasing. Moreover, the zeta potential of clay minerals decreases with the solution pH increasing,whereas that increases with the solution concentration increasing in different ammonium solutions. In addition,the swelling of clay minerals decreases while the zeta potential of clay minerals increasing in different ammonium solutions. The ability of compound ammonium to inhibit the swelling of clay minerals is lower than that of single ammonium solution.

Dissolved rare earth elements estimation of ion-absorption rare earth ores using reflectance spectroscopy in south Jiangxi province,China

Ion-absorption rare earth ores are an important mineral resource in China.Nowadays,the unauthorized mining has become a serious problem,resulting in severe water pollution and the wastage of rare earth elements(REEs).Being able to estimate the concentration of dissolved REEs in water bodies near mines is essential for tackling this environmental problem.Conventionally,quantitative analyses of the contents of dissolved REEs are performed using laboratory-based techniques,which can be time consuming and costly.Spectral reflectance is a rapid and cost-effective means of characterizing the chemical compositions of light-absorbing materials.In this study,reflectance spectroscopy was performed on dissolved REEs,and the correlation between their reflectance characteristics and REE content was determined.A total of 50 aqueous media samples collected in south Jiangxi Province and 25 laboratory-produced aqueous media samples were tested,and their reflectance spectra and REE contents were measured using reflectance spectroscopy and inductively coupled plasma mass spectrometry,respectively.Next,the reflectance,differential reflectance,and absorption depth were analysed based on the REE content.Six diagnostic absorption features related to REEs are recognised in the visible and near-infrared wavelength regions,along with several smaller peaks.It indicates that the results of the absorption depth analysis are in accordance with the absorption spectra characteristics of the REEs,with the R2 value being higher than 0.97.The intensity of each of the six absorption bands exhibits a linear correlation to the total REE content.Therefore,linear regressio n models can be derived for estimating the total concentration of REEs in aqueous media samples.What’s more,the detection limit for REEs is determined to be about 30μg/L.Thus,it can be concluded that reflectance spectroscopy is a suitable technique for estimating the concentration of dissolved REEs.

Leaching hydrodynamics of weathered elution-deposited rare earth ore

Both porosity ( φ ) and permeability ( k ) of the weathered elution deposited rare earth ores are basic hydrodynamic parameters for RE leaching. The relationship between k and φ of two typical rare earth ores of South China in the packed bed was investigated by measuring the flow ( Q ) under various leaching pressure difference (Δ p ). The experimental results show that the relationship between k and φ is unique, moreover the relationship between Q and Δ p is in accord with the Darcy’s law. The effects of the type of ores, the leaching reagents and its concentration, the granule ore size on the leaching permeability have also been investigated. It is demonstrated that k H (for heavy RE ore, k H=35.98?mm 2)> k M H (for middle heavy RE ore, k M H =28.50?mm 2), whereas k (NH 4NO 3)> k (NH 4Cl)> k [(NH 4) 2SO 4], and the k value increases with increasing leaching reagents concentration and granule ore size( k 0.60～0.75?mm =99.96?mm 2, k 0.125～0.60?mm =11.83?mm 2, k 0.074～0.125?mm =0.84?mm 2). [

Enhancing the leaching effect of an ion-absorbed rare earth ore by ameliorating the seepage effect with sodium dodecyl sulfate surfactant

Ameliorating the problem of low leaching efficiency,long leaching period,and high agent consumption should be studied to efficiently exploit ion-absorbed rare earth ore resources.In this study,the surfactant sodium dodecyl sulfate(SDS) is used to enhance the leaching effect of an ion-absorbed rare earth ore by ameliorating the seepage effect for the first time.The effects of surfactant concentration,leaching agent dosage,solution flow velocity,and solution pH on the leaching rate were explored,and the mechanism of SDS was discussed.Under the optimum conditions,the addition of a small amount of SDS(mass fraction0.04%) can increase the leaching rate by about 5%,shorten the leaching period,and reduce the consumption of the leaching agent.SDS significantly ameliorates the seepage effect of the ore body by reducing the surface tension of the leaching agent and ameliorating the wettability of the mineral surface.This effect is the main factor that improves the leaching efficiency.DFT(density functional theory) calculation results show that SDS can react with rare earth ions,which reduces the adsorption strength on clay mineral surfaces.Hence,rare earth ions are easily exchanged by ammonium ions,and mass transfer is enhanced.

Pore structure characterization and seepage analysis of ionic rare earth orebodies based on computed tomography images

Pore network structure of ore body is a diffusion channel of leaching agent solution that exerts a significant influence on seepage.The ore body structure,pore distribution,pore and throat size,and pore network characteristics of topsoil,weathered,and semiweathered layers of ionic rare earth ore in southern Jiangxi Province were explored in this study.The effect of leaching operation on the pore structure was investigated,and main factors affecting the seepage were analyzed.Results showed that the semiweathered layer presents a dense structure and a small number of unconnected pores.Pores of topsoil and weathered layers are mainly long and narrow column openings with some planar fractures.Even pore distribution and large size span were observed.Compared with the weathered layer,the topsoil layer demonstrates larger voids,smaller average pore volume and equivalent radius,and fewer coordination throats;however,the average equivalent radius of the throat in the topsoil layer is larger and largescale channels exist through ore body vertically.Hence,permeability of the topsoil layer is significantly higher than that of the weathered layer.Colloidal clay minerals migrate easily and the occurrence of silting in the small porosity blocks the throat and significantly decreases the permeability of the ore body in the leaching process.The equivalent radius of the throat is the key to the seepage.Reducing the migration of fine particles is an effective measure to protect the throat and shorten the leaching period.

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.

Readsorption of rare earth elements during leaching process of ion-adsorption-type rare earth ore

A leaching experiment on simulated rare earth ore pillars with uneven grade distribution was conducted because of the readsorption of rare earth elements in the in situ leaching process of ion-adsorption-type rare earth ore.Results show that the readsorption of rare earth elements in the barren layer is the main reason for the decrease in rare earth concentration in the leachate,decrease in rare earth recovery and extension of the leaching process.This limitation could be affected by the concentration of rare earth of the influent flow passing through the barren ore layer,and pH value of leaching agents shows minimal effect during leaching.The magnesium sulfate leaching process requires higher liquid-tosolid ratio than the ammonium sulfate leaching process.The former also has lower peak value of rare earth concentration and more significant tailing in the leaching curve.The readsorption of rare earth elements in the barren layer is more severe in magnesium sulfate leaching than in ammonium sulfate leaching.Thus,areas without ore belts should be avoided when magnesium sulfate is used for leaching.

Anti-swelling mechanism of DMDACC on weathered crust elution-deposited rare earth ore

In order to inhibit the swelling of the clay minerals in the in-situ leaching process of weathered crust elution-deposited rare earth ores(WCE-DREO),diallyl dimethyl ammonium chloride(DMDACC)was introduced as an anti-swelling agent and combined with(NH_(4))_(2)SO_(4)as a novel composite leaching agent.It can be found that the novel composite leaching agent exhibits a good anti-swelling performance and leaching capacity of rare earth,and has great potential on the actual exploitation of WCE-DREO.The antiswelling mechanism of DMDACC was studied by characterization analysis.The results show that DMDACC with positive charges can be adsorbed on the clay particles by the electrostatic attraction and hydrogen bonds,and neutralize the negative charge of the clay particles.The double electrical layers are suppressed and the repulsion force between clay sheets decreases.It causes the clay particles prone to aggregate.Moreover,DMDACC can enter the interlayer and expel out the water molecules in interlayer.The interlayer spacing is decreased and the hydration swelling of the clay particles is weakened.It can provide a theoretical basis for the development of novel anti-swelling agents.

Leaching hydrodynamics of weathered elution-deposited rare earth ore with ammonium salts solution

In order to reveal the permeability rule of leaching agent solution and the effects of anions in the leaching process of weathered crust elution-deposited rare earth（RE） ores, the effects of ammonium concentration, temperature, particle size and porosity on the permeability were discussed in detail with（NH4）2SO4, NH4Cl and NH4NO3 as the leaching agent. It was found that the permeation velocity of ammonium salts increased linearly with the increase of hydraulic gradient. The seepage of ammonium salts solution in the RE ores followed Darcy’s law and displayed a laminar flow. The properties of the leaching agent solution and RE ores were the main factors that affect the permeability of RE ores. With the decrease of ammonium concentration and increase of temperature, the viscosity of solution decreased and the permeability coefficients of RE ores increased. And the effects of temperature on the viscosity and permeability were larger than ammonium concentration. The permeability of RE ores became worse with the decrease of particle size and porosity, and the particle size played a more important role compared with porosity. The permeability coefficient of RE ores increased and the viscosity of ammonium salts solution decreased in the order of（NH4）2SO4, NH4Cl and NH4NO3, implying that the penetrating power of anions increased in the order of SO42-, Cl- and NO3-. The results may play a vital role in improving the permeability of weathered crust elution-deposited RE ores.

Reduction leaching of rare earth from ion-adsorption type rare earths ore with ferrous sulfate

The practice ofin-situ leaching of the ion-adsorption type rare earths ore with ammonium sulfate could only leach most of rare earth in ion-exchangeable phase, but not the colloidal sediment phase. Therefore, the reduction leaching of rare earth from the ion-adsorption type rare earths ore with ferrous sulfate was innovatively put forward. The soak leaching process and the column leaching process were investigated in the present study. It was determined that ion-exchangeable phase could be released, and part of colloidal sediment phase rare earth could be reduction leached by the cations with reduction properties. The mechanism of reduction leaching was discussed with the Eh-pH diagram of cerium. Moreover, the stronger reduction of reductive ions, the greater acidity of leaching agent solution, and the higher reductive ion concentration, could result in the higher rare earth efficiency and the bigger ce-rium partition in the leaching liquor. In the ferrous sulfate column leaching process, the rare earth leaching rate and the rare earth effi-ciency were a little higher than with （NH4）2SO4 agent, and the rare earth efficiency and the partitioning of cerium in leaching liquor could be about 102% and 5.31%, respectively. However, the ferrous sulfate leaching process revealed some problems, so compound leaching with magnesium sulfate and a small amount of ferrous sulfate was proposed to an excellent alternative leaching agent for further studies, which may realize efficiency extraction and be environment-friendly.

Recovery of rare earths from ion-absorbed rare earths ore with MgSO_4-ascorbic acid compound leaching agent

The magnesium sulfate leaching technology for the ion-absorbed rare earths ore can solve the ammonia pollution problem existing in ammonium sulfate leaching process. However, the leaching capacity of magnesium sulfate is slightly weaker than that of ammonium sulfate, resulting in a bigger consumption of magnesium sulfate. In this paper, the MgSO4-ascorbic acid compound leaching agent had been demonstrated to deal with the ion-absorbed rare earths ore. The ascorbic acid could form a stable coordination with rare earth ions, so that it can strengthen the leaching of ion-exchangeable phase.Moreover, ascorbic acid has a strong reductive property, it can leach the colloidal sediment phase rare earth as well. The present study investigates the effect of the initial pH and the composition of leaching agent on the rare earth leaching. It is determined that the rare earth leaching efficiency is 107.5% under the condition of pH 2.00,0.15 mol/L magnesium sulfate and 1.0 g/L ascorbic acid in leaching agent. In this case, the content of the ion-exchangeable phase and colloidal sediment phase rare earth in the leaching residues are both only 0.02‰. The leaching efficiency of colloid sediment phase rare earth can be 85.7%,so that the Ce partition in the leaching liquor increases to be 5.77%. The magnesium-ascorbic acid compound leaching agent is proposed to be a promising choice to deal with the ion-absorbed rare earths ore, which can realize the efficient leaching, low consumption of MgSO4 and environmentally friendly leaching.

Removing aluminum from a low-concentration lixivium of weathered crust elution-deposited rare earth ore with neutralizing hydrolysis

Aluminum,the main impurity in the lixivium of weathered crust elution deposited rare earth ore,not only results in an increasing consumption of precipitant in the rare earth precipitation process,but also lowers the purity of final rare earth product.Aluminum in the weathered crust elution-deposited rare earth ore lixivium should be removed.Neutralizing hydrolysis method was employed to remove aluminum from the lixivium.Hexamethylenetetramine was found to be the optimum pH regulator for the removal of aluminum in the low concentration.When used to adjust the pH value of the lixivium to 5.0,aluminum in the lixivium can be effectively removed in the form of aluminum hydroxide precipitation with removal rate of 97.60%.It shows that hexamethylenetetramine has a good effect on the removing of aluminum ions from the lowconcentration lixivium.Moreover,hexamethylenetetramine in removing aluminum from lixivium has little adverse effect on the RE precipitation process.

High throughput online sequential extraction of natural rare earth elements and determination by mass spectrometry

At the beginning of rare earth industry,several days are normally required for characterization of rare earth elements(REEs)fractionation in ore samples.Herein,rapid fractionation analysis of 15 REEs and accompanied metal(Fe,Mn,etc.)in ore samples has been achieved within 1 h using ICP-MS with a homemade device for online sequential solvent extraction.As a result,five fractionations for REEs occurrences,i.e.,water soluble,exchangeable,reducible,oxidizable and crystalline,have been identified,offering chemical insights which not only reveal the formation mechanism of REEs ores but also show great implications for guiding the exploitation and separation of REEs.In comparison with conventional methods,the present approach significantly shortened the analysis time(1 h vs.~80 h)and reduced the sample consumption(1.0 mg vs.5.0 g)with high recovery(>95%),providing a useful platform for the rapid quantitative fractionation analysis of REEs in complexed samples such as ore and fossils.

Process optimization of rare earth and aluminum leaching from weathered crust elution-deposited rare earth ore with compound ammonium salts

In order to intensify the leaching process of rare earth（RE） and reduce the impurities in the leachate, ammonium chloride（NH4Cl） and ammonium nitrate（NH4NO3） were mixed as a compound leaching agent to treat the weathered crust elution-deposited RE ore. Effects of molar ratio of NH~＋_4Cl and NH_4NO_3, ammonium（NH_4） concentration, leaching agent pH and flow rate on the leaching process of RE were studied and evaluated by the chromatographic plate theory. Leaching process of the main impurity aluminium（Al） was also discussed in detail. Results showed that a higher initial ammonium concentration in a certain range could enhance the mass transfer process of RE and Al by providing a driving force to overcome the resistance of diffusion. pH almost had no effects on the mass transfer efficiency of RE and Al in the range of 4 to 8. The relationship between the flow rate and height equivalent to a theoretical plate（HETP） could fit well with the Van Deemter equation, and the flow rate at the lowest HETP was determined. The optimum conditions of column leaching for RE and Al were 1：1（molar ratio） of NH_4Cl and NH_4NO_3, 0.2 mol/L of ammonium concentration, pH 4–8 of leaching agent and 0.5 mL /min of flow rate. Under this condition, the mass transfer efficiency of RE was improved, but no change was observed for Al compared with the most widely used ammonium sulfate. Moreover, the significant difference value（around 20 mL） of retention volume at the peak concentration between RE and Al provided a possibility for their separation. It suggested the potential application of the novel compound leaching agent（NH_4Cl/NH_4NO_3）. It was found that the relative concentration of RE in the leachate could be easily obtained by monitoring the pH of leachate.

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.