Column leaching process of rare earth and aluminum from weathered crust elution-deposited rare earth ore with ammonium salts

In order to better understand the leaching process of rare earth （RE） and aluminum （Al） from the weathered crust elutiondepositedRE ore, the mass transfer of RE and Al in column leaching was investigated using the chromatographic plate theory. Theresults show that a higher initial ammonium concentration in a certain range can enhance the mass transfer process. pH of leachingagent in the range of 2 to 8 almost has no effect on the mass transfer efficiency of RE, but plays a positive role in the mass transferefficiency of Al under strong acidic condition （pH〈4）. There is an optimum flow rate that makes the highest mass transfer efficiency.The optimum leaching condition of RE is the leaching agent pH of 4？8, ammonium concentration of 0.4 mol/L and flow rate of0.5 mL/min. The mass transfer efficiencies of RE and Al both follow the order： （NH4）2SO4〈NH4Cl〈NH4NO3, implying thecomplexing ability of anion.

Leaching process of rare earths from weathered crust elution-deposited rare earth ore

In order to strengthen the leaching procedure,the chemical processes of leaching rare earths (RE) from the weathered crust elution-deposited rare earth ore were investigated frow the viewpoints of kinetics,hydrodynamic and mass transfer.The results show that the leaching hydrodynamics follows the Darcy law.The leaching kinetics can be described by the shrinking core model;the leaching process is controlled by diffusion of porous solid layer;and the mass transfer can be described with Van Deemter equation.This provides a theoretic basis and a scientific approach with high efficiency and optimized extraction conditions in industrial practice.

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.

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). [

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.

Simulation of one-dimensional column leaching of weathered crust elution-deposited rare earth ore

The ion exchange model of the leaching process was determined via batch leaching experiments using the Kerr model, with the selectivity coefficient experimentally determined to be 12.59×10^-10 L^2/g^2. Solute transport laws of ammonium ions (NH4 +) and rare earth ions (RE^3+) in column leaching were described by the convection-dispersion equation (CDE). The source and sink in the CDE were determined by the Kerr model. The CDE with strong nonlinearity was solved using the sequential non-iterative method. Compared with the breakthrough curve of RE^3+, the correlation coefficient between the simulated and experimental curves reached 0.8724. Therefore, this method can simulate the one-dimensional column leaching of weathered crust elution-deposited rare earth ore. Moreover, the effects of different concentrations of ammonium sulfate ((NH4)2SO4) solution on the leaching rate of rare earth were analyzed. The optimal concentration of the (NH4)2SO4 solution had a linear relationship with the rare earth grade.

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.

Effect of particle size and grain composition on two-dimensional infiltration process of weathered crust elution-deposited rare earth ores

The two-dimensional infiltration experiment was carried out by means of digital image technology.The evolution process of the wetting body was described.The wetted front distance and the time show a very significant power function relationship.The horizontal wetted distance is larger than the vertical wetted distance in the initial stage.Then,the vertical distance of the wetted body gradually approaches to the horizontal distance.The infiltration distance decreases as the content of fine particles increases.The wetted front migration rate curve shows a three-stage change law,and it increases with the increase of coarse particle content.The directional velocity ratio is defined.The initial value of horizontal infiltration rate is larger than that of vertical one,and then the vertical infiltration rate is gradually close to the horizontal value.The empirical relationship between the characteristic particle size and the stable infiltration rate is established,which provides a theoretical basis for the prediction of the stable infiltration rate in in-situ leaching.

Soil−water characteristics of weathered crust elution-deposited rare earth ores

The permeability of the weathered crust elution-deposited rare earth ores directly affects the efficiency of in-situ leaching.The soil−water characteristic curve(SWCC)is an important constitutive relation for calculating the permeability of ore body,which is related to many factors.Soil−water characteristic tests of rare earth ore samples considering different factors were carried out by using the pressure plate instrument.Effects of dry density,particle size and solution leaching on water holding behavior and the mechanism were investigated.The experimental observations indicate that with the decrease of dry density,the pore ratio increases gradually,and the saturated water content increases.Under the same matric suction,the water content decreases gradually with the increase of particle size,thus decreasing water holding capacity of ore accordingly.In the same water content,matric suction is inversely proportional to particle size.Under the same matric suction,the water content of ore samples after leaching is less than that of the ore samples before leaching,indicating that solution leaching can decrease water holding capacity of ore.

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.

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.

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.

Leaching characteristics of ion-adsorption type rare earths ore with magnesium sulfate

Magnesium sulfate was proposed to be leaching agent to deal with the ion-adsorption type rare earths ore to reduce or even eliminate ammonia?nitrogen emissions. The effects of temperature, particle size and stirring speed on rare earth leaching process and the leaching behaviors of the single rare earth element were investigated in order to reveal the rare earth leaching characteristics. Besides, the comparison of leaching effects between magnesium sulfate and ammonium sulfate was also studied. The results showed that the rare earth leaching process could be well described with inner diffusion control model and the apparent activation energy was 9.48 kJ/mol. The leaching behaviors of the single rare earth element were brought into correspondence with rare earths. Moreover, when the concentration of leaching agent was 0.20 mol/L, the rare earth leaching efficiency could all reach above 95% and the leaching efficiency of aluminum impurities could be restrained by 10% using magnesium sulfate compared with ammonium sulfate.

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.

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.

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.

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.

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.

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.