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.

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.

Effect of surfactant addition on leaching process of weathered crust elution-deposited rare earth ores with magnesium sulfate

Surfactants were proposed to be added into magnesium sulfate solution to improve the leaching process of weathered crust elution-deposited rare earth ores(WREOs).Effects of surfactants and their concentration on the seepage of leaching solutions and the leaching efficiency of rare earth(RE)and aluminum(Al)were investigated,and the leaching kinetics,the mass transfer process,the adhesion work and the adhesion work reduction factor were analyzed to reveal its strengthening leaching mechanism.The results show that cetyltrimethylammonium bromide(CTAB)has a better strengthening effect on the leaching process than dodecyl trimethyl ammonium bromide(DTAB),sodium dodecyl sulfate(SDS),sodium oleate and oleic acid.In the presence of 0.04%CTAB in 0.2 mol/L solution,the permeability coefficient of WREOs increases from 0.945×10^(-5)to 1.640×10^(-5)cm·s^(-1),and the leaching efficiency of RE increases from 80%to 90%,confirming the promotion of surfactants on the leaching process of WREOs.Kinetic analysis shows that the leaching process conforms to the inner diffusion control model,and the leaching kinetics equations of RE and Al related to CTAB content are obtained.Mass transfer discussion shows a smaller height equivalent to theoretical plate(HETP)of RE and Al at CTAB content of 0.04%,suggesting the higher mass transfer efficiency here.According to the interfacial properties of leaching solutions,the calculated adhesion work and the adhesion work reduction factor further demonstrate the strengthening leaching effect of CTAB on the leaching process of WREOs.

Effect of particle gradation on pore structure and seepage law of solution in weathered crust elution-deposited rare earth ores

Both CT and Avizo software were used to explore the effect of particle gradation on the evolution characteristics of pore structure and seepage paths in weathered crust elution-deposited rare earth ores during leaching.The results showed that the pore areas in four kinds of ore samples before leaching were mainly concentrated in 10^(4)–10^(7)μm^(2),whose pore quantities accounted for 96.89%,94.94%,90.48%,and 89.45%,respectively,while the corresponding pore volume only accounted for 30.74%,14.55%,7.58%,and 2.84%of the total pore volume.With the decrease of fractal dimension,the average pore throat length increased,but pore throat quantities,the average pore throat radius and coordination number decreased.Compared with that before leaching,the change degree of pore structure during leaching increased with the fractal dimension decreasing.For example,the reduction rate of the average coordination number of ore samples was 14.36%,21.30%,28.00%,and 32.90%,respectively.Seepage simulation results indicated that seepage paths were uniformly distributed before leaching while the streamline density and seepage velocity increased with the fractal dimension decreasing.Besides,the phenomenon of the streamline interruption gradually reduced during leaching while preferential seepage got more obvious with the decrease of the fractal dimension.

Leaching behaviors of calcium and magnesium in ion-adsorption rare earth tailings with magnesium sulfate

The leaching behaviors of calcium and magnesium in the rare earth tailings leached with magnesium sulfate using deionized water,CaCl2 solution and lime water were investigated.Experimental data indicated that magnesium in the tailings was easy to be leached out since most of the magnesium was in the form of water-soluble phase.Most of calcium in the lime water was electrostatically adsorbed on the clay mineral of the tailings,and the water-soluble magnesium was also gradually converted into exchangeable phase because of back-adsorption of Mg2+on the clay mineral with increasing the pH values.When the liquid-to-solid ratio was 0.80,the contents of readily-available magnesium and calcium were 104.4−207.6 and 201.7−1426.3 mg/kg,respectively,which could meet the requirements for plants.These results suggest a promising route for the environmental remediation of ion-adsorption rare earth ore after in-situ leaching.

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.

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.

Correlation analysis on partition of rare earth in ion-exchangeable phase from weathered crust ores

The rare earth(RE)in weathered crust ores mainly exists as ion-exchangeable phase,approximately 80%.The correlation analysis on partition of 376 samples in ion-exchangeable phase from weathered crust ores was conducted.The results show that partition both among heavy RE elements and light RE elements with high partition appears positive correlation,but partition sums between the heavy RE elements and the light RE elements appear close negative correlation obviously.Clear negative correlations exist between the light RE elements(except Ce)and yttrium(Y).Matrix of correlation analysis on this partition can be divided into three zones.The correlated coefficient variation from negative to positive in zones B and C occurs at Gd,so does that in zones B and A(except Ce,Eu,and Sm),suggesting that RE elements can be divided into two groups with Gd as border.This phenomenon is called Gadolinium-broken effect.

A mathematical model for column leaching of ion adsorption-type rare earth ores

Column leaching experiments with ion adsorption-type rare earth ores for different lixiviant concentrations and different column heights were carried out.A mathematical model of column leaching was constructed based on the experimental data.Two parameters(a and b)in the model were determined according to the following methodology:the ore column was divided into several units;each unit was treated with multiple leaching steps.The leaching process was simulated as a series of batch leaching experiments.Parameter a of the model was determined based on the selectivity coefficient of the balanced batch leaching experiment.Further,the influences of ammonium sulfate concentration,rare earth grade,column height,permeability coefficient,and hydrodynamic dispersion coefficient on the extraction were analyzed.Relationships between parameter b,the ammonium sulfate concentration,and the physical and mechanical properties of the ore column,were examined using dimensional analysis.It was determined that the optimal ammonium sulfate concentration for different column heights(2.5,5.0,7.5,and 10.0 cm)using the mathematical model were 5.9,6.2,7.3,and 7.7 g/L,respectively.The mathematical model can be used to estimate the breakthrough curve,leaching rate,and leaching period of rare earth ores,to achieve optimal extraction.

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.

Scandium recovery from ion-adsorption rare earth concentrate with HEHEHP as extractant

An excellent extraction selectivity towards Sc over other REEs in 4 mol/L HCl solution was achieved with the separation factor βSc/REEs over 8000 by 2-ethylhexyl phosphoric acid mono 2-ethylhexyl ester(HEHEHP)and the extraction equilibrium can be obtained within 20 min.The extracted Sc can be stripped using 5 mol/L NaOH solution as eluent at 363 K with the stripping rate of 92.1%obtained.The extraction mechanism was clearly elucidated by slope analysis,saturation extraction,IR,and NMR analysis.It was revealed that the extraction of Sc in 4 mol/L HCl solution is still dominated by cation exchange process between P-O-H and Sc,and coordination process between P=O and Sc,with 6 molecules of extractant as dimer participating in the process.Finally,a flowsheet for the recovery of Sc from ion-adsorption rare earth elements(REEs)concentrate was proposed and proved in lab-scale experiment.

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.

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.

Kinetics of rare earth leaching from roasted ore of bastnaesite with sulfuric acid

Sulfuric acid leaching process was applied to extracting rare earth（RE） from roasted ore of Dechang bastnaesite in Sichuan,China.The effect of particle size,stirring speed,sulfuric acid concentration and leaching temperature on RE extraction efficiency was investigated,and the leaching kinetics of RE was analyzed.Under selected leaching conditions,including particle size（0.074-0.100 mm）,sulfuric acid concentration 1.50 mol/L,mass ratio of liquid to solid 8 and stirring speed 500 r/min,the leaching kinetics analysis shows that the reaction rate of leaching process is controlled by diffusion through the product/ash layer which can be described by the shrinking-core model,and the calculated activation energy of 9.977 kJ/mol is characteristic for a diffusion-controlled process.

Trace Elements and Rare Earth Elements of Sulfide Minerals in the Tianqiao Pb-Zn Ore Deposit,Guizhou Province,China

Trace elements and rare earth elements（REE） of the sulfide minerals were determined by inductively-coupled plasma mass spectrometry.The results indicate that V,Cu,Sn,Ga,Cd,In,and Se are concentrated in sphalerite,Sb,As,Ge,and Tl are concentrated in galena,and almost all trace elements in pyrite are low.The Ga and Cd contents in the light-yellow sphalerites are higher than that in the brown and the black sphalerites.The contents of Ge,Tl,In,and Se in brown sphalerites are higher than that in light-yellow sphalerites and black sphalerites.It shows that REE concentrations are higher in pyrite than in sphalerite,and galena.In sphalerites,the REE concentration decreases from light-yellow sphalerites,brown sphalerites,to black sphalerites.The ratios of Ga/In are more than 10, and Co/Ni are less than 1 in the studied sphalerites and pyrites,respectively,indicating that the genesis of the Tianqiao Pb-Zn ore deposit might belong to sedimentary-reformed genesis associated with hydrothermal genesis.The relationship between LnGa and LnIn in sphalerite,and between LnBi and LnSb in galena,indicates that the Tianqiao Pb-Zn ore deposit might belong to sedimentary-reformed genesis.Based on the chondrite-normalized REE patterns,δEu is a negative anomaly（0.13-0.88）,andδCe does not show obvious anomaly（0.88-1.31）;all the samples have low total REE concentrations（〈3 ppm） and a wide range of light rare earth element/high rare earth element ratios（1.12-12.35）.These results indicate that the ore-forming fluids occur under a reducing environment.Comparison REE compositions and parameters of sphalerites,galenas,pyrites,ores,altered dolostone rocks,strata carbonates,and the pyrite from Lower Carboniferous Datang Formation showed that the ore-forming fluids might come from polycomponent systems,that is,different chronostratigraphic units could make an important contribution to the ore-forming fluids.Combined with the tectonic setting and previous isotopic geochemistry evidence,we conclude that the ore-deposit genesis is hydrothermal,sedimentary reformed,with multisources characteristics of ore-forming fluids.

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.

Application of surfactant for improving leaching process of weathered crust elution-deposited rare earth ores

Weathered crust elution-deposited rare earth ores(WREOs)in China are the main source of medium and heavy rare earths in the world.In order to improve the seepage and the mass transfer of traditional ammonium salt leaching process of WREOs,surfactants were added in the ammonium sulfate leaching solution and the ammonium chloride leaching solution.The leaching kinetics,the mass transfer process,and the adhesion work reduction factor calculated from the interfacial properties were studied to reveal the strengthening mechanism of surfactant.In the presence of the tested five surfactants,cetyl trimethyl ammonium bromide(CTAB),dodecyl trimethyl ammonium bromide(DTAB),sodium dodecyl sulfate(SDS),sodium oleate and oleic acid,the permeability of WREOs is improved,the rare earth(RE)leaching efficiency increase and the impurity aluminum(Al)leaching efficiency decrease,indicating its promotional effect on the leaching process of WREOs.Furthermore,CTAB shows a better leaching enhancement,and the optimal addition dosage is 0.4 g/L for the two ammonium salt leaching agent systems.The kinetics analysis shows the internal diffusion controls model of RE and Al leaching process,and the leaching kinetics equations of RE and Al related to CTAB concentration were obtained for the two ammonium salt leaching systems.According to the chromatographic plate theory,the mass transfer efficiency of RE increases with the CTAB concentration increasing until 0.4 g/L,which confirms that the optimal CTAB addition is 0.4 g/L.Smaller adhesion work and adhesion work reduction factor indicate more favorable permeation as well as the leaching process.

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.

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.