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.

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.

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.

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 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.

Geochemistry of Rare Earth Elements in Xikeng Ag-Pb-Zn Ore Deposit, South Anhui, China

In this paper, a comparative study is done on the geochemical charateristics of REE in ore, ore-hosted rocks of Lantian group, granite related to ore deposit, and altered rocks for tracing origin of ore-forming materials. The result indicates that the ore-forming fluid and ore-forming materials for Xikeng silver-polymetallic ore deposit were derived from Yixian granite's magmatic activity. Water-rock reaction of the hydrothermal fluid with the carbonate-rich stratum led the altered rock to relatively enrich in HREE.

Geochemistry of Rare Earth Elements in Hydrothermal Ore Deposit in Heishan Area,Shaanxi Province

The study on rare earth elements in hydrothermal ore deposit in Heishan area indicates that the REE concentration in rock with very weak negative Ce and Eu anomaly is far higher than those in ore. The REE pattern in ore is characterized by very low REE concentration, typical enrichment in LRE and distinctive negative Eu and Ce anomaly. δ Eu and δ Ce values vary from 0 51～0 6 to 0 71～0 77 and 0 84～0 88 to 0 60～0 78, respectively, as shown in samples from Fe Cu ore to Au ore. Different δ Eu and δ Ce values reveal that temperature gradually decreases and oxygen fugacity gradually increases when ore bearing hydrothermal solution evolves from early to late stage. It is likely that REE in solution is mainly transported in the forms of(RE(CO 3) 3F) 4- , (RE(CO 3)F 2) -, (RE(F,Cl) 2) + , (RE(CO 3) 3) 3- and (RE(CO 3) 4) 5- complexes.

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.

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.

RECOVERING RE FROM LEACHING LIQUOR OF RARE EARTH ORE BY EXTRACTION

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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.

Calcination-Digestion-Desliming of Phosphorus Ore Bearing Rare Earth

The recoveries of phosphorus and RE of ore from Zhijin in Guizhou were studied.The influences of the calcination temperature, resident time, the digested time and water volume of the calcinating on concentrate yield by desliming were also investigated by orthogonal design.Appropriate calcination temperature is initial condition that makes carbonate mineral decomposition.The recovery of phosphorus is 83.02% and rare earth is 90.56% in phosphorus concentrate when calcined temperature is 900 ℃, other conditions include: calcined time is 30 min, digestion water volume is 300 ml, digestion time is 20 min.The results show that the pre-treatment of the ore is favorable for the separation and enrichment of rare earth from phosphorus ore, and a process of calcination-digestion-desliming was promised.

Geochemical Behavior of Rare Earth Elements in Jianchaling Ore Depositin Shaanxi Province

Studies on rocks and ores of Jianchaling ore deposit, southern Shaanxi, show that REE patterns in the ores clearly differ from that in ultrabasic and acidic rocks. The REE pattern in Ni ore is similar to that in Au ore and is characterized by typical enrichment in LREE and sharp negative Eu and Ce anomalies, indicating that Ni ore and Au ore were formed from the same hydrothermal solution. δ Eu and δ Ce variations reflect that Ni ore is formed at higher temperature and relative reduction environment, and Au ore at lower temperature and relative oxidation environment. The characteristics imply that the ore forming materials were derived from the ultrabasic rock and the hydrothermal solution is a post magmatic acidic solution.

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.

A Geochemical Study of Rare Earth and Trace Elements in Cassiterite from Dachang Sn-Polymetallic Ore Field,Guangxi Province

Rare earth and trace elements are determined for cassiterite from a vein-type orebody , a lens and a sheeted-type orebody in the Dachang Sn-polymetallic ore field ,Guangxi Province .Cassiterite from the vein-type orebody has rare earth and trace dement characteristics similar to that of Dachang biotite granite of Late Yanshan age, showing an inheritable and a genetic relationship. Cassiterites from the kns and sheeted-vein orebody have rare earth and trace element characteristics greatly different from those of the vein-type cassiterite and the granite,showing distinctly higher contents of the ore-forming elements As, Sb,Zn,Ag etc.and a positive Eu anomaly and a negative Ce anomaly.The difference of rare earth and trace element characteristics for cassiterite from two kinds of orebodies reflects the compositional difference of ore-forming solutions. Authors suggest that the kns and sheeted-vein orebody was of nonmagmatic , mixed with underground hot brine origin , and that this kind of hot brine reacted with Devonian and Predevonian older strata and extraced some ore-forming metals from the strata and finaly empbced along the bedding and interbyer fracture zone etc. on its ascending way driven by the Indonisian orogenic movement . The vein-type orebody was formed chiefly by post-magmatic hydrothermal sobtions derived from magma differentiation of the Dachang biotite granite .

Bibliography of Science and Technology of Rare Earths Published in China(1990)Geology and Ore Dressing

001 REE geochemistry characteristics of kimberlites in Shandong and Liaoning,China,Zhou Xiuzhong,Yang Jianminet al.,Acta Petrologica et Mineralogica,1990,9(4),308.002 Sr,Nd,Ce,O isotopes and trace element geochemistry of cenozoic volcanic rocks,kangsulake,yutian county,xinjiang,Liu Congqiang,Xie Guanghong et al.,Chinese science bulletin,1990,35(17),1450.003 Colour systems of mixed polynuclear complexes of lanthanum-2,7-bisazo-chromotropic acid dyes-zinc-O-phenanthroline,Shen Hanxi,Ling Rong,Chinese science bulletin,1990,35(17),1440.004 The isotopic ages and REE geochemistry of Damiao anorthosite and their geological implication,Hu Shiling et al.,Scientia Geologica Sinica,1990,(4),343.

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.

Behavior of leaching and precipitation of weathering crust ion-absorbed type by magnetic field

With weathering crust Ion-Absorbed Type Rare Earth （IATRE） ores in southern Jiangxi as an example, rare earth percolation leaching and leaching solution precipitation process research were carried out under conditions of magnetic field. The effect on the rare earth leaching process such as magnetic field strength, magnetization time, magnetization manner, and other factors were discussed. The effect on the mother rare earth liquor sedimentation rate, purity, and crystallization behavior such as magnetic field strength, magnetization time, and magnetization manner were investigated. Leaching and precipitation mechanism of magnetization on IATRE were analyzed. The results showed that the magnetic treatment can improve leaching rate of weathering crust IATRE and the sedimentation rate, and reduce consumption of reagents.