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 s...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.展开更多
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 leachin...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.展开更多
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...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.展开更多
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,hydrodynami...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.展开更多
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 tra...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.展开更多
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 p...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.展开更多
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 calculat...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.展开更多
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 leac...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.展开更多
Weathered crust elution-deposited rare earth ore is crucial source of medium and heavy rare earths,with in-situ leaching being the most common mining method.The high contents of impurity of aluminum in the leach solut...Weathered crust elution-deposited rare earth ore is crucial source of medium and heavy rare earths,with in-situ leaching being the most common mining method.The high contents of impurity of aluminum in the leach solution are a significant challenge for the subsequent enrichment process of rare earths.A comprehensive understanding of the occurrences and vertical distribution of aluminum and rare earths within typical vertical profiles can provide valuable insights into entire design of the in-situ leaching.This paper improves a five-step sequential extraction method to analyze the occurrence and vertical distribution of rare earths and aluminum in vertical profiles from Chongzuo and Longyan.Experimental results demonstrate that soil solution pH is the main factor affecting the vertical distribution of ionexchangeable rare earths.Both samples have distinct areas of enrichment for ion-exchangeable rare earths or aluminum.Ion-exchangeable rare earths are primary concentrated in the middle and lower parts of the ore layer(4-13 m in Chongzuo,14-22 m in Longyan),while the ion-exchangeable aluminum is mainly enriched in the upper part of the ore layer(1-5 m in Chongzuo,and 2-14 m in Longyan).The vertical distribution of inorganic hydroxy aluminum is likely influenced by the micromorphology and particle size of the clay minerals.The inorganic hydroxy aluminum concentration in Chongzuo samples decreases continuously from 415.65 to 120.95 mg/kg with increasing sampling depth,whereas the concentration in Longyan samples(110.55-171.27 mg/kg)is almost independence with sampling depth.These results provide direct guidance for the entire design of the injection well depth and the leaching parameters,thereby inhibiting the leaching of impurity of aluminum and lower the consumption of leaching agent.展开更多
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 p...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.展开更多
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 ...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.展开更多
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...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.展开更多
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-...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.展开更多
This present study focused on investigating the content and relative enrichment multiple of rare earth elements（REEs） in different terrain of weathered ore body, and the value of light rare earth elements/middle and...This present study focused on investigating the content and relative enrichment multiple of rare earth elements（REEs） in different terrain of weathered ore body, and the value of light rare earth elements/middle and heavy rare earth elements（LREEs/HREEs）, in order to understand the mobilization and redistribution of HREEs, Furthermore, the abrasion pH was investigated as well, The results show that the average contents of HREEs in the knap, ridge and col are 37.26, 61.71, and 271.3 μg/g, respectively. The value of LREEs/HREEs is decreased from 16.78 to 7.914 between knap and col and the relative enrichment multiple of HREEs is as follows： CCol-HREEs 〉 CRidge-HREEs 〉 0. It is indicated the HREEs is concentrated in the col and the enrichment degree of HREEs is stronger than the ridge and the knap. Rare earth elements fractionation is exhibited in the different terrain of weathered ore body. Based on this study, the finding that HREEs concentrate in the lower terrain of weathered crust elution-deposited rare earth ores, such as in the col, would become a marker or indicator to search for middle and heavy rare earth enriched zone.展开更多
Weathered crust elution-deposited rare earth ore is an important resource of rare earths, including grantic weathered crust elution-deposited rare earth ore and volcanic weathered crust elution-deposited rare earth or...Weathered crust elution-deposited rare earth ore is an important resource of rare earths, including grantic weathered crust elution-deposited rare earth ore and volcanic weathered crust elution-deposited rare earth ore. The development condition of the weathered crust, weathering degree and mineral composition of these ores will be different because of the differences between their parent rocks and weathered crust causes of mineralogy path. Therefore, mineral properties and leaching characteristics of volcanic weathered crust elution-deposited rare earth ore from Chongzuo（CZ）, Guangxi province were investigated. It was found that the CZ rare earth ore was a typical mid-yttrium and rich-europium ore, with the overall rare earth（REE） grade in ion-exchangeable phase of 0.15%. Partide size classification showed that finer particle had a higher REE grade. Column leaching tests showed that the leaching efficiency of REE was above 94% with leaching agent concentration of 0.20 mol/L, liquid-solid ratio of 4：3, flow rate of 0.60 mL/min, and initial pH value around 5.67. Compared to ammonium sulfate leaching, magnesium sulfate leaching was advantaged by nearly zero ammonia nitrogen emission while their REE leaching was almost equivalent.展开更多
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 conducte...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.展开更多
In order to increase efficiency and avoid NH^(4+)-N pollution in the leaching process of weathered crust elution-deposited rare earth ores,the mass transfer in heap leaching with Al_(2)(SO_(4))_(3) solution was simula...In order to increase efficiency and avoid NH^(4+)-N pollution in the leaching process of weathered crust elution-deposited rare earth ores,the mass transfer in heap leaching with Al_(2)(SO_(4))_(3) solution was simulated with column elution and experimentally optimized.The results indicate that the leaching yield is also up to 99%for leaching with aluminum sulfate instead of ammonium sulfate.The optimal flow rate is 60 mL/h,the height equivalent to a theoretical plate(HETP)is 1.29 mm correspondingly.The peak value position of RE^(3+)is 60 mL/h,Fe^(3+)is 100 mL/h,however,Al^(3+)is 150 mL/h,and the heap leaching process has kinetic separation effect.展开更多
A new type of rare earth elements （REEs） deposit was discovered from the gaolinite mudstone in the weathering crust of Permian basalt, Bijie region, western Guizhou, China. It contained ∑RE2O3 0.065%-1.086%. This t...A new type of rare earth elements （REEs） deposit was discovered from the gaolinite mudstone in the weathering crust of Permian basalt, Bijie region, western Guizhou, China. It contained ∑RE2O3 0.065%-1.086%. This type of REEs deposit was widely distributed with steady horizon and thickness of 3-4 m. The ore-bearing weathering crust （kaolinite） of the three discovered REEs deposits belonged to the third episode of the Emeishan basalt eruption. The new type of REEs deposit was suggested that basalt （tuff） weathering could lead to the enrichment of the rare earth elements. Therefore, it is of important economic significance to explore REEs deposits in the weathering crust of basalt （tuffs） in Yunnan, Guizhou, and Sichuan Provinces.展开更多
Microbes were cultured from the samples at various depths in a weathering profile of RE-bearing granite in Gonghe RE mine, Guangdong Province. The cultured microbes, existing at a depth of 0.2 similar to 12 in and bei...Microbes were cultured from the samples at various depths in a weathering profile of RE-bearing granite in Gonghe RE mine, Guangdong Province. The cultured microbes, existing at a depth of 0.2 similar to 12 in and being more plentiful within 3 in in the profile, include bacteria ( Bacillus, Enterobacter, Escherichia, Alkaligenes, Neisseria, Staphylococcus and anaerobic bacteria such as Clostridium), fungi ( Aspergillus niger, Aspergillus flavus, Penicillium, Mucor and Saccharomycete) and actinomyces. Experiments were made under room temperature by using solutions of the cultured microbes and their metabolites, compared with distilled water and the culture solution without microbes, to leach RE from the sample of the weathering crust. The results are shown by the experiments: (1) The mixed microbes cultured from the profile and their metabolites increase the quantity of RE leached from the sample and reduce the pH of the solutions. (2) The ability to leach RE from the sample varies with various microbes, decreasing in a sequence of fungi ( Mucor, saccharomycete, Aspegillus and Penicillium), zymotic bacilli (Enterobacter, Escherichia etc.), Staphylococcus, zymotic Bacillus, actinomyces and Alkaligenes. (3) The RE leached with bacteria is mainly related to the pH value of the solutions influenced by the metabolites of the bacteria; whereas that leached with fungi is mainly related to the adsorption and imbibition of RE by the fungi and the complexing of RE with their metabolites. (4) Compared with that leached with ammonium sulfate, the fractionation of the RE leached with microbes is characterized by higher delta (Ce), lower delta (Eu) and lower ratios of N-La/Sm and N-Gd/Yb . The result of the fractionation of RE accords with the distribution of RE in the various layers of a profile of weathering crust of granite in South China. The experimental results indicate that microbes and their metabolites should play a positive role in the mobilization, migration and fractionation of RE in the weathering crust in South China.展开更多
基金Financial supports for this work from National Natural Science Foundation of China(Nos.22078252 and 52274266)the Graduate Education Innovation Foundation of Wuhan Institute of Technology(No.CX2021463)the Young Top-notch Talent Cultivation Program of Hubei Province are greatly appreciated.
文摘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.
基金the National Natural Science Foundation of China(Nos.52174258,92162109,52222405 and 52004184).
文摘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.
基金Projects(51274152,41472071)supported by the National Natural Science Foundation of ChinaProject(T201506)supported by the Program for Excellent Young Scientific and Technological Innovation Team of Hubei Provincial Department of Education,China
文摘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.
基金Projects(50664004,50474022,50574069) supported by the National Natural Science Foundation of ChinaProjects(Q959612,Q972026) supported by the Natural Science Foundation of Jiangxi Province,China
文摘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.
基金Projects(51664015,41602311,51774156) supported by the National Natural Science Foundation of China
文摘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.
基金Projects(51764014,11902127)supported by the National Natural Science Foundation of ChinaProject(201810407004)supported by the National Undergraduate Innovation Training Program of ChinaProject(GJJ180457)supported by Jiangxi Education Department,China。
文摘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.
基金the financial supports from the National Natural Science Foundation of China(No.52004106)supports from Jiangxi Education Department,China(No.GJJ180457).
文摘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.
基金Project supported by the National Natural Science Foundation of China(22078252,51874212,52274266)。
文摘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.
基金Project supported by the National Key Research and Development Program of China(2020YFC1909002)the Major Research Plan of the National Natural Science Foundation of China(91962211)the Science and Technology Innovation Fund of GRINM(2022PD0102)。
文摘Weathered crust elution-deposited rare earth ore is crucial source of medium and heavy rare earths,with in-situ leaching being the most common mining method.The high contents of impurity of aluminum in the leach solution are a significant challenge for the subsequent enrichment process of rare earths.A comprehensive understanding of the occurrences and vertical distribution of aluminum and rare earths within typical vertical profiles can provide valuable insights into entire design of the in-situ leaching.This paper improves a five-step sequential extraction method to analyze the occurrence and vertical distribution of rare earths and aluminum in vertical profiles from Chongzuo and Longyan.Experimental results demonstrate that soil solution pH is the main factor affecting the vertical distribution of ionexchangeable rare earths.Both samples have distinct areas of enrichment for ion-exchangeable rare earths or aluminum.Ion-exchangeable rare earths are primary concentrated in the middle and lower parts of the ore layer(4-13 m in Chongzuo,14-22 m in Longyan),while the ion-exchangeable aluminum is mainly enriched in the upper part of the ore layer(1-5 m in Chongzuo,and 2-14 m in Longyan).The vertical distribution of inorganic hydroxy aluminum is likely influenced by the micromorphology and particle size of the clay minerals.The inorganic hydroxy aluminum concentration in Chongzuo samples decreases continuously from 415.65 to 120.95 mg/kg with increasing sampling depth,whereas the concentration in Longyan samples(110.55-171.27 mg/kg)is almost independence with sampling depth.These results provide direct guidance for the entire design of the injection well depth and the leaching parameters,thereby inhibiting the leaching of impurity of aluminum and lower the consumption of leaching agent.
基金financially supported by the National Natural Science Foundation of China(No.51404112)theNational Key Technology R&D Program(No.2012BAC11B07)+3 种基金the Technology Program for Benefitting the People(No.2013GS360203)the Program for Talents Training of“Gan Po Excellence 555 Project”the Program for New Century Excellent Talents in University(No.NCET-10-0183)the Program for Main Subject,Technology Leaders of Jiangxi Province(No.2010DD01200)
文摘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.
基金Project supported by the National Natural Science Foundation of China(51274152 and 41472071)the Program for Excellent Young Scientific and Technological Innovation Team of Hubei Provincial Department of Education,China(T201506)
文摘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.
基金financially supported by the National Natural Science Foundation of China (Nos. 41472071 and 51734001)
文摘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.
基金Project supported by the National Natural Science Foundation of China(U2002215,51734001)。
文摘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.
基金Project supported by National Natural Science Foundation of China(41472071,51734001)
文摘This present study focused on investigating the content and relative enrichment multiple of rare earth elements（REEs） in different terrain of weathered ore body, and the value of light rare earth elements/middle and heavy rare earth elements（LREEs/HREEs）, in order to understand the mobilization and redistribution of HREEs, Furthermore, the abrasion pH was investigated as well, The results show that the average contents of HREEs in the knap, ridge and col are 37.26, 61.71, and 271.3 μg/g, respectively. The value of LREEs/HREEs is decreased from 16.78 to 7.914 between knap and col and the relative enrichment multiple of HREEs is as follows： CCol-HREEs 〉 CRidge-HREEs 〉 0. It is indicated the HREEs is concentrated in the col and the enrichment degree of HREEs is stronger than the ridge and the knap. Rare earth elements fractionation is exhibited in the different terrain of weathered ore body. Based on this study, the finding that HREEs concentrate in the lower terrain of weathered crust elution-deposited rare earth ores, such as in the col, would become a marker or indicator to search for middle and heavy rare earth enriched zone.
基金supported by National Science and Technology Support Program of China(2015BAB16B01)Science and Technology Support Program of Guangxi(1598007-41)
文摘Weathered crust elution-deposited rare earth ore is an important resource of rare earths, including grantic weathered crust elution-deposited rare earth ore and volcanic weathered crust elution-deposited rare earth ore. The development condition of the weathered crust, weathering degree and mineral composition of these ores will be different because of the differences between their parent rocks and weathered crust causes of mineralogy path. Therefore, mineral properties and leaching characteristics of volcanic weathered crust elution-deposited rare earth ore from Chongzuo（CZ）, Guangxi province were investigated. It was found that the CZ rare earth ore was a typical mid-yttrium and rich-europium ore, with the overall rare earth（REE） grade in ion-exchangeable phase of 0.15%. Partide size classification showed that finer particle had a higher REE grade. Column leaching tests showed that the leaching efficiency of REE was above 94% with leaching agent concentration of 0.20 mol/L, liquid-solid ratio of 4：3, flow rate of 0.60 mL/min, and initial pH value around 5.67. Compared to ammonium sulfate leaching, magnesium sulfate leaching was advantaged by nearly zero ammonia nitrogen emission while their REE leaching was almost equivalent.
基金Project(59725408) supported by the National Outsanding Younger Scholar Foundation of ChinaProjects(59674021,50474022) supported by the National Natural Science Foundation of China
文摘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.
基金Project supported by the National Natural Science Foundation of China(51964021,51774156)China’s NationalKey R&D Plan Project(2019YFC060025000)。
文摘In order to increase efficiency and avoid NH^(4+)-N pollution in the leaching process of weathered crust elution-deposited rare earth ores,the mass transfer in heap leaching with Al_(2)(SO_(4))_(3) solution was simulated with column elution and experimentally optimized.The results indicate that the leaching yield is also up to 99%for leaching with aluminum sulfate instead of ammonium sulfate.The optimal flow rate is 60 mL/h,the height equivalent to a theoretical plate(HETP)is 1.29 mm correspondingly.The peak value position of RE^(3+)is 60 mL/h,Fe^(3+)is 100 mL/h,however,Al^(3+)is 150 mL/h,and the heap leaching process has kinetic separation effect.
基金the Major State Basic Research Development Program of China (2006CB403202)the Doctoral Discipline Foundation of Guizhou University
文摘A new type of rare earth elements （REEs） deposit was discovered from the gaolinite mudstone in the weathering crust of Permian basalt, Bijie region, western Guizhou, China. It contained ∑RE2O3 0.065%-1.086%. This type of REEs deposit was widely distributed with steady horizon and thickness of 3-4 m. The ore-bearing weathering crust （kaolinite） of the three discovered REEs deposits belonged to the third episode of the Emeishan basalt eruption. The new type of REEs deposit was suggested that basalt （tuff） weathering could lead to the enrichment of the rare earth elements. Therefore, it is of important economic significance to explore REEs deposits in the weathering crust of basalt （tuffs） in Yunnan, Guizhou, and Sichuan Provinces.
文摘Microbes were cultured from the samples at various depths in a weathering profile of RE-bearing granite in Gonghe RE mine, Guangdong Province. The cultured microbes, existing at a depth of 0.2 similar to 12 in and being more plentiful within 3 in in the profile, include bacteria ( Bacillus, Enterobacter, Escherichia, Alkaligenes, Neisseria, Staphylococcus and anaerobic bacteria such as Clostridium), fungi ( Aspergillus niger, Aspergillus flavus, Penicillium, Mucor and Saccharomycete) and actinomyces. Experiments were made under room temperature by using solutions of the cultured microbes and their metabolites, compared with distilled water and the culture solution without microbes, to leach RE from the sample of the weathering crust. The results are shown by the experiments: (1) The mixed microbes cultured from the profile and their metabolites increase the quantity of RE leached from the sample and reduce the pH of the solutions. (2) The ability to leach RE from the sample varies with various microbes, decreasing in a sequence of fungi ( Mucor, saccharomycete, Aspegillus and Penicillium), zymotic bacilli (Enterobacter, Escherichia etc.), Staphylococcus, zymotic Bacillus, actinomyces and Alkaligenes. (3) The RE leached with bacteria is mainly related to the pH value of the solutions influenced by the metabolites of the bacteria; whereas that leached with fungi is mainly related to the adsorption and imbibition of RE by the fungi and the complexing of RE with their metabolites. (4) Compared with that leached with ammonium sulfate, the fractionation of the RE leached with microbes is characterized by higher delta (Ce), lower delta (Eu) and lower ratios of N-La/Sm and N-Gd/Yb . The result of the fractionation of RE accords with the distribution of RE in the various layers of a profile of weathering crust of granite in South China. The experimental results indicate that microbes and their metabolites should play a positive role in the mobilization, migration and fractionation of RE in the weathering crust in South China.
