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

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

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

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

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.

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.

REE Geochemistry in the Weathered Crust of Granites, Longnan Area,Jiangxi Province

Warm and humid climate and gentle hilly topography have provided favourable conditions for the devel-opment of the weathering crust of the granite intrusions in the Longnan area, Jiangxi Province. REE is mostlyconcentrated in an adsorption state in clay in the wholly weathered zone. The rare-earth minerals enriched inthe parent rocks provided the source material for the REE enrichment. Exchangeable REE accounts for48-86%. Extraction experiments and stable isotopic study of clay minerals suggest that the downward infiltra-tion of meteoric water and increasing gradient of pH values have played an important role in the enrichment ofREE during the progressive weathering. Slight fractionation of individual REE can not change their distribu-tion patterns in the profiles. which are inherited from the parent rocks.

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.

Reservoir characteristics and hydrocarbon accumulation of Carboniferous volcanic weathered crust of Zhongguai high area in the western Junggar Basin, China

Based on the drilling,cores,logs,seismic,laboratory analysis and so on,reservoir characteristics and hydrocarbon accumulation of Carboniferous volcanic weathered crust in Zhongguai high area are studied.Volcanic rocks were formed in an island arc environment.The lithology is mainly andesite and tuff;Reservoir spaces are mainly secondary pore,fracture and their combination forms,fractures have a better effect on reservoir seepage;There are four layer structures of volcanic weathered crust,weathered clay layer,strongly weathered zone,weakly weathered zone and unweathered zone and strongly weathered zone is the best,which is the main reservoir development zone;The development of reservoir is mainly affected by weathering-leaching,lithology and lithofacies,and fault(fracture);Effective reservoirs could reach to 480 m thickness(high quality reservoirs are within 240 m).Carboniferous volcanic reservoirs are distributed along three zones,which are near the fault zone,high structural part,favorable lithofacies development zone,and one plane,which is near the unconformity.

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.

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.

A Study on Palaeogeography and Metallogenic Conditions of Early Carboniferous Bauxite Deposits of Old Weathered Crust in Guizhou, Sichuan, Hunan and Hubei Provinces

There are four subtypes. namely, Ia, Ib, Ic and Id of the Early Carboniferous bauxite deposits of the old weathered crust type in Guizhou, Sichuan, Hunan and Hubei provinces. They are all distributed in the Upper Yangtze old land. As a result of the Hunan-Guizhou palaeo-faulting, the crust on the northern side of the fault was uplifted and became land, thus suffering denudation. The bauxitic substances left in the weathered crust evolved and were reworked into bauxite. On the other hand, the crust on the southern side of the fault sank and remained to be part of an ocean. The bauxite deposits of Ia and Ib subtypes were formed by in-situ enrichment of residual bauxitic substances in the weathered crust of the old land, but bauxite deposits of Ic and Id subtypes resulted from transportation, accumulation and sedimentation of allothogenous bauxitic substances on the weathered crust of the old land. The processes of transportation may be distinguished as dry transportation and wet transportation, both of which proceeded under atmospheric conditions.

Salt-Lake Basin Bedrock Weathered Crust Gas Reservoir in the Altun Mountains Front of the Qaidam Basin,Western China

The bedrock weathered crust in front of the Altun Mountains in the Qaidam Basin,western China,is different from others because this is a salt-lake basin,where saline water fluid infiltrates and is deposited in the overlying strata.A large amount of gypsum infills the bedrock weathered crust,and this has changed the pore structure.Using core observation,polarized light microscopy,electron probe,physical property analysis and field emission scanning electron microscopy experiments,the characteristics of the weathered bedrock have been studied.There are cracks and a small number of dissolved pores in the interior of the weathered crust.Matrix micropores are widely developed,especially the various matrix cracks formed by tectonics and weathering,as well as the stress characteristics of small dissolved pores,and physical properties such as porosity and permeability.This‘dual structure’developed in the bedrock is important for guiding the exploration of the lake basin bedrock for natural gas.

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.

Occurrence and vertical distribution of aluminum and rare earths in weathered crust elution-deposited rare earth ore:Effect of soil solution pH and clay minerals

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.

Mass transfer in heap leaching of weathered crust elution deposited rare earth ore with Al_(2)(SO_(4))_(3) solution

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.

Geochemistry of Rare Earth Elements(REE) in the Weathered Crusts from the Granitic Rocks in Sulawesi Island, Indonesia

We report for the first time the geochemistry of rare earth elements（REE） in the weathered crusts of I-type and calc-alkaline to high-K（shoshonitic） granitic rocks at Mamasa and Palu region, Sulawesi Island, Indonesia. The weathered crusts can be divided into horizon A（lateritic profile） and B（weathered horizon）. Quartz, albite, kaolinite, halloysite and montmorrilonite prevail in the weathered crust. Both weathered profiles show that the total REE increased from the parent rocks to the horizon B but significantly decrease toward the upper part（horizon A）. LREE are enriched toward the upper part of the profile as shown by La/YbN value. However, HREE concentrations are high in horizon B1 in Palu profile. The total REE content of the weathered crust are relatively elevated compared to the parent rocks, particularly in the lower part of horizon B in Mamasa profile and in horizon B2 in Palu profile. This suggests that REE-bearing accessory minerals may be resistant against weathering and may remain as residual phase in the weathered crusts. The normalized isocon diagram shows that the mass balance of major and REE components between each horizon in Mamasa and Palu weathering profile are different. The positive Ce anomaly in the horizon A of Mamasa profile indicated that Ce is rapidly precipitated during weathering and retain at the upper soil horizon.

Local concentration of middle and heavy rare earth elements in the col on the weathered crust elution-deposited rare earth ores

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.

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

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

Characteristics and Genetic Analysis of the Deep-buried Weathered-crust Karst Hydrocarbon Reservoirs of the Lower Paleozoic Group in the Tarim Basin

The genetic analysis of the deep-buried reservoirs of the Lower Paleozoiccarbonate rocks in the Tarim basin is a difficult task involving many factors. Firstly, the objectof study is carbonate rocks, which have undergone a long term of modification. Secondly, the rocksare deeply buried with depths of 3800-7000 m in the Tarim basin. The primary reservoir propertiesformed in the deposition have been strongly modified during the deep burial process. Concurrently,the different burial depths in different areas result in diversities of burial temperature,pressure, underground water, hydrochemistry and various physicochemical changes, which further leadto differences in the diagenetic type, diagenetic property, diagenetic degree and their impacts onthe reservoir properties. The Lower Paleozoic Cambrian and Ordovician carbonate reservoirs in theTarim basin can be grouped into four types, i.e., paleo-weathered-crust reservoirs, reef reservoirs,buried karst reservoirs and dolomite reservoirs. This paper presents a detailed discussion on thevertical and horizontal distribution characteristics, morphological division, reservoir propertiesand the efficiency in accumulating hydrocarbons of the paleo-weathered-crust type. Furthermore, itsgenesis is also analyzed. We proposed that the composition of the carbonate rocks, the tectonicmovement with associated fractures and fissures, the paleomorphology and paleoclimate, the sea levelfluctuation, and the protection of the pores and fissures by the deep burial diagenesis and burialdissolution are the main factors controlling the formation of the paleo-weathered-crust reservoirs.We also consider that the petroleum exploration of the Lower Paleozoic carbonate rocks should befocused on the pale-weathered-crust reservoirs.

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

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

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

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