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.

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.

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.

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.

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.

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

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

A new type of rare earth elements deposit in weathering crust of Permian basalt in western Guizhou, NW China

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.

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.

RARE EARTH PARTITIONING OF GRANITOID WEATHERING CRUST IN SOUTHERN CHINA

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Study on Microbes and Their Effects on Rare Earth Extraction in Weathering Crust of Granite

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.

Anti-swelling mechanism of DMDACC on weathered crust elution-deposited rare earth ore

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.

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

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

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

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

Mineral properties and leaching characteristics of volcanic weathered crust elution-deposited rare earth ore

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.

Leaching hydrodynamics of weathered elution-deposited rare earth ore with ammonium salts solution

In order to reveal the permeability rule of leaching agent solution and the effects of anions in the leaching process of weathered crust elution-deposited rare earth（RE） ores, the effects of ammonium concentration, temperature, particle size and porosity on the permeability were discussed in detail with（NH4）2SO4, NH4Cl and NH4NO3 as the leaching agent. It was found that the permeation velocity of ammonium salts increased linearly with the increase of hydraulic gradient. The seepage of ammonium salts solution in the RE ores followed Darcy’s law and displayed a laminar flow. The properties of the leaching agent solution and RE ores were the main factors that affect the permeability of RE ores. With the decrease of ammonium concentration and increase of temperature, the viscosity of solution decreased and the permeability coefficients of RE ores increased. And the effects of temperature on the viscosity and permeability were larger than ammonium concentration. The permeability of RE ores became worse with the decrease of particle size and porosity, and the particle size played a more important role compared with porosity. The permeability coefficient of RE ores increased and the viscosity of ammonium salts solution decreased in the order of（NH4）2SO4, NH4Cl and NH4NO3, implying that the penetrating power of anions increased in the order of SO42-, Cl- and NO3-. The results may play a vital role in improving the permeability of weathered crust elution-deposited RE ores.

Organic Metallogeny of Weathering Crust RE Deposit

A series of experimental geochemical studies have been done to confirm the organic metallogenic mechanism of weathering crust RE deposits. It has been concluded that: (1) Rich REbearing weathering crusts contain abundant organisms such as monoacids, diacids and nonacid compounds. Varieties and quantities of the organisms decrease from the upper to the lower of the profile. Humic acids are mainly fulvic acids, which are characterized by containing conjugated π system, carboxylic group, hydroxyl group and only a few nitrogenous groups. No obvious benzene ring has been found. (2) The upper part of the weathering crust contains a great deal of microorganisms, of which the varieties and quantities decrease from the upper to the lower of the profile. No microorganism has been found in the deep part of the profile. The microorganisms and their metabolites such as aminoacids, shortchain acids and organic compounds with small molecular weights can form water soluble RE complexes, which accelerate the RE transportation from original rocks and precipitation states to watersoluble states and thus provide prerequisites for retransportation and reaccumulation of RE. (3) Medium and longchain acids can form REnAm(OH)x(H2O)y type mixedligand polynuclear RE complexes, which devoted to the RE accumulation, whereas shortchain acids and aminoacids can form not only mixedligand complexes with RE, but also water soluble complex ions, which also devoted to the transport and accumulation of RE. (4) The fulvic acids are very soluble in water. They are apt to be mobile in the weathering crust and are able to form soluble complex ions and insoluble mixedligand polynuclear complexes with RE at normal temperature and atmospheric pressure and pH4～6. The composition of these complexes varies with different conditions of the weathering crust. (5) All the organic acids, fulvic acids and microorgaisms have contributed to keeping constant pH condition of the weathering crust. (6) Complexes consisting of clays, RE(Al, Fe……) and fulvic acids have been found in the weathering crust and a bonding pattern has been preliminarily studied. As a conclusion, the dissolution, transport and accumulaiton of REE during weathering is a organic and inorganic interacted process.

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.

龙陵-潞西稀土矿成矿地质规律及找矿前景浅析

龙陵-潞西花岗岩带风化壳离子吸附型稀土矿主要赋存于花岗岩风化壳上部全风化层、中上部强风化层内,花岗岩出露面积大于1000km^(2),风化壳保存程度高,厚度大于10m,单工程平均稀土总量(ΣREE)0.05%~0.107%,成矿地质条件较好,具有较大找矿潜力。

广东南亩稀土矿床地球化学特征及成矿条件浅析

南亩稀土矿床位于南岭成矿带中段南侧,属离子吸附型稀土矿床,产于中三叠世坪田岩体的花岗岩风化壳中,其产状和形态特征受地形地貌控制。区域上发育多个同类型矿床,成矿条件研究还存在争议。本文针对南亩矿床地球化学特征及成矿标志进行研究,可为区域同类型稀土矿床的勘查找矿提供重要的依据。矿石矿物成分主要为风化后的黏土类矿物,稀土元素以离子状态赋存于黏土矿物上,95.96%离子型稀土赋存于粒径≥0.154 mm的矿物中,稀土组分分布均匀,品位变化稳定。未风化花岗岩包括黑云母花岗岩和碱长花岗岩,与稀土矿石稀土元素球粒陨石标准化配分曲线均为右倾平滑型,轻、重稀土分馏明显,均表现出轻稀土富集特征。通过对成矿条件的初步分析,中三叠世碱长花岗岩和黑云母花岗岩基岩发育区、亚热带温润气候条件、断层、节理发育的浅切割低缓丘陵地形及硅化蚀变带是南亩离子吸附型稀土矿的主要找矿标志。