China is the global leader in rare earth （RE） production using hydrometallurgical processes. Advantageous extraction techniques of rare earths from Baotou mixed rare earth minerals, bastnaesite, and ion-adsorption c...China is the global leader in rare earth （RE） production using hydrometallurgical processes. Advantageous extraction techniques of rare earths from Baotou mixed rare earth minerals, bastnaesite, and ion-adsorption clays of rare earth deposits have been developed in China. The separation and purification technologies have also achieved rapid development. The industrial application processes for rare earth hydrometallurgy were summarized in the present paper. With the large demands and rapid development of rare earths, the issues of resources and environment are more prominent. This review gives an overview of the main processes that were developed in the past toward greener hydrometallurgy of rare earths in China. Based on the development of the rare earth industry, comprehensive utilization and cleaner production should still be focused on in the future, to support the sustainable development.展开更多
In view of the problem of ammonia-nitrogen wastewater pollution in rare earths extraction and separation, the novel saponification agent of organic phase, which is magnesium bicarbonate solution, was prepared with the...In view of the problem of ammonia-nitrogen wastewater pollution in rare earths extraction and separation, the novel saponification agent of organic phase, which is magnesium bicarbonate solution, was prepared with the natural rich and cheap dolomite as raw material through carbonation process. The behavior and purification of main impurities ions in the carbonation process as well as the application effect of the novel saponification agent in the extraction and separation was researched. The results showed that the concentration of Fe, A1, Si im- purities ions was.less than 5 ppm in the saponification agent through the development of effective removal technology, respectively. When the novel saponification agent was used in the extraction and separation, magnesium utilization rate was more than 95%, and rare earths extrac- tion rate above 99.5% has achieved. Therefore, the technology could replace ammonia-water to saponify the organic phase in rare earth ex- traction and separation process.展开更多
The purpose of this study was to overcome the disadvantages of ammonia-nitrogen wastewater pollution and high cost of sodium saponification in rare earth separation process. The study focused on the non-saponification...The purpose of this study was to overcome the disadvantages of ammonia-nitrogen wastewater pollution and high cost of sodium saponification in rare earth separation process. The study focused on the non-saponification extraction technology with magnesia. The influences of the content and particle size of magnesia, reaction time, reaction temperature, and O/A on cerium extraction rate were also discussed. The results showed that the hydrogen ions of extractant were exchanged by rare earth ions when organic ex- tractant and rare earth solution were mixed with magnesia powder, and then the exchanged hydrogen dissolved magnesia to make the acidity of the system stable. The magnesium ions were not participated in the extraction reaction. Non-saponification extraction process of rare earth had been realized. The cerium extraction rate could reach up to 99% in single stage within the optimal reaction conditions.展开更多
Based on the new process named "Combination Method" for metallurgy and separation of Baotou mixed rare earth concentrate(BMREC),the aim of this paper is to clearly elucidate the phase change behavior of BMRE...Based on the new process named "Combination Method" for metallurgy and separation of Baotou mixed rare earth concentrate(BMREC),the aim of this paper is to clearly elucidate the phase change behavior of BMREC without additives during oxidative roasting at 450-800℃.The results indicate that the bastnaesite in BMREC is decomposed at 450-550℃,the weight loss is about 10.3 wt%,and the activation energy(E) is 144 kJ/mol.The bastnaesite in BMREC is decomposed into rare earth fluoride,rare earth oxides(La_(2)O_(3),Ce_(7)O_(12),Pr_(6)O_(11) and Nd_(2)O_(3)),and CO_(2),particularly,with the increase of roasting temperature,bastnaesite in BMREC is more completely decomposed into LaF_(3),which causes a decrease in leaching rate of La during the HCI leaching process.Additionally,the maximum cerium oxidation efficiency reaches about 60 wt% when the roasting temperature is equal to or above 500℃,and the oxidation reaction rate of cerium increases with the increasing roasting temperature.展开更多
Different rare earth （RE=La, Ce, Pr, Nd, Sm, Y） and Cu modified nickel catalysts for hydrogen production from meth-ane decomposition were synthesized by a sol-gel process and method. The catalysts were characterized...Different rare earth （RE=La, Ce, Pr, Nd, Sm, Y） and Cu modified nickel catalysts for hydrogen production from meth-ane decomposition were synthesized by a sol-gel process and method. The catalysts were characterized or analyzed through Brumauer-Emmett-Teller （BET）, X-ray diffraction （XRD）, scanning electron microscopy （SEM）, transmission electron microscopy （TEM） techniques. And the hydrogen production performance was also evaluated by a fixed-bed and micro-reaction technique with CH4→C＋H2 as a probe reaction. The results showed that rare earth modification had played a great role for nickel catalysts, for example, smaller nickel particles, good thermal stability, high activity, etc. La was the best additive among rare earth modification. The SEM of rare earth modified catalysts showed ordered flower-like structure and rare earth modification made the nickel particles move to the surface of catalysts. In addition, the SEM of nano-carbons was also changed by rare earth modification with long, narrow nano-carbon fibers or tubes obtained. Solid carbon formation was prevented by rare earth modification.展开更多
Magnesium bicarbonate, prepared by the carbonation of magnesium hydroxide slurry, was used as a novel saponifier to eliminate the ammonia nitrogen pollution in the rare earth extraction separation process. The effect ...Magnesium bicarbonate, prepared by the carbonation of magnesium hydroxide slurry, was used as a novel saponifier to eliminate the ammonia nitrogen pollution in the rare earth extraction separation process. The effect of impurity ions introduced by system on the carbonation reaction of magnesium hydroxide was studied in the work. The results showed that the presence of Ca2＋could lead to side reactions so as to reduce the conversion rate of magnesium hydroxide, and a small number of rare earth ions would have great influence on the carbonation reaction. What’s more, there was no influence on carbonation reaction with the low concen-tration of Na＋or Mg2＋, the conversion rate of magnesium hydroxide could reach above 96%. This paper showed a practical theory which could provide scientific guidance for the preparation of novel saponifier in rare earth extraction separation process.展开更多
The adsorption behaviors of rare earth elements on clay minerals would have great influence on the mineralization process and the leaching process of the ion-adsorption type rare earths ore.In this work,the adsorption...The adsorption behaviors of rare earth elements on clay minerals would have great influence on the mineralization process and the leaching process of the ion-adsorption type rare earths ore.In this work,the adsorption thermodynamics of REEs on kaolin were investigated thoroughly and systematically.The experimental results showed that the adsorption characteristics of La,Nd,Y on kaolin did fit well with the Langmuir isotherm model and their saturated adsorption capacities were 1.731,1.587 and 0.971 mg/g,respectively.The free energy change（ΔG）values were –16.91 kJ/mol（La）,–16.05 kJ/mol（Nd）and –15.58 kJ/mol（Y）,respectively.The negative values of ΔG demonstrated that the adsorption of rare earth on kaolin was a spontaneously physisorption process.The deposit characteristic of the volcanic ion-adsorption type rare earths ore and the behavior of the rare earth in the column leaching process were also developed here.With the increase of the ore body depth,the distribution of the LREEs decreased and the HREEs increased.And the slight differences in the adsorption ability of REEs on clay minerals led to the fractionation effect in the column leaching process.These developed more evidences and better understanding of metallogenic regularity,and provided a theoretical basis and scientific approach to separation of the HREEs and LREEs in the leaching process.展开更多
Gadolinium was prepared by conventional procedures of fluorination, reduction, distillation and solid state electrotransport（SSE）. The electronegativities of the metals were found to have an important influence on t...Gadolinium was prepared by conventional procedures of fluorination, reduction, distillation and solid state electrotransport（SSE）. The electronegativities of the metals were found to have an important influence on the electrotransport process and result of the impurity element. Meanwhile, titanium particles in the distilled gadolinium as major metallic impurities were studied by high resolution transmission electron microscopy（HRTEM） before and after solid state electrotransport. The results showed that impurities especially titanium transported from anode to cathode during SSE. In the metal before SSE, there were impurities of titanium in strip shape or embedded round shape. After SSE processing, titanium particles in the metal smaller than 50 nm in the cathode, but existed 6 to 10 times bigger in the anode.展开更多
In acid treatment technology of Baotou mixed rare earth ore,large quantities of ammonia-nitrogen wastewater are produced in the step of ammonium bicarbonate precipitation to transform rare earth sulfate.In this paper,...In acid treatment technology of Baotou mixed rare earth ore,large quantities of ammonia-nitrogen wastewater are produced in the step of ammonium bicarbonate precipitation to transform rare earth sulfate.In this paper,we adopted a green precipitant magnesium bicarbonate(Mg(HCO3)2) to substitute ammonium bicarbonate to eliminate ammonia-nitrogen pollution.The effects of n(HCO3^-):n(RE^3+),aging temperature and aging time on the crystallization using Mg(HCO3)2 precipitation method were investigated.The results indicate that the rare earths could be completely recovered when n(HCO3^-):n(RE^3+) is higher than 3.15:1.The crystal water content of rare earth carbonates is affected by the aging temperature.The precipitate has a bad filterability when the aging temperature is over 40℃.This can be attributed to the less crystallized water molecules of the hydrated rare earth carbonate precipitation.The mixed rare earth carbonates are prone to be crystalline,and have a good filterability at aging temperatures below 40℃.Meanwhile,the evolution mechanism of crystalline mixed rare earth carbonates is reasonably deduced,the amorphous rare earth carbonates are first dissolute and then recrystallized.Under the optimized aging conditions,the purity of the crystalline precipitate meets the requirements of the fine product standard(GB/T 16479-2008).The filtrated could be used to produce Mg(HCO3)2,thus to realize the recycling of magnesium sulfate.展开更多
The differences in the leaching and mass transfer characteristics of ion-adsorption type rare earth ore between rare earth and non-rare earth impurities were investigated. It is determined that the leaching kinetics o...The differences in the leaching and mass transfer characteristics of ion-adsorption type rare earth ore between rare earth and non-rare earth impurities were investigated. It is determined that the leaching kinetics of rare earths （REs）, Mg and Ca could be described by the shrinking-core model. The leaching rate is controlled by inner diffusion and is in the order of Mg 〉 Ca 〉 RE. The apparent activation energy is 8.48, 6.79 and 6.32 kJ·mol^-1, respectively. In leaching system of Al, the leaching efficiency decreases with the increase in temperature because of hydrolysis reactions. The leaching efficiency of aluminum increases firstly and then decreases with the passage of time when the temperature is higher than 35 ℃. Besides, there is a good consistency in leaching characteristics and mass transfer, and the order of the time-to- peak is Mg 〈 Ca 〈 RE 〈 Al. Therefore, rare earth and non-rare earth may be partly separated by expanding the separation coefficient. The research could provide a theoretic basis for the separation of rare earth and non-rare earth impurities. Furthermore, compound leaching with magnesium salt and calcium salt is innovatively proposed to solve the problem of calcium and magnesium nutrient loss in the soil as well as eliminate ammonia-nitrogen emissions from the source.展开更多
The leaching behaviors of calcium and magnesium in the rare earth tailings leached with magnesium sulfate using deionized water,CaCl2 solution and lime water were investigated.Experimental data indicated that magnesiu...The leaching behaviors of calcium and magnesium in the rare earth tailings leached with magnesium sulfate using deionized water,CaCl2 solution and lime water were investigated.Experimental data indicated that magnesium in the tailings was easy to be leached out since most of the magnesium was in the form of water-soluble phase.Most of calcium in the lime water was electrostatically adsorbed on the clay mineral of the tailings,and the water-soluble magnesium was also gradually converted into exchangeable phase because of back-adsorption of Mg2+on the clay mineral with increasing the pH values.When the liquid-to-solid ratio was 0.80,the contents of readily-available magnesium and calcium were 104.4−207.6 and 201.7−1426.3 mg/kg,respectively,which could meet the requirements for plants.These results suggest a promising route for the environmental remediation of ion-adsorption rare earth ore after in-situ leaching.展开更多
Granite belonged to intrusive rock and volcanic was extrusive rock. There may be many differences in their degree of weathering and mineral chemical composition. The present study investigated the minerals properties ...Granite belonged to intrusive rock and volcanic was extrusive rock. There may be many differences in their degree of weathering and mineral chemical composition. The present study investigated the minerals properties and the leaching mechanism of the granitic weathered crust elution-deposited rare earth ore from Longnan Rare Earth Mine area （LN ores） and volcanic weathered crust elution-deposited rare earth ore from Liutang Rare Earth Mine area （LT ores）. The X-ray diffraction （XRD）, Fourier transform infrared spectroscopy （FT-IR） were used to characterize the phase of rare earth ores. The particle size distributions and main composition of the ore were also presented in this paper. The leaching mechanisms of two kinds of rare earth ores were analyzed with different kinetics models and could be described by the shrinking-core model. They were all inner diffusion-controlled leaching processes. The leaching equation of the kinetics of the LN ores could be expressed as：4 LN LN 1.096 10 2/3 0.377 8.314 0 2 3=0.1061 （1 ） Tr e tη η×？？？ ？ ？, leaching equation of kinetics of LT ores was 3 LT LT 4.640 10 2/3 0.411 8.314 0 32 3=8.33 101 （1 ） Tr e tη η×？？ ？×？ ？ ？. The rare earth leaching rate of LT ores was always lower in the same condition, and it would need more time and more （NH4）2SO4 consump-tion to achieve the same rare earth leaching efficiency, which would lead to more serious ammonia-nitrogen pollution. Therefore, magnesium salt was proposed as the leaching agent to eliminate ammonia-nitrogen pollution and further studies would be taken in the future.展开更多
The practice ofin-situ leaching of the ion-adsorption type rare earths ore with ammonium sulfate could only leach most of rare earth in ion-exchangeable phase,but not the colloidal sediment phase.Therefore,the reducti...The practice ofin-situ leaching of the ion-adsorption type rare earths ore with ammonium sulfate could only leach most of rare earth in ion-exchangeable phase,but not the colloidal sediment phase.Therefore,the reduction leaching of rare earth from the ion-adsorption type rare earths ore with ferrous sulfate was innovatively put forward.The soak leaching process and the column leaching process were investigated in the present study.It was determined that ion-exchangeable phase could be released,and part of colloidal sediment phase rare earth could be reduction leached by the cations with reduction properties.The mechanism of reduction leaching was discussed with the Eh-pH diagram of cerium.Moreover,the stronger reduction of reductive ions,the greater acidity of leaching agent solution,and the higher reductive ion concentration,could result in the higher rare earth efficiency and the bigger ce-rium partition in the leaching liquor.In the ferrous sulfate column leaching process,the rare earth leaching rate and the rare earth effi-ciency were a little higher than with(NH4)2SO4 agent,and the rare earth efficiency and the partitioning of cerium in leaching liquor could be about 102%and 5.31%,respectively.However,the ferrous sulfate leaching process revealed some problems,so compound leaching with magnesium sulfate and a small amount of ferrous sulfate was proposed to an excellent alternative leaching agent for further studies,which may realize efficiency extraction and be environment-friendly.展开更多
The extraction of Nd^3＋ and Sm^3＋, including the extraction and stripping capability as well as the separation effect of Nd^3＋ or Sm^3＋, from a sulfuric acid medium, by mixtures of di-（2-ethylhexyl） phosphoric a...The extraction of Nd^3＋ and Sm^3＋, including the extraction and stripping capability as well as the separation effect of Nd^3＋ or Sm^3＋, from a sulfuric acid medium, by mixtures of di-（2-ethylhexyl） phosphoric acid （HDEHP, H2A2（0）） and 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester （HEH/EHP, H2L2（0）） were studied. The distribution ratios and synergistic coefficients of Nd^3＋ and Sm^3＋ in different acidities were also determined. A synergistic extractive effect was found when HDEHP and HEH/EHP were used as mixed extractants for Sm^3＋ or Nd^3＋. The chemical compositions of the extracted complex were determined as Nd.（HA2）2-HL2 and Sm.（HA2）2-HL2. The extraction equilibrium constants, enthalpy change, and entropy change of the extraction reaction were also determined.展开更多
Phosphorite ore is a potential resource of rare earths （RE） as well as phosphate; therefore, the recovery of RE from wet-process phosphoric acid （WPA） is promising. This study investigated the influence of rotatio...Phosphorite ore is a potential resource of rare earths （RE） as well as phosphate; therefore, the recovery of RE from wet-process phosphoric acid （WPA） is promising. This study investigated the influence of rotational speed, extractant concentration, flow ratio and phase contact time on the centrifugal extraction of RE from WPA and the separation of RE from impurities. The results indicate that higher rotational speed, higher extractant concentration and larger flow ratio are beneficial to the extraction of RE and impurities from phosphoric acid. It is found that the phase contact time for efficiently extracting RE and that for iron are of great difference, which provides an effective method for separating RE from iron using the non-equilibrium extraction process in centrifugal contactors. Compared with equilibrium extraction, the separation factor βRE/Fe is enhanced from 0.07 to 17.6.展开更多
This paper investigated the recovery of rare earth elements(REEs)and aluminum(AI)from the waste slag discharged by FCC catalyst factory(FCC waste slag)via acid leaching and selective precipitation.Analysis methods suc...This paper investigated the recovery of rare earth elements(REEs)and aluminum(AI)from the waste slag discharged by FCC catalyst factory(FCC waste slag)via acid leaching and selective precipitation.Analysis methods such as ICP-AES,XRF and XRD were applied to obtain experiment data.The maximum leaching efficiency of REEs and Al was achieved at pH value of 1 and with liquid to solid ratio of 4:1,Under such conditions,91.01%,92.24%and 94.77%of La,Ce and Al were extracted at 20℃for 2 h from the FCC waste slag,respectively.The SiOcontent in the leaching residue was 88.3%,which can be used as an available silicon resource.The REEs can be precipitated in the form of REEs and sodium double sulfate(NaRE(SO)·xHO)by adding NaSOto the leaching solution,while Al remained in the solution.Afterwards,the pH value of the filtrate was adjusted to 4.5,and Al was precipitated as AI(OH).Finally,NaRE(SO)·xHO and Al(OH)were converted into RECland Al(SO4)solution,respectively,which were recycled to manufacture zeolite.This process recovered REEs and Al from the FCC waste slag and reduced the emissions of waste slag simultaneously,which has an important economic and environment significance.展开更多
In order to develop a highly sensitive material for nondestructive testing(NDT),(Tb_(0.3) Dy_(0.7))Fe_(1.95) thin films were deposited on FeCo substrates at room temperature by magnetron sputtering and annealed.The ma...In order to develop a highly sensitive material for nondestructive testing(NDT),(Tb_(0.3) Dy_(0.7))Fe_(1.95) thin films were deposited on FeCo substrates at room temperature by magnetron sputtering and annealed.The magnetostrictive properties and the detection efficiency of the composite films were investigated.Results demonstrate that the detection efficiency roughly shows regular consistency with the magnetostrictive strain of the TbDyFe films. Heat treatment has a great effect on the crystalline state and the magnetostrictive strain of the composite materials. The as-deposited(Tb_(0.3) Dy_(0.7))Fe_(1.95) films are amorphous, and the saturation magnetostriction(ls) is only 90 ppm. However, the nanostructured crystalline REFe2 is partially separated out in amorphous matrix after annealing at 600C for 1 h, and the ls increases to 265 ppm. Simultaneously, the detection efficiency of the composite materials is obviously improved compared to that of the as-deposited films. The detection signal of traditional FeCo strip is0.4 V at the excitation power of 1.0 P and frequency of 128 kHz and that of the strip increases significantly by depositing one layer of(Tb_(0.3) Dy_(0.7))Fe_(1.95) film. The detection signal of the composite material annealed at 600C is the best, even reaching saturation value of 2.5 V(1.0 P, 128 kHz). The results may provide us with a method for preparing new materials for NDT.展开更多
Phosphate rock has been considered as one of the potential promising resources for rare earth elements(REEs). But the cost issues and the technical challenges caused by the low content of REEs in ores did hinder the f...Phosphate rock has been considered as one of the potential promising resources for rare earth elements(REEs). But the cost issues and the technical challenges caused by the low content of REEs in ores did hinder the further development of REEs recovery technologies. In order to explore a green process for the recovery of REEs from phosphate rock, this study investigates the effects of phosphoric acid concentration, liquid-to-solid ratio(L/S ratio), leaching time and temperature on the leaching efficiencies of the major components from phosphate rock. A REEs recovery of 94.3% and a phosphorus recovery of 95.3%are achieved under the optimal conditions of attacking phosphate rock using 30%P_2 O_5 acid with an L/S ratio of 10:1 and a stirring speed of 250 r/min at 25 ℃ for 4 h. Then,the selective precipitation of REEs with 81.3% REEs recovery is realized by heating up the leaching solution from 25 to 90 ℃ and keeping for4 h. Thereafter, more than 95% phosphoric acid is recovered by H_2 SO_4 and high purity gypsum, more than95% CaSO_4(tested by XRF), is also produced at the same time. Ultimately, a green process that leaches phosphate rock with H_3 PO_4, selectively precipitates REEs from leaching solution by heating up, recovers H_3 PO_4 with H2 SO4 is proposed. Compared with REE recovery in traditional processes, this process owns the merits of simple operation, energy saving and minimum wastes.展开更多
The precipitation of the water-leaching solution of Baotou mixed rare earth(RE) concentrate roasted with sulfuric acid using ammonium bicarbonate for producing RE carbonate produces a mass of ammonia-nitrogen wastewat...The precipitation of the water-leaching solution of Baotou mixed rare earth(RE) concentrate roasted with sulfuric acid using ammonium bicarbonate for producing RE carbonate produces a mass of ammonia-nitrogen wastewater because of the relatively low solubility of rare earth sulfate.To solve the serious problem of ammonia-nitrogen pollution,new precipitators need to be developed urgently so as to meet the requirements of environmental protection and impurities content of the product(SO_(4)^(2-)<1.8 wt% in RE carbonates products).In this paper,we studied the effects of feeding modes on the behavior of SO_(4)^(2-) during the preparation of light RE carbonate(RE=La,Ce,Pr,Nd) from their sulfate solutions using Mg(HCO_(3))_(2) as a precipitant.The results indicate that the contents of SO_(4)^(2-) in the La and Ce precipitates using positive feeding mode exceed 16 wt% because of the formation of La_(2)(CO_(3))2.15(-SO_(4))0.85·4 H_(2)O and Ce_(2)(CO_(3))_(2).15(SO_(4))0.85·3H_(2)O,while those of the Pr and Nd precipitates are 4 wt%-5 wt% since they exist in the form of n-carbonate.The precipitates prepared using synchronous feeding mode are all RE carbonate with only 4 wt%-5 wt% of SO_(4)^(2-) enclosed in the precipitation.The content of SO_(4)^(2-) in the RE carbonate obtained using reverse feeding mode is the lowest.Among them,the content of SO_(4)^(2-) in La precipitate is only 1.40 wt%.Both synchronous and reverse feeding modes can effectively reduce the content of SO_(4)^(2-)in RE carbonate,which provides theoretical guidance for the preparation of qualified light RE carbonate products by Mg(HCO3)2 precipitation method.展开更多
In order to provide practical fundamental data for rare-earth elements （REEs） recovery from phosphoric acid and to betterunderstand REEs behavior during the phosphoric acid evaporation process, the solubilities of R...In order to provide practical fundamental data for rare-earth elements （REEs） recovery from phosphoric acid and to betterunderstand REEs behavior during the phosphoric acid evaporation process, the solubilities of REEs in phosphoric acid with variousconcentrations of phosphorus at different temperatures were measured. A simple linear model between REEs solubility andphosphoric acid concentration is built and the experimental data are found to fit it very well （R2〉0.94）. Hydrogen-ion concentration isfound to be the predominant factor controlling the solubility of REEs in phosphoric acid. In addition, the solubility of REEs inphosphoric acid is found to sharply decrease with increasing temperature, which can be attributed to the increase of the Gibbs energyof the REEPO4 dissolution reaction or the restraint of the disassociation of phosphoric acid molecules owing to the elevatedtemperature.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.50934004 and 51404035)
文摘China is the global leader in rare earth （RE） production using hydrometallurgical processes. Advantageous extraction techniques of rare earths from Baotou mixed rare earth minerals, bastnaesite, and ion-adsorption clays of rare earth deposits have been developed in China. The separation and purification technologies have also achieved rapid development. The industrial application processes for rare earth hydrometallurgy were summarized in the present paper. With the large demands and rapid development of rare earths, the issues of resources and environment are more prominent. This review gives an overview of the main processes that were developed in the past toward greener hydrometallurgy of rare earths in China. Based on the development of the rare earth industry, comprehensive utilization and cleaner production should still be focused on in the future, to support the sustainable development.
基金Project supported by the National High Technology Research and Development Program of China (2010AA03A405)the Key Program of National Natural Science Foundation of China (50934004)
文摘In view of the problem of ammonia-nitrogen wastewater pollution in rare earths extraction and separation, the novel saponification agent of organic phase, which is magnesium bicarbonate solution, was prepared with the natural rich and cheap dolomite as raw material through carbonation process. The behavior and purification of main impurities ions in the carbonation process as well as the application effect of the novel saponification agent in the extraction and separation was researched. The results showed that the concentration of Fe, A1, Si im- purities ions was.less than 5 ppm in the saponification agent through the development of effective removal technology, respectively. When the novel saponification agent was used in the extraction and separation, magnesium utilization rate was more than 95%, and rare earths extrac- tion rate above 99.5% has achieved. Therefore, the technology could replace ammonia-water to saponify the organic phase in rare earth ex- traction and separation process.
基金supported by National High Technology Research and Development Program of China(863plan,2010AA03A405)the Key Program of National Natural Science Foundation of China(50934004)
文摘The purpose of this study was to overcome the disadvantages of ammonia-nitrogen wastewater pollution and high cost of sodium saponification in rare earth separation process. The study focused on the non-saponification extraction technology with magnesia. The influences of the content and particle size of magnesia, reaction time, reaction temperature, and O/A on cerium extraction rate were also discussed. The results showed that the hydrogen ions of extractant were exchanged by rare earth ions when organic ex- tractant and rare earth solution were mixed with magnesia powder, and then the exchanged hydrogen dissolved magnesia to make the acidity of the system stable. The magnesium ions were not participated in the extraction reaction. Non-saponification extraction process of rare earth had been realized. The cerium extraction rate could reach up to 99% in single stage within the optimal reaction conditions.
基金Project supported by the National Key Research and Development Program of China(2020YFC1909104)Science and Technology Major Project of Guangxi(GuikeAA18242022)Hebei Province Key Research and Development Plan Project(20374104D)。
文摘Based on the new process named "Combination Method" for metallurgy and separation of Baotou mixed rare earth concentrate(BMREC),the aim of this paper is to clearly elucidate the phase change behavior of BMREC without additives during oxidative roasting at 450-800℃.The results indicate that the bastnaesite in BMREC is decomposed at 450-550℃,the weight loss is about 10.3 wt%,and the activation energy(E) is 144 kJ/mol.The bastnaesite in BMREC is decomposed into rare earth fluoride,rare earth oxides(La_(2)O_(3),Ce_(7)O_(12),Pr_(6)O_(11) and Nd_(2)O_(3)),and CO_(2),particularly,with the increase of roasting temperature,bastnaesite in BMREC is more completely decomposed into LaF_(3),which causes a decrease in leaching rate of La during the HCI leaching process.Additionally,the maximum cerium oxidation efficiency reaches about 60 wt% when the roasting temperature is equal to or above 500℃,and the oxidation reaction rate of cerium increases with the increasing roasting temperature.
基金supported by the Twelfth Five-year National Science and Technology Pillar Program(2012BAE01B02)
文摘Different rare earth （RE=La, Ce, Pr, Nd, Sm, Y） and Cu modified nickel catalysts for hydrogen production from meth-ane decomposition were synthesized by a sol-gel process and method. The catalysts were characterized or analyzed through Brumauer-Emmett-Teller （BET）, X-ray diffraction （XRD）, scanning electron microscopy （SEM）, transmission electron microscopy （TEM） techniques. And the hydrogen production performance was also evaluated by a fixed-bed and micro-reaction technique with CH4→C＋H2 as a probe reaction. The results showed that rare earth modification had played a great role for nickel catalysts, for example, smaller nickel particles, good thermal stability, high activity, etc. La was the best additive among rare earth modification. The SEM of rare earth modified catalysts showed ordered flower-like structure and rare earth modification made the nickel particles move to the surface of catalysts. In addition, the SEM of nano-carbons was also changed by rare earth modification with long, narrow nano-carbon fibers or tubes obtained. Solid carbon formation was prevented by rare earth modification.
基金Project supported by Key Program of National Natural Science Foundation of China(50934004)National High Technology Research and Development Program of China(2010AA03A405)National Science and Technology Support Program of China(2012BAE01B02)
文摘Magnesium bicarbonate, prepared by the carbonation of magnesium hydroxide slurry, was used as a novel saponifier to eliminate the ammonia nitrogen pollution in the rare earth extraction separation process. The effect of impurity ions introduced by system on the carbonation reaction of magnesium hydroxide was studied in the work. The results showed that the presence of Ca2＋could lead to side reactions so as to reduce the conversion rate of magnesium hydroxide, and a small number of rare earth ions would have great influence on the carbonation reaction. What’s more, there was no influence on carbonation reaction with the low concen-tration of Na＋or Mg2＋, the conversion rate of magnesium hydroxide could reach above 96%. This paper showed a practical theory which could provide scientific guidance for the preparation of novel saponifier in rare earth extraction separation process.
基金Project supported by National Science and Technology Support Program of China(2015BAB16B01)Training Program of Major Academic and Technical Leaders in Jiangxi Province(20142BCB22005)Top Youth Talent Training Program of"Gan Po 555 Talents Project"of Jiangxi Province
文摘The adsorption behaviors of rare earth elements on clay minerals would have great influence on the mineralization process and the leaching process of the ion-adsorption type rare earths ore.In this work,the adsorption thermodynamics of REEs on kaolin were investigated thoroughly and systematically.The experimental results showed that the adsorption characteristics of La,Nd,Y on kaolin did fit well with the Langmuir isotherm model and their saturated adsorption capacities were 1.731,1.587 and 0.971 mg/g,respectively.The free energy change（ΔG）values were –16.91 kJ/mol（La）,–16.05 kJ/mol（Nd）and –15.58 kJ/mol（Y）,respectively.The negative values of ΔG demonstrated that the adsorption of rare earth on kaolin was a spontaneously physisorption process.The deposit characteristic of the volcanic ion-adsorption type rare earths ore and the behavior of the rare earth in the column leaching process were also developed here.With the increase of the ore body depth,the distribution of the LREEs decreased and the HREEs increased.And the slight differences in the adsorption ability of REEs on clay minerals led to the fractionation effect in the column leaching process.These developed more evidences and better understanding of metallogenic regularity,and provided a theoretical basis and scientific approach to separation of the HREEs and LREEs in the leaching process.
基金Project supported by Major State Basic Research Development Program of China(973 Program:2012CBA01207)the National High Technology Research and Development Program of China(863 Program:2011AA03A409)
文摘Gadolinium was prepared by conventional procedures of fluorination, reduction, distillation and solid state electrotransport（SSE）. The electronegativities of the metals were found to have an important influence on the electrotransport process and result of the impurity element. Meanwhile, titanium particles in the distilled gadolinium as major metallic impurities were studied by high resolution transmission electron microscopy（HRTEM） before and after solid state electrotransport. The results showed that impurities especially titanium transported from anode to cathode during SSE. In the metal before SSE, there were impurities of titanium in strip shape or embedded round shape. After SSE processing, titanium particles in the metal smaller than 50 nm in the cathode, but existed 6 to 10 times bigger in the anode.
基金supported by the National Science and Technology Support Program of China(2015BAB16B02)the National Natural Science Foundation of China(51504034).
文摘In acid treatment technology of Baotou mixed rare earth ore,large quantities of ammonia-nitrogen wastewater are produced in the step of ammonium bicarbonate precipitation to transform rare earth sulfate.In this paper,we adopted a green precipitant magnesium bicarbonate(Mg(HCO3)2) to substitute ammonium bicarbonate to eliminate ammonia-nitrogen pollution.The effects of n(HCO3^-):n(RE^3+),aging temperature and aging time on the crystallization using Mg(HCO3)2 precipitation method were investigated.The results indicate that the rare earths could be completely recovered when n(HCO3^-):n(RE^3+) is higher than 3.15:1.The crystal water content of rare earth carbonates is affected by the aging temperature.The precipitate has a bad filterability when the aging temperature is over 40℃.This can be attributed to the less crystallized water molecules of the hydrated rare earth carbonate precipitation.The mixed rare earth carbonates are prone to be crystalline,and have a good filterability at aging temperatures below 40℃.Meanwhile,the evolution mechanism of crystalline mixed rare earth carbonates is reasonably deduced,the amorphous rare earth carbonates are first dissolute and then recrystallized.Under the optimized aging conditions,the purity of the crystalline precipitate meets the requirements of the fine product standard(GB/T 16479-2008).The filtrated could be used to produce Mg(HCO3)2,thus to realize the recycling of magnesium sulfate.
基金financially supported by the National Science and Technology Support Program of China(No.2012BAE01B02)
文摘The differences in the leaching and mass transfer characteristics of ion-adsorption type rare earth ore between rare earth and non-rare earth impurities were investigated. It is determined that the leaching kinetics of rare earths （REs）, Mg and Ca could be described by the shrinking-core model. The leaching rate is controlled by inner diffusion and is in the order of Mg 〉 Ca 〉 RE. The apparent activation energy is 8.48, 6.79 and 6.32 kJ·mol^-1, respectively. In leaching system of Al, the leaching efficiency decreases with the increase in temperature because of hydrolysis reactions. The leaching efficiency of aluminum increases firstly and then decreases with the passage of time when the temperature is higher than 35 ℃. Besides, there is a good consistency in leaching characteristics and mass transfer, and the order of the time-to- peak is Mg 〈 Ca 〈 RE 〈 Al. Therefore, rare earth and non-rare earth may be partly separated by expanding the separation coefficient. The research could provide a theoretic basis for the separation of rare earth and non-rare earth impurities. Furthermore, compound leaching with magnesium salt and calcium salt is innovatively proposed to solve the problem of calcium and magnesium nutrient loss in the soil as well as eliminate ammonia-nitrogen emissions from the source.
基金The authors are grateful for the financial supports from the National Key Research and Development Program of China(2018YFC1801803)the Major Research Plan of the National Natural Science Foundation of China(91962211).
文摘The leaching behaviors of calcium and magnesium in the rare earth tailings leached with magnesium sulfate using deionized water,CaCl2 solution and lime water were investigated.Experimental data indicated that magnesium in the tailings was easy to be leached out since most of the magnesium was in the form of water-soluble phase.Most of calcium in the lime water was electrostatically adsorbed on the clay mineral of the tailings,and the water-soluble magnesium was also gradually converted into exchangeable phase because of back-adsorption of Mg2+on the clay mineral with increasing the pH values.When the liquid-to-solid ratio was 0.80,the contents of readily-available magnesium and calcium were 104.4−207.6 and 201.7−1426.3 mg/kg,respectively,which could meet the requirements for plants.These results suggest a promising route for the environmental remediation of ion-adsorption rare earth ore after in-situ leaching.
基金Project supported by the National Science and Technology Support Program of China(2012BAE01B02)
文摘Granite belonged to intrusive rock and volcanic was extrusive rock. There may be many differences in their degree of weathering and mineral chemical composition. The present study investigated the minerals properties and the leaching mechanism of the granitic weathered crust elution-deposited rare earth ore from Longnan Rare Earth Mine area （LN ores） and volcanic weathered crust elution-deposited rare earth ore from Liutang Rare Earth Mine area （LT ores）. The X-ray diffraction （XRD）, Fourier transform infrared spectroscopy （FT-IR） were used to characterize the phase of rare earth ores. The particle size distributions and main composition of the ore were also presented in this paper. The leaching mechanisms of two kinds of rare earth ores were analyzed with different kinetics models and could be described by the shrinking-core model. They were all inner diffusion-controlled leaching processes. The leaching equation of the kinetics of the LN ores could be expressed as：4 LN LN 1.096 10 2/3 0.377 8.314 0 2 3=0.1061 （1 ） Tr e tη η×？？？ ？ ？, leaching equation of kinetics of LT ores was 3 LT LT 4.640 10 2/3 0.411 8.314 0 32 3=8.33 101 （1 ） Tr e tη η×？？ ？×？ ？ ？. The rare earth leaching rate of LT ores was always lower in the same condition, and it would need more time and more （NH4）2SO4 consump-tion to achieve the same rare earth leaching efficiency, which would lead to more serious ammonia-nitrogen pollution. Therefore, magnesium salt was proposed as the leaching agent to eliminate ammonia-nitrogen pollution and further studies would be taken in the future.
基金Project supported by National Science and Technology Support Program of China(2015BAB16B01)Training Program of Major Academic and Technical Leaders in Jiangxi Province(20142BCB22005)Top Youth Talent Training Program of"Gan Po 555 Talents Project"of Jiangxi Province
文摘The practice ofin-situ leaching of the ion-adsorption type rare earths ore with ammonium sulfate could only leach most of rare earth in ion-exchangeable phase,but not the colloidal sediment phase.Therefore,the reduction leaching of rare earth from the ion-adsorption type rare earths ore with ferrous sulfate was innovatively put forward.The soak leaching process and the column leaching process were investigated in the present study.It was determined that ion-exchangeable phase could be released,and part of colloidal sediment phase rare earth could be reduction leached by the cations with reduction properties.The mechanism of reduction leaching was discussed with the Eh-pH diagram of cerium.Moreover,the stronger reduction of reductive ions,the greater acidity of leaching agent solution,and the higher reductive ion concentration,could result in the higher rare earth efficiency and the bigger ce-rium partition in the leaching liquor.In the ferrous sulfate column leaching process,the rare earth leaching rate and the rare earth effi-ciency were a little higher than with(NH4)2SO4 agent,and the rare earth efficiency and the partitioning of cerium in leaching liquor could be about 102%and 5.31%,respectively.However,the ferrous sulfate leaching process revealed some problems,so compound leaching with magnesium sulfate and a small amount of ferrous sulfate was proposed to an excellent alternative leaching agent for further studies,which may realize efficiency extraction and be environment-friendly.
基金the National Natural Science Foundation of China (50674016)the National High Technology Research and Develop-ment Program of China (863 Program) ( 2006AA06Z123)
文摘The extraction of Nd^3＋ and Sm^3＋, including the extraction and stripping capability as well as the separation effect of Nd^3＋ or Sm^3＋, from a sulfuric acid medium, by mixtures of di-（2-ethylhexyl） phosphoric acid （HDEHP, H2A2（0）） and 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester （HEH/EHP, H2L2（0）） were studied. The distribution ratios and synergistic coefficients of Nd^3＋ and Sm^3＋ in different acidities were also determined. A synergistic extractive effect was found when HDEHP and HEH/EHP were used as mixed extractants for Sm^3＋ or Nd^3＋. The chemical compositions of the extracted complex were determined as Nd.（HA2）2-HL2 and Sm.（HA2）2-HL2. The extraction equilibrium constants, enthalpy change, and entropy change of the extraction reaction were also determined.
基金the National High Technology Research and Development Program of China (No.2006AA06Z126) for the financial aid
文摘Phosphorite ore is a potential resource of rare earths （RE） as well as phosphate; therefore, the recovery of RE from wet-process phosphoric acid （WPA） is promising. This study investigated the influence of rotational speed, extractant concentration, flow ratio and phase contact time on the centrifugal extraction of RE from WPA and the separation of RE from impurities. The results indicate that higher rotational speed, higher extractant concentration and larger flow ratio are beneficial to the extraction of RE and impurities from phosphoric acid. It is found that the phase contact time for efficiently extracting RE and that for iron are of great difference, which provides an effective method for separating RE from iron using the non-equilibrium extraction process in centrifugal contactors. Compared with equilibrium extraction, the separation factor βRE/Fe is enhanced from 0.07 to 17.6.
基金Project supported by the Rare-earth Adjustment Upgrade Projects of Ministry of Industry and Information Technology of ChinaBeijing Nova Program(Z161100004916108)
文摘This paper investigated the recovery of rare earth elements(REEs)and aluminum(AI)from the waste slag discharged by FCC catalyst factory(FCC waste slag)via acid leaching and selective precipitation.Analysis methods such as ICP-AES,XRF and XRD were applied to obtain experiment data.The maximum leaching efficiency of REEs and Al was achieved at pH value of 1 and with liquid to solid ratio of 4:1,Under such conditions,91.01%,92.24%and 94.77%of La,Ce and Al were extracted at 20℃for 2 h from the FCC waste slag,respectively.The SiOcontent in the leaching residue was 88.3%,which can be used as an available silicon resource.The REEs can be precipitated in the form of REEs and sodium double sulfate(NaRE(SO)·xHO)by adding NaSOto the leaching solution,while Al remained in the solution.Afterwards,the pH value of the filtrate was adjusted to 4.5,and Al was precipitated as AI(OH).Finally,NaRE(SO)·xHO and Al(OH)were converted into RECland Al(SO4)solution,respectively,which were recycled to manufacture zeolite.This process recovered REEs and Al from the FCC waste slag and reduced the emissions of waste slag simultaneously,which has an important economic and environment significance.
基金Project supported by the National Natural Science Foundation of China(51501016)
文摘In order to develop a highly sensitive material for nondestructive testing(NDT),(Tb_(0.3) Dy_(0.7))Fe_(1.95) thin films were deposited on FeCo substrates at room temperature by magnetron sputtering and annealed.The magnetostrictive properties and the detection efficiency of the composite films were investigated.Results demonstrate that the detection efficiency roughly shows regular consistency with the magnetostrictive strain of the TbDyFe films. Heat treatment has a great effect on the crystalline state and the magnetostrictive strain of the composite materials. The as-deposited(Tb_(0.3) Dy_(0.7))Fe_(1.95) films are amorphous, and the saturation magnetostriction(ls) is only 90 ppm. However, the nanostructured crystalline REFe2 is partially separated out in amorphous matrix after annealing at 600C for 1 h, and the ls increases to 265 ppm. Simultaneously, the detection efficiency of the composite materials is obviously improved compared to that of the as-deposited films. The detection signal of traditional FeCo strip is0.4 V at the excitation power of 1.0 P and frequency of 128 kHz and that of the strip increases significantly by depositing one layer of(Tb_(0.3) Dy_(0.7))Fe_(1.95) film. The detection signal of the composite material annealed at 600C is the best, even reaching saturation value of 2.5 V(1.0 P, 128 kHz). The results may provide us with a method for preparing new materials for NDT.
基金Project supported by the National Natural Science Foundation of China(51674036)the Beijing Nova Program(Z161100004916108)
文摘Phosphate rock has been considered as one of the potential promising resources for rare earth elements(REEs). But the cost issues and the technical challenges caused by the low content of REEs in ores did hinder the further development of REEs recovery technologies. In order to explore a green process for the recovery of REEs from phosphate rock, this study investigates the effects of phosphoric acid concentration, liquid-to-solid ratio(L/S ratio), leaching time and temperature on the leaching efficiencies of the major components from phosphate rock. A REEs recovery of 94.3% and a phosphorus recovery of 95.3%are achieved under the optimal conditions of attacking phosphate rock using 30%P_2 O_5 acid with an L/S ratio of 10:1 and a stirring speed of 250 r/min at 25 ℃ for 4 h. Then,the selective precipitation of REEs with 81.3% REEs recovery is realized by heating up the leaching solution from 25 to 90 ℃ and keeping for4 h. Thereafter, more than 95% phosphoric acid is recovered by H_2 SO_4 and high purity gypsum, more than95% CaSO_4(tested by XRF), is also produced at the same time. Ultimately, a green process that leaches phosphate rock with H_3 PO_4, selectively precipitates REEs from leaching solution by heating up, recovers H_3 PO_4 with H2 SO4 is proposed. Compared with REE recovery in traditional processes, this process owns the merits of simple operation, energy saving and minimum wastes.
基金Project supported by the National Natural Science Foundation of China(51674037,51674036)Guangxi Science and Technology Major Project(Guike-AA18242022)。
文摘The precipitation of the water-leaching solution of Baotou mixed rare earth(RE) concentrate roasted with sulfuric acid using ammonium bicarbonate for producing RE carbonate produces a mass of ammonia-nitrogen wastewater because of the relatively low solubility of rare earth sulfate.To solve the serious problem of ammonia-nitrogen pollution,new precipitators need to be developed urgently so as to meet the requirements of environmental protection and impurities content of the product(SO_(4)^(2-)<1.8 wt% in RE carbonates products).In this paper,we studied the effects of feeding modes on the behavior of SO_(4)^(2-) during the preparation of light RE carbonate(RE=La,Ce,Pr,Nd) from their sulfate solutions using Mg(HCO_(3))_(2) as a precipitant.The results indicate that the contents of SO_(4)^(2-) in the La and Ce precipitates using positive feeding mode exceed 16 wt% because of the formation of La_(2)(CO_(3))2.15(-SO_(4))0.85·4 H_(2)O and Ce_(2)(CO_(3))_(2).15(SO_(4))0.85·3H_(2)O,while those of the Pr and Nd precipitates are 4 wt%-5 wt% since they exist in the form of n-carbonate.The precipitates prepared using synchronous feeding mode are all RE carbonate with only 4 wt%-5 wt% of SO_(4)^(2-) enclosed in the precipitation.The content of SO_(4)^(2-) in the RE carbonate obtained using reverse feeding mode is the lowest.Among them,the content of SO_(4)^(2-) in La precipitate is only 1.40 wt%.Both synchronous and reverse feeding modes can effectively reduce the content of SO_(4)^(2-)in RE carbonate,which provides theoretical guidance for the preparation of qualified light RE carbonate products by Mg(HCO3)2 precipitation method.
基金Project(51674036)supported by the National Natural Science Foundation of ChinaProject(Z161100004916108)supported by the Beijing Nova Program,China
文摘In order to provide practical fundamental data for rare-earth elements （REEs） recovery from phosphoric acid and to betterunderstand REEs behavior during the phosphoric acid evaporation process, the solubilities of REEs in phosphoric acid with variousconcentrations of phosphorus at different temperatures were measured. A simple linear model between REEs solubility andphosphoric acid concentration is built and the experimental data are found to fit it very well （R2〉0.94）. Hydrogen-ion concentration isfound to be the predominant factor controlling the solubility of REEs in phosphoric acid. In addition, the solubility of REEs inphosphoric acid is found to sharply decrease with increasing temperature, which can be attributed to the increase of the Gibbs energyof the REEPO4 dissolution reaction or the restraint of the disassociation of phosphoric acid molecules owing to the elevatedtemperature.
