To explore the spontaneous magnetization of iron-bearing rare earth ores during suspension roasting,binary minerals containing hematite and bastnaesite were used to investigate the effects of the roasting temperature,...To explore the spontaneous magnetization of iron-bearing rare earth ores during suspension roasting,binary minerals containing hematite and bastnaesite were used to investigate the effects of the roasting temperature,roasting time,and bastnaesite-to-hematite mass ratio on in-situ reduction of hematite in a N_(2)atmosphere.Relevant analytical tests were used to explore the mineral phase evolution during roasting,the magnetism and microstructure of the roasted products,the phase composition,and the surface element valence of concentrate.It was found that magnetic separation of the iron concentrate afforded an iron grade of 68.87%and a recovery of 93.18%under the optimum roasting conditions.During roasting,bastnaesite decomposed to generate CO_(2)and CO,and the compact structure of hematite was gradually destroyed,resulting in microcracks.Subsequently,the CO entered the surface of the hematite through the microcracks and reacted to form a magnetite shell,and the magnetite-encapsulated hematite particles were recovered via low-intensity magnetic separation.展开更多
In order to reveal the effect of 2-hydroxy-3-naphthyl hydroxamic acid(H205)on the flotation behavior and action mechanism of bastnaesite,single-mineral flotation experiments of bastnaesite were conducted.The flotation...In order to reveal the effect of 2-hydroxy-3-naphthyl hydroxamic acid(H205)on the flotation behavior and action mechanism of bastnaesite,single-mineral flotation experiments of bastnaesite were conducted.The flotation recovery of bastnaesites can be achieved more than 90%when the aeration rate is 40 mL/min,the rotational speed is 200 r/min,the H205 dosage is 120 mg/L,and the pulp pH ranges from 7 to 9.The action mechanism of H205 on the surface of bastnaesite was studied by simultaneous thermogravimetry and differential scanning calorimetry(TG-DSC),Zeta potential measurements,Fourier transform-infrared spectra(FT-IR)and X-ray photoelectron spectroscopy(XPS).These analysis results show that under suitable flotation conditions,H205 has an obvious adsorption phenomenon on the surface of bastnaesite.The adsorption involves electrostatic interactions and chemical interactions,namely H205 has a strong collecting ability of bastnaesite due to the synergism of electrostatic adsorption and chemical adsorption.This study systematically reveals the flotation behavior and adsorption mechanism of H205 on the surface of bastnaesite,and provides useful theoretical guidance for efficient flotation separation of bastnaesite.展开更多
Roasting bastnaesite concentrates is a crucial process in extracting rare earths.This study explored an efficient suspension roasting technology and investigated the bastnaesite pyrolysis and cerium(Ce)oxidation.Relev...Roasting bastnaesite concentrates is a crucial process in extracting rare earths.This study explored an efficient suspension roasting technology and investigated the bastnaesite pyrolysis and cerium(Ce)oxidation.Relevant analytical tests were applied to evaluate the phase and surface property variations of bastnaesite,and isothermal kinetic analysis of bastnaesite pyrolysis and Ce oxidation was performed.The results revealed that bastnaesite decomposed rapidly and accompanied by Ce oxidation,and the gas-solid products were identified as CO_(2),Ce_(7)O_(12),La_(2)O_(3),CeF_(3) and LaF_(3),with Ce oxidation restricted by bastnaesite pyrolysis.As roasting time prolonged,cracks and pores appeared on bastnaesite surface;the BET specific surface and pore diameter increased.In later roasting period,the pore diameter continued to increase but the specific surface decreased,assigned to particle fusion agglomeration and pore consolidation.Additionally,the surface C content reduced and Ce(Ⅳ)content increased gradually as roasting progressed.The reaction kinetics all followed Avrami-Erofeev equations,the reaction orders of bastnaesite pyrolysis and Ce oxidation decreased with decreasing reaction temperature.The calculated activation energies at lower temperatures were higher than those calculated at higher temperatures.This study analyzed the bastnaesite reaction mechanism to supply a reference for the application of suspension roasting technology in bastnaesite smelting.展开更多
Bastnaesite((Ce,La,Pr,Nd)CO_(3)F) is a significant light rare earth mineral found in nature,known for its fine-grained properties.Flotation is commonly employed for the recovery of fine-grained bastnaesite particles.C...Bastnaesite((Ce,La,Pr,Nd)CO_(3)F) is a significant light rare earth mineral found in nature,known for its fine-grained properties.Flotation is commonly employed for the recovery of fine-grained bastnaesite particles.Collectors serve as an essential flotation reagent that enhance the surface hydrophobicity of target minerals.A novel collector,N-hydroxy-9-octadecenamide(N-OH-9-ODA),was synthesised in this study.N-OH-9-ODA exhibits superior selectivity compared to the traditional collector oleic acid in the flotation separation of bastnaesite and fluorite.The experimental and co mputational results indicate that N-OH-9-ODA exhibits superior selectivity due to its higher adsorption affinity for bastnaesite surface compared to fluorite surface.The zeta potential and the binding energies of the Ce 3d peaks in the X-ray photoelectron spectrum(XPS) of bastnaesite surface exhibit significant shifts.Conversely,fluorite surface demonstrates minimal alterations in its zeta potential and the binding energies of the Ca 2p peaks in its XPS after its interaction with N-OH-9-ODA.展开更多
Effectively separating bastnaesite from calcium-bearing gangue minerals(particularly calcite)presents a formidable challenge,making the development of efficient collectors crucial.To achieve this,we have designed and ...Effectively separating bastnaesite from calcium-bearing gangue minerals(particularly calcite)presents a formidable challenge,making the development of efficient collectors crucial.To achieve this,we have designed and synthesized a novel,highly efficient,water-soluble cationic collector,N-dodecylisopropanolamine(NDIA),for use in the bastnaesite-calcite flotation process.Density functional theory(DFT)calculations identified the amine nitrogen atom in NDIA as the site most susceptible to electrophilic attack and electron loss.By introducing an OH group into the traditional collector dodecylamine(DDA)structure,NDIA provided additional adsorption sites,enabling synergistic adsorption on the surface of bastnaesite,thereby significantly enhancing both the floatability and selectivity of these minerals.The recovery of bastnaesite was 76.02%,while the calcite was 1.26%.The NDIA markedly affected the zeta potential of bastnaesite,while its impact on calcite was relatively minor.Detailed Fourier-transform infrared spectroscopy(FTIR)and X-ray photoelectron spectroscopy(XPS)results elucidated that the―NH―and―OH groups in NDIA anchored onto the bastnaesite surface through robust electrostatic and hydrogen bonding interactions,thereby enhancing bastnaesite's affinity for NDIA.Furthermore,in situ atomic force microscopy(AFM)provided conclusive evidence of NDIA aggregation on the bastnaesite surface,improving contact angle and hydrophobicity,and significantly boosting the flotation recovery of bastnaesite.展开更多
To investigate the thermal decomposition behavior and reaction kinetics of bastnaesite in suspension roasting,the gas and solid products of bastnaesite roasted in N2 and air atmospheres were examined using a gas analy...To investigate the thermal decomposition behavior and reaction kinetics of bastnaesite in suspension roasting,the gas and solid products of bastnaesite roasted in N2 and air atmospheres were examined using a gas analyzer,X-ray diffraction(XRD),scanning electron microscopy(SEM),and energy dispersive spectrometry(EDS).Subsequently,the kinetic parameters of bastnaesite in the suspension roasting process were derived and calculated using the isothermal method.The results show that the decomposition product of bastnaesite in N_(2) is CeOF.However,once the roasting temperature exceeds 600℃,CO is generated in addition to CO_(2),and all the XRD diffraction peaks of CeOF are shifted to the right,indicating that CO_(2) can oxidize CeOF and lead to the transformation of Ce(Ⅲ) into Ce(Ⅳ).When roasted in air,the decomposition product CeOF can be completely converted to CeF3 and Ce_(7)O_(12) as it easily oxidizes.Additionally,the reaction rate of bastnaesite in air is higher than that of N_(2),and the starting reaction temperature is lower than that of N_(2).A large number of irregular cracks and holes appear on the surface of solid-phase products following suspension roasting,which are due to the thermal decomposition of bastnaesite that produces CO_(2) as well as the reconstruction of the lattice of the solid-phase products.The reaction kinetic model of bastnaesite roasted in N_(2)(temperature range 600-750℃) and air(temperatu re range 500-575℃) confo rms to the A_(3/2) model with the mechanism function G(α)=-ln(1-α)^(2/3),and the reaction activation energy is 59.78 kj/mol and lnA is 1.65 s^(-1) in N_(2) atmosphere.In air,the reaction activation energy is 100.30 kj/mol and lnA is 9.63 s^(-1).展开更多
The separation of rare earths is difficult due to their similar properties and the complex characteristics of associated vein o res.Complexation-ultrafiltration(CUF)and shear induced o rderly dissociation coupling wit...The separation of rare earths is difficult due to their similar properties and the complex characteristics of associated vein o res.Complexation-ultrafiltration(CUF)and shear induced o rderly dissociation coupling with ultrafiltration(SIODUF)were used to separate metal ions(M,M=La(Ⅲ),Ce(Ⅳ)and Ca(Ⅱ))from simulated bastnaesite leaching solution using acidic phosphonic chitosan(aPCS)and rotating disk membrane.Effect of simultaneous removal of metallic ions was investigated by CUF,and suitable conditions were obtained for C/M 10.0(mass ratio of complexant to metal ions)and pH 5.0.The shear stabilities of aPCS-M complexes were explored at different pH values and the results show that the complexes can dissociate at a certain rotational speed,the critical one.The critical s hear rates of aPCS-La,aPCS-Ce and aPCS-Ca complexes at pH 5.0 were calculated as 1.42×10^(5).1.69×10^(5) and 9.75×10^(4) s^(-1),respectively.The order of complexes shear stability is aPCS-Ca aPCS-La<aPCS-Ce.The high selective separation of M and regeneration of aPCS were achieved by SIODUF in the light of the difference of aPCSM complexes shear stabilities.The separation coefficientsβLa/Ce andβCa/La reach 31.2 and 53.9,respectively.展开更多
Rare earth elements have been widely applied in various sectors.Bastnaesite and monazite are crucial rare earth minerals,and flotation is a vital technique for recovering fine-grained rare earth minerals and separatin...Rare earth elements have been widely applied in various sectors.Bastnaesite and monazite are crucial rare earth minerals,and flotation is a vital technique for recovering fine-grained rare earth minerals and separating them from associated gangue minerals such as fluorite and apatite.Flotation collectors play a key role in selectively adsorbing valuable minerals,enhancing their surface hydrophobicity,which has prompted considerable research interest.However,the interaction between minerals and reagents relies on the reactivity and selectivity of the reagent groups,as well as the reactive properties of the surface atoms of the minerals.This study proposes the use of H_(2)O_(2)oxidation to enhance the flotation process of rare earth minerals.The flotation experiments demonstrated that pre-adding H_(2)O_(2)before introducing the flotation collector significantly improved the grade and recovery of rare earth concentrates.The adsorption mechanisms of 2-hydroxy-3-naphthyl hydroxamic acid collector on rare earth mineral surfaces before and after H_(2)O_(2)pre-oxidation were studied.The 2-hydroxy-3-naphthyl hydroxamic acid interacts with Ce^(3+)on the surface of unoxidized rare earth minerals,forming chelate compounds with five-membered ring structures.The H_(2)O_(2)exhibited potent oxidizing properties and oxidized the Ce^(3+)on the bastnaesite and monazite surfaces to more stable Ce^(4+),which demonstrated stronger binding capability with hydroxamic acid.展开更多
Sulfuric acid leaching process was applied to extracting rare earth（RE） from roasted ore of Dechang bastnaesite in Sichuan,China.The effect of particle size,stirring speed,sulfuric acid concentration and leaching te...Sulfuric acid leaching process was applied to extracting rare earth（RE） from roasted ore of Dechang bastnaesite in Sichuan,China.The effect of particle size,stirring speed,sulfuric acid concentration and leaching temperature on RE extraction efficiency was investigated,and the leaching kinetics of RE was analyzed.Under selected leaching conditions,including particle size（0.074-0.100 mm）,sulfuric acid concentration 1.50 mol/L,mass ratio of liquid to solid 8 and stirring speed 500 r/min,the leaching kinetics analysis shows that the reaction rate of leaching process is controlled by diffusion through the product/ash layer which can be described by the shrinking-core model,and the calculated activation energy of 9.977 kJ/mol is characteristic for a diffusion-controlled process.展开更多
The leaching kinetics of bastnaesite concentrate in HCl solution was investigated with respect to the effects of HCl concentration by changing HCl concentration,leaching temperature,liquid to solid ratio,and particle ...The leaching kinetics of bastnaesite concentrate in HCl solution was investigated with respect to the effects of HCl concentration by changing HCl concentration,leaching temperature,liquid to solid ratio,and particle size.A particle size of 25 μm was required to leach 89.6% RE2（CO3）3 and 1.5%REF3 at 90 ℃ for 90 min,when HCl concentration was 6 mol/L and liquid to solid ratio was 15：1.The leaching kinetics of bastnaesite concentrate is represented by shrinking core model with diffusion through a porous product layer.The activation energies for the dissolution reaction of RE2（CO3）3 and REF3 were calculated to be 59.39 kJ/mol and 66.13 kJ/mol respectively.展开更多
To clearly elucidate the oxidative roasting behaviors of the bastnaesite, the thermal decomposition and oxidation of the bastnaesite concentrate in inert and oxidative atmosphere have been investigated in detail. Expe...To clearly elucidate the oxidative roasting behaviors of the bastnaesite, the thermal decomposition and oxidation of the bastnaesite concentrate in inert and oxidative atmosphere have been investigated in detail. Experimental data indicated that the initial decomposition temperature of the concentrate under N2 atmosphere is 150 ℃ higher than that under O2 atmosphere,most likely because the oxidation of the cerium induces the decomposition of the concentrate. For the roasted samples under N2 atmosphere at500 ℃ and above,the oxidation efficiency of the cerium is 19.8%-26.8% because of the fact that rareearth fluorocarbonate is first decomposed to form rare-earth oxyfluoride and CO2, and the cerium oxyfluoride is then partially oxidized by the CO2 gas. The rest cerium in these samples can be further oxidized in air at room temperature, with the oxidation efficiency of the cerium gradually increasing to above 80% in 7 d. This can be attributed to the obvious changes in the inner morphology of the roasted samples under N2 atmosphere at high temperatures, which largely induce the diffusion of the air and improves the oxidation activity of CeOF, and further induces the oxidation of CeOF by the air. XRD and XPS techniques were used to further verify the significant differences in the thermal decomposition behaviors of the bastnaesite concentrate under N2 and O2 atmosphere. Moreover, no oxidation of Pr^（3＋） to Pr^（4＋） in the roasted samples under both N2 and O2 atmosphere is observed. This gives an overall understanding of the oxidative roasting of the bastnaesite concentrate without additives.展开更多
To understand the flotation mechanism of bastnaesite using reactive oily bubble, the interaction between bastnaesite parti-cles and reactive oily bubbles was investigated by electro-kinetic studies, induction time mea...To understand the flotation mechanism of bastnaesite using reactive oily bubble, the interaction between bastnaesite parti-cles and reactive oily bubbles was investigated by electro-kinetic studies, induction time measurements and small-scale flotation ex-periments. The bastnaesite flotation could be seen as a hetero-coagulation between bastnaesite particles and reactive oily bubbles which was confirmed by the zeta potential distribution and induction time measurements from pH 4.8 to pH 9.0. The small-scale flotation tests were consistent with the hetero-coagulation results, and showed a better flotation of reactive oily bubble than air bubble among all pH range. The interaction force between bastnaesite particles and reactive oily bubbles was evaluated by the classical DLVO theory. It indicated that the attachment could be predicted well by the DLVO theory only in a restricted pH range due to the absence of hydrophilic interaction repulsion force and chemical interaction force.展开更多
Extracting rare earths from bastnaesite concentrate treated by calcification transition was studied through the single factor test and XRD patterns of bastnaesite after calcification and slags after leaching in HCl so...Extracting rare earths from bastnaesite concentrate treated by calcification transition was studied through the single factor test and XRD patterns of bastnaesite after calcification and slags after leaching in HCl solution. And the effects of the main calcified parameters such as temperature, liquid/solid and calcified time on transition performance of bastnaesite were investigated. It was found that under the optimal conditions of calcification temperature of 250 oC, liquid/solid of 20 mL/g, calcification time of 180 min, the highest leaching rate of rare earth were obtained, with the leaching ratio of rare earths 83.70% and Ce 77.01%, La 90.55%, Nd 92.03%, respectively; loss rates of fluorine with different calcification conditions were always less than 1% and XRD patterns of calcification slags and leaching slags showed that fluorine existed in the form of CaF2.展开更多
Bastnaesite is an important rare earth mineral and is usually beneficiated by flotation.Sodium silicate is commonly used to depress calcium-bearing gangue minerals,however it can also depress bastnaesite when Ca^(2+) ...Bastnaesite is an important rare earth mineral and is usually beneficiated by flotation.Sodium silicate is commonly used to depress calcium-bearing gangue minerals,however it can also depress bastnaesite when Ca^(2+) ions exist in the pulp.In this study,the effect of Ca^(2+) ions and sodium silicate individually or in combination on bastnaesite flotation was studied through micro-flotation,zeta potential,fluorescence spectroscopy and X-ray photoelectron spectroscopy(XPS) measurements.Micro-flotation results show that the combination of Ca^(2+) ions and sodium silicate depresses bastnaesite more severely due to their synergistic effect.Zeta potential results show that the combination renders the surface potential of bastnaesite negatively shifted more significantly.Fluorescence spectroscopy shows that the combination decreases the surface hydrophobicity of bastnaesite more severely.XPS shows that the combination increases the adsorption of sodium silicate on bastnaesite by forming hydrophilic Ca-SiO_(3) precipitate,which causes more serious depression on bastnaesite flotation.展开更多
The structural and electronic properties of bastnaesite were studied by using the first-principles method based on the density functional theory(DFT).The geometry structure of bastnaesite was first optimized,and then ...The structural and electronic properties of bastnaesite were studied by using the first-principles method based on the density functional theory(DFT).The geometry structure of bastnaesite was first optimized,and then the Mulliken populations,electron density and density of states were calculated and further analyzed in detail.The calculation results reveal that it mainly ruptures along the ionic Ce-O and Ce-F bonds during the cleavage of bastnaesite,leaving≡Ce^+,≡F^-and≡CO3^-dangling bonds exposed on the cleavage surface of bastnaesite.Combined with contact angle measurement,surface complexation theory and XPS analysis,the implications of structural and electronic properties on bastnaesite flotation reactions were studied.The hydration of exposed strong ionic bond on cleavage surface results in hydrophilic surface.According to surface complexation theory,the formed surface groups are≡CeOH^0,≡CO3 H^0 and≡FH^0 groups.The investigated metal ions and flotation reagents complex with surface≡CeOH^0 groups,while≡CO3H^0 and≡FH^0 groups are not involved in the complexation.The high activity of Ce atoms facilitates these surface reactions.展开更多
Mechanochemical reaction involves simultaneous chemical reaction and particle crushing;the latter increases the effective reaction area and improves the reactivity,thus enhancing its kinetics.The classical shrinking c...Mechanochemical reaction involves simultaneous chemical reaction and particle crushing;the latter increases the effective reaction area and improves the reactivity,thus enhancing its kinetics.The classical shrinking core model was used to model the kinetics of bastnaesite mechanochemical decomposition in NaOH solution,which shows a questionable result.Mechanochemical reaction is a dynamic process,where the particle shape and concentration in reaction interface undergo constant change.Thus,a physically consistent model was applied to describe the kinetics.The variations in OH^-concentration and particle shape were considered in the revision of model.Considering the variation in OH^-concentration in solution with time,the model with varying OH^-concentration agrees better with the experimental data,improving the regression coefficients to between 0.936 and 0.992.By introducing fractal geometry to deal with the irregular system,the model was further optimized,and the regression coefficients increase to between 0.940 and 0.997.All these models considere shrinking particle approaches and controlling mechanisms for the diffusion and chemical reaction.Finally,the fractal model with varying OH^-concentration was selected to describe the mechanochemical decomposition of bastnaesite,which indicates that the process is controlled by chemical reaction.展开更多
Flotation separation and recovery of rare earth minerals(REM) have returned to an important position due to the growing strategy demand for rare earth elements(REE).In this paper,a comparative investigation into the f...Flotation separation and recovery of rare earth minerals(REM) have returned to an important position due to the growing strategy demand for rare earth elements(REE).In this paper,a comparative investigation into the floatability of bastnaesite((Ce,La)FCO3) was conducted by using three di/trialkyl phosphate collectors,di(2-ethylhexyl) phosphate(DEHPA),dibutyl phosphate(DBP) and tributyl phosphate(TBP).The density functional theory(DFT) computation recommends that the chemical activity of the three phosphate collectors is in order of DEHPA≥ DBP >> TBP,and their hydrophobization assuggested by the IgP(oil-water partition coefficient) value is in the order of DEHPA> TBP> DBP.The micro-flotation indicates that the preferable pH values for flotation of bastnaesite with the three phosphate collectors are 7.0-8.0,and DEHPA achieves much higher flotation recovery of bastnaesite,followed by DBP,and then TBP,which coincides with their reactivity and hydrophobicity,the two prerequisites for froth flotation.The contact angle,zeta potential,Fourier transform infrared spectroscopy(FTIR) and X-ray photoelectron spectroscopy(XPS) deduce that DEHPA likely reacts with the Ce(Ⅲ)atoms of bastnaesite interface through its O atom(s) of the P(=O)-O-group to generate the Ce-O-P bonds,and its two 2-ethylhexyl groups orient outside for attaching bubbles,resulting in flotation enrichment of bastnaesite.Furthermore,this investigation offers a novel strategy for developing collectors in selective beneficiation of REM.展开更多
Isoconversional methods combined with thermogravimetry were applied to investigate the decomposition kinetics of bastnaesite concentrates with different amounts of calcium hydroxide added.The apparent activation energ...Isoconversional methods combined with thermogravimetry were applied to investigate the decomposition kinetics of bastnaesite concentrates with different amounts of calcium hydroxide added.The apparent activation energy was calculated,and the results indicate that the overall reaction involves more than one single step.The reaction with a lower content(<15 wt%)of calcium hydroxide can be divided into two steps,while the reaction with a higher content(>15 wt%)involves another step which denotes the decomposition of newly formed calcium carbonate during roasting.The activation energy increases with increasing amount of calcium hydroxide in the lower range(0-15 wt%).This is due to the resistance of calcium hydroxide to heat and mass transport,However,more calcium can promote the decomposition reaction more effectively and thus reduce the activation energy.Nonlinear fitting was performed by fitting the experimental data to Avrami-Erofeev model to determine the reaction model and pre-exponential factor.The theoretical models were proven to be reliable for kinetic prediction.展开更多
Rare earth element is an important strategic metal,but the supply of high purity rare earth ores is growing slowly,which is in sharp contradiction with the rapidly growing demand.Froth flotation has been confirmed to ...Rare earth element is an important strategic metal,but the supply of high purity rare earth ores is growing slowly,which is in sharp contradiction with the rapidly growing demand.Froth flotation has been confirmed to be an effective method to separate bastnaesite from its gangue minerls.However,the traditional collectors are facing serious problems in flotation separation of minerals,requiring the addition of excess depressant and regulator in the flotation process.Herein,we proposed and synthesized novel Gemini hydroxamic acids Octyl-bishydroxamic acid(OTBHA),Decyl-bishydroxamic acid(DCBHA)and Dodecyl-bishydroxamic acid(DDBHA)as the collectors in bastnaesite-barite flotation system.The effect of different carbon chain lengths on the molecular properties were explored by density functional theory(DFT)calculations.DCBHA possessed a stronger reactivity compared with OCBHA and DDBHA.The flotation results verified the consistency of the computational calculation about the performance prediction of Gemini hydroxamic acids.Compared with OCBHA and DDBHA,DCBHA displayed superior collecting affinity toward bastnaesite,and did not float barite.Zeta potential results showed that the presence of DCBHA increased the potential of bastnaesite,while it had almost no effect on barite,indicating DCBHA had a stronger affinity for bastnaesite.Then,Fourier transform infrared(FTIR)and X-ray photoelectron spectroscopy(XPS)analyses indicated that the adsorption mechanism was due to two hydroxamate groups of DCBHA co-anchored on bastnaesite surface by forming five-membered hydroxamic―(O―O)―Ce complexes.In addition,atomic force microscopy(AFM)clearly observed that DCBHA uniformly aggregated on bastnaesite surface,which increased surface contact angle and improved the hydrophobicity of bastnaesite.展开更多
A novel process of calcification-leaching for bastnaesite concentrate(REFCO3) was proposed. The prior calcification was carried out in the system of NaOH-CaO-H2O and the lgC-pH pattern for Ce-F-Ca-C-H2O system was dra...A novel process of calcification-leaching for bastnaesite concentrate(REFCO3) was proposed. The prior calcification was carried out in the system of NaOH-CaO-H2O and the lgC-pH pattern for Ce-F-Ca-C-H2O system was drawn. The thermodynamics result indicates that decomposition for bastnaesite requires certain alkaline condition, but excessive alkalinity also causes decomposition of CaF2. XRD and SEM-EDS analyses on the calcification-leaching process reveal that bastnaesite first decomposes into RE(OH)3 and CaF2. Then, by HCl leaching rare earths were extracted,while CaF2 was left in the leaching residue. In addition, effects of temperature, time, NaOH and CaO on the calcification were investigated. The results show that the leaching rate of rare earths(REs)reaches 72.5 wt%, at the same time 99.2 wt% of F is left in leaching residue with 20 wt% NaOH and 38 wt% CaO at 493 K for 180 min.展开更多
基金the financial support from the National Key R&D Program of China(No.2022YFC2905800)the National Natural Science Foundation of China(Nos.52174242,52130406)。
文摘To explore the spontaneous magnetization of iron-bearing rare earth ores during suspension roasting,binary minerals containing hematite and bastnaesite were used to investigate the effects of the roasting temperature,roasting time,and bastnaesite-to-hematite mass ratio on in-situ reduction of hematite in a N_(2)atmosphere.Relevant analytical tests were used to explore the mineral phase evolution during roasting,the magnetism and microstructure of the roasted products,the phase composition,and the surface element valence of concentrate.It was found that magnetic separation of the iron concentrate afforded an iron grade of 68.87%and a recovery of 93.18%under the optimum roasting conditions.During roasting,bastnaesite decomposed to generate CO_(2)and CO,and the compact structure of hematite was gradually destroyed,resulting in microcracks.Subsequently,the CO entered the surface of the hematite through the microcracks and reacted to form a magnetite shell,and the magnetite-encapsulated hematite particles were recovered via low-intensity magnetic separation.
基金Project supported by the Natural Science Foundation Innovation Group Project of Hubei Province(2023AFA044)the National Natural Science Foundation of China(52222405)+1 种基金the Science and Technology Research Project of Education Department of Hubei Province(Q20221505)the China Postdoctoral Science(2023M731041)。
文摘In order to reveal the effect of 2-hydroxy-3-naphthyl hydroxamic acid(H205)on the flotation behavior and action mechanism of bastnaesite,single-mineral flotation experiments of bastnaesite were conducted.The flotation recovery of bastnaesites can be achieved more than 90%when the aeration rate is 40 mL/min,the rotational speed is 200 r/min,the H205 dosage is 120 mg/L,and the pulp pH ranges from 7 to 9.The action mechanism of H205 on the surface of bastnaesite was studied by simultaneous thermogravimetry and differential scanning calorimetry(TG-DSC),Zeta potential measurements,Fourier transform-infrared spectra(FT-IR)and X-ray photoelectron spectroscopy(XPS).These analysis results show that under suitable flotation conditions,H205 has an obvious adsorption phenomenon on the surface of bastnaesite.The adsorption involves electrostatic interactions and chemical interactions,namely H205 has a strong collecting ability of bastnaesite due to the synergism of electrostatic adsorption and chemical adsorption.This study systematically reveals the flotation behavior and adsorption mechanism of H205 on the surface of bastnaesite,and provides useful theoretical guidance for efficient flotation separation of bastnaesite.
基金Projects(2022YFC2905800,2021YFC2901000)supported by the National Key R&D Program of ChinaProject(52174242)supported by the National Science and Technology of ChinaProject(52130406)supported by the National Science and Technology Major Project of China。
文摘Roasting bastnaesite concentrates is a crucial process in extracting rare earths.This study explored an efficient suspension roasting technology and investigated the bastnaesite pyrolysis and cerium(Ce)oxidation.Relevant analytical tests were applied to evaluate the phase and surface property variations of bastnaesite,and isothermal kinetic analysis of bastnaesite pyrolysis and Ce oxidation was performed.The results revealed that bastnaesite decomposed rapidly and accompanied by Ce oxidation,and the gas-solid products were identified as CO_(2),Ce_(7)O_(12),La_(2)O_(3),CeF_(3) and LaF_(3),with Ce oxidation restricted by bastnaesite pyrolysis.As roasting time prolonged,cracks and pores appeared on bastnaesite surface;the BET specific surface and pore diameter increased.In later roasting period,the pore diameter continued to increase but the specific surface decreased,assigned to particle fusion agglomeration and pore consolidation.Additionally,the surface C content reduced and Ce(Ⅳ)content increased gradually as roasting progressed.The reaction kinetics all followed Avrami-Erofeev equations,the reaction orders of bastnaesite pyrolysis and Ce oxidation decreased with decreasing reaction temperature.The calculated activation energies at lower temperatures were higher than those calculated at higher temperatures.This study analyzed the bastnaesite reaction mechanism to supply a reference for the application of suspension roasting technology in bastnaesite smelting.
基金supported by National Natural Science Foundation of China (52104287,91962223)Hubei Key Laboratory for Efficient Utilisation and Agglomeration of Metallurgic Mineral ResourcesOpen Foundation of State Key Laboratory of Mineral Processing (BGRIMM-KJSKL-2022-14)。
文摘Bastnaesite((Ce,La,Pr,Nd)CO_(3)F) is a significant light rare earth mineral found in nature,known for its fine-grained properties.Flotation is commonly employed for the recovery of fine-grained bastnaesite particles.Collectors serve as an essential flotation reagent that enhance the surface hydrophobicity of target minerals.A novel collector,N-hydroxy-9-octadecenamide(N-OH-9-ODA),was synthesised in this study.N-OH-9-ODA exhibits superior selectivity compared to the traditional collector oleic acid in the flotation separation of bastnaesite and fluorite.The experimental and co mputational results indicate that N-OH-9-ODA exhibits superior selectivity due to its higher adsorption affinity for bastnaesite surface compared to fluorite surface.The zeta potential and the binding energies of the Ce 3d peaks in the X-ray photoelectron spectrum(XPS) of bastnaesite surface exhibit significant shifts.Conversely,fluorite surface demonstrates minimal alterations in its zeta potential and the binding energies of the Ca 2p peaks in its XPS after its interaction with N-OH-9-ODA.
基金supported by the the National Key R&D Program of China(No.2021YFC2900800)National Natural Science Foundation of China(Nos.52425406,51874247,51922091,and 52204285)+4 种基金the Open Research Fund of State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization(No.CNMRCUKF2001)Science and Technology Major Project of Ordos City-Iconic Innovation Team and “Rejuvenating Inner Mongolia through Science and Technology”(No.202204/2023)Yueqi Outstanding Scholar Award of CUMTB(No.202022)Funded by Open Foundation of State Key Laboratory of Mineral Processing(No.BGRIMM-KJSKL-2023-05)Fundamental Research Funds for the Central Universities(Ph.D.Top Innovative Talents Fund of CUMT BBJ2024048)。
文摘Effectively separating bastnaesite from calcium-bearing gangue minerals(particularly calcite)presents a formidable challenge,making the development of efficient collectors crucial.To achieve this,we have designed and synthesized a novel,highly efficient,water-soluble cationic collector,N-dodecylisopropanolamine(NDIA),for use in the bastnaesite-calcite flotation process.Density functional theory(DFT)calculations identified the amine nitrogen atom in NDIA as the site most susceptible to electrophilic attack and electron loss.By introducing an OH group into the traditional collector dodecylamine(DDA)structure,NDIA provided additional adsorption sites,enabling synergistic adsorption on the surface of bastnaesite,thereby significantly enhancing both the floatability and selectivity of these minerals.The recovery of bastnaesite was 76.02%,while the calcite was 1.26%.The NDIA markedly affected the zeta potential of bastnaesite,while its impact on calcite was relatively minor.Detailed Fourier-transform infrared spectroscopy(FTIR)and X-ray photoelectron spectroscopy(XPS)results elucidated that the―NH―and―OH groups in NDIA anchored onto the bastnaesite surface through robust electrostatic and hydrogen bonding interactions,thereby enhancing bastnaesite's affinity for NDIA.Furthermore,in situ atomic force microscopy(AFM)provided conclusive evidence of NDIA aggregation on the bastnaesite surface,improving contact angle and hydrophobicity,and significantly boosting the flotation recovery of bastnaesite.
基金Project supported by the National Key R&D Program of China (2022YFC2905800)National Natural Science Foundation of China(52174242)。
文摘To investigate the thermal decomposition behavior and reaction kinetics of bastnaesite in suspension roasting,the gas and solid products of bastnaesite roasted in N2 and air atmospheres were examined using a gas analyzer,X-ray diffraction(XRD),scanning electron microscopy(SEM),and energy dispersive spectrometry(EDS).Subsequently,the kinetic parameters of bastnaesite in the suspension roasting process were derived and calculated using the isothermal method.The results show that the decomposition product of bastnaesite in N_(2) is CeOF.However,once the roasting temperature exceeds 600℃,CO is generated in addition to CO_(2),and all the XRD diffraction peaks of CeOF are shifted to the right,indicating that CO_(2) can oxidize CeOF and lead to the transformation of Ce(Ⅲ) into Ce(Ⅳ).When roasted in air,the decomposition product CeOF can be completely converted to CeF3 and Ce_(7)O_(12) as it easily oxidizes.Additionally,the reaction rate of bastnaesite in air is higher than that of N_(2),and the starting reaction temperature is lower than that of N_(2).A large number of irregular cracks and holes appear on the surface of solid-phase products following suspension roasting,which are due to the thermal decomposition of bastnaesite that produces CO_(2) as well as the reconstruction of the lattice of the solid-phase products.The reaction kinetic model of bastnaesite roasted in N_(2)(temperature range 600-750℃) and air(temperatu re range 500-575℃) confo rms to the A_(3/2) model with the mechanism function G(α)=-ln(1-α)^(2/3),and the reaction activation energy is 59.78 kj/mol and lnA is 1.65 s^(-1) in N_(2) atmosphere.In air,the reaction activation energy is 100.30 kj/mol and lnA is 9.63 s^(-1).
基金Project supported by the National Natural Science Foundation of China(22178392)the Fundamental Research Funds for the Central Universities of Central South University,China(2022ZZTS0493)。
文摘The separation of rare earths is difficult due to their similar properties and the complex characteristics of associated vein o res.Complexation-ultrafiltration(CUF)and shear induced o rderly dissociation coupling with ultrafiltration(SIODUF)were used to separate metal ions(M,M=La(Ⅲ),Ce(Ⅳ)and Ca(Ⅱ))from simulated bastnaesite leaching solution using acidic phosphonic chitosan(aPCS)and rotating disk membrane.Effect of simultaneous removal of metallic ions was investigated by CUF,and suitable conditions were obtained for C/M 10.0(mass ratio of complexant to metal ions)and pH 5.0.The shear stabilities of aPCS-M complexes were explored at different pH values and the results show that the complexes can dissociate at a certain rotational speed,the critical one.The critical s hear rates of aPCS-La,aPCS-Ce and aPCS-Ca complexes at pH 5.0 were calculated as 1.42×10^(5).1.69×10^(5) and 9.75×10^(4) s^(-1),respectively.The order of complexes shear stability is aPCS-Ca aPCS-La<aPCS-Ce.The high selective separation of M and regeneration of aPCS were achieved by SIODUF in the light of the difference of aPCSM complexes shear stabilities.The separation coefficientsβLa/Ce andβCa/La reach 31.2 and 53.9,respectively.
基金financially supported by the National Natural Science Foundation of China(No.52174236)Fundamental Research Funds for the Central Universities(No.FRF-DF-23-001)the Natural Science Foundation of Inner Mongolia of China(Nos.2024MS05061 and 2023LHMS05050)。
文摘Rare earth elements have been widely applied in various sectors.Bastnaesite and monazite are crucial rare earth minerals,and flotation is a vital technique for recovering fine-grained rare earth minerals and separating them from associated gangue minerals such as fluorite and apatite.Flotation collectors play a key role in selectively adsorbing valuable minerals,enhancing their surface hydrophobicity,which has prompted considerable research interest.However,the interaction between minerals and reagents relies on the reactivity and selectivity of the reagent groups,as well as the reactive properties of the surface atoms of the minerals.This study proposes the use of H_(2)O_(2)oxidation to enhance the flotation process of rare earth minerals.The flotation experiments demonstrated that pre-adding H_(2)O_(2)before introducing the flotation collector significantly improved the grade and recovery of rare earth concentrates.The adsorption mechanisms of 2-hydroxy-3-naphthyl hydroxamic acid collector on rare earth mineral surfaces before and after H_(2)O_(2)pre-oxidation were studied.The 2-hydroxy-3-naphthyl hydroxamic acid interacts with Ce^(3+)on the surface of unoxidized rare earth minerals,forming chelate compounds with five-membered ring structures.The H_(2)O_(2)exhibited potent oxidizing properties and oxidized the Ce^(3+)on the bastnaesite and monazite surfaces to more stable Ce^(4+),which demonstrated stronger binding capability with hydroxamic acid.
基金Project(NDRC high-tech No.606,2009) supported by the Major Industries Technological Development Special Fund of Development and Reform Commission,ChinaProject(50934004) supported by the National Natural Science Foundation of China
文摘Sulfuric acid leaching process was applied to extracting rare earth（RE） from roasted ore of Dechang bastnaesite in Sichuan,China.The effect of particle size,stirring speed,sulfuric acid concentration and leaching temperature on RE extraction efficiency was investigated,and the leaching kinetics of RE was analyzed.Under selected leaching conditions,including particle size（0.074-0.100 mm）,sulfuric acid concentration 1.50 mol/L,mass ratio of liquid to solid 8 and stirring speed 500 r/min,the leaching kinetics analysis shows that the reaction rate of leaching process is controlled by diffusion through the product/ash layer which can be described by the shrinking-core model,and the calculated activation energy of 9.977 kJ/mol is characteristic for a diffusion-controlled process.
基金Project(50974042)supported by the National Natural Science Foundation of ChinaProject(20090042120015)supported by Scientific Research Special Foundation of Doctor Subject of Chinese UniversitiesProject(N090302007)supported by the Fundamental Research Funds for the Central Universities,China
文摘The leaching kinetics of bastnaesite concentrate in HCl solution was investigated with respect to the effects of HCl concentration by changing HCl concentration,leaching temperature,liquid to solid ratio,and particle size.A particle size of 25 μm was required to leach 89.6% RE2（CO3）3 and 1.5%REF3 at 90 ℃ for 90 min,when HCl concentration was 6 mol/L and liquid to solid ratio was 15：1.The leaching kinetics of bastnaesite concentrate is represented by shrinking core model with diffusion through a porous product layer.The activation energies for the dissolution reaction of RE2（CO3）3 and REF3 were calculated to be 59.39 kJ/mol and 66.13 kJ/mol respectively.
基金supported by the National Natural Science Foundation of China(51404035)Beijing Nova program(Z161100004916108)
文摘To clearly elucidate the oxidative roasting behaviors of the bastnaesite, the thermal decomposition and oxidation of the bastnaesite concentrate in inert and oxidative atmosphere have been investigated in detail. Experimental data indicated that the initial decomposition temperature of the concentrate under N2 atmosphere is 150 ℃ higher than that under O2 atmosphere,most likely because the oxidation of the cerium induces the decomposition of the concentrate. For the roasted samples under N2 atmosphere at500 ℃ and above,the oxidation efficiency of the cerium is 19.8%-26.8% because of the fact that rareearth fluorocarbonate is first decomposed to form rare-earth oxyfluoride and CO2, and the cerium oxyfluoride is then partially oxidized by the CO2 gas. The rest cerium in these samples can be further oxidized in air at room temperature, with the oxidation efficiency of the cerium gradually increasing to above 80% in 7 d. This can be attributed to the obvious changes in the inner morphology of the roasted samples under N2 atmosphere at high temperatures, which largely induce the diffusion of the air and improves the oxidation activity of CeOF, and further induces the oxidation of CeOF by the air. XRD and XPS techniques were used to further verify the significant differences in the thermal decomposition behaviors of the bastnaesite concentrate under N2 and O2 atmosphere. Moreover, no oxidation of Pr^（3＋） to Pr^（4＋） in the roasted samples under both N2 and O2 atmosphere is observed. This gives an overall understanding of the oxidative roasting of the bastnaesite concentrate without additives.
基金supported by Program for Changjiang Scholars and Innovative Research Team in University of China(IRT0974)National Natural Science Foundation of China(50574069)Industrial Research Chair Program in Oil Sands Engineering from Natural Sciences and Engineering Research Council(NSERC)
文摘To understand the flotation mechanism of bastnaesite using reactive oily bubble, the interaction between bastnaesite parti-cles and reactive oily bubbles was investigated by electro-kinetic studies, induction time measurements and small-scale flotation ex-periments. The bastnaesite flotation could be seen as a hetero-coagulation between bastnaesite particles and reactive oily bubbles which was confirmed by the zeta potential distribution and induction time measurements from pH 4.8 to pH 9.0. The small-scale flotation tests were consistent with the hetero-coagulation results, and showed a better flotation of reactive oily bubble than air bubble among all pH range. The interaction force between bastnaesite particles and reactive oily bubbles was evaluated by the classical DLVO theory. It indicated that the attachment could be predicted well by the DLVO theory only in a restricted pH range due to the absence of hydrophilic interaction repulsion force and chemical interaction force.
基金Project supported by National Basic Research Program of China(973 Program)(2012CBA01205)
文摘Extracting rare earths from bastnaesite concentrate treated by calcification transition was studied through the single factor test and XRD patterns of bastnaesite after calcification and slags after leaching in HCl solution. And the effects of the main calcified parameters such as temperature, liquid/solid and calcified time on transition performance of bastnaesite were investigated. It was found that under the optimal conditions of calcification temperature of 250 oC, liquid/solid of 20 mL/g, calcification time of 180 min, the highest leaching rate of rare earth were obtained, with the leaching ratio of rare earths 83.70% and Ce 77.01%, La 90.55%, Nd 92.03%, respectively; loss rates of fluorine with different calcification conditions were always less than 1% and XRD patterns of calcification slags and leaching slags showed that fluorine existed in the form of CaF2.
基金Project supported by the National Natural Science Foundation of China(51764045)the Open Project of State Key Laboratory of Mineral Processing(BGRIMM-KJSKL-2020-23)+2 种基金the Excellent Youth Foundation of IMUST(2017YQL05)the Inner Mongolia Natural Science Foundation(2020LH05027,2019MS05039)the Inner Mongolia Major Basic Research Open Project(0406091701)。
文摘Bastnaesite is an important rare earth mineral and is usually beneficiated by flotation.Sodium silicate is commonly used to depress calcium-bearing gangue minerals,however it can also depress bastnaesite when Ca^(2+) ions exist in the pulp.In this study,the effect of Ca^(2+) ions and sodium silicate individually or in combination on bastnaesite flotation was studied through micro-flotation,zeta potential,fluorescence spectroscopy and X-ray photoelectron spectroscopy(XPS) measurements.Micro-flotation results show that the combination of Ca^(2+) ions and sodium silicate depresses bastnaesite more severely due to their synergistic effect.Zeta potential results show that the combination renders the surface potential of bastnaesite negatively shifted more significantly.Fluorescence spectroscopy shows that the combination decreases the surface hydrophobicity of bastnaesite more severely.XPS shows that the combination increases the adsorption of sodium silicate on bastnaesite by forming hydrophilic Ca-SiO_(3) precipitate,which causes more serious depression on bastnaesite flotation.
基金supported by the National Natural Science Foundation of China(51574240,U1704252)Natural Science Foundation of Jiangsu Province(BK20150192).
文摘The structural and electronic properties of bastnaesite were studied by using the first-principles method based on the density functional theory(DFT).The geometry structure of bastnaesite was first optimized,and then the Mulliken populations,electron density and density of states were calculated and further analyzed in detail.The calculation results reveal that it mainly ruptures along the ionic Ce-O and Ce-F bonds during the cleavage of bastnaesite,leaving≡Ce^+,≡F^-and≡CO3^-dangling bonds exposed on the cleavage surface of bastnaesite.Combined with contact angle measurement,surface complexation theory and XPS analysis,the implications of structural and electronic properties on bastnaesite flotation reactions were studied.The hydration of exposed strong ionic bond on cleavage surface results in hydrophilic surface.According to surface complexation theory,the formed surface groups are≡CeOH^0,≡CO3 H^0 and≡FH^0 groups.The investigated metal ions and flotation reagents complex with surface≡CeOH^0 groups,while≡CO3H^0 and≡FH^0 groups are not involved in the complexation.The high activity of Ce atoms facilitates these surface reactions.
基金Project supported by the Fundamental Research Funds for the Central Universities(N172506009,N170908001,N182515007,N180725023)National Natural Science Foundation of China(U1508217).
文摘Mechanochemical reaction involves simultaneous chemical reaction and particle crushing;the latter increases the effective reaction area and improves the reactivity,thus enhancing its kinetics.The classical shrinking core model was used to model the kinetics of bastnaesite mechanochemical decomposition in NaOH solution,which shows a questionable result.Mechanochemical reaction is a dynamic process,where the particle shape and concentration in reaction interface undergo constant change.Thus,a physically consistent model was applied to describe the kinetics.The variations in OH^-concentration and particle shape were considered in the revision of model.Considering the variation in OH^-concentration in solution with time,the model with varying OH^-concentration agrees better with the experimental data,improving the regression coefficients to between 0.936 and 0.992.By introducing fractal geometry to deal with the irregular system,the model was further optimized,and the regression coefficients increase to between 0.940 and 0.997.All these models considere shrinking particle approaches and controlling mechanisms for the diffusion and chemical reaction.Finally,the fractal model with varying OH^-concentration was selected to describe the mechanochemical decomposition of bastnaesite,which indicates that the process is controlled by chemical reaction.
文摘Flotation separation and recovery of rare earth minerals(REM) have returned to an important position due to the growing strategy demand for rare earth elements(REE).In this paper,a comparative investigation into the floatability of bastnaesite((Ce,La)FCO3) was conducted by using three di/trialkyl phosphate collectors,di(2-ethylhexyl) phosphate(DEHPA),dibutyl phosphate(DBP) and tributyl phosphate(TBP).The density functional theory(DFT) computation recommends that the chemical activity of the three phosphate collectors is in order of DEHPA≥ DBP >> TBP,and their hydrophobization assuggested by the IgP(oil-water partition coefficient) value is in the order of DEHPA> TBP> DBP.The micro-flotation indicates that the preferable pH values for flotation of bastnaesite with the three phosphate collectors are 7.0-8.0,and DEHPA achieves much higher flotation recovery of bastnaesite,followed by DBP,and then TBP,which coincides with their reactivity and hydrophobicity,the two prerequisites for froth flotation.The contact angle,zeta potential,Fourier transform infrared spectroscopy(FTIR) and X-ray photoelectron spectroscopy(XPS) deduce that DEHPA likely reacts with the Ce(Ⅲ)atoms of bastnaesite interface through its O atom(s) of the P(=O)-O-group to generate the Ce-O-P bonds,and its two 2-ethylhexyl groups orient outside for attaching bubbles,resulting in flotation enrichment of bastnaesite.Furthermore,this investigation offers a novel strategy for developing collectors in selective beneficiation of REM.
基金Project supported by the National Basic Research Program(973 Program,2012CBA01205)。
文摘Isoconversional methods combined with thermogravimetry were applied to investigate the decomposition kinetics of bastnaesite concentrates with different amounts of calcium hydroxide added.The apparent activation energy was calculated,and the results indicate that the overall reaction involves more than one single step.The reaction with a lower content(<15 wt%)of calcium hydroxide can be divided into two steps,while the reaction with a higher content(>15 wt%)involves another step which denotes the decomposition of newly formed calcium carbonate during roasting.The activation energy increases with increasing amount of calcium hydroxide in the lower range(0-15 wt%).This is due to the resistance of calcium hydroxide to heat and mass transport,However,more calcium can promote the decomposition reaction more effectively and thus reduce the activation energy.Nonlinear fitting was performed by fitting the experimental data to Avrami-Erofeev model to determine the reaction model and pre-exponential factor.The theoretical models were proven to be reliable for kinetic prediction.
基金the National Key R&D Program of China(No.2021YFC2900800)National Natural Science Foundation of China(Nos.51922091,51874247 and 52204285)+1 种基金Sichuan Science and Technology Program(Nos.2023NSFSC1978 and 2022YFS0455)Open Foundation of State Key Laboratory of Mineral Processing(No.BGRIMM-KJSKL-2023-05).
文摘Rare earth element is an important strategic metal,but the supply of high purity rare earth ores is growing slowly,which is in sharp contradiction with the rapidly growing demand.Froth flotation has been confirmed to be an effective method to separate bastnaesite from its gangue minerls.However,the traditional collectors are facing serious problems in flotation separation of minerals,requiring the addition of excess depressant and regulator in the flotation process.Herein,we proposed and synthesized novel Gemini hydroxamic acids Octyl-bishydroxamic acid(OTBHA),Decyl-bishydroxamic acid(DCBHA)and Dodecyl-bishydroxamic acid(DDBHA)as the collectors in bastnaesite-barite flotation system.The effect of different carbon chain lengths on the molecular properties were explored by density functional theory(DFT)calculations.DCBHA possessed a stronger reactivity compared with OCBHA and DDBHA.The flotation results verified the consistency of the computational calculation about the performance prediction of Gemini hydroxamic acids.Compared with OCBHA and DDBHA,DCBHA displayed superior collecting affinity toward bastnaesite,and did not float barite.Zeta potential results showed that the presence of DCBHA increased the potential of bastnaesite,while it had almost no effect on barite,indicating DCBHA had a stronger affinity for bastnaesite.Then,Fourier transform infrared(FTIR)and X-ray photoelectron spectroscopy(XPS)analyses indicated that the adsorption mechanism was due to two hydroxamate groups of DCBHA co-anchored on bastnaesite surface by forming five-membered hydroxamic―(O―O)―Ce complexes.In addition,atomic force microscopy(AFM)clearly observed that DCBHA uniformly aggregated on bastnaesite surface,which increased surface contact angle and improved the hydrophobicity of bastnaesite.
基金Project supported by the Fundamental Research Funds for the Central Universities(973 program,No.N172506009,N170908001)
文摘A novel process of calcification-leaching for bastnaesite concentrate(REFCO3) was proposed. The prior calcification was carried out in the system of NaOH-CaO-H2O and the lgC-pH pattern for Ce-F-Ca-C-H2O system was drawn. The thermodynamics result indicates that decomposition for bastnaesite requires certain alkaline condition, but excessive alkalinity also causes decomposition of CaF2. XRD and SEM-EDS analyses on the calcification-leaching process reveal that bastnaesite first decomposes into RE(OH)3 and CaF2. Then, by HCl leaching rare earths were extracted,while CaF2 was left in the leaching residue. In addition, effects of temperature, time, NaOH and CaO on the calcification were investigated. The results show that the leaching rate of rare earths(REs)reaches 72.5 wt%, at the same time 99.2 wt% of F is left in leaching residue with 20 wt% NaOH and 38 wt% CaO at 493 K for 180 min.
