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 bastnaesite crystal about 12×20 mm 2 in size collected from a pegmatitic aegirine augite barite bastnaesite vein of the Maoniuping rare earth deposit, Mianning County, Sichuan Province, has been analyzed for...A bastnaesite crystal about 12×20 mm 2 in size collected from a pegmatitic aegirine augite barite bastnaesite vein of the Maoniuping rare earth deposit, Mianning County, Sichuan Province, has been analyzed for La, Ce, Pr and Nd by synchronous radiative X ray fluorescence(SRXRF) technics at the National BEPC Laboratory. The results show an apparent compositional variation along vertical and horizontal sections accross the crystal which may be divided into three compositional zones(A, B and C). Significant difference exists between the inner portion(zone A), averaging at 28 35% La 2O 3, 35 04% CeO 2, 2 01% Pr 6O 11 and 5 44% Nd 2O 3, and the outer portion(zone B), averaging at 32 81% La 2O 3, 42 26% CeO 2 3 30% Pr 6O 11 and 7 08%. Nd 2O 3, of the crystal. Only one analysis is available on the egde of the crystal(zone C) yielding 14 50% La 2O 3, 21 41% CeO 2, 4 19% Pr 6O 11 and 16 71% Nd 2O 3, which demonstrates probably fractionations between LREE and HREE. The La/Ce ratio, however, is nearly constant around 0 84±0 08 among the three zones, while the La/Pr and La/Nd ratios erratically fluctuate due to low and variable contents of Pr and Nd. These results indicate that the REE bearing hydrothermal system underwent a significant compositional change during the stepwise growth of the bastnaesite crystal.展开更多
The flotation behaviour and mechanism of bastnaesite with N-hydroxyl phthalicimide were investigated by ξ-potential measurement,infrared spectrum and quantum chemistry calculation.The results show that 3 oxygen atoms...The flotation behaviour and mechanism of bastnaesite with N-hydroxyl phthalicimide were investigated by ξ-potential measurement,infrared spectrum and quantum chemistry calculation.The results show that 3 oxygen atoms from N-hydroxyl phthalicirnide chelate the rare earth ions on the surface of bastnaesite to form double five-chain O=C-N-O- RE(Ⅲ)-O chelate which is chemically adsorbed on the surface of bastnasite,thus making N-hydroxyl phthalicimide an effective collector for bastnaesite.展开更多
Vapor phase extraction and mutual separation of rare earth (RE) elements from bastnaesite concentrate were investigated using stepwise chlorination chemical vapor transport reactions mediated by vapor complexes LnAl ...Vapor phase extraction and mutual separation of rare earth (RE) elements from bastnaesite concentrate were investigated using stepwise chlorination chemical vapor transport reactions mediated by vapor complexes LnAl n Cl 3 n +3 (Ln=RE elements). The bastnaesite was heated to 800 K and chlorinated between 800～1300 K with C+Cl 2+SiCl 4 to remove CO 2, SiF 4 and high volatile chlorides. At the temperature of 1300 K for 6 h, the resulted RE chlorides were chemically transported and mutual separated with the vapor complexes while CaCl 2 and BaCl 2 were remained in the residues. Significantly different CVT characteristics were observed for gradually decreased and wave form temperature gradients.展开更多
The content of REE(La.Ce.Pr.Nd.Sm) in bastnaesite was measured by synchrotron radiation X-ray fluorescence microprobe.Scanning analysis makes use of excitation of the REE K lines between 33 and 50 keV.SR white beam fr...The content of REE(La.Ce.Pr.Nd.Sm) in bastnaesite was measured by synchrotron radiation X-ray fluorescence microprobe.Scanning analysis makes use of excitation of the REE K lines between 33 and 50 keV.SR white beam from a Wiggler source at the Beijing Electron Positron Collider(BEPC) of the National Laboratory,in order to excite the REE.The bastnaesite from the same mineral area was powdered to particle size≤300 mesh.It was then divided into two parts.One portion was used to be determined by XRF after depositing with oxalate and transforming into oxide.The other was pressed into disk without any binder as the reference sample.The weight and the diamieter of the disk were 15 g and 26 mm respectively.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
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.
文摘A bastnaesite crystal about 12×20 mm 2 in size collected from a pegmatitic aegirine augite barite bastnaesite vein of the Maoniuping rare earth deposit, Mianning County, Sichuan Province, has been analyzed for La, Ce, Pr and Nd by synchronous radiative X ray fluorescence(SRXRF) technics at the National BEPC Laboratory. The results show an apparent compositional variation along vertical and horizontal sections accross the crystal which may be divided into three compositional zones(A, B and C). Significant difference exists between the inner portion(zone A), averaging at 28 35% La 2O 3, 35 04% CeO 2, 2 01% Pr 6O 11 and 5 44% Nd 2O 3, and the outer portion(zone B), averaging at 32 81% La 2O 3, 42 26% CeO 2 3 30% Pr 6O 11 and 7 08%. Nd 2O 3, of the crystal. Only one analysis is available on the egde of the crystal(zone C) yielding 14 50% La 2O 3, 21 41% CeO 2, 4 19% Pr 6O 11 and 16 71% Nd 2O 3, which demonstrates probably fractionations between LREE and HREE. The La/Ce ratio, however, is nearly constant around 0 84±0 08 among the three zones, while the La/Pr and La/Nd ratios erratically fluctuate due to low and variable contents of Pr and Nd. These results indicate that the REE bearing hydrothermal system underwent a significant compositional change during the stepwise growth of the bastnaesite crystal.
文摘The flotation behaviour and mechanism of bastnaesite with N-hydroxyl phthalicimide were investigated by ξ-potential measurement,infrared spectrum and quantum chemistry calculation.The results show that 3 oxygen atoms from N-hydroxyl phthalicirnide chelate the rare earth ions on the surface of bastnaesite to form double five-chain O=C-N-O- RE(Ⅲ)-O chelate which is chemically adsorbed on the surface of bastnasite,thus making N-hydroxyl phthalicimide an effective collector for bastnaesite.
文摘Vapor phase extraction and mutual separation of rare earth (RE) elements from bastnaesite concentrate were investigated using stepwise chlorination chemical vapor transport reactions mediated by vapor complexes LnAl n Cl 3 n +3 (Ln=RE elements). The bastnaesite was heated to 800 K and chlorinated between 800～1300 K with C+Cl 2+SiCl 4 to remove CO 2, SiF 4 and high volatile chlorides. At the temperature of 1300 K for 6 h, the resulted RE chlorides were chemically transported and mutual separated with the vapor complexes while CaCl 2 and BaCl 2 were remained in the residues. Significantly different CVT characteristics were observed for gradually decreased and wave form temperature gradients.
文摘The content of REE(La.Ce.Pr.Nd.Sm) in bastnaesite was measured by synchrotron radiation X-ray fluorescence microprobe.Scanning analysis makes use of excitation of the REE K lines between 33 and 50 keV.SR white beam from a Wiggler source at the Beijing Electron Positron Collider(BEPC) of the National Laboratory,in order to excite the REE.The bastnaesite from the same mineral area was powdered to particle size≤300 mesh.It was then divided into two parts.One portion was used to be determined by XRF after depositing with oxalate and transforming into oxide.The other was pressed into disk without any binder as the reference sample.The weight and the diamieter of the disk were 15 g and 26 mm respectively.
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.
