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

In order to inhibit the swelling of the clay minerals in the in-situ leaching process of weathered crust elution-deposited rare earth ores (WCE-DREO), diallyl dimethyl ammonium chloride (DMDACC) was introduced as an anti-swelling agent and combined with (NH₄)₂SO₄ as a novel composite leaching agent. It can be found that the novel composite leaching agent exhibits a good anti-swelling performance and leaching capacity of rare earth, and has great potential on the actual exploitation of WCE-DREO. The anti-swelling mechanism of DMDACC was studied by characterization analysis. The results show that DMDACC with positive charges can be adsorbed on the clay particles by the electrostatic attraction and hydrogen bonds, and neutralize the negative charge of the clay particles. The double electrical layers are suppressed and the repulsion force between clay sheets decreases. It causes the clay particles prone to aggregate. Moreover, DMDACC can enter the interlayer and expel out the water molecules in interlayer. The interlayer spacing is decreased and the hydration swelling of the clay particles is weakened. It can provide a theoretical basis for the development of novel anti-swelling agents.     

Leaching kinetics of ionic rare-earth in ammonia-nitrogen wastewater system added with impurity inhibitors

Ammonia-nitrogen wastewater is produced during the dressing and smelting process of rare-earth ores.Such wastewater includes a very high concentration of NH4＋, as well as other ions（e.g., NH4＋, RE3＋, Al3＋, Fe3＋, Ca2＋, Cl–, and Si O32–） with a p H of 5.4–5.6.Its direct discharge will pollute, yet it can be recycled and used as a leaching reagent for ionic rare-earth ores.In this study, leaching kinetics studies of both rare earth ions and impurity ion Al3＋ were conducted in the ammonia-nitrogen wastewater system with the aid of impurity inhibitors.Results showed that the leaching process of rare-earth followed the internal diffusion kinetic model.When the temperature was 298 K and the concentration of NH4＋ was 0.3 mol/L, the leaching reaction rate constant of ionic rare-earth was 1.72 and the apparent activation energy was 9.619 k J/mol.The leaching rate was higher than that of conventional leaching system with ammonium sulfate, which indicated that ammonia-nitrogen wastewater system and the addition of impurity inhibitors could promote ionic rare-earth leaching.The leaching kinetic process of impurity Al3＋ did not follow either internal diffusion kinetic model or chemical reaction control, but the hybrid control model which was affected by a number of process factors.Thus, during the industrial production the leaching of impurity ions could be reduced by increasing the concentration of impurity inhibitors, reducing the leaching temperature to a proper range, accelerating the seepage velocity of leaching solution, or increasing the leaching rate of rare earths.     

Coordination-reduction leaching process of ion-adsorption type rare earth ore with ascorbic acid

The magnesium sulfate(MgSO₄)-ascorbic acid(Vc) compound leaching technique can extract rare earth elements(REEs) existing in ion-exchangeable phase and colloidal phase from ion-adso rption type rare earth ore through the synergy effect of coordination and reduction,but its reaction process and mechanism remain unclear.In this paper,the coordination-reduction leaching mechanism was analyzed from the perspectives of leaching thermodynamics and kinetics,which provide theoretical guidance...     

离子吸附型稀土矿除铝技术研究进展

赣南离子吸附型稀土矿富含中、重稀土元素,具有极高的经济价值及重要的战略意义.在对大量文献资料进行查阅及分析的基础上,介绍铝在离子吸附型稀土矿中的赋存形态、浸出行为以及对稀土工业生产的影响,系统地阐述离子吸附型稀土矿浸取过程中除铝技术的研究和实践进展,并对现有技术进行分析总结,提出未来离子吸附型稀土矿除铝技术应向环境友好型发展,并实现除铝产物资源化、商品化.      

Progress in green and efficient enrichment of rare earth from leaching liquor of ion adsorption type rare earth ores

Ion adsorption type rare earth ores (IATREOs) are a valuable strategic mineral resource in China, which feature a complete composition of fifteen rare earth elements and are rich in medium and heavy rare earth (RE) elements. In the leaching process for recovering rare earth elements from IATREOs, many impurities will be leached together with rare earth elements and enter the leaching liquor. An impurity removal-precipitation enrichment technique is currently applied to selectively recovery rare earth elements from the leaching liquor with the high content of impurities and low concentration of rare earth elements by using ammonium bicarbonate in the industry. However, a high loss of rare earth elements and severe ammonia nitrogen pollution are caused by this process. Therefore, more beneficial impurities removal technologies, mainly for aluminum, and green enrichment technologies with lower pollution are now urgently needed. For this purpose, this paper analyzed two aspects of research progress in recent decades: the green separation of rare earth elements and aluminum from leaching liquor and the green and efficient enrichment of rare earth elements. Finally, an approach for the high-efficiency and green enrichment of rare earth elements from leaching liquor of the IATREOs is proposed in several aspects, including impurity inhibition leaching, neutralization and impurity removal, alkaline calcium and magnesium salt precipitation enrichment, and centrifugal extraction enrichment.     

Local vibration around rare earth ions in alkaline earth fluorosilicate transparent glass and glass ceramics using Eu probe

By heat treating the alkaline earth fluorosilicate glass, transparent glass ceramics containing alkaline earth fluoride nanocrystallites were prepared. The luminescence spectra and phonon sideband associated with the Eu^3＋：^5D2→^7F0 in glass and glass ceramics were investigated to analyze the local environment around Eu^3＋. Judd-Ofelt parameters were also calculated from emission spectra, which indicated that the Eu^3＋ ions entered the precipitated CaF2, SrF2, and BaF2 nanocrystallites. Heat treating could not pledge Eu^3＋ ions to coordinate with F^- in the precipitated MgF2 nanocrystallites, owing to the smaller radius of Mg^2＋ than that of Eu^3＋.     

风化壳淋积型稀土矿的基础研究

文章评述了40年来风化壳淋积型稀土矿的基础研究,包括矿床的成因及特征、稀土矿物的组成及性质,稀土与黏土矿物的关系、稀土在黏土矿物中的吸附及迁移理论,论述了风化壳淋积型稀土矿的稀土元素配分的特征及四大效应,并探讨了稀土浸出机理和风化壳淋积型稀土矿稀土浸取的三代工艺,提出了风化壳淋积型稀土矿基础研究和浸出工艺的发展方向及亟待解决的问题.      

Effect of impurity ions on preparation of novel saponifier for rare earth extraction

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 concentration 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.     

Effect of rare earth ions doping on properties of LiFePO4/C cathode material

LiFe0.99RE0.01PO4/C cathode material was synthesized by solid-state reaction method using FeC2O4·2H2O, Li2CO3, NH4H2PO4, RE(NO3)3·nH2O as raw materials and glucose as a carbon source. The doping effects of rare earth ions, such as La3+, Ce3+, Nd3+, on the structure and electrochemical properties of LiFePO4/C cathode material were systematically investigated. The as-prepared samples were characterized by means of X-ray diffraction(XRD), scanning electron microscopy(SEM) and particle size analysis. The electrochemical properties were investigated in terms of constant-current charge/discharge cycling tests. The XRD results showed that the rare earth ions doping did not change the olivine structure of LiFePO4, and all the doped samples were of single-phase with high crystallinity. SEM and particle size analysis results showed that the doping of La3+, Ce3+ and Nd3+led to the decrease of particle size. The electrochemical results exhibited that the doping of La3+ and Ce3+ could improve the high-rate capability of LiFePO4/C cathode material, among which, the material doped with 1% Ce3+ exhibited the optimal electrochemical properties, whose specific discharge capacities could reach 128.9, 119.5 and 104.4 mAh/g at 1C, 2C and 5C rates, respectively.     

High-efficiency simultaneous extraction of rare earth elements and iron from NdFeB waste by oxalic acid leaching

Iron can not be recovered at high value because only rare earth elements are effectively recovered from NdFeB waste via oxidation roasting-hydrochloric acid leaching process.In this study,a new method for leaching NdFeB waste with oxalic acid was developed.The high-efficiency,simultaneous and high-value recovery of rare earth elements and iron was realized to simplify the process and improve the economic benefit.Results of the oxalic acid leaching experiments show that under the optimum leaching conditions at 90℃ for 6 h in the aqueous solution of oxalic acid(2 mol/L) with a liquid-solid ratio of60 mL/g,the iron leaching efficiency and precipitation rate of rare earth oxalate reach 93.89% and 93.17%,respectively.Rare earth oxalate and Fe(C₂O₄)3^3- were left in the residue and the leaching solution,respectively.The leaching mechanism was further analyzed by characterising the leach residues obtained through X-ray powder diffraction(XRD) and scanning electron microscopy-energy dispersive X-ray spectroscopy(SEM-EDS).Results of the leaching kinetics study indicate that the process of oxalic acid leaching follows the shrinking nucleus model,and the leaching kinetics model is controlled by the mixed factors of diffusion and chemical reaction.The leaching residue was calcined at 850℃ for 3 h and then decomposed into rare earth oxide,which can be directly used to prepare rare earth alloy via molten salt electrolysis.For the leaching solution,ferric oxalate solution was reduced using Fe powder to prepare the ferrous oxalate(FeC₂O₄-2H₂O).     

A novel polystyrene-poly(hydroxamic acid) interpenetrating polymer network and its adsorption towards rare earth ions

A novel polystyrene-poly(hydroxamic acid)interpenetrating network resin(PS-PHA IPNs)was successfully synthesized by suspension polymerization and interpenetrating network technology.The effects of various experimental parameters,including pH,contact time and initial concentrations of rare earth ions on the adsorption capacity were discussed in detail.Under the condition of pH 4.0(La³⁺),1.0(Ce³⁺)and 3.0(Y³⁺),respectively,PS-PHA IPNs can reach equilibrium adsorption in 6 h and get maximum adsorption capacities(1.08,1.43 and 1.36 mmol/g).The adsorption process of PS-PHA IPNs for La(Ⅲ),Ce(Ⅲ)and Y(Ⅲ)ions can be described by liquid membrane diffusion,particle diffusion and chemical reaction.The adsorption process is a spontaneous and endothermic process and can be better simulated by Langmuir adsorption isotherm.The studies of SEM-EDS indicate that rare earth ions are adsorbed on the surface of PS-PHA IPNs.Fourier transform infrared spectroscopy(FTIR)and X-ray photoelectron spectroscopy(XPS)analysis further prove that rare earth ions are chemisorbed on the surface of PS-PHA IPNs.These results reveal that the as-prepared PS-PHA IPNs is a promising adsorbent for adsorption of rare earth ions due to their higher adsorption capacity than other adsorbents.     

Nano-preparation promoting effectively luminescent properties of one-dimensional rare earth oxides

Rare earth (La,Nd and Tb) oxides with one-dimensional micro/nanostructures were synthesized hydrothermally under facile and mild conditions with two surfactants, and characterized by X-ray diffraction (XRD), thermal gravimetry (TG), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and photoluminescence. The results showed that the synthesized rare earth oxides behaved regular nano-and micro-scale structures. And the morphologies of samples depended on the radii of rare earth ions, with the help of two surfactants of sodium dodecyl sulfonic and PEG 600. Nanocrystalline La2O3:Eu3+ possessed good photoluminescence (PL) property and might be used as a nanosized phosphor, its PL intensity was altered by the doping Eu3+ concentration and the optimum concentration of Eu3+ was 3 mol.%. In comparison with bulk Eu3+/La2O3, Eu3+/nano-La2O3 showed better photoluminescence property, nearly equal to that of nanocrtstal-line La2O3:Eu3+. Tb4O7 microwires showed interesting photoluminescence properties.     

Effect of roasting activation of rare earth molten salt slag on extraction of rare earth,lithium and fluorine

A new process was proposed to extract rare earth elements(REEs),Li and F from electrolytic slag of rare earth molten salt by synergistic roasting and acid leaching.Firstly,the thermodynamic analysis of roasting reaction was carried out,then the effects of roasting factors on leaching REEs,Li and F in slag were investigated.In additions,the mineral phase and morphology of molten salt slag,roasting slag and acid leaching slag were characterized,and the migration mechanism of REES,Li and F minerals...     

Molecular dynamics simulation of aluminum inhibited leaching during ion-adsorbed type rare earth ore leaching process

Molecular dynamics simulation was adopted to study the interaction between sulfosalicylic acid and aluminum,lanthanum and yttrium,and adsorption on kaolinite surfaces.A complexation reaction occurs between sulfosalicylic acid and aluminum,with an interaction energy of-10472.05 kJ/mol.O—Al covalent bonds are formed with a peak value of 7.93,while there is only weak adsorption between sulfosalicylic acid and rare earth ions.A hydrogen bonding reaction with 13605.82 kJ/mol energy occurs between sulfosalicylic acid and the surface of kaolinite(100).Thus,sulfosalicylic acid can form a complex with free aluminum ions,and can also be adsorbed on kaolinite by hydrogen bonding with aluminum in kaolinite(100) surfaces.Leaching of ion-adsorbed type rare earth ore was performed with aluminum inhibited,results show that when sulfosalicylic acid dosage increases from 0 to 0.15 wt%,aluminum ion concentration in the leaching solution decreases from 273.23 to 47.19 mg/L.And the effect of leaching pH value on the effect of sulfosalicylic acid on aluminum inhibition was studied,the result shows that,when the leaching pH value is 4.0—5.0,the rare earth leaching rate and the aluminum ion concentration basically remain unchanged.The molecular dynamics simulation results were verified by detection and analysis of XPS and SEM.     

Adsorption behavior of rare earth elements using polyethyleneglycol (phosphomolybdate and tungstate) heteropolyacid sorbents in nitric solution

A new type of crystalline sorbent was prepared by the reaction of polyethyleneglycol (PEG) with phosphomolybdic (PMo) and phosphotungstic (PW) heteropolyacids. The morphology of the obtained sorbents was studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM). It has been shown that a complexing reaction occurs between PEG and the heteropolyacids. By using these sorbents, the adsorption behaviors of rare earth elements in nitric solution were studied. The effects of temperature, contact time, nitric acid and initial metal ion concentration on the adsorption were investigated. In 0.1–5.0 mol L^− 1HNO₃, the adsorption percentage decreases with the increase of acid concentration. H,PEG400,PW and H,PEG400,PMo exhibited a different selectivity for rare earth metals, with H,PEG400,PW adsorbing in the order of La³⁺ > Y³⁺ > Pr³⁺ > Gd³⁺ > Sm³⁺, and H,PEG400,PMo in the order of Y³⁺ > La³⁺ > Pr³⁺ > Gd³⁺ > Sm³⁺. The experimental maximum adsorption capacities of the sorbents are in the range of 90–225 mg g^− 1 for Y³⁺, La³⁺, Pr³⁺, Sm³⁺ and Gd³⁺. In all cases, the maximum adsorption capacities of H,PEG400,PW are near to those of H,PEG400,PMo. The equilibrium data were evaluated according to the Freundlich and Langmuir isotherms and the Langmuir equation gave a better fit and modeled the adsorption well.     

Effects of organic acids on the leaching process of ion-adsorption type rare earth ore

To examine the activation of organic acids on the leaching process of ion-adsorption type rare earth ore(IRE-ore), the leaching behavior of rare earth(RE) and zeta potential of IRE-ore were investigated in the absence and presence of carboxylic acids. The results show that all the tested organic acids(acetic acid,malonic acid, citric acid, tartaric acid, succinic acid, and malic acid) can promote RE extraction. At relatively high concentrations of organic acids, the activation efficiency of organic acids on RE extraction is generally consistent with their complexation ability; whereas at their low concentrations, the change of zeta potential on the IRE-ore surface with organic acid concentration and p H has a close association with RE extraction, which indicates that organic acids can impact the surface electrical property of IREore via their adsorption/desorption, and thereby increase/decrease the affinity of RE ions to IRE-ore.Therefore the influence of organic acids on the IRE-ore surface electrical property also plays an important role in RE extraction in addition to their complexation with RE ions.     

纳滤膜对稀土离子的动态吸附行为及截留特性

采用经碳纳米管改性的亲水化纳滤膜浓缩提取稀土浸出液中的稀土离子,探究纳滤膜表面对La3+、Nd3+、Pr3+、Ce3+和Y3+5种稀土离子吸附动力学行为,考察稀土离子半径的大小对纳滤膜吸附性能和截留性能的影响.结果表明,Freundlich吸附方程比Langmuir方程能更好地描述稀土离子在纳滤膜表面上的动态吸附行为,用Freundlich吸附方程拟合后的结果相关度系数R2能达到0.999以上;在初始浓度为5×105 μg/L,温度为25 ℃,运行压力为0.6 MPa的实验条件下,纳滤膜对稀土离子的浓缩提取过程中,初始阶段的截留机理取决于纳滤膜表面的吸附作用和膜孔的机械筛分效应,膜面吸附达到平衡后以膜孔的机械筛分效应为主,此时La3+、Nd3+、Pr3+、Ce3+和Y3+的截留率分别为94.21 %、81.25 %、85.80 %、89.90 %和81.18 %,表明经碳纳米管改性的亲水化纳滤膜能高效浓缩截留稀土浸出液中的稀土离子.      

Non-ammonia enrichment of rare earth by magnesium oxide from rare earth leaching liquor in magnesium salt system

In order to solve the problem of ammonia-nitrogen pollution in the enrichment process of the ionadsorption type rare earth ore,the technology of non-ammonia precipitation with magnesium oxide precipitant was carried out.It is determined that the rare earth precipitation efficiency is 99.6% and the purity of rare earth concentrates is only 85.89 wt%under the optimum precipitation conditions.And the contents of MgO,SO_3 and Al_2O_3 in the rare earth concentrates are 5.12 wt%,6.77 wt%and 1.78 wt%,respectively.Furthermore,the thermo-decomposition process of precipitates was investigated by TGDSC,XRD and FI-IR.The thermal decomposition process consists of two stages:the dehydration of rare earth hydroxide and alkaline rare earth sulfate within 900 ℃ and the thermal decomposition of RE_2O_2SO_4 at 900-1300 ℃.Therefore,a high-temperature calcinations method for removing SO_3 from precipitates is proposed.When the precipitates are calcined at 1300 ℃ for 2 h,the rare earth concentrates with a purity of 92.03 wt%can be acquired.Moreover,the content of SO_3 in the concentrate is only 0.46 wt%.In the MgO precipitation and high-temperature calcinations process,the raw material cost is low and the quality of rare earth concentrates is acceptable.It could have great significance for nonammonia enrichment of rare earth from the rare earth leaching liquor,and finally solve the problem of ammonia nitrogen in the extraction process of the ion-adsorption type rare earth ore within magnesium salt system.     

Behavior of phase transformation of Baotou mixed rare earth concentrate during oxidation roasting

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 °C. The results indicate that the bastnaesite in BMREC is decomposed at 450–550 °C, 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 (La₂O₃, Ce₇O₁₂, Pr₆O₁₁ and Nd₂O₃), and CO₂, particularly, with the increase of roasting temperature, bastnaesite in BMREC is more completely decomposed into LaF₃, which causes a decrease in leaching rate of La during the HCl leaching process. Additionally, the maximum cerium oxidation efficiency reaches about 60 wt% when the roasting temperature is equal to or above 500 °C, and the oxidation reaction rate of cerium increases with the increasing roasting temperature.     

稀土电解熔盐渣焙烧产物酸浸提取稀土、锂和氟

稀土电解熔盐渣经过氧化钙和硫酸铝协同焙烧活化得到焙烧渣,采用硫酸浸出高效提取焙烧渣中稀土、锂、氟,系统考察了不同酸浸条件对稀土、锂、氟浸出率的影响。针对较优酸浸条件下的浸出液,用硫酸钠沉淀析出稀土复盐沉淀,实现稀土分离。结果表明:较优酸浸条件为硫酸浓度4 mol/L、液固体积质量比10:1（单位:mL/g）、浸出温度90 ℃、浸出时间4 h,熔盐渣中镨、钕、钆、锂、氟的浸出率分别为95.83%、96.55%、93.06%、95.52%、94.85%。稀土复盐沉淀纯度高,稀土回收率达99.3%以上。该方法可以高效回收稀土熔盐电解渣中稀土、锂、氟有价元素,对提升稀土熔盐电解渣的全组分利用具有重要意义。