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...     

Behavior of sulfate in preparation of single light rare earth carbonate by Mg(HCO_3)_2 precipitation method

The precipitation of the water-leaching solution of Baotou mixed rare earth(RE) concentrate roasted with sulfuric acid using ammonium bicarbonate for producing RE carbonate produces a mass of ammonia-nitrogen wastewater because of the relatively low solubility of rare earth sulfate.To solve the serious problem of ammonia-nitrogen pollution,new precipitators need to be developed urgently so as to meet the requirements of environmental protection and impurities content of the product(SO_4~(2-)1.8 wt% in RE carbonates products).In this paper,we studied the effects of feeding modes on the behavior of SO_4~(2-) during the preparation of light RE carbonate(RE=La,Ce,Pr,Nd) from their sulfate solutions using Mg(HCO_3)_2 as a precipitant.The results indicate that the contents of SO_4~(2+) in the La and Ce precipitates using positive feeding mode exceed 16 wt% because of the formation of La2(CO_3)_(2.15)(-SO_4)_(0.85)·4 H_2 O and Ce2(CO_3)_(2.15)(SO_4)_(0.85)·3 H_2 O,while those of the Pr and Nd precipitates are 4 wt%-5 wt%since they exist in the form of n-carbonate.The precipitates prepared using synchronous feeding mode are all RE carbonate with only 4 wt%-5 wt% of SO_4~(2-) enclosed in the precipitation.The content of SO_4~(2-) in the RE carbonate obtained using reverse feeding mode is the lowest.Among them,the content of SO_4~(2-) in La precipitate is only 1.40 wt%.Both synchronous and reverse feeding modes can effectively reduce the content of SO_4~(2-)in RE carbonate,which provides theoretical guidance for the preparation of qualified light RE carbonate products by Mg(HCO_3)_2 precipitation method.     

Thermal physical properties and dephosphorisation kinetics of rare earth oxides containing slags

ABSTRACT

The melting properties and viscosity of CaO–SiO₂–MnO–La₂O₃–CeO₂ slags, with mass ratios of 0.97 and 1.05 between CaO and SiO₂, were measured using the hot stage microscopy method and rotating cylinder method, respectively. In addition, the dephosphorisation kinetics of rare earth (RE) oxides containing slags was studied. For increasing mass contents of the RE oxides, La₂O₃ and CeO₂ (0, 3, 6, 9, and 12?wt.%), in the slag, the melting temperature initially decreases and then increases. Minimum values appeared for mass contents of 6?wt.%. RE oxide concentrations below 9?wt.% are beneficial to the decrease in viscosity, which increases significantly with the mass fraction of RE oxides in molten slags with a basicity of 1.05. In slags with a basicity of 0.97, the RE oxides favour the decrease in viscosity, which does not change noticeably as their mass fraction is increased above 6?wt.%. Finally, it was found that the rate-limiting step of the dephosphorisation process is the diffusion of phosphorus.     

The Thermodynamics of Some Transition Metals in Molten Slags

In the present paper, the thermodynamic behaviour of transition metals, such as Cr, Ti, Nb and V in molten slags is systematically analysed based on a literature survey. These metals exist in molten slags with multi valences. Oxygen partial pressure, slag basicity, total content of each transition metal, content of each component in slag, and temperature are the influential factors on their thermodynamic properties in molten slags. Higher basicity and strong oxidative atmosphere are generally favourable for the stable existence of transition‐metal ions with higher oxidation states. Temperature is a factor that is less influential than the above‐mentioned ones. For a transition metal in molten slag, the concentration ratio of ions of different valences depends on the activity coefficient ratio of their oxides. The present paper summarizes the activity studies regarding the transition metal oxides in various molten slags. For chromium and titanium oxides, information on CaO? SiO₂ based systems is involved. For titanium oxides, its thermodynamic behaviour in MnO? SiO₂ based slags is introduced. For niobium and vanadium, the information in Na₂O? SiO₂, CaO? CaF₂? SiO₂ systems is provided. Thermodynamic studies are described for Nb₂O₅? MnO? SiO₂ molten slag equilibrated with liquid iron at 1828 K.     

Phase change,micro-structure and reaction mechanism during high temperature roasting of high grade rare earth concentrate

The deposit of Bayan Obo in Inner Mongolia is the world's largest rare earth element(abbreviated as REE)resource.The exploration of the theory of mineral formation of Bayan Obo is an important foundation for mineralogical research,and is the scientific basis for mining,industrial beneficiation,smelting and extraction,and processing and utilization.With the rapid development of science and technology,the demand for the utilization of rare earth elements is increasing,and the separation process between rare earth elements needs to be developed.The purpose of this paper is to provide high temperature experimental information for the formation and application of rare earth minerals.To this end,the mineral evolution of high-grade rare earth concentrates with increasing temperature and the migration of rare earths at different stages and their reaction mechanisms were studied.According to thermogravimetric analysis and differential scanning calorimetry(TG-DSC),calcination was carried out at different temperature ranges,and the calcined products were characterized by X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FT-IR),scanning electron micro scope and energy dispers ive spectrometer(SEM-EDS)and other analytical techniques.The re sults are shown in this process,the ra re earth phase is first converted into rare earth oxide and rare earth oxyfluoride.As the temperature increases,Ca_5(PO_4)_3 F and a large number of self-shaped spherical Ca-RE-OF and Ca-RE-PO_4 particles are formed,and the separation of La and Ce elements is discovered.Acco rding to the phase diagram analysis,the production of Ca_5(PO_4)_3 F is due to the reaction of monazite and fluorite,and the phases CeF_2 and Ce F_3 are formed during the reaction.When it reaches 1500℃,barium ferrite is produced and a new substance containing Ba~(2+)is formed.     

Chemical equilibrium constants of rare earth nitrates and tri-n-butyl phosphate complex formation

Mixed rare earth nitrates (REi(NO3)3) in the aqueous solution was mixed with tri-n-butyl phosphate (TBP, (n-C4H9O)3PO) dissolved in kerosene for the formation of their corresponding complexes (REi(NO3)3·ni(n-C4H9O)3PO) at 303 K. The effects of initial concentrations of both TBP and mixed rare earth nitrates on the equilibrium constants of their complex formations were investigated. The complexes were formed almost immediately after mixing. The simultaneous formations reached their chemical equilibria within a few minutes by shaking the mixture at 200 r/min. The chemical equilibrium constants of the complex formations were independent of the initial TBP concentrations. However, they were decreased by reducing the concentration of REi(NO3)3. All equilibrium constants of the simultaneous complex formations were less than 0.7, while the average molar ratio of TBP to REi(NO3)3 of the complexes varied between 1.0 and 1.6. The chemical equilibrium constant for the formation of La(NO3)3·(n-C4H9O)3PO was 0.09, while that of Dy(NO3)3·(n-C4H9O)3PO was 0.68. The ascending sequence of chemical equilibrium constants for the simultaneous formations was La, Ce, Pr, Nd, Eu, Y, Sm, Gd, and Dy.     

Research on anti-corrosion property of rare earth inhibitor for X70 steel

Three kinds of rare earth nitrates were adopted to sodium molybdate to get three kinds of LnN-M compounded inhibitors(La(NO3)3+Na2MoO4(LaN-M),Ce(NO3)3+Na2MoO4(CeN-M),Pr(NO3)3+Na2MoO4(PrN-M)).The combination of weight-loss method and the electrochemical test,was used to evaluate and analyze the corrosion inhibition efficiency of these LnN-M inhibitors to make the research on their corrosion inhibition performance,and the sequential order of their performance was found as follows:CeN-M> LaN-M>PrN-M,among which,the inhibition efficiency of CeN-M for the X70 steel could reach 98.21%.The synergism parameters were calculated by weight-loss method,these computational data indicated that the synergistic effect between rare earth nitrates and sodium molybdate was obvious and significant.Surface morphology,chemical composition and phase components of the precipitation films were tested for discussing the mechanism of LnN-M inhibitors.The outer electronic configuration of the lanthanide was found to have an important influence on the inhibition efficiency.The CeN-M inhibitor was discovered to have the best inhibition effect with the amorphous cerium oxides.The results of this research revealed that the precipitation films formed on the surface of the steel samples had a crucial influence on the inhibition efficiencies after adding LnN-M inhibitors.     

Impact of backmixing of the aqueous phase on two-component rare earth separation process

Solvent extraction based on mixer-settler is the major industrial method of rare earth (RE) separation. In the mixer-settler extraction process, due to the insufficient settling time in normal circumstances, backmixing of the aqueous phase could have significant impact on the process of RE extraction separation. Therefore on the basis of the extraction equilibrium and mass balance of the mixer-settler extraction process, here we developed a mathematic expression of the aqueous phase backmixing in a two-component separation process, and obtained a quantitative analysis of the backmixing effect on the purification process by the approximations according to certain hypotheses. Two extraction systems of La/Ce and Pr/Nd separation were chosen as the examples to analyze the backmixing effect, and the results showed that the aqueous backmixing had greater influence in the scrubbing segment than in the extraction segment, especially in the system with a high separation factor such as La/Ce separation. Therefore it was suggested that the aqueous backmixing effect should be well attended in the design and application of RE extraction separation.     

Characterization and corrosion behavior of Al–Co–rare earth (Ce–La) amorphous alloy

A new Al-based amorphous alloy with excellent corrosion resistance and high thermal stability was produced in the Al–Co–RE (Ce–La) system. In this regard, two different amorphous-nanocrystalline ribbons: Al_87.6–Co_6.4–Ce_3.8–La_2.2 (M₁) and Al_82.3–Co_10.1–Ce_4.8–La_2.8 (M₂) were prepared using melt spinning. The results reveal the supercooled liquid region (ΔT_x) of 218 °C which shows that the M₂ alloy has higher thermal stability in comparison to the M₁ alloy. The M₂ ribbons present the superior corrosion resistance because of the formation of amorphous phase. The i_corr, E_corr, E_pit, and E_pit – E_corr values of fully amorphous Al–Co–Ce–La metallic ribbons have a better trend of anti-corrosion performance compared to other crystalline and amorphous aluminum alloys.     

Fractionation and fixation of rare earth elements in soils: Effect of spiking with lanthanum,cerium, and neodymium chlorides

Industrial and agricultural activities lead to the release of rare earth elements(REEs)in wastewater and aquatic ecosystems,and their accumulation in soils.However,the behavior of REEs in soils remains somewhat unclear.In the present work the fractionation and fixation of REEs in soddy-podzolic and chernozem soils spiked with La,Ce,and Nd chlorides were studied using dynamic(continuous flow)extraction,which allows natural conditions to be mimicked and artefacts to be minimised.The eluents applied are aimed to dissolve exchangeable,specifically sorbed,bound to Mn oxides,bound to metal-organic complexes,and bound to amorphous and poorly ordered Fe/Al oxides fractions extractable by 0.05 mol/L Ca(NO₃)2,0.43 mol/L CH₃COOH,0.1 mol/L NH₂OH·HCl,0.1 mol/L K₄P₂O₇ at pH 11,and 0.1 mol/L(NH4)₂C₂O₄ at pH 3.2,respectively.It is found that the fixations of added La,Ce,and Nd in the form of metal-organic complexes is predominant for both types of soils:35%-38%in soddy-podzolic soil and 50%-79%in chernozem.The fixation of added elements in the first three fractions(exchangeable,specifically sorbed,and bound to Mn oxides)is significant for soddy-podzolic soil(5%-25%).For chernozem,the relative contents of added Ce and Nd in these fractions are nearly negligible.Only the content of exchangeable La is notable,about 5%.Adding any of three elements(La,Ce,or Nd)at the level of100 mg/kg to an initial sample results in changing the fractionation and bioaccessibility of other REEs present in soil.Their contents increase in the first three fractions and decrease in fifth(oxalate extractable)fraction for both soddy-podzolic soil and chernozem.The main difference is the behavior of REEs in pyrophosphate extractable fraction.For soddy-podzolic soil,adding La,Ce,or Nd results in decreasing the contents of other REEs associated with organic matter.For chernozem,on the contrary,the contents of REEs in the form of metal-organic complexes slightly increase.These processes may be attributed to competitive binding of elements and soil properties;they must be taken into account when assessing the environmental risks of soil pollution with REEs.     

Effects of oxygen atmosphere,FeOx and basicity on mineralogical phases of CaO–SiO2–MgO–Al2O3–FetO–P2O5 steelmaking slag

ABSTRACT

The mineralogical phase of slag after crystallisation is essential to utilisation of steelmaking slag. The mineralogical phases of cooled multicomponent CaO–SiO₂–MgO–Al₂O₃–Fe_tO–P₂O₅ slag with different iron oxide contents and basicities (defined as the ratio of mass percentage of CaO to mass percentage of SiO₂ (w(CaO)/w(SiO₂))) in different atmospheres were investigated in the present work by scanning electronic microscopy and energy dispersed spectroscopy analysis and X-ray diffraction. The mineralogical phases in steelmaking slag cooled in argon are mainly nCa₂SiO₄-Ca₃(PO₄)₂ (thereafter nC₂S-C₃P) solid solution, (Fe, Mn, Mg)O (RO) phase. Some CaMgSiO₄ phases could be found in slag with lower basicity. The mineralogical phases in steelmaking slag cooled in air are mainly nC₂S-C₃P solid solution, spinel phase. The overall crystallisation of slag cooled in both argon and air was enhanced with increasing basicity. However, the crystal sizes become smaller in sample with high basicity. The Fe-enriched phases were transformed from non-faceted RO phase in sample cooled in argon to faceted spinel phases in sample cooled in air. The crystallisation of slag cooled in both argon and air was promoted with increasing FeO_x content. The phosphorus content in solid solution was elevated with decreasing basicity and increasing FeO_x content. It was implied by the present work that appropriate basicity and air oxidation would be beneficial to magnetic separation and phosphorus utilisation.     

Chromium Oxide Reduction from Slag by Silicon and Magnesium

Experimental and theoretical studies were performed in order to estimate the effect of the basicity of the slag as well as the amount of reducing agents on the reduction of chromium oxide from a slag in contact with molten steel at 1600 °C. The aim of this work was to compare the efficiency of magnesium and silicon as reducing agents of Cr₂O₃. The slag system contained CaO, MgO, SiO₂, CaF₂ and Cr₂O₃ together with Fe‐alloys (Fe‐Si or Fe‐Si‐Mg). The maximum Cr yield was about 81% with Fe‐44%Si‐9%Mg and 88% with Fe‐75%Si. That means that the reducing effect of Mg was much better than that of Si. Some experiments were conducted to study the effect of initial Cr in steel on the chromium oxide reduction reaction. Three initial Cr contents were tested (0.15, 2 and 4 mass%). It was found that chrome was partially bound into stable spinel phase MgO·Cr₂O₃ in the final slag. Thermodynamic estimations were made to determine the effect of process temperature, slag basicity and the amount of reducing agents in the slag on the Cr recovery. The efficiency of Cr reducing agents increased in the order: Si, Al, Ca and Mg. The Cr yield increased with slag basicity and amount of reducing agents.     

Influence of magnesium on electrochemical properties of RE3-xMgx(Ni0.7Co0.2Mn0.1)9（x=0.5-1.25） alloy electrodes

RE3-xMgx(Ni0.7Co0.2Mn0.1)9 (x=0.5-1.25) alloys were prepared by induction melting and the influence of the partial substitution of RE (where RE stands for La-rich mischmetal) by Mg on the hydrogen storage and electrochemical properties of the alloys were investigated systematically. These alloys mainly consisted of three phases, La(Ni,Mn,Co)5 phase, La2Ni7 phase and Mg2Ni phase. The P-C-T isotherms showed that with Mg content increasing in the alloys, the hydrogen storage capacity first increased and reached the maximum capacity of 1.36 wt.% when x=1.0, and then decreased with x increasing further. Electrochemical studies revealed that the discharge capacity reached the maximum value of 380 mAh/g and the alloy electrode presented better cyclic stability when RE/Mg=2. The high rate discharge ability of the alloy electrodes was also improved by the substitution of Mg for RE. The RE2Mg(Ni0.7Co0.2Mn0.1)9 alloy exhibited better hydrogen absorption kinetics (x=1.0).)     

Effect of rare earth on the coating-forming and mechanism of phosphatization

It was ascertained that when a RE element was added in bath, the sample was improved on the anti-corrosion power of the coating because of the increasing of covering rate of formless crystal Zn₂Fe(PO₄)₂·4H₂O (marked P) crystals and the ratio of P/(P+H) (H was the mark of Zn₃(PO₄)₂ crystal) in the coating, combination of which with components parsing by EDS indicated that the sequence of contribution elements P and Zn to erosion resistance of coatings was P>Zn. And the correlative mechanism was discussed, which made it clear that owing to the particularity of the outer-shell electron structure and larger ionic radius, RE was so easy to be polarized and metamorphosed itself that it adsorbed lightly on the basic body to pose gels. They efficiently reduced the activation energy which was required for formation of a new solid phase of phosphates and made it also possible to engender effectively active nucleation regions of cathode and anode under low temperature phosphating condition, which was propitious to formation, densification and uniformization of the phosphate crystal nucleus and growth of the crystallite and coating buildup. Thus it could be seen that REN played the role of surface regulator and accelerant, which speeded up the phosphating, as well as bids amount of porosity of the coating fall to improve the corrosion resistance of the coating.     

Preparation of crystalline mixed rare earth carbonates by Mg(HCO_3)_2 precipitation method

In acid treatment technology of Baotou mixed rare earth ore,large quantities of ammonia-nitrogen wastewater are produced in the step of ammonium bicarbonate precipitation to transform rare earth sulfate.In this paper,we adopted a green precipitant magnesium bicarbonate(Mg(HCO_3)_2) to substitute ammonium bicarbonate to eliminate ammonia-nitrogen pollution.The effects of n(HCO_3~-):n(RE~(3+)),aging temperature and aging time on the crystallization using Mg(HCO_3)_2 precipitation method were investigated.The results indicate that the rare earths could be completely recovered when n(HCO_3~-):n(RE~(3+)) is higher than 3.15:1.The crystal water content of rare earth carbonates is affected by the aging temperature.The precipitate has a bad filterability when the aging temperature is over 40℃.This can be attributed to the less crystallized water molecules of the hydrated rare earth carbonate precipitation.The mixed rare earth carbonates are prone to be crystalline,and have a good filterability at aging temperatures below 40℃.Meanwhile,the evolution mechanism of crystalline mixed rare earth carbonates is reasonably deduced,the amorphous rare earth carbonates are first dissolute and then recrystallized.Under the optimized aging conditions,the purity of the crystalline precipitate meets the requirements of the fine product standard(GB/T 16479-2008).The filtrated could be used to produce Mg(HCO_3)_2,thus to realize the recycling of magnesium sulfate.     

Thermodynamic Analysis of Deoxidation of Titanium Through the Formation of Rare-Earth Oxyfluorides

In this work, the possibility of the direct removal of oxygen species from metallic Ti through the formation of rare-earth oxyfluorides has been investigated from a thermodynamic viewpoint. The deoxidation limit of β-Ti using rare-earth metals (M: Y, La, Ce, and Nd) as deoxidants was evaluated. It was found that Ti metal with an oxygen concentration of 200 mass ppm or less could be theoretically obtained under the M/MOF/MF₃ equilibrium at 1300 K (1027 °C), which suggested a possibility of reducing the oxygen content in Ti below 500 mass ppm utilizing a fluoride-based molten salt. Furthermore, a new deoxidation process, in which oxygen was removed in the form of MOF compounds using Mg deoxidant, was discussed as well. The obtained results revealed that the oxygen content in β-Ti could be theoretically reduced to a level below 1000 mass ppm using a MF₃-containing molten salt equilibrated with Mg. Rare-earth metals and their alloys are usually produced by the electrolysis in a fluoride-based molten salt; hence, the modern industrial electrolysis techniques can be potentially utilized for deoxidizing Ti scrap.     

动态氧化条件下含钛高炉熔渣中钙钛矿析出与长大机理

动态氧化不仅有利于含钛高炉熔渣中钛组分富集于设计相(钙钛矿相),同时还会促进钙钛矿相析出与粗化,在自然重力作用下粗化的钙钛矿实现重力富集与沉降分离.本文运用玻璃形成动力学方程,对动态氧化条件下含钛熔渣中钙钛矿相形核速率和晶体生长速率进行分析和研究.结果表明,向熔渣鼓入氧气,低价钛逐渐氧化为四价钛,促进钙钛矿析出反应的进行,提高了钙钛矿晶体生长速率.继续通入氧气则氧化时间过长,熔渣中高熔点TiC和TiN固体颗粒基本消失,黏度降低,异相形核转化为均相形核,析出温度显著降低,析晶温度区间缩短,不利于钙钛矿晶粒粗化和长大.      

Effect of composition on the crystallisation behaviour of blast furnace slag using single hot thermocouple technique

When the content of glass in blast furnace slag is over 95%, it can be used as a raw material in the manufacture of cement. The critical cooling rate required for the formation of glassy slag is one of the important characteristics for molten BF slag. The crystallisation behaviour of molten BF slag has been studied by in situ observation with the single hot thermocouple technique. The isothermal and non-isothermal experiments were performed to construct time–temperature-transformation and continuous-cooling-transformation diagrams. The effect of MgO, Al₂O₃ and binary basicity (CaO/SiO₂) on the critical cooling rate of the CaO–SiO₂–MgO–Al₂O₃ slags were studied under conditions of CaO/SiO₂?=?1.1–1.4, 6–12?mass% MgO and 10–16?mass% Al₂O₃. The following finding are reported in the present paper: (i) Higher MgO content increased the critical cooling rate; higher Al₂O₃ content decreased the critical cooling rate; higher CaO/SiO₂ increased the critical cooling rate. (ii) The crystallisation temperature of molten BF slag lowers as the cooling rate increases, the slag have larger critical cooling rate, higher crystallisation temperature. The results could be used to design proper cooling path of molten BF slag for the formation of glassy.     

Structural analysis by Rietveld refinement of calcium and lanthanum phosphosilicate apatites

Britholites with the general formula Ca10-xLnx(PO4)6-x(SiO4)xF2, (0≤x≤6) are considered to be promising matrices for the confinement of the by-products in the nuclear industry. A thermodynamic study sh...     

Thermodynamics on the formation of spinel (MgO·Al<Subscript>2</Subscript>O<Subscript>3</Subscript>) inclusion in liquid iron containing chromium

The stability diagram of MgO, spinel solid solution (MgO·(Al _X Cr_1−X )₂O₃), and sesquioxide solid solution ((Al _Y Cr_1−Y )₂O₃) as a function of Mg, Al, and O contents at a constant chromium content (18 mass pct) in liquid iron is drawn at 1873 K. The interaction parameters between Mg and other solutes (Al, Cr, Ni, Ti, Si, and C) are determined by the experimental method, which assures equilibrium between Mg vapor and liquid iron, were applied to calculate the diagram. Titanium deoxidation is not recommended for the prevention of spinel formation, because Ti accelerates Mg dissolution from refractory or slag due to its high affinity for Mg (e _Mg ^Ti = − 0.64). The standard Gibbs free energies of formation for the three inclusions (periclase, spinel, and sesquioxide solid solutions) and the tielines between two solid solutions were calculated with the aid of the regular solution model and the thermochemical F*A*C*T database computing system, respectively. The phase stability regions and oxygen content in steel for the current Fe-Mg-Al-Cr (18 mass pct)-O system are compared with those of the previous non-Cr system. Detailed information on the spinel composition according to Mg and Al contents is also available from the present stability diagram.