Formation mechanism of micro emulsion on aluminum and lanthanum extraction in P507-HCl system

P507 solvent extraction is the main method to separate and purify the rare earth products.The emulsification may be caused by the impurities in process of extracting rare earths,and these result in huge economic loss and decrease the quality of rare earth products.In recent researches,the extractant was prone to emulsification,and aluminum content of rare earth products also increased,while aluminum concentration of feed was higher.Pointing to this problem,the structural change of saponification P507 extracting aluminum and lanthanum was investigated by infrared spectroscopy,and the results showed that Al ions exchanged with H of P-O-H to become P-O-Al.Because aluminum held the characteristic of hydrophilic after extracted in the form of hydroxyl polymer ions and this provided conditions for the formation of micro emulsion.The organic phase and aqueous phase were investigated by polarizing microscope after aluminum was extracted.The results showed that the organic phase was clear when the extraction capacity of Al was less than 5 g/L.If the extraction capacity of Al exceeded 5 g/L,it formed W/O of ME(micro emulsion),leading to form emulsion of the organic phase.When Al concentration of feed was less than 1 g/L,the aqueous phase would form O/W of ME.If aluminum was extracted by saponification P507 firstly,then the the organic phase loading aluminum extracted rare earth continually,the organic and aqueous phase formed emulsification easily.     

Formation mechanism of micro emulsion on aluminum and lanthanum extraction in P507-HCl system

P507 solvent extraction is the main method to separate and purify the rare earth products. The emulsification may be caused by the impurities in process of extracting rare earths, and these result in huge economic loss and decrease the quality of rare earth products. In recent researches, the extractant was prone to emulsification, and aluminum content of rare earth products also increased, while aluminum concentration of feed was higher. Pointing to this problem, the structural change of saponification P507 extracting aluminum and lanthanum was investigated by infrared spectroscopy, and the results showed that Al ions exchanged with H of P-O-H to become P-O-Al. Because aluminum held the characteristic of hydrophilic after extracted in the form of hydroxyl polymer ions and this provided conditions for the formation of micro emulsion. The organic phase and aqueous phase were investigated by polarizing microscope after aluminum was extracted. The results showed that the organic phase was clear when the extraction capacity of Al was less than 5 g/L. If the extraction capacity of Al exceeded 5 g/L, it formed W/O of ME (micro emulsion), leading to form emulsion of the organic phase. When Al concentration of feed was less than 1 g/L, the aqueous phase would form O/W of ME. If aluminum was extracted by saponification P507 firstly, then the the organic phase loading aluminum extracted rare earth continually, the organic and aqueous phase formed emulsification easily.     

Study on preparation and application of novel saponification agent for organic phase of rare earths extraction

In view of the problem of ammonia-nitrogen wastewater pollution in rare earths extraction and separation, the novel saponification agent of organic phase, which is magnesium bicarbonate solution, was prepared with the natural rich and cheap dolomite as raw material through carbonation process. The behavior and purification of main impurities ions in the carbonation process as well as the application effect of the novel saponification agent in the extraction and separation was researched. The results showed that the concentration of Fe, Al, Si impurities ions was less than 5 ppm in the saponification agent through the development of effective removal technology, respectively. When the novel saponification agent was used in the extraction and separation, magnesium utilization rate was more than 95%, and rare earths extraction rate above 99.5% has achieved. Therefore, the technology could replace ammonia-water to saponify the organic phase in rare earth extraction and separation process.     

杂质离子对萃取法从石煤酸浸液中分离纯化钒的影响

含钒石煤经焙烧、硫酸浸出后,酸浸液中含有高浓度的Fe3+、Fe2+、Al 3+和Mg2+等杂质离子。以D2EHPA和TBP为萃取剂,磺化煤油为稀释剂,采用萃取法对该酸浸液进行钒的提纯试验,考察杂质离子对钒萃取率的影响。结果表明,在配制的纯溶液中,V4+的萃取率明显高于V5+;Fe3+质量浓度大于5g/L时会显著降低V4+萃取率;Al 3+和Mg2+的质量浓度低于10g/L时,其共萃率明显降低。对实际酸浸液进行还原处理后,99%的V4+能够被萃取回收,而大部分Fe2+、Al 3+和Mg2+则存在于萃余液中。少数共萃的Fe2+在反萃作业后留在贫有机相中,Al 3+和Mg2+在沉钒后留在沉钒尾水中,不影响V2O5纯度。     

Solvent extraction of La（III） with 2-ethylhexyl phosphoric acid-2-ethylhexyl ester （EHEHPA） by membrane dispersion micro-extractor

The conventional rare earth solvent extraction equipments have many problems such as long mixing time, low processing capacity, large factory area occupation, high energy consumption and so on. In order to solve the problems, many types of equipments were brought out. In this work, studies were carried out on the La（III） extraction process with 2-ethylhexyl phosphoric acid-2-ethylhexyl ester （EHEHPA） by membrane dispersion micro-extractor. Equilibrium studies showed that the initial aqueous pH value 4.15 with the saponification rate 40%was the optimal operation condition. The effects of membrane dispersion micro-extractor operational conditions such as dispersion mode, bulk flow rate and organic phase flow rate on the extraction efficiency were studied. The results showed that when the organic solution was the dispersed phase, the extraction efficiency was higher than that of others. Increasing bulk flow ratio could enhance the extraction efficiency greatly. When the ratio of organic phase flow rate to that of aque-ous phase was 80：80, the extraction efficiency was over 95%. The effect of stripping phase acidity on the La（III） recovery was studied. The results showed that when the stripping phase pH was 2.0, organic phase flow rate to stripping phase flow rate was 20：80;the re-covery efficiency of La（III） can reach 82%.     

Preparation and Evaluation of High-Purity La2O3

A separation procedure based on extraction chromatography using the di(2-ethylhexyl) phosphoric acid (D2EHPA) impregnated resin, anion exchange with DIAION SA 10 resin, and oxalate precipitation has been developed for the preparation of high-purity La₂O₃ in hydrochloric acid media at a high La concentration. The metallic impurities Ce, Pr, Nd, Sm, K, Mg, Ca, Zn, Cu, Co, Mn, Pb, Al, In, and Fe, but not Bi, were removed efficiently from La by extraction chromatography using a D2EHPA impregnated resin. The Bi was separated from the La by anion exchange (DIAION SA 10) separation. Thus, a high-purity LaCl₃ solution was obtained by anion exchange separation and extraction chromatography. La₂O₃ was prepared from the purified LaCl₃ solution by oxalate precipitation. Glow discharge mass spectrometry was applied for purity evaluation of the prepared La₂O₃. The purity of the prepared La₂O₃ was more than 99.9998 pct total rare earth oxide.     

Research Advance on Magnetocaloric Effect of La-Fe-M(Al, Si) Compounds

Inviewofenergysavingandenvironmentalpro tection ,magneticrefrigerationnearroomtemperaturehasastrongimpactonconventionalgascompressiontechnology .However ,coolingefficiencyofthesystemformagneticrefrigerationismainlydecidedbythemagnitudeofmagnetocaloriceffectformagneticrefrig eratingmaterialsinthesystemunderacertainmagnet icfieldchange .Therefore ,developmentofnewrefrig eratingmaterialswithgreatmagnetocaloriceffectnearroomtemperatureisespeciallyimportant .Therearetwoparameterswhichareusedtochara…     

Electrochemical properties of cobalt-free La0.80Mg0.20Ni2.85Al0.11M0.53 （M=Ni, Si, Cr, Cu, Fe） alloys

In order to investigate the effect of different B-site additions on phase structure and electrochemical properties of cobalt-free La-Mg-Ni based alloys, La0.80Mg0.20Ni2.85Al0.11M0.53 (M=Ni, Si, Cr, Cu, Fe) hydrogen storage alloys were prepared and studied systemati-cally. X-ray powder diffraction showed that the alloys consisted mainly of LaNi3 phase and LaNi5 phase except that Cr addition caused a minor Cr phase. Electrochemical testing indicated that alloys with additional Ni, Cr, Cu or Fe were activated within only 1-2 cycles, while that with Si addition needed 4 cycles. Adding Si, Cu and Fe increased cycling stability of La-Mg-Ni based alloys. However, maximum discharge capacity decreased from 362 mAh/g to 215 mAh/g in the order of Ni>Fe>Cu>Cr>Si. In addition, electrochemical kinetics of alloy electrodes was also researched by measuring high rate discharge ability (HRD), hydrogen diffusion coefficient (D) and limiting current density (IL).     

Influence of chromium and impurities on the grain- refining behavior of aluminum

The grain-refining behavior of high purity aluminum (HPA1) and commercial purity aluminum (CPA1) containing Fe and Si as impurities (<0.2 wt pct each) has been studied with and without the presence of Cr in small and large quantities (0.2 and 2 wt pct). The Al-5Ti-lB master alloy ingot (0.2 wt pct) was used as a grain refiner. The emphasis was on the influence of individual elements and their interactions with the other elements on the grain-refining behavior of Al. Good grain refinement with insignificant fading in CPA1 was observed in comparison to HPA1. Similar results were obtained with a small concentration of Cr in HPA1 in HPA1-0.2 wt pct Cr alloy. The CPA1 and HPA1-0.2 wt pct Cr alloy have given the best grain-refining results among all the cases studied. A combination of small quantities of Fe, Si, and Cr (CPA1-0.2 wt pct Cr) has shown early and significant fading. A large concentration of Cr (2 wt pct) has shown a poisoning effect irrespective of the presence or absence of impurities such as Fe and Si in Al. Thus, Cr was found to be beneficial for grain refinement at smaller concentrations in the absence of impurities. But at higher concentrations of Cr, it had an adverse effect,i.e., led to coarser grain sizes both in the presence and absence of impurities.     

The Sequence of Intermetallics Formation during the Solidification of an Al-Mg-Si Alloy Containing La

A mechanism by which La modifies the Fe-bearing intermetallics in a 6xxx series Al alloy is examined using calorimetry. Thermal events accompanying the formation of various phases are identified by establishing a correspondence between them and microstructures of as-cast alloys. It is concluded that a previously suggested surface adsorption mechanism is unlikely to be operative. During solidification, the addition of lanthanum results in the formation of the La(Al,Si)₂ phase and the depletion of the remaining melt of Si. It is hypothesized that the decreased Si/Fe ratio in the melt caused by the presence of La favors the formation of the α-AlFeSi phase, which is less detrimental to the formability of the alloy than the β-AlFeSi phase.     

Solvent extraction of Pr and Nd (III) from chloride-acetate medium by 8-hydroquinoline with and without 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester as an added synergist in heptane diluent

In this paper, solvent extraction of Pr (III) and Nd (III) using 8-hydroxyquinoline in chloride-acetate medium has been systematically investigated. The effect of various parameters, such as equilibrium time, aqueous pH, extractant concentration, acetate ion concentration, chloride ion concentration, and organic solvent, on the extraction has been discussed. The synergistic effect in the mixtures of 8-hydroxyquinoline (HQ) and 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester (P507) has been explored, and the largest synergistic enhancement factor has been calculated. The separations of Pr (III), Nd (III) and La (III) by 8-hydroquiloline alone and by mixtures of HQ and P507 have been studied, and the results demonstrate that it is possible to separate Pr (III), Nd (III) and La (III) with the mixtures of HQ and P507. At last, the stripping of Pr, Nd and La (III) has been performed.     

环烷酸萃取脱除废旧稀土荧光粉酸浸液中铁铝

研究了废旧稀土荧光粉酸浸液在环烷酸萃取过程中关于铁、铝杂质的除杂效果,考察环烷酸对于铁、铝、稀土的选择性;有机相组成、氨水浓度、温度对分离效果的影响;水洗温度、水洗相比对水洗效果的影响;盐酸浓度、相比、反萃时间对反萃效果的影响.结果表明:选择环烷酸:异辛醇:磺化煤油体积比为20:20:60、氨水浓度为2 mol/L、温度为20 ℃、氨水滴加速度为3 mL/min时,分离效果较优;水洗温度为40 ℃、相比（A/O）为2时,铁铝稀土的洗脱率分别为1.5%、4.2%和26.4%;反萃剂盐酸浓度为3 mol/L、反萃相比（A/O）为1、反萃时间为20 min时,铁、铝、稀土萃取率分别高达99.5%、99.8%和99.8%.      

Thermodynamic modeling of the reaction of lanthanum with components of iron-based melts

Thermodynamic analysis of binary and ternary oxide systems containing the oxide La₂O₃ permits the formulation of a database of energy parameters in the theory of subregular solutions for oxide melts adjacent to the region of existence of metallic melts in the phase diagram of the system. The temperature dependence of the equilibrium constants for the heterogeneous reduction of steel is established. The solubility surfaces of components in oxygen-bearing steel are plotted for the Fe–Al–La–O–C, Fe–Ca–La–O–C, Fe–Mg–La–O–C, Fe–Si–La–O–C, and Fe–Cr–La–O–C systems. Diagrams are plotted for the complex reduction of steel by alloys and mixtures containing active and alloying elements: Ca, Mg, Si, Al, Cr, and La. Analysis is undertaken for thoroughly reduced and sulfur-free steel. With the usual reduction system, in which rare-earth metals are added to the steel after the introduction of calcium, silicon, and aluminum, the inclusions that form—consisting of a conglomerate of calcium and magnesium aluminates—provide the substrate for the deposition of small fractions, actively interact with the liquid component of the inclusions, and dissolve in the liquid component. Therefore, La₂O₃ is not present as an independent phase in the metallic inclusions.     

Efficient extraction and stripping of Nd(III), Eu(III) and Er(III) by membrane dispersion micro-extractors

The extraction of low concentration rare earth elements at high phase ratio was investigated. The traditional extraction set-up, such as mixer-settler, have drawbacks of easy emulsification, difficult separation and low efficiency if operated at the above condition. Membrane dispersion micro-extractor, owing to its well-dispersed, high surface-to-volume ratio and fast mass transfer rate, was employed in our work. Nd(III), Eu(III), Er(III) were chosen to represent light, medium, heavy rare earth elements (REEs). The extraction process of REEs with 2-ethylhexyl phosphoric acid-2-ethylhexyl ester (P507) was investigated by membrane dispersion micro-extractors. Firstly, the extraction equilibrium of these three elements was explored in the stirred conical flasks, and it is indicated that the extraction efficiencies can be 0.95, 0.97 and 0.98, respectively within 40 min at phase ratio of 100:1. Then the effects of operational conditions such as the residence time, organic and aqueous flow rates on extraction efficiency were also explored in micro-extractors. The results indicate that the efficiency decreases and then increases if increasing aqueous phase flow rate, residence time and droplets' diameter are the key factors of this process. Increasing the phase ratio reduces the extraction efficiency significantly. When the REEs solution has an initial pH of 4.00, the flow rates of continuous and dispersed phase are 40 and 1.6 mL/min, respectively, and 90 mg/L Nd (III), Eu(III) and Er(III) is extracted by 1 mol/L P507 at the out-let length of 8 m. The extraction efficiencies are 0.978, 0.983 and 0.991, respectively. Finally the stripping process was also studied with the micro-extractor. The stripping efficiencies of Nd(III), Eu(III) and Er(III) can reach 0.99, 0.96 and 0.91, respectively when the out-let length is 8 m and the concentration of hydrochloric acid is 1 mol/L. The developed approach offers a novel and simple strategy on the fast extraction and enrichment of low concentration rare earth elements from waste water.     

Determination of Trace Metal Impurities in Cerium Oxide by Fluorination-Assisted ETV-ICP-AES after HPLC Separation

A new method for the separation and detection of trace metal impurities in cerium oxide (CeO2) using HPLC combined with electrothermal vaporization (ETV)-ICP-AES was developed. This combination links the high separation power of HPLC and high sensitivity of ETV-ICP-AES. The 2-ethylhexyl hydrogen 2-ethylhexylphosphate (P507) resin was used as stationary phase for the separation of metallic impurities in order to eliminate severe spectral interferences of the matrix. The dilute nitric acid was adopted as mobile phase for eluting Cu, Mn, Ni and La. The separation process can be accomplished in about 30 min. After concentrating the eluate by evaporation, the trace impurities were determined by using ETV-ICP-AES with the addition of 6% PTFE slurry as chemical modifier. The proposed method was applied to the analysis of CeO2 with satisfactory recoveries.     

Effect of Impurities and Cerium on Stress Concentration Sensitivity of Al-Li Based Alloys

Ｔｈｅｒｅａｒｅａｌｗａｙｓｓｏｍｅｇｅｏｍｅｔｒｉｃａｌｄｉｓｃｏｎ ｔｉｎｕｉｔｉｅｓ ,ｓｕｃｈａｓｆａｓｔｅｎｅｒｈｏｌｅｓ ,ｆｉｌｌｅｔｓａｎｄｇｒａｖｅｓ ,ｉｎｐｒａｃｔｉｃａｌａｉｒｃｒａｆｔｃｏｎｓｔｒｕｃｔｉｏｎｃｏｍ ｐｏｎｅｎｔｓ .Ｉｎｔｈｅｖｉｅｗｏｆｍａｔｅｒｉａｌｍｅｃｈａｎｉｃｓ ,ｔｈｅｓｅｇｅｏｍｅｔｒｉｃａｌｄｉｓｃｏｎｔｉｎｕｉｔｉｅｓｃａｎｂｅｃｏｎ ｓｉｄｅｒｅｄａｓｎｏｔｃｈｅｓ .Ｓｔｒｅｓｓｃｏｎｃｅｎｔｒａｔｉｏｎｕｓｕａｌ ｌｙｏｃｃｕｒｓａｔｎｏｔｃｈ…     

A novel method for synthesis of styryl phosphonate monoester and its application in La(III) extraction

Herein, styryl phosphonate monoester (SPE) was synthesized and first introduced as rare earth extractant. The solvent extraction of lanthanum (III) from nitrate solution using styryl phosphonate mono-iso-octyl ester (SPE108), di-2-ethylhexyl phosphoric acid (D2EHPA) and 2-ethylhexyl phosphonic acid-mono-2-ethylhexyl ester (EHEHPA) as extractants was investigated. The effects of experimental parameters including equilibrium time, extractant concentration, aqueous pH, phase ratio and salt concentration on the extraction process were studied. The results indicate that the extraction ability and capacity of the extractants follow the order: SPE108 > D2EHPA > EHEHPA. What's more, the extraction process is less affected by ammonium sulfate in the aqueous phase with SPE108. The results of the separation between lanthanum and adjacent lanthanides (Ce, Pr, Nd, Sm) show that SPE108 can separate lanthanides efficiently at low pH. The extraction mechanism of SPE108 is proved to be similar to D2EHPA, and the density functional theory (DFT) calculation results infer that SPE108 exhibits superior extraction ability due to its strong electron-accepting ability.     

Extraction of vanadium from direct acid leach solution of converter vanadium slag

Direct acid leaching of converter vanadium slag by titanium dioxide waste is eco-friendly and efficient, but with low selectivity. This novel technique can result in a vanadium solution which contains chromium(III), aluminium(III), magnesium(II), manganese(II) and high amount of iron(II) and iron(III). Bis (2-ethylhexyl) phosphoric acid (D2EHPA) and tri-butyl-phosphate (TBP) diluted with sulphonated kerosene were applied for vanadium extraction from the multi-element leach solution. The effects of the initial pH, concentration of D2EHPA, ratio of organic to aqueous phase, and the extraction time on the extraction efficiency of vanadium were investigated in saponification and unsaponifiable systems, respectively. The results showed that the vanadium extraction percentage can be up to 97% and the iron extraction percentage can be less than 10% in a thirteen-stage counter-current simulation test and the separation coefficient between vanadium and iron can reach to 109.8. Furthermore, vanadium(IV) can also be separated from other impurities such as aluminium(III), magnesium(II), manganese(II), chromium(III) efficiently. The loaded organic phase was stripped by 184?g?L^?1 sulphuric acid solution in a three-stage counter-current stripping process and with the total vanadium stripping percentage of greater than 99.5%. In the end, the vanadium pentoxide products with a purity of 99.14% were obtained.     

Treatment of Chloride Waste Pickle Liquor by Solvent Extraction for the Recovery of Iron

A systematic study of the extraction of Fe(III) from chloride waste pickle liquor has been investigated using Cyanex 923 diluted with kerosene to recover iron values from the pickle liquor. Various parameters were studied to optimize the conditions for maximum recovery of iron. Extraction increases with increasing concentration of both hydrochloric acid and extractant. The species extracted into the organic phase appears to be HFeCl₂ with 1 M of the solvent. Effect of various salts as additives on Fe extraction was also studied and it was found that addition of NaCl enhanced the extraction about 2.5 times as compared to that without its addition.

Saturated loading capacity was found to be 60.9 g/L Fe in four contacts at O/A of 1. The stripping of Fe(III) with different concentration of hydrochloric acid and nitric acid from the loaded Cyanex 923 was found to increase up to 1 M of both the acids and then decrease with further increase in acid concentration up to 10 M. However, 100% stripping efficiency of Fe(III) was achieved with 0.8 M oxalic acid in two countercurrent stages at an aqueous:organic phase ratio of 3:1. Extraction parameters for maximum extraction of Fe(III) were optimized.     

A novel extractant bis(2-ethylhexyl) ((2-ethylhexylamino)methyl) phosphine oxide for cerium(IV) extraction and separation from sulfate medium

By introducing the amine group into phosphorus extractant, a novel aminophosphine compound bis(2-ethylhexyl) ((2-ethylhexylamino)methyl) phosphine oxide (DEHAPO, abbreviated as A) was synthesized for the extraction of cerium (IV) (Ce(IV)) from sulfate medium (H₂SO₄). The influence factors including extractant concentration, H₂SO₄ concentration and temperature on the Ce(IV) extraction were investigated and discussed. It is found that the extraction ability of Ce(IV), thorium (IV) (Th(IV)) and rare earths (REs(III)) (La, Gd, Yb) decreases in sulphate medium in the following order: Ce(IV) > Th(IV) > REs(III). The extraction process is an exothermic reaction and the thermodynamic parameters were calculated. The extracted complex of Ce(HSO₄)₂SO₄·A in loaded organic solution was identified by the slope methods and further proved by FT-IR spectral analysis. Stripping studies indicate that Ce(IV) can be effectively stripped from the organic phase. The results of separation factors (β) and saturation loading capacity demonstrate that DEHAPO could be used to selectively extract Ce(IV) from sulphate medium with high separation efficiency and good extraction ability.