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.     

Synergistic extraction of cerium from sulfuric acid medium using mixture of 2-ethylhexyl phosphonic acid mono 2-ethylhexyl ester and Di-（2-ethyl hexyl） phosphoric acid as extractant

Synergistic extraction of cerium(IV) from sulfuric acid medium using mixture of 2-ethylhexyl phosphonic acid mono 2-ethylhexyl ester(HEH/EHP, HL) and Di-(2-ethyl hexyl) phosphoric acid (HDEHP, HA) as extractant was investigated. The results indicated that the maximum synergistic enhancement coefficients were obtained at the mole fraction of HEH/EHP=0.6, and cerium(IV) was extracted into organic phase in the form of Ce(SO4)0.5HL2A2. A cation exchange mechanism was proposed for the synergistic extraction of Ce(IV). The equilibrium constants and thermodynamic functions such as △G, △H, and △S were determined in the extraction of Ce(IV) from sulfuric medium using mixture of HEH/EHP and HDEHP.     

Electro-Oxidation of Concentrated Ce（ Ⅲ ） at Carbon Felt Anode in Nitric Acid Media

Ceriumiswidelyusedinindustry,mainlyinthe formofceria(CeO2),asamaterialforceramic,cata lysts,polishingpowdersandsoon.Inmetallurgyceri umhasbeenusedassulfidecontrollingadditivefor steelandotheralloys.Itsabundanceinvariousminer als,inwhichCebeisaccompaniedbyotherrare earths,makesCeoneofthecheapestRE[1].Ce(Ⅲ),incontrasttootherbasicallytrivalentREions,canbe oxidizedtorelativelystableCe(Ⅳ)statethathas quitedifferentchemicalproperties.Tetravalentcerium isusedasanoxidizingagentinorganicsynthesis…     

Adsorption of Ce（ Ⅳ ） Anionic Nitrato Complexes onto Anion Exchangers and Its Application for Ce （Ⅳ） Separation from Rare Earths （ Ⅲ ）

Ceriumis one of the cheapest[1]and most abun-dant rare earths (RE) .However ,high purityis usual-ly required for its utilization in industry , where it isusedfor sulfur control insteels ,pyrophoric alloys ,ce-ramic ,catalyst support ,polishing powders ,etc .In its minerals ,as well as in the spent nuclearfuel ,ceriumis accompanied by other RE.They basi-cally exist in solution as stable RE(Ⅲ) species ,which makes their mutual separation rather difficult .In contrast to other RE, Ce(Ⅲ) can…     

磷类萃取剂萃取钼(Ⅵ)的性能研究

系统研究了酸性磷类萃取剂二（2-乙基已基）磷酸（P204）和中性磷类萃取剂磷酸三丁酯（TBP）从硫酸体系中萃取钼的性能，稀释剂为乙酸丁酯、二甲苯和煤油。试验结果表明，溶解在3种稀释剂中的TBP对钼萃取效果均不显著，而P204与3种稀释剂组成的有机相均对钼有良好的萃取性能，萃取率与水相pH、萃取时问、酸体系有关。萃取机理属于离子交换缔合机理。     

Adsorption of Ce(IV) in nitric acid medium by imidazolium anion exchange resin

N-methylimidazolium functionalized anion exchange resin in NO3-form(RNO3) was prepared and used for adsorption of Ce(IV)in nitric acid medium.The adsorption amount increased with shaking time increasing and the adsorption equilibrium was obtained within 180min.Ce(IV) was partially reduced to Ce(III) and the reduction percent of Ce(IV) increased with shaking time increasing.But RNO3 was morestable than other resins due to the high resistance to oxidation.A little increase of adsorption amount was found with ...     

Application of Ce(IV) in industrial wastewater treatment

At present,rare earth application in wastewater treatment has become more and more widely,according to the fact that the Ce(IV) has the strong oxidation ability under acid condition,we have studied the application of Ce(IV) in industrial wastewater treatment originally.Results showed that oxidation-reduction reaction occurred between Ce(IV) and the organic compounds or other reducing substances in industrial wastewater,thereby the colority and CODcr reduced effectively.Ce(IV) formed [Ce(OH)x·nH2O](4-x)+ after hydrolyzation and Ce(III) obtained after Ce(IV) reduction formed [Ce(OH)x·nH2O](3-x)+ after hydrolyzation,these hydrate had big specific surface area,could adsorb the suspension substances and removed toxic or harmful ions in industrial wastewater.After treatment by Ce(IV),the analytical results of industrial wastewater are as follows:The CODcr became 58 mg/L from 1646 mg/L,the total COD removal efficiency was more than 95.0%.Turbidity reduced to no more than 10NTU from 87NTU.The chroma became 6 degree from 26 degree,suspension substances content decreased to no more than 2 mg/L from 36 mg/L,and total arsenic and fluorion became <0.05 mg/L and <0.10 mg/L from 0.60 and 15.3 mg/L.Total cadmium reduced to 0.01 mg/L from the 0.58 mg/L.These all indicated that Ce(IV) was one kind of latent good water treatment chemical.     

The Recovery of a Mixed Rare-Earth Oxide and the Preparation of Cerium,Europium and Neodymium Oxides from a South African Phosphoric Acid Sludge by Solvent Extraction

Abstract

A novel process based largely on solvent-extraction methods has been developed for the recovery of rare-earth oxides from waste calcium sulphate sludges obtained during the manufacture of phosphoric acid from a South African apatite ore. A mixed rare-earth oxide (90-98% purity) was first recovered from calcium nitrate leach liquors by extraction with TBP or DBBP, after which it was dissolved in nitric acid to enable pure cerium dioxide (99.98%) to be prepared by selective extraction of cerium(IV) nitrate into TBP. The heavy (yttrium), middle, and light rare-earth fractions were then separated by sequential extraction into D2EHPA at controlled pH values. Pure europium oxide (99.98%) was isolated from the middle fraction by reductive precipitation of europim(II) sulphate, followed by conversion to soluble europium(II) chloride and removal of trivalent rare-earth impurities by extraction with D2EHPA or Versatic 10 acid. Finally, magnet-grade neodymium oxide (95-96%) was obtained from the light rare-earth fraction by extraction of the contained lanthanum, cerium and praseodymium into Aliquat 336 nitrate.     

Ce~(4 ) Extraction Mechanism from RE Sulfate Solution Containing Fluorine with DEHPA

RE sulfate solutioncontaining fluorine is obtainedfrom bastnasite which is roasted inair and then leached with sulfuricacid. Solvent extraction of Ce4 with DEHPA in sulphonatingkerosene from the solution is investigated. It is found that fluorineion is extracted into organic phasewith Ce4 . The extraction mechanism is proposed by slope analysisand studying the influence ofaqueous acidity, fluorine concentration and DEHPA concentrationon CF- /cC4 in equilibrium organic phase.Ce~(4 ) Ext…     

Application of Ce(IV) in industrial wastewater treatment

At present, rare earth application in wastewater treatment has become more and more widely, according to the fact that the Ce(IV) has the strong oxidation ability under acid condition, we have studied the application of Ce(IV) in industrial wastewater treatment originally. Results showed that oxidation-reduction reaction occurred between Ce(IV) and the organic compounds or other reducing substances in industrial wastewater, thereby the colority and CODcr reduced effectively. Ce(IV) formed [Ce(OH)x·nH₂O]^(4-x)+ after hydrolyzation and Ce(III) obtained after Ce(IV) reduction formed [Ce(OH)x·nH₂O]^(3-x)+ after hydrolyzation, these hydrate had big specific surface area, could adsorb the suspension substances and removed toxic or harmful ions in industrial wastewater. After treatment by Ce(IV), the analytical results of industrial wastewater are as follows: The CODcr became 58 mg/L from 1646 mg/L, the total COD removal efficiency was more than 95.0%. Turbidity reduced to no more than 10NTU from 87NTU. The chroma became 6 degree from 26 degree, suspension substances content decreased to no more than 2 mg/L from 36 mg/L, and total arsenic and fluorion became <0.05 mg/L and <0.10 mg/L from 0.60 and 15.3 mg/L. Total cadmium reduced to 0.01 mg/L from the 0.58 mg/L. These all indicated that Ce(IV) was one kind of latent good water treatment chemical.     

Separation chemistry and clean technique of cerium（IV）： A review

The separation method of changeable valence RE element of cerium(Ce) was reviewed in this paper. Solvent extraction is the most effective and efficient method to separate Ce(IV) from RE(Ⅲ), usually accompanied with fluorine(F) and phosphor(P) from bastnaesite and monazite etc. By roast or wet-air oxidation, Ce(Ⅲ) of bastnaesite and monazite was oxidized into Ce(IV), and Cyanex923 and [A336][P507] have been investigated to co-extract and recover Ce(IV), F and P from H2SO4 leaching liquor, leading to favorable conditions for the subsequent separation of Th(IV) and RE(Ⅲ). The interaction of Ce(IV) and F and/or P enhances the roasting, leaching and extraction of Ce(IV) due to increasing of the stability of Ce(IV), and the formation of CeF3 and CePO4 after reductive stripping will benefit the utilization of F and P. For dealing with RE ores of high-content Ce, the clean process of oxidation roasting and Ce(IV)-F separation for Sichuan bastnaesite highlights the advantages of Ce(IV) based clean technique, which firstly demonstrates the comprehensive utilization of Ce(IV), Th(IV), F and RE(Ⅲ) and prevention of environmental pollution from fountainhead. A preliminary flowsheet of two-step oxidation and extraction of Ce(IV) for Bayan Obo mixed ores was further proposed to process the oxidation and extraction of Ce(IV) in presence of both F and P, indicating the possibility of similar effects with clean process of Sichuan bastnaesite. Ce(IV) separation chemistry and clean technique will open up new realms for light RE resources utilization, meeting "Emission Standards of Pollutants from Rare Earths Industry" promulgated by China's Ministry of Environment Protection(MOP) in 2011.     

有机次膦酸在硝酸体系下提取稀土研究

本文采用溶剂萃取法,用有机次磷酸萃取剂从富含稀土元素镧(La）、钕(Nd）、钇(Y)、铈(Ce）的硝酸溶液中提取稀土。选择盐酸为反萃剂。考察了酸度、萃取剂浓度、相比和萃取时间对萃取率和反萃率的影响,结果表明,二异丁基膦酸萃取稀土的最佳条件为：室温,酸度0.2mol/l,萃取剂浓度40%,A/O比1:5,萃取时间15min,镧（La）、钕（Nd）,铈（Ce）和钇（Y）分别为41.68%、81.30%、81.29%和100%。当利用盐酸作为反萃实验的反萃剂时其最佳条件为：室温,初始水相稀土溶液为0.3 mol/L,反萃剂盐酸为6 mol/L,负载有机相与反萃剂盐酸溶液的体积比为1:6,将反萃的震荡时间改变为5min,应用上述条件的镧(La）、钕(Nd）、铈(Ce）、钇(Y)的反萃率分别为92.45%、94.88%、95.76%、93.34%。有机次膦酸对稀土元素（La）、钕（Nd）、铈（Ce）和钇（Y）的萃取效率不同。钇的提取率高于镧、钕和铈。它是一种有机次膦酸,对轻稀土元素亲和力低,对重稀土元素亲和力强。     

Preparation and luminescence properties of Ce3＋/Dy3＋-codoped fluorosilicate glass ceramics

The Ce3+and Dy3+ co-doped fluorosilicate glass and glass ceramics containing SrF2 or CeF3 nanocrystals were prepared under re-ducing atmosphere. The precipitated nano-crystalline phase shifted from cubic SrF2 to hexagonal CeF3 gradually with the heat treatment tem-perature increasing from 620 to 680 °C. The glass and glass ceramics emitted white light, deriving from a combination of the Ce3+ blue and the Dy3+ yellow light. The CIE coordinates could be tuned by adjusting the ratio of Ce3+/Dy3+ concentration. The luminescence could be en-hanced significantly by annealing the samples at the temperatures lower than 640 °C.     

The extraction of Zinc(II) from sulphate and chloride solutions with kelex 100 and versatic 911 in kerosene

Zinc(II) is extracted from sulphate or chloride solutions by Kelex 100 (HX) in kerosene, comparable extraction taking place under more acid conditions from chloride media. The addition of Versatic 911 (HA) leads to synergistic enhancement of extraction; equilibrium studies with the mixed extractants indicate that a mixed complex of the form ZnX₂ · (HA)₂ is extracted, and infra-red spectra suggest that Versatic is present as a solvating agent. The effect of chloride ion concentration on extraction was examined, and tracer studies showed that chloride takes no part in the constitution of the extracted zinc complex.     

Electrochemical behavior of Ce（III） in LiF-BaF2 melts

The electrochemical behavior of Ce(III) was investigated in the molten LiF-BaF2 (81 mol.%-19 mol.%) on a molybdenum elec-trode in the temperature range of 1098-1188 K using cyclic voltammetry and chronopotentiometry. It was observed that CeF3 could be re-duced into cerium metal in a reversible one-step process exchanging three electrons (Ce(III)+3e-→Ce(0)) at the operating temperatures on a molybdenum cathode. The electrochemical reduction process was controlled by the diffusion of Ce(III) in the solution. The Ce(III) diffusion coefficients were calculated at different temperatures and the values obeyed the Arrhenius law with an activation energy of 87.5 kJ/mol.     

Electro-Oxidation of Concentrated Ce(Ⅲ) at Carbon Felt Anode in Nitric Acid Media

Electro-oxidation of Ce( Ⅲ) to Ce( Ⅳ ) in parallel plate flow type electrolyzer divided with cation exchange membrane was carried out in nitric acid media at carbon felt anode under galvanostatic conditions. Carbon felt was used as an anode for its high specific surface area and high oxygen evolution overpotential. Pt coated Ti plates were used as cathcurrent efficiency (92%) until about 80% of Ce( Ⅲ) was oxidized. Then, oxygen evolution, accompanied by terminal voltage jump, took place, lowering current efficiency. Ce( Ⅲ ) was oxidized up to 90% with current efficiency of 62%. In this mode, strong carbon felt anode oxidation was observed. The wear out of carbon felt was 46% in six consequent runs (6 h of operation). After each run, carbon felt surface had to be renewed with slightly alkaline solution to remove carbon oxidation products and ensure regular operational conditions. When anode surface was blocked, oxygen evolution took place from the beginning of electrolysis due to higher actual current density. The wear out of carbon felt anode could be minimized by means of oxygen evolution prevention. In the case when electrolysis had been stopped before oxygen evolution started (at Ce( Ⅳ ) conversion of about 80% ), the wear out of anode was less than 2% during 6 consequent runs (4 h of operation).     

Solvent extraction of Ce(III) and Pr(III) with P507 using SiC foam as a static mixer

Extraction reactor is a major research area of interest within the field of rare earths extraction and separation. SiC foam offers excellent material characteristics as well as three-dimensional (3-D) reticulated structure; however, very little research has been carried out on its application in extraction reactor so far. In this work, a static mixer reactor based on SiC foam was designed and demonstrated to extract and separate Ce(III) and Pr(III) from nitric acid media by using 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester (P507) as extractant. The structure–performance relationship between SiC foam and extraction performance was studied by experiment combined with computational fluid dynamics (CFD) simulation. The experiment data are in good agreement with the simulation results. Contrast experiment by using a Kenics mixer was carried out, and SiC foam shows better extraction and mass transfer performance. Using the optimal structural SiC foam (pore size D = 2.3 mm, open porosity ε = 85%, foam length L = 80 mm), high extraction efficiency η (Pr(III): 94.6%, Ce(III): 88.5%) and separation factor β (2.27) between Ce(III) and Pr(III) is achieved at a high total throughput of 200 mL/min. Besides, overall volumetric mass transfer coefficient K_La of Pr(III) and Ce(III) are 0.519 and 0.378 s^?1 at the residence time τ of 3.6 s, respectively, which reach the high level of microchannel reactors and are better than conventional extractors and other static mixers. SiC foam is found to be applicable as a static mixer for efficient and high-throughput extraction and separation of rare earths.     

离子交换法合成硫酸四氨钯(Ⅱ)

以二氯化钯为原料,通过氨水络合、离子交换、硫酸中和、重结晶提纯等工序,得到了硫酸四氨钯(Ⅱ)产品,并分析了产品特征组分的含量。结果表明,采用离子交换工艺合成硫酸四氨钯的产率为86.82%,产品纯度高,适于规模化生产。     

Effects of MO_x(M=Mn,Cu,Sb,La)on V-Mo-Ce/Ti selective catalytic reduction catalysts

A series of MO_x-V_2O_5-MoO_3-CeO_2/TiO_2(M=Mn,Cu,Sb,and La) catalysts were prepared via an impregnation method.The physico-chemical properties of the catalysts were characterized and their NH_3-SCR of NO performance was compared.The Mn-loaded catalyst(Mn5V1Mo3Ce7/Ti) exhibits a large number of acid sites of varying strength,and together with good reducibility of the catalyst,contributes to the optimal SCR performance.The sulphate species formed in the presence of SO_2 significantly enhance the H_2O and SO_2 tolerance of Mn5V1Mo3Ce7/Ti.The Cu-loaded catalyst(Cu5V1Mo3Ce7/Ti)demonstrates potential in flue gas applications in the absence of SO_2 at low temperatures because of the excellent redox ability observed and the high degree of weak acid sites.The Sb and La loaded catalysts(Sb5V1Mo3Ce7/Ti and La5V1Mo3Ce7/Ti),especially La5V1Mo3 Ce7/Ti,exhibit the largest number of acid sites and the lowest reducibility,and therefore,may be suitable for use in high temperature denitrification applications.     

Technology of Chloride-Ion Utilization from Filtrates of Carbonate Circuit of Nickel Production

The problem of sulphate solution purification, in particular solutions of carbonate branch after nickel precipitation, from chloride ion can be solved effectively by extraction process. Trialkylamine available commercially (TAA) (alkyl—C₈-C₁₀ and C₇-C₉) has been used in this study. The dependences of chloride ion extraction on temperature, pH and composition of aqueous phase, and composition of organic phase have been investigated. Triethylbenzene, kerosene, diesel oil, syntin with different additions (2-ethylhexanol, hexanol, tributylphosphate) were used as the solvents. The optimum composition of organic phase (0.5-0.6 M TAA in kerosene with addition of 2-ethylhexanol) and the conditions of chloride ion extraction from sulphate solutions have been determined. Chloride ion stripping from organic phase was conducted by alkali solutions to obtain a concentrated solution of sodium chloride.

The technology of chloride ion recovery from filtrates of carbonate branch of nickel plant (Norilsk Mining and Metallurgical plant) has been developed and tested on an industrial scale. The initial filtrate contained in g/l: chloride ion I6-I8, sulphate ion 60-65, impurities of metals. After purification, the chloride ion concentration in solution was less than 0.3 g/l (chloride ion recovery was more than 95%). After stripping of chloride ion with alkali solution, the stripping solutions containing 200-220 g/l NaCl and < 2 g/l sulphate ion. The stripping solutions underwent an electrolysis to obtain chlorine and sodium hydroxide solutions.

The developed technology allows recovery of chloride ion from sulphate solution.