Loading capacity and emulsification phenomena of HREE extraction by dialkylphosphinic acids with different β,γ,δ-substituents

The relationship between dialkylphosphinic acid structure and their loading capacity for HREEs and emulsification phenomena has rarely been studied.In this paper,we took Lu extraction as an example to study the effect of β,γ,δ-substituents of dialkylphosphinic acids on their loading capacity and anti-emulsification performance for HREEs.To discuss conveniently,the dialkylphosphinic acids were classified into two groups:β-substituent group(P208,INET-1,P218,USTB-1 and P227) and γ,δ-substituent gro...     

Clean separation technologies of rare earth resources in China

After a review on the conventional separation process of rare earths (RE), hyperlink extraction technology was introduced and a potential process was proposed for clean separation of RE. A great amount of acid, base and water was consumed in the conventional RE separation process which included the procedures of raw material dissolving, extraction separation and precipitation. Therefore hyperlink extraction technology had been developed, by which the repeated consumption of acid and base could be avoided during the extraction process. And based on the theory and successful applications of the hyperlink extraction technology, we proposed the integral hyperlink process in which the intermediate acid resulted in individual procedures would be recycled and reused after being treated. The proposed process would make it feasible to consume no chemicals except for oxalic acid, and so could be a promising clean separation technology with a significant reduction on consumption and emission.     

Solvent extraction and separation of light rare earth elements (La,Pr and Nd) in the presence of lactic acid as a complexing agent by Cyanex 272 in kerosene and the effect of citric acid,acetic acid and Titriplex Ⅲ as auxiliary agents

At present, the use of rare earth elements(REEs) has become an inevitable necessity in many modern industries. In general, liquid extraction is the best commercial method for extracting REEs due to its ability to control high volumes of liquids with electrical load. With the aim of improving a separation technology that would be superior to the existing extraction systems, the extraction behaviors of La(Ⅲ),Pr(Ⅲ), and Nd(Ⅲ) from an HCI medium with Cyanex 272 in the presence of the complexing agent lactic acid(HLac) and auxiliary agents citric acid(H_3 Cit), acetic acid(HAc), and Titriplex Ⅲ have been reported.The effect of pH and lactic acid concentration has been examined. The use of lactic acid as a complexing agent leading to a high extraction of REEs with Cyanex 272 at pH = 5 was compared with systems without lactic acid. The results show that the use of acetic acid along with lactic acid leads to an increase in the extraction percentage of LREEs. While use of citric acid and Titriplex Ⅲ reduces the extraction percentage of LREEs. Finally, the presence of Titriplex Ⅲ together with lactic acid could lead to an increase in the separation factor of Pr and Nd.     

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.     

Synthesis of Mono-esters of Phenyl-and Substituted Phenylphosphonic Acids and Their Performance in Rare Earth Extraction

Methodsfor the synthesis of acidic phenyl-and substituted phenylphosphonates bearing a branched longchain ester alkyl group are described.These synthetic routes are incomparably superior to other methods in vari-ous aspects including better reaction yield and higher purity of the product.The behaviour of themono(2-butyloctyl)esters and mono(2-methyldodecyl)esters of both phenyl-and o-methylphenylphosphonicacids thus obtained in extraction of lanthanum,praseodymium,neodymium and lutecium as representatives oflight and heavy rare earths,is investigated and discussed on the basis of their chemical structure.The dependenceof the extraction constants and separation factors accords with the Reactivity-Selectivity Principle in solvent ex-traction proposed by us.The composition and structure of the extracted species have been characterized byinfra-red and proton nuclear magnetic resonance spectroscopy in addition to elemental analyses.     

Toxicity of Lanthanum to Pathogenic Fungi and Its Morphological Characteristics

Rare earth (RE) ,a kind of natural mineral hasbeen used as a beneficial element to crops for quite alongti me . Withthe solution of a series of keytechnolo-gies such as extraction,separation of radioactive ingre-dients ,sanitary toxicology,and environmental safety,China became the first countryto apply commercial REproducts asfertilizer or growthsti mulatorin agriculture ,which produced considerable economic and social ben-efits[1 ,2].RE has been found to have some controllingeffects on many…     

Monoalkyl Esters of Isoalkylphosphonic Acid as Extractants in Rare Earth Separation

Four monoalkyl esters of isoalkylphosphonic acids have been studied for the chromatographic separation ofrare earths (RE).The relationship between distribution ratios and acid concentration of the eluants forsamarium and ytterbium has been explored.The characteristics of these extractants loaded onto macroreticularpoly (methyl methacrylate) resin beads for the separation of lanthanum,cerium,praseodymium and neodymiumhave been compared.Among the extractants studied,mono(1-methylheptyl) ester of isooctylphosphonic acidwas found to be the best for RE separation.The acidity for separation is lower than any known P-containingextractants for the same purpose.For instance,with 1.73 mol·L~(-1) nitric acid as eluent,thulium,ytterbium andlutetium can be separated quantitatively.The extractant-loaded resins possess high column efficiency with goodkinetic characteristics.The extraction mechanism was also explored.     

New Methodological Approach to Investigation of Kinetics of REE Extraction in Nonstationary Conditions

The influence of periodical oscillations of the temperature on extraction and stripping processes in the extraction systems was studied. Two extraction systems were investigated： （1） 6 mol · L^-1 NaNO3-Nd（NO3）3-Pr（NO3）3-TBP kerosene and （2） [Nd（NO3）3 · 3TBP] -[ Pr（NO3）3 · 3TBP] -kerosene - 0.1 mol · L^-1 HNO3. Mathematical modeling of the nonstationary membrane extraction has been enhanced by including the dependence of the extraction rate constants on temperature. The values of activation energy for direct and reverse extraction and stripping reactions of Pr and Nd were calculated from experimental temporal dependencies of metal concentration and temperature by solving the reverse kinetics problem using the proposed mathematical model, A series of experiments with periodical oscillations of the temperature on the extraction system for the separation of rare earth elements （REE） using bulk liquid membrane between two extractors were performed. The mathematical model adequately describes the experimental data. The optimization of the extraction process for separation of REE by liquid membrane, under the influence of periodical oscillation of the temperature, was made based on the extraction rate constants and activation energies. The optimal conditions of separation by liquid membrane were found： frequency and amplitude of thermal oscillations, liquid membrane flow rate, and optimal ratio between organic and aqueous phase in extractors.     

Thermodynamics and kinetics of lutetium extraction with HEH(EHP) in hydrochloric acid medium

Solvent extraction has been the most widely used technique for rare earths separation. In this study, thermodynamics and kinetics of lutetium extraction with HEH(EHP) in hydrochloric acid medium were investigated. The extraction mechanism and the relevant parameters were determined by experiment research which can guide the practical extraction process. The data indicated that chloride ion had no effect on lutetium extraction, the rate constant increased when stirring speed was enhanced. Effects of temperature, HEH(EHP) concentration, acidity, and chloride concentration were also studied. Thickness of the diffusion film was also calculated to be 4.66×10~(–3) cm at 150 r/min.     

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.     

Study on non-saponification extraction process for rare earth separation

The purpose of this study was to overcome the disadvantages of ammonia-nitrogen wastewater pollution and high cost of sodium saponification in rare earth separation process. The study focused on the non-saponification extraction technology with magnesia. The influences of the content and particle size of magnesia, reaction time, reaction temperature, and O/A on cerium extraction rate were also discussed. The results showed that the hydrogen ions of extractant were exchanged by rare earth ions when organic extractant and rare earth solution were mixed with magnesia powder, and then the exchanged hydrogen dissolved magnesia to make the acidity of the system stable. The magnesium ions were not participated in the extraction reaction. Non-saponification extraction process of rare earth had been realized. The cerium extraction rate could reach up to 99% in single stage within the optimal reaction conditions.     

Solvent extraction and separation of light rare earths from chloride media using HDEHP-P350 system

Solvent extraction is the most important method for rare earth extraction and separation.Currently,di(2-ethylhexyl)phosphoric acid(HDEHP)and 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester(HEH/EHP)are widely used in industrial production,but there are still obvious deficiencies that require further research to resolve.In this paper,the unsaponification extraction of light rare earth ions in a hydrochloric acid medium by di(2-ethylhexyl)phosphoric acid-di(1-methyl-heptyl)methyl phosphonate(HDEHPP350)system was studied.The results show that the addition of P350 reduces the extraction capacity of HDEHP,and also greatly reduces the concentration of acidity required for the back-extraction.It still has a good separation factor for light rare earths without saponification,and the extractant is not easy to emulsify.With an aqueous phase of pH=2.85,and HDEHP mole fraction XHDEHP=0.9(compared with O/A=2),the separation effect of light rare earth is the best,resulting in the separation coefficientβCe/La=3.39,βPr/Ce=1.67 andβNd/Pr=1.45,respectively.The loaded light rare earth ions extracted by HDEHP-P350 can be easily stripped when 2 mol/L HCl is used as the stripping agent.Finally,the extraction mechanism is discussed using a slope method,and the final structure of the extracted complex is determined to be RECl[(DEHP)₂]₂P350_(o),based on a combination of infrared spectra and 1 H NMR and 31P NMR analyses.     

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-isooctyl ester(SPE108),di-2-ethylhexyl phosphoric acid(D2 EHPA) and 2-ethylhexyl phosphonic acidmono-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 D2 EHPA 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 D2 EHPA,and the density functional theory(DFT) calculation results infer that SPE108 exhibits superior extraction ability due to its strong electron-accepting ability.     

Studies on Expert System for Extraction of Rare Earths

An expert system has been developed,using LISP,for extraction of rare earths.The expert system was de-signed to mimic the deduction of chemists for rare earth separation.The knowledge base consists mainly of threeparts:(1)the extractant solvents common use and the separations of the individual rare earths;(2)the recom-mendation of process for the separation of mixed rare earths with extraetant P507;(3)the evaluation of econo-my for planning to build a rare earth factory The knowledge base of this system was organized as files includingframe files and rules.In addition,removing of the rules can be carried out in the file compiling window under theLISP environment.Both the forward-chaining and the reverse chaining were used simultaneously as the infer-ence strategies.The machine used was a microcomputer IBM PC-XT.     

Separation of Scandium and Rare Earths with the Method of PSO-Extraction Chromatography

Separation of scandium and rare earths was investigated by using a new extraction chromatography whichPSO was used as a stationary phase,while HCl-NH_4SCN solution as a mobile phase.The separation conditionswere studied.In this system, the separation factor(β_(Nd)~(Sc))can reach up to 1.3×10~4.The method can be applied tothe purposes of separation,purification and analysis of microquantity of Sc in the mixed rare earth.     

Adjacent stage impurity ratio in rare earth countercurrent extraction process

Impurity components decrease stage by stage in a cascade of rare earth (RE) extraction separation, and adjacent stage impurity ratio (ASIR) which is defined as the ratio of an impurity’s contents in the aqueous/organic phase of two adjacent stages can be used to evaluate the capacity of impurity removal for the two stages. On the basis of extraction equilibrium and mass balance, the ASIR in a two-component extraction separation was deducted and its simplified expressions were given for different process sections according to reasonable assumptions. The calculation simulation was then carried out to obtain the ASIR distribution in the cascade. The results showed that in both the extraction and scrubbing sections the ASIR principally increased with the decrease of the molar proportion of the impurity but along with a flat appearing in the purification zone located in the middle of the cascade. The ASIR intuitively exhibits the running status of RE extraction separation and purification, which could provide a theoretic guide for investigating the influence factors of RE extraction separation process in practical industry.     

Solvent extraction and separation of light rare earths from chloride media using HDEHP-P350 system

Solvent extraction is the most important method for rare earth extraction and separation.Currently,di(2-ethylhexyl)phosphoric acid(HDEHP)and 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester(HEH/EHP)are widely used in industrial production,but there are still obvious deficiencies that require further research to resolve.In this paper,the unsaponification extraction of light rare earth ions in a hydrochloric acid medium by di(2-ethylhexyl)phosphoric acid-di(1-methyl-heptyl)methyl phosphonate(HDEHPP350)system was studied.The results show that the addition of P350 reduces the extraction capacity of HDEHP,and also greatly reduces the concentration of acidity required for the back-extraction.It still has a good separation factor for light rare earths without saponification,and the extractant is not easy to emulsify.With an aqueous phase of pH=2.85,and HDEHP mole fraction XHDEHP=0.9(compared with O/A=2),the separation effect of light rare earth is the best,resulting in the separation coefficientβCe/La=3.39,βPr/Ce=1.67 andβNd/Pr=1.45,respectively.The loaded light rare earth ions extracted by HDEHP-P350 can be easily stripped when 2 mol/L HCl is used as the stripping agent.Finally,the extraction mechanism is discussed using a slope method,and the final structure of the extracted complex is determined to be RECl[(DEHP)₂]₂P350_(o),based on a combination of infrared spectra and 1 H NMR and 31P NMR analyses.     

Study on separation technology of Pr and Nd in D₂EHPA-HCl-LA coordination extraction system

The separation coefficient of Nd/Pr was lower in D2EHPA-HCl system. Pointing to this problem,the effect of the acidity of feed and the concentration of lactic acid on the distribution ratio,separation coefficient and extraction capacity was investigated in unsaponified D2EHPA-HCl-LA system,and the regression equations were calculated in this paper. The results showed that the distribution ratio and separation coefficient both increased with decreasing of feed acidity and increasing of the lactic acid concentration,and the extraction capacity increased with increasing of lactic acid concentration in D2EHPA-HCl-LA system. When the pH value of the feed was 3.5 and lactic acid concentration was 0.6 mol/L,the max separation coefficient was 1.57,and the extraction capacity was 27.87 g/L.     

STUDY ON THE SEPARATION AND EXTRACTION MECHANISM OF RARE EARTH ELEMENTS BY MEANS OF REVERSED-PHASE PAPER CHROMATOGRAPHY

Reversed-phase paper chromatography technique is used for study on the extraction mechanism and sep-aration of rare earth elements.As the stationary phase,chromatographic paper strips are impregnated with asolution of monomyristyl phosphoric acid (MPA) in chloroform.Mineral acids are used as developers.The effect of concentration of acids and/or salts upon R_f has been investigated.According to the re-sults of R_f values for a given rare earth element in various acids,the order of extraction ability isHCl>HNO_3>H_2SO_4.A tetrad effect is clearly observed.for the R_f value of rare earth elements.Theeffects of other parameters on the R_f value,such as the quantities of extractant retained by the paper and thetemperature are also examined.Based on the determination of the molar ratio of MPA to rare earth elementsand the number of H~ ions released in extraction reaction,a reasonable mechanism is proposed.The mutualseparation of heavy rare earth elements will be better than that of the light rare earth group because of thelarger separation coefficient of the former.A mixture of Ho-Er-Tm-Lu is successfully separated by thepresent method.     

Study on separation of rare earth elements in complex system

The effect of the feed acidity,acetic acid concentration and rare earth concentration on the distribution ratio,separation coefficient and extraction capacity of light rare earth elements were studied in the P204(DEHPA)-HCl system and P507(HEH/EHP)-HCl system both containing acetic acid,respectively. The results showed that the distribution ratio and separation coefficient decreased with increasing of acidity,and increased with increasing of acetic acid concentration and rare earths concentration,and the extraction capacity increased with increasing of acetic acid concentration. When pH value of feed was 2.0,[RE]/[acetic acid] was 1:1 and rare earth concentration 0.35 mol/L,in P204(DEHPA) -HCl system with acetic acid,the maximum separation coefficient(β) reached to βCe /La=4.09,βPr/Ce=1.96 and βNd/Pr=1.53,and the separation ability of this extraction system was better than P507(DEHPA)-HCl system.