Solvent extraction is the main method used to separate and purify rare earth elements.In the process of rare earths extraction,emulsification often generated due to the instability of the aqueous and organic phases or...Solvent extraction is the main method used to separate and purify rare earth elements.In the process of rare earths extraction,emulsification often generated due to the instability of the aqueous and organic phases or improper operating conditions.Once emulsification occurs,it would not only lead to low rare earths recovery efficiency,small product quantities,high production costs and the losing of extractant and rare earth resources,but also result in serious environmental pollution.Therefore,it is very important to study the micro-mechanisms of emulsification and establish new methods to prevent emulsification at the source.In this paper,possible factors resulting in emulsification,such as the compositions and properties of the organic and aqueous phases,the operating conditions of the rare earths extraction are reviewed.The micro-mechanisms of emulsification are summarized basing on the microscopic structures in the bulk phase,aggregations of the extractants at the organic-aqueous interface,spectral characterizations and computational simulations.On this basis,new formation mechanisms are proposed for emulsification.Preliminary explorations are employed to verify the correctness of these new viewpoints.Finally,future directions for studies of the emulsification micro-mechanism are proposed.This study provides a theoretical basis for further understanding the micro-mechanisms of interfacial instability resulting in emulsification in the process of rare earths extraction.展开更多
This paper reviews the development course of separating rare earths with acid phosphorus extractants,including extraction chemistry(thermodynamics and kinetics), separation process and industrial application, the loss...This paper reviews the development course of separating rare earths with acid phosphorus extractants,including extraction chemistry(thermodynamics and kinetics), separation process and industrial application, the loss/degradation of extractants, etc.展开更多
Modifiers have a broad array of influences on extraction with liquids in standard state, supercritical fluid extraction (SFE), trapping by SFE and supercritical fluid chromatography (SFC). They can significantly chang...Modifiers have a broad array of influences on extraction with liquids in standard state, supercritical fluid extraction (SFE), trapping by SFE and supercritical fluid chromatography (SFC). They can significantly change the qualitative and quantitative results. Quantitative and qualitative results can be influenced by different extractants and modifiers in different ways as it was shown by Brondz et al. at 2007 in “The real nature of the indole alkaloids in Cortinarius infractus: Evaluation of artifact formation through solvent extraction method development”, J. Chromatography A, 1148, 1-7. The choice of correct extractant, modifier, and trapper to the bulk mobile phase for supercritical fluids (SFs) or for liquids in subcritical or in the liquids in standard state is a challenge in any extraction procedure. This is the second paper in a sequence that describes the influence of extractants and modifiers on the performance of SFs and results of extraction with liquids in standard state and SFE. Here, attention is given to possible mistakes in qualitative and quantitative results by poor understanding of the influence of extractants, modifiers, and trappers on extraction and trapping process by a careless choice of extractant, modifier, and trapper for extraction with liquids in standard state and SFE. The SF chosen for discussion in the paper is CO2. However, similar effects can be observed with use of other SFs and fluids in subcritical and standard states. In this paper, the discussion of lipids, fatty and carboxylic acids have been chosen as target analytes for extraction, trapping and analysis. Some examples from extraction with liquids in the standard state and trapping in the supercritical state (collection) have been furnished with the wrong extractant, modifier, or trapper which is presented for illustration of inappropriate choice of extractants, modifiers, and trappers.展开更多
The efficiency of EDTA, HNO3 and CaCl2 as extractants to remove Pb, Zn and Cu from tailing soils without varying soil pH was investigated with distributions of Pb, Zn and Cu being determined before and after extractio...The efficiency of EDTA, HNO3 and CaCl2 as extractants to remove Pb, Zn and Cu from tailing soils without varying soil pH was investigated with distributions of Pb, Zn and Cu being determined before and after extraction using the sequential extraction procedure of the optimized European Community Bureau of Reference (BCR). Results indicated that EDTA and HNO3 were both effective extracting agents.The extractability of extractants for Pb and Zn was in the order EDTA > HNO3 > CaCl2, while for Cu it was HNO3 > EDTA > CaCl2. After EDTA extraction, the proportion of Pb, Zn and Cu in the four fractions varied greatly, which was related to the strong extraction and complexation ability. Before and after extraction with HNO3 and CaCl2, the percentages of Pb, Zn and Cu in the reducible, oxidizable and residual fractions changed little compared to the acid-extractable fraction. The lability of metal in the soil and the kinds of extractants were the factors controlling the effects of metal extraction.展开更多
To get high purity caprolactam is a challenging task in the chemical fiber industry. To date, reports on the prediction of the distribution of caprolactam and its derivative chemicals have been few. In this study, the...To get high purity caprolactam is a challenging task in the chemical fiber industry. To date, reports on the prediction of the distribution of caprolactam and its derivative chemicals have been few. In this study, the extraction of caprolactam with toluene as the extractant and N-methyl caprolactam with benzene and toluene as theextractants has been camed out. By defining new UNIFAC groups and calibrating related interaction parameters, aUNIFAC method was introduced to predict the equilibrium concentration of caprolactam and methyl caprolactam intoluene or benzene extraction processes. The calculated results fit very well With the experimental data. Using theUNIFAC model, the selectivity of extractants can be predicted.展开更多
N,N-dibutyldiglycol amic acid （HL1） and N,N-dioctyldiglycol nmic acid （HLu） were synthesized and characterized by conventional spectroscopic methods. These molecules were examined as extractants for extraction-sep...N,N-dibutyldiglycol amic acid （HL1） and N,N-dioctyldiglycol nmic acid （HLu） were synthesized and characterized by conventional spectroscopic methods. These molecules were examined as extractants for extraction-separation of La（Ⅲ）, Eu（Ⅲ） and Er（Ⅲ）, as representative ions of light, middle and heavy rare earths, from aqueous chloride solutions. The analysis of the extraction equilibria revealed that the extracted species of lanthanum and europium ions by both of the extractants had a 1：3 metal to ligand ratio It was suggested that erbium ions were extracted into the organic phase via the formation ofEr（LIor Ⅱ）2Cl complexes. The effect of the organic diluents on the extraction-separation efficiency of the studied rare earths by HLI and HLⅡ was investigated by comparing the results obtained in dichloromethane and carbon tetrachloride. Regardless to the diluent used, the order of selectivity presented by the investigated extractants was Er（Ⅲ）〉Eu（Ⅲ）〉La（Ⅲ）. It is noteworthy that, a significant enhancement in separation of the studied rare earths by the extractants was achieved in their competitive extraction experiments with respect to that obtained in single component extraction experiments. Applicability of the extractants for the removal of rare earth ions from spent Ni-MH batteries was tested by removal ofLa（Ⅲ）, Eu（Ⅲ） and Er（Ⅲ） ions from simulated leach solution of such batteries.展开更多
Some key factors on the heavy metals removal efficiencies were studied when soil washing technology was used in the remediation of soils contaminated by multiple heavy metals. The results show that the dissolubilities...Some key factors on the heavy metals removal efficiencies were studied when soil washing technology was used in the remediation of soils contaminated by multiple heavy metals. The results show that the dissolubilities of Cu and Zn are promoted by humic acids, but Pb and Cd are inhibited by humic acids; heavy metals in the clay are more difficult to be extracted than silt; the strong acidic soils can cause the protonation of EDTA and weaken its extracting ability; EDTA is effective for extracting Pb and Cd, while oxalate (OX) is effective for extracting Cu and Zn; and biosurfactant can be used as additive to improve the removal of some particular heavy metals.展开更多
Direct extraction of molybdenum from sulfate solution with synergistic extractants(mixture of D2EHPA and TBP)was studied in the rotation column.The influence of extractant concentration and initial pH of aqueous phase...Direct extraction of molybdenum from sulfate solution with synergistic extractants(mixture of D2EHPA and TBP)was studied in the rotation column.The influence of extractant concentration and initial pH of aqueous phase was studied in the bench scale experiments.The outcomes demonstrated that the synergistic solvent extraction enhances the constancy of the extracted complexes for transfer into the organic phase.In the continuous experiments,the effect of different operating parameters such as speed of agitation,inlet solvent flow rate and inlet aqueous flow rate on the holdup,mean drop size,drop size distribution,slip and characteristic velocities and extraction percentage were examined.Modified correlations were proposed for prediction of hydrodynamic parameters with consideration of reaction extraction condition in the rotation column.Furthermore,these correlations were compared with the experimental data.According to the results,the direct extraction of Mo(Ⅵ)from aqueous solution and sulfuric media with extraction efficiency of 90.4%was obtained at higher rotor speed(240 r·min–1 rpm)in this column.展开更多
Developing the novel ionic liquids as the potential substitutes for conventional organic solvents in extraction of the rare-earth metals is highly desirable but challenges still remain.In this study,the welldesigned c...Developing the novel ionic liquids as the potential substitutes for conventional organic solvents in extraction of the rare-earth metals is highly desirable but challenges still remain.In this study,the welldesigned carboxylic acid functionalized phosphonium based ionic liquids,(4-carboxyl)butyl-trioctylphosphonium chloride/nitrate,were synthesized and characterized.The as-prepared samples were tested as the undiluted hydrophobic acidic extractant for rare-earth metal ions,affording the maximal loading of 3 mol/mol towards Nd(Ⅲ)in aqueous solution and the remarkable stripping performance.The results also reveal their excellent extractability and selectivity for Sc(Ⅲ)in the mixtures of six rare-earth ions,as well as the outstanding separation properties between rare-earth and first row transition-metal ions(i.e.,La/Ni,Sm/Co).Moreover,the extraction mechanism indicates that the extracted rare-earth complex via a proton exchange in the ionic liquid phase is structurally similar to the complexes obtained with neutral extractants.This work presents a prototype for the fabrication of the hydrophobic cation-functionalized ionic liquids for highly efficient rare-earth extraction and provides the future application in recycling of rare-earth metals from the spent magnets.展开更多
Synergistic extraction has been proven to enhance extractability and selectivity for the separation of cadmium and zinc from magnesium and calcium in the sulfuric acid medium with Mextral V10 and Mextral 622H(aromatic...Synergistic extraction has been proven to enhance extractability and selectivity for the separation of cadmium and zinc from magnesium and calcium in the sulfuric acid medium with Mextral V10 and Mextral 622H(aromatic hydroxamic)mixtures diluted in DT100.Mixtures of Mextral V10 and 622H are highly selective for Zn and Cd over Mg and Ca compared with the single Mextral V10,resulting in larger synergistic shifts for zinc and cadmium with theΔpH_(50(Zn–Ca))values increasing substantially from0.83 to 1.73 pH units andΔpH_(50(Cd–Ca))values increasing from 0.63 to 2.13 p H units.The aqueous to organic ratio(A/O ratio),the saponification ratio of Mextral V10 and extracting agent concentration were studied on the effect of metal ions extraction,which helped to increase the organic capacity of metal extraction.The Mc Cabe-Thiele plot for Cd and Zn extraction with 5%(volume fraction)Mextral V10 and 5%Mextral 622H extractants mixture indicate the necessity of only one theoretical stages at an A/O ratio of 1.5:1.One stage extraction simulation test conducted at pH 6.50 shows that Cd and Zn reach the extraction of 99.6%and 97.9%,respectively,and only low levels of magnesium and calcium are extracted in the organic phase.The extracted Zn^(2+)or Cd^(2+)-organic species are Zn(A_1)(A_2)or Cd(A_1)(A_2)with the mixture system by slope analysis.展开更多
This paper deals with the enantioseparation of phenylsuccinic acid(H2A)enantiomers by liquid-liquid reactive extraction usingβ-CD derivatives as aqueous selectors.Cyclodextrin and its derivatives can interact with gu...This paper deals with the enantioseparation of phenylsuccinic acid(H2A)enantiomers by liquid-liquid reactive extraction usingβ-CD derivatives as aqueous selectors.Cyclodextrin and its derivatives can interact with vip molecules selectively to form complexes with different stabilities.Cyclodextrin derivatives are not soluble in organic liquids,but highly soluble in water.In this work,hydroxypropyl-β-cyclodextrin(HP-β-CD),hydroxyethyl- β-cyclodextrin(HE-β-CD)and methyl-β-cyclodextrin(Me-β-CD)were selected as chiral selectors in aqueous phase for the reactive extraction of phenylsuccinic acid enantiomers from organic phase to aqueous phase.The results show that the efficiency of the extraction depends,often strongly,on a number of process variables,including the types of organic solvents andβ-CD derivatives,the concentrations of the extractants and H2A enantiomers,pH and temperature.HP-β-CD,HE-β-CD and Me-β-CD have stronger recognition abilities for R-phenylsuccinic acid than for S-phenylsuccinic acid.Among the three kinds ofβ-CD derivatives,HP-β-CD has the strongest separation ability. Excellent enantioseparation was achieved under the optimal conditions of pH of 2.5 and temperature of 5°C with a maximum enantioselectivity(a)of 2.38.Reactive extraction of enantiomers with hydrophilicβ-CD derivatives is of strong chiral separation ability and can be hopeful for separations of various enantiomers at a large-scale.展开更多
This paper compares the efficiency of D2EHPA and Cyanex 272 to extract the divalent manganese cation from an actual leaching solution obtained by reductive leaching of a low-grade pyrolusite ore, using SO2 gas. The st...This paper compares the efficiency of D2EHPA and Cyanex 272 to extract the divalent manganese cation from an actual leaching solution obtained by reductive leaching of a low-grade pyrolusite ore, using SO2 gas. The studied variables were the extractant concentration in the organic phase, the pH of the leached liquor and the volume ratio between organic phase and leached liquor. It was observed that D2EHPA is a better extractant than Cyanex272. Therefore, with the best experimental conditions found, both extractants reach a manganese recovery around 95% with five extraction stages conducted under the following conditions: 25?C, O/A = 2, 10% volume of extractant concentration in the organic phase, pH of the leached liquor before the mixing between 8 and 8.5, and one minute of mixing time for each extraction stage.展开更多
This paper describes the study of the extraction of Zr and Hf in nitric and hydrochloric media by solvent extraction technique using different types of extractants. The effect of the extractants DEHPA, IONQUEST?801 an...This paper describes the study of the extraction of Zr and Hf in nitric and hydrochloric media by solvent extraction technique using different types of extractants. The effect of the extractants DEHPA, IONQUEST?801 and CYANEX?272, TBP, CYANEX?923, PRIMENE?JTM, ALAMINE?336 and ALIQUAT?336 was investigated. For acid extractants in both nitric and hydrochloric media, a high degree of extraction was observed, although they had low selectivity in separating the metals. For the acid extractants also, it was not possible to strip the metals from the organic phase through acid solutions. In this case, a stripping solution with very high acidity would be required, and this is not viable. When the basic extractants were used, no metal extraction was observed under the conditions investigated, indicating no extractable anionic species in either media. The optimum zirconium/hafnium separation was achieved using an acidity of 7.0 mol?L?1, nitrate concentration of 9.2 mol?L?1 and 1.5 mol?L?1 of TBP. In these conditions, a separation factor of 12.6 was obtained.展开更多
A comprehensive<em> in vitro</em> study on single and sequential extraction methods for Cu exraction by different extractants of distinct chemical nature from some peat soils of Bangladesh was conducted to...A comprehensive<em> in vitro</em> study on single and sequential extraction methods for Cu exraction by different extractants of distinct chemical nature from some peat soils of Bangladesh was conducted to assess the pattern of metal-extractability in drying and wetting sequences. Samples were collected from peat basins of two different districts of Bangladesh (Gopalgonj and Bagerhat) and an incubation study was designed and conducted in which soils were incubated to three alternate drying and wetting cycles for 21 days. Single and sequentially extracted Cu ions in all three cycles and by all three selective extractants were compared. Maximum amount of Cu was extracted in drying days and 1M HCl extracted the largest proportion of Cu from all the soils in each incubation time. Conversely, 1M NH<sub>4</sub>Cl was the least effective extractant for extracting Cu by both single and sequential process in either day of incubation. Considerable amount of Cu was extracted by 0.005 M DTPA in dry periods. In general, single extraction was found to be more effective in extracting Cu in the alternate drying and wetting cycles from the peat soil samples except for 1M HCl in initial drying days.展开更多
Solvent extraction of base metals using bis((1-decylbenzimidazol-2-yl)methyl)amine (BDNNN) showed a lack of pH-metric separation of the metals. The extraction system was described quantitatively using the equilibria i...Solvent extraction of base metals using bis((1-decylbenzimidazol-2-yl)methyl)amine (BDNNN) showed a lack of pH-metric separation of the metals. The extraction system was described quantitatively using the equilibria involved to derive the mathematical explanation for the two linear log D vs pHe plots for each metal ion extraction curve, and coordination numbers could also be extracted from the two slopes. The lack of separation was attributed to the absence of stereochemical “tailor making” since the complexes isolated from the reaction of the ligand, bis((1H-benzimidazol- 2-yl)methyl)amine (NNN), with base metals suggested the formation of similar octahedral complex species from spectral and crystal structure evidence. The bis tridentate coordination observed was in agreement with information extracted from the extraction data. This investigation opens up an opportunity and an approach for the evaluation of amines as extractants but cautions against tridentate ligands.展开更多
The correlation relationships of apparent extraction equilibrium constant (1gK(ex)) with the electronic effect parameter( Sigma sigma(Phi)) and the steric effect parameter ( Sigma upsilon ) of the substituents in extr...The correlation relationships of apparent extraction equilibrium constant (1gK(ex)) with the electronic effect parameter( Sigma sigma(Phi)) and the steric effect parameter ( Sigma upsilon ) of the substituents in extractant molecules are investigated by linear regression analysis in the extraction of rare earths by various classes and structures of monoacidic organophosphorus extractants. The results indicate that in Linear free energy relationship formula 1gK(ex) = rho Sigma sigma(Phi) + psi Sigma upsilon + h generally follows for this kind of extraction systems. Accordingly, the quantitative structure-behaviour relationships of extractants are discussed. These relationships can be preliminarily applied to predict the 1gK(ex) values of rare earth extraction with definite structures of this class of extractants, and thus can provide some directions for the design of new RE extractants.展开更多
The variety of newly synthesized diamides of dipicolinic acid(DPA)bearing methyl-and oxymethyl substituents in various positions of phenyl ring was investigated as potential ligands for liquid-liquid extraction of rar...The variety of newly synthesized diamides of dipicolinic acid(DPA)bearing methyl-and oxymethyl substituents in various positions of phenyl ring was investigated as potential ligands for liquid-liquid extraction of rare earth metal ions and as membrane active compounds in plasticized polymeric membranes of potentiometric sensors.It is found that scandium is extracted with 2,6-pyridinedicarboxylic acid diamides similarly to heavy lanthanides,while yttrium is extracted together with light group lanthanides.DPA shows high selectivity for the separation of cadmium/zinc,lead/nickel or copper/nickel pairs.The four out of six studied ligands demonstrate significant potentiometric sensitivity towards scandium,yttrium and lanthanides in 10^(-7)-10^(-3)mol/L concentration range in nitric acid solutions.The trends in sensitivity values vary depending on a ligand structure and the highest values are observed for Sc^(3+)and heavy lanthanides.According to the evaluated selectivity Sm^(3+)is the most preferred ion,while La^(3+)is the most discriminated.The differences in sensor behavior in rare earth metal solutions assume that such devices can be applied in sensor arrays for potentiometric analysis of lanthanide mixtures.展开更多
Seventy organic compounds including various organophosphorus esters, amines and oxygen-based ligands were investigated as extractants. The experiment results show that amines are excellent extractants for W and Mo. Th...Seventy organic compounds including various organophosphorus esters, amines and oxygen-based ligands were investigated as extractants. The experiment results show that amines are excellent extractants for W and Mo. Their sequence of extraction ability for W is as follows: quarternary amine > tertiary amine > secondary amine > primary amine. Acidic organophosphorus extractants do not extract W, but can extract Mo with high extraction ability from the acidic solution. These extractants could provide a potential process for separating W from Mo.展开更多
Four monoalkyl esters of isoalkylphosphonic acids have been studied for the chromatographic separation of rare earths (RE).The relationship between distribution ratios and acid concentration of the eluants for samariu...Four monoalkyl esters of isoalkylphosphonic acids have been studied for the chromatographic separation of rare earths (RE).The relationship between distribution ratios and acid concentration of the eluants for samarium and ytterbium has been explored.The characteristics of these extractants loaded onto macroreticular poly (methyl methacrylate) resin beads for the separation of lanthanum,cerium,praseodymium and neodymium have been compared.Among the extractants studied,mono(1-methylheptyl) ester of isooctylphosphonic acid was found to be the best for RE separation.The acidity for separation is lower than any known P-containing extractants for the same purpose.For instance,with 1.73 mol·L^(-1) nitric acid as eluent,thulium,ytterbium and lutetium can be separated quantitatively.The extractant-loaded resins possess high column efficiency with good kinetic characteristics.The extraction mechanism was also explored.展开更多
Molecular mechanics, molecular dynamics and semi empirical quantum chemical method have been used to study the geometric and electronic structures of six phosphonate ester as rare earth extractants. The results show ...Molecular mechanics, molecular dynamics and semi empirical quantum chemical method have been used to study the geometric and electronic structures of six phosphonate ester as rare earth extractants. The results show that the phosphorus atom exhibits sp 3 hybridization. The structures of the extractants are determined by the repulsion of the hydrocarbon groups. In the extractants that have two 2 ethyl hexyl groups, one 2 ethyl hexyl extends straight, and the other extends twistily. When the number of oxygen atom decreases, the negative charge of the phosphoryl oxygen atom increases, but the negative charge of oxygen atom and the positive charge of hydrogen of the hydroxyl group decreases, and the energies of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital(LUMO) increase. The energies of the occupied frontier orbitals are close to each other.展开更多
基金Project supported by the National Natural Science Foundation of China(52074031)the Key Research and Development Program of Shandong Province(ZR2021MB051,ZR2020ME256)the Open Project of Key Laboratory of Green Chemical Engineering Process of Ministry of Education(GCP202117)。
文摘Solvent extraction is the main method used to separate and purify rare earth elements.In the process of rare earths extraction,emulsification often generated due to the instability of the aqueous and organic phases or improper operating conditions.Once emulsification occurs,it would not only lead to low rare earths recovery efficiency,small product quantities,high production costs and the losing of extractant and rare earth resources,but also result in serious environmental pollution.Therefore,it is very important to study the micro-mechanisms of emulsification and establish new methods to prevent emulsification at the source.In this paper,possible factors resulting in emulsification,such as the compositions and properties of the organic and aqueous phases,the operating conditions of the rare earths extraction are reviewed.The micro-mechanisms of emulsification are summarized basing on the microscopic structures in the bulk phase,aggregations of the extractants at the organic-aqueous interface,spectral characterizations and computational simulations.On this basis,new formation mechanisms are proposed for emulsification.Preliminary explorations are employed to verify the correctness of these new viewpoints.Finally,future directions for studies of the emulsification micro-mechanism are proposed.This study provides a theoretical basis for further understanding the micro-mechanisms of interfacial instability resulting in emulsification in the process of rare earths extraction.
基金Project supported by the National Basic Research Program of China(973 Program,2006CB403302)
文摘This paper reviews the development course of separating rare earths with acid phosphorus extractants,including extraction chemistry(thermodynamics and kinetics), separation process and industrial application, the loss/degradation of extractants, etc.
文摘Modifiers have a broad array of influences on extraction with liquids in standard state, supercritical fluid extraction (SFE), trapping by SFE and supercritical fluid chromatography (SFC). They can significantly change the qualitative and quantitative results. Quantitative and qualitative results can be influenced by different extractants and modifiers in different ways as it was shown by Brondz et al. at 2007 in “The real nature of the indole alkaloids in Cortinarius infractus: Evaluation of artifact formation through solvent extraction method development”, J. Chromatography A, 1148, 1-7. The choice of correct extractant, modifier, and trapper to the bulk mobile phase for supercritical fluids (SFs) or for liquids in subcritical or in the liquids in standard state is a challenge in any extraction procedure. This is the second paper in a sequence that describes the influence of extractants and modifiers on the performance of SFs and results of extraction with liquids in standard state and SFE. Here, attention is given to possible mistakes in qualitative and quantitative results by poor understanding of the influence of extractants, modifiers, and trappers on extraction and trapping process by a careless choice of extractant, modifier, and trapper for extraction with liquids in standard state and SFE. The SF chosen for discussion in the paper is CO2. However, similar effects can be observed with use of other SFs and fluids in subcritical and standard states. In this paper, the discussion of lipids, fatty and carboxylic acids have been chosen as target analytes for extraction, trapping and analysis. Some examples from extraction with liquids in the standard state and trapping in the supercritical state (collection) have been furnished with the wrong extractant, modifier, or trapper which is presented for illustration of inappropriate choice of extractants, modifiers, and trappers.
基金Project supported by the National High Technology Research and Development Program (863 Program) of China(No. 2001AA644020)the Natural Science Foundation of Hunan Province (No. 04JJ3013)
文摘The efficiency of EDTA, HNO3 and CaCl2 as extractants to remove Pb, Zn and Cu from tailing soils without varying soil pH was investigated with distributions of Pb, Zn and Cu being determined before and after extraction using the sequential extraction procedure of the optimized European Community Bureau of Reference (BCR). Results indicated that EDTA and HNO3 were both effective extracting agents.The extractability of extractants for Pb and Zn was in the order EDTA > HNO3 > CaCl2, while for Cu it was HNO3 > EDTA > CaCl2. After EDTA extraction, the proportion of Pb, Zn and Cu in the four fractions varied greatly, which was related to the strong extraction and complexation ability. Before and after extraction with HNO3 and CaCl2, the percentages of Pb, Zn and Cu in the reducible, oxidizable and residual fractions changed little compared to the acid-extractable fraction. The lability of metal in the soil and the kinds of extractants were the factors controlling the effects of metal extraction.
基金Supported by the National Natural Science Foundation of China （No.20490200, No.20525622）.
文摘To get high purity caprolactam is a challenging task in the chemical fiber industry. To date, reports on the prediction of the distribution of caprolactam and its derivative chemicals have been few. In this study, the extraction of caprolactam with toluene as the extractant and N-methyl caprolactam with benzene and toluene as theextractants has been camed out. By defining new UNIFAC groups and calibrating related interaction parameters, aUNIFAC method was introduced to predict the equilibrium concentration of caprolactam and methyl caprolactam intoluene or benzene extraction processes. The calculated results fit very well With the experimental data. Using theUNIFAC model, the selectivity of extractants can be predicted.
文摘N,N-dibutyldiglycol amic acid （HL1） and N,N-dioctyldiglycol nmic acid （HLu） were synthesized and characterized by conventional spectroscopic methods. These molecules were examined as extractants for extraction-separation of La（Ⅲ）, Eu（Ⅲ） and Er（Ⅲ）, as representative ions of light, middle and heavy rare earths, from aqueous chloride solutions. The analysis of the extraction equilibria revealed that the extracted species of lanthanum and europium ions by both of the extractants had a 1：3 metal to ligand ratio It was suggested that erbium ions were extracted into the organic phase via the formation ofEr（LIor Ⅱ）2Cl complexes. The effect of the organic diluents on the extraction-separation efficiency of the studied rare earths by HLI and HLⅡ was investigated by comparing the results obtained in dichloromethane and carbon tetrachloride. Regardless to the diluent used, the order of selectivity presented by the investigated extractants was Er（Ⅲ）〉Eu（Ⅲ）〉La（Ⅲ）. It is noteworthy that, a significant enhancement in separation of the studied rare earths by the extractants was achieved in their competitive extraction experiments with respect to that obtained in single component extraction experiments. Applicability of the extractants for the removal of rare earth ions from spent Ni-MH batteries was tested by removal ofLa（Ⅲ）, Eu（Ⅲ） and Er（Ⅲ） ions from simulated leach solution of such batteries.
基金Project(20050532009) supported by the Doctoral Foundation of Ministry of Education of ChinaProjects(2006BAD03A1704, 2006BAD03A1706) supported by the National 11th-Five Technology Supporting Project
文摘Some key factors on the heavy metals removal efficiencies were studied when soil washing technology was used in the remediation of soils contaminated by multiple heavy metals. The results show that the dissolubilities of Cu and Zn are promoted by humic acids, but Pb and Cd are inhibited by humic acids; heavy metals in the clay are more difficult to be extracted than silt; the strong acidic soils can cause the protonation of EDTA and weaken its extracting ability; EDTA is effective for extracting Pb and Cd, while oxalate (OX) is effective for extracting Cu and Zn; and biosurfactant can be used as additive to improve the removal of some particular heavy metals.
文摘Direct extraction of molybdenum from sulfate solution with synergistic extractants(mixture of D2EHPA and TBP)was studied in the rotation column.The influence of extractant concentration and initial pH of aqueous phase was studied in the bench scale experiments.The outcomes demonstrated that the synergistic solvent extraction enhances the constancy of the extracted complexes for transfer into the organic phase.In the continuous experiments,the effect of different operating parameters such as speed of agitation,inlet solvent flow rate and inlet aqueous flow rate on the holdup,mean drop size,drop size distribution,slip and characteristic velocities and extraction percentage were examined.Modified correlations were proposed for prediction of hydrodynamic parameters with consideration of reaction extraction condition in the rotation column.Furthermore,these correlations were compared with the experimental data.According to the results,the direct extraction of Mo(Ⅵ)from aqueous solution and sulfuric media with extraction efficiency of 90.4%was obtained at higher rotor speed(240 r·min–1 rpm)in this column.
基金Project supported by the National Natural Science Foundation of China(51804223)。
文摘Developing the novel ionic liquids as the potential substitutes for conventional organic solvents in extraction of the rare-earth metals is highly desirable but challenges still remain.In this study,the welldesigned carboxylic acid functionalized phosphonium based ionic liquids,(4-carboxyl)butyl-trioctylphosphonium chloride/nitrate,were synthesized and characterized.The as-prepared samples were tested as the undiluted hydrophobic acidic extractant for rare-earth metal ions,affording the maximal loading of 3 mol/mol towards Nd(Ⅲ)in aqueous solution and the remarkable stripping performance.The results also reveal their excellent extractability and selectivity for Sc(Ⅲ)in the mixtures of six rare-earth ions,as well as the outstanding separation properties between rare-earth and first row transition-metal ions(i.e.,La/Ni,Sm/Co).Moreover,the extraction mechanism indicates that the extracted rare-earth complex via a proton exchange in the ionic liquid phase is structurally similar to the complexes obtained with neutral extractants.This work presents a prototype for the fabrication of the hydrophobic cation-functionalized ionic liquids for highly efficient rare-earth extraction and provides the future application in recycling of rare-earth metals from the spent magnets.
基金Projects(20151BBG70009,20151BBE50115)supported by Jiangxi Science and Technology Projects,ChinaProjects(2014-YYB-06,2014-YYB-11)supported by Scientific Research and Development Project of Jiangxi Academy of Sciences,China
文摘Synergistic extraction has been proven to enhance extractability and selectivity for the separation of cadmium and zinc from magnesium and calcium in the sulfuric acid medium with Mextral V10 and Mextral 622H(aromatic hydroxamic)mixtures diluted in DT100.Mixtures of Mextral V10 and 622H are highly selective for Zn and Cd over Mg and Ca compared with the single Mextral V10,resulting in larger synergistic shifts for zinc and cadmium with theΔpH_(50(Zn–Ca))values increasing substantially from0.83 to 1.73 pH units andΔpH_(50(Cd–Ca))values increasing from 0.63 to 2.13 p H units.The aqueous to organic ratio(A/O ratio),the saponification ratio of Mextral V10 and extracting agent concentration were studied on the effect of metal ions extraction,which helped to increase the organic capacity of metal extraction.The Mc Cabe-Thiele plot for Cd and Zn extraction with 5%(volume fraction)Mextral V10 and 5%Mextral 622H extractants mixture indicate the necessity of only one theoretical stages at an A/O ratio of 1.5:1.One stage extraction simulation test conducted at pH 6.50 shows that Cd and Zn reach the extraction of 99.6%and 97.9%,respectively,and only low levels of magnesium and calcium are extracted in the organic phase.The extracted Zn^(2+)or Cd^(2+)-organic species are Zn(A_1)(A_2)or Cd(A_1)(A_2)with the mixture system by slope analysis.
基金Supported by the National Natural Science Foundation of China(20976041)the Program for New Century Excellent Talents in University,the Natural Science Foundation of Hunan Province(10JJ1004)the Open Fund Project of Key Laboratory in Hunan University(09K095)
文摘This paper deals with the enantioseparation of phenylsuccinic acid(H2A)enantiomers by liquid-liquid reactive extraction usingβ-CD derivatives as aqueous selectors.Cyclodextrin and its derivatives can interact with vip molecules selectively to form complexes with different stabilities.Cyclodextrin derivatives are not soluble in organic liquids,but highly soluble in water.In this work,hydroxypropyl-β-cyclodextrin(HP-β-CD),hydroxyethyl- β-cyclodextrin(HE-β-CD)and methyl-β-cyclodextrin(Me-β-CD)were selected as chiral selectors in aqueous phase for the reactive extraction of phenylsuccinic acid enantiomers from organic phase to aqueous phase.The results show that the efficiency of the extraction depends,often strongly,on a number of process variables,including the types of organic solvents andβ-CD derivatives,the concentrations of the extractants and H2A enantiomers,pH and temperature.HP-β-CD,HE-β-CD and Me-β-CD have stronger recognition abilities for R-phenylsuccinic acid than for S-phenylsuccinic acid.Among the three kinds ofβ-CD derivatives,HP-β-CD has the strongest separation ability. Excellent enantioseparation was achieved under the optimal conditions of pH of 2.5 and temperature of 5°C with a maximum enantioselectivity(a)of 2.38.Reactive extraction of enantiomers with hydrophilicβ-CD derivatives is of strong chiral separation ability and can be hopeful for separations of various enantiomers at a large-scale.
文摘This paper compares the efficiency of D2EHPA and Cyanex 272 to extract the divalent manganese cation from an actual leaching solution obtained by reductive leaching of a low-grade pyrolusite ore, using SO2 gas. The studied variables were the extractant concentration in the organic phase, the pH of the leached liquor and the volume ratio between organic phase and leached liquor. It was observed that D2EHPA is a better extractant than Cyanex272. Therefore, with the best experimental conditions found, both extractants reach a manganese recovery around 95% with five extraction stages conducted under the following conditions: 25?C, O/A = 2, 10% volume of extractant concentration in the organic phase, pH of the leached liquor before the mixing between 8 and 8.5, and one minute of mixing time for each extraction stage.
文摘This paper describes the study of the extraction of Zr and Hf in nitric and hydrochloric media by solvent extraction technique using different types of extractants. The effect of the extractants DEHPA, IONQUEST?801 and CYANEX?272, TBP, CYANEX?923, PRIMENE?JTM, ALAMINE?336 and ALIQUAT?336 was investigated. For acid extractants in both nitric and hydrochloric media, a high degree of extraction was observed, although they had low selectivity in separating the metals. For the acid extractants also, it was not possible to strip the metals from the organic phase through acid solutions. In this case, a stripping solution with very high acidity would be required, and this is not viable. When the basic extractants were used, no metal extraction was observed under the conditions investigated, indicating no extractable anionic species in either media. The optimum zirconium/hafnium separation was achieved using an acidity of 7.0 mol?L?1, nitrate concentration of 9.2 mol?L?1 and 1.5 mol?L?1 of TBP. In these conditions, a separation factor of 12.6 was obtained.
文摘A comprehensive<em> in vitro</em> study on single and sequential extraction methods for Cu exraction by different extractants of distinct chemical nature from some peat soils of Bangladesh was conducted to assess the pattern of metal-extractability in drying and wetting sequences. Samples were collected from peat basins of two different districts of Bangladesh (Gopalgonj and Bagerhat) and an incubation study was designed and conducted in which soils were incubated to three alternate drying and wetting cycles for 21 days. Single and sequentially extracted Cu ions in all three cycles and by all three selective extractants were compared. Maximum amount of Cu was extracted in drying days and 1M HCl extracted the largest proportion of Cu from all the soils in each incubation time. Conversely, 1M NH<sub>4</sub>Cl was the least effective extractant for extracting Cu by both single and sequential process in either day of incubation. Considerable amount of Cu was extracted by 0.005 M DTPA in dry periods. In general, single extraction was found to be more effective in extracting Cu in the alternate drying and wetting cycles from the peat soil samples except for 1M HCl in initial drying days.
文摘Solvent extraction of base metals using bis((1-decylbenzimidazol-2-yl)methyl)amine (BDNNN) showed a lack of pH-metric separation of the metals. The extraction system was described quantitatively using the equilibria involved to derive the mathematical explanation for the two linear log D vs pHe plots for each metal ion extraction curve, and coordination numbers could also be extracted from the two slopes. The lack of separation was attributed to the absence of stereochemical “tailor making” since the complexes isolated from the reaction of the ligand, bis((1H-benzimidazol- 2-yl)methyl)amine (NNN), with base metals suggested the formation of similar octahedral complex species from spectral and crystal structure evidence. The bis tridentate coordination observed was in agreement with information extracted from the extraction data. This investigation opens up an opportunity and an approach for the evaluation of amines as extractants but cautions against tridentate ligands.
文摘The correlation relationships of apparent extraction equilibrium constant (1gK(ex)) with the electronic effect parameter( Sigma sigma(Phi)) and the steric effect parameter ( Sigma upsilon ) of the substituents in extractant molecules are investigated by linear regression analysis in the extraction of rare earths by various classes and structures of monoacidic organophosphorus extractants. The results indicate that in Linear free energy relationship formula 1gK(ex) = rho Sigma sigma(Phi) + psi Sigma upsilon + h generally follows for this kind of extraction systems. Accordingly, the quantitative structure-behaviour relationships of extractants are discussed. These relationships can be preliminarily applied to predict the 1gK(ex) values of rare earth extraction with definite structures of this class of extractants, and thus can provide some directions for the design of new RE extractants.
文摘The variety of newly synthesized diamides of dipicolinic acid(DPA)bearing methyl-and oxymethyl substituents in various positions of phenyl ring was investigated as potential ligands for liquid-liquid extraction of rare earth metal ions and as membrane active compounds in plasticized polymeric membranes of potentiometric sensors.It is found that scandium is extracted with 2,6-pyridinedicarboxylic acid diamides similarly to heavy lanthanides,while yttrium is extracted together with light group lanthanides.DPA shows high selectivity for the separation of cadmium/zinc,lead/nickel or copper/nickel pairs.The four out of six studied ligands demonstrate significant potentiometric sensitivity towards scandium,yttrium and lanthanides in 10^(-7)-10^(-3)mol/L concentration range in nitric acid solutions.The trends in sensitivity values vary depending on a ligand structure and the highest values are observed for Sc^(3+)and heavy lanthanides.According to the evaluated selectivity Sm^(3+)is the most preferred ion,while La^(3+)is the most discriminated.The differences in sensor behavior in rare earth metal solutions assume that such devices can be applied in sensor arrays for potentiometric analysis of lanthanide mixtures.
文摘Seventy organic compounds including various organophosphorus esters, amines and oxygen-based ligands were investigated as extractants. The experiment results show that amines are excellent extractants for W and Mo. Their sequence of extraction ability for W is as follows: quarternary amine > tertiary amine > secondary amine > primary amine. Acidic organophosphorus extractants do not extract W, but can extract Mo with high extraction ability from the acidic solution. These extractants could provide a potential process for separating W from Mo.
基金The project supported by the National Natural Science Foundation of China
文摘Four monoalkyl esters of isoalkylphosphonic acids have been studied for the chromatographic separation of rare earths (RE).The relationship between distribution ratios and acid concentration of the eluants for samarium and ytterbium has been explored.The characteristics of these extractants loaded onto macroreticular poly (methyl methacrylate) resin beads for the separation of lanthanum,cerium,praseodymium and neodymium have been compared.Among the extractants studied,mono(1-methylheptyl) ester of isooctylphosphonic acid was found to be the best for RE separation.The acidity for separation is lower than any known P-containing extractants for the same purpose.For instance,with 1.73 mol·L^(-1) nitric acid as eluent,thulium,ytterbium and lutetium can be separated quantitatively.The extractant-loaded resins possess high column efficiency with good kinetic characteristics.The extraction mechanism was also explored.
文摘Molecular mechanics, molecular dynamics and semi empirical quantum chemical method have been used to study the geometric and electronic structures of six phosphonate ester as rare earth extractants. The results show that the phosphorus atom exhibits sp 3 hybridization. The structures of the extractants are determined by the repulsion of the hydrocarbon groups. In the extractants that have two 2 ethyl hexyl groups, one 2 ethyl hexyl extends straight, and the other extends twistily. When the number of oxygen atom decreases, the negative charge of the phosphoryl oxygen atom increases, but the negative charge of oxygen atom and the positive charge of hydrogen of the hydroxyl group decreases, and the energies of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital(LUMO) increase. The energies of the occupied frontier orbitals are close to each other.
