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
Enlarging the steric hindrance to the molecular structures of extractants is a common way to improve their selectivity.To improve the separation factor of thorium(Ⅳ)and cerium(Ⅳ),cyclic groups having large steric hi...Enlarging the steric hindrance to the molecular structures of extractants is a common way to improve their selectivity.To improve the separation factor of thorium(Ⅳ)and cerium(Ⅳ),cyclic groups having large steric hindrance such as phenyl,cyclohexyl,and benzyl were introduced into theα-aminophosphonate extractant molecules.Bis(2-ethylhexyl)((phenylamino)methyl)phosphonate(PAMP),bis(2-ethylhexyl)((cyclohexylamino)methyl)phosphonate(CAMP),and bis(2-ethylhexyl)((benzylamine)methyl)phosphate(BAMP)were synthesized and applied in the separation and recovery of thorium(Ⅳ)and cerium(Ⅳ)from sulfuric acid solution.The separation ability between cerium(Ⅳ)and thorium(Ⅳ)descends in the order of CAMP>BAMP≈Cextrant230>DEHAMP>>PAMP,which is consistent with the decreasing order of steric hindrance.Nearly non-extraction of both cerium(Ⅳ)and thorium(Ⅳ)and the lowest separation ability for PAMP will be due to the conjugation of the lone pair of the amino N atom and benzene ring in PAMP.Furthermore,the extraction of REs(Ⅲ)by CAMP is lower than that of thorium(Ⅳ).Thermodynamic parameters(ΔG^(0),ΔH^(0),ΔS^(0))and extraction equilibrium constants were determined.An extraction process was developed to separate and retrieve thorium(Ⅳ)and cerium(Ⅳ)from a bastnaesite leaching solution.The final product purity of CeO2and ThO2is 99%and 98.4%,respectively,and the yields are 90.2%and 97.6%,respectively.展开更多
Rational design of extractant structure to improve the extraction and separation capacity of rare earth elements(REEs)is a long-standing challenge.Herein,a new strategy was proposed to improve the stability of the che...Rational design of extractant structure to improve the extraction and separation capacity of rare earth elements(REEs)is a long-standing challenge.Herein,a new strategy was proposed to improve the stability of the chelating structure formed by malonamide and REEs.The stability of the chelating structure is greatly improved by using a double-ring framework structure which makes the two carbonyl groups of malonamide unable to rotate freely and both of them point to the metal ion position.Three benzyl groups were used to construct the hydrophobicity of the extractant and the organic shell of the extracted species.Tribenzylhexahydro-pyrrolo-pyridine-dione(THPPD)was designed and synthesized.The structure reduces the energy consumed by rotating carbonyl group in the coordination with metal ions and then improves the extraction ability of extractant.The crystal structure was preorganized as expected,with the two carbonyls pointing in a favorable coordination direction to the structural complement of the metal ion.The extraction behaviors of REEs with THPPD in a nitric acid medium were studied.Compared with N,N’-dibenzyl-N,N’-dimethylmalonamide(DBDM-MA)with a chain structure,the extraction capacity of THPPD is 360 times higher than that of DBDM-MA at 5.0 mol/L sodium nitrate.Furthermore,the binding energy and Gibbs free energy were investigated by density functional theory(DFT)in conjunction with the B3LYP.The theoretical results show that THPPD has more effective interaction with Pr(NO_(3))3 than DBDM-MA.The construction of chelating groups conformation is a worthy direction to improve the coordination ability and even selectivity of extractant.展开更多
In the petrochemical industry process, the relative volatility between the components to be separated is close to one or the azeotrope that systems are difficult to separate. Liquid-liquid extraction is a common and e...In the petrochemical industry process, the relative volatility between the components to be separated is close to one or the azeotrope that systems are difficult to separate. Liquid-liquid extraction is a common and effective separation method, and selecting an extraction agent is the key to extraction technology research. In this paper, a design method of extractants based on elements and chemical bonds was proposed. A knowledge-based molecular design method was adopted to pre-select elements and chemical bond groups. The molecules were automatically synthesized according to specific combination rules to avoid the problem of “combination explosion” of molecules. The target properties of the extractant were set, and the extractant meeting the requirements was selected by predicting the correlation physical properties of the generated molecules. Based on the separation performance of the extractant in liquid-liquid extraction and the relative importance of each index, the fuzzy comprehensive evaluation membership function was established, the analytic hierarchy process determined the mass ratio of each index, and the consistency test results were passed. The results of case study based on quantum chemical analysis demonstrated that effective determination of extractants for the analysis of benzene-cyclohexane systems. The results unanimously prove that the method has important theoretical significance and application value.展开更多
The extraction kinetics of Ce（Ⅳ） and Ce（Ⅳ）-F^- mixture systems from sulfuric solutions to n-heptane solution containing Bif-ILE[A336][P204]（[trialkylmethylammonium][di-2-ethylhewanxylphosphinate]） with a const...The extraction kinetics of Ce（Ⅳ） and Ce（Ⅳ）-F^- mixture systems from sulfuric solutions to n-heptane solution containing Bif-ILE[A336][P204]（[trialkylmethylammonium][di-2-ethylhewanxylphosphinate]） with a constant interfacial area cell with laminar flow were studied,just to elucidate the extraction mechanism and the mass transfer models.The data were analyzed in terms of pseudo-first-order constants.The effects of stirring speed,specific interfacial area and temperature on the extraction rate in both systems were discussed,suggesting that the extractions were mixed bulk phases-interfacial control process.Supported by the experimental data,the corresponding rate equations for Ce（Ⅳ） extraction system and Ce（Ⅳ）-F^- mixture extraction system were obtained.The experimental results indicated the rate-controlling step.The kinetics model was deduced from the rate-controlling step and consistent with the rate equation.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
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
Soil test for availability of nutrients and heavy metals is extensively served as a means for the evaluations of soil fertility, and environmental effects and phytotoxicity of pollutants in soils, and for the fertiliz...Soil test for availability of nutrients and heavy metals is extensively served as a means for the evaluations of soil fertility, and environmental effects and phytotoxicity of pollutants in soils, and for the fertilizer recommendation in agricultural and environmental sciences. Therefore, great attention has been paid to the measurement of elemental availability in soil test.展开更多
A new chelating resin （CPS-DMA-SABA） was synthesized with the chloromethylated crossqinked polystyrene porous beads （CPS） as raw materials, which were bonded with salicylidene-o-aminobenzoic acid （SABA） on the s...A new chelating resin （CPS-DMA-SABA） was synthesized with the chloromethylated crossqinked polystyrene porous beads （CPS） as raw materials, which were bonded with salicylidene-o-aminobenzoic acid （SABA） on the surface via a quaternary ammonium unit as a linker. The results showed that CPS-DMA-SABA would easily change into a zwitterionic chelating resin （CPS-DMA-SABZ） when washed with distilled water. CPS-DMA-SABA was characterized by elemental analysis, infrared spectra and thermo-gravimetric analysis. The ion sorption capacities of CPS-DMA-SABA were found to be 1916 μg/g for Zn2＋ withpH at 4.5, 1620μg/g for Cu2＋ with pH at 6.2, 1291 μg/g for Ni2＋ withpH at 6.6 and 780 μg/g for Cr3＋ withpH at 5.5, respectively. The experiments showed CPS-DMA-SABA also changed its color when meeting with the metal ion in the aqueous solution. As a consequence, CPS-DMA-SABA can not only be used as a solid phase extractant but also an indicator for confirming the heavy metal ion in solutions.展开更多
The phosphorous mixer introduced could replace D2EHPA as an extractant applied in the extraction of indium. The extraction properties of the phosphorous mixer were studied. The influences of extractant concentration, ...The phosphorous mixer introduced could replace D2EHPA as an extractant applied in the extraction of indium. The extraction properties of the phosphorous mixer were studied. The influences of extractant concentration, organic/aqueous (O/A) phase ratio, equilibrium time, and pH value of the feed solutions on the extraction of indium, and separation of indium-iron were investigated experimentally. Under the best operating conditions, more than 98% of indium. was extracted through two-stage counter-current extraction. The optimizing condition of indium extraction is determined as follows: O/A = 1 : (9-12) in volume ratio; 30% PPD in sulphonated kerosene; pH of the feed, about 0.6; equilibrium time, 3-5 min. The extractant has good reusing and anti-aging properties.展开更多
By introducing the amine group into the structure of P227,a novel extractant 2-ethylhexyl((2-ethylhexylamino)methyl)phosphonic acid(EEAMPA,abbreviated as HA)was synthesized for the extraction and separation of trivale...By introducing the amine group into the structure of P227,a novel extractant 2-ethylhexyl((2-ethylhexylamino)methyl)phosphonic acid(EEAMPA,abbreviated as HA)was synthesized for the extraction and separation of trivalent rare earths(REs)from nitrate medium.The influence factors including extractant concentration,equilibrium time,HNO_(3)concentration,separation factors,cycle regeneration,stripping acidity,and actual leach liquor of metal ions,were studied systematically.The results show that the extraction ability of EEAMPA for REs decreases with increasing acidity.A possible extraction mechanism is proposed and the extracted species as REHA_(3)(NO_(3))are confirmed by the slope analysis method.The extraction equilibrium can reach faster than P227.It shows good chemical stability and cycling regeneration.Stripping studies show that HCl is an excellent stripping agent and REs can be effectively stripped from the organic phase.展开更多
The stripping and regeneration of the loaded organic phase of phosphorousmixer extractant (PPD) were studied. The mixed solutions (3 mol/L HCl +2 mol/L ZnC1_2) were used asthe stripping agent and more than 99 percent ...The stripping and regeneration of the loaded organic phase of phosphorousmixer extractant (PPD) were studied. The mixed solutions (3 mol/L HCl +2 mol/L ZnC1_2) were used asthe stripping agent and more than 99 percent of indium can be stripped after three-stage strippingwhen the volume ratio of organic phase to stripping agent is 1:1. The organic phase can he recycledto use alter regeneration with HCl. The parallel contrast experiments with D_2EHPA (di-2-ethyl hexylphosphoric acid) were carried out under the same conditions. The results show that the mixerextractant has good reusability and the stripping and regeneration of PPD are superior to those ofD_2EHPA.展开更多
A database-based strategy of candidate generation was proposed for molecular design of new de-phenol extractants following the idea of finding new applications of existing commercial compounds. The strategy has the ad...A database-based strategy of candidate generation was proposed for molecular design of new de-phenol extractants following the idea of finding new applications of existing commercial compounds. The strategy has the advantage that the environmental, safety and health risks of candidate compounds are known and controllable. In this work, the Existing Commercial Compounds(ECC) database and special combined search strategy were developed as the base for the proposed CAMD method following such idea, and molecules for phenol extraction used in coking wastewater treatment were selected from the ECC database. The candidate solvents cover the following categories: ketones, esters, ethers, alcohols, anhydrides and benzene compounds, which are consistent with the de-phenol extractants commonly used in the industry or experiment. The compounds with higher partition coefficient and selectivity than widely used methyl isobutyl ketone(MIBK) are mainly ketones. 26 obtained molecules show higher partition coefficient and selectivity than MIBK, which are suggested to be further investigated by experiment. Furthermore, analysis of these potential molecules may present the effective functional groups as the initial group set to generate new molecular structures of de-phenol extractants. The results show that the proposed method enables us to efficiently generate chemicals with benefits of less time, less economical cost, and known environmental impact as well.展开更多
The extraction of Yb3+ by HA [1-phenyl-3-methyl-4-(α-furoyl)-5-pyrazolone] and by HA in combination with a neutral extractant B in toluene have been studied, where B represents n-butyloctyl sulfoxide (BOSO), n-pentyl...The extraction of Yb3+ by HA [1-phenyl-3-methyl-4-(α-furoyl)-5-pyrazolone] and by HA in combination with a neutral extractant B in toluene have been studied, where B represents n-butyloctyl sulfoxide (BOSO), n-pentylhexyl sulfoxide (PHSO), ethyl-n-dodecyl sulfoxide (EDSO), diphenyl sulfoxide (DPSO) or TBP. The composition of the synergistic extraction complexes have been shown to be YbA3·B and their extraction equilibrium constants have been determined separately.展开更多
The equilibria and kinetic characteristics of a micelle mixed extractant system-D<sub>2</sub> EHPA-MPA（MPA-monoalkyl phosphoric acid with long carbon chain and micellization）in extractionof the Al<sup...The equilibria and kinetic characteristics of a micelle mixed extractant system-D<sub>2</sub> EHPA-MPA（MPA-monoalkyl phosphoric acid with long carbon chain and micellization）in extractionof the Al<sup>3+</sup>ions were studied.It was found that the system has double synergistic effects on theextraction of the Al<sup>3+</sup>ions.The compositions of the synergistic complexes were determined andthe synergistic reaction equations were obtained.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 influence of different concentrations of copper solvent extractant ZJ 988 on the growth and activity of acidophilic microorganisms was studied and the microbial community structures were compared by 16S rRNA gene ...The influence of different concentrations of copper solvent extractant ZJ 988 on the growth and activity of acidophilic microorganisms was studied and the microbial community structures were compared by 16S rRNA gene clone library analysis.The total bacteria numbers are reduced when 0.5%(volume fraction) extractant is added.The proportions of Acidithiobacillus ferrooxidans and Acidiphilium organovorum are increased,whereas the proportion of Leptospirillum ferriphilum is reduced.When the concentration of extractant is elevated to 1%,growth of all bacteria is inhibited.Clone library results reveal that the dominant bacteria in the culture solution with/without the extractant are At.ferrooxidans,A.organovorum and L.ferriphilum.The sensitivity order of the three bacteria to the extractant from the most to the least is found to be L.ferriphilum>At.ferrooxidans>A.organovorum.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
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
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
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 Natural Science Foundation of China(92262301)。
文摘Enlarging the steric hindrance to the molecular structures of extractants is a common way to improve their selectivity.To improve the separation factor of thorium(Ⅳ)and cerium(Ⅳ),cyclic groups having large steric hindrance such as phenyl,cyclohexyl,and benzyl were introduced into theα-aminophosphonate extractant molecules.Bis(2-ethylhexyl)((phenylamino)methyl)phosphonate(PAMP),bis(2-ethylhexyl)((cyclohexylamino)methyl)phosphonate(CAMP),and bis(2-ethylhexyl)((benzylamine)methyl)phosphate(BAMP)were synthesized and applied in the separation and recovery of thorium(Ⅳ)and cerium(Ⅳ)from sulfuric acid solution.The separation ability between cerium(Ⅳ)and thorium(Ⅳ)descends in the order of CAMP>BAMP≈Cextrant230>DEHAMP>>PAMP,which is consistent with the decreasing order of steric hindrance.Nearly non-extraction of both cerium(Ⅳ)and thorium(Ⅳ)and the lowest separation ability for PAMP will be due to the conjugation of the lone pair of the amino N atom and benzene ring in PAMP.Furthermore,the extraction of REs(Ⅲ)by CAMP is lower than that of thorium(Ⅳ).Thermodynamic parameters(ΔG^(0),ΔH^(0),ΔS^(0))and extraction equilibrium constants were determined.An extraction process was developed to separate and retrieve thorium(Ⅳ)and cerium(Ⅳ)from a bastnaesite leaching solution.The final product purity of CeO2and ThO2is 99%and 98.4%,respectively,and the yields are 90.2%and 97.6%,respectively.
基金Project supported by the National Natural Science Foundation of China(21876062)Shandong Provincial Natural Science Foundation(ZR2022QB067)。
文摘Rational design of extractant structure to improve the extraction and separation capacity of rare earth elements(REEs)is a long-standing challenge.Herein,a new strategy was proposed to improve the stability of the chelating structure formed by malonamide and REEs.The stability of the chelating structure is greatly improved by using a double-ring framework structure which makes the two carbonyl groups of malonamide unable to rotate freely and both of them point to the metal ion position.Three benzyl groups were used to construct the hydrophobicity of the extractant and the organic shell of the extracted species.Tribenzylhexahydro-pyrrolo-pyridine-dione(THPPD)was designed and synthesized.The structure reduces the energy consumed by rotating carbonyl group in the coordination with metal ions and then improves the extraction ability of extractant.The crystal structure was preorganized as expected,with the two carbonyls pointing in a favorable coordination direction to the structural complement of the metal ion.The extraction behaviors of REEs with THPPD in a nitric acid medium were studied.Compared with N,N’-dibenzyl-N,N’-dimethylmalonamide(DBDM-MA)with a chain structure,the extraction capacity of THPPD is 360 times higher than that of DBDM-MA at 5.0 mol/L sodium nitrate.Furthermore,the binding energy and Gibbs free energy were investigated by density functional theory(DFT)in conjunction with the B3LYP.The theoretical results show that THPPD has more effective interaction with Pr(NO_(3))3 than DBDM-MA.The construction of chelating groups conformation is a worthy direction to improve the coordination ability and even selectivity of extractant.
基金supported by the National Natural Science Foundation of China(22178190).
文摘In the petrochemical industry process, the relative volatility between the components to be separated is close to one or the azeotrope that systems are difficult to separate. Liquid-liquid extraction is a common and effective separation method, and selecting an extraction agent is the key to extraction technology research. In this paper, a design method of extractants based on elements and chemical bonds was proposed. A knowledge-based molecular design method was adopted to pre-select elements and chemical bond groups. The molecules were automatically synthesized according to specific combination rules to avoid the problem of “combination explosion” of molecules. The target properties of the extractant were set, and the extractant meeting the requirements was selected by predicting the correlation physical properties of the generated molecules. Based on the separation performance of the extractant in liquid-liquid extraction and the relative importance of each index, the fuzzy comprehensive evaluation membership function was established, the analytic hierarchy process determined the mass ratio of each index, and the consistency test results were passed. The results of case study based on quantum chemical analysis demonstrated that effective determination of extractants for the analysis of benzene-cyclohexane systems. The results unanimously prove that the method has important theoretical significance and application value.
基金Project (2012CBA01202) supported by the National Basic Research Program of ChinaProject (51174184) supported by the National Natural Science Foundation of China+2 种基金Project (KGZD-EW-201-1) supported by the Key Research Program of the Chinese Academy of SciencesProject (BK2013030) supported by Science and Technology Plan of Nantong City,ChinaProject (RERU2014016) supported by Open Subject of Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,China
文摘The extraction kinetics of Ce（Ⅳ） and Ce（Ⅳ）-F^- mixture systems from sulfuric solutions to n-heptane solution containing Bif-ILE[A336][P204]（[trialkylmethylammonium][di-2-ethylhewanxylphosphinate]） with a constant interfacial area cell with laminar flow were studied,just to elucidate the extraction mechanism and the mass transfer models.The data were analyzed in terms of pseudo-first-order constants.The effects of stirring speed,specific interfacial area and temperature on the extraction rate in both systems were discussed,suggesting that the extractions were mixed bulk phases-interfacial control process.Supported by the experimental data,the corresponding rate equations for Ce（Ⅳ） extraction system and Ce（Ⅳ）-F^- mixture extraction system were obtained.The experimental results indicated the rate-controlling step.The kinetics model was deduced from the rate-controlling step and consistent with the rate equation.
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.
文摘Soil test for availability of nutrients and heavy metals is extensively served as a means for the evaluations of soil fertility, and environmental effects and phytotoxicity of pollutants in soils, and for the fertilizer recommendation in agricultural and environmental sciences. Therefore, great attention has been paid to the measurement of elemental availability in soil test.
基金supported by the National Natural Science Foundation of China(No.50873042)the Natural Science Foundation for Colleges and Universities of Jiangsu Province(No.11KJA430008)
文摘A new chelating resin （CPS-DMA-SABA） was synthesized with the chloromethylated crossqinked polystyrene porous beads （CPS） as raw materials, which were bonded with salicylidene-o-aminobenzoic acid （SABA） on the surface via a quaternary ammonium unit as a linker. The results showed that CPS-DMA-SABA would easily change into a zwitterionic chelating resin （CPS-DMA-SABZ） when washed with distilled water. CPS-DMA-SABA was characterized by elemental analysis, infrared spectra and thermo-gravimetric analysis. The ion sorption capacities of CPS-DMA-SABA were found to be 1916 μg/g for Zn2＋ withpH at 4.5, 1620μg/g for Cu2＋ with pH at 6.2, 1291 μg/g for Ni2＋ withpH at 6.6 and 780 μg/g for Cr3＋ withpH at 5.5, respectively. The experiments showed CPS-DMA-SABA also changed its color when meeting with the metal ion in the aqueous solution. As a consequence, CPS-DMA-SABA can not only be used as a solid phase extractant but also an indicator for confirming the heavy metal ion in solutions.
文摘The phosphorous mixer introduced could replace D2EHPA as an extractant applied in the extraction of indium. The extraction properties of the phosphorous mixer were studied. The influences of extractant concentration, organic/aqueous (O/A) phase ratio, equilibrium time, and pH value of the feed solutions on the extraction of indium, and separation of indium-iron were investigated experimentally. Under the best operating conditions, more than 98% of indium. was extracted through two-stage counter-current extraction. The optimizing condition of indium extraction is determined as follows: O/A = 1 : (9-12) in volume ratio; 30% PPD in sulphonated kerosene; pH of the feed, about 0.6; equilibrium time, 3-5 min. The extractant has good reusing and anti-aging properties.
基金Project supported by the National Natural Science Foundation of China(21701146)the National Science Foundation for Post-doctoral Scientists of China(2018M632798)the Open Funds of the State Key Laboratory of Rare Earth Resource(RERU2017019)。
文摘By introducing the amine group into the structure of P227,a novel extractant 2-ethylhexyl((2-ethylhexylamino)methyl)phosphonic acid(EEAMPA,abbreviated as HA)was synthesized for the extraction and separation of trivalent rare earths(REs)from nitrate medium.The influence factors including extractant concentration,equilibrium time,HNO_(3)concentration,separation factors,cycle regeneration,stripping acidity,and actual leach liquor of metal ions,were studied systematically.The results show that the extraction ability of EEAMPA for REs decreases with increasing acidity.A possible extraction mechanism is proposed and the extracted species as REHA_(3)(NO_(3))are confirmed by the slope analysis method.The extraction equilibrium can reach faster than P227.It shows good chemical stability and cycling regeneration.Stripping studies show that HCl is an excellent stripping agent and REs can be effectively stripped from the organic phase.
基金The project is financially supported by the "95" National Key Research Project (96-119-03-03-02-A)
文摘The stripping and regeneration of the loaded organic phase of phosphorousmixer extractant (PPD) were studied. The mixed solutions (3 mol/L HCl +2 mol/L ZnC1_2) were used asthe stripping agent and more than 99 percent of indium can be stripped after three-stage strippingwhen the volume ratio of organic phase to stripping agent is 1:1. The organic phase can he recycledto use alter regeneration with HCl. The parallel contrast experiments with D_2EHPA (di-2-ethyl hexylphosphoric acid) were carried out under the same conditions. The results show that the mixerextractant has good reusability and the stripping and regeneration of PPD are superior to those ofD_2EHPA.
基金Supported by the National Natural Science Foundation of China(Grant No.2156112001)National Basic Science Data Sharing Service Project(DKA2017-12-02-05)
文摘A database-based strategy of candidate generation was proposed for molecular design of new de-phenol extractants following the idea of finding new applications of existing commercial compounds. The strategy has the advantage that the environmental, safety and health risks of candidate compounds are known and controllable. In this work, the Existing Commercial Compounds(ECC) database and special combined search strategy were developed as the base for the proposed CAMD method following such idea, and molecules for phenol extraction used in coking wastewater treatment were selected from the ECC database. The candidate solvents cover the following categories: ketones, esters, ethers, alcohols, anhydrides and benzene compounds, which are consistent with the de-phenol extractants commonly used in the industry or experiment. The compounds with higher partition coefficient and selectivity than widely used methyl isobutyl ketone(MIBK) are mainly ketones. 26 obtained molecules show higher partition coefficient and selectivity than MIBK, which are suggested to be further investigated by experiment. Furthermore, analysis of these potential molecules may present the effective functional groups as the initial group set to generate new molecular structures of de-phenol extractants. The results show that the proposed method enables us to efficiently generate chemicals with benefits of less time, less economical cost, and known environmental impact as well.
文摘The extraction of Yb3+ by HA [1-phenyl-3-methyl-4-(α-furoyl)-5-pyrazolone] and by HA in combination with a neutral extractant B in toluene have been studied, where B represents n-butyloctyl sulfoxide (BOSO), n-pentylhexyl sulfoxide (PHSO), ethyl-n-dodecyl sulfoxide (EDSO), diphenyl sulfoxide (DPSO) or TBP. The composition of the synergistic extraction complexes have been shown to be YbA3·B and their extraction equilibrium constants have been determined separately.
基金Supported by the National Natural Science foundation of China
文摘The equilibria and kinetic characteristics of a micelle mixed extractant system-D<sub>2</sub> EHPA-MPA（MPA-monoalkyl phosphoric acid with long carbon chain and micellization）in extractionof the Al<sup>3+</sup>ions were studied.It was found that the system has double synergistic effects on theextraction of the Al<sup>3+</sup>ions.The compositions of the synergistic complexes were determined andthe synergistic reaction equations were obtained.
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.
基金Project(50904011) supported by the National Natural Science Foundation of China
文摘The influence of different concentrations of copper solvent extractant ZJ 988 on the growth and activity of acidophilic microorganisms was studied and the microbial community structures were compared by 16S rRNA gene clone library analysis.The total bacteria numbers are reduced when 0.5%(volume fraction) extractant is added.The proportions of Acidithiobacillus ferrooxidans and Acidiphilium organovorum are increased,whereas the proportion of Leptospirillum ferriphilum is reduced.When the concentration of extractant is elevated to 1%,growth of all bacteria is inhibited.Clone library results reveal that the dominant bacteria in the culture solution with/without the extractant are At.ferrooxidans,A.organovorum and L.ferriphilum.The sensitivity order of the three bacteria to the extractant from the most to the least is found to be L.ferriphilum>At.ferrooxidans>A.organovorum.
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.
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.
