The efficient separation of amphoteric organic compounds from dilute solutions is of great importance in the industrial field. In the present work, the reactive extractions of 4-hydroxypyridine(4-HP) with tributyl pho...The efficient separation of amphoteric organic compounds from dilute solutions is of great importance in the industrial field. In the present work, the reactive extractions of 4-hydroxypyridine(4-HP) with tributyl phosphate(TBP), di(2-ethylhexyl) phosphoric acid(D2EHPA) and TBP + D2EHPA dissolved in 1-octanol were investigated, respectively. The influences of the initial concentrations of TBP, D2EHPA and TBP + D2EHPA on distribution ratio(D) were discussed, as well as the reactive extraction mechanism were proposed. The obvious intensification effect was observed when the mixture of TBP and D2EHPA was used as extractant. The best extraction conditions were found to be of the molar ratio of D2EHPA and TBP at 2:1 and the equilibrium aqueous pH at 3.50-4.50. D values increased with the increase of the total concentration of TBP and D2EHPA in 1-octanol. Especially, the analysis on the extraction mechanisms clearly indicate(i) TBP in 1-octanol shows negligible reactive extraction toward 4-HP,(ii) D2EHPA in 1-octanol exhibits moderate extraction effect by forming 4-HP:D2EHPA(1:1) and 4-HP:2D2EHPA(1:2) type complexes, while(iii) D2EHPA in TBP/1-octanol demonstrates the maximum distribution ratio with the 4-HP:D2EHPA(1:1) type complex domination. The discussion provides new insights on the mechanism and opens a new way for the intensified extraction of amphoteric organic compounds by using the mixture of multiple extractants in the diluent.展开更多
The extraction of Nd^3＋ and Sm^3＋, including the extraction and stripping capability as well as the separation effect of Nd^3＋ or Sm^3＋, from a sulfuric acid medium, by mixtures of di-（2-ethylhexyl） phosphoric a...The extraction of Nd^3＋ and Sm^3＋, including the extraction and stripping capability as well as the separation effect of Nd^3＋ or Sm^3＋, from a sulfuric acid medium, by mixtures of di-（2-ethylhexyl） phosphoric acid （HDEHP, H2A2（0）） and 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester （HEH/EHP, H2L2（0）） were studied. The distribution ratios and synergistic coefficients of Nd^3＋ and Sm^3＋ in different acidities were also determined. A synergistic extractive effect was found when HDEHP and HEH/EHP were used as mixed extractants for Sm^3＋ or Nd^3＋. The chemical compositions of the extracted complex were determined as Nd.（HA2）2-HL2 and Sm.（HA2）2-HL2. The extraction equilibrium constants, enthalpy change, and entropy change of the extraction reaction were also determined.展开更多
The adsorption of rare earths,lanthanum,cerium,neodymium,and yttri um by di(2-ethylhexyl) phosphoric acid(D2EHPA) resin in the presence of a compl exing agent,EDTA,was investigated. Flow injection was selected as the ...The adsorption of rare earths,lanthanum,cerium,neodymium,and yttri um by di(2-ethylhexyl) phosphoric acid(D2EHPA) resin in the presence of a compl exing agent,EDTA,was investigated. Flow injection was selected as the injectin g method. Various parameters,sample pH,sample loading time,sample flow rate,EDTA concentration,EDTA flow rate,eluent concentration,and eluent flow rate,were studied and optimized. Under the optimum conditions,the method allowed the determination of rare earths with detection limits of 1.09 μg/L(lanthanum),3 .31 μg/L(cerium),2.05 μg/L(neodymium),and 1.25 μg/L(yttrium) . High repea tabilities were obtained for all the four rare earths(RSD【5%) . The proposed met hod was applied to the determination of the rare earths in water samples with a recovery range of 95.8%-103.3%.展开更多
In this work, a novel room temperature ionic liquid (2-butyl-imidazolium di-(2-ethylhexyl) phosphate) ([C4mim] [D2EHPA]) was synthesized and tested as extractant in the mercury(II) liquid-liquid extraction. The effect...In this work, a novel room temperature ionic liquid (2-butyl-imidazolium di-(2-ethylhexyl) phosphate) ([C4mim] [D2EHPA]) was synthesized and tested as extractant in the mercury(II) liquid-liquid extraction. The effects of parameters such as aqueous to organic phase’s volume ratio, metal concentration IL concentration, pH levels, ionic strength, and temperature were reported. For the extraction of metal, [C4mim]3[R.HR]3[HgCl2]org and [C4mim]3[R.HR]3 [HgClOH]org species were formed where (H2R2) was D2EHPA. In the case of ionic strength, the results showed that the addition of sodium acetate at 0.302 mmol·L?1 to the aqueous phase strongly increased the mercury extraction yield (R = 100%). The extracted species were investigated by a calculation program using CHEAQS V. L20.1 inorder to determine the relation between the percentages of the extracted species and the extraction yield. The results showed that the extracted species in the best conditions were HgCl2 and HgClOH with respective percentages 80.66% and 18.29%.展开更多
The transport of Tb（III） in dispersion supported liquid membrane（DSLM） with polyvinylidene fluoride membrane（PVDF） as the support and dispersion solution including HCl solution as the stripping solution and di（...The transport of Tb（III） in dispersion supported liquid membrane（DSLM） with polyvinylidene fluoride membrane（PVDF） as the support and dispersion solution including HCl solution as the stripping solution and di（2-ethylhexyl） phosphoric acid（D2EHPA） dissolved in kerosene as the membrane solution, has been studied. The effects of pH value, initial concentration of Tb（III） and different ionic strength in the feed phase, volume ratio of membrane solution to stripping solution, concentration of HCl solution, concentration of carrier, different stripping agents in the dispersion phase on the transport of Tb（III） have also been investigated, respectively. As a result, the optimum transport conditions of Tb（III） were obtained, i.e., the concentration of HCl solution was 4.0 mol/L, the concentration of D2EHPA was 0.16 mol/L, the volume ratio of membrane solution to stripping solution was 30：30 in the dispersion phase and pH value was 4.5 in the feed phase. Ionic strength had no obvious effect on the transport of Tb（III）. Under the optimum conditions, the transport percentage of Tb（III） was up to 96.1% in a transport time of 35 min when the initial concentration of Tb（IIl） was 1.0× 10 -4 mol/L. The diffusion coefficient of Tb（III） in the membrane and the thickness of diffusion layer between feed phase and membrane phase were obtained and the values were 1.82×10 -8 m2/s and 5.61 um, respectively. The calculated results were in good agreement with the literature data.展开更多
Different separation techniques such as solvent extraction, ion exchange, and precipitation are often used for recovery of rare earth elements (REEs) from pregnant leach solutions obtained from acid leaching. Solvent ...Different separation techniques such as solvent extraction, ion exchange, and precipitation are often used for recovery of rare earth elements (REEs) from pregnant leach solutions obtained from acid leaching. Solvent extraction is generally accepted as the most appropriate commercial technology for separating REEs due to the need to be able to handle larger volumes of diluted pregnant solutions. This study focused on the development of selective separation of light and heavy REEs from the pregnant leach solution obtained from leaching of apatite ore in 1 M sulfuric acid (H2SO4) using solvent extraction. Three different commercial organophosphorus extractants (di-(2-ethylhexyl) phosphoric acid (D2EHPA), 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (PC88A) and tributyl phosphate (TBP)), and the influences of experimental parameters such as extractant concentration, organic/aqueous phase ratio, diluent type, pH, extraction time and stripping agent concentration were examined. Results showed that light REEs (LREEs) and heavy REEs (HREEs) in the pregnant leach solution were selectively separated with D2EHPA via a two-stage extraction process. In the first-stage of solvent extraction, >90% of (0.05 g/L) HREEs was extracted with 1.8 M D2EHPA in kerosene while the vast majority (>95%) of LREEs was remained in raffinate. In the second-stage, >93% (1.01 g/L) of LREEs was extracted from the raffinate with 1.8 M D2EHPA dissolved in kerosene at pH 1.6. HREEs (>95%) and LREEs (>90%) loaded with D2EHPA after the first and second-stage of extraction were stripped by 4 M H2SO4 and 1 M H2SO4 solutions, respectively. Distribution of middle rare earth elements (MREEs) was discussed through the extraction processes in this study.展开更多
The dimeric property of bis(2 - ethylhexyl) phosphoric acid(HDEHP) in different diluents has been studied. The experimental results show that the dimeric degree of HDEHP increases with the decrease of the polarity of ...The dimeric property of bis(2 - ethylhexyl) phosphoric acid(HDEHP) in different diluents has been studied. The experimental results show that the dimeric degree of HDEHP increases with the decrease of the polarity of diluents.This kind of effect has been discussed from the point of view of intermolecular interactions between the extractant molecules and the diluent ones. The dimeric constantswere related to the physical constants and experiencial parameters of the diluents.The following expression hasbeen obtained lg K2 =6 .4 5 9- 4 .4 6 4 (ε- 1) /(2 ε+ 1) - 1.96 5 (n D2 - 1) /(n D2 +1) - 3.199α- 5 .6 6β.展开更多
The extraction of zinc from zinc sulfate solution was investigated, using 20% saponified D2EHPA as an extractam and 260^# sulfonate kerosene as a diluent. The solution was stirred for 8 min at phase ratio （Vσ/Va） o...The extraction of zinc from zinc sulfate solution was investigated, using 20% saponified D2EHPA as an extractam and 260^# sulfonate kerosene as a diluent. The solution was stirred for 8 min at phase ratio （Vσ/Va） of 1.0：1.0, initial pH of 2.0 and stirring speed of 200 r/min. The results show that 75% zinc can be extracted from the zinc sulfate solution when the concentration of zinc is 18.7 g/L after being settled for 10 min. 88.60% zinc can be stripped by 196 g/L sulfuric acid, and zinc ion can be separated from ferric ion.展开更多
The extraction ability of organophosphorus extractant D2EHPA(di-2-ethylhexyl phosphoric acid) and hydroximic extractant Lix984N are investigated by the extraction equilibrium experiments.Effects of carrier concen-trat...The extraction ability of organophosphorus extractant D2EHPA(di-2-ethylhexyl phosphoric acid) and hydroximic extractant Lix984N are investigated by the extraction equilibrium experiments.Effects of carrier concen-tration and organic/aqueous volume ratio on the mass transfer of hollow fiber renewal liquid membrane(HFRLM) are studied.Results show that,in the extracting process,kerosene and n-heptane are more suitable than methyl-isobutyl ketone,butylacetate and benzene as the diluents of D2EHPA or Lix984N.The favorable feed pH is 4.4 for D2EHPA and 2.6 for Lix984N.The mass transfer flux of HFRLM increases with carrier concentration and finally reaches a plateau.The mass transfer flux and the overall transfer coefficient increase with the organic/aqueous volume ratio,reach the maximum and then decrease.展开更多
The separation of Sm（III） through stripping dispersion hollow fiber liquid membrane system （SDHFLM） containing feed phase adding acetate buffer solution and dispersion solution with HC1 solution as the stripping s...The separation of Sm（III） through stripping dispersion hollow fiber liquid membrane system （SDHFLM） containing feed phase adding acetate buffer solution and dispersion solution with HC1 solution as the stripping solution and membrane solution of di（2-ethylhexyl） phosphoric acid （p204） dissolved in kerosene, has been studied. A set of factors were studied, including pH value, initial concentration of Sm（III） and different ionic strength of feed phase, volume ratio of membrane solution and stripping solution （O/W）, HC1 concentration, carrier concentration, different stripping agents of dispersion phase on Sm（III） separation. Experimental results indicate that the optimum separa- tion conditions of Sm（III） were obtained as that HC1 concentration was 4.00 tool/L, p204 concentration was 0.150 mol/L, and volume ratio of membrane solution and stripping solution （O/W） was 1.00 in the dispersion phase, and pH value was 4.60 in the feed phase. Ionic strength had no obvious effect on separation of Sm（III）. When initial Sm（III） concentration was 1.00 × 10^-4 mol/L, the separation rate of Sm（III） was up to 93.5% in 85 min. The kinetic equation was developed in terms of the law of mass diffusion and the theory of interface chemistry. The modeled results were in good agreement with the experiment data.展开更多
Separation of rare earths was investigated by extraction chromatography where H(DEHP)was used as a stationary phase,while HCl and H_2SO_4 solutions as a mobile phase.The average separation fac- tors of rare earths,β_...Separation of rare earths was investigated by extraction chromatography where H(DEHP)was used as a stationary phase,while HCl and H_2SO_4 solutions as a mobile phase.The average separation fac- tors of rare earths,β_(HCl) and β_(H_2SO_4),are 3.79 and 4.57.respectively.The β_(La)^(Ce) in HCl and H_2SO_4 systems are as high as 28.5 and 26.3,respectively.The elution acidity in the study can be down to one tenth and one four- teenth of that in HEH(EHP)system.展开更多
基金supported by the Science and Technology Research Project of Henan Province (192102310490 and 212102310505)。
文摘The efficient separation of amphoteric organic compounds from dilute solutions is of great importance in the industrial field. In the present work, the reactive extractions of 4-hydroxypyridine(4-HP) with tributyl phosphate(TBP), di(2-ethylhexyl) phosphoric acid(D2EHPA) and TBP + D2EHPA dissolved in 1-octanol were investigated, respectively. The influences of the initial concentrations of TBP, D2EHPA and TBP + D2EHPA on distribution ratio(D) were discussed, as well as the reactive extraction mechanism were proposed. The obvious intensification effect was observed when the mixture of TBP and D2EHPA was used as extractant. The best extraction conditions were found to be of the molar ratio of D2EHPA and TBP at 2:1 and the equilibrium aqueous pH at 3.50-4.50. D values increased with the increase of the total concentration of TBP and D2EHPA in 1-octanol. Especially, the analysis on the extraction mechanisms clearly indicate(i) TBP in 1-octanol shows negligible reactive extraction toward 4-HP,(ii) D2EHPA in 1-octanol exhibits moderate extraction effect by forming 4-HP:D2EHPA(1:1) and 4-HP:2D2EHPA(1:2) type complexes, while(iii) D2EHPA in TBP/1-octanol demonstrates the maximum distribution ratio with the 4-HP:D2EHPA(1:1) type complex domination. The discussion provides new insights on the mechanism and opens a new way for the intensified extraction of amphoteric organic compounds by using the mixture of multiple extractants in the diluent.
基金the National Natural Science Foundation of China (50674016)the National High Technology Research and Develop-ment Program of China (863 Program) ( 2006AA06Z123)
文摘The extraction of Nd^3＋ and Sm^3＋, including the extraction and stripping capability as well as the separation effect of Nd^3＋ or Sm^3＋, from a sulfuric acid medium, by mixtures of di-（2-ethylhexyl） phosphoric acid （HDEHP, H2A2（0）） and 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester （HEH/EHP, H2L2（0）） were studied. The distribution ratios and synergistic coefficients of Nd^3＋ and Sm^3＋ in different acidities were also determined. A synergistic extractive effect was found when HDEHP and HEH/EHP were used as mixed extractants for Sm^3＋ or Nd^3＋. The chemical compositions of the extracted complex were determined as Nd.（HA2）2-HL2 and Sm.（HA2）2-HL2. The extraction equilibrium constants, enthalpy change, and entropy change of the extraction reaction were also determined.
基金Project supported by State Key Laboratory of Rare Earth Resource Utilization,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences
文摘The adsorption of rare earths,lanthanum,cerium,neodymium,and yttri um by di(2-ethylhexyl) phosphoric acid(D2EHPA) resin in the presence of a compl exing agent,EDTA,was investigated. Flow injection was selected as the injectin g method. Various parameters,sample pH,sample loading time,sample flow rate,EDTA concentration,EDTA flow rate,eluent concentration,and eluent flow rate,were studied and optimized. Under the optimum conditions,the method allowed the determination of rare earths with detection limits of 1.09 μg/L(lanthanum),3 .31 μg/L(cerium),2.05 μg/L(neodymium),and 1.25 μg/L(yttrium) . High repea tabilities were obtained for all the four rare earths(RSD【5%) . The proposed met hod was applied to the determination of the rare earths in water samples with a recovery range of 95.8%-103.3%.
文摘In this work, a novel room temperature ionic liquid (2-butyl-imidazolium di-(2-ethylhexyl) phosphate) ([C4mim] [D2EHPA]) was synthesized and tested as extractant in the mercury(II) liquid-liquid extraction. The effects of parameters such as aqueous to organic phase’s volume ratio, metal concentration IL concentration, pH levels, ionic strength, and temperature were reported. For the extraction of metal, [C4mim]3[R.HR]3[HgCl2]org and [C4mim]3[R.HR]3 [HgClOH]org species were formed where (H2R2) was D2EHPA. In the case of ionic strength, the results showed that the addition of sodium acetate at 0.302 mmol·L?1 to the aqueous phase strongly increased the mercury extraction yield (R = 100%). The extracted species were investigated by a calculation program using CHEAQS V. L20.1 inorder to determine the relation between the percentages of the extracted species and the extraction yield. The results showed that the extracted species in the best conditions were HgCl2 and HgClOH with respective percentages 80.66% and 18.29%.
基金Supported by the National Natural Science Foundation of China(No90401009)the Natural Science Foundation of Shaanxi Province, China(NoSJ08B16)+1 种基金the Science Research Program of Education Department of Shaanxi Province, China (No06JK215)the Research Fund for Excellent Doctoral Thesis of Xi'an University of Technology, China (No602-210805)
文摘The transport of Tb（III） in dispersion supported liquid membrane（DSLM） with polyvinylidene fluoride membrane（PVDF） as the support and dispersion solution including HCl solution as the stripping solution and di（2-ethylhexyl） phosphoric acid（D2EHPA） dissolved in kerosene as the membrane solution, has been studied. The effects of pH value, initial concentration of Tb（III） and different ionic strength in the feed phase, volume ratio of membrane solution to stripping solution, concentration of HCl solution, concentration of carrier, different stripping agents in the dispersion phase on the transport of Tb（III） have also been investigated, respectively. As a result, the optimum transport conditions of Tb（III） were obtained, i.e., the concentration of HCl solution was 4.0 mol/L, the concentration of D2EHPA was 0.16 mol/L, the volume ratio of membrane solution to stripping solution was 30：30 in the dispersion phase and pH value was 4.5 in the feed phase. Ionic strength had no obvious effect on the transport of Tb（III）. Under the optimum conditions, the transport percentage of Tb（III） was up to 96.1% in a transport time of 35 min when the initial concentration of Tb（IIl） was 1.0× 10 -4 mol/L. The diffusion coefficient of Tb（III） in the membrane and the thickness of diffusion layer between feed phase and membrane phase were obtained and the values were 1.82×10 -8 m2/s and 5.61 um, respectively. The calculated results were in good agreement with the literature data.
文摘Different separation techniques such as solvent extraction, ion exchange, and precipitation are often used for recovery of rare earth elements (REEs) from pregnant leach solutions obtained from acid leaching. Solvent extraction is generally accepted as the most appropriate commercial technology for separating REEs due to the need to be able to handle larger volumes of diluted pregnant solutions. This study focused on the development of selective separation of light and heavy REEs from the pregnant leach solution obtained from leaching of apatite ore in 1 M sulfuric acid (H2SO4) using solvent extraction. Three different commercial organophosphorus extractants (di-(2-ethylhexyl) phosphoric acid (D2EHPA), 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (PC88A) and tributyl phosphate (TBP)), and the influences of experimental parameters such as extractant concentration, organic/aqueous phase ratio, diluent type, pH, extraction time and stripping agent concentration were examined. Results showed that light REEs (LREEs) and heavy REEs (HREEs) in the pregnant leach solution were selectively separated with D2EHPA via a two-stage extraction process. In the first-stage of solvent extraction, >90% of (0.05 g/L) HREEs was extracted with 1.8 M D2EHPA in kerosene while the vast majority (>95%) of LREEs was remained in raffinate. In the second-stage, >93% (1.01 g/L) of LREEs was extracted from the raffinate with 1.8 M D2EHPA dissolved in kerosene at pH 1.6. HREEs (>95%) and LREEs (>90%) loaded with D2EHPA after the first and second-stage of extraction were stripped by 4 M H2SO4 and 1 M H2SO4 solutions, respectively. Distribution of middle rare earth elements (MREEs) was discussed through the extraction processes in this study.
文摘The dimeric property of bis(2 - ethylhexyl) phosphoric acid(HDEHP) in different diluents has been studied. The experimental results show that the dimeric degree of HDEHP increases with the decrease of the polarity of diluents.This kind of effect has been discussed from the point of view of intermolecular interactions between the extractant molecules and the diluent ones. The dimeric constantswere related to the physical constants and experiencial parameters of the diluents.The following expression hasbeen obtained lg K2 =6 .4 5 9- 4 .4 6 4 (ε- 1) /(2 ε+ 1) - 1.96 5 (n D2 - 1) /(n D2 +1) - 3.199α- 5 .6 6β.
基金Project(50774094) supported by the National Natural Science Foundation of China
文摘The extraction of zinc from zinc sulfate solution was investigated, using 20% saponified D2EHPA as an extractam and 260^# sulfonate kerosene as a diluent. The solution was stirred for 8 min at phase ratio （Vσ/Va） of 1.0：1.0, initial pH of 2.0 and stirring speed of 200 r/min. The results show that 75% zinc can be extracted from the zinc sulfate solution when the concentration of zinc is 18.7 g/L after being settled for 10 min. 88.60% zinc can be stripped by 196 g/L sulfuric acid, and zinc ion can be separated from ferric ion.
基金Supported by the Program for New Century Excellent Talents in University（NCET-05-0122） the National Natural Science Foundation of China（20576008 20706003）
文摘The extraction ability of organophosphorus extractant D2EHPA(di-2-ethylhexyl phosphoric acid) and hydroximic extractant Lix984N are investigated by the extraction equilibrium experiments.Effects of carrier concen-tration and organic/aqueous volume ratio on the mass transfer of hollow fiber renewal liquid membrane(HFRLM) are studied.Results show that,in the extracting process,kerosene and n-heptane are more suitable than methyl-isobutyl ketone,butylacetate and benzene as the diluents of D2EHPA or Lix984N.The favorable feed pH is 4.4 for D2EHPA and 2.6 for Lix984N.The mass transfer flux of HFRLM increases with carrier concentration and finally reaches a plateau.The mass transfer flux and the overall transfer coefficient increase with the organic/aqueous volume ratio,reach the maximum and then decrease.
基金Project supported by the National Natural Science Foundation of China （or Young Scientists （Nos. 41001131 and 51009126）, the Action Plan for the Development of Western China of the Chinese Academy of Sciences （No. KZCX2-XB2-13）, the Knowledge Innovation Program of the Chinese Academy of Sciences （No. KSCX2-YW-N-003） and Research Fund for Excellent Doctoral Thesis of Xi＇an University of Technology （Nos. 602-210805 and 602-210804）.
文摘The separation of Sm（III） through stripping dispersion hollow fiber liquid membrane system （SDHFLM） containing feed phase adding acetate buffer solution and dispersion solution with HC1 solution as the stripping solution and membrane solution of di（2-ethylhexyl） phosphoric acid （p204） dissolved in kerosene, has been studied. A set of factors were studied, including pH value, initial concentration of Sm（III） and different ionic strength of feed phase, volume ratio of membrane solution and stripping solution （O/W）, HC1 concentration, carrier concentration, different stripping agents of dispersion phase on Sm（III） separation. Experimental results indicate that the optimum separa- tion conditions of Sm（III） were obtained as that HC1 concentration was 4.00 tool/L, p204 concentration was 0.150 mol/L, and volume ratio of membrane solution and stripping solution （O/W） was 1.00 in the dispersion phase, and pH value was 4.60 in the feed phase. Ionic strength had no obvious effect on separation of Sm（III）. When initial Sm（III） concentration was 1.00 × 10^-4 mol/L, the separation rate of Sm（III） was up to 93.5% in 85 min. The kinetic equation was developed in terms of the law of mass diffusion and the theory of interface chemistry. The modeled results were in good agreement with the experiment data.
文摘Separation of rare earths was investigated by extraction chromatography where H(DEHP)was used as a stationary phase,while HCl and H_2SO_4 solutions as a mobile phase.The average separation fac- tors of rare earths,β_(HCl) and β_(H_2SO_4),are 3.79 and 4.57.respectively.The β_(La)^(Ce) in HCl and H_2SO_4 systems are as high as 28.5 and 26.3,respectively.The elution acidity in the study can be down to one tenth and one four- teenth of that in HEH(EHP)system.
