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
Two reagents including salicylhydroxamic acid(SHA) and tributyl phosphate(TBP) were tested as collectors either separately or together for electro-flotation of fine cassiterite(<10 μm).Subsequently,the flotation m...Two reagents including salicylhydroxamic acid(SHA) and tributyl phosphate(TBP) were tested as collectors either separately or together for electro-flotation of fine cassiterite(<10 μm).Subsequently,the flotation mechanism of the fine cassiterite was investigated by adsorbance determination,electrophoretic mobility measurements and Fourier transform infra-red(FT-IR) spectrum checking.Results of the flotation experiments show that with SHA as a collector,the collecting performance is remarkably impacted by the pulp pH value as the floatability of cassiterite varies sharply when the pH changes,and flotation with SHA gives distinct maximum at about pH 6.5.Additionally,the floatability of cassiterite is determined by using SHA and TBP as collectors.The range of pulp pH for good floatability is broadened in the presence of TBP as auxiliary collector,and the utilization of TBP improves the recovery of cassiterite modestly.Moreover,the optimum pH value for cassiterite flotation is associated with adsorbance.The results of FT-IR spectrum and the electrophoretic mobility measurements indicate that the adsorption interaction between the collectors and the cassiterite is dominantly a kind of chemical bonding in the form of one or two cycle chelate rings due to the coordination of carbonyl group,hydroxamate and P=O group to the metal tin atoms,where the oxygen atoms contained in carbonyl group,hydroxamate and P=O group of the polar groups have the stereo conditions to form five-membered rings.In addition,the adsorption interactions of SHA and TBP on the surfaces of cassiterite are also dominated by means of hydrogen bonds.展开更多
Tributyl phosphate(TBP) was employed for the Bi(Ⅲ) extraction from hydrochloric acid medium.The effects of extraction time and material concentration were examined.The replacement mechanism between the anion(Cl^-) an...Tributyl phosphate(TBP) was employed for the Bi(Ⅲ) extraction from hydrochloric acid medium.The effects of extraction time and material concentration were examined.The replacement mechanism between the anion(Cl^-) and TBP was proposed for extraction.The results show the species extracted into the organic phase were found to be mainly BiCl_3·x TBP(x=2 or 3).Thermodynamic parameters of the extraction reaction were obtained from the thermodynamics analysis,which illustrates that higher temperatures show a negative effect on the extraction.Extraction isotherm was obtained with 2.16 mol/L TBP for a typical solution containing 0.1 mol/L of bismuth and 1.0 mol/L of hydrochloric acid.About 98.5 % of bismuth has been extracted from the leaching solution under the optimum condition.Moreover,oxalate was explored as a precipitation stripping agent for BiCl_3·x TBP(x=2 or 3) complexes,by which Bi(Ⅲ) was stripped in the form of Bi_2(C_2O_4)_3·7H_2O.A stripping efficiency of 99.3% was obtained in only one stage at the phase ratio of 1 and TBP also could be recycled.Therefore,the method is an efficient,effective and highly selective approach to extract Bi(Ⅲ) and to recover metal bismuth.展开更多
Lithium(Li)is an important energy metal in the 21st century.However,the selective recovery of Li is still a big challenge,especially from acidic solutions with multiple metal ions existence.Herein we report a new ion ...Lithium(Li)is an important energy metal in the 21st century.However,the selective recovery of Li is still a big challenge,especially from acidic solutions with multiple metal ions existence.Herein we report a new ion pair induced mechanism for selectively extracting Li^(+)from acidic chloride solutions by tributyl phosphate(TBP).It is shown that the acidity and the chloride ions in the aqueous phase have great effects on the extraction of Li^(+).The FT-IR,UV-Vis and ESI-MS experiments provide solid evidence for the formation of ion-pair complex[Li(TBP)_n(H_(2)O)_(m)]^(+)[FeCl_(4)]^(-)(n-1,2,3;m-0,1)in the organic phase,which brings about the effective and efficient extraction of Li^(+).This mechanism can overcome the Hofmeister bias and allow for the selective extraction of Li^(+) from the extremely hydrophilic chlorides.It has also been proved that the loaded Li in TBP can be effectively stripped by concentrated HCl solution with a Li/Fe separation factor>500.The understanding of the ion-pair transport mechanism is helpful for optimizing the recovery process or further advancing more efficient recovery techniques for Li from acidic liquor.展开更多
First,the hierarchical ZSM-5 zeolite was prepared by hydrothermal method using mesoporous template cetyltrimethylammonium bromide(CTAB).The physical and chemical properties of the hierarchical ZSM-5 zeolite were chara...First,the hierarchical ZSM-5 zeolite was prepared by hydrothermal method using mesoporous template cetyltrimethylammonium bromide(CTAB).The physical and chemical properties of the hierarchical ZSM-5 zeolite were characterized by X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FT-IR)and N2 adsorption-desorption and Scanning electron microscope(SEM).Then,the as-prepared hierarchical ZSM-5 zeolite and ion exchange resin were used as catalysts to evaluate the reaction performance of the synthesis of tributyl citrate.Compared with the ion exchange resin,the as-prepared ZSM-5 has a microporous and mesoporous composite structure and a large specific surface area,so that significantly improving the catalytic performance of synthesizing tributyl citrate and increasing the esterification rate of the reaction 8.7%.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Project(50774094) supported by the National Natural Science Foundation of ChinaProject(2010CB630905) supported by the National Basic Research Program of China
文摘Two reagents including salicylhydroxamic acid(SHA) and tributyl phosphate(TBP) were tested as collectors either separately or together for electro-flotation of fine cassiterite(<10 μm).Subsequently,the flotation mechanism of the fine cassiterite was investigated by adsorbance determination,electrophoretic mobility measurements and Fourier transform infra-red(FT-IR) spectrum checking.Results of the flotation experiments show that with SHA as a collector,the collecting performance is remarkably impacted by the pulp pH value as the floatability of cassiterite varies sharply when the pH changes,and flotation with SHA gives distinct maximum at about pH 6.5.Additionally,the floatability of cassiterite is determined by using SHA and TBP as collectors.The range of pulp pH for good floatability is broadened in the presence of TBP as auxiliary collector,and the utilization of TBP improves the recovery of cassiterite modestly.Moreover,the optimum pH value for cassiterite flotation is associated with adsorbance.The results of FT-IR spectrum and the electrophoretic mobility measurements indicate that the adsorption interaction between the collectors and the cassiterite is dominantly a kind of chemical bonding in the form of one or two cycle chelate rings due to the coordination of carbonyl group,hydroxamate and P=O group to the metal tin atoms,where the oxygen atoms contained in carbonyl group,hydroxamate and P=O group of the polar groups have the stereo conditions to form five-membered rings.In addition,the adsorption interactions of SHA and TBP on the surfaces of cassiterite are also dominated by means of hydrogen bonds.
基金Project(2011AA061002)supported by the High-Tech Research and Development Program of ChinaProject(2010SK2010)supported by the Key Program of Science and Technology of Hunan Province,ChinaProject supported by the Hunan Nonferrous Metals Fund,China
文摘Tributyl phosphate(TBP) was employed for the Bi(Ⅲ) extraction from hydrochloric acid medium.The effects of extraction time and material concentration were examined.The replacement mechanism between the anion(Cl^-) and TBP was proposed for extraction.The results show the species extracted into the organic phase were found to be mainly BiCl_3·x TBP(x=2 or 3).Thermodynamic parameters of the extraction reaction were obtained from the thermodynamics analysis,which illustrates that higher temperatures show a negative effect on the extraction.Extraction isotherm was obtained with 2.16 mol/L TBP for a typical solution containing 0.1 mol/L of bismuth and 1.0 mol/L of hydrochloric acid.About 98.5 % of bismuth has been extracted from the leaching solution under the optimum condition.Moreover,oxalate was explored as a precipitation stripping agent for BiCl_3·x TBP(x=2 or 3) complexes,by which Bi(Ⅲ) was stripped in the form of Bi_2(C_2O_4)_3·7H_2O.A stripping efficiency of 99.3% was obtained in only one stage at the phase ratio of 1 and TBP also could be recycled.Therefore,the method is an efficient,effective and highly selective approach to extract Bi(Ⅲ) and to recover metal bismuth.
基金supported by the National Natural Science Foundation of China(21706257,21878180)the Shanxi Province Coal Based Low-carbon Technology Major Projects(MC2016-05)the Xiangyuan Key Technology Research Projects(2018XYSDYY-02)。
文摘Lithium(Li)is an important energy metal in the 21st century.However,the selective recovery of Li is still a big challenge,especially from acidic solutions with multiple metal ions existence.Herein we report a new ion pair induced mechanism for selectively extracting Li^(+)from acidic chloride solutions by tributyl phosphate(TBP).It is shown that the acidity and the chloride ions in the aqueous phase have great effects on the extraction of Li^(+).The FT-IR,UV-Vis and ESI-MS experiments provide solid evidence for the formation of ion-pair complex[Li(TBP)_n(H_(2)O)_(m)]^(+)[FeCl_(4)]^(-)(n-1,2,3;m-0,1)in the organic phase,which brings about the effective and efficient extraction of Li^(+).This mechanism can overcome the Hofmeister bias and allow for the selective extraction of Li^(+) from the extremely hydrophilic chlorides.It has also been proved that the loaded Li in TBP can be effectively stripped by concentrated HCl solution with a Li/Fe separation factor>500.The understanding of the ion-pair transport mechanism is helpful for optimizing the recovery process or further advancing more efficient recovery techniques for Li from acidic liquor.
文摘First,the hierarchical ZSM-5 zeolite was prepared by hydrothermal method using mesoporous template cetyltrimethylammonium bromide(CTAB).The physical and chemical properties of the hierarchical ZSM-5 zeolite were characterized by X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FT-IR)and N2 adsorption-desorption and Scanning electron microscope(SEM).Then,the as-prepared hierarchical ZSM-5 zeolite and ion exchange resin were used as catalysts to evaluate the reaction performance of the synthesis of tributyl citrate.Compared with the ion exchange resin,the as-prepared ZSM-5 has a microporous and mesoporous composite structure and a large specific surface area,so that significantly improving the catalytic performance of synthesizing tributyl citrate and increasing the esterification rate of the reaction 8.7%.
