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
For the accurate prediction of equilibrium distribution ratios of rare earth metals during solvent extraction under non-ideal conditions, the extraction equilibria of yttrium （Ⅲ） and europium （Ⅲ） from the hydroc...For the accurate prediction of equilibrium distribution ratios of rare earth metals during solvent extraction under non-ideal conditions, the extraction equilibria of yttrium （Ⅲ） and europium （Ⅲ） from the hydrochloric acid solutions with P507 in Shellsol D70 were studied. A chemically-based model was established and the extraction equilibrium constants were determined by the nonlinear least squares method. The proposed model involves the cation exchange reaction and the solvation extraction in the low and high acidity regions, respectively. In the model, the nonideality of the aqueous phase and was corrected by considering the complexation of the metals with Cl- and by replacing with its effective concentration, respectively. This model was verified by fair agreement between the calculated metal distribution ratios and those experimentally obtained in the single metal systems. The feed concentrations for the systems are in wide ranges of the metal （up to 0.1 mol/L）, hydrochloric acid （0.07-3.00 mol/L） and the extractant （0.25-1.00 mol/L）. The model enables the engineering prediction of the equilibrium distribution ratios with good accuracy in a binary metal system.展开更多
Mechanisms that control the extraction rate of essential oil from Zataria multiflora Boiss. (Z. multiflora) with subcritical water (SW) were studied. The extraction curves at different solvent flow rates were used to ...Mechanisms that control the extraction rate of essential oil from Zataria multiflora Boiss. (Z. multiflora) with subcritical water (SW) were studied. The extraction curves at different solvent flow rates were used to deter-mine whether the extractions were limited primarily by the near equilibrium partitioning of the analyte between the matrix and solvent (i.e. partitioning thermodynamics) or by the rates of analyte desorption from the matrix (i.e. ki-netics). Four simple models have been applied to describe the extraction profiles obtained with SW: (1) a model based solely on the thermodynamic distribution coefficient KD, which assumes that analyte desorption from the ma-trix is rapid compared to elution; (2) one-site kinetic model, which assumes that the extraction rate is limited by the analyte desorption rate from the matrix, and is not limited by the thermodynamic (KD) partitioning that occurs dur-ing elution; (3) two-site kinetic model and (4) external mass transfer resistance model. For SW extraction, the thermodynamic elution of analytes from the matrix was the prevailing mechanism as evidenced by the fact that ex-traction rates increased proportionally with the SW flow rate. This was also confirmed by the fact that simple re-moval calculations based on determined KD (for major essential oil compounds) gave good fits to experimental data for flow rates from 1 to 4 ml·min-1. The results suggested that the overall extraction mechanism was influenced by solute partitioning equilibrium with external mass transfer through liquid film.展开更多
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(P02426)supported by the Japan Society for the Promotion of Science for Postdoctoral Fellowships for Foreign Researchers
文摘For the accurate prediction of equilibrium distribution ratios of rare earth metals during solvent extraction under non-ideal conditions, the extraction equilibria of yttrium （Ⅲ） and europium （Ⅲ） from the hydrochloric acid solutions with P507 in Shellsol D70 were studied. A chemically-based model was established and the extraction equilibrium constants were determined by the nonlinear least squares method. The proposed model involves the cation exchange reaction and the solvation extraction in the low and high acidity regions, respectively. In the model, the nonideality of the aqueous phase and was corrected by considering the complexation of the metals with Cl- and by replacing with its effective concentration, respectively. This model was verified by fair agreement between the calculated metal distribution ratios and those experimentally obtained in the single metal systems. The feed concentrations for the systems are in wide ranges of the metal （up to 0.1 mol/L）, hydrochloric acid （0.07-3.00 mol/L） and the extractant （0.25-1.00 mol/L）. The model enables the engineering prediction of the equilibrium distribution ratios with good accuracy in a binary metal system.
基金support is gratefully acknowledged to the Semnan University and the Iranian Research Organization for Science and Technology (IROST)
文摘Mechanisms that control the extraction rate of essential oil from Zataria multiflora Boiss. (Z. multiflora) with subcritical water (SW) were studied. The extraction curves at different solvent flow rates were used to deter-mine whether the extractions were limited primarily by the near equilibrium partitioning of the analyte between the matrix and solvent (i.e. partitioning thermodynamics) or by the rates of analyte desorption from the matrix (i.e. ki-netics). Four simple models have been applied to describe the extraction profiles obtained with SW: (1) a model based solely on the thermodynamic distribution coefficient KD, which assumes that analyte desorption from the ma-trix is rapid compared to elution; (2) one-site kinetic model, which assumes that the extraction rate is limited by the analyte desorption rate from the matrix, and is not limited by the thermodynamic (KD) partitioning that occurs dur-ing elution; (3) two-site kinetic model and (4) external mass transfer resistance model. For SW extraction, the thermodynamic elution of analytes from the matrix was the prevailing mechanism as evidenced by the fact that ex-traction rates increased proportionally with the SW flow rate. This was also confirmed by the fact that simple re-moval calculations based on determined KD (for major essential oil compounds) gave good fits to experimental data for flow rates from 1 to 4 ml·min-1. The results suggested that the overall extraction mechanism was influenced by solute partitioning equilibrium with external mass transfer through liquid film.
