The present work aimed at the study of citric acid solvent extraction in order to establish the composition of the organic phase and to obtain thermodynamic and kinetic data for the chosen system. Discontinuous extrac...The present work aimed at the study of citric acid solvent extraction in order to establish the composition of the organic phase and to obtain thermodynamic and kinetic data for the chosen system. Discontinuous extraction experiments in a single stage were performed from a synthetic solution of citric acid, with the typical concentration (10% w/v) observed in industrial fermented musts. Exploratory experiments were carried out using different organic phases in order to select the most suitable solvent phase to further continuous extraction tests in a mechanically agitated column. The selected organic phase composition was: Alamine? 336, ExxalTM 13 tridecyl alcohol, and the aliphatic diluent EscaidTM 110. Next, the effects of the contact time and of the concentrations of extractant and modifier on the citric acid extraction were studied. Among the investigated conditions, the best one was 10 minutes of contact time, 30% w/v of Alamine? 336, and 10% w/v of ExxalTM 13 tridecyl alcohol. For this condition, the equilibrium isotherm (28°C ± 2°C) was determined, and the equilibrium constant was calculated (36.8 (mol·L-1)-1.5). It was considered that trioctylamine and citric acid complexation reaction occurs mainly with non-dissociated citric acid form, because the aqueous feed solutions’ pH is lower than the citric acid pKa1. It was found that 1.5 molecules of the extractant, on average, are required to react with one citric acid molecule, which can indicate that reactions with different extractant/citric acid ratios occur simultaneously. Next, the rate constants for the direct and inverse reactions, 2.10 (mol·L-1)-1.5·s-1 and 5.69 × 10-2 s-1, respectively, were calculated. Coefficients of determination (R2) values higher than 0.93 were found in these calculations, suggesting that the results obtained using a computer modeling would be very close to those results obtained experimentally. Therefore, the present work provides data required to future modelling, design, and simulation of citric acid solvent extraction processes.展开更多
In this work, the individual and combined effects of the extractant, surfactant and modifier concentrations on the droplet coalescence time of the primary emulsion in the liquid surfactant membrane extraction process ...In this work, the individual and combined effects of the extractant, surfactant and modifier concentrations on the droplet coalescence time of the primary emulsion in the liquid surfactant membrane extraction process were evaluated, through emulsification experiments. Adogen 464 was used as extractant (carrier), and Escaid 110, as diluent. Two systems were studied. The first one composed by the extractant, the surfactant and the diluent, and the second one composed by the same reagents, but with the addition of 1-decanol as modifier. It was observed that, when the modifier is not present in the membrane phase, the surfactant not only stabilizes the primary emulsion, but, apparently, it also plays a role similar to that of the alcohol, promoting the solvation of the amine in a low polarity diluent. Furthermore, the extractant, a quaternary amine, helps to stabilize the primary emulsion in systems without a modifier. For membrane phases consisting of 1 or 5% w/w of Adogen 464 and 2% or 5% w/w of ECA 4360, a concentration of 3% w/w of 1-decanol was sufficient to promote the solvation of Adogen 464 in Escaid 110 and to obtain a low droplet coalescence time.展开更多
文摘The present work aimed at the study of citric acid solvent extraction in order to establish the composition of the organic phase and to obtain thermodynamic and kinetic data for the chosen system. Discontinuous extraction experiments in a single stage were performed from a synthetic solution of citric acid, with the typical concentration (10% w/v) observed in industrial fermented musts. Exploratory experiments were carried out using different organic phases in order to select the most suitable solvent phase to further continuous extraction tests in a mechanically agitated column. The selected organic phase composition was: Alamine? 336, ExxalTM 13 tridecyl alcohol, and the aliphatic diluent EscaidTM 110. Next, the effects of the contact time and of the concentrations of extractant and modifier on the citric acid extraction were studied. Among the investigated conditions, the best one was 10 minutes of contact time, 30% w/v of Alamine? 336, and 10% w/v of ExxalTM 13 tridecyl alcohol. For this condition, the equilibrium isotherm (28°C ± 2°C) was determined, and the equilibrium constant was calculated (36.8 (mol·L-1)-1.5). It was considered that trioctylamine and citric acid complexation reaction occurs mainly with non-dissociated citric acid form, because the aqueous feed solutions’ pH is lower than the citric acid pKa1. It was found that 1.5 molecules of the extractant, on average, are required to react with one citric acid molecule, which can indicate that reactions with different extractant/citric acid ratios occur simultaneously. Next, the rate constants for the direct and inverse reactions, 2.10 (mol·L-1)-1.5·s-1 and 5.69 × 10-2 s-1, respectively, were calculated. Coefficients of determination (R2) values higher than 0.93 were found in these calculations, suggesting that the results obtained using a computer modeling would be very close to those results obtained experimentally. Therefore, the present work provides data required to future modelling, design, and simulation of citric acid solvent extraction processes.
基金acknowledge CAPES,CNPq,FAPEMIG and PRPq by the financial support.
文摘In this work, the individual and combined effects of the extractant, surfactant and modifier concentrations on the droplet coalescence time of the primary emulsion in the liquid surfactant membrane extraction process were evaluated, through emulsification experiments. Adogen 464 was used as extractant (carrier), and Escaid 110, as diluent. Two systems were studied. The first one composed by the extractant, the surfactant and the diluent, and the second one composed by the same reagents, but with the addition of 1-decanol as modifier. It was observed that, when the modifier is not present in the membrane phase, the surfactant not only stabilizes the primary emulsion, but, apparently, it also plays a role similar to that of the alcohol, promoting the solvation of the amine in a low polarity diluent. Furthermore, the extractant, a quaternary amine, helps to stabilize the primary emulsion in systems without a modifier. For membrane phases consisting of 1 or 5% w/w of Adogen 464 and 2% or 5% w/w of ECA 4360, a concentration of 3% w/w of 1-decanol was sufficient to promote the solvation of Adogen 464 in Escaid 110 and to obtain a low droplet coalescence time.
