“…This is equivalent to a synergistic reactive extraction by two extractants found in the literature for organic acids. For example, it was shown that tri-n-butylphosphate, a phosphorous bonded oxygen donor and a strongly solvating agent [1], was a good synergistic extractant with TOA for organic acids [23,24], as was di-2-ethylhexylphosphoric acid [25,26], a water insoluble phosphoric acid. These binary extractant systems allow stoichiometrically defined complexes consisting of three types of units: the organic acid, the amine and the synergistic extractant.…”
Section: Model 1: the Solvent As A Synergistic Extractantmentioning
A comprehensive study of equilibrium states involved in the reactive extraction of 3hydroxypropionic acid (3-HP) by tri-n-octylamine (TOA) in n-decanol is described. Complexation phenomena between 3-HP and TOA were revealed by infrared spectroscopy (FT-IR). This study demonstrated that the main extraction mechanism is the formation of an ion pair involving the dissociated form of 3-HP. Chemical models were then formulated, taking the formation of the ion pair between 3-HP and TOA and the influence of the amount of solvent in the organic phase into account. Two models are proposed: (1) a stoichiometric model where the solvent is seen as a reagent that is involved in the complexation as a synergistic extractant, but with competition for solvation via H-bond interactions with TOA; (2) a model where the solvent is seen as a phase modifier that improves the physicochemical properties of the extractant and that changes the complexation equilibrium. Both models describe the extraction yields in the investigated ranges, with Model (2) being particularly predictive since it provides a mean absolute prediction error of less than 2% in yield units. According to this latter model, the complexation equilibrium coefficient increases with the increase of the n-decanol proportion in the organic phase. Model (2) shows that solvation effects are better described as non-stoichiometric interactions. Therefore, the two mechanistic models accurately represent extraction yields over a wide range of initial conditions and are potentially
“…This is equivalent to a synergistic reactive extraction by two extractants found in the literature for organic acids. For example, it was shown that tri-n-butylphosphate, a phosphorous bonded oxygen donor and a strongly solvating agent [1], was a good synergistic extractant with TOA for organic acids [23,24], as was di-2-ethylhexylphosphoric acid [25,26], a water insoluble phosphoric acid. These binary extractant systems allow stoichiometrically defined complexes consisting of three types of units: the organic acid, the amine and the synergistic extractant.…”
Section: Model 1: the Solvent As A Synergistic Extractantmentioning
A comprehensive study of equilibrium states involved in the reactive extraction of 3hydroxypropionic acid (3-HP) by tri-n-octylamine (TOA) in n-decanol is described. Complexation phenomena between 3-HP and TOA were revealed by infrared spectroscopy (FT-IR). This study demonstrated that the main extraction mechanism is the formation of an ion pair involving the dissociated form of 3-HP. Chemical models were then formulated, taking the formation of the ion pair between 3-HP and TOA and the influence of the amount of solvent in the organic phase into account. Two models are proposed: (1) a stoichiometric model where the solvent is seen as a reagent that is involved in the complexation as a synergistic extractant, but with competition for solvation via H-bond interactions with TOA; (2) a model where the solvent is seen as a phase modifier that improves the physicochemical properties of the extractant and that changes the complexation equilibrium. Both models describe the extraction yields in the investigated ranges, with Model (2) being particularly predictive since it provides a mean absolute prediction error of less than 2% in yield units. According to this latter model, the complexation equilibrium coefficient increases with the increase of the n-decanol proportion in the organic phase. Model (2) shows that solvation effects are better described as non-stoichiometric interactions. Therefore, the two mechanistic models accurately represent extraction yields over a wide range of initial conditions and are potentially
“…29,30,32 . For extraction of carboxylic acids, the first types of solvents provide low distribution coefficient because of high affinity of acid molecule towards water molecules, whereas the second and the third types of solvents give higher distribution coefficients in organic phase.…”
Section: Stoichiometric and Spectroscopic Study Of Reactive Extractiomentioning
Phenylacetic acid is widely used in the pharmaceutical industry for production of antibiotics. The recovery of phenylacetic acid from dilute aqueous waste with tri-n-butyl phosphate in methyl isobutyl ketone and petroleum ether has been attempted, and the results are presented in terms of distribution coefficient, extraction efficiency, apparent equilibrium constant, and loading ratio. The mechanism of reactive extraction was analyzed and the stoichiometric ratio of phenylacetic acid to tri-n-butyl phosphate in methyl isobutyl ketone and petroleum ether was found to be 1:0.5 and 1:1.2. Mass action law was used to represent the reactive extraction equilibrium for phenylacetic acid−tri-n-butyl phosphate−diluents which satisfied much in the present study. FTIR spectroscopy was studied for confirmation of the formation of a complex between acid and extractant. Further relative basicity approach has been extended to represent the experimental results. The model is best suited to experimental results.
“…In conventional extraction processes, inert organic solvents such as toluene, benzene, xylene, hexane, heptane, and decane are used as diluents to adjust the viscosity and density of the extractant, and water-insoluble organic acids, fatty amides, and fatty alcohols are used as modifiers to further increase the distribution coefficient. [2][3][4][28][29][30][31] 3.2. Selection of Extractant and Modifier.…”
Section: Background For Extraction Of Acetic Acid From Dilute Aqueousmentioning
confidence: 99%
“…There is generally an optimum concentration for a mixture of an extractant and a modifier where the value of K d is the highest. 3,4,28 The reactive extraction mechanism of the monocarboxylic acid HA is usually expressed in the literature as where B org is the extractant. When amines (TOA, TLA, or tridecylamine) are used as extractants and fatty alcohols as modifiers for acetic acid extraction, the governing extraction mechanism is by ion-pair formation and H-bonding.…”
Section: Extraction and Mass-transfer Mechanism 331 Forward Extractionmentioning
confidence: 99%
“…The value of m can be up to 5. 4,28,34,35 Several complexes can exist in the organic phase, and the complex can be stabilized by the modifier. Therefore, the value of K d is a complicated function of the species and the concentration of the acid in the feed, the species and the concentration of the extractant and the modifier in the organic phase, and the temperature.…”
Section: Extraction and Mass-transfer Mechanism 331 Forward Extractionmentioning
Supported liquid membrane pervaporation (SLMPV) is a pervaporation process for separating
volatile organic compounds (VOCs) from their dilute aqueous solution. It simultaneously
integrates extraction of the VOCs from the aqueous solution with flash distillation of the VOCs
from the organic phase. By using a liquid membrane consisting of reactive extractants,
pervaporation of primarily acetic acid from its aqueous solutions was studied. Limited studies
of butyric acid were also done. Among various extractants tested, trioctylamine (TOA) and
tridodecylamine demonstrated better performances. The SLM is permselective for acetic acid
and butyric acid. The acetic acid selectivity can be as high as 33 for a feed of 1 M at 60°C, an
order of magnitude higher than that obtained by any solid polymeric membrane reported in the
literature. The simple SLM system demonstrated long-term stability; for example, decreases of
about 30% in both pervaporation flux and selectivity were observed over an operational period
of 500 h. A new technique of continuous on-line regeneration of the LM during operation
maintains completely stable operational performance.
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