Mechanistic modeling and equilibrium prediction of the reactive extraction of organic acids with amines: A comparative study of two complexation-solvation models using 3-hydroxypropionic acid

• Published in: Separation and purification technology Vol. 189; pp. 475 - 487
• Main Authors: Chemarin, F., Moussa, M., Allais, F., Athès, V., Trelea, I.C.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 2017; Elsevier
• Subjects: Chemical and Process Engineering; Chemical engineering; Chemical Sciences; Complex solvation; Computer Science; Engineering Sciences; Equilibrium modeling; Infrared spectroscopy; Modeling and Simulation; Organic acid; Solvent extraction; Infrared spectroscopy; Equilibrium modeling; Solvent extraction; Complex solvation; Organic acid
• ISSN: 1383-5866; 1873-3794
• DOI: 10.1016/j.seppur.2017.07.083

•IR spectroscopy demonstrated ion pair formation with dissociated 3-HP.•Two chemical models predict the solvation influence on extraction yields.•Considering the solvent as a synergistic extractant induces a 6% yield prediction error.•Considering physicochemical changes on the complexation induces a 2% yield prediction error.•Predictions are made over a wide range of concentrations. A comprehensive study of equilibrium states involved in the reactive extraction of 3-hydroxypropionic 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 transposable to other reactive extraction systems. Such knowledge is essential for further implementation of downstream processes.