Liquid–Liquid Equilibria of Ternary Mixtures Containing n-Tetradecane + γ-Valerolactone + Aldehyde [Butanal or Pentanal or (E)-2-Undecenal] at 298.15 K

Abstract

γ-Valerolactone (GVL) is a biomass-based chemical with appealing physicochemical properties for use as a solvent, but its actual development of extraction processes still requires an extensive mapping of the thermodynamic equilibrium involved and accurate models for simulation. In this sense, this work aimed at evaluating the liquid–liquid equilibrium of model systems, composed of n-tetradecane + GVL + aldehyde [butanal or pentanal, or (E)-2-undecenal] at 298.15 K, related to the extraction of oxygenated contaminants in a Fischer–Tropsch diesel process. Phase compositions in equilibrium were indirectly determined by means of density correlation along the solubility curve. Both short-chain aldehydes, butanal and pentanal, distributed preferably within the solvent phase, resulting in the partition ratio (K i ) within the range of 1.36–2.9 and selectivity higher than 33.1, which reveals the suitability for using GVL as the solvent. The binary interaction parameters of the NRTL and UNIQUAC models successfully correlated the experimental data, resulting in maximum root mean square deviations of 0.38 and 0.47%, respectively.

γ-Valerolactone as a Green Solvent for Extracting Carboxylic Acids and Alcohols from n-Tetradecane: Equilibrium Data for Model Systems at 298.15 K

“…Effects of solute chain length and of organic function are less expressive in the GVL-rich side, as curves are close to each other, especially for a low amount of solute, whereas they are dispersed in the raffinate side in this same region. This result also agrees with similar systems containing ketones and aldehydes. , …”

“…High coefficients of determination as well as low standard deviations for the correlation parameters were desired to guarantee a good description of experimental data and low uncertainties associated with the calculated equilibrium compositions. This set of equations provided reliable results in previous works for ternary LLE systems containing GVL + n -tetradecane + oxygenated solutes and was therefore applied in this work as well. − in which ρ, w 1 , and w i (for i = 3, 4, 5, 6, and 7) are density, n -tetradecane, and solute mass fractions, respectively; subscripts ext and raf stand for extract and raffinate side of the solubility curve, respectively; letters a–f are parameters of the correlations; and k 1 – k 4 are constants of the correlations.…”

“…Solubility curve data are relevant to determine the size of the partial miscibility region of a system and are also the base to indirectly quantify phase equilibrium compositions. As in previous works, − it was determined by means of the cloud point method, which consists in adding into a homogeneous mixture a component that promotes phase split. For obtaining the solubility curve in the raffinate ( n -tetradecane rich) side, GVL (solvent) was added into a binary homogeneous mixture of n -tetradecane + oxygenated solute (carboxylic acid or alcohol).…”

“…GVL belongs to the same solvent category, but it is less harmful to the environment and human safety. In this sense, our research group initiated a series of investigations to study GVL as an extracting agent for carboxylic acids (butanoic and hexanoic acid), ketones (propanone and 2-butanone), and aldehydes (butanal and pentanal) from n -tetradecane, representing model systems for the diesel FT synthesis. In this work, we extended this investigation to two more carboxylic acids (propanoic and pentanoic acid) and to three alcohols (1-propanol, 1-butanol, and 1-pentanol).…”

Revision and Extension of a Generally Applicable Group-Additivity Method for the Calculation of the Refractivity and Polarizability of Organic Molecules

“…Another important extension that has not been covered in the earlier paper [1] is the class of ionic liquids [10,. In addition, several papers have been added which contributed various subjects that could not be assigned to any specific subject of the aforementioned ones [2,[371][372][373][374][375][376][377][378][379][380][381][382][383][384][385][386][387][388][389]. Finally, a number of papers published experimental data of the polarizability of molecules, in many cases derived from their refractivity values [6,[390][391][392][393][394][395][396][397][398][399][400][401].…”