Liquid–Liquid Equilibria of Ternary Mixtures (1-Heptanol, Propanone, 2-Butanone or 2-Heptanone + γ-Valerolactone + n-Tetradecane)

Abstract

Although petroleum is widely used to make solvents and to produce energy, solvents derived from it, such as acetonitrile, may not be the safest and most sustainable options currently available. Additionally, processes such as the Fischer–Tropsch synthesis emerge as an intelligent alternative to produce energy from coal, biomass, or natural gas to supply the increasing demand for petroleum-derived products. Thus, with a green solvent, γ-valerolactone, applied to the removal of oxygenated compounds from a Fischer–Tropsch process stream, this work suggests the application of a less toxic solvent to an alternative energy production process through model systems. In this sense, liquid–liquid equilibrium experimental data were measured for systems composed of an oxygenated solute (1-heptanol, propanone, 2-butanone, or 2-heptanone) + γ-valerolactone + n-tetradecane at 298.15 K. The liquid–liquid equilibrium data were successfully correlated by the nonrandom two-liquid model with a medium average deviation lower than 1%. Therefore, the measured experimental data may contribute to the design of a liquid–liquid extraction process applied to the refinement of synthetic crude oil from a Fischer–Tropsch synthesis.

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

“…As the alkyl chain length, which is responsible for the nonpolar part of the oxygenated solutes, becomes longer, it can form more dissipative forces with the n -tetradecane molecule, which is also nonpolar, while the polar end of the oxygenated solute interacts with the solvent, resulting in a higher amount of solute and solvent in the raffinate ( n -tetradecane rich) side. In this sense, results from this work are in agreement with those from Corrêa et al and Paz et al In relation to the former, data from butanoic acid are in between those from propanoic and pentanoic acid along the entire curve, while hexanoic acid attributes the highest miscibility for the ternary mixtures containing a carboxylic acid. In relation to the latter, miscibility raises from 1-propanol to 1-heptanol, and experimental compositions for 1-pentanol do not overlap with those of 1-heptanol on the raffinate side.…”

“…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).…”

Isobaric Vapor–Liquid Equilibria for Binary Mixtures of Biomass-Derived γ-Valerolactone + Tetrahydrofuran and 2-Methyltetrahydrofuran

“…The separation of liquid mixtures can easily be performed by distillation even at an industrial scale, for which the thermodynamic data of the liquid mixture is fundamentally important. It was demonstrated that GVL could be separated from water, , C 1 –C 3 alcohols, formic acid, and furfural without the formation of any azeotropic mixtures, while its liquid–liquid equilibrium was studied in its mixtures with ketones and carboxylic acids . Since GVL exhibits appreciable performance as a fossil fuel additive, the liquid–liquid equilibrium of mixtures containing hydrocarbons and its solubility in diesel were also investigated.…”