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• 3-Component Margules equation was used to predict vapor–liquid equilibria. • Infinite dilution activity coefficients are the sole input for solvent pre-selection. • Industrial cases were used to validate the approach. • Molecular solvents, ILs and DESs were incorporated in the screening. We present an easily accessible, open-access approach for fast pre-selection of solvents for extractive distillation at isobaric and isothermal conditions. The method uses the three-component Margules equation, which can predict vapor–liquid equilibria (VLE) in ternary systems with the infinite dilution activity coefficients, γ i ∞ , as sole input parameters. This approach is accessible for anybody regardless of the availability of process simulators or other dedicated software to predict VLE, and can be combined with open access γ i ∞ to perform solvent screening. This approach shows a deviation in VLE of <5% for non-hydrogen bond donating mixtures, while for highly dissimilar (e.g. alkane – alcohol) mixtures the deviation can be >10%. The presented method identifies molecular solvents for case studies where the same or similar solvents have also been reported in literature or are already applied on the industrial level, showing realistic pre-selection outcomes. Furthermore, small, cyclic, polar, molecular solvents are identified to induce preferential interactions and several structurally similar solvents, e.g. ethylene carbonate, dihydrolevoglucosenone and y-valerolactone, are identified to be potential alternative solvents. Among the ionic liquids (ILs) and deep eutectic solvents (DESs), the morpholinium and ammonium structures are identified to have the highest potential for increasing relative volatilities, they also show lower toxicity than other cations. This method thus proves to be able to perform early-stage pre-screening among new classes of solvents which generates information on the minimum required solvent to feed ratio (S F min ) for energy-efficient distillation from γ i ∞ obtained by measurement or from literature. [ABSTRACT FROM AUTHOR]

[Display omitted] • Acetone and diisopropyl ether form an azeotropic vapor-liquid equilibrium system. • A range of 35 biobased entrainers have been investigated. • DL-Limonene was the only entrainer found to be able to eliminate the azeotrope. • Other entrainers with strong influence were water and ethylene carbonate. • Although shifting the azeotrope, water and ethylene carbonate did not overcome it. This work focuses on the assessment of biobased solvents for the industrial separation of acetone and diisopropyl ether employing extractive distillation. From the experimental screening of 35 (biobased) solvents at 1000 mbar, 84/16 mol ratio acetone/ diisopropyl ether, and a solvent to feed ratio of 1 (mass based) it was observed that DL-limonene entrained diisopropyl ether, resulting in an acetone relative volatility of 1.44. This is a consequence of the selective repulsion of the low-boiling and more polar acetone by DL-limonene. More extensive vapor-liquid equilibrium (VLE) analysis over the entire acetone-diisopropyl ether (pseudo-)binary composition range showed that DL-limonene was the only biobased solvent able to break the azeotrope. The experimentally investigated VLE data of this ternary system was successfully correlated with the NRTL and UNIQUAC models. The other solvents that appeared most interesting in the initial screening were water and ethylene carbonate, entraining acetone with the highest observed diispropyl ether relative volatilities of 2.71 and 11.6. Although the high induced relative volatility for the 84/16 mol ratio acetone/ diisopropyl ether appeared interesting, over the entire composition range this resulted however in a shift in location of the azeotrope rather than removing the azeotrope. Therefore, it was concluded that DL-limonene is for this system the best performing biobased entrainer of the screening study. The observations are in agreement with observations from literature on similar systems, where oxygenated polar solvents were seen to have more affinity towards the ketone than towards the ether, while apolar solvents induce a higher volatility of the ketones. [ABSTRACT FROM AUTHOR]