Vapor–Liquid–Liquid Equilibria Measurements for the Dehydration of Ethanol, Isopropanol, and n‑Propanol via Azeotropic Distillation Using DIPE and Isooctane as Entrainers

Vapor–liquid equilibrium (VLE) and vapor–liquid–liquid equilibrium (VLLE) data were measured for the ethanol/diisopropyl ether (DIPE)/water, n-propanol/DIPE/water, and n-propanol/2,2,4-trimethylpentane (isooctane)/water systems at 101.3 kPa. The data were carefully measured in a Guillespie type still, equipped with an ultrasonic homogenizer. The VLE data were found to be thermodynamically consistent, and the LLE part of the VLLE data followed a regular profile according to the Othmer–Tobias correlation. VLLE were observed in the temperature ranges of (334.19 to 336.29) K, (335.31 to 345.76) K, and (347.74 to 352.31) K for the ethanol/DIPE/water, n-propanol/DIPE/water, and n-propanol/isooctane/water systems, respectively. These VLLE regions encompassed wide ranges for water and entrainer composition, with alcohol mole fractions of up to approximately 0.4. The ethanol/DIPE/water and n-propanol/isooctane/water systems displayed ternary heterogeneous azeotropes at (334.19 and 347.74) K, respectively. However, no ternary heterogeneous azeotrope was found for the n-propanol/DIPE/water system. The measured data were subsequently modeled in Aspen Plus with the nonrandom two-liquid (NRTL), universal functional UNIFAC(VLE), UNIFAC(LLE), and universal quasichemical UNIQUAC activity coefficient models, applying the default regression parameters built into Aspen Plus. UNIFAC(VLE) predicted the ethanol/DIPE/water system most accurately, while UNIQUAC performed the best for the n-propanol/DIPE/water. However, none of these models could predict the n-propanol/isooctane/water system with acceptable accuracy. The results of this study strongly support proposals that DIPE or di-n-propyl ether (DNPE) could be used as effective entrainers for alcohol dehydration, replacing the more traditional entrainers like benzene and cyclohexane.